JPS61107243A - Heat developing sensitive material - Google Patents

Abstract

PURPOSE:To obtain a positive image having a good S/N with an easiness by incorporating at least one of an inner latent image type silver halide emulsion, a core forming agent, an org. silver salt oxidizing agent and a base and/or a base precursor releasing a base by heating to the titled material. CONSTITUTION:The inner latent image type emulsion is a preferable core/shell type emulsion. The silver halide emulsion having the inner latent image type is prepared by dopping the emulsion with a metal ion or by chemically sensitizing the emulsion or by both prescribed methods to form an inner core of silver halide and then by coating the surface of the inner core with an outer core of silver halide followed by chemically sensitizing. The core forming agent comprises a metallocyanine shown by formulas I-III which contains a hydrazide substituent and has a strong affinity against silver halide, and more preferably arylthiourea hydrazide derivatives shown by formula III. The base precursor comprises a compd. capable of releasing the base by the thermal decomposition or a compd. capable of releasing an amine salt of the base and an org. acid by the thermal decarboxylation.

Description

Detailed Description of the Invention (1) Background Technical Field of the Invention The present invention relates to a heat-developable photosensitive material that forms a positive image by heating.

Prior art and its problems Photography using silver halide has been the most widely used method since it has superior photographic properties such as sensitivity and gradation control compared to other photographic methods such as electrophotography and diazo photography. It is used. In recent years, a technology has been developed that allows images to be easily and quickly obtained by changing the image forming method for photosensitive materials using silver halide from the conventional wet processing using a developing solution to a dry processing using heating, etc. has been done.

Heat-developable photosensitive materials are well known in this technical field, and for more information about heat-developable photosensitive materials and their processes, see, for example, Fundamentals of Photographic Engineering (published by Corona Publishing, 1979), pages 553-555, published in April 1978, II! IL image information page 4o, Ne
bullets Handbook of Photog
raphy and reprography? t1
3 Ed, (VanNostrsnd Re1nh
old Company), pages 32-33.

U.S. Patent No. 3,152,904, U.S. Patent No. 3,301.6
No. 78, No. 3.392.020.

No. 3.457.075, British Patent No. 1,131.1
No. 08, No. 1,167.777, and Research Disclosure Magazine, June 1978, No. 9-15, Heshi (RD-17029).

Many methods have been proposed for obtaining color images. Regarding a method of forming a color image by combining an oxidized developer and a coupler, U.S. Pat.
・In U.S. Patent No. 3,761,270, ・P-
7 Minov's ethanol-based reducing agent is disclosed in Belgian Patent No. 802.
No. 519 and Research Disclosure Magazine 1975
September issue, pages 31 and 32, propose a sulfonamidophenol reducing agent, and US Pat. No. 4,021,240 proposes a combination of a sulfonamidophenol reducing agent and a 4-equivalent coupler.

In addition, a method of introducing a nitrogen-containing heterocyclic group into a dye, forming a silver salt, and releasing the dye by heat development is described in Research Disclosure Magazine, May 1978 issue, pages 54-58 HD.
-16966. Also, JP-A-58-
A method using a dye-providing compound described in No. 58543, No. 58-79247, etc. is known.

However, all of these methods are methods for obtaining negative images.

It is difficult to obtain various types of images as negative images except in special cases, and there is a long-awaited method for easily obtaining positive images.

As a method to obtain positive images without using difficult-to-handle processing chemicals, a method using the movement of silver ions has long been proposed.

However, in this method, the silver halide that can be used is limited to those with low sensitivity, and it is necessary to dissolve the silver halide in a dry state, so it is difficult to obtain an image with a good S/N ratio.

For positive color dye images, there is a method of forming a positive color image using a photosensitive silver dye bleaching method.
December issue, pages 14-15 (RD-15227).

Useful dyes and bleaching methods are described, such as in U.S. Pat. No. 4,235,957.

However, this method requires extra steps and materials, such as stacking and heating activator sheets to accelerate the bleaching of the dye, and the resulting color images may coexist during long-term storage. It has the disadvantage of being gradually reductively bleached by free silver and the like.

■! OBJECTS OF THE INVENTION An object of the present invention is to provide a heat-developable photosensitive material that can easily form positive images with a good S/N ratio.

m Disclosure of the Invention These objects are achieved by the present invention as described below.

That is, the present invention provides at least an internal S-image type silver halogen emulsion on a support,
This photothermographic material is characterized by having a nucleating agent, an organic silver salt brewing agent, a base, and/or a base precursor that releases the base upon heating.

■Specific structure of the invention Hereinafter, a specific configuration of the present invention will be explained in detail.

The heat-developable photosensitive material of the present invention contains an internal latent image type silver halide emulsion.

Direct reversal halogenated emulsions are used in image transfer processes requiring a reversal mechanism, such as those in which negative-acting image dye-providing materials are used.

As a direct reversal halogenated emulsion, U.S. Patent No. 3,22
Internal latent image reversal as described in US Pat. No. 7,550 is more preferably used.

Unlike conventional chemically sensitized silver halide grains which form latent images preferentially on the surface, internal latent image silver halide emulsions form latent images preferentially within the silver halide grains.

In general, an internal latent image type silver halide emulsion is produced by coating a standard amount of the emulsion on a transparent support and exposing it to light for a certain period of time within the range of 1 x 10-2 to 1 second. All) When developed using Developer Y, a developer for latent images, at 18°C for about 5 minutes and tested according to the standard photographic test method, the following surface latent image development was performed after exposure to S' in the same manner. developer X
The maximum density (Dmax-) is at least 5 times higher than that of the same sample developed for 6 minutes at 20°C.

Preferably, D+sax in developer Y is
and/or the grains of the emulsion have a ratio of total sensitivity to surface sensitivity of at least 5 times or more.

SatoJJLχ N-methyl-p-7 minophenol sulfate 25.0g Ascorbic acid 10.0g Potassium metaborate
35.0g potassium bromide
Add 1.0g water 1
1 pH 9,5 1 or JLX N-Methyl-p-7 minophenol sulfate 2.0g Dry sodium sulfate 90.0g ゝHydroquinone 8.0g Sodium carbonate monohydrate 52.5g Potassium bromide
5.0g potassium iodide
Add 0.5g water
Examples of internal latent image type silver halide emulsions include:
A converged emulsion obtained by a method (catastrophe precipitation method) of converting highly soluble silver salt particles such as silver chloride into less soluble silver salts such as (iod)silver bromide (catastrophe precipitation method).
For example, U.S. Pat. No. 2,592,250), a core/shell emulsion in which a silver halide shell is coated on the core grains by mixing a chemically sensitized large grain core emulsion with a fine grain emulsion and ripening the mixture. (e.g. U.S. Pat. No. 3,206
, No. 313), a silver halide shell was formed on the core grains by simultaneously adding a soluble silver salt solution and a soluble halide solution to a chemically sensitized monodisperse core emulsion while keeping the silver ion concentration constant. Coated core/shell emulsions (e.g. British Patent No. 1,027,146, U.S. Pat. No. 3,76
1,276), a core/shell emulsion in which a silver halide shell is coated by depositing silver halide on silver halide core grains doped with metal ions inside the grains, and a core/shell emulsion in which there are two or more emulsion grains. It has a laminated structure, with the first phase and the second phase
Halogen localized emulsions with different phases and halogen compositions (
For example, U.S. Pat. No. 3,935.014) and emulsions in which silver halide grains are formed in a female medium containing trivalent metal ions to incorporate different metals (U.S. Pat. No. 3,447).
.

No. 927], etc. are Al, Seo (7), et al., E, J, Wa.
Written by ll, Photographic Fist Emal, Shons (Ph
otographic emulsion)
Pages 35-36.

52N53 pages, American Photograp
hicPublishing Co-, (1929)
, and U.S. Patent Nos. 2,497,875 and 2,5.
No. 63.785, same No. 3. all, No. 662, same No. 4
, 395, 478, West German Patent Application (OL S) No. 2.728,108, and the like.

Among the internal latent image type emulsions described above, particularly preferred for application of the present invention are the core/shell type emulsions as described above.

That is, the preferred surface chemically sensitized internal latent image type silver halide emulsion of the present invention is doped with metal ions or
A silver halide inner core (core particle) that has been chemically sensitized or both is prepared, and its surface is then coated with an outer layer (shell) of silver halide; The surface of silver halide grains has been optimally chemically sensitized.

Optimal surface chemical sensitization here means the Dmax of the inverted image.
, Dmin of the inverted image, sensitivity of the inverted image, and re-inverted image (
This means chemically sensitizing the image so that the sensitivity of the negative image (negative image) maintains the best balance.

The method of doping the inner core of silver halide with metal ions is 1. For example, in the process of forming silver halide grains of the inner core or physical ripening, doping with cadmium salt, zinc salt, lead salt, thallium salt, erbium salt, bismuth salt, iridium salt, etc. Rhodium salts or complex salts thereof, iron salts or
A method can be adopted in which a metal ion source such as a complex salt thereof is allowed to coexist.

The metal ion is usually 10-1 per mole of silver halide.
Use at a ratio of 6 moles or more.

The silver halide grains in the inner core can be chemically sensitized without doping with the metal ions mentioned above, or by using one or more of noble metal sensitizers, sulfur sensitizers, and reduction sensitizers along with the doping. Good. In particular, if the inner core silver halide grain surface is subjected to gold sensitization and sulfur sensitization and then covered with an outer shell to prepare a core/shell type silver halide grain whose surface is further chemically sensitized, good results can be obtained. Reversal performance can be obtained.

The ratio of silver halide in the inner core to silver halide in the outer film is arbitrary, but the outer film only needs to cover at least the photosensitive sites (sites that produce photodecomposed silver upon exposure) of the inner core; For 1 mole of nuclear silver halide,
That of the outer membrane contains 0.1 to 10 mol (preferably 1 to 8
mole) used.

The silver halides of the inner core and the outer film preferably have the same composition, but may have different compositions.

As each silver halide, silver bromide, silver iodide, silver chloride, silver chlorobromide, silver bromoiodide, silver chlorobromoiodide, etc. can be used, but preferred silver halide emulsions include at least 5
The most preferred emulsion is silver bromide or silver bromoiodide (particularly one containing 10 mole % or less of silver iodide).

