JPH06214367A - Heat developable color photosensitive material - Google Patents

Abstract

PURPOSE:To provide the heat developable color photosensitive material which has the high max. density, forms less stained bright images and has an excellent property to be stably produced with less image defects in spite of production over a long period of time. CONSTITUTION:This heat developable color photosensitive material contains the compd. expressed by formula. In the formula, R<1> denotes a methyl substd. or unsubstd. amino group or hydroxyl group; R<2> denotes a hydrogen atom or hydroxyl group; R<3> denotes a methyl substd. or unsubstd. amino group, methyl group, hydroxyl group or hydrogen atom; R<4> denotes a methyl substd. or unsubstd. aminoalkyl group, methyl group, ethyl group or hydroxyalkyl group; R<5> denotes a hydroxyl group or methylamino group; either of R<6> and R<7> is a hydroxyl group and the other is a hydrogen atom or methyl group.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photothermographic material, and more particularly to a photothermographic material having a high maximum density, an image with less stains, less image defects and excellent manufacturability. Is.

[0002]

2. Description of the Related Art Photothermographic materials are well known in the art, and the photothermographic materials and their processes are described, for example, in "Basics of Photographic Engineering", Non-silver photography (eds. 1982, Corona Publishing Co., pp. 242-255). Page, US Patent No. 450062
No. 6, etc.

In addition, for example, a method of forming a dye image by a coupling reaction between an oxidized product of a developing agent and a coupler is described in US Pat. Nos. 3,761,270 and 4,021,240. Further, a method of forming a positive color image by a photosensitive silver dye bleaching method is described in US Pat. No. 4,235,957.

Further, recently, a method has been proposed in which a diffusible dye is released or formed imagewise by heat development and the diffusible dye is transferred to a dye fixing element. In this method, a negative dye image or a positive dye image can be obtained by changing the type of dye-donor compound used or the type of silver halide used. More specifically, U.S. Pat. Nos. 4,500,626, 4,483,914 and 45,
03137, 4559290, JP-A-58-14.
9046, JP-A-60-133449, 59-2.
No. 18443, No. 61-238056, European Patent Publication 220746A2, Open Technical Report 87-6199, European Patent Publication 210660A2, and the like.

Many methods have been proposed for obtaining a positive color image by heat development. For example, in U.S. Pat. No. 4,559,290, a so-called DRR compound, which is an oxidized compound having no color image releasing ability, is allowed to coexist with a reducing agent or a precursor thereof, and the reducing agent is added according to the exposure amount of silver halide by heat development. A method has been proposed in which the diffusible dye is released by being oxidized and reduced by the reducing agent remaining without being oxidized. Further, in European Patent Publication No. 220746A and Kokai Giho No. 87-6199 (Vol. 12, No. 22), as a compound that releases a diffusible dye by a similar mechanism, an N—X bond (X is an oxygen atom, a nitrogen atom or sulfur) Photothermographic materials are described which use compounds which release diffusible dyes by the reductive cleavage of (representing atoms).

[0006]

In the photothermographic material as described above, a silver halide emulsion layer and various auxiliary layers (undercoat layer, intermediate layer, filter layer, antihalation layer, protective layer) are formed on a support. , A back layer, etc.) and a hydrophilic binder typified by gelatin is used for these coating layers. However, it is known that hydrophilic binders are decomposed or decomposed by the action of bacteria or mold. Especially, when these hydrophilic binders are decomposed or decomposed during the production of the photothermographic material, the viscosity of the coating solution or In addition to the decrease in the physical strength of the coated film, there is a problem in that coating failure that may be caused by the decomposition product of the hydrophilic binder may occur.

[0007] Therefore, in order to prevent the decay and decomposition action due to such bacteria and mold, a preservative or antifungal agent has conventionally been added at any stage of the process for producing a light-sensitive material. Examples of such antiseptics or antifungal agents include those disclosed in JP-A-54-27424 and JP-A-63-27.
Various compounds such as those described in No. 1247 are known, but unless a large amount is added to the hydrophilic binder,
There is a problem that the effect is small, and because of that, there is a problem such as precipitation, or it is harmful to the human body.

It is also known to use antibiotics such as neomycin, kanamycin, streptomycin, polymycin, and flamycin for this purpose, but they have a low antibacterial ability and must be added in large amounts, or they are photographically harmful. There was such a problem.

Further, particularly in the case of a photothermographic material, since the development processing is carried out at a high temperature, the silver halide is apt to be fogged during development,
It has been difficult to add a preservative or an antifungal agent that has been conventionally used in an amount sufficient to obtain an antiseptic or antifungal effect.

(Object of the Invention) The object of the present invention is to achieve both high maximum density and low stain, and to reduce image defects.
It is to obtain a photothermographic material having excellent manufacturing stability.

[0011]

The object of the present invention is to provide a photosensitive silver halide, a reducing agent, a hydrophilic binder on a support,
And a photothermographic material having a dye-providing compound, which comprises at least one layer containing a compound represented by the following general formula (I).

[0012]

[Chemical 2]

Where R¹Is methyl-substituted or unsubstituted
Amino group or hydroxyl group, R²Is a hydrogen atom or
Hydroxyl group, R³Is a methyl-substituted or unsubstituted
Mino group, methyl group, hydroxyl group or hydrogen atom, R
^FourIs a methyl-substituted or unsubstituted aminoalkyl group, methyl
Group, ethyl group, or hydroxyalkyl group, R ^FiveIs
Hydroxyl group or methylamino group, R⁶And R⁷Haso
One of them is a hydroxyl group and the other is a hydrogen atom or
Represents a methyl group.

Japanese Patent Application No. 3-287239 describes a silver halide light-sensitive material containing a compound represented by formula (I) above. The compound represented by the general formula (I) is
The present invention has been found out that it is specifically useful, that is, silver halide does not cause fog during heat development and has sufficient antiseptic and antifungal effects.

Specific examples of the compound of the present invention will be described below.

Specific examples of the hydroxyalkyl group of the compound of the present invention are hydroxymethyl group and hydroxyethyl group, and the aminoalkyl group is aminomethyl group and aminoethyl group.

Listed below are typical examples of the compounds of the present invention.

[0018]

[Table 1]

[0019]

[Table 2]

The compound of the present invention can be contained in at least one layer, preferably all layers, of the silver halide emulsion layer coated on the support and the auxiliary layer as exemplified above.

The compound of the present invention is preferably used by dissolving it in water and adding it to a coating solution containing a hydrophilic binder.

The amount of the compound of the present invention added is about 0.01-2.
Preferably ^{0mg / m 2, 0.1~5mg / m} 2 is more preferable. Further, the above-mentioned conventionally known antibacterial agents, antifungal agents, and preservatives may be used in combination within a range that does not cause a problem in photographic properties and safety.

In the heat-developable color light-sensitive material of the present invention, basically, a photosensitive silver halide, a reducing agent, a binder and a dye-donating compound (which may also serve as a reducing agent as described below) are formed on a support. In addition, an organic metal salt oxidizing agent and the like can be added as necessary. These components are often added to the same layer,
If it is in a state where it can react, it can be divided and added to another layer. For example, when a colored dye-donating compound is present in the lower layer of the silver halide emulsion, the reduction in sensitivity can be prevented.
The reducing agent is incorporated in the photothermographic material, and further, for example, by a method of diffusing from a dye fixing element described later,
You may use together the method supplied from the outside. By incorporating a reducing agent in the light-sensitive material, an effect of promoting color image formation can be obtained.

In order to obtain a wide range of colors in the chromaticity diagram by using the three primary colors of yellow, magenta and cyan, a combination of at least three silver halide emulsion layers sensitive to different spectral regions is used. . For example, there are a combination of three layers of a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer, a combination of a green-sensitive layer, a red-sensitive layer and an infrared-sensitive layer. Each of the light-sensitive layers can take various arrangement orders known in a conventional type color light-sensitive material. Further, each of these photosensitive layers may be divided into two or more layers if necessary.

The photothermographic material may be provided with various auxiliary layers such as an undercoat layer, an intermediate layer, a yellow filter layer, an antihalation layer and a back layer, in addition to the above-mentioned protective layer.

