JPH03260645A - Heat-developable photosensitive material - Google Patents

Abstract

PURPOSE:To maintain image density sufficient even if reducing an amount of silver used and amounts of additives, such as a reducing agent, by specifying the composition of the heat-developable photosensitive material. CONSTITUTION:This heat-developable photosensitive material is provided on a support with a photosensitive layer containing photosensitive silver halide, the reducing agent, a binder, and the like and a dye donor represented by formula I in which A is a coupler group; L is a bonding group; B is a ballasting group; Dye is a dye group; n is 1, 2, or 3; a part of A may serve as a part of Dye. The maximum absorption wavelength in the visible region of the Dye is made different by >=50 nm from the maximum absorption wavelength. The component of formula I is embodied by a copolymer of a compound of formula II and butyl acrylate in an amount of 40 wt.% of the copolymer.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a heat-developable light-sensitive material, and more particularly to a heat-developable light-sensitive material capable of forming substantially black and white images by diffusion transfer of dyes.

[Background of the invention]

A photosensitive material (thermally developable photosensitive material) that can easily and quickly form an image by carrying out a dry process using heat in the development process is well known. Publication No. 43-4924, pages 553-555 of "Basics of Photographic Engineering" Silver Salt Photo W (published by Corona Publishing in 1879), and Research Disclosure Magazine June 1978 issue, pages 9-15 (RD-170).
29) etc.

Obtaining a black and white image by heat development is usually achieved by forming a silver image by heat development, and has been put into practical use with 3M's "Dry Silver J" and the like.

However, this method has the problem that unused silver halide and organic silver salts remain in the image area even after development, so the white background area gradually becomes colored (printed out) while the image is being stored. Ta. As a method for solving such printout problems, Japanese Patent Application Laid-Open No. 162251/1983 discloses a method in which yellow, magenta, and cyan dyes are released as a result of development and are transferred to form a black and white image. has been done. However, the method disclosed in the patent publication is substantially the same as the known color image forming method, and requires a large amount of silver and other additives, which increases the cost compared to the conventional black and white image forming method. However, since the film thickness is increased, the sharpness deteriorates. In addition, in the method disclosed in the publication, since yellow, magenta, and cyan dyes are contained in the photosensitive layer, the filter effect of the dyes works regardless of the wavelength of light used during visible light exposure, and this causes a significant This had the disadvantage of causing sensitivity loss.

[Purpose of the invention]

The present invention has been made in view of the above-mentioned drawbacks of the prior art.

That is, an object of the present invention is to provide a photothermographic material capable of forming a black and white image by forming a substantially black or gray dye image, which can reduce the amount of silver used, and
In addition, it is possible to reduce the amount of additives such as reducing agents used, and it is also possible to make the photosensitive layer thinner, thereby improving dye transferability and sharpness. The goal is to provide photosensitive materials.

Still another object of the present invention is to provide a photothermographic material for forming black and white images that can be written on at least in part of visible light without loss of sensitivity.

[Means for solving problems]

As a result of intensive studies, the present inventors have found that the object of the present invention is to provide a heat developable material having at least a photosensitive silver halide, a reducing agent, a binder, and a dye-providing substance represented by the following general formula (1) on a support. It was discovered that this can be achieved using a photosensitive material, leading to the present invention.

-B In the formula, A represents a coupler moiety that can form a dye by coupling reaction with an oxidized form of a reducing agent, and L represents A
represents two bonding groups bonded to A at the active site of the coupler 1 site, and B represents the general formula (1) during thermal development.
represents a ballast group having a molecular size or shape capable of rendering the dye-donor represented by substantially immobile, and Dye represents a dye moiety. n represents 1, 2 or 3. Further, a part of the coupler moiety represented by A may also serve as a part of the dye moiety represented by Dye.

The present invention will be explained in more detail below.

First, the dye-providing substance represented by the general formula (1) that the heat-developable photosensitive material of the present invention has (in the following description, it may also be appropriately referred to as "the dye-providing substance of the present invention") will be described in detail.

