JPS62136648A - Heat developable color photosensitive material - Google Patents

Abstract

PURPOSE:To obtain a photosensitive material having improved transferrability, adhesiveness and strippability by incorporating a polymer latex into at least one layer of photograph constituting layers and incorporating an org. fluoro compd. into at least one layer of nonphotosensitive protective layers. CONSTITUTION:This heat developable color photosensitive material has the photograph constituting layers consisting of at least one layer of heat developable photosensitive layer and at least one layer of nonphotosensitive layer on a base. At least one layer of the nonphotosensitive protective layer is provided on the heat developable photosensitive layer furthest from the base of such color photosensitive material on the side opposite from the base and the polymer latex is incorporated into at lest one layer of the photograph constituting layers. The org. fluoro compd. is incorporated into at least one layer of the nonphotosensitive protective layer. The heat developable color photosensitive material having the excellent transferrability of yes and the strippability in the stage of stripping and the good brightness on the surface of an image receiving member after stripping is thus obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a heat-developable 7J color light-sensitive material, and more particularly to a heat-developable color light-sensitive material with improved transferability, adhesion and peelability.

[Front of the Invention] In recent years, heat-developable photosensitive materials whose developing step can be performed by heat treatment have been attracting attention as photosensitive materials.

Regarding such a heat-developable photosensitive layer, for example,
No. 4921 and No. 43-4924 disclose a photosensitive material comprising an organic silver salt, silver halide, a reducing agent, and a binder, which is commercialized as dry silver by 3M Company.

Attempts have been made to improve such heat-developable light-sensitive materials and to obtain the image by various methods.

For example, U.S. Patent Nos. 3,531,286 and 3,7
61.270 and 3.764.328, etc., a method for avoiding the formation of a dye image by the reaction of an oxidized product of an aromatic first-handling amine developing agent with a coupler, Research Disclosure p- (Research D 1s
closure) 15108 and 15127,
A dye is formed by the reaction of a coupler with an oxidized form of a reducing agent (hereinafter also referred to as developer or developing agent), which is a sulfonamide phenol or sulfonamide aniline derivative described in U.S. Pat. No. 4,021,240, etc. The method, as disclosed in British Patent No. 1.590.956, uses an organic imino silver salt having a dye moiety and releases the dye in a heat development section to release a dye image on a separately provided image receiving layer. The method is also described in JP-A No. 52-105821,
52-105822, 5G-50328, U.S. Pat. No. 4,235,957, etc., methods for obtaining positive dye images by the silver cord bleaching method, Zarani U.S. Pat. No. 3,180,731, Same No. 3,985,565, Same No. 4,022,617, Same No. 4.452.883,
Various methods have been proposed, such as the method of obtaining a dye image using a leuco dye disclosed in Japanese Patent Application Laid-Open No. 59-206831.

However, these proposals regarding the heat-developable color photosensitive material r1 have problems in that it is difficult to bleach-fix the black and white silver images formed at the same time, it is difficult to obtain a clear color image, and the image is rough. These methods require complicated post-processing and are not yet satisfactory for practical use.

In recent years, as a new type of color image forming method using heat development, Japanese Patent Application Laid-open Nos. 57-179840 and 57-186 have been developed.
No. 744, No. 57-198458, No. 57-2072
No. 50, etc., disclosed a method of obtaining a color image by transferring a diffusible dye released by thermal development.

By further improving these methods, for example, non-diffusible unidimensional dye-donating substances disclosed in JP-A-58-58543 and JP-A-5'1-IG8439 are oxidized to allow diffusion. A method for releasing sex pigments, JP-A-58
-79247, 59-174834, 59-1
No. 2431, No. 59-159159, No. 60-295
A method of releasing a diffusible dye by coupling with an oxidized form of a developing agent as disclosed in No. 0, etc.;
JP-A-58-149046, JP-A No. 58-149047
No. 5L124339, No. 59-181345, No. 60-2950, Japanese Patent Application No. 59-181604,
No. 59-182506, No. 59182507,
A method using a non-diffusible compound that reacts with an oxidized product of a phenomenon agent to form a diffusible dye as disclosed in JP-A No. 59-272335, etc.;
No. 440, No. 59-124327, No. 59-1544
No. 45, No. 59-166954, etc., are non-diffusible reducible dye-donating substances that lose the ability to release diffusible dyes upon oxidation, and conversely, non-diffusible reducible dye-donating substances that release diffusible dyes upon reduction. Some methods have been proposed, such as a method containing a pigment-providing substance.

The basic structure of a color type heat-developable photosensitive material that obtains a color image using these emitted or formed diffusive dyes is as follows:
It consists of a light-sensitive element and an image-receiving element, and the light-sensitive element basically contains a light-sensitive silver halide, an organic silver salt, a reducing agent, a dye-providing substance,
It consists of a binder. In the present invention, only the photosensitive element is referred to as a heat-developable photosensitive material in a narrow sense, and the image receiving element is referred to as an image receiving member.

The above heat-developable photosensitive material is one in which a dye image is obtained by transferring the released or formed diffusible dye onto a passive layer of an image receiving member provided on the same support or another independent support. In terms of image sharpness, stability, etc., it has been improved in many respects compared to previous heat-blocking color photosensitive materials.

These heat-developable photosensitive materials generally have a layer on at least one side of a support, which mainly contains a hydrophilic colloid such as gelatin as a binder. The dye formed or released by thermal phenomena passes through this hydrophilic colloid layer and is stained onto the image receiving member, which fixes the dye.

Therefore, it goes without saying that the hydrophilic colloid layer plays an important role not only during the formation of the dye but also during the diffusion of the dye. - By way of example, by increasing the hardness of the hydrophilic colloid, the rate of dye diffusion and the amount of dye reaching the image receiving member is significantly reduced.

In order to improve the drawbacks caused by hydrophilic colloids, techniques to make the binder flexible are known, such as U.S. Pat. No. 2.376,005, U.S. Pat. .166, 3.397.988
No. 3.411,911, No. 3. ．． 111,9
No. 12 and Special Publication No. 39-4272, No. 39-1770
Specification J of No. 2, No. 43-13482, No. 45-5331, etc. describes two methods of incorporating polymer latex into the binder.

By incorporating a polymer latex such as polyethyl acrylate or polymethyl acrylate into a binder made of hydrophilic colloid, the transferability of the dye released or formed by heat development is improved, and the hardening film of the binder layer is improved. The influence on the transferability of the dye due to temperature fluctuations is also reduced.

However, when a polymer latex is contained in the binder of a heat-developable photosensitive material, the adhesion and/or tackiness increases in high humidity, especially in a high temperature and high humidity atmosphere, and it easily adheres to other objects by coming into contact with them. , to prevent inconveniences such as film peeling.
In addition to the above, in so-called "two-sheet type" heat-developable photosensitive materials that use an image-receiving member in which an image-receiving layer is formed on a support separate from the photosensitive layer, both of them after heat development and transfer. It has become clear that when the sheet is peeled off, its peelability is significantly reduced.

As a means to improve the adhesion of a layer containing polymer latex, it is generally possible to add a so-called matting agent, typified by silica, colloidal silica, polymethyl methacrylate, etc., with an average particle size of about 1 to 5 μm to the outermost layer. It is known to make it difficult to adhere to other objects.

However, if a matting agent is added to the collar, which can sufficiently improve adhesion, the matting agent will aggregate after heat development and cause uneven gloss on the surface, or in the case of the above-mentioned "two-sheet type" heat-developable photosensitive material. is the time of ring 1 elephant! It has been discovered that due to wear, the surface of the receiving stage member loses its luster, significantly lowering the product price.

[Object of the Invention] Therefore, the first object of the present invention is to provide a heat-developable color photosensitive material which has improved dye transferability and good peelability.

A second object of the present invention is to provide a heat-developable color photosensitive material that has excellent dye transferability and peelability when peeled off, and also has good gloss on the surface of an image-receiving member after peeling.

[Structure of the Invention] The above-mentioned object of the present invention is to provide a heat agglomerated color photosensitive material having a photographic constituent layer consisting of at least one heat-developable photosensitive layer and at least one non-photosensitive layer on a support.
The heat-developable photosensitive layer furthest from the support has at least one non-photosensitive protective layer on the side opposite to the support, and at least one of the photographic constituent layers contains a polymer latex; This was achieved by providing a heat-developable color photosensitive material containing an organic fluoro compound in at least one of the non-photosensitive protective layers.

[Specific Structure of the Invention] In the present invention, an organic fluoro compound is a compound having at least one carbon atom, preferably three or more carbon atoms in the molecule, and has a fluorine atom and a carbon atom in the main chain or side chain. It also includes polymer compounds that have.

For organic fluoro compounds, see U.S. Pat. No. 3,589.
．． No. 906, No. 3,666.478, No. 3,75
No. 4,924, @3.775.126, 3,850
, 640, West German Patent Publication No. 1.942.665, West German Patent Publication No. 1,961,638, West German Patent Publication No. 2.124.262, British Patent No. 1,330,356, Belgian Patent No. 742,
eao@, JP-A-46-7781, JP-A No. 4B-971
No. 5, No. 49-46733, No. 49-133023
No. 50-99529, No. 50-113221, No. 50-160034, No. 51-43131, No. 51-129229, No. 51-106419,
No. 53-84712, No. 54-111330, No. 56-109336, No. 59-30536, No. 5
No. 9-45441, Special Publication No. 47-9303, No. 48-
No. 43130 and No. 59-5887, etc., and these can be used.

Specific compound examples are shown below.

Below margin F-/ CF3(CF2)6 COONH4 CF3(CF2)9- (CHzho COOHC-
Fs (CFz)s-(CHz) to COONaC
LCFz (CF-CFz)a C0OHt F-taH(CF2CF2)s COONa HOOC-(CFz CF)4 C0OH■ t CL(CFz-CF)s CF2-C00Kt F- & CF3 (CF2)6 CH-CH(CH2 )3-
COONaCF3-(CF2)3 CF (CH2
)1G-COONaCF3 F-1゜CF3(CF2)7 CON (CH2)Z C
OONaCH3 -1I CL(CF2CF2)3-COONa F-1″1 CF3(CF2)3-CH2CH2SO2N CH2
COONaC2 Xun F-, noon-tl- CF2 (CF2)? Sow-N-(CHz)s-C
OOK2H5 CFx(CF2)7 5O2-N-CH2-COOK3
H7 F-1fi' CF3 (CFri7 Sow-N-COOK3H7 F-+9 CFs (CF2)? SO2N CH25O3H
2H5 CF2 (CF2)6-co-N (CH2)2 5
O3K2Hs - F-2/ F-phantom CF3 (CF2)7 5O3K CF3 (CF2)11 CHzO3O3NaF-2
5 CF3 (CF2)6 Coo (CH2)3
SO3NaH(CF2)6 CH20-(CH2)3
5OaNaCH2-COOCH2(CF2)6-HN
a03S CH-COOCH2(CF2)6-HCI
6R13CH-COOCH2-CF3 0jNa C16H330H-CONHCH2CF2-CFzHS
Os Na CF3 (CF2) Two 5O2-N-CH2CH2
0SO3HCH3 (SOsNa is at 4- or 5-position) CF3 (CF, )12 Coo (CH2CH
20) 2G-HCF3 (CF2)6 Co-N
(CH2)2 0 (CHzCHzOhHsaH3 CF3(CF2)7 SOz N (CH2)2-
0 (CH2CH20)20 H2H5 CF3 (CFz)a Coo (CH2CH2
0)5 CH3H-(,CF2CF2)5-CH20
HH-(CF2CF2)3 CH20HCF3 (C
F2)6 Coo(CH2-CHO)4 (CH2C
H20) CH3 CF3(CF2)4-Coo(CH2CH-0)3-(
CH2CH20)1G-(BACH3*-(- :J- \CHs CH2CH3 2F5 F-50 F-51 ↓ H(CHz)a CH20-CH2CHCH2SO3
H 0HCH3 H(CF2)4 CH20CH2CF2H20(CH
2CH20)4HH H(CF2)6 CH20CHCH20CH2CF2
CF2H0(ni'H2CH20)5H The organic fluoro compounds used in the present invention include, for example, U.S. Pat.
2,732.398, 2,764,602,
No. 2,80G, No. 8GG, No. 2,809,998,
No. 2,915,376, No. 2,915,528, No. 2,934.450, No. 2,937,098, No. 2
, No. 957.031, No. 3.472.894, No. 3.
Specifications of No. 555.089, Japanese Patent Publication No. 45-37304, and Japanese Patent Publication No. 47-9613, Journal of the British Chemical Society (J,
Chem, Soe, ), 1950, 2789
Pages: 1957, pp. 2574 and 2640; Journal of the American Chemical Society (J, Amer, Cheln, S.
ac, ), Vol. 79, p. 2594 (1957); and Oil Chemist (J, Japan Oil Chemist
It can be synthesized according to the method described in, for example, Sc. Soe, ), Vol. 12, p. 653.