The silver halide emulsion (emulsion containing photosensitive silver halide) in the present invention may have various shapes. Examples of these are cubes, octahedra,
Examples thereof include regular grains having regular crystals such as tetradecahedrons, tabular grains, spherical grains, and grains having irregular crystal forms such as potato grains.

As the silver halide composition of the grains, any one of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, silver chloroiodide, and silver chloride is used. Good, but
Silver bromide or silver chlorobromide is preferred. Further, it may contain silver thiocyanate, silver cyanate and the like. The silver halide composition in the grain may be uniform, may have different halogen compositions inside and outside, or may have a layered structure (JP-A-57-154232, JP-A-58-154232).
-108533, 58-248469, 59-
48755, 59-52237, U.S. Pat.
505, 068, 4,433, 048, 4, 4
44,877, European Patent 100,984, and British Patent 1,027,146).

The silver halide emulsion may be monodisperse or polydisperse, and monodisperse emulsions may be mixed and used. The particle size is preferably 0.01 μm to 10 μm, particularly preferably 0.1 μm to 3 μm. Here, a monodisperse silver halide emulsion is defined as 95% or more of the total weight or the total number of silver halide grains contained therein is within ± 40% of the average grain size, more preferably within ± 30%. To be done.

Specifically, US Pat. No. 4,500,62
No. 6, Column 50, No. 4,628,021, Research
Disclosure magazine (hereinafter abbreviated as RD) 1702
9 (1978) and any of the silver halide emulsions described in JP-A No. 62-253159 and the like can be used.

The silver halide emulsion used in the present invention may be either a surface latent image type emulsion or an internal latent image type emulsion. The internal latent image type emulsion is used as a direct reversal emulsion in combination with a nucleating agent or an optical fogging.

In the present invention, two or more kinds of silver halides having different crystal habits, halogen compositions, grain sizes, grain size distributions and the like can be used in combination, and they can be used in different emulsion layers and / or the same emulsion layer. It is possible to use.

In particular, tabular silver halide grains have already been reported in US Pat. Nos. 4,434,226 and 4,4.
39,520, 4,414,310, 4,43
3,048, 4,414,306, 4,45
9,353, JP-A-59-99433, 62-2.
No. 09445 discloses the production method and use technique. Further, JP-A-63-220238 and JP-A-1-
No. 201649 discloses tabular silver halide grains in which dislocations are intentionally introduced.

The ratio of the average grain diameter to the average grain thickness in tabular grains (hereinafter referred to as grain diameter / thickness) is preferably 2 or more, and is preferably 3 to 12, and particularly preferably 5.
It is preferably -8. Here, the grain diameter / thickness can be obtained by averaging the grain diameters / thicknesses of all tabular grains, but a simple method is to use the ratio of the average diameter of all tabular grains to the average thickness of all average grains. You can also ask. The diameter of the tabular grains (corresponding to a circle) is 0.3 μm or more, preferably 0.3 to 10 μm, more preferably 0.5 to 5.0.
μm, and more preferably 0.5 to 2.0 μm. The particle thickness is less than 1.0 μm, preferably 0.05-0.
It is 5 μm, more preferably 0.08 to 0.3 μm.

In the present invention, the tabular grains account for 50% or more of the total grain projected area in the emulsion containing the tabular grains. It is preferably 70% or more, more preferably 90% or more. The grain diameter and grain thickness of tabular grains can be measured by electron micrographs of grains as described in US Pat. No. 4,434,226. Specific examples of the halogen composition of tabular grains include silver chloroiodide, silver iodobromide, silver chloride, silver chlorobromide, silver bromide, and silver chloroiodobromide. Alternatively, silver chlorobromide is preferable. It may also contain silver thiocyanate, silver cyanate and the like. Further, in the present invention, the tabular grains are preferably monodisperse. The structure and manufacturing method of monodisperse tabular grains are described in, for example, JP-A-63-151618.

In the tabular grains, silver halides having different compositions may be joined by epitaxial joining, or may be joined with compounds other than silver halide such as silver thiocyanate and oxides. These emulsion grains are described in U.S. Pat.
142,900, 4,459,353, British Patent 2,038,792, U.S. Patent 4,349,62.
No. 2, No. 4,395, 478, No. 4,433, 501
Issue 4,463,087, Issue 3,656,962
No. 3,852,067, JP-A-59-16254.
No. 0 and the like.

The silver halide grains used in the present invention are
Graphide, "Physics and Chemistry of Photography", published by Paul Montell (P. Glafkides, Chimie et P.
hysique Photographique, Pa
ul Montel, 1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (GF Duffi).
n, Photographic Emulsion C
chemistry, Focal Press, 196
6), "Production and Coating of Photographic Emulsions" by Zelikmann et al., Published by Focal Press (VL Zelikman et.
al, Making and Coating Pho
topographic Emulsion, Focal
Press, 1964) and the like. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and as a method of reacting a soluble silver salt and a soluble halogen salt, any of a one-sided mixing method, a simultaneous mixing method and a combination thereof may be used. . A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. As one form of the simultaneous mixing method, a method of keeping pAg in a liquid phase where silver halide is formed constant, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained. In addition, 2 formed separately
A mixture of two or more silver halide emulsions may be used.

The silver halide emulsion comprising the above regular grains can be obtained by controlling pAg and pH during grain formation. For more information, for example,
Science and Engineering (Photog
radical Science and Engine
ering), Vol. 6, 159-165 (196)
2); Journal of Photographic Science (Journal of Photographics)
c Science), Volume 12, pp. 242-251 (1
964), U.S. Pat. No. 3,655,394 and British Patent No. 1,413,748.

Regarding the monodisperse emulsion, JP-A-48-
No. 8600, No. 51-39027, No. 51-8309
No. 7, No. 53-137133, No. 54-48521
No. 54-99419, No. 58-37635, No. 58-49938, Japanese Patent Publication No. 47-11386, US Pat. No. 3,655,394 and British Patent No. 1,41.
3, 748 and the like.

During the production of emulsions containing tabular grains, a silver salt solution (eg AgN) added to accelerate grain growth.
A method of increasing the addition rate, the addition amount, and the addition concentration of the O ₃ aqueous solution) and the halide solution (for example, KBr aqueous solution) is preferably used. Regarding these methods, for example, British Patent No. 1,335,925 and US Pat. No. 3,67
2,900, 3,650,757, 4,24
No. 2,445, JP-A Nos. 55-142329 and 55-
The description of No. 158124 can be referred to.

To accelerate the ripening of silver halide grains,
Silver halide solvents are useful. For example, it is known to have excess halogen ions present in the reactor to accelerate aging. Therefore, introduction of a silver halide solution into the reactor can accelerate ripening. Other ripening agents can be used, and the total amount of these ripening agents can be added to the dispersion medium in the reactor before the addition of silver and halide salts, or 1 or 2 or more. It is also possible to add the halide salt, silver salt or peptizer of the above and to introduce them into the reactor. As another variant, the ripening agent can be introduced independently at the halide salt and silver salt addition stages.

As the ripening agents other than halogen ions, ammonia, amine compounds, thiocyanate salts,
For example, alkali metal thiocyanate salts, especially sodium and potassium thiocyanate salts, and ammonium thiocyanate salts can be used. The use of thiocyanate ripening agents is described in US Pat. No. 2,222,264.
Nos. 2,448,534 and 3,320,06
Instructions can be found in No. 9. US Pat. No. 3,271,1
57, 3,574,628 and 3,73
Conventional thioether ripening agents as described in 7,313 can also be used. In addition, JP-A-53-8
It is also possible to use thione compounds as disclosed in 2408 and 53-144319.

The properties of the silver halide grains can be controlled by allowing various compounds to be present in the silver halide precipitation forming process. Such compounds may be initially present in the reactor. In addition, one or more salts can be added together with the salt according to a conventional method. US Patent Nos. 2,448,060 and 2,628,167
Issue 3, Issue 3,737,313, Issue 3,772,031
Issue, and Research Disclosure, Vol. 134,
June 1975, 13452, copper, iridium, lead, bismuth, cadmium, zinc, (sulfur,
The characteristics of silver halide can be controlled by allowing compounds such as chalcogen compounds such as selenium and tellurium), compounds such as gold and compounds of Group VII noble metals to be present during the silver halide precipitation formation process. Japanese Patent Publication 58-1410
Issue, Moisar et al., Journal of Photographic Science, 25, 1977.
As described on pages 19 to 27, the silver halide emulsion can reduce-sensitize the inside of the grain during the precipitation formation process.