In the above general formula (1), the coupler moiety represented by A is preferably 470r+m ~ 520nm or 570nm ~ 6
This is a part of a coupler that can form a dye image having a maximum absorption wavelength of 20 nm. Particularly preferred coupler moieties include the following general formulas (2) to 2 R2, in which R', R", and R3 each represent an alkyl group (e.g., methyl group, ethyl group, n-propyl group, i-propyl group, t-propyl group,
-butyl group) or an aryl group (e.g. phenyl group) or a hydrogen atom, and the alkyl group or aryl group may be substituted, in which case the substituent is, for example, an alkyloxy group.

Carboxyl group, cyano group, nitro group, aryloxy group, acyl group, acyloxy group, carbamoyl group, sulfamoyl group, acylamino group, alkylsulfonylamino group, sulfamoylamino group, alkoxycarbamoyl group, hydroxyl group or halogen atom (fluorine atom) , chlorine atom, bromine atom, etc.). Furthermore, R
', R'' is substituted with a dye moiety represented by Dye in general formula (1), or serves as a part of the dye moiety. l represents O or l, m is 0 or 1
represents.

X represents CO or SO2.

In the general formula (1), L represents a divalent bonding group, and preferably the following groups can be mentioned as L.

0-, -5-, -NIISO□-, -3o, -,
-0CI+C0OH.

Represents a gathering. In particular, those having a carbonyl group at a position adjacent to the binding site of the active site of the coupler site are preferred).

In general formula (1), the ballast group represented by B is 8
As mentioned above, preferably an organic group having 12 or more and 40 or less carbon atoms (which may be substituted with a substituent, especially a hydrophilic group such as 5O3H, C00I+) or a polymer residue is preferable, and a polymer residue is particularly preferable. .

When B is a polymer residue, the dye-providing substance represented by general formula (1) is preferably a polymer derived from a monomer represented by general formula (12) below.

General formula (12) %formula%) Lf R5 loincloth type J'　afflicted R''h type Jzh5C=CH.

7 In the formula, A, L, and Dye have the same meanings as defined in the general formula (1), and R5R& is a divalent hydrocarbon group (for example, an alkylene group or an arylene group).

aralkylene group, alkylenearylene group, arylenealkylene group), and J' and J'' represent divalent bonding groups (e.g. -NHCO, -CONH- -03-, -QCO-,
-Coo-, -3o2-), P+, pz, q+
and q2 each represent an integer of 0 or l.

R7 represents a hydrogen atom or an alkyl group (eg, methyl group, ethyl group, n-butyl group).

Examples of the dye moiety represented by Dye include azo dye,
Azomethine dye, anthraquinone dye.

naphthoquinone dyes, styryl dyes, nitro dyes.

Examples include quinoline dyes, carbonyl dyes, and phthalocyanine dyes. These dye moieties preferably have a molecular weight of 600 or less in order to improve diffusibility.

Further, these dyes may be in a time-shortened form that can restore color during thermal development or transfer. In addition, these dyes are used for the purpose of increasing the light resistance of images, for example, in
Chelatable dyes described in No. 48765 and No. 59-124337 may also be used.

Furthermore, the combination of the absorption maximum wavelength (λwax(1)) in the visible region of the dye moiety represented by Dye and the coupling reaction between the coupler moiety represented by A and the oxidized form of the reducing agent is as follows: 570n-≦λwax(1)≦6
20nm, and 470ns+≦λwax (2)≦52
0nm combination or 470nm≦λwax (
1)≦520nm and 570nm≦λwax (2)≦
It is a combination of 620nw+.

Specific examples of the dye-providing substance of the present invention are shown below.

However, it goes without saying that the invention is not limited to the examples below.

(1) Copolymer of 11+1 and BA (BA: 40% by weight) <BA, = butyl acrylate 2 (2) OCIICOO)! ■ I2H2S Cpm (3) Cpm - (4) Copolymer of BA and BA (BA: 60% by weight) Copolymer of BA (BA: 50% by weight) Cpm (5) CHl Cpm (7) Cpm - (8 ) and BA copolymer (BA: 40% by weight) and BA copolymer Cpm (6) L Cpm- (9) 1 Cpm (10) C11゜The dye-donating substance of the present invention can be prepared by the following means. It can be synthesized with In other words, after synthesizing A-L-B, it can be synthesized by introducing a separately synthesized Dye (however, Dye is introduced into A and started as A-Dye, and then L-B is introduced, or Dye is introduced into A-L). or A-L or A-L-B having an anilino group (however, the anilino group is not included in L and B) may be diazotized and then with a suitable coupler. It is obtained by a coupling reaction (in the case of A-L, B is subsequently introduced).