In the present invention, the organic fluoro compound is contained in at least one of the non-photosensitive protective layers (hereinafter referred to as the protective layer), but it is preferable that the organic fluoro compound be contained in at least one of the protective layers furthest from the support. is most preferred. Further, the specific fluoro compound may optionally be included in other photographic constituent layers other than the protective layer.

In the present invention, the specific fluoro compound added n is 0.1 mg to 10 (J), preferably 1.0 mg to 1.0 (l) per 112 of the photosensitive material.

In the present invention, two or more fluoro compounds may be used in combination.

There are no restrictions on the method of adding the organic fluoro compound of the present invention, such as adding it as a solution in water or an organic solvent, adding it as a powder or suspension after grinding it with a ball mill or sand mill, or adding it as a powder or suspension by dissolving it in a high boiling point solvent. There are methods such as adding it as an oil-in-water emulsion.

The polymer latex used in the present invention is an aqueous dispersion of polymers, and such polymers are mainly classified into condensation polymers and vinyl polymers.

Examples of the condensation polymer include polyamide, polypeptide, polyester, polycarbonate, polyacid anhydride, polyurethane, polyurea, polyether, and the like. Examples of unsaturated compound-based polymers include addition polymers with vinyl groups, such as adipose hydrochloride-based, mercury-based, vinyl alcohol-based, nitrile-based, acrylic-based, methacrylic-based, acrylonitrile-based, and halogen-based polymers. Examples include single polymers and copolymers of combinations thereof.

Polyester or vinyl polymers are preferably selected from the viewpoint of ease of production of polymer latex. The polymerizable unsaturated compound serving as a raw material for these polymers may be a polymerizable unsaturated ethylenic compound or a diolefin compound. For example, acrylic acid and its esters, methacrylic acid and its esters, crotonic acid and its esters, vinyl esters, maleic acid and its diesters, fumaric acid and its diesters, itaconic acid and its diesters, olefins. , styrenes, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl ketones, polyfunctional monomers,
Examples include vinyl heterocyclic compounds, glycidyl esters, unsaturated di-lyl compounds, and the like.

Specific examples of these polymerizable unsaturated compounds include acrylic esters such as methyl acrylate, ethyl acrylate, low propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, 5ec-butyl acrylate, and amyl acrylate. , hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, tert
-Octyl acrylate, 2-chloroethyl acrylate, 2-bromoethyl acrylate, 4-chloro1cobutyl acrylate, cyanoethyl acrylate, 2-7cetoxyethyl acrylate, dimethylaminoethyl acrylate, benzyl acrylate, methoxybenzyl acrylate, 2-chlorosif O hexyl acrylate,
Cyclohexyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, phenyl acrylate, 5-hydroxypentyl acrylate, 2.
2=dimethyl-3-hydroxypropyl acrylate,
2-methoxyethyl acrylate, 3-methoxyethyl acrylate, 2-ethoxyethyl acrylate, 2-
iso-propoxy acrylate, 2-butoxyethyl acrylate, 2-(2-methoxyethoxy)ethyl acrylate, 2-(2-butoxyethoxy)ethyl acrylate, ω-methoxypolyethylene glycol acrylate-1 to (addition mole 1n=9) , 1-bromo-2-methoxyethyl acrylate, 1,1-dichloro-2-ethoxyethyl acrylate, and the like.

Examples of methacrylic acid esters include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, 0-butyl methacrylate, isobutyl methacrylate, 5ec-butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, Chlorobenzyl methacrylate, ocdyl methacrylate, sulfopropyl methacrylate, N-ethyl-N-phenylaminoethyl methacrylate, 2-(3-phenylpropyloxy)ethyl methacrylate, dimethylaminophenoxyethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, Phenyl methacrylate, cresyl meccrylate, naphthyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, triethylene glycol monomethacrylate, dipropylene glycol monomethacrylate, 2
-Methoxyethyl methacrylate, 3-methoxybutyl methacrylate, 2-acetoxyethyl methacrylate, 2-acetoacetoxyethyl methacrylate, 2-■
Toxyethyl methacrylate, 2-iso-propoxyethyl methacrylate, 2-butoxyethyl methacrylate, 2-(2-methoxyethoxy)ethyl methacrylate, 2-(2-ethoxyethoxy)ethyl methacrylate, 2-(2-butoxyethoxy)ethyl methacrylate , ω-methoxypolyethylene glycol methacrylate (additional mole number n-6).

Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl chloroacetate.
Examples include 1-1 methoxy acetate, vinyl phenyl acetate, vinyl benzoate, vinyl salicylate, and the like.

Examples of olefins include dicyclopentadiene, ethylene, propylene, 1-butene, 1-pentene,
Examples include vinyl chloride, vinylidene chloride, isoprene, chloroprene, butadiene, and 2,3-dimethylbutadiene.

Examples of styrenes include styrene, methylstyrene, dimethylstyrene, 1-dimethylstyrene, ethylstyrene, isopropylstyrene, chloromethylstyrene, methoxystyrene, acetoxystyrene, chlorstyrene, dichlorostyrene, bromstyrene, and methyl vinylbenzoate. Examples include esters.

Examples of crotonate esters include butyl crotonate, hexyl crotonate, and the like.

Examples of itaconic diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

Examples of maleic acid diesters include diethyl maleate, dimethyl maleate, and dibutyl maleate.

Examples of the fumaric acid diesters include diethyl fumarate, dimethyl fumarate, and dibutyl fumarate.

Acrylamides include acrylamide, methylacrylamide, ethylacrylamide, propylacrylamide, butylacrylamide, tert-butylacrylamide, cyclohexylacrylamide, benzylacrylamide, hydroxymethylacrylamide,
Examples include methoxyethyl acrylamide, dimethylaminoethyl acrylamide, phenylacrylamide, dimethylacrylamide, diethyl acrylamide, β-cyanoethylacrylamide, and N-(2-acedo is toxyethyl)acrylamide.

Examples of methacrylamide include methacrylamide, methylmethacrylamide, ethylmethacrylamide, propylmethacrylamide, butylmethacrylamide, ter
t-Butylmethacrylamide, cyclohexylmethacrylamide, benzylmethacrylamide, hydroxymethylmethacrylamide, methoxyethylmethacrylamide, dimylaminoethylmethacrylamide, phenylmethacrylamide, dimethylmethacrylamide, diethylmethacrylamide, β-cyanoethylmethacrylamide , N-(2-acetoacetoxyethyl)methacrylamide, and the like.

Examples of the furyl compound include allyl acetate, allyl caproate, allyl laurate, and allyl benzoate.

Examples of vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether, and dimylaminoethyl vinyl ether. Examples of vinyl ketones include methyl vinyl ketone, phenyl vinyl ketone, and methoxyethyl vinyl ketone.

Examples of the vinyl heterocyclic compound include vinylpyridine, N-vinylimidazole, N-vinyloquinasilidone, N-vinyltriazole, and N-vinylpyrrolidone.

Examples of glycidyl esters include glycidyl acrylate and glycidyl methacrylate.

Examples of unsaturated nitriles include acrylonitrile and methacrylate trile.

Examples of polyfunctional monomers include divinylbenzene, methylene bisacrylamide, and ethylene glycol dimethacrylate.

Furthermore, acrylic acid, methacrylic acid, itaconic acid, maleic acid, monoalkyl itaconate, such as monomethyl itaconate, monoethyl itaconate, motuptil itaconate, etc.: monoalkyl maleate, monomethyl maleate, maleic acid, w1 monoethyl maleate, etc. , motuptil maleate, etc. Niditoraconic acid, styrene sulfonic acid, vinylbenzyl sulfonic acid, vinyl sulfonic acid, acryloyloxyalkylsulfonic acid, such as acryloyloxymethylsulfonic acid, acryloyloxyethylsulfonic acid, acryloyloxypropylsulfonic acid, etc.; methacryloyloxy Alkyl sulfonic acids, such as methacryloyloxymethylsulfonic acid, methacryloyloxyethylsulfonic acid, methacryloyloxypropylsulfonic acid, etc. Niacrylamidoalkylsulfonic acids, such as 2-acrylamido-2-methylethanesulfonic acid, 2-acrylamido-2- Methylpropanesulfonic acid, 2-acrylamido-2-methylbutanesulfonic acid, etc.: methacrylamide alkylsulfonic acid,
Niacryloyloxyalkyl phosphates such as 2-methacrylamido-2-methylethanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylbutanesulfonic acid, e.g. acryloyloxyethylbosphate ,3
-Acryloyloxypropyl-2-phosphate-1~, etc.; Methacryloyloxyalkyl phosphates, such as methacryloyloxyethyl phosphate, 3-methacryloyloxypropyl-2-phosphate, etc.; 3-aryloxy-2-hydroxy having two hydrophilic groups Examples include sodium propane sulfonate. These acids may be salts of alkali metals (eg, Na, etc.) or ammonium ions. Furthermore, as other polymerizable unsaturated compounds, U.S. Patent No. 3.459.7
No. 90, No. 3,438,708, No. 3,554,
No. 987, No. 4,215, 195J! , No. 4, 24
Crosslinkable monomers described in JP-A-57-205735 and the like can be used. Specific examples of such crosslinkable monomers include N-(2-acetoacetoxyethyl)acrylamide, N-(2-(2-acetoacetoxyethoxy)ethyl)acrylamide, and the like.

Among the polymers constituting the polymer latex used in the present invention, particularly preferred ones include polymethyl acrylate, polyethyl acrylate-1-, poly〇-butyl acrylate, a copolymer of ethyl acrylate and acrylic acid, vinylidene chloride, and Butyl acrylate-1
Copolymers of ., copolymers of butyl acrylate and acrylic acid, copolymers of vinyl acetate and butyl acrylate, copolymers of vinyl acetate and ethyl acrylate, copolymers of ethyl acrylate and 2-acrylamide, etc. These polymer latexes can generally be produced by polymerizing monomers forming a hydrophobic polymer with vigorous stirring in the presence of a high concentration of a surfactant containing a hydrophilic group.

The method for producing these polymer latexes is described in detail in, for example, Takayuki Otsu and Masayuki Kinoshita, "Experimental Methods of Polymer Synthesis," Kagaku Dojinsha (1975).

In the production of the polymer latex used in the present invention, general anionic, cationic, nonionic, and amphoteric surfactants are used as surfactants. These may be used alone or in combination of two or more.

The polymer latex used in the present invention preferably has a polymer dispersoid having an average molecular size of 50,000 or more, particularly 200,000 to 500,000. In addition, the particle size of the polymer latex used in the present invention can be arbitrarily adjusted depending on the packaging conditions (monomer base, surfactant amount, handling temperature, stirring speed, etc.), but preferably the average particle size is 0.02 μm. -0,2μ
It is an aqueous dispersion of m. The polymer latex is used in at least one of the photographic constituent layers, but is particularly preferably used in the heat-sensitive layer, and the polymer latex is used in a dry weight ratio relative to the hydrophilic colloid used as a binder in the layer to which it is added. 0.03 to 0.5, particularly preferably 0.05 to
It is 0.3.

The heat-developable photosensitive material of the present invention basically contains (1) photosensitive silver halide, (2) reducing agent, (3) dye-providing substance, and (4) binder in one heat-developable photosensitive layer. It is preferable to contain (5) an organic silver salt as necessary. However, these do not necessarily need to be contained in a single photographic constituent layer; for example, the heat-developable photosensitive layer is divided into two layers, and the components (1), (2), (4), and (5) are Two or more compositions can be used as long as they are in a state where they can react with each other, such as containing the dye-providing substance (3) in the heat-developable photosensitive layer on one side and the dye-providing substance (3) in the layer on the use side adjacent to this photosensitive layer. It may be contained in separate layers.