It is also possible to carry out chemical sensitization in the presence of a chemical sensitization aid. As the chemical sensitization aid used, compounds such as azaindene, azapyridazine, and azapyrimidine which are known to suppress fog and increase sensitivity in the process of chemical sensitization are used. Examples of chemical sensitization aids are
US Pat. Nos. 2,131,038 and 3,411,91
No. 4, 3,554, 757, JP-A-58-1265.
36, JP-A-62-253159 and Duffin, "Photographic Emulsion Chemistry", pages 138 to 143 (published by Focal Press, 1966).

The silver halide grains used in the present invention are
Usually, those which have been physically aged, chemically aged and spectrally sensitized are used. The additives used in such a process are Research Disclosure No. 17643 and N
o. 18716.

As the protective colloid used when preparing the emulsion of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, etc .; sugar derivatives such as sodium alginate and starch derivatives; Polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid,
Various synthetic hydrophilic polymer substances such as single or copolymers such as polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. can be used.

Examples of gelatin include lime-processed gelatin, acid-processed gelatin and Bull. Soc. Sci. Ph
oto. Japan, No. 16, P30 (1966)
You may use the enzyme-treated gelatin as described in,
Further, a hydrolyzate or an enzymatic hydrolyzate of gelatin can be used.

Various antifoggants or photographic stabilizers can be used in the present invention. Examples thereof include azoles and azaindenes described in RD17643 (1978), pages 24 to 25, JP-A-59-16844.
Nitrogen-containing carboxylic acids and phosphoric acids described in JP-A No. 2-11, mercapto compounds and metal salts thereof described in JP-A-59-111636, and acetylene compounds described in JP-A-62-87957 are used.

The silver halide used in the present invention may be spectrally sensitized with methine dyes and the like. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, polo polar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Specifically, U.S. Pat. No. 4,617,257 and JP-A-59-180550.
No. 60-140335, RD17029 (197).
8 years) sensitizing dyes described on pages 12 to 13 and the like.
These sensitizing dyes may be used alone or in combination thereof, and the combination of sensitizing dyes is often used particularly for the purpose of supersensitization.

Along with the sensitizing dye, a dye having no spectral sensitizing effect itself or a compound which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion (eg, US Pat. Nos. 3,615,641 and JP-A-63-23145).

The time for adding these sensitizing dyes to the emulsion may be during or after chemical ripening, or according to US Pat. Nos. 4,183,756 and 4,225,666. It may be before or after nucleation. In particular, the presence of a sensitizing dye at the time of chemical sensitization often gives a preferable effect. The addition amount is generally about 10 ⁻⁸ to 10 ⁻² mol per mol of silver halide.

Useful sensitizing dyes used in the present invention are, for example, US Pat. Nos. 3,522,052 and 3,619,1.
No. 97, No. 3,713, 828, No. 3, 615, 64
No. 3, No. 3,615, 632, No. 3,617, 293
No. 3,628,964, 3,703,377
Issue No. 3,666,480 Issue 3,667,960
Nos. 3,679,428 and 3,672,897
Issue No. 3,769,026 Issue No. 3,556,800
Issue No. 3,615,613 Issue No. 3,615,638
Nos. 3,615,635 and 3,705,809
No. 3,312,349, No. 3,677,765
Nos. 3,770,449, 3,770,440
Issue No. 3,769,025 Issue No. 3,745,014
Nos. 3,713,828 and 3,567,458
Nos. 3,625,698, 2,526,632
No. 2,503,776, JP-A-48-76525.
And Belgian Patent No. 691,807.

Photosensitive halogen used in the present invention
Silver halide coating amount is 1 mg / m in terms of silver. ³-10g / m³of
It is a range.

In the present invention, an organic metal salt may be used as an oxidizing agent together with the photosensitive silver halide. Among such organic metal salts, organic silver salts are particularly preferably used. Organic compounds that can be used to form the above organic silver salt oxidizing agents include US Pat.
There are benzotriazoles, fatty acids and other compounds described in No. 26, columns 52 to 53. In addition, JP-A-60-1
Silver salts of carboxylic acids having an alkynyl group such as silver phenylpropiolate described in 13235, and JP-A-61-161
The acetylene silver described in No. 249044 is also useful. Two or more kinds of organic silver salts may be used in combination.

The above organic silver salts are photosensitive silver halides.
0.01 to 10 moles per mole, preferably 0.1.
01 to 1 mol can be used in combination. The total coating amount of the photosensitive silver halide and the organic silver salt is preferably 50 mg to 10 g / m ² in terms of silver.

Various antifoggants or photographic stabilizers can be used in the present invention. Examples thereof include azoles and azaindenes described in RD17643 (1978), pages 24 to 25, JP-A-59-1684.
42-containing nitrogen-containing carboxylic acids and phosphoric acids,
Alternatively, the mercapto compound and its metal salt described in JP-A-59-111636, the acetylene compounds described in JP-A-62-87957, etc. may be used.

As the reducing agent used in the present invention, those known in the field of photothermographic materials can be used. Further, a dye-donor compound having a reducing property described later is also included (in this case, other reducing agents can be used together). Further, a reducing agent precursor which has no reducing property itself but exhibits reducing property by the action of a nucleophile or heat during the development process can also be used.

Examples of the reducing agent used in the present invention include:
U.S. Pat. No. 4,500,626, columns 49-50, 44
No. 83, col. 31, columns 31-43;
No. 4,590,152, JP-A No. 60-140335, pages (17) to (18), Nos. 57-40245, 56.
-138736, 59-178458, 59-
No. 53831, No. 59-182449, No. 59-18
No. 2450, No. 60-119555, No. 60-128
436 to 60-128439, 60-1
No. 98540, No. 60-181742, No. 61-25.
9253, 624244044, 62-131
From 253 to 62-131256, there are reducing agents and reducing agent precursors described on pages 78 to 96 of EP 220746A2. US Patent No. 303986
Combinations of various reducing agents such as those disclosed in No. 9 can also be used.

When a diffusion resistant reducing agent is used, if necessary, an electron transfer agent and / or an electron transfer agent may be added in order to promote electron transfer between the diffusion resistant reducing agent and the developable silver halide.
Alternatively, electron transfer agent precursors can be used in combination. The electron transfer agent or its precursor can be selected from the above-mentioned reducing agent or its precursor. It is desirable that the electron transfer agent or its precursor has a mobility higher than that of the diffusion resistant reducing agent (electron donor). Particularly useful electron transfer agents are 1-phenyl-3-pyrazolidones or aminophenols.

The diffusion-resistant reducing agent (electron donor) used in combination with the electron transfer agent may be any of those reducing agents which do not substantially move in the layer of the photosensitive element.
Hydroquinones, sulfonamide phenols, sulfonamide naphthols, JP-A-53-11 are preferred.
Examples thereof include compounds described as electron donors in No. 0827, and dye-donating compounds having diffusion resistance and reducing properties described below.

In the present invention, the reducing agent is added in an amount of 0.001 to 20 mol, and particularly preferably 0.1 to 20 mol, based on 1 mol of silver.
It is from 01 to 10 mol.

In the present invention, when a silver ion is reduced to silver under a high temperature condition, a compound that produces or releases a mobile dye in response to this reaction or in the opposite response, that is, a dye-donor. It may also contain a sex compound. Examples of the dye-donating compound that can be used in the present invention include a compound (coupler) that forms a dye by an oxidative coupling reaction. The coupler may be a 4-equivalent coupler or a 2-equivalent coupler. A 2-equivalent coupler having a diffusion resistant group as a leaving group and forming a diffusible dye by an oxidative coupling reaction is also preferable. The diffusion resistant group may form a polymer chain.
For specific examples of color developers and couplers, see TH James “Th
e Theory of the Photographic Process "4th Edition 291
To 334 and 354 to 361, JP-A-58-1
No. 23533, No. 58-149046, No. 58-14
No. 9047, No. 59-111148, No. 59-124
No. 399, No. 59-174835, No. 59-2315.
No. 39, No. 59-231540, No. 60-2950.
No. 60, No. 60-2951, No. 60-14242, No. 6
0-23474, 60-66249 and the like.