In carrying out the present invention, the dye-providing substance of the present invention is one of the
A species may be used alone or two or more species may be used. Additionally, U.S. Pat. No. 4,631,251. 4, 656.

124, 4,650.748.

The amount of the dye-providing substance to be used is not limited, and it depends on the type of dye-providing substance, whether it is used alone or in combination of two or more types, or whether the photographic constituent layer of the light-sensitive material of the present invention is a single layer or two or more types. Although the amount may be determined depending on the number of layers, for example, the amount used is preferably o, oos g to 50 g, more preferably 0.1 g to 10 g per bottle.

Any method can be used to incorporate the dye-providing substance into the photographic constituent layer of the heat-developable photosensitive material. ) and then ultrasonically dispersed or dissolved in an alkaline aqueous solution (for example, sodium hydroxide 10
% aqueous solution, etc.) and then neutralized with mineral acid (e.g., hydrochloric acid or nitric acid, etc.), or use a ball mill with an appropriate polymer aqueous solution (e.g., gelatin, polyvinyl butyral, polyvinyl pyrrolidone, etc.). After dispersing, it can be used.

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

Furthermore, it is possible to use an emulsion containing grains having a multilayer structure in which the halogen composition of the grains differs on the surface and inside. For example, a silver halide emulsion having core/shell type silver halide grains in which the halogen composition changes stepwise or continuously can be used.

In addition, the shape of photosensitive silver halide is cubic, spherical, 8
It is possible to use materials that have a clear crystal habit, such as a hedron, dodecahedron, and tetradecahedron, or those that do not. This type of silver halide is described in JP-A-60-215948.

Also, for example, JP-A-58-111933, JP-A No. 5B-1
No. 11934, No. 5B-108526, Research Disclosure No. 22534, etc., each of these crystal planes has two parallel crystal planes, and each of these crystal planes is smaller than the other single crystal of this particle. It is also possible to use a silver halide emulsion containing tabular silver halide grains having a large area and an aspect ratio, that is, a ratio of grain diameter to thickness of 5:1 or more.

Further, in the present invention, a silver halide emulsion containing internal latent image type silver halide grains whose surfaces are not coupled in advance can be used. For internal latent image type silver halide whose surface is not previously coupled, for example, U.S. Pat.
No. 592,250, No. 3.206313, No. 3.31
7.322, 3,511,622, 3447.
No. 927, No. 3,761,266, No. 3,103.5
No. 84, No. 3,736.140, and other specifications.

Internal latent image type silver halide grains whose surfaces are not coupled in advance are silver halide grains in which the sensitivity inside the grain is higher than the sensitivity on the surface of the silver halide grain, as described in the above specifications. be. Also, U.S. Patent No. 3,271,15
No. 7, No. 3,447.927 and No. 3,531,
Silver halide emulsions having silver halide grains incorporating polyvalent metal ions as described in US Pat. No. 291, or silver halide containing dopants as described in U.S. Pat. Silver halide emulsion whose grain surface is weakly chemically sensitized, or JP-A-50-852
Silver halide emulsions consisting of grains having a laminated structure described in publications such as No. 4 and No. 50-38525, and other publications such as JP-A-52-156614 and JP-A-55-1.2.
Silver halide emulsions such as those described in No. 7549 can be used.

The silver halide in the photosensitive emulsion may have coarse or fine grains, but the preferred grain size is about 0.005 μm to about 1.5 μm, more preferably about 0.005 μm to about 1.5 μm. .01 μm to 0.5 μm.

In the present invention, as another method for preparing photosensitive silver halide, a photosensitive root salt-forming component may be allowed to coexist with an organic silver salt described below to form photosensitive silver halide in a part of the organic silver salt.

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

The light-sensitive silver halide emulsion may be chemically sensitized by any method in the photographic art.

Further, the photosensitive silver halide emulsion used can be spectral sensitized using a known spectral sensitizing dye to impart sensitivity to blue, green, red, and near-infrared light.