In the present invention, core/shell type silver halide grains having a variety of grain sizes can be used, but core/shell type silver halide grains having an average grain diameter of 0.1 to 4 microns, preferably 0.2 to 3 microns, can be used. Silver halide grains give good results.

Core/shell type silver halide grains may have regular crystal bodies such as cubes and octahedrons, or irregular crystal bodies such as spherical or plate shapes.
Plate-like particles may have a crystalline form (gular), a composite form of these crystal forms, or even be composed of a mixture of particles of various crystal forms. aspect ratio
) may be 5 or more, especially 8 or more (for example, the one described in JP-A-5-108528).

Surface chemical sensitization can be carried out singly or in combination, such as a sulfur sensitization method using a sulfur-containing compound that can react with silver ions or active gelatin, a reduction sensitization method using a reducing substance, a noble metal compound method using gold or other noble metal compounds, etc. It can be done.

Conditions for the chemical sensitization step may be arbitrarily determined, but it is generally preferred to carry out the chemical sensitization step at a pH of 9 or lower, a pAgll or lower, and a temperature of 50° C. or higher.

However, conditions may be set outside this range depending on the case.

・Reducing substances used in the above reduction sensitization method include:
Examples include stannous salts, amine salts, hydrazine derivatives, formamidine sulfinic acid, and silane compounds. Further, examples of the noble metal compound include complex salts of metals of Group I of the periodic table, such as Pt, Ir, and Pd.

Among the above chemical sensitization methods, the one that provides the best reversal performance is the sulfur sensitization method that uses a sulfur sensitizer, and is further sulfur sensitized by coexisting a polymer such as the above-mentioned poly(N-vinylpyrrolidone). If this is done, even better reversal performance can be obtained.

Further, depending on the case, a sulfur sensitizer and a total complex salt may be used in combination.

Sulfur sensitizers include compounds such as thiosulfates, thioureas, thiazoles, rhodanines, etc. Specific examples thereof are described in U.S. Pat. No. 1,574.944 and U.S. Pat. No. 2,41
No. 0,689, No. 2.278.947, No. 2,
No. 728, No. 668, No. 3,656,955, and Japanese Unexamined Patent Publication No. 55-45016.

The coating amount of the internal latent image type silver norogenide used in the present invention is 0.01 to 5 g/l in terms of silver per 17
n' range.

The photothermographic material of the present invention contains a nucleating agent (fogging agent).

The nucleating agent typically initiates development of the internal latent image type silver halide in the presence of the reducing agent at commonly used thermal development times and conditions such that no thermal development occurs. Nucleation occurs on unexposed particle surfaces. The mechanism for directly forming a positive image by internal latent image reversal is considered to be as follows.

Photoelectrons generated by imagewise exposure are preferentially trapped inside the particles, forming an internal latent image.

For imagewise exposed particles, the internal latent image acts as an effective trap for conducting odd electrons, and the electrons generated during the nucleation step are attracted to the existing internal latent image and collect inside the particle. In this case, all of the latent image necessarily collects inside, so these particles are not developed even on overheating.

For unexposed particles, the electrons generated during the nucleation step are at least temporarily trapped on one particle surface, resulting in the formation of capris that can be grown by heating in the presence of a transition agent.

The incorporation of nucleating agents, such as the 7-aryl hydrazides and hydrazones described in U.S. Pat. No. 3,227,522, into the silver halide emulsion layer is particularly effective in the present invention.

The preferred concentration range is 500g to 5g per mole of crocodile.
It is.

Nucleation of development is more than sufficient if the nucleating agent is adsorbed to the silver halide grains. A smaller amount is sufficient to achieve gmDmax.

Some examples of adsorptive nucleating agents include heterocyclic quaternary salts containing certain hydrazinoalkyl substituents and cyanine dyes (U.S. Pat. No. 3,615.61 and U.S. Pat. No. 3,7
18.470), quaternary salts of heterocycles containing 2-7 sylethyl substituents (U.S. Pat. No. 1,734,738) and a series of quaternary salts of heterocycles containing fused dihydroaromatic rings. (U.S. Pat. No. 3,719°494).

Certain merocyanines containing hydrazide substituents are also strongly adsorbed to silver halide grains and are effective as nucleating agents. Such nucleating agents are represented by the following general formulas (I) and (■).

gI
tone “
: In the above general formulas (1) and (II), Zl and 22 complete a 5- or 6-membered nitrogen-containing heterocycle of the type contained in cyanine dyes.
Represents the required atoms.

Both Ql and Q2 represent atoms necessary to complete the rhodanine, thiohydantoin, thioxasolydinedione, or barbic acid or thiobarbic acid core.

R1 represents a substituted or unsubstituted alkyl group (having 6 or less carbon atoms) or an arylalkyl group (having 8 or less carbon atoms), respectively.

R2 represents a substituted or unsubstituted aryl group (having 8 or less carbon atoms).

R3 represents a hydrogen atom or a substituted or unsubstituted alkyl group (having 6 or less carbon atoms) or an allyl group (having 8 or less carbon atoms), respectively.

X] represents a substituted or unsubstituted alkyl group (with a carbon number of 6 or less), x2 represents a substituted or unsubstituted aryl (with a carbon number of 8 or less), p and n are each O or l
It is.

Another embodiment useful as a nucleating agent is the following formula (III
) is a hydrazide store conductor of allylthiourea.

(m) In the above formula (m), R is hydrogen or an aryl, alkyl, alkylaryl or arylalkyl substituent, ill is an arylene group, R2 is an alkyl or aryl substituent, R
3 is a hydrogen atom or a benzyl substituent.

Adsorptive nucleating agents also act as reductive sensitizers in sulfur- and gold-surface sensitized emulsions.

For example, compound 28 below gives a tremendous speed increase of 0,351 og E (E: exposure dose) when used in a high speed color negative emulsion at a concentration equivalent to that of the nucleation stage of an internal latent image emulsion. .

Specific examples of the dyes shown in the above formulas (I) to (m) are given below.

Formula CI) (1) 5-[1-ethylnat(1,2-d)thiazolin-2-ylidene ethylidene]-1-(2-phenylcarbazoyl)methyl-3-(4-sulfamoylphenyl)-2 -Thiohydantoin (2) 5-[(3-ethyl-2-penzothiazolinyritene)ethylidene] -3-(2-phenylcarbazoylmethyl)rhodanine (3) 5-(3-ethyl-2-pene) zothiazolinylidene) 3-(2-phenylcarbazoylmethyl)rhodanine (4) 5-[(3-ethyl-2-penzoxazolinylidene)ethylidene]-3-(2-p-methoxy-phenylcarba zoylmethyl) rhodanine (5) 5-[(3-ethyl-2-penzoxazolinylidene) ethylidene]-3-(2-p-tolyl-carbazoylmethyl) lognin formula (■) (El) 5-( 3-ethyl-2-penzothiazolinylidene)-3-[4-(2-formyl-hydrazino)phenyl]rhodanine (7) 3-[4-(2-formylhydrazino)phenyl] 5- [3 -(3-sulfopropyl)-2-penzothiazolinylidene] rognin triethylamine salt (8) 3-[4-(2-7cetylhydrazino)phenyl]-5-[(3-sulfopropyl)-2- pensothiazolinylidene] rognin triethylamine salt (9) 3-C4-(2-benzoylhydrazino)phenyl] -5-(3-methyl-2-penzoxazolinylidene) rhodanine (10) 3-[4 -(2-formylhydrazino)phenyl 35-(3-methyl-2-penzoxazolinylidene) rhodanine (11) 3-[4-(2-7cetylhydrazino)phenyl] -5-(3-methyl-2 -penzoxazolinylidene] rhodanine (12) 5- ((3-ethyl-2-penzoxazolinylidene) ethylidene] -3-[4-(2-formylhydrazino)phenyl] rhodanine (13) 3- [4-(2-7cetylhydrazino)phenyl15-[(3-ethyl-2-penzoxazolinylidene)ethylidene]rhodanine (14)3-[4-(2
-benzoylhydrazino)phenyl]-5-[(3-ethyl-2-penzoxazolinylidene)ethylidene]rhodanine (15°)5-[(3-ethyl-2-penzothiazo'1
nonylidene) ethylidene] -3-[4-(2-formylhydrazino)phenyl] rhodanine (1B) 3- [4
-(2-acetylhydrazino)phenyl35-[(3-
Ethyl-2-penzthiazolinylidene)ethylidene] rhodanine (17) 3-[4-(2-benzoylhydrazino)phenyl]-5-[(3-ethyl-2-benzothiazolinylidene)ethylidene] rhodanine (18) 3-(4-(2-benzoylhydrazino)phenyl]-5-[(3-ethyl-2-penzothiazolinylidene)]rhodanine formula (m) (1!a) 1 , 3- Bis(4-(2-formylhydrazino)phenylcothiourea (20)l, 3-bis[4-(2-acetylhydrazino)phenylcothiourea (21)1,3-bis(4-(2-hexanoylhydrazino) dino) phenylcothiourea (22) l, 3-bis [4-(2-benzoylhydrazino) phenylcothiourea (23) l, 3-bis [:4- (2-0-
toluoylhydrazino)phenylcothiourea (24) l-[4-(2-formylhydrazino)phenyl]-3-methylthiourea (25) l -C4-(2-formylhydrazino)phenyl]-3-ethylthiourea (2BLL -[4-(2-7cetylhydrazino)phenyl]-3-ethylthiourea(27)l -[4-(2-7cetylhydrazino)phenyl]-3-methylthiourea(28)l -[4-(2 -formylhydrazino)phenyl]-3-phenylthiourea(29)1-[4-(2-7cetylhydrazino)phenyl]-3-phenylthiourea(30)l-[4-(2-7cetylhydrazino)phenyl]- 1-benzyl-3-phenylthiourea and some other pacifying compounds have also been found to act as nucleating agents. All of them do not absorb silver halide in principle, and the formulas CPn and (V) below are:
It represents a series of pyrimidines and pyrazoles, each hydroxy- and amine-substituted, each of which can also exist as a variant.

In the above formula (rlr), Gl and G2 are respectively Fl,
OH4<t*NHR (R: hydrogen atom, alkyl group, aryl group), and G3 is NHR or N=CH
R1 (R1 neararyl group), and G4 is NHR.

In the above formula (V), G5 is OH or NHR, G6 and G7 are NHR, and Z is a hydrogen atom, an alkyl group, or an aryl group.