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

The heat-developable photosensitive material of the present invention has one or more heat-developable photosensitive layers on a support. In the case of color, it generally 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.

Typically, but not exclusively, a yellow dye is combined in the blue-sensitive layer, a magenta dye in the edge-sensitive layer, and a cyan dye in the red-sensitive layer. 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 the support, or a structure in which a blue-sensitive layer is sequentially formed on the support. layer, a green-sensitive layer, a red-sensitive layer, or sequentially on a support,
There are configurations such as a green photosensitive layer, a red photosensitive layer, and a blue 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 in addition to the thermal phenomenon photosensitive 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.

Namely, dip method, roller method, reverse roll method, air knife method, doctor blade method, spray method,
There are methods and apparatuses for the bead method, extrusion method, stretch method, curtain method, etc.

Various additives used in the photographic field can be used in the protective layer of the present invention. The additives include various matting agents, colloidal silica, slip agents, antistatic agents, ultraviolet absorbers, high boiling point solvents, antioxidants, hydroquinone m4fA, surfactants (including polymer surfactants). ), hardeners (including polymer hardeners), silver salt particles, non-photosensitive silver halide particles, and the like.

The matting agent used in the protective layer of the present invention is fine particles of inorganic or organic substances that are incorporated into the photothermographic material to increase the roughness of the surface of the photosensitive material and make it matte. be.

Methods of using matting agents to prevent adhesion that occurs during manufacturing, storage, and use of photosensitive materials, and to prevent static electricity caused by contact, friction, and peeling between materials of the same or different types are known in the art. It is well known. Specific examples of matting agents include silicon dioxide described in JP-A-50-46316, JP-A-53-7231, JP-A-58-66937,
Alkali-soluble matting agents such as alkyl methacrylate/methacrylic copolymers described in JP-A No. 60-8894, alkali-soluble polymers having anionic groups described in JP-A-58-166341, JP-A-58-145935 A combination of two or more types of fine particle powders with different Mohs hardnesses, a combination of oil droplets and fine particle powders as described in JP-A-58-147734, two types with different average particle sizes as described in JP-A-59-149356 Combined use of the above spherical matting agents, special j1 ■ 1982
A combination of a fluorinated surfactant and a matting agent described in No.-44411, and British IEIvF Patent No. 1,055,713,
U.S. Patent Nos. 1,939,213 and 2,221,81
No. 3, No. 2,268,662, No. 2.322.0
No. 37, No. 2,376.005, No. 2,391,1
No. 81, No. 2.701.245, No. 2.992, 10
No. 1, No. 3,079, 25i', No. 3,262,78
No. 2, No. 3.443.946, No. 3.516.832
M, No. 3,539.344, No. 3,591,379
No. 3.754.924, No. 3, 767, 44
8@, JP-A-49-106821, JP-A No. 57-1483
Ariiso matting agent described in No. 5 etc., West German patent 2,5
No. 29.321, British Patent No. 760.775, 1.
No. 260.772, U.S. Patent No. 1,201,905@,
2.192.241, 3.053.662, 3,062,649, 3.257.206, 3
, No. 322,555, No. 3.353.958, No. 3.
370.951, 3.411.907, 3.
No. 437.484, No. 3.523,022, No. 3,
No. 615,554, No. 3.635□714, No. 3,7
No. 69,020, No. 4,021,245, @ 4,0
29,504 etc. is a matting agent, or JP-A No. 46-7781, JP-A No. 49-106821, JP-A No. 51-6017, JP-A No. 53-116143, JP-A No. 53-100226, JP-A No. 57. -14835, same 5
No. 7-82832, No. 53-70426, No. 59-1
No. 49357, Special Publication No. 57-9053 and EP
A matting agent having physical properties such as those described in Japanese Patent No. 107,378 and the like is preferably used.

In the protective layer of the present invention, addition 1 of the matting agent is 1112
It is preferably 1Qmg/2.0g, more preferably 20mg to 1.0g. The particle size of the matting agent is 0.5
~10μm is preferable, more preferably 1.0~6μm
It is.

The matting agents may be used in combination of two or more.

Examples of the slipping agent used in the protective layer of the present invention include solid paraffin, oils and fats, surfactants, natural waxes, synthetic waxes, etc. Specifically, French Patent Nos. 2 and 1
80,465, British Patent No. 955.061, 1.
No. 143.118, No. 1,270,578, No. 1.3
No. 20564, No. 1.320.757, Japanese Unexamined Patent Publication No. 1973-
No. 5017, No. 51-141623, No. 54-15
No. 9221, No. 56-81841, Research Disclosure
) 13969, U.S. Patent No. 1,263.722
No. 2.588.765, No. 2.739.891, No. 3,018.178, No. 3,042,522,
3,080,317, 3,082.087, 3,121,060, 3,222.178,
No. 3,295,979, No. 3,489.56i',
Those described in 3,516,832, 3,658,573, 3,619,411, 3,870°, 521, etc. can be preferably used.

The protective layer of the present invention contains a high boiling point organic solvent (for example, U.S. Pat. No. 2,322,027, U.S. Pat.
No. 533,514, No. 2.882.157, Special Publication No. 4
No. 6-23233, British Patent No. 958,441, No. 1
, 222.753, U.S. Patent No. 2.353.282@
, No. 3.676, No. 142, No. 3.700.454,
Esters (e.g. phthalates, phosphoric esters, fatty acid esters, etc.), amides (e.g. fatty acid amides, (sulfonic acid amide, etc.), ethers, alcohols, paraffins, etc. ) may contain oil droplets in which a water-insoluble oil compound is emulsified and dispersed. Furthermore, these oil droplets may contain photographic additives for various purposes.

The binder used in the YJ layer of the present invention is as follows:
Polyvinyl butyral, polyvinyl acetate, ethyl cellulose, polymethyl methacrylate, cellulose acetate butyrate, polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylamide, gelatin and phthalated geladine.
The above can be used in combination.

In particular, gelatin (including gelatin derivatives), polyvinylpyrrolidone (molecular layer m 1.ooo to 400.000 is preferable), polyvinyl alcohol (molecular layer m 1.000 to 400.000),
ioo, ooo are preferred) and polyoxazolines (
Preferable binders are gelatin alone or gelatin and a hydrophilic binder with good compatibility with gelatin such as polyvinylpyrrolidone, polyvinyl alcohol and polyoxazoline. Particularly preferred is a binder in which a polymer is used in combination. Gelatin is by lime treatment, i! i! 2 treatment, ion exchange treatment, ossein gelatin, big skin gelatin, hydrogelatin, or modified gelatin obtained by esterifying or phenylcarbamoylating these gelatin.

The thickness of the protective layer of the present invention is preferably 0.05 to 5 μm, more preferably 0.1 to 1.0 μm. The protective layer may be a single layer or may be composed of two or more layers.

Further, in order to increase film strength and prevent film destruction, it is also preferable that the hardness of the protective layer is greater than that of the photosensitive layer. One way to make the hardness of the protective layer higher than that of the photosensitive layer, that is, to control the hardness of each layer, is to use a diffusion-resistant hardener. By using it in the protective layer, only the degree of hardness of the protective layer can be made greater than that of the photosensitive layer. Polymer hardeners are known as diffusion-resistant hardeners, such as those disclosed in U.S. Pat.
No. 29, No. 4.161.407, JP-A-58-505
Hardeners described in No. 28 and the like can be used.

Another way to control the degree of dura for each layer is to
The protective layer can be formed by containing a diffusible hardener (for example, a vinyl sulfone hardener) only in the protective layer, or by making the content n of the protective layer higher than that of the photosensitive layer, and quickly drying it after simultaneous multilayer coating. The degree of hardness of the photosensitive layer can be made greater than that of the photosensitive layer.

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
It can be prepared by any method in the photographic field, such as a single jet method or a double jet method. For example, by applying the method described in JP-A-54-48521, monodisperse silver halide grains can be obtained by the double jet method while keeping I) A(+ constant).

In this case, a highly monodisperse silver halide emulsion can be obtained by appropriately selecting the time function of eruption acceleration, l)H, I)A(], temperature, etc. For example, a silver halide emulsion having silver halide grains with a shell can be used.The silver halide grains with a shell can be prepared by forming silver halide grains with good monodispersity into cores using the method described above. can be obtained by sequentially growing shells on this.

The monodisperse silver halide emulsion used in the present invention refers to an emulsion having a particle size distribution in which the variation in the silver halide grain size contained in the emulsion is less than a certain percentage of the average grain size as shown below. .

Since the grain size distribution of an emulsion (hereinafter referred to as a monodisperse emulsion) consisting of a group of photosensitive silver halide grains with uniform grain morphology and small grain size variations is almost a normal distribution, standard deviations can be easily determined. When the width of the distribution is defined by the relational expression, the width of the distribution of the silver halide grains used in the present invention is preferably 15% or less, more preferably monodispersity of 10% or less. It is something.

Also, for example, JP-A-58-111933, JP-A No. 58-1
No. 14934, No. 58-108526, Research Disclosure No. t-22534, etc., it has two parallel crystal planes, and each of these crystal planes has a single fraction of this particle. It is also possible to use a silver halide emulsion consisting of 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.
, No. 592, 250, No. 3.206.313, No. 3
, No. 317,322, No. 3,511,862, No. 3
．． As described in No. 447,927, No. 3.761, No. 266, No. 3.703.584N, No. 3.736.140, etc., the sensitivity inside the grain is more important than the surface sensitivity of silver halide grains. Silver halide is more expensive. The method for producing silver halide emulsions containing these internal latent image type silver halides is as described in the above-mentioned patents, for example, first A(](1! grains are prepared, and then bromide or a small amount of this is added. A method in which halide exchange is carried out by adding iodide of Many methods are known, such as a method in which a fine grain emulsion is mixed with a chemically sensitized or non-chemically sensitized coarse grain emulsion and a fine grain emulsion is deposited on the coarse grain emulsion. No. 157, No. 3.447.927 and Zhou i 3,531,291
Silver halide emulsions having silver halide grains incorporating polyvalent metal ions as described in US Pat. No. 3,761,276 or silver halide grains containing dopants as described in U.S. Pat. Silver halide emulsions whose grain surfaces have been weakly chemically sensitized, or silver halide emulsions consisting of grains having an SIn structure as described in JP-A-50-8524 and JP-A-50-38525, and other JP-A-Sho 50-38525. No. 52-156614 and JP-A No. 55-12754
These include silver halide emulsions described in No. 9.

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 sensitization, sulfur sensitization, gold-sulfur sensitization, and reduction sensitization.

The silver halide in the above-mentioned photosensitive emulsion 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, and more preferably about 0.001 μm to about 1.5 μm. .01 μm to about 0.5 μm.

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

In the present invention, as another method for preparing photosensitive silver halide, it is also possible to allow a photosensitive silver salt-forming component to coexist with an organic silver salt described below to form photosensitive silver halide in a part of the organic silver salt. . The photosensitive silver salt-forming component used in this method I is an inorganic halide, for example, a halide represented by MXn (where M represents an H atom, an NH4 group, or a metal atom, and x represents a C2, 3r or I, n is 1 when M is an H atom or an N84 group, and the valence when M is a metal atom.Metal atoms include lithium, sodium, potassium, rubidium, cesium, copper,
Gold, beryllium, magnesium, calcium, strontium, barium cum, zinc, cadmium, mercury, aluminum, indium, lanthanum, ruthenium, darium, germanium, tin, lead, antimony, bismuth, chromium, molybdenum, tungsten, manganese, rhenium,
Examples include iron, cobalt, nickel, rhodium, palladium, osmium, iridium, platinum, and cerium.

), halogen-containing total diagonal complexes (e.g., K2 Pt Cj!
s, 2 Pt 3r 6, HA (IC14゜(
NH+ )2 1r C1e , (NH4)31r
cz,.