Typical spectral sensitizing dyes that can be used include, for example, cyanine, merocyanine, complex (that is, trinuclear or tetranuclear) cyanine, holopolar cyanine,
Examples include styryl, hemicyanine, oxonol, and the like.

The preferred amount of these sensitizing dyes is 1 x 10-1 per mole of photosensitive silver halide or silver halide forming component.
b mole - 1 mole. More preferably, I Xl0-
5 to 1X10-' moles.

The sensitizing dye may be added at any stage of the preparation of the silver halide emulsion. That is, any time may be used, such as during silver halide grain formation, removal of soluble salts, before the start of chemical sensitization, during chemical sensitization, or after the end of chemical sensitization.

In the heat-developable photosensitive material of the present invention, it is preferable to use various organic silver salts, if necessary, for the purpose of increasing sensitivity and improving developability.

Examples of organic silver salts that can be used in the heat-developable photosensitive material of the present invention include JP-A Nos. 53-4921 and 49-5262.
No. 6, No. 52-141222, No. 53-36224, No. 53-37626, and No. 53-37610, as well as U.S. Patent No. 3,330,633, No. 3,794,496, Silver salts of long-chain aliphatic carboxylic acids and silver salts of carboxylic acids having heterocycles, such as silver behenate, α(1-phenyl Tetrazolethio) silver acetate, etc., Japanese Patent Publication No. 44-26582, No. 45-12
No. 700, No. 45-18416, No. 45-22185
No., JP-A-52-137321, JP-A No. 5B-11863
No. 8, No. 58-118639, U.S. Patent No. 4.123
．． There are silver salts of imino groups described in various publications such as No. 274.

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

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

The amount of the organic silver salt used is generally preferably 0.01 to 500 moles, more preferably 0.1 to 100 moles per mole of photosensitive silver halide. More preferably 0.
It is 3 to 30 moles.

The heat-developable light-sensitive material of the present invention may contain a reducing agent (a reducing agent precursor is also included in the term "reducing agent" in this specification), which is generally used in the field of heat-developable light-sensitive materials. You can use whatever is available.

Examples of reducing agents that can be used in the present invention include U.S. Pat. Nos. 3,531,286 and 3,761.27
No. 0, No. 3.764, 328 specifications, and RD (
Research Disclosure + -) Nn12], 46
, No. 15108, No. 15127, JP-A-56-27132, U.S. Patent No. 3.342,5
99. No. 3,719,492, P-phenylenediamine and p-aminophenol developing agents, phosphorus, etc., described in the specifications of JP-A-53-135628, JP-A No. 57-79035, etc. Amidophenol-based, sulfonamide-aniline-based developing agents, hydrazone-based color developing agents and their precursors, or phenols, sulfonamidophenols, or polyhydroxybenzenes, naphthols, hydroxybinaphthyls, and methylene bisnaphthols, Methylene bisphenols, ascorbic acid, 3-pyrazolidones, and pyrazolones can be used.

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

N-dialkyl) phenylsulfamate can be mentioned.

Two or more types of reducing agents may be used simultaneously.

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

Binders that can be used in the heat-developable photosensitive material of the present invention include polyvinyl butyral, polyvinyl acetate,
These include synthetic or natural polymeric substances such as ethyl cellulose, polymethyl methacrylate, cellulose acetate butyrate, polyvinyl alcohol, polyvinyl pyrrolidone, gelatin, gelatin derivatives such as phthalated gelatin, cellulose derivatives, proteins, starch, and gum arabic. can be used alone or in combination of two or more. In particular, it is preferable to use gelatin or its KA form together with a hydrophilic polymer such as polyvinylpyrrolidone or polyvinyl alcohol, and more preferably to use a mixed binder of gelatin and polyvinylpyrrolidone described in JP-A-59-229556. It is to use.

The preferred amount of binder used is usually 0.05g to 50g per support, more preferably 0.2g to 50g.
It is 20g.

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

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

Various thermal solvents are preferably added to the heat-developable photosensitive material of the present invention, and further to the heat-developable photosensitive material and/or the image-receiving member when the photosensitive material is of a transfer type and an image-receiving member is used.