As another example of the dye-donating compound,
Examples thereof include compounds having a function of releasing or diffusing a diffusible dye in an image form. This type of compound can be represented by the following general formula [LI]. (Dye-Y) n-Z [LI] Dye represents a dye group, a temporarily shortened dye group or a dye precursor group, Y represents a simple bond or linking group, and Z represents an image latent image. Corresponding to or opposite to the photosensitive silver salt having a difference in the diffusivity of the compound represented by (Dye-Y) n-Z, or releasing Dye and releasing Dye and (Dye- Y) represents a group having a property of causing a difference in diffusibility from n-Z, n represents 1 or 2, and when n is 2, two Dye-Y are the same or different. Good.

Specific examples of the dye-donating compound represented by the general formula [LI] include the following compounds (1) to (4). In addition, the following items (1) to (4) are for forming a diffusible dye image (positive dye image) in the opposite manner to the development of silver halide, and the terms and are the diffusible dye image (corresponding to the development of silver halide ( To form a negative dye image).

US Pat. Nos. 3,134,764 and 336.
2819, 3597200, 3544545.
No. 3,482,972 and the like, a dye developer in which a hydroquinone-based developer and a dye component are linked. This dye developing agent is diffusible in an alkaline environment, but becomes non-diffusible when it reacts with silver halide.

As described in US Pat. No. 4,053,137, a non-diffusible compound which releases a diffusible dye in an alkaline environment but loses its ability when reacted with silver halide can be used. Examples thereof include compounds that release a diffusible dye by an intramolecular nucleophilic substitution reaction described in US Pat. No. 3,980,479, and US Pat. No. 4,199.
Compounds that release a diffusible dye by the intramolecular rewinding reaction of the isoxazolone ring described in JP-A No. 354 and the like.

US Pat. No. 4,559,290, European Patent No. 220746A2, US Pat. No. 4,783,396,
As described in Published Technical Report 87-6199, a non-diffusible compound which releases a diffusible dye by reacting with a reducing agent left unoxidized by development can also be used.

An example of this is US Pat. No. 4,13,938.
No. 9, 4139379, JP-A-59-185333.
Nos. 57-84453 and the like, which release a diffusible dye by a nucleophilic substitution reaction in the molecule after reduction, U.S. Pat.
No. 101649, No. 61-88257, RD240
25 (1984) and the like, which release a diffusible dye by intramolecular electron transfer reaction after reduction, West German Patent No. 3008588A, JP-A-56-14.
2530, U.S. Pat. Nos. 4,343,893 and 4619.
Compounds that release a diffusible dye by cleavage of a single bond after reduction, as described in U.S. Pat.
Examples thereof include nitro compounds described in U.S. Pat. No. 223, which release a diffusible dye after electron acceptance, compounds described in U.S. Pat. No. 4,609,610 which release a diffusible dye after electron acceptance, and the like.

Further, as more preferable ones, European Patent No. 220746A2, Kokai Giho No. 87-6199, US Pat. No. 4,783,396, and Japanese Patent Laid-Open No. 63-201653.
No. 63, 2016-654, etc.
A compound having a —X bond (X represents an oxygen, sulfur or nitrogen atom) and an electron-withdrawing group, SO ₂ —X (X has the same meaning as above) in one molecule described in JP-A-1-26842. Compound having electron-withdrawing group, JP-A-63-271344
Compounds having a PO-X bond (X has the same meaning as above) and an electron-withdrawing group in one molecule described in JP-A-63-27.
C-X 'bond (X' in marked within one molecule in 1341 issue X synonymous or or -SO ₂ - and represented) include compounds having an electron-withdrawing group.

Of these, a compound having an N—X bond and an electron-withdrawing group in one molecule is particularly preferable. Specific examples thereof include the compound (1) described in EP 220746A2
(3), (7) to (10), (12), (13), (15), (23) to (26), (3
1), (32), (35), (36), (40), (41), (44), (53) to (5
9), (64), (70), compound (1) of Open Technical Report 87-6199
1) to (23).

A compound (DDR coupler) which is a coupler having a diffusible dye as a leaving group and releases the diffusible dye by a reaction with an oxidant of a reducing agent. Specifically, British Patent No. 1330524, Japanese Patent Publication No. 48-39165, U.S. Patent Nos. 3443940, 4474867, 448.
3914 and the like.

A compound (DRR compound) which is reducible to a silver halide or an organic silver salt and releases a diffusible dye when its partner is reduced. Since this compound does not need to use another reducing agent, it is preferable because there is no problem of image contamination due to oxidative decomposition products of the reducing agent. Typical examples thereof are U.S. Pat. Nos. 3,928,312, 4,053,312 and 405.
No. 5428, No. 4336322, JP-A-59-658.
No. 39, No. 59-69839, No. 53-3819,
51-104343, RD17465, U.S. Pat. Nos. 3,725,062, 3,728,113 and 3,443.
939, JP-A-58-116537, 57-17.
9840, U.S. Pat. No. 4,500,626 and the like. Specific examples of the DRR compound include the compounds described in the above-mentioned U.S. Pat. No. 4,500,626, columns 22 to 44, among which the compounds (1) to (3) described in the U.S. patents, (10) ~ (13), (16) ~ (19), (28)
To (30), (33) to (35), (38) to (40), and (42) to (64) are preferable. Further, the compounds described in US Pat. No. 4,639,408, columns 37 to 39 are also useful.

In addition, as a dye-donor compound other than the above-mentioned coupler and the general formula [LI], a dye silver compound in which an organic silver salt and a dye are bonded (Research Disclosure, May 1978, pp. 54-58). , Etc., azo dyes used in the heat developable silver dye bleaching method (US Pat.
957, Research Disclosure, 1976.
Year 4 issue, pages 30 to 32, etc.), leuco dyes (US Pat. Nos. 3,985,565 and 4,022,617, etc.) can also be used.

Hydrophobic additives such as dye-providing compounds and antidiffusive reducing agents can be incorporated into the layers of the light-sensitive material by known methods such as the method described in US Pat. No. 2,322,027. In this case, JP-A-59-83154,
59-178451, 59-178452, 59-178453, 59-178454, 5
9-178455, 59-178457 and the like, a high boiling point organic solvent, if necessary, a boiling point of 50 ° C.
It can be used in combination with an organic solvent having a low boiling point of up to 160 ° C.

The amount of the high boiling point organic solvent is 10 g or less, preferably 5 g or less, relative to 1 g of the dye-donor compound used. Further, 1 cc or less, more preferably 0.5 cc or less, and especially 0.3 cc or less is suitable for 1 g of the binder.

JP-B-51-39853 and JP-A-51-
The dispersion method using a polymer described in 59943 can also be used.

In the case of a compound which is substantially insoluble in water, fine particles can be dispersed and contained in a binder in addition to the above method.

When dispersing the hydrophobic compound in the hydrophilic colloid as the binder, various surfactants can be used. For example, the surfactants listed on pages (37) to (38) of JP-A-59-157636 can be used.

In the present invention, a compound capable of activating development and stabilizing an image at the same time can be used in the light-sensitive material. Specific compounds preferably used are described in US Pat. No. 4,500,626, columns 51 to 52.

In a system for forming an image by diffusion transfer of a dye, a dye fixing element is used together with a light-sensitive material. The dye-fixing element may be applied separately on a support different from the photosensitive element, or may be applied on the same support as the photosensitive element. Regarding the relationship between the light-sensitive element and the dye fixing element, the relationship with the support, and the relationship with the white reflective layer, the relationship described in column 57 of US Pat. No. 4,500,626 can be applied to the present application.

In order to include the form in which the light-sensitive element and the dye-fixing element are coated on the same support as described above, the light-sensitive material of the present invention will be referred to as the light-sensitive element hereinafter for the sake of convenience. explain. The dye fixing element is also called a dye fixing material.