Also, 1,2-dihydro-1- represented by the following formula (VI)
Hydroxy-quinazoline-3-oxides are also used.

In the above formula (Vl), R3 is an alkyl group, an aryl group, a styryl group or a heterocyclic group.

Representative examples of the compounds represented by the above formulas (IV), (V) and (Vl) are shown below.

(31) 5,6-diami-2,4-dihydroxypyrimidine (32) 2,5,6-triamino-4-hydroxypyrimidine (33) 4,5,6-1lyamino-4-hydroxypyrimidine (34) 2, 6-Diami2-5-benzylamino-
4-Hydroxypyrimidine (35) 2 ,6-diamitu-5-p-ethoxybenzylamino-4-hydroxypyrimidine (38) 2
, 6-Diami2-5-benzylidine amino-4-hydroxypyrimidine (37) 2,4,5,6-tetraaminopyridine (38) 2,5,6-triamino-4-p-methoxyanilinopyrimidine (39) 2,3-diamino-4-hydroxypyrimide (1,2,-a)benzimidazole (40) 4
,5-diamino-3-hydroxypyrazole (41) 4,5-diamino-3-hydroxy-1-
Phenylpyrazole (42) 4,5-diamino-3-hydroxy-1-
Methylpyrazole (43) 3,4,5-triaminovirazole (44)
1,2-dihydro-1-hydroxy-2-p-methoxyphenylquinazoline-3-oxide (45) 1,2-dihydro-1-hydroxy-2-
Styrylquinazoline-3-oxide (4G) l,
2-dihydro-1-hydroxy-2-(2-pyrrolyl)quinazoline-3-oxide (47) 1,2-dihydro-1-hydroxy-2
As the -(2-thioxo-4-thiazolin-5-yl)-quinazoline-3-oxide nucleating agent, one represented by the following formula (■) may also be used.

In the above formula (■), R1 represents an aliphatic residue or an aromatic residue, R2 represents a hydrogen atom, an aliphatic residue, or an aromatic residue, and xl and xl may be the same or different. Often each represents a divalent aromatic residue.

More specifically, the aliphatic residues of R1 and R2 include linear and branched alkyl groups, cycloalkyl groups, substituents thereof, and alkenyl groups.

The linear and branched alkyl group for R1 is, for example, a furkyl group having 1 to 101 carbon atoms, preferably 1 to 8 carbon atoms, and specifically, for example, a methyl group, an ethyl group, an isobutyl group, a t-octyl group, etc. It is. The alkyl group for R2 is, for example, one having 1 to 6 carbon atoms, and specifically includes a methyl group, an ethyl group, a propyl group, and the like.

Moreover, as a cycloalkyl group, for example, carbon number 3-1
'0, specifically 1, such as a cyclopropyl group,
These include cyclohexyl group and adamantyl group. Examples of substituents include alkoxy groups (e.g., methoxy, ethoxy, propoxy, butoxy, etc.), halogen atoms (e.g., chlorine, bromine, fluorine, iodine, etc.), and aryl groups (e.g., phenyl groups). , p-chlorophenyl group, p-methylphenyl group), etc. As a result, specific examples of substituted groups include 1
Examples include 3-methoxyfurovir group, 4-chlorocyclohexyl group, benzyl group, p-methylbenzyl group, and p-chlorobenzyl group.

Further, as an alkenyl group, for example, allyl (ally
l) Groups can be mentioned.

On the other hand, examples of aromatic residues for R1 and R2 include phenyl crystals, naphthyl groups, and those with substituents (e.g., alkyl groups, alkoxy groups, halogen atoms, etc.). For example,
Examples include p-methoxyphenyl group, tolyl group, p-chlorophenyl group, and 1m-fluorophenyl group.

The divalent aromatic residues of xl and xl include phenylene groups, naphthylene groups, and substituted phenylene groups (substituents include alkyl groups (e.g., methyl groups), halogen atoms (e.g., chlorine, etc.)), Among these, the phenylene group is most preferable, that is, the case where S -NHNHCR2 is bonded via a divalent linking group (ΣC0NH).

More preferably, the RI N)IC-NH- group is <
This is the case where the 0 group is bonded to the meta or para position of the :)=CONH- group, and the 0 group is bonded to the meta or para position of the -NHNHCR2 -CONH-<=>.

Specific examples of the compound represented by the above formula (■) are shown below.

(48) l-formyl-2-(4-(3-(3-phenylthioureido)benzamido)phenyl]hydrazide (49) l-7cetyl-2-(4-(4-(3-phenylthioureido)benzamide) ) phenyl]hydrazide (50) l-acetyl-2-(4-(3-(3-phenylthioureido)benzamido)phenyl]hydrazide (51) l-formyl-2,-(4-(4-(3- phenylthioureido)benzamido)phenyl]hydrazide (52) l-7 cetyl-2- (4-(4-(3-allylthioureido)benziamido)phenyl]hydrazide (53) 2- (4-(4-(3- ethylthioureido)benz7mido)phenyl]-1-formyl doracito[501-formyl-2-(3-(3-(3-phenylthioureido)benzamido)phenyl]hydrazide (55) l-formyl-2- (3-(4-(3-phenylthioureido)benzamido)phenyl]hydrazide (5B) 2- C4-(3-(3-7ylthioureido)benz7mido)phenylcou 1-formylhydrazide (57) 2- ( 4-(3-(3-(4-chlorophenyl)thioureido)benzamide)phenylcou-1-formylhydrazide (58) l-acetyl-2-(4-(4-(3-butylthioureido)benzamide)phenyl]hydrazide (58) 1-Acetyl-2-(4-(4-(3-cyclohexylthioureido)benzamido)phenyl]hydrazide (80) 1-7cetyl-2-(3-(4-(3-phenylthioureido)benzamide ) phenyl]hydrazide ($1) l-benzoyl-2-(4-(3-(3-ethylthioureido)benzamido)phenyl)nyl]
Hydrazide (82) l -(4-chlorobenzoyl)-2-(
3-(3-(3-phenylthioureido)benzamido)phenyl]hydrazide (83) 1-acetyl-2-(3-(4-(3-methylthioureido)benzamido)phenyl]hydrazide (84) 2- (4 -(3-(3-ethylthioureido)benzamide)phenylcou 1-formylhydrazide (65) l-formyl-2-(4-(3-(3-t-
octylthioureido)benzamido)phenyl]hydrazide (88) 2-(4-(3-(3-cyclohexylthioureido)benz7midoIphynyl)-1-formylhydrazide (67) l-7cetyl2- ( 4-(3-(3-allylthioureido)benzamido)phenyl]hydrazide (88) 1-7cetyl-2- (3-(3-(3-phenylthioureido)benzamido)phenyl]hydrazide (89) 2- ( 4-(3-(3-phenylthioureido)benzamide)phenyl-1-propionylhydrazide (70) l-7 cetyl-2- (4-(3-1(3-
ethylthioureido)benzamido)phenyl]hydrazide (71) 2-(3-(・4-(3-7suthioureido)benzamido)phenylcou 1-formylhydrazide (72) l-formyl-2-(4-(3 -(3-(4
-methoxyphenyl)thioureido)benzamido)phenyl]hydrazide (73) 2- (4-(3-(3-7 liothioureido)benz7mido)phenyl)-1-(3-methylbenzoyl)hydrazide (701-acetyl-2 -(4-(3-(3-(3-fluorophenyl)thioureido)penzusamide)phenyl]hydrazide (75) 1-7 cetyl-2-(4-(3-(3-(
4-methoxyphenyl)thioureido)benzamide)
phenyl]hydrazide (7B) 2- (4-(4-(3-inbutylthioureido)benzamido) phenyl) -1-formylhydrazide (77) l-formyl-2-(4-(4-(3-( 4
-methoxyphenyl)thioureido)benzamide I phenyl]hydrazide and others, JP-A-54-133096, JP-A-55-151
No. 635, No. 55-74536, No. 55-16353
No. 3, No. 55-163534, and No. 55-166
Nucleating agents described in No. 221 can also be used.

Among these, those represented by formula (m) or (■) are particularly preferred.

A synergistic effect can be obtained when nucleating agents are used in combination. The permissible range of processing temperature can be determined depending on whether one nucleating agent or a combination of nucleating agents is used. It is often effective to use a combination of an adsorptive nucleating agent and a non-adsorptive nucleating agent.

alone, or an adsorbent nucleating agent, especially the formula (III)
) and (■) are used in combination with l-formyl-2-p-tolylhydrazine, l-acetyl-2-(4-[5-amino −
2-(2,4-di-t-pentylphenoxy)benzamitocophenyl I hydrazine, niacetyl-2-(
4-(5-(3-methylthioureido)-2-(2,4
-di-t-pentylphenoxy)benzamido]-phenyl)hydrazine and l-[2,2-bis(hydroxymethyl)propynyl]-2-phenylhydrazine.

Improved dye density is disclosed in U.S. Patent $3.227.552
2-octa-decylhydroquinone-5- described in No.
When nucleation occurs in the presence of sulfonated hydroquinones, such as sodium sulfone, internal latent image emulsions are used.N.

It is obtained in a heat-developable photosensitive material. 'Other hydroquinones, such as tetramethylhydroquinone and tetramethoxyhydroquinone, not only aid in nucleation, but can also act solely as nucleating agents.

As a method for forming the silver halide grains used in the present invention, the known single jet method or double jet method can be used. In the latter method, furthermore, the pAg in the reaction solution is kept constant. So-called chondrold
This can be done by using the double jet method. In addition, a combination of these methods may be used.In any of the above-mentioned silver halide emulsion forming methods, either the known single-stage addition method or multi-stage addition method may be used, and the addition rate may be constant. , or a stepwise or continuous rate change (e.g., while keeping the concentration of soluble silver salt and/or halide constant).
This can be achieved by changing the addition flow rate of those solutions, by changing the concentration of soluble silver salt and/or halide in the additive solution while keeping the addition flow rate constant, or by a combination of these methods. ) but that's fine.

Further, the reaction solution may be stirred by any known stirring method, and the concentration and pH of the reaction solution for forming silver halide grains may be set in any manner.