The thermal solvent is a compound that is liquid during thermal development and promotes thermal development and/or thermal transfer. These compounds include, for example, U.S. Pat. No. 3,347,675. No. 3
, No. 667.959, RD (Research Disclosure) No. 17643 (X II), Japanese Patent Publication No. 5
No. 9-229556, No. 59-68730, No. 59-
No. 84236, No. 60191251, No. 60-232
No. 547, No. 60-14241, No. 61-52643
No. 62-78554, No. 62-42153, No. 62-4213, etc., U.S. Patent No. 3.438, 7
No. 76, No. 3.666477, No. 3,667.959
Specifications of each issue, JP-A No. 51-19525, JP-A No. 53-24
No. 829, No. 53-60223, No. 58-11864
0 and No. 5B-198038, examples of which are particularly useful in carrying out the present invention include urea derivatives (e.g., dimethylurea, diethyl urea, phenylurea, etc.), amide derivatives (e.g., acetamide, benzamide, p-toluamide, etc.), sulfonamide derivatives (e.g., Hensensulfonamide, α-toluenesulfonamide, etc.), polyhydric alcohols (e.g., 1,6 hexanediol, 1,2-cyclohexanediol, pentaerythritol, etc.), or polyethylene glycols.

Among the above thermal solvents, water-insoluble solid thermal solvents are particularly preferably used.

Specific examples of the above-mentioned water-soluble heat solvent include, for example, JP-A-62
No. 436645, No. 62-139549, No. 63-5
Publications No. 3548, Japanese Patent Application No. 63-205228, No. 6
There is one described in No. 3-541.13.

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

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

The organic silver salt and the thermal solvent may be dispersed in the same dispersion. The same binder, dispersion medium, and dispersion device as used for producing each dispersion can be used.

In addition to the above-mentioned components, the photothermographic material of the present invention may contain various additives, such as a development accelerator, an antifoggant, a base breaker, etc., if necessary.

As development accelerators, compounds described in JP-A-59-177550, JP-A-59-111636, and JP-A-59-124333 are used, as well as compounds described in JP-A-61-159642 and JP-A-62-203908. The development accelerator-releasing compounds described above or metal ions having an electronegativity of 4 or more as described in Japanese Patent Application No. 104645/1988 can also be used.

As the antifoggant, for example, U.S. Patent No. 3.645.
Higher fatty acids described in specification No. 739, Japanese Patent Publication No. 4
Second mercury salt described in Publication No. 7-11113, JP-A-51
N-halogen compounds described in Japanese Patent Publication No. 47419, U.S. Pat.
Mercapto compound releasing compound described in Publication No. 725,
Aryl sulfonic acids described in JP 49125016, carboxylic acid lithium salts described in JP 51-47419, British Patent No. 1,455,271, JP 50-101. The oxidizing agent described in Publication No. O19, 53-
Sulfinic acids or thiosulfonic acids described in Publication No. 19825, 2-thiouracils described in Publication No. 51-3223, simple sulfur described in Publication No. 5126019, No. 51-42529, No. 51-81124, No. 55-
Disulfide and polysulfide compounds described in Publication No. 93149, rosins or diterpenes described in Publication No. 51-57435, polymer acids having free carboxyl groups or sulfonic acid groups described in Publication No. 51-104338, and US Pat. Thiazolinthion as described in 4.138.265, 1.2.1-1-lyazole or 5-mercapto as described in JP-A-54-51821 and U.S. Patent No. 4.137,079. −
1,2,4-triazole, JP-A-14088-1955
Thiosulfinate esters described in No. 3, No. 55-1
1,2゜3.4-thiatriazoles described in Publication No. 42331, No. 59-46641, No. 59-57233
No., dihalogen compounds or trihalogen compounds described in Publication No. 59-57234, and furthermore, No. 59-111.
Thiol compound described in Publication No. 636, No. 601985
Hydroquinone derivatives described in Publication No. 40, 60-2
Examples include the combined use of a hydroquinone derivative and a hensitriazole derivative described in Japanese Patent No. 27255.

Still another particularly preferred antifoggant is disclosed in JP-A No. 6
Inhibitors having a hydrophilic group as described in JP-A No. 2-78554, polymer inhibitors as described in JP-A-62-121452, and inhibitors having a ballast group as described in JP-A-62-123456. can be mentioned.