The dye fixing element preferably used in the present invention has at least one layer containing a mordant and a binder. As the mordant, those known in the photographic field can be used, and specific examples thereof include US Pat. No. 4,500,626, columns 58 to 59 and JP-A No. 61-88256 (32).
The mordant described on page (41), JP-A-62-244043.
No. 62-244036 and the like. Further, a dye-receptive polymer compound as described in US Pat. No. 4,463,079 may be used. If necessary, a protective layer, a release layer,
An auxiliary layer such as an anti-curl layer can be provided. In particular, it is useful to provide a protective layer.

A hydrophilic binder is preferably used as the binder of the constituent layers of the light-sensitive element and the dye fixing element. As an example thereof, pages (26) to (2) of JP-A No. 62-253159.
8) The thing described in page is mentioned. Specifically, a transparent or translucent hydrophilic binder is preferable, and for example, gelatin, proteins such as gelatin derivatives or cellulose derivatives, starch, gum arabic, dextran, natural compounds such as polysaccharides such as pullulan, and polyvinyl alcohol, Examples thereof include polyvinylpyrrolidone, acrylamide polymer, and other synthetic polymer compounds. Furthermore, superabsorbent polymers described in JP-A-62-245260, i.e. -COOM or -SO ₃ M (M is a hydrogen atom or an alkali metal) homopolymer or a vinyl monomer together or with other vinyl monomers with A copolymer with a vinyl monomer (for example, sodium methacrylate, ammonium methacrylate, Sumika Gel L-5H manufactured by Sumitomo Chemical Co., Ltd.) is also used. These binders can be used in combination of two or more.

When a system in which a small amount of water is supplied for thermal development is adopted, it is possible to quickly absorb water by using the above superabsorbent polymer. Also, the use of superabsorbent polymers in the dye-fixing layer or its protective layer can prevent the dye from retransferring from the dye-fixing element to another after transfer.

In the present invention, the coating amount of the binder is 1
It is preferably 20 g or less per m ² , particularly 10 g or less, more preferably 7 g or less.

As the hardener used for the constituent layers of the light-sensitive element and the dye-fixing element, US Pat. No. 4,678,739, No. 4,
Column 1, JP-A-59-116655 and JP-A-64-2452.
No. 61, No. 61-18942, etc. are mentioned. More specifically, aldehyde type hardeners (formaldehyde etc.), aziridine type hardeners, epoxy type hardeners, vinyl sulfone type hardeners (N, N'-ethylene-
Bis (vinylsulfonylacetamide) ethane etc.), N
-Methylol type hardeners (such as dimethylol urea) and polymer hardeners (compounds described in JP-A-62-234157).

In the present invention, an image formation accelerator can be used in the light-sensitive element and / or the dye fixing element.
The image formation accelerator includes a redox reaction between a silver salt oxidizing agent and a reducing agent, a reaction such as generation of a dye from a dye-donor substance, decomposition of the dye or release of a diffusible dye, and a light-sensitive material layer. Has a function of accelerating the transfer of the dye from the dye to the dye fixing layer, and from the physicochemical function, a base or a base precursor, a nucleophilic compound, a high boiling organic solvent (oil), a thermal solvent, a surfactant, silver Alternatively, they are classified into compounds that interact with silver ions. However, these substance groups generally have a composite function, and usually have some of the above-mentioned accelerating effects together. These details are described in US Pat. No. 4,678,739, columns 38 to 40.

Examples of the base precursor include salts of organic acids and bases that are decarboxylated by heat, compounds that release amines by intramolecular nucleophilic substitution reaction, Rossen rearrangement or Beckmann rearrangement. A specific example is US Pat. No. 45114.
93, JP-A-62-65038 and the like.

In a system in which heat development and dye transfer are carried out simultaneously in the presence of a small amount of water, it is preferable to add a base and / or a base precursor to the dye-fixing element in order to improve the storage stability of the light-sensitive element.

In addition to the above, a combination of a sparingly soluble metal compound described in European Patent Publication No. 210660 and a compound (referred to as a complex forming compound) capable of undergoing a complex formation reaction with a metal ion constituting the sparingly soluble metal compound, JP-A-61-2
The compounds that generate a base by electrolysis as described in No. 32451 can also be used as the base precursor. The former method is particularly effective. The sparingly soluble metal compound and the complex-forming compound are advantageously added separately to the light-sensitive element and the dye-fixing element.

In the light-sensitive element and / or the dye-fixing element of the present invention, various development terminators can be used for the purpose of always obtaining a constant image with respect to variations in processing temperature and processing time during development. The term "development terminating agent" as used herein refers to a compound that immediately neutralizes or reacts with a base to reduce the concentration of the base in the film to stop the development after proper development, or inhibits development by interacting with silver and a silver salt. Compound. Specific examples thereof include an acid precursor that releases an acid when heated, an electrophilic compound that causes a substitution reaction with a coexisting base when heated, or a nitrogen-containing heterocyclic compound, a mercapto compound and a precursor thereof. For more details, see JP-A-62-25
No. 3159, pages (31) to (32).

The constituent layers (including the back layer) of the light-sensitive element or the dye-fixing element are used for the purpose of improving physical properties of the film such as dimensional stability, curl prevention, adhesion prevention, film cracking prevention and pressure increase / decrease prevention. Various polymer latices can be included. Specifically, any of the polymer latexes described in JP-A Nos. 62-245258, 62-136648, 62-110066 and the like can be used. In particular,
When a polymer latex having a low glass transition point (40 ° C. or less) is used in the mordant layer, cracking of the mordant layer can be prevented, and when a polymer latex having a high glass transition point is used in the back layer, a curl preventing effect can be obtained. .

In the constituent layers of the light-sensitive element and the dye-fixing element, a plasticizer, a slipping agent, or a high boiling point organic solvent can be used as an agent for improving the releasability of the light-sensitive element and the dye-fixing element. A specific example is (2) in JP-A-62-253159.
5), No. 62-245253 and the like.

Further, various silicone oils (all silicone oils from dimethylsilicone oil to modified silicone oils obtained by introducing various organic groups into dimethylsiloxane) can be used for the above purpose. For example, various modified silicone oils described in “Modified Silicone Oil” technical data P6-8B issued by Shin-Etsu Silicone Co., Ltd., particularly carboxy-modified silicone (trade name X-22-3710) are effective. In addition, JP-A-6
The silicone oils described in JP-A No. 2-219553 and JP-A No. 63-46449 are also effective.

An anti-fading agent may be used in the dye fixing element. As the anti-fading agent, there are, for example, an antioxidant, an ultraviolet absorber, or a kind of metal complex.

Examples of the antioxidants include chroman compounds, coumarane compounds, phenol compounds (eg hindered phenols), hydroquinone derivatives, hindered amine derivatives and spiroindane compounds. The compounds described in JP-A-61-159644 are also effective.

As the ultraviolet absorber, benzotriazole compounds (US Pat. No. 3,533,794, etc.), 4-
Thiazolidone compounds (US Pat. No. 3,352,681, etc.), benzophenone compounds (JP-A-46-2784)
Etc.) and others, JP-A Nos. 54-48535 and 62-
There are compounds described in Nos. 136641 and 61-8256. Further, the ultraviolet absorbing polymer described in JP-A-62-260152 is also effective.

Examples of the metal complex include US Pat.
55, 42425018, columns 3 to 36, 4,25
4,195, columns 3 to 8, JP-A-62-174741.
No. 61-88256, pages (27) to (29), JP-A-1-75568, JP-A-62-31096, JP-A-1.
There are compounds described in, for example, -74272.

Examples of useful anti-fading agents are disclosed in JP-A-62-21.
5272 (125)-(137).

The anti-fading agent for preventing the fading of the dye transferred to the dye-fixing element may be contained in the dye-fixing element in advance, or may be supplied to the dye-fixing element from the outside such as a light-sensitive element. May be.

The above-mentioned antioxidant, ultraviolet absorber and metal complex may be used in combination.

A fluorescent whitening agent may be used in the light-sensitive element and the dye-fixing element. In particular, it is preferable to incorporate a fluorescent brightening agent in the dye fixing element or supply it from the outside such as a light sensitive element. As an example, K. Veenkataraman edited by "The Chem
istry of Synthetic Dyes ", Volume V, Chapter 8, JP-A-61
The compound described in -143752 etc. can be mentioned. More specifically, a stilbene compound,
Examples include coumarin-based compounds, biphenyl-based compounds, benzoxazolyl-based compounds, naphthalimide-based compounds, pyrazoline-based compounds, and carbostyryl-based carboxy compounds. The fluorescent whitening agent can be used in combination with an anti-fading agent.