In the present invention, an organic silver salt relatively stable to light is used as an oxidizing agent together with photosensitive silver halide.
In this case, the photosensitive silver halide and the silver salt must be in contact with each other or at a close distance. In this way, when a silver salt is used in combination, the heat-developable photosensitive material becomes 80%
When heated to a temperature of 100° C. or higher, preferably 100° C. or higher, the organic silver salt oxidizing agent is also considered to participate in redox using the latent image of silver halide as a catalyst.

Examples of organic compounds that can be used to form the organic silver salt oxidizing agent mentioned above include aliphatic or aromatic carboxylic acids, thiocarbonyl group-containing compounds having a mercapto group or α-mercapto group, and imine-7 group-containing compounds. Examples include compounds.

Silver salts of aliphatic carboxylic acids include behenic acid, stearic acid, oleic acid, lauric acid, capric acid, myristic acid, palmitic acid, maleic acid, fumaric acid, tartaric acid, furoic acid, linoleic acid, lilunic acid, and adipic acid. Typical examples include silver salts derived from , 7/succinic acid, succinic acid, acetic acid, acetic acid, or camphoric acid. Silver salts derived from these fatty acids, such as 7\logen atom or hydroxyl, $ substituted product, or aliphatic carboxylic acid having 1,000 onythyl group, can also be used.

Silver salts of aromatic carboxylic acids and other carboxyl-based compounds include benzoic acid, 35-dihydroxybenzoic acid, o-, m- or p-methylbenzoic acid, 2.
4-dichlorobenzoic acid, acetamidobenzoic acid, p-phenylbenzoic acid, gallic acid, tannic acid, phthalic acid, tele, phthalic acid, salicylic acid, phenylacetic acid, pyromellitic acid or 3-carboxymethyl-4-methyl-4 A typical example is a silver salt derived from -thiazoline-2-thousand. , 3-mercapto-4-phenyl-1,2,4-triazole as the compound silver salt having a mercapto or thiocarbonyl group.

° 2-mercaptobenzimidazole, 2-mercapto-5-7 minothiadiazole, 2-mercaptobenzthiazole, S-furkylthioglycolic acid (alkyl group having 12 to 22 carbon atoms), dithiocarboxylic acids such as dithioacetic acid, thiostear Thioamides such as roamide, 5-carboxy-1-methyl-2-phenyl-4-thiopyridine, mercaptotriazine, 2-mercaptobenzoxazole, mercaptooxadiazole or 3-amino-5-benzylthio-1,2,4- Examples include silver salts derived from triazoles and mercapto compounds described in US Pat. No. 4,123,274.

As a silver salt of a compound having an imino group,
30270 or 45-18416, or derivatives thereof, such as benzotriazole, alkyl-substituted benzotriazoles such as methylbenzotriazole, 5-chlorobenzotriazole, etc./\rogen-substituted benzotriazoles, butylcarboimidobenzotriazole Carboimidobenzotriazoles such as nitrobenzotriazoles described in JP-A-58-118639, sulfobenzotriazole, carboxybenzotriazole or a salt thereof, or human b-xybenzotriazole as described in JP-A-58-118638, etc. Typical examples include silver salts derived from 1.2.4-) lyazole, IH-tetrazole, carbazole, saccharin, imidazole, and derivatives thereof described in Patent No. 4.220.709.

Also, Research Disclosure Magazine No. 170, 1702
Silver salts of carboxylic mackerel having an alkyl group, such as those described in Japanese Patent Application No. 9 (June 1978) and phenylpropiolic acid described in Japanese Patent Application No. 58-221535, can also be used in the present invention.

The following organic silver salt contains 0 per mole of photosensitive silver halide.
．． 01 to 10 mol, preferably o, oi to 1 mol can be used in combination. The total coating noise of photosensitive silver halide and organic silver salt is suitably 50 mg to 10 g/rn'.

The silver halide used in the present invention may be spectrally sensitized with methine dyes and others.

The dyes used include cyanine dyes, merocyania dyes, complex cyanine dyes, complex merocyanine dyes, poropolar-cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei commonly used for cyanine color 2M can be used as the basic heterocyclic nucleus for these dyes. That is, pi, loline nucleus, oxazoline nucleus, thiazoline nucleus, virol nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus,
Imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; Nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and aromatic IS hydrocarbons in these nuclei; nucleus in which I ring is fused, i.e., indolenine nucleus, benzindo renin nucleus, indole nucleus, benzoxadole nucleus.

A naphthoxazole nucleus, a benzothiazole nucleus, a natthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus, a quinoline nucleus, etc. are applicable. These nuclei may be substituted with carbon atoms -H.

Merocyanine dyes or composite merocyanine dyes include a pyrazolin-5-one nucleus, a thiohydantoin nucleus, and a 2-thioxazolidine-2 nucleus having a ketomethylene structure.
,4-dione nucleus.

5-6@heterocyclic nuclei such as thiazolidine-2,4-dione, rhodanine, and thiobarbic acid nuclei can be applied.

These sensitizing dyes may be used alone, but -
Combinations thereof may also be used, and combinations of sensitizing dyes are often used, particularly for the purpose of supersensitization.

Along with the sensitizing dye, it is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
The emulsion may contain a substance exhibiting supersensitization, for example, an aminostyryl compound substituted with a nitrogen-containing heterocyclic group (eg, U.S. Pat. No. 2,933,390, U.S. Pat.
635.721), aromatic organic acid formaldehyde condensates (such as those described in U.S. Pat. No. 3.743),
．． No. 510, etc.), cadmium loading, azaindene compounds, etc., U.S. Pat. No. 3,61
No. 5,613, No. 3.615.641, No. 3,6
The combinations described in No. 17°295 and fiS3,635.721 are particularly useful.

In order to incorporate these sensitizing dyes into a silver halide photographic emulsion, they may be directly dispersed in the emulsion, or they may be dispersed in a solvent such as water, methanol, ethanol, acetone, methyl cellosolve, etc. alone or in a mixture. They may be dissolved in a solvent and added to the emulsion, or they may be dissolved in a solvent immiscible with arsenic water such as phenoxyethanol, then dispersed in water or parent colloid, and this dispersion added to the emulsion. May be added.

Furthermore, these sensitizing dyes can be mixed with a lipophilic compound such as a dye-donating compound and added at the same time. In addition, when dissolving these sensitizing dyes, the sensitizing dyes used in combination may be dissolved separately, or a mixture may be dissolved, and when added to an emulsion, they may be mixed. They may be added at the same time, separately, or at the same time as other additives.They may be added to the emulsion during or before chemical ripening. No. 4.183.756, No. 4.225.
It may be carried out before or after nucleation of silver halide grains according to No. 666.

The amount added is generally about 10-a to 10-2 mol per mol of #It halide.

In the present invention, reduced silver can be used as an image-forming substance, and also dye-providing substances such as those described below can be used.

Examples of dye-donating substances that can be used in the present invention include couplers that can react with a developer. This method using a coupler, in which an oxidized product of the developer produced by an oxidation-reduction reaction between a silver salt and a developer reacts with the coupler to form a dye, is described in numerous documents. Illustrative examples of developers and couplers are found, for example, in "Thetheo" by T. H0JaIleS.
ry of the photography
process"4th, Ed, , 291-3
34, and pages 354 to 361, written by Makoto Kikuchi, "Photo Chemistry Pa. 4th edition (Kyoritsu Shuppan), pages 284 to 295, etc."

Further, a dye silver compound in which an organic silver salt and a dye are combined can also be cited as an example of the dye-donating substance. Specific examples of dye silver compounds can be found in Research φ Disclosure Magazine, 1978, 5.
Monthly issue, pages 54-58, (RD-16966), etc.

Furthermore, azo dyes used in heat-developable silver dye bleaching methods can also be cited as examples of dye-donating substances. Specific examples of azo dyes and bleaching methods are disclosed in U.S. Patent No. 4.235.957.
No., Research φ Disclosure Magazine, April 1976 issue, pages 30-32 (RD-14433).

Also, US Pat. No. 3', 985, 565.

Leuco dyes described in 4,022.617 and the like can also be cited as examples of dye-donating substances.

Another example of the dye-donating substance is a compound that has the function of releasing or diffusing a diffusible dye in one image.

This type of compound can be represented by the following general formula (LI).

(Dye-X)n-Y (LI)
'.

Dye represents a dye group or a dye precursor group, or a fluorescent bond or linking group, and Y corresponds to or inversely corresponds to a photosensitive silver salt having a latent image in an imagewise manner (Dye-X)n
-Creating a difference in the diffusivity of the compound represented by Y,
Alternatively, Dye is released and the released Dye and (Dye
-X) represents a group that has the property of causing a difference in diffusivity between n and Y, n represents 1 or 2, and when n is 2, the two Dye-Xs may be the same or different. It's okay.

Specific examples of the dye-donating substance represented by the general formula (LI) include 1. For example, a dye developer in which a hydroquinone developer and a dye component are linked is disclosed in US Patent No. 3,134,769.
issue.

Same No. 3.362,819, Same No. 3
, No. 597, 200.

Same 3rd. 544. No. 545, same.
No. 3,482,972, etc. In addition, a substance that releases a diffusible dye through an intramolecular nucleophilic substitution reaction was disclosed in JP-A-51-636.
No. 18, etc., a substance that releases a diffusible dye through an intramolecular rewinding reaction of the inoxacilone ring is disclosed in JP-A No. 49-1.
It is described in No. 11628, etc. In all of these methods, the diffusible dye is released or diffused in areas where development has not occurred, and the dye is neither released nor diffused in areas where development has occurred. In addition, in these methods, development and dye release or diffusion occur in parallel, so S/
It is very difficult to obtain an image with a high N ratio. Therefore, in order to improve this drawback, the dye-releasing compound is made into an oxidized form that does not have the ability to release the dye, and is made to coexist with the reducing agent or its precursor. A method has also been devised in which a diffusible dye is released by reduction with a reducing agent that remains unoxidized after development, and specific examples of dye-donating substances used in this method are disclosed in #Kokai No. 53-110827 and Id. No. 54-130927.

Same number 56-164342, Same number 53-35533 It is described in.

On the other hand, as a substance that releases a diffusible dye in the area where development occurs, a substance that releases a diffusible dye through the reaction between a coupler having a diffusible dye as a leaving group and an oxidized form of a developer is disclosed in British Patent No. 1. No. .330.524.

Japanese Patent Publication No. 48-39165, U.S. Patent No. 3,443,940, etc. also disclose substances that produce diffusible dyes through the reaction of a coupler having a diffusion-resistant group as a leaving group and an oxidized form of a developer. It is described in U.S. Pat. No. 3,227.550, et al.