Furthermore, colorless couplers described in Japanese Patent Application No. 62-320599 are also preferably used.

Examples of base precursors include compounds that release basic substances by decarboxylation upon heating (e.g., guanidinium trichloroacetate), compounds that decompose and release amines through reactions such as intramolecular nucleus displacement reactions, and the like. For example, Japanese Patent Application Publication No. 56-130745, Japanese Patent Application Publication No. 56-132332, British Patent No. 2,079,480, U.S. Patent No. 4,0
Specification No. 60,420, JP-A-59-157637,
No. 59-166943, No. 59-180537, No. 59-174830, No. 59-195237, No. 6
Examples include base release agents described in JP2-108249, JP62174745, and the like.

In addition, various additives used in heat-developable photosensitive materials as necessary, such as antihalation dyes, fluorescent brighteners, hardeners, antistatic agents, plasticizers, spreading agents, matting agents, and surfactants. , an antifading agent, etc., and these are specifically described in RD (Research Disclosure) Magazine Vol.

170. June 1978, No. 17029, JP-A-62
-135825, etc.

These various additives may be added not only to the photosensitive layer but also to non-photosensitive layers such as an intermediate layer, a protective layer or a backing layer.

The heat-developable photosensitive material of the present invention contains (a) a photosensitive silver halide, (b) a reducing agent, (C) a binder, and a dye-providing substance of the present invention. It is preferable to contain silver. Basically, these may be contained in one heat-developable photosensitive layer, but it is not necessarily necessary to contain it in a single photographic constituent layer. For example, silver is contained in a heat-developable photosensitive layer (a) above.

A configuration in which the components (b), (C), and (e) are contained in one heat-developable photosensitive layer, and the other layer adjacent to this photosensitive layer contains the dye donor ¥t(d). But okay,
As long as they are in a state where they can react with each other, they may be contained in two or more constituent layers.

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

In addition to the heat-developable photosensitive layer, the heat-developable photosensitive material of the present invention may optionally include non-photosensitive layers such as an undercoat layer, an intermediate layer, a protective layer, a filter layer, a backing layer, and a release layer. . To coat the heat-developable photosensitive layer and these non-photosensitive layers on the support-1-, a method similar to that used for coating and preparing general silver halide photosensitive materials can be applied.

The heat-developable photosensitive material of the present invention can be exposed to light using an appropriate light source, and examples of the exposure light source include a tungsten lamp,
Various types such as halogen lamps, xenon lamps, mercury lamps, cathode ray tube flying spots, light emitting diodes, lasers (e.g. gas lasers, YAG lasers, dye lasers, semiconductor lasers, etc.), CRT light sources, and FOT can be used singly or in combination. It can be used as It is also possible to use a semiconductor laser and a second harmonic generation element (Sl- (G element).
Exposure may be performed using light emitted from a phosphor excited by L'A, r-rays, α-rays, or the like. Exposure times include not only exposure times of 1/1000 seconds to 1 second, which are normally used with cameras, but also exposures shorter than 1/1000 seconds, such as exposures of 1/10 to 1/10" seconds using xenon flash lamps and cathode ray tubes. If necessary, the spectral composition of the light used for exposure can be adjusted with a color filter.The light-sensitive material of the present invention can be used for scanner exposure using a laser or the like.

The heat-developable photosensitive material of the present invention usually preferably has a
0°C to 200°C1, more preferably 100'C to 17
at a temperature range of 0°C, preferably for 1 second to 180 seconds,
More preferably, development can be carried out by simply heating for 1.5 seconds to 120 seconds. Transfer of the diffusible dye to the image-receiving layer may be carried out simultaneously with heat development by bringing the image-receiving member into close contact with the photosensitive surface of the photosensitive material and the image-receiving layer during heat development, or by bringing the image-receiving member into close contact with the image-receiving member after heat development. Alternatively, the transfer may be carried out by supplying water and then applying heat if necessary. Also, before exposure,
Preheating may be performed in the temperature range of "C." In addition, as described in JP-A-60-143338 and JP-A-61-162041, the photosensitive material and the image receiving member may be heated in order to improve their mutual adhesion. 80″C~2 just before heat development transfer
Each may be preheated at a temperature of 50'C.