(NH4)2 Ru Cff1s, (NH+)
3 Ru Cf1b(NH4)2 Rh Cff1s
, (NH-)3Rh3r, etc.), onium halides (e.g., tetramethylammonium bromide,
Quaternary ammonium halides such as trimethylphenylammonium bromide, cetylethyldimethylammonium bromide, 3-methylthiazolium bromide, trimethylbenzylammonium bromide, quaternary phosphonium halides such as tetraethylphosphonium bromide, benzylethylmethylsulfonium bromide, tertiary sulfonium halide such as 1-ethylthiazolium bromide, etc.), halogenated hydrocarbons (e.g., iodoform, bromoform, carbon tetrabromide, 2-bromo-2-methylpropane, etc.), N-halogen compounds (N-chlorosuccinimide, 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 (eg, triphenylmethyl chloride, triphenylmethyl bromide, 2-bromobutyric acid, 2-bromoethanol, etc.).

These photosensitive halogens (arsenic and photosensitive silver salt forming components) can be used in combination in various methods, and the amounts used are as follows:
For each layer per support tA 1 v2, 0.001(1
It is preferable that it is 50 degrees, more preferably 0.
1g to 10 (+)

The heat-developable photosensitive material of the present invention has a multilayer structure including 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. You can also. In addition, two or more photosensitive layers of the same color (for example,
It is also possible to provide 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, oxonol, and the like. Among the cyanine dyes, those having a basic nucleus such as deazoline, oxazoline, pyrroline, pyridine, oxazole, thiazole, selenazole, and imidazole are more preferred. Such nuclei include alkyl groups, alkylene groups,
It may have an enamine group capable of forming a hydroxyalkyl group, a sulfoalkyl group, or a carboxyalkyl fused carbocyclic or heterocyclic ring. 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 dyes may have acidic nuclei such as thiohydantoin nucleus, rhodanine nucleus, oxazolidione nucleus, thiazolidinedione nucleus, barbyl nucleation, thiazolinthione nucleus, malononitrile nucleus, and pyrazolone nucleus. good.

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 B We conductors, azaindene cadmium salts, sulfonic acids, etc., such as those described in US Patent No. 2. 93
3. A supersensitizing additive that does not absorb visible light, as described in the specifications of No. 3'30, No. 2, 937,089, etc., can be used in combination.

The amount of these sensitizing dyes added is from 1.times.10@-4 mol to 1 mol per mol of photosensitive silver halide or silver halide-forming component. More preferably, 1X 10-4 mol to I
X10-1 mol.

In the heat-developable photosensitive layer of the present invention, various organic silver salts can be used, if necessary, for the purpose of increasing sensitivity and improving developability.

Examples of the hardened silver salts used in the heat-developable photosensitive layer of the present invention include Japanese Patent Publication No. 43-4921, Japanese Patent Publication No. 52626-1980, Japanese Patent Publication No. 52-141222, Japanese Patent Publication No. 53-36224, and Japanese Patent Publication No. 53-37610. and other publications, as well as U.S. Patent No. 3,330,633 and U.S. Patent No. 3,794,49.
Silver salts of long-chain aliphatic carboxylic acids and silver salts of carboxylic acids having a heterocycle, such as silver laurate, as described in the specifications of No. 6, No. 4,105,451, etc.
Silver myristate, Valmitin IS! i Silver, silver stearate, silver arachidonate, silver behenate, silver α-(1-phenyltetrazolthio)acetate, silver aromatic carboxylates,
For example, silver benzoate, silver phthalate, etc.
No. 582, No. 45-12700, No. 45-18416
No. 45-22185, JP-A-52-137321
No., JP-A-58-118638, JP-A No. 58-11863
There are silver salts of imino groups described in various publications such as No. 9 and US Pat. No. 4,123,274.

Examples of silver salts of imino groups include silver benztriazole. The penztriazole silver may be substituted or unsubstituted. Representative examples of substituted benztriazole silver include, for example, argyl-substituted benztriazole silver (preferably an alkyl group of 022 or less,
Silver alkylamidobenzotriazole (preferably an alkyl group of 04 or less, such as silver methylbenzotriazole, silver ethylbenzotriazole, silver n-octylbenzotriazole, etc.), preferably silver substituted with an alkyl group of 04 or less Those substituted with amide groups, such as silver acetamidobenztriazole, silver propionamidebenztriazole, silver 1so-butylamidebenztriazole, silver laurylamidebenztriazole, etc.), silver alkylsulfamoylbenztriazole (preferably silver with 022 or less) those substituted with alkylsulfamoyl groups, such as silver 4-(N,N-diethylsulfamoyl)penztriazole, silver 4-(N-propylsulfamoyl)penztriazole, silver 4-(N-diethylsulfamoyl)penztriazole,
-octylsulfamoyl)penztriazole silver, 4
silver salts of halogen-substituted benztriazoles (VA, silver 5-chlorobenztriazole, silver 5-chlorobenztriazole, etc.) silver benztriazole, etc.), alkoxybenztriazole silver (preferably those purchased with an alkoxy group of 022 or less, more preferably an alkoxy group of 04 or less, such as 5-methoxybenztriazole silver, 5-ethoxybenztriazole silver, etc.) ), 5-nitrobenztriazole silver, 5-aminobenztriazole silver, 4-hydroxybenz1-riazole silver, 5-carboxybenztriazole silver, 4-sulfobenztriazole silver,
Examples include silver 5-sulfobenztriazole.

Examples of other silver salts having an imino group include imidazole silver, benzimidazole silver, 6-nidropenzimidazole silver, pyrazole silver, urazole silver, 1,2
．． Silver salts of other mercapto compounds such as 4-triazole silver, 1-tetrazole silver, 3-amino-5-benzylthio-1,2,4-triazole silver, saccharin silver, phthalazinone silver, phthalimide silver, etc., such as 2-mercaptobenzo Silver oxazole, silver mercaptooxadiazole, silver 2-mercaptobenzothiazole, silver 2-mercaptobenzimidazole capto-4-phenyl-1.2.4-triazole,
4-Hydroxy-6-methyl-1.3.

3a,7-thitrazaindene silver and 5-methyl-7-
Examples include silver hydroxy-1.2.3.4.6-bentanindene.

In addition, silver complex compounds with a stability constant of 94.5-10.0 as described in JP-A No. 52-31728, as described in U.S. Patent No. 4,168,980 Various imidazolynchyl, silver salts, 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 Nunoma silver salts used in the present invention may be used alone or in combination of two or more. Also, in a suitable binder! ! Prepare the salt and simply put! It may be used as it is, or it may be isolated and used after being dispersed in a binder by an appropriate means. Dispersion methods include, but are not limited to, ball mills, sand mills, colloid mills, vibration mills, and the like.

In addition, the method for preparing organic silver salts is generally to dissolve and mix silver nitrate and raw material organic compounds in water or an organic solvent, but if necessary, binders may be added, sodium hydroxide, etc. It is also effective to add an alkali to promote the dissolution of organic compounds, or to use an ammoniacal silver nitrate solution.

The amount of the organic silver salt used is usually preferably 0.01 to 500 mol, more preferably 0.1 to 100 mol, per 1 mol of photosensitive silver halide. Moreover, it is more preferably 0.3 to 30 mol.

As the reducing agent used in the photothermographic material of the present invention, those commonly used in the field of photothermographic materials can be used.

The dye-providing substance used in the heat-developable photosensitive material of the present invention is, for example, JP-A-57-186744;
-79247, 58-149046, 5g
-149047, 59-124339, 5
In the case of a dye-donating substance that releases or forms a diffusible dye by coupling with an oxidized form of a reducing agent such as those disclosed in No. 9-181345 and No. 60-2950, the present invention Examples of transition agents used in
No. 61.270, No. 3.764.328 for each Ming/Winter version
Also, RD No. 12146, N 0.1
5108, same N 0.15127 and JP-A-1987-
p-phenylenediamine-based and p-aminephenol-based developing agents, Phosph, 10, described in Japanese Patent No. 27132
Amidophenol type, sulfonamide phenol type developing agents, sulfonamide aniline type color developing agents, hydrazone type color developing agents, etc. can be used. Also, U.S. Patent Nos. 3,342,599 and 3,719,492.
No., JP-A-53-135628, JP-A No. 54-79035
Color-forming and imaging drug precursors, etc., described in No. 1, etc., can also be advantageously used.

As a particularly preferable reducing agent, JP-A-56-146133
Examples include reducing agents represented by the following general formula (1) described in No.

In the blank formula below, R1 and R2 represent a hydrogen atom or an alkyl group having 1 to 30 carbon atoms (preferably 1 to 4) which may have a substituent, and R1 and R2 are ring-closed to form a heterocyclic ring. may be formed. R3, R4R5 and R6 are hydrogen atoms,
Number of carbon atoms: 1 to 1, which may have a halogen atom, hydroxy group, amino group, alkoxy group, acylamide group, sulfonamide group, alkylsulfonamide group, or a substituent
30 (preferably 1 to 4) alkyl group, R3
and R1, and R5 and R2 may each be ring-closed to form a heterocycle. M represents an alkali synthetic atom, an ammonium group, a nitrogen-containing organic base, or a compound containing a quaternary nitrogen atom.

In the above general formula (1), the 11 nitrogen-containing groups mean no g1
It is an organic compound containing a basic nitrogen atom that can form salts, and particularly important organic bases include amine compounds. And as a chain amine compound, the first
amines, secondary amines, tertiary amines, etc. Typical examples of cyclic amine compounds include lysine, quinoline, pibe'lysine,
Examples include imidazole. In addition, compounds such as hydroxylamine, hydrazine, and amidine are also useful as chain amines. Further, as the salt of the nitrogen-containing organic j8 group, the above-mentioned modified acid salts of organic bases (eg, hydrochloride, sulfate, nitrate, 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 covalent bond of 4fil[i.

Below is a margin.Next, preferred specific examples of the reducing agent represented by the general formula (1) are shown below.

(R-5) (R-8) (R-9) (R-10) (R-11) (R-12) H Hs C2H4NHCOCH3 C)゛.

(R-20) (R-21) (R-23) The reducing agent represented by the above general formula (1) can be prepared by a known method,
For example, Houben Peil, Methoden der Organitsien l\mi, Band XI/2 (Houben
-'vVeVl, Methoden der○r
Ganischen Chemie, 3and
It can be synthesized according to the method described in XI/2), pages 645-703.

Furthermore, it is also possible to use two or more of the above-mentioned reducing agents at the same time, or to use a black and white developer described below in combination for the purpose of increasing developability.

Further, the dye-donating substance used in the present invention is JP-A No. 57-179840, No. 58-58543, No. 5
Compounds that release dyes upon oxidation, compounds that lose their ability to release dyes when oxidized, compounds that release dyes when reduced, etc. as shown in Nos. 9-152440 and 59-154445, etc. (or when simply obtaining a silver image), a developing agent as described below can also be used.

For example, phenols C such as p-phenylphenol, p-methoxyphenol, 2,6-tert-
Butyl-p-cresol, N-methyl-p-aminephenol, etc.>, sulfonamide phenols [e.g. 4-
Benzenesulfonamidophenol, 2-benzenesulfonamidophenol, 2,6-dichloro-4-benzenesulfonamidophenol, 2.6-dipbmo4-
(I]-Toluenesulfonamide) phenol, etc., or polyhydroxybenzenes (e.g., hydroquinone, tert-butylhydroquinone, 2,6-dimethylhydroquinone, chlorohydroquinone, carboxyhydroquinone, catechol, 3-carboxycatechol, etc.), naphthol (e.g. α-naphthol, β-naphthol, 4-aminonaphthol, 4-methoxynaphthol, etc.), hydroxybinaphthyls and methylene naphthols [e.g. 1,1'-dihydroxy-2,2'
-binaphthyl, 6,6'-dibromo-2,2'-dihydroxy-1,1'-binaphthyl, 6,6-sinitro2,2'-dihydroxy-1,1'-binaphthyl, 4
,4'-dimethoxy-1,1'-dihydroxy-2,2
'-binaphthyl, bis(2-hydroxy-1-naphthyl)methane, etc.], methylene bisphenols such as 1,
1-bis(2-hydroxy-3,5-dimethylphenyl)-3゜5.5-1-limethylhexane, 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-hydroxy-3-tert-butyl-5-methylphenyl)-4-methylphenol, α
-phenyl-α,α-bis(2-hydroxy-3-te
rt-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-
Ethylbentane, 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-di-tert-butylphenyl)propane, etc.],
Mention may be made of ascorbic acids, 3-pyrazolidones, pyrazolones, hydrazones and paraphenylenediamines.