In addition, in systems using these color developers, image contamination due to oxidative decomposition products of the developer and chemicals becomes a serious problem.
Dye-releasing compounds that themselves have reducing properties have also been devised.

1. ″″″″ti'lt*! tl&, :#C1! Tk
−*Li° −“Definitions in the formula are described in each document.

U.S. Patent No. 3,928.312, etc. U.S. Patent No. 4.053.312 etc. U.S. Patent No. 4.055.428 etc. ::.

U.S. Patent No. 4,336,322 JP 59-65839 JP 59-69839 Ballist JP 53-3819 JP 51-104,343 JP 51-104.343 Ba1list JP-A-51-104,343 Research Disclosure Magazine No. 17465 U.S. Patent No. 3,725,062 U.S. Patent No. 3,728,113 Ba1list U.S. Patent No. 3,443,939 JP-A-58-116 No. 537 I:vB Any of a variety of dye-donating substances can be used in the present invention.

Specific examples of imaging materials for use in the present invention are described in the patent documents cited above. Since it is not possible to list all the preferable compounds here, some of them are shown as examples. For example, the dye-donating substance represented by the above general formula (LI) may include the following: I can do it.

1-I Z Ll-2 LI-3 LI-4 LI-5 LI-6 LI-7 LI-8 LI-9 LI-10 LI-11 Sun i-12 LI-14 Ll-15 Compounds described below is an example, and is not limited to these. In the present invention, the dye-donating substance is described in U.S. Patent No. 2.32.
It can be introduced into the layer of the photosensitive material by a known method such as the method described in No. 2.027. In that case, the following high boiling point organic solvents and low boiling point organic solvents can be used.

For example, 7-tanolic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (
diphenyl phosphate, triphenyl phosphate,
tricresyl phosphate, dioctyl butyl phosphate), citric acid esters (e.g. acetyl tributyl citrate), benzoic acid esters (octyl benzoate),
Alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate, dioctyl azelate), trimesic acid esters (e.g. dibutoxyethyl succinate, dioctyl azelate),
organic solvents with a boiling point of 30°C to 160°C, such as lower alkyl acetates such as ethyl acetate, butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, After being dissolved in β-ethoxyethyl acetate, methyl cellosolve acetate, cyclohexanone, etc., it is dispersed in a wood-philic colloid. The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be mixed and used.

Also, Japanese Patent Publication No. 51-39853, Japanese Patent Publication No. 51-5994
The dispersion method using a polymer described in No. 3 can also be used. In addition, various surfactants can be used when dispersing the dye-donating substance in the woody colloid, and these surfactants include those listed as surfactants elsewhere in this specification. can be used.

The content of the high boiling point organic solvent used in the present invention is 10 g or less, preferably 5 g per 1 g of the dye-donating substance used.
It is as follows.

In the present invention, it is desirable to include a reducing substance in the light-sensitive material. Examples of the reducing substance include those generally known as reducing agents, as well as the above-mentioned dye-donating substances having reducing properties.

Also included are reducing agent precursors that do not themselves have reducing properties but exhibit reducing properties through the action of nucleophiles and heat during the development process.

Examples of reducing agents used in the present invention include inorganic additives such as sodium sulfite and sodium hydrogen sulfite, benzenesulfinic acids, hydroxylamines, hydrazines, and hydrazides.

Poran-amine complexes, hydroquinones, ami/phenols, catechols, p-phenylenediamines, 3
-pyrazolidinones, droxytetronic acid, ascorbic acid, 4-amino-5-pyrazolones, etc., as well as "The theory" by T. H. James,
of thephotographic proc
Reducing agents described in ess''4th+Ed., pages 291-334 can also be used.

Also, JP-A-56-138736, JP-A No. 57-40
Reducing agent precursors described in US Pat. No. 245, US Pat. No. 4,330,617, and the like can also be used.

Examples of more preferable reducing agents include the following.

3-pyrazolidones and their precursors [e.g. 1
-Phenyl-3-pyrazolidone, 1-phenyl-4,4
-dimethyl-3-pyrazolidone, 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone, l-
m-tolyl-3-pyrazolidone, 1-p-tolyl-3-
Pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, l-7enyl-5-methyl-3-pyrazolidone, l-phenyl-4°4-bis-(hydroxymethyl)
-3-pyrazolidone, 1,4-di-methyl-3-pyrazolidone, 4-methyl-3-pyrazolidone, 4,4-dimethyl-3-pyrazolidone, 1-(3-chlorophenyl)
-4-Methyl-3-pyrazolidone, 1-(4-chlorophenyl)-4-methyl-3-pyrazolidone, 1-(4-
tolyl)-4-methyl-3-pyrazolidone, 1-(2-
tolyl)-4-methyl-3-pyrazolidone.

1-(4-tolyl)-3-pyrazolidone, 1-(3-
tolyl)-3-pyrazolidone, 1-(3-tolyl)-4
, 4-dimethyl-3-pyrazolidone, 1-(2-)lifluoroethyl)-4,4-dimethyl-3-pyrazolidone, 5-methyl-3-pyrazolidone, 1,5-diphenyl-3-pyrazolidone, 1- phenyl-4-methyl-4-
Stearoyloxymethyl-3-pyrazolidone, l-phenyl-4-methyl-4-lauroyloxymethyl-3
-pyrazolidone, l-phenyl-4,4-bis-(lauroyloxymethyl)-3-pyrazolidone, l-2phenyl-2-acetyl-3-pyrazolidone, 1-phenyl-
3-7cetoxypyrazolidone], idofquinones and their precursors [e.g., hydroquinone, toluhydroquinone, 2゜6-dimethylhydroquinone, t-
Butylhydroquinone, 2.5-di-t-butylhydroquinone, t-octylhydroquinone, 2゜5-di-
t-octylhydroquinone, pentadecylhydroquinone, sodium 5-pentadecylhydroquinone-2-sulfonate, P-penzoyloxyphenol, 2-
Methyl-4-henzoyloxyphenol, 2-t-butyl-4-(4-chlorobenzoyloxy)phenol] Various reducing agents such as those disclosed in U.S. Pat. No. 3,039,889 are used in the present invention. Combinations of can also be used.

In the present invention, the amount of reducing agent added is 0 per mole of silver.
．． 0.01 to 20 mol, particularly preferably 0.1N and 10 mol.

An image formation accelerator can be used in the heat-developable photosensitive material and dye-fixing material in the present invention, but # in the present invention,
A base or a base precursor that releases the base upon heating is essential.

This is because without this, development will hardly occur even if heated.

Image formation promoters include promoting redox reactions between silver salt oxidizing agents and transition agents, promoting reactions such as production of dyes from dye-donating substances, decomposition of dyes, and release of mobile dyes, and photosensitive materials. It has functions such as promoting the movement of dye from the layer to the dye fixing layer, and from a physicochemical function, it interacts with bases or base precursors, nucleophilic compounds, oils, hot solvents, surfactants, silver or silver ions. It is classified as a compound with action. However, these groups of substances generally possess multiple functions and usually have some of the above-mentioned promoting effects.

Below, these image formation accelerators are categorized by function.
Although specific examples of each will be shown, this classification is for convenience, and in reality, one compound often has multiple functions.

1211 Examples of preferred bases include alkali metal or alkaline earth metal hydroxides, secondary or tertiary phosphates, borates, carbonates, quinolates, metaborates as inorganic bases; Examples include ammonium hydroxide; hydroxide of quaternary alkyl ammonium; hydroxide of other metals, etc. Examples of organic bases include aliphatic amines (trialkylamines, hydroxylamines, aliphatic polyamines)
; Aromatic amines (N-alkyl substituted aromatic amines,
N-hydroxylalkyl-substituted aromatic amines and bis(p-(dialkylamino)phenylcomethanes),
Examples include heterocyclic amines, amidines, cyclic amidines, guanidines, and cyclic guanidines, and those having a pKa of 8 or more are particularly preferred.

b Precursor base Precursors include salts of organic acids and bases that are decarboxylated and decomposed by heating, and decomposed by N)1° reactions such as intramolecular nucleophilic substitution reactions, Rossen rearrangement, and Beckmann rearrangement to release amines. Preferably used are compounds that cause some kind of reaction upon heating and release a base. Preferred base precursors include salts of trichloroacetic acid as described in British Patent No. 998.949, α-sulfonylacetic acid as described in U.S. Pat. No. 4,060,420, and salts of trichloroacetic acid as described in U.S. Pat. salts of propiolic acids, the 2-carboxylic rupoxamide derivatives described in US Pat. A with a thermally decomposable acid that uses alkali metals and alkaline earth metals in addition to base components (Japanese Patent Application No. 58-69597), hydroxamic carbamates described in Japanese Patent Application No. 58-43860 that utilize Rossen rearrangement, fludoxime carbamates described in Japanese Patent Application No. 58-31614 that generate nitrile by heating, etc. can be mentioned. Other British Patent No. 99
No. 8.945, U.S. Patent No. 3.220.846, #Kokai No. 50-22625, British Patent No. 2,079,480
The base precursors described in No. 1, etc. are also useful.

Specific examples of base precursors particularly useful in the present invention are shown below.

Guanidine trichloroacetate, methylguanidine trichloroacetate, potassium trichloroacetate, guanidine phenylsulfonylacetate, p-chlorophenylsulfonylacetate guanidine, p-methanesulfonylphenylsulfonylacetate guanidine, potassium phenylpropioleate, cesium phenylpropioleate, guanidine phenylpropioleate, P -guanidine chlorophenylpropiolate, guanidine 2,4-dichlorophenylpropiolate, diguanidine p-phenylene-bis-propiolate, tetramethylammonium phenylsulfonylacetate, tetramethylammonium resistant to phenylpropiol.

C. Water and water-releasing compounds, amines, amidines, guanidines, hydrohuadylamines, hydrazine ml, hydrazides, oximes, hydroxamic acids, sulfonamides, active methylene compounds, alcohols, thiols. It is also possible to use salts or precursors of the above compounds.

A high boiling point organic solvent (so-called regrinding) used as a solvent when emulsifying and dispersing a hydrophobic compound can be used.

It is a solid at ambient temperature, and it melts near the development temperature and acts as a solvent. 40 for ketones and ether compounds
Those that are solid at temperatures below ℃ can be used.