In the constituent layers of the light-sensitive element and the dye-fixing element, various surfactants can be used for the purpose of coating aid, improvement of releasability, improvement of sliding property, prevention of electrification, acceleration of development and the like. Specific examples of the surfactant are disclosed in JP-A-62-173463.
No. 62-183457 and the like.

The constituent layers of the light-sensitive element and the dye-fixing element may contain an organic fluoro compound for the purpose of improving slipperiness, preventing electrification, improving releasability and the like. Typical examples of organic fluoro compounds include Japanese Patent Publication No. 57-9053, columns 8 to 17,
Fluorine-based surfactants described in JP-A-61-29444 and JP-A-62-135826, or oily fluorine-based compounds such as fluorine oil or solid fluorine-based compound resins such as tetrafluoroethylene resin And the hydrophobic fluorine compound.

A matting agent can be used in the light-sensitive element and the dye-fixing element. Matting agents such as silicon dioxide, polyolefins, polymethacrylates, etc.
Japanese Patent Application No. 62-110064, such as benzoguanamine resin beads, polycarbonate resin beads, AS resin beads and the like, in addition to the compounds described on page 1-88256 (29).
No. 62-110065.

In addition, the constituent layers of the light-sensitive element and the dye-fixing element may contain a thermal solvent, a defoaming agent, an antibacterial / antifungal agent, colloidal silica and the like. Specific examples of these additives are described in JP-A-61-88256, pages (26) to (32).

As the support for the light-sensitive element and the dye-fixing element of the present invention, those which can withstand the processing temperature are used. Generally, paper and synthetic polymer (film) are used. Specifically, polyethylene terephthalate (P
ET), polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, celluloses (for example, triacetyl cellulose) or those films containing a pigment such as titanium oxide, and synthetic film made by polypropylene or the like. Blended paper made from synthetic resin pulp such as polyethylene and natural pulp, Yankee paper, baryta paper, coated paper (particularly Cascote paper), metal, cloth, glass and the like are used.

These can be used alone or
It can also be used as a support having one or both sides laminated with a synthetic polymer such as polyethylene. In addition to these, the supports described in JP-A-62-253159, pages (29) to (31) can be used. A hydrophilic binder, a semiconductive metal oxide such as alumina sol or tin oxide, carbon black and other antistatic agents may be coated on the surface of these supports.

As a method for exposing and recording an image on a photosensitive element, for example, a method of directly photographing a landscape or a person by using a camera, a method of exposing through a reversal film or a negative film by using a printer or an enlarger, A method of scanning and exposing an original image through a slit or the like using an exposure device of a copying machine, a method of exposing image information by emitting light from a light emitting diode or various lasers through an electric signal, a CRT, a liquid crystal display of image information, There is a method of outputting to an image display device such as an electroluminescence display and a plasma display, and exposing directly or through an optical system.

As a light source for recording an image on the photosensitive element,
As described above, the natural light, tungsten lamp, light emitting diode, laser light source, CRT light source, etc.
The light source described in 500626, column 56 can be used.

Further, the image information is a video camera,
An image signal obtained from an electronic still camera or the like, a television signal represented by Nippon Television Signal Standard (NTSC),
An image signal obtained by dividing an original image into a large number of pixels such as a scanner, or an image signal created by using a computer represented by CG and CAD can be used.

In the present invention, water is used to promote the migration of the dye released during the development process (this water is referred to as dampening water in the present invention). That is, JP-A-59-21
As described in detail in No. 8443, No. 61-238056 and the like, development and transfer are carried out simultaneously or successively by heating in the presence of a small amount of solvent (particularly water). In this method,
The heat development temperature is preferably 50 ° C. or higher and 100 ° C. or lower. In this case, the amount of water used is equal to or less than the weight of water corresponding to the maximum swelling volume of the entire coated film (especially, less than or equal to the amount of water corresponding to the maximum swelling volume of the entire coated film minus the weight of the entire coated film). A small amount is enough.

As a heating method in the developing and / or transferring step, a heated block or plate is contacted, or a hot plate, a hot presser, a heat roller, a halogen lamp heater, an infrared or far infrared lamp heater or the like is contacted. And passing through a high temperature atmosphere. Further, a resistance heating element layer may be provided on the photosensitive element or the dye fixing element, and the resistance heating element layer may be energized for heating. As the heating element layer, those described in JP-A-61-145544 can be used.

Superimposing the light-sensitive element and the dye-fixing element,
The pressure condition and the method for applying the pressure when closely contacting each other are disclosed in Japanese Patent Laid-Open Publication No.
The method described in page 1-147244 (27) can be applied.

Any of a variety of heat developing apparatus can be used in processing the photographic elements of this invention. For example, JP-A-59-7
No. 5247, No. 59-177547, No. 59-181.
No. 353, No. 60-18951, No. 62-259.
The device described in No. 44 etc. is preferably used.

[0115]

The present invention will be described with reference to the following examples.
The present invention is not limited to these.

Example 1

A method for preparing a dispersion of zinc hydroxide will be described. Zinc hydroxide with an average particle size of 0.2 μm 12.5
g, 1 g of carboxymethyl cellulose as a dispersant, and 0.1 g of sodium polyacrylate as a 4% gelatin aqueous solution 10
In addition to 0 ml, it was ground in a mill for 30 minutes using glass beads having an average particle size of 0.75 mm. The glass beads were separated to obtain a zinc hydroxide dispersion.

Next, a method for preparing a dispersion of the electron transfer agent will be described. 10 g of electron transfer agent (1), 0.5 g of polyethylene glycol nonylphenyl ether as a dispersant, and 0.5 g of anionic surfactant (1) were added to a 5% gelatin aqueous solution, and glass beads having an average particle size of 0.75 mm were milled. Was used for 60 minutes. The glass beads were separated to obtain a dispersion of the electron transfer agent having an average particle size of 0.35 μm.

[0119]

[Chemical 3]

Next, a method for preparing a dye trapping agent dispersion will be described. Polymer latex (A) (13% solid content)
While stirring a mixed solution of 108 ml, 20 g of the surfactant (1) and 1232 ml of water, 600 ml of a 5% aqueous solution of the anionic surfactant (1) was added over 10 minutes. Using the ultrafiltration module, the dispersion thus prepared is 500 ml.
It was concentrated and desalted. Next, 1500 ml of water is added, and the same operation is repeated once more to repeat the dye trapping agent dispersion 500.
g was obtained.

[0121]

[Chemical 4]

[0122]

[Chemical 5]

Next, a method for preparing a gelatin dispersion of a hydrophobic additive will be described. Cyan, magenta, yellow and electron donor gelatin dispersions were prepared according to the formulations in Table 3, respectively. That is, each oil phase component was dissolved by heating at about 60 ° C. to form a uniform solution, and this solution and an aqueous phase component heated at about 60 ° C. were added, and the mixture was stirred and mixed, followed by a homogenizer for 13 minutes,
Dispersed at 12000 rpm. Water was added to this and stirred to obtain a uniform dispersion.

[0124]

[Table 3]

[0125]

[Chemical 6]

[0126]

[Chemical 7]

[0127]

[Chemical 8]

[0128]

[Chemical 9]

[0129]

[Chemical 10]

[0130]

[Chemical 11]

[0131]

[Chemical 12]

[0132]

[Chemical 13]

[0133]

[Chemical 14]

[0134]

[Chemical 15]

Next, a method for preparing a photosensitive silver halide emulsion will be described.

Light-Sensitive Silver Halide Emulsion (1) [For Red-Sensitive Emulsion Layer] Well-stirred aqueous gelatin solution (20 g of gelatin in 480 ml of water, 0.5 g of potassium bromide, 3 parts of sodium chloride).
g and 30 mg of the chemical (A) were added and kept at 45 ° C.), the solutions (I) and (II) in Table 2 were simultaneously added at an equal flow rate for 20 minutes. After 5 minutes, solution (III) and solution (IV) in Table 2 were simultaneously added at the same flow rate for 25 minutes. In addition, 10 minutes after the start of addition of the liquids (III) and (IV), an aqueous solution of a gelatin dispersion of the dye (containing 105 g of water, 1 g of gelatin, 70 mg of the dye (a), 139 mg of the dye (b), and 5 mg of the dye (c)) was added. (Incubated at 45 ° C.) was added over 20 minutes.