These developing agents mentioned above can also be used alone or in combination of two or more kinds. Although it depends on the type of organic acid silver salt and the type of other additives, it is usually 0.01 per mol of photosensitive silver halide.
-1500 mol, preferably 0.1-20
It is 0 mole.

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 JP-A-59-229556.

This binder includes gelatin and vinylpyrrolidone polymer. The vinyl pyrrolidone polymer may be polyvinyl pyrrolidone, which is a polymer A of vinyl pyrrolidone, or may include a copolymer or a graft copolymer of vinyl pyrrolidone with one or more other monomers copolymerizable with vinyl pyrrolidone. . ). These polymers can be used regardless of their degree of polymerization. Polyvinylpyrrolidone may be substituted polyvinylpyrrolidone, and preferred polyvinylpyrrolidone has a molecular weight of 1.000 to 40.
0,000. Other monomers copolymerizable with vinylpyrrolidone include (meth)acrylic acid esters such as acrylic acid, methacrylic acid and alkyl esters thereof, vinyl alcohols, vinylencetenites,
Examples include vinyl nail polishers such as vinyl imidazoles, (meth)acrylamides, vinyl carbinols, and vinyl alkyl ethers, but at least 20% (1% by weight, same hereinafter) of the composition ratio is polyvinylpyrrolidone. Preferred examples of such copolymers are those in which the molecule m is from s,ooo 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 field, 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 a mixture of polyvinylpyrrolidone with a molecular weight of 1,000 to 400,000 and one or more other polymeric substances, gelatin and a molecular weight of 15,000 to 400.0
A mixture of the vinylpyrrolidone copolymer No. 00 and one or more other polymeric substances is preferred. Other polymeric substances that can be used include polyvinyl alcohol, polyacrylamide, polymethacrylamide, polyvinyl butyral, polyethylene glycol, polyethylene glycol ester, or proteins such as cellulose derivatives,
Natural substances such as starch, polysaccharides such as gum arabic and the like can be mentioned. These range from 0 to 85%, preferably from 0 to 70%
% may be contained.

Note that the vinyl pyrrolidone polymer may be a crosslinked polymer, but in this case, it is preferable to crosslink it after coating it on the support (including the case where the crosslinking reaction progresses by leaving it to stand).

The amount of binder used is usually 0.05i; 1 to 50 g per 1 f of support, preferably 0.021 g.
g~10(].

In addition, the binder is 0.1% per 1g of the dye-providing substance.
It is preferable to use ~10a, more preferably 0.2
It is 5 to 4 g.

The support used in the heat-developable photosensitive material of the present invention includes:
For example, polyethylene film, cellulose acetate film and polyethylene terephthalate film, synthetic plastic films such as polyvinyl chloride, paper supports such as photographic base paper, printing paper, baryta paper and resin-coated paper; Examples include a support coated with an electron beam curable resin composition and cured.

When the photothermographic material of the present invention and the photosensitive material are of a transfer type and an image receiving member is used, various heat solvents are preferably added to the photothermographic material and/or the image receiving member. The thermal solvent used in the present invention is a compound that promotes thermal development and/or thermal transfer. These compounds are described in, for example, U.S. Patent No. 3,347,675, U.S. Pat.
556, Japanese Patent Application No. 59-47787, etc.; those particularly useful in the present invention include, for example, urea derivatives such as dimethylurea, diethylurea, phenyl urea, etc.),
amide derivatives (e.g., acetamide, benzamide, etc.), polyhydric alcohols (e.g., 1.5-bentanediol, 1.6-bentanediol, 1.2-cyclohexanediol, pentaerythritol, trimethylolethane, etc.), or polyethylene Examples include glycols.

Among the above thermal solvents, water-insoluble solid thermal solvents described below are most preferably used.

Water-insoluble solid thermal solvents are compounds that are solid at normal humidity but become liquid at high temperatures (60°C or higher, preferably 100°C or higher, particularly preferably 130°C or higher and 250°C or lower), and are inorganic/organic Sex ratio (“organic conceptual diagram” Yoshio Koda,
Sankyo Publishing, 1984) is in the range of 0.5 to 3.0, preferably 0.7 to 2.5, particularly preferably 1.0 to 2.0, and the solubility in water at room temperature is 1
Refers to smaller compounds.

Specific examples of water-insoluble solid thermal solvents are shown below, but the invention is not limited thereto.

C (CI) 5cONHz 141°
1.44 or less Many of the compounds used as water-insoluble solid heat solvents are commercially available, or can be easily synthesized by those skilled in the art.

The method of adding the water-insoluble hot solvent is not particularly limited, but it may be added by grinding and dispersing it using a ball mill, sand mill, etc.
There are methods such as adding it by dissolving it in an appropriate solvent, and adding it as an oil-in-water dispersion by dissolving it in a high boiling point solvent.
It is preferable to pulverize and disperse the solid particles using a ball mill, sand mill, etc. and add them while maintaining the solid particle shape.

Layers to which the water-insoluble solid thermal 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, and the like, so that the respective effects can be obtained.

The amount of the water-insoluble heat solvent added is usually 10% to 500% by weight, preferably 50% by weight to 300% by weight, based on the amount of the binder.

Note that even when the melting point of the water-insoluble solid thermal solvent of the present invention is higher than the thermal development temperature, the melting point is lowered by being added to the binder, so that it can be effectively used as a thermal solvent.

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

For example, melt formers such as acetamide and succinimide described in U.S. Pat. No. 3,438.776; compounds such as polyalkylene glycols described in U.S. Pat. No. 3,666.477 and JP-A-51-19525; , United States l No. 3,667.959 tj, (D -C0-
There are non-aqueous polar compounds having a melting point of 20'C or higher, such as lactones having a 1-8○2-1-80- group.

Furthermore, benzophenone derivatives described in JP-A-49-115540, JP-A-53-24829 and JP-A-53-24829;
Phenol derivatives described in No. 60223, JP-A-5
Examples include carboxylic acids described in JP-A No. 8-1.18640, polyhydric alcohols described in JP-A-58-198038, and sulfamoylamide compounds described in JP-A-59-84236.

Further, a color toning agent known in heat-developable photosensitive materials may be added as a development accelerator to the photothermographic material of the present invention. As a color toning agent, for example, JP-A-46-4
No. 928, No. 46-6077, No. 49-5019,
49-5020, 49-91215, 4
9-107727@, No. 50-2524, No. 50-
No. 67732, No. 50-67641, No. 50-114
No. 217, No. 52-33722, No. 52-99813
No. 53-1020, No. 53-55115, No. 53-76020, No. 53-125014, No. 54
-1565234, No. 54-156524, No. 54
-156525, 54-156526, 55
-4060, 55-4061, 55-3201
Publications such as No. 5 and West German Patent No. 2,140,406, West German Patent No. 2,141゜063@, West German Patent No. 2,220,61.9
No. 3,847,612, U.S. Patent No. 3,782
, No. 941, No. 4,201,582 and JP-A No. 5
No. 7-207244, No. 57-207245, No. 58
Phthalazinone, phthalimide, pyrazolone, quinazolinone, N-hydroxynaphthalimide, benzoxazine, naphthoxazinedione, 2,3-dihydro-phthalazine, which are compounds described in specifications such as No. 189628 and No. 58-193541. Dione, 2,3-dihydro-1,3-okinadine-2,4-dione, oxypyridine, aminopyridine, hydroxyquinoline, aminoquinoline, isocarbostyryl, sulfonamide, 2
H-1,3-benzothiazine-2,4-(3H) dione, benzotriazine, mercaptotriazole, dimercapto-1-razabentalene, aminomercaptotriane-/, acylaminomercaptotriazoles,
phthalic acid, naphthalic acid, phthalamic acid, etc.; a mixture of one or more of these with an imidazole compound; and a mixture of at least one acid anhydride such as phthalic acid, naphthalic acid, etc. and a phthalazine compound; Further examples include combinations of phthalazine and maleic acid, itaconic acid, quinolinic acid, gentisic acid, and the like.

Antifoggants include, for example, U.S. Pat. No. 3,645;
Higher fatty acids (e.g. behenic acid, stearic acid, etc.) described in Japanese Patent Publication No. 739, mercuric salts described in Japanese Patent Publication No. 11113/1983, and N-
Halogen compounds (e.g. N-halogenoacetamide, N
-halogenosuccinimide, etc.), U.S. Patent No. 3,700
, 457, mercapto compound-releasing compounds described in JP-A No. 51-50725, arylsulfonic acids (e.g. benzenesulfonic acid, etc.) described in JP-A No. 49-125016, lithium carboxylates described in JP-A No. 51-47419. salts (e.g. lithium laurate), British Patent No. 1,45
5,271, oxidizing agents (e.g. perchlorates, inorganic peroxides, persulfates, etc.) described in JP-A-50101019;
Sulfinic acids or thiosulfonic acids described in No. 53-19825, 2-thiouracils described in No. 51-3223, simple sulfur described in No. 51-26019, No. 51-42529, No. 51-81124, Disulfide and polysulfide compounds described in No. 55-93149, rosins or diterpenes (e.g. abietic acid, pimaric acid, etc.) described in No. 51-57435, free carboxyl groups or sulfonic acids described in No. 51-104338. thiazolinthione, as described in U.S. Pat. No. 4,138,265,
JP 54-51821, U.S. Patent No. 4.137,0
1.2.4-t-lyazole or 5 described in No. 79
-Mercapto-1,2,4-1-lyazole, 55-
Thiosulfinate esters described in No. 140833,
1,2,3,4-thiatriazoles described in No. 55-142331, No. 59-46641, No. 59-57
Dihalogen compounds or trihalogen compounds described in No. 233, No. 59-57234, and No. 59-11
Examples include thiol compounds described in No. 1636.

In addition, as other antifoggants, Japanese Patent Application No. 59-565
Hydroquinone derivatives described in No. 06, for example, di-t
-octylhydroquinone, dodecanylhydroquinone, etc.) or the hydroquinone derivatives described in Japanese Patent Application No. 1983-66380, and benzotriazole derivatives (e.g., 4-sulfobenzotriazole, 5-carpoxybenzotriazole, etc.) are preferably used in combination. I can do it.

Silver image stabilizers include U.S. Pat. No. 3,707.37.
Polyhalogenated organic oxidizing agents (e.g., tetrabromobutane, tribromoquinaridine, etc.) described in Specification No. 1, 5-methoxycarbonylthio-1-phenyltetrazole described in Belgian Patent No. 768,071, The mono-yado compound described in JP-A-50-119624 (for example, 2-bromo-2-tolylsulfonylacetamide, etc.), the bromine compound described in JP-A-50-120328 (
Examples include 2-bromomethylsulfonylbenzothiazole, 2,4-bis(tribromomethyl)-6-methyltriazine, etc.), and tribromoethanol described in JP-A-53-46020. Also, Japanese Patent Application Publication No. 1973-
Various monohalogenated organic antifoggants for silver halide emulsions, such as those described in No. 119624, can be used.

Other image stabilizers include U.S. Pat. No. 3,220.
No. 846, No. 4,082,555, No. 4,088
, No. 496, JP-A-50-22625, Research Disclosure (RD) No. 12021, No. 1516
No. 8, No. 15567, No. 15732, No. 1573
No. 3, No. 15734, No. 15776, etc. Compounds called activator precursors that release basic substances by heat, such as compounds such as guanidinium trichloroacetate that release bases by decarboxylation with heat, galactonamide Aldonamide compounds such as
Compounds such as amine imide, 2-carboxycarboxamide, and JP-A No. 56-130745, No. 56-
Sodium phosphate base generator described in No. 132332, compound generating amine by intramolecular nucleophilic reaction described in British Patent No. 2,079,480, JP-A-59-
Aldoxime carbamates described in No. 157637, hydroxamic acid carbamates etc. described in No. 59-166943, and No. 59-180537, No. 59
Examples include base release agents described in Japanese Patent No. 174830 and No. 59-195237.