Pyridinium salts, ammonium salts, and phosphonium salts described in JP-A-59-74547, JP-A-59-57
Examples include polyalkylene oxides described in No. 231.

), are ion thiimides, nitrogen-containing heterocycles described in Japanese Patent Application No. 58-51657, thiols and thioureas described in Japanese Patent Application No. 57-222247,
Examples include thioethers.

The image formation accelerator may be incorporated into either of the photosensitive material 1, the dye-fixing material, or both.The layers in which it is incorporated may also include the emulsion layer, the intermediate layer, the protective layer, the dye-fixing layer, and the layers in which they are incorporated. May be built into any adjacent layer.
The same applies to the embodiment in which the photosensitive layer and the dye fixing layer are provided on the same support.

The image formation accelerator can be used alone or in combination of several types, but generally a greater accelerating effect can be obtained when several types are used in combination. - Particularly in the present invention, since a base or a base precursor is used as described above, a remarkable promoting effect can be obtained by using other promoters in combination.

In the present invention, various development stoppers can be used in order to always obtain a constant image despite fluctuations in processing temperature and processing time during thermal development.

The development stopper referred to here is a compound that neutralizes the base immediately after proper development or reacts with the base to lower the base concentration in the film and stop development, or a compound that inhibits development by interacting with silver and silver salts. It is a compound that Specific examples include acid precursors that release acids when heated, electrophilic compounds that cause a substitution reaction with a coexisting base when heated, nitrogen-containing heterocyclic compounds, mercapto compounds, and the like. Examples of acid precursors include oxime esters described in Japanese Patent Application No. 58-216928 and Japanese Patent Application No. 59-48305;
Examples include compounds that release acids through Rossen rearrangement as described in Tokusho No. 5S-85834, and examples of electrophilic compounds that cause a substitution reaction with a base when heated.

Examples include compounds described in Japanese Patent Application No. 59-85838.

The above-mentioned development stoppers are particularly effective when a base precursor is used, which is preferable.

In that case, the ratio (molar ratio) of base precursor/brewing precursor is preferably 1/20 to 20/l, and 115 to 20/l.
5/l is more preferred.

Further, in the present invention, it is possible to use a compound that activates the development and stabilizes the image at the same time. Among them, inthiuroniums represented by 2-hydroxyethylinthiuronium trichloroacetate described in U.S. Patent No. 3,301,678, U.S. Patent No. 3,669.670
1,8-(3,6-thioxaoctane)bis(
Bis( incicuronium trichloroacetate) etc.
isothiuronium), West German Patent Publication No. 2.162,7
Thiol compounds described in No. 14, U.S. Pat. No. 4,012
2-Amino-2-thiazolium trichloroacetate, 2-7 minnow 5-bromoethyl-2 described in No. 260
- Thiazolium compounds such as thiazolium trichloroacetate, bis(2-amino-2-thiazolium)methylenebis(sulfonylacetate) and 2-amino-2-thiazolium phenylsulfonylacetate described in U.S. Pat. No. 4,060,420 Compounds having 2-carboxycarboxamide as an acidic moiety, such as, for example, are preferably used.

Furthermore, the 7-zole thioether and blocked azolinthione compounds described in Belgian Patent No. 768,071,
U.S. Pat. No. 3,893.

4-7 Lee-1-carbamyl-2-tetrazoline-5-thione compound described in No. 859, and other US patents! 3,
No. 839,041, No. 3 844.788, No. 3
, 877.940 are also preferably used.

In the present invention, an image toning agent may be contained if necessary. Effective toning agents are 1.2.4-) lyazole, IH-tetrazole, thiouracil and 1,3
．． Compounds such as 4-thiadiazole. Examples of preferred toning include 5-amino-1,3,4-thiadiazole-2-thiol, 3-mercapto-1,2,4-
Examples include triazole, bis(dimethylcarbamyl) disulfide, 6-methylthiouracil, and 1-phenyl-2-tetraazoline-5-thousand. Particularly effective toning agents are compounds capable of forming black images.

The concentration of the toning agent to be contained varies depending on the type of heat-developable photosensitive material, processing conditions, desired image, and other factors, but generally it is about 0.0% per mole of silver in the photosensitive material. 00
It is 1 to 0.1 mole.

The binders used in the present invention may be contained alone or in combination.

A hydrophilic binder can be used for this binder. A typical example of a wood-loving binder is a transparent or semi-transparent wood-loving binder.

For example, it includes proteins such as gelatin, gelatin derivatives, cellulose derivatives, natural substances such as polysaccharides such as starch and gum arabic, and synthetic polymeric substances such as water-soluble polyvinyl compounds such as polyvinylpyrrolidone, lylamide polymers, etc. Other synthetic polymeric substances include dispersed vinyl compounds, which increase the dimensional stability of photographic materials, especially in the form of lattices.

The binder of the present invention has a coating amount of 208 g or less per lrn'', preferably 10 g or less, more preferably 7 g.
The following are appropriate.

The ratio of the high boiling point organic solvent dispersed in the binder together with a hydrophobic compound such as a dye-donating substance and the binder is 1 g of binder to 1 g of solvent or less, preferably 0.
A suitable amount is 5 cc or less, more preferably 0.3 cc or less.

The photographic light-sensitive materials and dye-fixing materials of the present invention may contain inorganic or organic hardeners in the photographic emulsion layer and other binder layers, such as chromium salts (chromium alum,
chromium acetate, etc.), aldehydes, (formaldehyde,
glyoxal, geltaraldehyde, etc.), N-methylol compounds/substances (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.), active xenyl compounds (1,3,
, 5-triacryloyl-hexahydro-s-triazine, 1,3-vinylsulfonyl-2-propatol, 1
．． 2-bis(vinylsulfonylacetamido)ethane
□, etc.), active halogen compounds (2,4-dichloro-
6-hydroxy-s-triazine, etc.), mucohalogenic acid a, (mucochloric acid, mucophenoxychloroic acid, etc.), etc. can be used alone or in combination.

The support used in the light-sensitive material and dye-fixing material used in the present invention is one that can withstand processing temperatures. As a general support,
glass, paper.

Not only metals and their analogs are used, but also cellulose acetate films, cellulose ester films, polyvinyl acetal films, polystyrene films, polycarbonate films, polyethylene terephthalate films and related films or resin materials. A paper support laminated with a polymer such as polyethylene can also be used. U.S. Patent No. 3,634°089, U.S. Patent No. 3.
Polyesters described in No. 725.070 are preferably used.

When using a dye-donating substance that releases an image-wise mobile dye in the present invention, a dye transfer aid can be used to transfer the dye from the photosensitive layer to the dye-fixing layer.

In a system in which the transfer aid is externally supplied, water or a basic aqueous solution containing caustic soda, caustic potash, or an inorganic alkali metal salt is used as the dye transfer aid. Also used are low boiling point solvents such as methanol, N,N-dimethylformamide, acetone and diisobutyl ketone, or a mixed solution of these low boiling point solvents and water or a basic aqueous solution. The dye transfer aid may be used in such a way that the image-receiving layer is wetted with the transfer aid.

If the transfer aid is built into the photosensitive material or dye fixing material, there is no need to supply the transfer aid from the outside. Alternatively, it may be incorporated as a precursor that releases the solvent at high temperatures. More preferably, a wood-philic thermal solvent that is solid at room temperature and dissolves at high temperatures is incorporated into the light-sensitive material or dye-fixing material. The wood-philic thermal solvent may be incorporated into either the photosensitive material or the dye-fixing material, or may be incorporated into both.The layer in which it is incorporated may also be an emulsion layer, an intermediate layer, a protective layer, or a dye-fixing layer. )'1 Examples of hydrophilic heat solvents include ureas, lysines, amides, sulfonamides, imides, and alcohols. ,
There are oximes and other heterocycles.

Among the photosensitive materials used in the present invention, in particular, the general formula (L
1) if it contains a dye-donating substance represented by 1)
Since the dye-donating substance is colored, it is not so necessary to further include an irradiation prevention substance, a halation prevention substance, or various dyes in the light-sensitive material, but it does improve the sharpness of the image. In order to
No. 3692, U.S. Pat. No. 3,253.921, U.S. Pat. No. 2,527,583, U.S. Pat. It can be included. These dyes are preferably heat-decolorizable, such as those described in U.S. Pat. No. 3,769,019, U.S. Pat. is preferred.

The photosensitive material used in the present invention may optionally contain various additives known as heat-developable photosensitive materials and layers below the photosensitive layer, such as an antistatic layer, a conductive layer, a protective layer, an intermediate layer,
It can contain AH scraps, a release layer, etc. As for various additives, Research No. Disclosure Clogging. ■.

170. June 1978 17) Additives described in No. 17029, such as plasticizers, sharpness improving dyes, AH dyes, sensitizing dyes, matting agents.

Additives include surfactants, optical brighteners, and anti-fading agents.

The photographic element of the present invention is comprised of a light-sensitive element that forms or releases a dye upon heat development and, optionally, a dye-fixing element that fixes the dye.

In particular, in systems that form images by diffusion transfer of dyes, a photosensitive element and a dye fixing element are essential, and in one typical form, the photosensitive element and dye fixing element are separately coated on two supports. It is broadly divided into two types: a form in which it is coated on the same support and a form in which it is coated on the same support.

There are two types of forms in which the photosensitive element and the dye-fixing element are formed on separate supports: one is a peelable type and the other is a peelable type. In the case of the former peel-off type, after image exposure or heat development, the coated surface of the photosensitive element and the coated surface of the dye-fixing element are overlapped, and the photosensitive element is immediately peeled off from the dye-fixing element after the transfer image is formed. Depending on whether the final image is of a reflection type or a transmission type, the support of the dye fixing element can be selected as an opaque support or a transparent support.
In addition, a white reflective layer may be coated if necessary. In the latter type, which does not require peeling, a white reflective layer is interposed between the photosensitive layer in the photosensitive element and the dye fixing layer in the dye fixing element. This white reflective layer may be coated on either the photosensitive element or the dye-fixing element.The support of the dye-fixing element must be a transparent support.