After washing with water and desalting by a conventional method, 22 g of lime-treated ossein gelatin was added to adjust pH to 6.2 and pAg to 7.7, and sodium thiosulfate and 4-hydroxy- were added.
6-Methyl-1,3,3a, 7-tetrazaindene and chloroauric acid were added for optimum chemical sensitization at 60 ° C., and then an antifoggant (2) was added, followed by cooling. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.30 μm was obtained.

[0138]

[Chemical 16]

[0139]

[Table 4]

[0140]

[Chemical 17]

Photosensitive Silver Halide Emulsion (2) [For Red Sensitive Emulsion Layer] Well stirred gelatin aqueous solution (gelatin 20 g, potassium bromide 0.5 g, sodium chloride 6 in 783 ml of water).
g and 30 mg of the chemical (A) were added and kept at 65 ° C.), the solutions (I) and (II) in Table 3 were simultaneously added at an equal flow rate for 30 minutes. After 5 minutes, solution (III) and solution (IV) in Table 3 were added simultaneously at the same flow rate for 15 minutes. Two minutes after the addition of the solutions (III) and (IV), an aqueous solution of a gelatin dispersion of a dye (0.9 g of gelatin in 76 ml of water, 76 mg of the dye (a),
The dye (b) (150 mg) and the dye (c) (5 mg) which had been kept at 50 ° C.) were added over 18 minutes.

After washing with water and desalting by a conventional method, 22 g of lime-treated ossein gelatin was added to adjust the pH to 6.2 and pAg to 7.8, and sodium thiosulfate and 4-hydroxy- were added.
6-Methyl-1,3,3a, 7-tetrazaindene and chloroauric acid were added and optimal chemistry was performed at 60 ° C, and then an antifoggant (1) was added and then cooled. Thus, monodisperse cubic silver chlorobromide emulsion 6 having an average grain size of 0.50 μm
35 g were obtained.

[0143]

[Chemical 18]

[0144]

[Table 5]

Photosensitive Silver Halide Emulsion (3) [For Green Sensitive Emulsion Layer] Well-stirred aqueous gelatin solution (20 g of gelatin in 690 ml of water, 0.5 g of potassium bromide, 4 parts of sodium chloride).
g and 15 mg of the chemical (A) were added and kept at 48 ° C.), the solutions (I) and (II) in Table 4 were simultaneously added at an equal flow rate for 8 minutes. After 10 minutes, solution (III) and solution (IV) in Table 4 were simultaneously added at the same flow rate for 32 minutes. In addition, 1 minute after the addition of the solutions (III) and (IV), an aqueous solution of a gelatin dispersion of the dye (2.5 g of gelatin and 250 mg of the dye (d) in 100 ml of water and kept at 45 ° C.) was put together. Was added.

After washing with water and desalting by a conventional method, 20 g of lime-treated ossein gelatin was added to adjust the pH to 6.0 and pAg to 7.6, and sodium thiosulfate and 4-hydroxy- were added.
6-Methyl-1,3,3a, 7-tetrazaindene and chloroauric acid were added for optimum chemical sensitization at 68 ° C., antifoggant (1) was added, and then the mixture was cooled. Thus, a monodisperse cubic silver chlorobromide emulsion 63 having an average grain size of 0.27 μm was obtained.
5 g was obtained.

[0147]

[Table 6]

[0148]

[Chemical 19]

Photosensitive Silver Halide Emulsion (4) [For Green Sensitive Emulsion Layer] Well-stirred aqueous gelatin solution (20 ml of gelatin, 700 g of water, 0.3 g of potassium bromide, 6 ml of sodium chloride)
solution (I) and solution (II) shown in Table 5 were simultaneously added to the above solution at a constant flow rate for 20 minutes. After 10 minutes, solution (III) and solution (IV) in Table 5 were further added simultaneously at an equal flow rate for 20 minutes. Also (III), (IV)
One minute after the end of the addition of the solution, an aqueous solution of a gelatin dispersion of a dye (1.8 g of gelatin in 95 ml of water, 180 mg of dye (d))
Which was kept at 45 ° C.) was added all at once.

After washing with water and desalting by a conventional method, 20 g of lime-treated ossein gelatin was added to adjust the pH to 6.0 and pAg to 7.6, and sodium thiosulfate and 4-hydroxy- were added.
6-Methyl-1,3,3a, 7-tetrazaindene and chloroauric acid were added for optimum chemical sensitization at 68 ° C, and then an antifoggant (1) was added, followed by cooling. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.45 μm was obtained.

[0151]

[Table 7]

Light-Sensitive Silver Halide Emulsion (5) [For Blue-Sensitive Emulsion Layer] Well-stirred gelatin aqueous solution (gelatin 20 g, potassium bromide 0.5 g, sodium chloride 5 in 690 ml of water).
solution (I) and solution (II) shown in Table 6 were simultaneously added at a constant flow rate for 8 minutes. After 10 minutes, solution (III) and solution (IV) in Table 6 were added simultaneously at the same flow rate for 32 minutes. One minute after the addition of solutions (III) and (IV) was completed, 220 mg of dye (e) and 110 mg of dye (f) were added to an aqueous solution of dye (in 95 ml of water and 5 ml of methanol).
Which was kept at 45 ° C.) was added all at once.

After washing with water and desalting by a conventional method, 22 g of lime-treated ossein gelatin was added to adjust pH to 6.0 and pAg to 7.8, and sodium thiosulfate and 4-hydroxy- were added.
6-Methyl-1,3,3a, 7-tetrazaindene was added for optimum chemical sensitization at 68 ° C, and then an antifoggant (1) was added, followed by cooling. Thus, a monodisperse cubic silver chlorobromide emulsion 635 having an average grain size of 0.30 μm
g was obtained.

[0154]

[Table 8]

[0155]

[Chemical 20]

Photosensitive Silver Halide Emulsion (6) [For Blue Sensitive Emulsion Layer] Well-stirred aqueous gelatin solution (20 g of gelatin, 0.3 g of potassium bromide, 9 g of sodium chloride in 695 ml of water).
g and 15 mg of the chemical (A) were added and kept at 63 ° C.), the solutions (I) and (II) in Table 7 were simultaneously added at an equal flow rate for 10 minutes. After 10 minutes, solution (III) and solution (IV) shown in Table 7 were added simultaneously at the same flow rate for 30 minutes. Also (III), (IV)
One minute after the end of the addition of the solution, an aqueous solution of the dye (in 66 ml of water and 4 ml of methanol, 155 mg of the dye (e) and 78 mg of the dye (f)) was added.
Which was kept at 60 ° C.) was added all at once.

After washing with water and desalting by a conventional method, 22 g of lime-treated ossein gelatin was added to adjust pH to 6.0 and pAg to 7.8, and sodium thiosulfate and 4-hydroxy- were added.
6-Methyl-1,3,3a, 7-tetrazaindene and chloroauric acid were added for optimum chemical sensitization at 68 ° C, and then an antifoggant (1) was added, followed by cooling. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.55 μm was obtained.

[0158]

[Table 9]

A coating solution was prepared as follows using the above dispersion and emulsion.

First Layer (Red Sensitive Emulsion Layer) 648.5 g of the photosensitive silver halide emulsion (1), 351.5 g of the photosensitive silver halide emulsion (2), and 1050 g of a 16% aqueous solution of lime-processed gelatin, 40 g each. Melted at ° C and mixed. Further, 4563 g of a gelatin dispersion of a cyan dye-providing compound was dissolved at 45 ° C and added. Then, a 5% aqueous solution of the water-soluble polymer (1) was 83.6 m
l, the weight ratio of the compounds 10, 11 and 12 of the present invention 1: 1:
5 ml of a 5% aqueous solution of the mixture of 1 was added to prepare a coating solution for the first layer. Viscosity at 40 ° C is 85 centipoise, pH
Was 6.3.