Furthermore, U.S. Patent Nos. 3,301,678 and 3,506
, No. 444, No. 3,824,103, No. 3,844
．． Illithiuronium compounds, S-rubamoyl derivatives of mercapto-containing compounds, and nitrogen-containing heterocyclic compounds described in RD No. 788, RD 12035, RD 18016, etc. may be used for the purpose of stabilizing images. Patent No. 3,669,670, Patent No. 4,012,260,
No. 4,060,420, No. 4,207,392,
Nitrogen-containing organic bases called activator stabilizer and activator stabilizer precursor described in RD 15109, RD 17711, etc., such as α-sulfonylacetate of 2-aminothiazoline or trichloroacetic acid g33, acylhydrazine heptacompound, etc., respectively. It can be used for the purpose of accelerating development or for stabilizing images.

Also, for example, JP-A-56-430745, JP-A No. 59-2
18443, or by spraying a small amount of water or applying a fixed amount of water before heating, or by supplying water by spraying a small amount of water or applying a fixed amount of water before heating, as described in U.S. Pat. 3,3
12,550q and the like, development may be carried out using hot steam, hot air containing moisture, or the like. Compounds that release water into heat-developable photosensitive materials, such as Japanese Patent Publication No. 44-2658
Compounds containing water of crystallization as described in No. 2, such as sodium phosphate dodecahydrate, ammonium alum diquadrate, etc., may be included in the photothermographic material.

In addition, various additives such as antihalation dyes, optical brighteners, hardeners, antistatic agents, plasticizers, and spreading agents, coating aids, and the like may be used.

The heat-developable photosensitive material of the present invention includes a heat-developable photosensitive layer and/or a non-photosensitive layer (for example,
Colloidal silica can be used for the undercoat layer, intermediate layer, protective layer, etc.).

The colloidal silica used in the present invention is a colloidal solution of silicic anhydride with an average particle size of 3 to 120 mμ mainly using water as a dispersion medium, and the main component is 3i02 (silicon dioxide).
It is. Regarding colloidal silica, for example, JP-A-56-109336, JP-A-53-123916, JP-A-5
It is described in No. 3-112732, No. 53-100226, etc. The amount of colloidal silica used is 0.05 to 0.05 to the binder of the layer to be mixed and coated in terms of dry weight ratio.
A range of 2.0 is preferred.

The heat-developable photosensitive material of the present invention includes a heat-developable photosensitive layer and/or
Alternatively, an antistatic agent can be used in a non-photosensitive layer (for example, an undercoat layer, an intermediate layer, a protective layer, etc.).

As the antistatic agent used in the present invention, British Patent No. 1
, No. 466.600, Research Disclosure t-
(Research [) 1 closure)
No. 15840, No. 16258, No. 46630,
U.S. Patent Nos. 2,327,828 and 2,861,05
No. 6, No. 3,206,312, No. 3,245,833
No. 3,428,451, No. 3,775,126, No. 3,963.498, No. 4,025,342,
Examples include compounds described in 4,025,463, 4,025,691, and 4,025,704, and these can be preferably used.

The heat-developable photosensitive material of the present invention includes a heat-developable photosensitive layer and/or
Alternatively, an ultraviolet absorber can be used in a non-photosensitive layer (for example, an undercoat layer, an intermediate layer, a protective layer, etc.).

As the ultraviolet absorber used in the present invention, benzophenone compounds (for example, those described in JP-A-46-2784, U.S. Pat. No. 3,215,530, and U.S. Pat. No. 3,698,907), butadiene compounds (for example, , U.S. Patent No. 4
, 045,229), 4-thiazolidone compounds (e.g., those described in U.S. Pat. No. 3,314,794 and U.S. Pat. No. 3,352,681), benzotriazole compounds substituted with an aryl group (For example, Tokko Sho 3G
-10466, 41-1687, 42-26
No. 187, No. 44-29620, No. 48-41572
No. 1)! ? No. 54-95233, No. 57-142
No. 975, US special:! F No. 3,253,921, same 3
, 533, 794, 3,754,919, 3,
No. 794,493, No. 4.009,038, No. 4,
No. 220,711, No. 4,323,633, Research Disclosure (Research[)isc
22519), benzoxidol compounds (e.g., those described in U.S. Pat.
0.455), cinnamate ester compounds (e.g., U.S. Pat. No. 3,705,805, U.S. Pat. No. 3,7
No. 07,375 and JP-A No. 52-49029). Additionally, U.S. Patent Nos. 3 and 4
Those described in No. 99,762 and JP-A-54-48535 can also be used. Ultraviolet absorbing couplers (e.g. α-naphthol cyan dye-forming couplers) and ultraviolet absorbing polymers (e.g. JP-A-58-11
No. 1942, No. 478351, No. 181041, No. 59-19945, No. 23344, and those described in the official gazette).

The heat-developable photosensitive material of the present invention includes a heat-developable photosensitive layer and/or
Further, a hardening agent can be used in the non-photosensitive layer (eg, undercoat layer, intermediate layer, protective layer, etc.).

Hardeners used in the present invention include aldehyde-based and aziridine-based hardeners (for example, PB Report 19.921, U.S. Pat. No. 2,950,197, U.S. Pat. No. 2,964,404).
No. 2,983,611, No. 3,271,47
Specifications of No. 5, Japanese Patent Publication No. 46-40898, Japanese Patent Publication! !
! ? 50-91315), isoxazole systems (for example, those described in U.S. Pat. No. 331,609), epoxy systems (for example, U.S. Pat. No. 3,047,394, West German patent No. 1,085,663
No. 1, British Patent No. 1,033,518, those described in Japanese Patent Publication No. 48-35495), vinyl sulfones (e.g., PB Report 19,920, West German Patent No. 1,100,942) No. 2,337,412, No. 2,545.722, No. 2,635,518,
No. 2,742,308, No. 2,749,260, British Patent No. 1,251,091, Patent Application No. 1974-5423
No. 6, No. 48-110996, U.S. Patent No. 3.539
, No. 644 and No. 3,490.9N), acryloyl type (for example, Japanese Patent Application No. 1983-27
No. 949, U.S. Pat. No. 3,640,720), carbodiimides (e.g., U.S. Pat. No. 2,938,892, U.S. Pat. No. 4,043,818, U.S. Pat. No. 4,061) .499 each Mei Card, Special Publication No. 46-387
No. 15, those described in Japanese Patent Application No. 15095/1983), triazine type (for example, West German Patent No. 2,410)
, No. 973, No. 2,553.915, U.S. Patent No. 3,
325,287, JP 52-12722
In addition, maleimide-based, acetylene-based, methanesulfonic acid ester-based, and N-methylol-based hardening agents can be used alone or in combination. As a useful combination technique, for example, West German Patent No. 2,447,5
No. 87, No. 2,505.746, No. 2,514,24
No. 5, U.S. Patent No. 4,047,957, U.S. Patent No. 3,832
, 181, 3,840,370, JP-A-48-43319, JP-A-50-63062, JP-A-52
Examples include combinations described in Japanese Patent Publication No. 127329 and Japanese Patent Publication No. 48-32364.

The heat-developable photosensitive material of the present invention includes a heat-developable photosensitive layer and/or
Alternatively, a polymer hardener can be used in a non-photosensitive layer (for example, an undercoat layer, an intermediate layer, a protective layer, etc.).

Examples of the polymeric hardening agent used in the present invention include polymers having aldehyde groups (e.g., acrolein copolymers, etc.) described in U.S. Pat. No. 3,396,029.
, No. 3,362,827, Research Disclosure No. 17333 (1978), etc., polymers having dichlorotriazine groups, US Pat. No. 3,62
Polymers having epoxy groups described in No. 3,878, Research Disclosure No. 16725 <1978)
, U.S. Patent No. 4,161,407, Japanese Patent Publication No. 54-6
Examples thereof include polymers having an active vinyl group or a group that can be a precursor thereof, as described in Japanese Patent Application Laid-open No. 56-142524, and polymers having an active ester group as described in JP-A-56-668414.

The heat-developable photosensitive material of the present invention has various interfaces in the heat-developable photosensitive layer and/or non-photosensitive layer (e.g., undercoat layer, intermediate layer, protective layer, etc.) for the purpose of improving coating properties. Activators can be used.

The surfactant used in the present invention may be any of anionic, cationic, amphoteric, and nonionic surfactants.

Examples of anionic surfactants include alkyl carbonylbenzene sulfonates, alkylnaphthalene sulfonate 1L alkyl sulfur M esters, alkyl phosphates, N-acyl-N-alkyl taurines, sulfosuccinates, and sulfosuccinates. Those containing acidic groups such as a carboxy group, a sulfo group, a phospho group, a sulfuric acid ester group, and a phosphoric acid ester group, such as alkyl polyoxyethylene alkylphenyl ethers and polyoxyethylene alkyl phosphoric acid esters, are preferable.

Examples of cationic surfactants include alkylamine salts, aliphatic or aromatic quaternary ammonium salts,
Heterocyclic quaternary ammonium salts such as pyridinium and imidazolium, and phosphonium or sulfonium salts containing aliphatic or heterocyclic rings are preferred.

Preferred examples of the amphoteric surfactant include amino acids, aminoalkyl sulfone 1m, aminoalkyl sulfuric acid or phosphoric acid esters, alkyl betaines, and amine oxides.

Examples of nonionic surfactants include saponin (steroid type), algylene oxide W<g form (for example, polyethylene glycol, polyethylene glycol/polypropylene glycol condensate, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkyl amines or amides, silicone polyethylene oxide adducts), glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides),
Fats and esters of polyhydric alcohols, alkyl esters of sugars, etc. are preferred.

The heat-developable photosensitive material of the present invention includes a heat-developable photosensitive layer and/or a non-photosensitive layer (for example, an undercoat layer, an intermediate layer, etc.) for the purpose of improving developability, improving image dye transferability, improving optical properties, etc. ,
Safe ST? i, etc.) may contain 7 non-photosensitive silver halide grains.

The non-photosensitive silver halide grains used in the present invention may have any silver halide composition such as silver chloride, silver bromide, silver iodide, silver iodobromide, silver chlorobromide, silver chloroiodobromide, etc. Can be used. The preferred grain size of the non-photosensitive silver halide grains is about 0.
．． It is 3 μm or less.

Also, the amount added is 0.00% in terms of silver amount for the layer to be added.
A range of 02 to 3 g/i' is preferred.

The heat-developable photosensitive material of the present invention includes a heat-developable photosensitive layer and/or a non-photosensitive layer (undercoat layer,
(intermediate layer, protective layer, etc.), for example, JP-A-51-10433.
It is possible to contain polymers having carboxyl groups or sulfo groups as described in No. 8.

The vinyl polymer used preferably has a dry weight ratio of 0.05 to 2.0 with respect to the binder of the layer to be added.

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

Dye-providing substances that can be used in the present invention will be explained below. The dye-donating substance may be any substance as long as it participates in the reduction reaction of the photosensitive silver halide and/or the organic silver salt used as necessary and can form or release a diffusible dye as a function of the reaction. Depending on their reaction form, negative-working dye-donors act on a positive function (i.e., form a negative dye image when negative-working silver halide is used) and negative-acting dye-donors act on a negative function. It can be classified as a positive-working dye-donor (that is, it forms a positive dye image when negative-working silver halide is used). Negative dye-donating substances are further classified as follows.

Release type compound　　　Formation type compound Each dye-providing substance will be further explained.

As the lW-based dye-releasing compound, for example, general formula (2)
Examples include compounds represented by:

General formula (2) % formula % In the formula, Car is a reducing substrate (so-called car) that is converted into a dye and releases a dye upon reduction of the photosensitive silver halide and/or the organic silver salt used as necessary. , Dye is a diffusible dye residue. Specific examples of the above-mentioned reducing dye-releasing compounds include JP-A-57-179840 and JP-A-58-11.
No. 6537, No. 59-634, No. 59-65839, No. 59-71046, No. 59-874, No. 59-
No. 88730, No. 59-123837, No. 59-16
No. 54, No. 59-165055, Winter Horoscope, etc., and include, for example, the following compounds.