A typical configuration in which the photosensitive element and the dye-fixing element are coated on the same support is a configuration in which there is no need to peel off the photosensitive element from the image-receiving element after the transfer image is formed. In this case, a photosensitive layer, a dye fixing layer and a white reflective layer are laminated on a transparent or opaque support. Preferred embodiments include, for example, transparent or opaque support/photosensitive layer/white reflective layer/dye fixing layer/transparent support/dye fixing layer/white reflective layer/photosensitive layer.

Another typical form in which a photosensitive element and a dye fixing element are coated on the same support includes, for example, Japanese Patent Application Laid-Open No. 56-67840.
, Canadian Patent No. 674°082, U.S. Patent No. 3.73
As described in No. 0.718, there is a form in which part or all of the photosensitive element is peeled off from the dye fixing element, and a peeling layer is coated at an appropriate position.

The photosensitive element or dye-fixing element may have a conductive heating layer as a heating means for thermal development or diffusion transfer of the dye.

・1 Using the three primary colors of yellow, magenta, and cyan 1.
In order to obtain a wide range of colors in the chromaticity diagram, the light-sensitive elements used in the present invention must have silver halide emulsion layers sensitive to at least three different spectral regions.

Typical combinations of at least three light-sensitive silver halide emulsion layers sensitive to different spectral regions include a combination of a blue-sensitive emulsion layer, a green-sensitive emulsion layer and a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a red-sensitive emulsion layer. A combination of a sensitive emulsion layer and an infrared sensitive emulsion layer, a combination of a blue sensitive emulsion layer, a green sensitive emulsion layer and an infrared sensitive emulsion layer, a blue sensitive emulsion layer, a red sensitive emulsion layer and an infrared sensitive emulsion. There are combinations of layers, etc.

Note that the infrared light-sensitive emulsion layer is an emulsion layer that is sensitive to light of 700 nA or more and 740 ns or more.

The light-sensitive material used in the present invention may have two or more emulsion layers sensitive to the same spectral region, depending on the sensitivity of the emulsion, if necessary.

Each emulsion layer and/or a non-photosensitive woody colloid layer adjacent to each emulsion layer contains a dye-donating substance that releases or forms a yellow woody dye, a magenta hydrophilic dye, and a dye-donating substance that releases or forms a yellow woody dye. It is necessary to contain at least one of a dye-donating substance that releases or forms a cyan wood-loving dye and a dye-donating substance that releases or forms a cyan wood-loving dye.
In other words, each emulsion layer and/or the non-photosensitive lignophilic colloid layer adjacent to each emulsion layer includes:
It is necessary to contain a dye-donating substance that releases or forms hydrophilic dyes of different hues. If desired, two or more dye-providing substances of the same hue may be mixed and used. If the dye-providing substance has a clear color from the beginning, one dye-providing substance may be mixed with this emulsion layer. In addition to the above-mentioned layers, the photosensitive material used in the present invention may optionally contain a retaining layer, an intermediate layer, an antistatic layer, an anti-curl layer, and a release layer. , an auxiliary layer such as a matting agent layer can be provided.

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

In addition, the intermediate layer may contain a reducing agent to prevent color mixing, a UV absorber, and a white pigment such as TiO2.The white pigment may be added not only to the intermediate layer but also to the emulsion layer for the purpose of increasing sensitivity. Good too.

In order to impart each of the above-mentioned color sensitivities to a silver halide emulsion, each silver halide emulsion may be dye-sensitized using a known sensitizing dye to obtain the desired spectral sensitivity.

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

Furthermore, a water-absorbing layer or a layer containing a dye transfer aid can be provided in order to sufficiently contain a dye transfer aid, or to control the dye transfer aid, if necessary.

These layers may be adjacent to the dye fixing layer or may be applied via an intermediate layer.

The dye fixing layer used in the present invention may be composed of two or more layers using mordants having different mordant powers, if necessary.

In addition to the above-mentioned layers, the dye fixing element used in the present invention can be provided with auxiliary layers such as a release layer, a matting agent layer, and an anti-curl 1F layer, if necessary.

The one or more layers described in h include a base and/or base precursor to promote dye transfer, a wood-philic heat solvent, an anti-fade agent to prevent color mixing of the dye, a UV absorber, and a dimensional stabilizer. Dispersed vinyl compound to increase the properties of
A fluorescent whitening agent or the like may be included.

The binder in the above layer is preferably hydrophilic, and transparent or translucent hydrophilic colloids are typical. For example, proteins such as gelatin, gelatin derivatives, polyvinyl alcohol, cellulose derivatives, polysaccharides such as starch, gum arabic, etc.
Natural substances such as ``1'', synthetic polymer substances such as dextrin, pullulan, polyvinyl alcohol, polyvinylpyrrolidone, and water-soluble polyvinyl compounds such as acrylamide polymers are used. Among these, gelatin and polyvinyl alcohol are particularly effective.

In addition to the above, pigment fixing elements include a reflective layer and a neutralizing layer that contain white pigments such as titanium oxide, depending on the purpose.

It may also have a neutralization timing layer or the like.

These layers may be coated not only in the dye-fixing element but also in the light-sensitive element, such as the reflective layer described above.

The configurations of the neutralization layer and the neutralization timing layer are described, for example, in U.S. Pat. No. 2,983,606, U.S. Pat.
It is described in Canadian Patent No. 3.362.821, Canadian Patent No. 3.415,844, Canadian Patent No. 928.559, etc.

Furthermore, it is advantageous for the dye fixing element of the present invention to contain a transfer aid as described below. The transfer aid may be included in the dye fixing layer, or may be included in a separate layer.

In the present invention, the transparent or opaque heat generating element when electrical heating is employed as the developing means can be made using conventionally known techniques as a resistance heating element.

As a resistance heating element, there are two methods: one uses a thin film of an inorganic material exhibiting semiconductivity, and the other uses a thin film of an organic material in which conductive fine particles are dispersed in a paint. Materials that can be used in the former method include silicon carbide, molybdenum silicide, lanthanum chromate, barium titanate ceramics used as PTC thermistors, tin oxide, and zinc oxide, and transparent or opaque thin films are made using known methods. be able to. In the latter method, conductive particles such as metal particles, carbon black, and graphite are dispersed in rubber, synthetic polymers, and gelatin to create a resistor with desired temperature characteristics. These resistors may be in direct contact with the photosensitive element or may be separated by a support, intermediate layer, or the like.

An example of the positional relationship between the heat generating element and the photosensitive element is shown below.

Heat-generating element/support/photosensitive element support 7 Heat-generating element/photosensitive element support/heat-generating element/intermediate layer/photosensitive element support/photosensitive element/heat-generating element support/photosensitive element/intermediate N/heat-generating element Image in the present invention The image-receiving layer includes a dye fixing layer used in heat-developable color photosensitive materials.

Any mordant can be selected from commonly used mordants, but polymer mordants are particularly preferred among them.
Here, the polymer mordant includes a polymer containing a tertiary amine group, a polymer having a diaryne-containing heterocyclic moiety, a polymer containing a certain quaternary cation thereof, and the like.

Regarding polymers containing one vinyl unit having a tertiary amino group, Japanese Patent Application No. 58-169012 and Japanese Patent Application No. 1983
8-166135, etc., and specific examples of polymers containing one vinyl nitrate unit having a tertiary imidazole group include Japanese Patent Application Nos. 58-226497 and 58-2.
No. 32071, U.S. Patent No. 4.282゜305%, U.S. Patent No. 4,115,124, U.S. Pat.
Ru.

Preferred specific examples of polymers containing one vinyl nitrate unit having a quaternary imidazolium salt include British Patent No. 2,0
No. 56,101, No. 2.093.041, No. 1.
No. 594°961, U.S. Patent No. 4,124,386,
Id. No. 4,115,124, Id. No. 4, 273.

No. 853, No. 4,450,224, Japanese Unexamined Patent Publication No. 48-2
8.225 etc.

Other preferred specific examples of polymers containing one vinyl nitrate unit having a quaternary ammonium salt include U.S. Pat. No. 3,709,890, U.S. Pat.
No. 3,958°995, patent application No. 58-166135
No. 58-169012, No. 58-232070, No. 58-232072, and No. 59-91620.

In the present invention, as well as the heat-developable photosensitive layer, coating solutions for the protective layer, intermediate layer, undercoat layer, backing layer, and other layers are prepared for each layer using the dipping method, air knife method, curtain coating method, or U.S. A light-sensitive material can be prepared by sequentially coating onto a support by one of various coating methods, such as the hopper coating method described in Japanese Patent No. 3,681,294, and drying.

Additionally, two or more layers can be applied simultaneously if desired by the methods described in US Pat. No. 2,761.791 and British Patent No. 837,095.

Radiation including visible light can be used as a light source for image exposure to form an image on a heat-developable photosensitive material. Generally, in addition to the light sources used for normal color printing, such as tungsten lamps, various light sources such as mercury lamps, halogen lamps such as iodine lamps, xenon lamps, laser light sources, CRT light sources, fluorescent tubes, and light-emitting diodes (LEDs) may be used. I can do it.

The heating temperature in the heat development step can be developed at about 0°C to about 250°C, but about 10°C to about 180°C is particularly useful, and within this range, 140°C or higher is preferable, especially 1
The heating temperature in the transfer process is preferably 50”0 or higher.
Transfer is possible at a temperature ranging from the temperature in the heat development process to room temperature, but especially at a temperature of about 10°C below the temperature in the heat development process.
As a heating means in the development and/or transfer step, which is more preferably at a low temperature, a simple hot plate, an iron, a hot roller, a heating element using carbon, titanium white, etc. can be used.

A dye transfer aid (for example, water) is added between the photosensitive layer of a heat-developable photosensitive material and the dye fixing layer of a dye fixing material to promote image transfer. Alternatively, a dye transfer aid may be applied to both, and then the two may be superimposed.

Examples of methods for applying the dye transfer aid to the photosensitive layer or the dye fixing layer include the roller coating method or wire bar coating method as described in Japanese Patent Application Laid-open No. 58-55907, and the method described in Japanese Patent Application No. 58-55908. A method of applying water to a dye-fixing material using a water-absorbing member as described above, and a method of applying water between a heat-developable photosensitive material and a dye-fixing material as described in Japanese Patent Application No. 58-55906. Method for applying dye transfer aid by forming, Japanese Patent Application No. 58-5591
As described in No. 0, a method of applying a dye transfer aid by forming a bead between a water-repellent roller and a dye fixing layer, and other methods include a dipping method, an extrusion method, and applying by ejecting it as a jet from pores. Various methods can be used, such as a method of applying the material by crushing the bod, and a method of applying the material by crushing the bod.