[0161]

[Chemical 21]

Second layer and sixth layer (intermediate layer) To a 1000% 16% aqueous solution of lime-processed gelatin was added 1845 g of a dispersion of zinc hydroxide dissolved at 45 ° C, and 41 ml of a 25% aqueous solution of dextran, electron-donated. 748 g of body gelatin dispersion dissolved at 45 ° C, 527 ml of dye trapping agent dispersion, 5 parts of water-soluble polymer (1)
% Aqueous solution (20 ml) and 5 ml of a 5% aqueous solution of a mixture of the compounds 10, 11 and 12 of the present invention in a weight ratio of 1: 1: 1 were added to prepare coating solutions for the second and sixth layers. At 40 ° C, the viscosity was 80 centipoise and the pH was 7.9.

Third Layer (Green Sensitive Emulsion Layer) 710.0 g of the photosensitive silver halide emulsion (3) and 290.0 g of the photosensitive silver halide emulsion (4) were each 40 °.
Dissolved in C and mixed. Further, 2511 g of a gelatin dispersion of a magenta dye-donor compound was dissolved at 45 ° C and added. Next, 9.6 ml of a 9.8% aqueous solution of sulfuric acid, 70.5 ml of a 5% aqueous solution of the water-soluble polymer (1), and 5% of a mixture of the compounds 10, 11 and 12 of the present invention in a weight ratio of 1: 1: 1. 5 ml of an aqueous solution was added to obtain a coating solution for the third layer. At 40 ° C, the viscosity was 75 centipoise and the pH was 5.4.

Fourth layer (intermediate layer) A solution prepared by dissolving 317 g of the dispersion of the electron transfer agent at 45 ° C in 1000 g of a 16% aqueous solution of lime-processed gelatin was added, and 3777 ml of ion-exchanged water and a gelatin dispersion of the electron donor. 962 g dissolved at 45 ° C., 61 ml 25% aqueous dextran solution, 426 m dye dispersion
l, 19.8 ml of 9.8% aqueous solution of sulfuric acid, water-soluble polymer
138 ml of 5% aqueous solution of (1), compound 10 of the present invention, 1
5 ml of a 5% aqueous solution of a mixture of 1 and 12 in a weight ratio of 1: 1: 1
Was added to obtain a coating liquid for the fourth layer. At 40 ° C, the viscosity was 85 centipoise and the pH was 5.3.

Fifth layer (blue-sensitive emulsion layer) 765.2 g of the light-sensitive silver halide emulsion (5) and 234.8 g of the light-sensitive silver halide emulsion (6) were each 40 °.
Dissolved in C and mixed. Further, 2064 g of a gelatin dispersion of a yellow dye-providing compound was dissolved at 45 ° C and added. Next, 11.4 ml of a 9.8% aqueous solution of sulfuric acid, 51.1 ml of a 5% aqueous solution of the water-soluble polymer (1), and 5% of a mixture of the compounds 10, 11, and 12 of the present invention in a weight ratio of 1: 1: 1.
5 ml of an aqueous solution was added to obtain a coating solution for the fifth layer. At 40 ° C, the viscosity was 75 centipoise and the pH was 5.3.

Seventh Layer (Protective Layer) A gelatin dispersion of a matting agent (18 g of polymethyl methacrylate having an average particle diameter of 3.5 μm dispersed in a 5% aqueous solution of acid-treated gelatin) in 1000 g of a 16% aqueous solution of acid-treated gelatin. ) 38 g, ion-exchanged water 1640 ml, 70% methanol solution 1 of the following anionic surfactant (1)
0.6 ml, 20.6 ml of a 5% methanol solution of the following fluorine-containing surfactant (1), 2.5 m of a 32% aqueous solution of NaOH
l, the weight ratio of the compounds 10, 11 and 12 of the present invention 1: 1:
5 ml of a 5% aqueous solution of the mixture of 1 was added to prepare a coating solution for the seventh layer. At 40 ° C., the viscosity was 14 centipoise and the pH was 8.7.

[0167]

[Chemical formula 22]

[0168]

[Chemical formula 23]

Using the above coating solution, the wet film thickness shown in Table 11 was obtained on the support having the constitution shown in Table 10 below.
A photosensitive material 101 was prepared by applying the coating liquids of the first to seventh layers.

[0170]

[Table 10]

[0171]

[Table 11]

While the coating solution was being sent to the fourth layer, a 1.6% aqueous solution of the following hardener (1) was added by a mixing system immediately before the coating amount was 2.39 ml / m ² . . That is, a mixing tank equipped with stirring blades was provided at a position immediately before the coating of the liquid feeding system for the fourth layer, and the coating solution and the aqueous solution of the hardener were combined on the upstream side of the mixing tank for coating.

[0173]

[Chemical formula 24]

Next, as comparative examples, the compounds 10 and 1 of the present invention were used.
A light-sensitive material 102 is used in the same manner as the light-sensitive material 101 except that the following compound (a) is used instead of the mixture of 1 and 12 in a weight ratio of 1: 1: 1, and the following compound (b) is used. Except for the above, except that the photosensitive material 101 is processed in the same manner as the photosensitive material 101
No. 03, and a photosensitive material 104 was prepared in the same manner as the photosensitive material 101 except that the following compound (c) was used. Since compound (a) and compound (b) are difficult to dissolve in water, they were added in a finely divided form using a mill.

[0175]

[Chemical 25]

[0176]

[Chemical formula 26]

[0177]

[Chemical 27]

Next, a method for producing the image receiving material will be described. An image receiving material R101 having a constitution as shown in Table 12 was prepared.

[0179]

[Table 12]

[0180]

[Table 13]

[0181]

[Chemical 28]

[0182]

[Chemical 29]

[0183]

[Chemical 30]

[0184]

[Chemical 31]

[0185]

[Chemical 32]

[0186]

[Chemical 33]

[0187]

[Chemical 34]

[0188]

[Chemical 35]

Using the above-mentioned photographic materials 101 to 104 and image receiving material R101, processing was carried out using the image recording apparatus described in Japanese Patent Application No. 63-137104. That is, an original image [a test chart on which Y, M, Cy and gray wedges whose densities are continuously changed is recorded] is scanned and exposed through a slit, and the exposed photosensitive material is exposed to water kept at 40 ° C. After soaking for 4 seconds, it was squeezed with a roller and immediately superposed so that the image receiving material and the film surface were in contact with each other. Then, using a heat drum whose temperature has been adjusted so that the water-absorbed film surface becomes 80 ° C., the photosensitive material is peeled from the image receiving material by heating for 15 seconds, and a clear color image corresponding to the original image is obtained on the image receiving material. Was given.

Next, Y (yellow) and M of the obtained image
Table 14 shows the results of measuring Dmax and Dmin of (magenta) and Cy (cyan) with a densitometer.

[0191]

[Table 14]

Next, when the photosensitive materials 101 to 104 were continuously manufactured for 72 hours and the surface condition of the coating film was inspected, the results shown in Table 15 below were obtained.

[0193]

[Table 15]

From the above results, the light-sensitive material 101 of the present invention
Has a higher maximum density and less stain than the light-sensitive materials 102 to 104 of Comparative Examples. Further, it can be seen that even if it is manufactured for a long time, there are few surface defects and it is excellent in manufacturing suitability.

Further, the compound of the present invention can be obtained by applying Japanese Patent Application No. 4-298.
It was found that even when it was used in the photosensitive material 201 described in Example 2 of No. 185, the maximum density was high, the stain was small, and the planar defects were small even when it was manufactured for a long time.

Claims (1)

[Claims] 1. A photosensitive silver halide, reduced on a support.
Agent, hydrophilic binder, and dye-donor compound
In the photothermographic material, a photothermographic material represented by the following general formula (I)
It has at least one layer containing a compound
A heat-developable color photosensitive material. [Chemical 1]Where R¹Is a methyl-substituted or unsubstituted amino group or
Is a hydroxyl group, R²Is a hydrogen atom or hydroxyl
Group, R³Is a methyl-substituted or unsubstituted amino group, methyl
Group, hydroxyl group or hydrogen atom, R^FourIs methyl
Substituted or unsubstituted aminoalkyl group, methyl group, ethyl
Group, or a hydroxyalkyl group, R ^FiveIs hydroxyl
Group or methylamino group, R⁶And R⁷Is one of them
One with a hydroxyl group and the other with a hydrogen atom or a methyl group
Represent.