Margin below q Required Exemplary dye-donor substance OC16H33[n] IJU,,1ka3(n) OC+aHss ■ 0　　　　　　■ 1NtJ.

α ■ 0 Another reducing dye-releasing compound is, for example, the general formula (3)
Examples include compounds represented by:

General formula (3) where A1. A2 each represents a hydrogen atom, a hydroxy group, or an amino group, and Dye is Dye represented by the general formula (2).
is synonymous with Specific examples of the above compounds are given in JP-A-59-12
This is shown in Japanese Patent No. 4329.

As a coupled dye-releasing compound, general formula (4) is used.
Examples include compounds represented by:

General formula (4) % formula % In the formula, CI) + is an organic group (so-called coupler residue) that can react with the oxidized form of the reducing agent to release a diffusible dye, and J is a divalent Exemplary dye-donor substance OL with a binding group? +aH33tn) The bond between Cpl and J is cleaved by the reaction with the reducing agent in the infused form. nl represents ○ or 1, Dye has the same meaning as defined in the general formula (2), and CD+ is substituted with various ballast groups to make the coupled dye-releasing compound non-diffusible. The ballast group is preferably a ballast group having 8 or more carbon atoms (more preferably 12 or more), or a hydrophilic group such as a sulfo group or a carboxy group, depending on the form of the photosensitive material used. 8
It is a group having both carbon atoms (more preferably 12 or more) and a hydrophilic group such as a sulfo group or a carboxy group. Other particularly preferred balas l-groups include polymer chains.

Specific examples of the compound represented by the above general formula (4) include JP-A-57-186744 and JP-A-57-122596.
No. 57-160698, No. 59-174834, No. 57-224883, No. 59-159159,
It is described in each specification 1 of No. 59-231540, and includes, for example, the following compounds.

As a coupling dye-forming compound, -1 formula (5)
Examples include compounds represented by:

General formula (5) % formula % In the formula, CI)2 is a paid group (so-called coupler residue) that can react (coupling reaction) with the oxidized form of the reducing agent to form a diffusible dye, F represents a divalent bonding group, and B represents a ballast group.

The coupler residue represented by CI]2 preferably has a molecular weight of 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 (4), 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 single tower represented by the general formula (6).

General formula (6) % formula %) In the formula, Cp2 and F have the same meaning as defined in general formula (5), Y represents an alkylene group, an arylene group, or an aralkylene group, and 2 represents 0 or 1. In the formula, 2 represents a divalent organic group, and L represents an ethylenically unsaturated group or a group having an ethylenically unsaturated group.

Specific examples of the coupled dye-forming compounds represented by general formulas (5) and (6) include JP-A-59-1243
No. 39, No. 59-181345, No. 60-295
No. 0, Japanese Patent Application No. 59-179657, No. 59-1816
Q4, No. 59-182506, No. 59-18250
It is described in each specification of No. 7, etc., and the following compounds are mentioned, for example.

The following margins are exemplified dye-donor substances OCRC14H29 Total OOH Polymer M-1 PM-3CHs M-4 H3 ■ M-5 H x: 60% by weight y: 40% by weight PM-6 0Hy: 50% by weight M-8 General formula above In (4), (5) and (6), Cp
More specifically, the coupler residue defined by 1 or CI)2 is preferably a group represented by the following general formula.

General formula (7) General formula (8) General formula (9) General formula (10) General formula (11) General formula (12) R8R1
1 General formula (13) General formula (14) General formula (15) General formula (16) R'
0 In the blank formula below, R7, R'', R' and RID are each a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an acyl group, an alkyloxycarbonyllkylsulfonyl group, an arylsulfonyl group, a carbamoyl group, Sulfamoyl group, acyloxy group, amiLL
It represents an alkoxy group, an aryloxy group, a cyano group, an alkylsulfonyl group, an arylsulfonyl group, a ureido group, an alkylthio group, an arylthio group, a carboxy group, a sulfo group, or a heterocyclic residue, which further includes water'tM,
Carboxy group, sulfo group, alkoxy group, cyano group, nitro group, alkyl group, aryl group, aryloxy group,
It may be substituted with an acyloxy group, an acyl group, a sulfamoyl group, a carbamoyl group, an imide group, a halogen atom, or the like.

These exchange groups are selected depending on the purpose of CD+ and CI)2, and as described above, in <Cl)+, one of the exchange groups is preferably a ballast group, and in CI)2, it is preferable that one of the exchange groups is a ballast group. In order to improve the diffusibility of the dye formed, the substituents are preferably selected so that the number of molecular groups is 700 or less, more preferably 500 or less.

As a positive dye-donating substance, for example, the following general formula (1
There is an oxidizable dye-releasing compound represented by 7).

General formula (17) In the formula, Wl represents a collection of atoms necessary to form a quinone ring (which may have a substituent on this ring),
R'' represents an alkyl group or a hydrogen atom, and represents -N-.

) or -8○2-, r represents ○ or 1, D
ye has the same meaning as defined in general formula (2). Specific examples of this compound are JP-A-59-166954 and JP-A-59-166954;
No. 9-154445, etc., and include, for example, the following compounds.

Margin below Exemplary dye-donor substances CH.

[Phase] 0°1-2 Another positive dye-providing substance is represented by the following general formula (18)
There is a compound represented by the following, which loses its dye-releasing ability when exposed to acid.

General formula (18) In the formula, W2 represents a collection of atoms necessary to form a benzene ring (which may have a substituent on the ring), and R''
, r, E, and Dye have the same meanings as defined in general formula (17). Specific examples of this compound are described in the specifications of JP-A-59-124327 and JP-A-59-152440, and include the following compounds.

Below is an example of a dye-providing substance in the margin ◎ 0CH8 As another positive dye-providing substance, the following general formula (
Examples include compounds represented by 19).

General formula (19) In the above formula, W2, R”, and Dye are represented by the general formula (1
It has the same meaning as defined in 8).

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

Below are blank spaces illustrating dye-providing substances of general formula (2), <3), (4), (17) (18
) and (1), the residues of the diffusible dye represented by Dye will be roughly detailed. The residue of the diffusible dye preferably has a molecular weight of 800 or less, more preferably 600 or less, for the sake of the diffusibility of the dye;
Examples include residues such as azomethine dyes, anthraquinone dyes, naphthoquinone dyes, styryl dyes, nitro dyes, quinoline dyes, carbonyl dyes, and phthalocyanine dyes.

These residual dye bases may be in a temporary short wave form that can be multicolored 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
The chelatable dye residues described in No. 48765 and No. 59-124337 are also preferred.

These dye-providing substances may be used alone or in combination of two or more. Its use is not limited, and it depends on the type of dye-donating vIJ material, whether it is used alone or in combination of two or more types,
Alternatively, the photographic constituent layer of the light-sensitive material of the present invention is a single layer or two layers.
The amount to be used may be determined depending on whether it is a layer of more than one species, but for example, the amount to be used is 1 TI' + 0. 5 g to 5 og of oO, preferably 0.1 g to 10 g can be used.

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. mA! It can be used after being neutralized with (e.g., hydrochloric acid or nitric acid, etc.), or after being dispersed in a ball mill with an aqueous solution of an appropriate polymer (e.g., gelatin, polyvinyl butyral, polyvinylpyrrolidone, etc.). .

The useless (!J!) photosensitive material of the present invention is usually 80%
℃~200℃, preferably 100℃~170℃ humidity range, 1 second~180 seconds, preferably 1.5 seconds~1
Just heat it for 20 seconds and it will work. 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 and heating. Or, again,
Transfer may be performed by supplying water and then applying heat if necessary. Also, before exposure, 70℃~
Preheating may be performed in a temperature range of 180°C. In addition, as described in Japanese Patent Application Laid-open No. 60-143338 and Japanese Patent Application No. 60-3644, the photosensitive material and image receiving member are heated at 80°C to 250°C immediately before thermal development transfer in order to improve their mutual adhesion.
Each may be preheated at a temperature of

Various exposure means can be used for the photothermographic material according to the present invention. The latent image is obtained by imagewise exposure to radiation, including visible light. In general, light sources commonly used for color printing, such as tungsten lamps, mercury lamps, xenon lamps, laser beams, CRT beams, etc., can be used as the light source.

As the heating means, any method applicable to ordinary photothermographic materials can be used, such as contacting with a heated block or plate, contacting with a heated roller or heated drum, 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 on the image receiving member for thermal transfer, and Joule heat generated by energization may be utilized. . There are no particular restrictions on the heating pattern, and preheating (breheating) is required.
Although methods such as heating again after heating, continuously rising, falling, or repeating heating at a high temperature for a short time or at a low temperature for a long time, and even discontinuous heating are possible, a simple pattern is preferable. Alternatively, a method in which exposure and heating proceed simultaneously may be used.

The image-receiving layer of the image-receiving member that can be effectively used in the present invention includes:
It is sufficient that the polymer has the function of receiving the dye in the heat-developable photosensitive layer released or formed by heat development, for example, a polymer containing a tertiary amine or a quaternary ammonium salt, as described in US Pat.
, 709,690 are preferably used. For example, as a polymer containing an ammonium salt, the ratio of polystyrene to N,N,N-trilowhexyl-N-vinyl-benzylammonium chloride is 1:4 to 4:1, preferably 1:1.

Examples of polymers containing tertiary amines include polyvinylpyridine. 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-57-2072.
The glass transition temperature described in No. 50 etc. is 40°C or higher, 2
Examples include those formed of polymeric substances that have heat resistance of 50° C. or less.

These polymers may be supported on a support as a support hm, or they may themselves be used as a support.

As an example of the heat-resistant polymeric substance, the molecule ffl
2,000 to 85,000 polystyrene, polystyrene derivatives 1 having substituents having 4 or less carbon atoms, polyvinylcyclohexane, polydivinylbenzene, polyvinylpyrrolidone, polyvinylcarbazole, polyallylbenzene, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral, etc. polyacetals, polyvinyl chloride, chlorinated polyethylene, polytrichloride fluoroethylene, polyacrylonitrile, poly N, N-dimethylallylamide, polys with p-cyanophenyl group, pentachlorophenyl group and 2,4-dichlorophenyl group. Acrylate, polyacryl chloroacrylate,
Polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, polyisopropyl methacrylate, polyisobutyl methacrylate, poly t
Polyesters such as ert-butyl methacrylate, polycyclohexyl methacrylate, polyethylene glycol dimethacrylate, poly-2-cyano-ethyl methacrylate, polyethylene terephthalate, polycarbonates such as polysulfone, sphenol A polycarbonate, polyanhydrides, polyamides, and cellulose. Examples include acetates. In addition, Polymer Handbook Second Edition (edited by G.I. Brandrup and E.H. Inmargat), John Willy and Sons (Polymer Han
dbook 2nd ed.

LJ, 3randrup, E, H, I mm
ergut 4-,) John W 1ley & S
ons) The glass transition temperature stated in the publication 40
Synthetic polymers having C or less are also useful. These polymeric substances may be used alone or in a blend of two or more types, or may be used in combination of two or more types as a copolymer.

Useful polymers include cellulose acetate, hepta, triacetate, diacetate, etc.

Polyamides made from combinations such as methylene diamine and terephthalic acid, fluorenediepropylamine and adipic acid, hexamethylene diamine and diphenic acid, hexamethylene diamine and isophthalic acid, combinations such as diethylene glycol and diphenylcarboxylic bis-p-carboxyphenoxybutane and ethylene glycol. Examples include polyester, polyethylene terephthalate, and polycarbonate. These polymers may be modified. For example, cyclohexane dimetatool,
Isophthalic acid, methoxypolyethylene glycol, 1
．． Polyethylene terephthalate using 2-dicarbomethoxy-4-benzenesulfonic acid or the like as a modifier is also effective.

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

As the support for the image-receiving member, any material such as a transparent support or an opaque support may be used. supports containing pigments such as titanium oxide, barium sulfate, calcium carbonate, and talc, baryta paper, RC paper laminated with thermoplastic resin containing pigments, cloth, glass, aluminum, etc. Gold scraps, etc., supports on which electron beam curable resin compositions containing pigments are coated and cured, and supports on which coating layers containing pigment β are provided. Examples include the body.