The dye transfer aid may be measured in advance and given in an amount within the range as described in Japanese Patent Application No. 58-37902, or
Give it enough, and then use it by squeezing it out by applying pressure with a roller, etc., or by drying it by applying heat and adjusting the amount = k 2><-c 6.
7. For example, there is a method in which a dye transfer aid is applied to a dye fixing material using the above method, the excess dye transfer aid is squeezed out through pressurized rollers, and then the material is overlapped with a heat-developable photosensitive material. .

The heating means in the transfer process includes heating by passing between hot plates or heating by contacting with the hot plates (for example, Japanese Patent Application Laid-Open No. 50-62635).
(No. 10791), heating by contacting a heated drum or heated roller while rotating (for example, Japanese Patent Publication No. 43-10791), hot air,
Heating by passing through the inside (for example, JP-A-53-327
37), heating by passing through an inert liquid kept at a constant temperature, heating by passing it along a heat source using a roller, belt, or guide member (for example, Japanese Patent Publication No. 44-2546), etc. can be used. . Alternatively, a layer of an electrically conductive material such as graphite, carbon black, or metal may be applied to the dye-fixing material in an overlapping manner, and an electric current may be passed through this electrically conductive layer to heat it directly.

The heating temperature applied in the transfer step can be in the range from the temperature in the heat development step to room temperature, but in particular 6
The temperature is preferably 0° C. or more and 10° C. or more lower than the temperature in the heat development step.

The pressure when overlapping the heat-developable photosensitive material and the dye-fixing material and bringing them into close contact varies depending on the embodiment and the materials used.
0, 1 to 100 kg/cm2, preferably 1 to 50 K
g/cm2 is appropriate (eg.
91).

Methods for applying pressure to the photothermographic material and the dye-fixing material include a method of passing the material between a pair of rollers, a method of pressing using a plate with good smoothness, and the like.

Various methods can be used. Furthermore, the roller and plate used to apply pressure can be heated within a range from room temperature to the temperature used in the thermal development process.

(2) Specific effects of the invention According to the invention, at least an internal latent image type silver halide emulsion, a nucleating agent, an organic silver salt oxidizing agent, a base and/or a base breaker that releases the base upon heating are provided on a support. Therefore, a heat-developable photosensitive material that easily forms a positive image with a good S/N ratio can be obtained.

(2) Specific Examples of the Invention Hereinafter, specific examples of the present invention will be shown, and the effects of the present invention will be explained in further detail.

Example 1 Preparation of benzotriazole silver emulsion 28 g of gelatin and 13.2 g of benozotriazole were dissolved in 3000 d of water. Add this solution to 4
The mixture was kept at 0°C and stirred. Add 417 g of nitric acid to this solution and 1 liter of water.
The solution dissolved in ooom was added over 2 minutes. The benzotriazole silver emulsion pH was adjusted and allowed to settle to remove excess salt. Adjust the *pH to 6.0, yield 400
A benzotriazole silver emulsion of g was obtained.

The following photosensitive coatings were prepared using this benzotriazole silver emulsion.

(a) Silver bromide emulsion 20g 1!1 An aqueous solution of potassium bromide and an aqueous solution of silver nitrate were simultaneously added to an aqueous gelatin solution over a period of about 100 minutes at 75°C with vigorous stirring, so that the average particle size was about 1. A 3 micron silver bromide emulsion was obtained.

Next, 2.511 g of sodium thiosulfate per mol of silver and 1.2 B of potassium chloride #I per mol of silver were added to the silver bromide grains, and a chemical sensitization treatment was performed by heating at 75°C for 80 minutes. Ta.

One mole of chemically sensitized particles was further grown by further treatment for 40 minutes in the same precipitation environment as the first time, and the final average particle size was 1.5 J, lm.

Next, 0.34 layers of sodium thiosulfate and 68 g of poly(N-vinylpyrrolidone) were added to this emulsion per mole of silver, and heated at 60°C for 60 minutes to sensitize the grain surfaces. went.

(b) Benzotriazole silver emulsion log (c) Addition of 6.8 mg of nucleating agent (48) per mole of silver bromide (d) Dispersion of dye-providing substance 33 g L 1 Dye-donating as below Weighed out 5 g of a sexual substance, 0.5 g of sodium succinate-2-ethyl-hexyl ester sulfonate as a surfactant, and 7.5 g of tricresyl phosphate, added 30 ml of ethyl acetate, and dissolved them by heating at about 60°C. to obtain a homogeneous solution. This solution and 100 g of a lO% solution of lime-treated gelatin were stirred and mixed, and then dispersed using a homogenizer at 10,000 rpm for 10 minutes.

(e) 5% aqueous solution of the following compound 10allCg
H+q[NixO model 40ζH (f) 10% aqueous solution of the following compound 4dlH2N
SO2N (CH3) 2 (g) Guanidine trichloroacetic acid 2,5 g (h) Gelatin dispersion of the following acid precursor
8IllI(i) Water 12
4 The gelatin dispersion of the acid precursor (h) above was prepared as follows.

The log of the compound shown below was added to a 1% aqueous solution of gelatin at 100%
g and milled in a mill for 10 minutes with 100 g of glass beads having an average particle size of about 0.6 mm. The glass peas were separated by filtration to obtain a gelatin dispersion of acid precursor.

After mixing the above (a) to (h) and heating and dissolving them, a 30 m thick wet film was applied onto a 180 x m thick polyethylene terephthalate film.

Furthermore, the following composition was applied as a protective layer thereon.

b) Gelatin 10% aqueous solution 30d) Water
45ai c) A solution in which 0.8 g of guanidine phenylpropiolate was dissolved in 20 d of water A mixture of solutions a) to c) was applied to a wet film thickness of 304 m and dried to prepare a photosensitive material A.

Next, a method for forming an image receiving material having an image receiving layer will be described.

Dissolve 10 g of poly(methyl acrylate-N,N,N-trimethyl-N-vinylbenzylammonium chloride) (ratio of methyl acrylate and vinylbenzylammonium chloride is 1:1) in 200-g of water,
% lime-treated gelatin and 100 g of the lime-treated gelatin. This liquid mixture was uniformly applied to a wet film thickness of 907 zm on a paper support laminated with polyethylene in which titanium dioxide was dispersed. After drying, this sample was used as an image-receiving material.

Photosensitive material A was imagewise exposed for 10 seconds at 2000 lux using a tungsten bulb.

Thereafter, it was uniformly heated for 30 seconds using a heat block F heated to 140°C.

This heated photosensitive material is stacked so that the film surface is in contact with the image-receiving material soaked in water, heated for 6 seconds on a heat block at 80°C, and then the image-receiving material is peeled off from the photosensitive material. A magenta color image was obtained.
The density of this positive image was measured using a Macbeth reflection densitometer (RD-51).
9). The results obtained are shown.

Maximum density: 1.60 Minimum density: 0.45 These results show that the photothermographic material of the present invention provides a positive image with a high maximum density and a low minimum density.

From the above, the effects of the present invention are clear.

Example 2 A photosensitive material B was prepared in the same manner as in Example 1, except that the dispersion of the dye-providing substance in Example 1 was replaced with the following gelatin dispersion of the dye-providing substance.

Zelan ・ 10g of a dye-donating substance with the following structure.

As a surfactant, we weighed 0.5 g of sodium succinate-2-ethyl-hexyl ester sulfonate and 4 g of treble resin phosphate (TPO), added 20 dl of cyclohexanone, and heated and dissolved them at about 60°C to form a homogeneous solution. shall be.

After stirring and mixing this solution and 100 g of a 1O% solution of stone-treated gelatin, the mixture was heated with a homogenizer for 10 minutes.
Disperse at 00 rpm.

Thereafter, the same treatment as in Example 1 was carried out, and the density of the positive image was measured.

The results obtained are shown.

Maximum density: 1.48 Minimum density: 0.48 These results show that the photothermographic material of the present invention provides a high maximum density and a low minimum density.

From the above, the effects of the present invention are clear.

Example 3 A silver iodobromide emulsion was prepared in the same manner as the silver bromide emulsion of Example 1, except that 2.3 mol % of KI was present during the second precipitation.

A photosensitive material C was prepared in the same manner as in Example 1 except that this silver iodobromide emulsion was used, and after the same processing, the density of the positive image was measured.

The results obtained are shown.

Maximum density: 1.40 Minimum density: 0.43 From these results, it can be seen that the photothermographic material of the present invention provides a high maximum density and a low minimum density.

From the following, the effects of the present invention are clear.

Applicant Fuji Film Co., Ltd. Agent Patent Attorney Minoru Watanabe 1
Patent attorney Yo Ishii
- Procedural amendment (method) 1. Indication of the case Patent Application No. 228550 filed in 1982 2. Name of the invention Heat-developable photosensitive material 3. Person making the amendment Relationship to the case Patent applicant address 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Address Name (520) Fuji Photo Film Co., Ltd. 4, Agent
101 Phone: 864-4498 Address: 3-2-2-6 Iwamoto-cho, Chiyoda-ku, Tokyo Subject of amendment 7 Contents of amendment (1) rNeblets Handbook of page 3, lines 1 to 3 of the specification
Photograph7 andReprograph
hy 7th Ed, (Van No5tr
snd Reinhold Company (Neblatts Hand)
book ofPhotozraph2 and
Reprograpby) 7th edition (7th Ea,
) Van Nostrand Reinhold Company (
Van No5trand Re1nhold
Company) J.

(2) r E, J, WallJ on page 11, line 6
E Ku-Wall (E, J, profanity) Correct with J.

(3) T Asian Photographic on page 11, lines 9-10
PublishingGo, American Photographic Publishing Company
ricanPhotographic Publicis
hing Co,) J and correct.

(4) r on page 51, lines 9 to 11 and page 79, lines 4 to 3 from the bottom, by T. H. James, '↑
the theory of the photo
graphic process″4th+Ed, J
The Theory of the Photographic Process, by T.H. James
otographic process) 4th edition (4
th Ed,) J.

Claims (1)

[Claims] 1. A photothermographic material comprising, on a support, at least an internal latent image type silver halide emulsion, a nucleating agent, an organic silver salt oxidizing agent, a base and/or a base precursor that releases the base upon heating.