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

When the present invention is applied to a heat-developable color light-sensitive material, the various polymers mentioned above can be used as mordants for dye images and as an image-receiving layer. It may be an image-receiving element or the image-receiving layer may be a single layer that is part of a natural color photographic material. If necessary, an opacifying layer (reflection layer) may be included in the light-sensitive material, such layer reflecting the desired degree of radiation, such as visible light, that can be used to detect the dye image in the image-receiving layer. It is used to make The opacifying layer (reflective layer) can contain various reagents that provide the necessary reflection, such as titanium dioxide.

The image-receiving layer of the image-receiving member can also be formed into a type that can be peeled off from the heat-developable photosensitive layer. For example, after imagewise exposure of a heat-developable color photosensitive material, an image-receiving layer can be superimposed on the heat-developable photosensitive layer and uniformly heat-developed. Further, after imagewise exposure and uniform heat development of the heat-developable color light-sensitive material, an image-receiving layer may be superimposed and heated at a temperature lower than the development temperature to transfer the dye image released or formed from the dye-providing substance.

[Examples] Specific examples of the present invention will be described in detail below, but the present invention is not limited to these embodiments.

Example-1 [Preparation of silver iodobromide emulsion] In 50'C, JP-A No. 57-92523, No. 57
Using the mixing and stirring method shown in Memorandum No. 92524, 5 ooty of an aqueous solution containing 11.6 g of potassium iodide and 130 g of potassium bromide was added to solution A in which 20 g of ossein gelatin, 1000 d of distilled water, and ammonia were dissolved. Aqueous solution 5 containing Solution B, 1 mol of silver nitrate, and ammonia
Solution C of 00d was added at the same time as 1) while keeping the AO and pH constant. Further, by controlling the addition speed of Solution B and Solution C, a core emulsion with a silver iodide content of 7 mol %, a regular hexahedron, and an average grain size of 0.25 μm was prepared. Next, in the same manner as above, a shell of silver halide containing 1 mol% of silver iodide was coated to form a regular hexahedral grain with an average grain size of 0.3 μm.
A core/shell type silver halide emulsion (shell thickness: 0.05 μm) was prepared. (Monodispersity was 8%.

) The above emulsion was washed with water and desalted to obtain Q700-Al1. Furthermore, three types of red-sensitive silver halide emulsions were prepared at 11% by using the silver halide prepared above as shown below.

a) Preparation of red-sensitive silver iodobromide emulsion The above silver halide emulsion 7001Q 4-hydroxy-6-methyl-1°3.3a, 7-chitrazainde 70.4 g gelatin
32 Q Sodium thiosulfate 10mg Sensitizing dye below (a) 1% methanol solution 80. +2 distilled water 1200d sensitizing dye (a
) The following margin b) Green-sensitive silver iodobromide emulsion manufactured by FJI Silver halide emulsion 700iR4-Hydroxy-6-methyl-1°3.3a,7-chitrazaindene 0.4g gelatin
329 Sodium thiosulfate
10mg sensitizing dye (b) below 1% methanol solution 801g distilled water
1200d sensitizing dye (b) C) Blue-sensitive silver iodobromide emulsion manufactured by WA 700ij24-
Hydroxy-6-methyl-1゜3.3a, 7-chitrazaindene 0.4 g Gelatin 32 g Sodium thiorate 1% sensitizing dye (C) Methanol 1% solution Some distilled water
1200m12 sensitizing dye (C
) 128.8 g of 5-methylbenzotriazole obtained by reacting 5-methylbenzotriazole and nitrate Ml in a water-alcohol mixed solvent, poly(N-vinyl and lolidon) ) 16.0g was dispersed in an alumina ball mill, and the pH
5.5 and set it to 200-.

<Preparation of dye-providing substance dispersion-1> Exemplary polymeric dye-providing substance (PM-7) 35.5 g,
and the following hydroquinone compound s, oog were dissolved in ethyl acetate 200-200%, and a 5 mm% aqueous solution (manufactured by Alkanolne) was prepared using 124-sided phenylcarbamoylated gelatin (Rouslow, type 17819P C).
The mixture was mixed with 720 ml of an aqueous gelatin solution containing 30.5 g of gelatin, dispersed using an ultrasonic homogenizer, and after distilling off ethyl acetate, the pH was adjusted to 1951 to 5.5.

Preparation of hydroquinone compound reducing agent dispersion> Exemplary reducing agent (R-11) 23,3Q, the following development accelerator? , fog, poly(N-vinylpyrrolidone 1)
4.6Q, the following surfactant o. Dissolve sog in water and add p
Set H to 5.5: C 2sov (set to 2).

Development accelerator surfactant C) (x C O O C H z C H (Cz
．． H”) C+ HqCH COOCHfCHCC.H
r) C4H'? S Q s Na <Preparation of heat-developable photosensitive material-1 Wired silver salt dispersion 12.5d, blue-sensitive silver iodobromide emulsion 6,0
0, β, 39.81N of dye-donor dispersion-1, reducing agent dispersion 12.5d, and 20% solutions of various aqueous latexes as shown in Table-1 were mixed, and roughly mixed with hardener solution (tetra (vinylsulfonylmethyl)methane and taurine 1
:1 (weight:2 ratio) and dissolved in a 1% aqueous solution of phenylcarbamoylated gelatin so that the amount of tetra(vinylsulfonylmethyl)methane was 3% by weight. )
2,50d1 polyethylene glycol 3 as a hot solvent
After adding 3.80 CJ of 00 (Kanto Kagaku Kansei),
It was coated on a photographic polyethylene terephthalate film with a thickness of 180 μm that had been undercoated so that the silver side was 1.761 J/i, and then the carbamoylated gelatin and poly(N-vinylpyrrolidone) were coated on top of it. A protective layer having a dry film thickness of 1.0 μm was provided consisting of a mixture of 1.

Further, organic fluoro compounds shown in Table 1 were added to the protective layer as an aqueous solution or a methanol solution.

Below is a margin table-1. Preparation of image receiving member-1> Polyvinyl chloride (n=1.100
．． A tetrahydrofuran solution of Wako Pure Mulberry) was applied so that the ratio of polyvinyl chloride was 12(]/1'.

The photothermographic material is exposed to 1,600 C, M, and S through a step wedge, and combined with the image receiving member, the developer module 277.
After heat development at 150°C for 1 minute at 3M Company,
When the photosensitive material and the image receiving member were quickly peeled off, a magenta step wedge negative image was obtained on the polyvinyl chloride surface of the image receiving member. The results of the peelability evaluation at this time are shown in Table-2.

Furthermore, the reflection of the obtained negative image at 11 degrees was measured using an m-degree meter (PDA-
65, manufactured by Konishiroku Photo Industry), and the maximum density (D
Table 2 shows the minimum concentration (Dmin).

Table 2 *O: Good peelability Δ: Slightly poor peelability The releasability of the image-receiving member when peeled off was actually worse than that of the sample containing no polymer latex, and it is clear that this had an adverse effect.

In contrast, the sample of the present invention, in which the photosensitive material contains polymer latex and the protective layer contains an organic fluoro compound, has improved peelability, has a high maximum density, and has good dye transferability. It can be seen that it is.

Practical Example-2 Preparation of Dye-Providing Substance Dispersion-2〉 30.0 g of the exemplary dye-providing substance <@> was dissolved in 30.0 d of tricresyl phosphate and 90.0 d of ethyl acetate. After mixing with 460 d of the same gelatin aqueous solution containing a surfactant and dispersing with an ultrasonic homogenizer, ethyl acetate was distilled off, and water was added to give a solution of 500.

Preparation of heat-developable photosensitive material-2> The silver halide emulsion 40. (hnR1 organic silver salt dispersion 25.0%, dye-providing substance dispersion-2 50.Oi12
Add and mix various water-based latexes (20% - 8 liquids) shown in Table 3, and use polyethylene glycol 300 (Kanto Chemical Co., Ltd.) 4.20 g, 1-phenyl-4,4'- as a heat solvent. 10 of dimethyl-3-pyrazolidone
Weight% methanol solution 1.5. p, 3.00 d of the same hardener as in Example-1 and 10 of guanidine trichloroacetic acid.
A 20.0i12 wt.
The gelatin was coated at a concentration of 5.3+J/i2.

Furthermore, a protective layer having a dry film thickness of 1.0 μm was provided thereon, consisting of a mixture of 0.8 parts of the carbamoylated gelatin and 1 part of poly(N-vinylpyrrolidone).

Further, an organic fluoro compound shown in Table 3 was added to the protective layer as an aqueous solution.

Table 3 <Preparation of Image Receiving Member 2> The following layers were sequentially coated on a 100 μm thick transparent polyethylene terephthalate film.

(1) Layer made of polyacrylic acid (7,000/12)
(2) Layer consisting of cellulose acetate <4.000/l'
) (3) A layer consisting of a 1=1 copolymer of styrene and N-benzyl-"N,N-dimethyl-N-(3-maleimidopropyl) ammonium chloride and gelatin (
Copolymer 3.00! II/i', gelatin 3.00 l/
1”) (4) Urea and polyvinyl alcohol (saponification degree 98%)
) of urea 4.00/i' and polyvinyl alcohol 3,0 (1/f) The photothermographic material-2 was exposed to light of 1,600 C, M, S through a step wedge, and After overlapping with Image Receiving Member -2 and thermally developing it at 150° C. for 1 minute in an unused machine, Image Receiving Member -2 was immediately peeled off. The transmission density of the yellow transparent image obtained on the surface of the image receiving member was measured using a densitometer (PDA-65° manufactured by Konishiroku Photo Industry ■), and the maximum density (Qmax) and minimum density (Din) were determined in Table-4. Shown below.

In addition, the peelability was evaluated in the same manner as in Example 1, and the results are shown in Table 4.

Table 4 The results in Soji Table 4 below show that although the transferability of the dye is improved in the sample containing polymer latex in the thermal development material, sticking occurs, and the releasability when peeling off the image receiving member does not contain polymer latex. It is clear that the condition is even worse than the sample, and that it is having an adverse effect.

On the other hand, the sample of the present invention, which contains a polymer latex in the photosensitive material and an organic fluoro compound in the protective film, has improved peelability and a high maximum density ( It can be seen that the results are good.

Example 3 A multilayer photosensitive material was prepared with the configuration shown in Table 5. Polymer latexes shown in Table 6 were added to each emulsion layer of the multilayer samples, and organic fluoro compounds shown in Table 6 were contained in the protective layers of these multilayer samples.

Margin below However, those used in Table 5 are as follows.

/? ! , l2:"+1tcS (SC-1) Filter dye (YR-1) H3 <weight ratio) S-1 polyethylene glycol (average molecular weight 300) The photothermographic material prepared in this example was used in Example-1 It was exposed to light at 16000.M and S in the same manner as above.It was brought into close contact with the image receiving member prepared in Example-1, and after being exposed at 150°C for 1 minute,
The image receiving member was torn off.

The density of the obtained mapped image was measured in the same manner as in Example-1, and the glossiness of the surface of the support member was measured using a pseudophotometer.

Glossiness is a value calculated by measuring the reflected light I for the incident light IO from a certain predetermined angle on the sample. The larger the value, the higher the surface gloss of the sample. show.

Moreover, the isolation property was also evaluated in the same manner as in Example-1. These results are shown in Table-7.

As is clear from Margin Table 7 below, the effects of the present invention are exhibited even in multilayer heat-developable materials, which have better transferability and peelability compared to comparative samples, and even after peeling. It can be seen that the image receiving element also has excellent gloss.

Patent applicant Konishiroku Photo Industry Co., Ltd. Procedural amendment oral form March 13, 1985

Claims (1)

[Claims] In a heat-developable color photosensitive material having a photographic constituent layer consisting of at least one heat-developable photosensitive layer and at least one non-photosensitive layer on the support, the support of the heat-developable photosensitive layer furthest from the support. has at least one non-photosensitive protective layer on the opposite side, at least one of the photographic constituent layers contains a polymer latex, and at least one of the non-photosensitive protective layers contains an organic A heat-developable color photosensitive material characterized by containing a fluoro compound.