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

As the heating means, any method applicable to ordinary heat-developable photosensitive materials can be used, such as contacting with a heated block or plate, contacting with a heated roller or drum, or passing through a high-temperature atmosphere. Alternatively, high-frequency heating may be used, or furthermore, a conductive layer containing a conductive substance such as carbon black may be provided on the back surface of the photosensitive material of the present invention or the back surface of the image receiving member for thermal transfer, and the Joule heat generated by energization may be utilized. You can also do that. There are no particular restrictions on the heating pattern, and the method of preheating and then reheating is used to continuously raise the temperature, whether heating at a high temperature for a short time or at a low temperature for a long time. It is also possible to heat the mixture intermittently or repeatedly, and discontinuous heating is also possible, but a simple pattern is preferable. Alternatively, a method in which exposure and heating proceed simultaneously may be used.

When the present invention is used as a transfer type photothermographic material, an image receiving member is used as described in -L. In this case, the image-receiving layer that can be effectively used in the image-receiving member may be one that has the function of receiving the dye in the heat-developable photosensitive layer released or formed by heat development, such as tertiary amine or quaternary amine. Polymers containing ammonium salts, U.S. Pat. No. 3,709,6
Those described in the specification of No. 90 are preferably used. Typical image-receiving layers for diffusion transfer include those obtained by mixing a polymer containing ammonium salt, tertiary amine, etc. with gelatin, polyvinyl alcohol, etc., and coating the mixture on a support. Another useful dye-receiving material is one made of a heat-resistant organic polymer substance with a glass transition temperature of 40°C or more and 250°C or less, which is described in JP-A-57-207250. .

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

Regarding polymers, "Polymer Handbook, 2nd Edition" (edited by Joy Brandrup and E.H. Inmargat), published by John Willi and Sons (Polymer Handbook, 2nd Edition)
ed, (J. Brandrup, E.), I++une
rgut edition) John Wiley & 5ons l
Also useful are synthetic polymers with a glass transition temperature of 40°C or higher, as described in . - For boat fishing, a molecular weight of 2,000 to 200,000 is useful for the polymeric substance. These polymeric substances may be used alone or in a blend of two or more thereof, or may be used in combination as a copolymer.

A particularly preferable image-receiving layer is JP-A-59-22342
A layer made of polyvinyl chloride as described in Japanese Patent No. 5 and a polycarbonate as described in Japanese Patent Application Laid-Open No. 1988-19138, and ii.
A layer consisting of J plastics may be mentioned.

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

As the support for the image-receiving member, any material such as a transparent support or an opaque support may be used, and examples thereof include films of polyethylene terephthalate, polycarbonate, polystyrene, polyvinyl chloride, polyethylene, polypropylene, and supports thereof. Supports containing pigments such as titanium oxygen, barium sulfate, calcium carbonate, and talc, baryta paper, resin coated paper laminated with thermoplastic resin containing pigments on paper, fabrics, glasses, metals such as aluminum, supports on which an electron beam curable resin composition containing pigments is coated and cured, and coating layers containing pigments are provided on these supports. Examples include supports such as Furthermore, various coated papers such as the cast coated paper described in JP-A-62-283333 are also useful as supports.

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

Appropriate additives, such as various known additives, can be added to the image receiving member. Examples of such additives include ultraviolet absorbers, image stabilizers, development accelerators, antifoggants, pHgJtll regulators (various acids and acid precursors, bases and base precursors, etc.), and heat solvents. can be mentioned.

Typical examples of the ultraviolet absorber include penzotriazole compounds and hensiphenone compounds. Examples of image stabilizers include hindered amine type, hindered phenol type, dialkoxybenzene type, chroman type, indane type, thioether type,
Examples include hydroquinone compounds, chlorine-substituted S-triazine compounds, and the like. The development accelerator and antifoggant can be appropriately selected from compounds added to heat-developable photosensitive materials.

The heat-developable photosensitive material of the present invention is published in RD (Research Disclosure Magazine) No. 15108, JP-A-57-1984.
No. 58, No. 57-207250, No. 61-80148
The photothermographic material may be a so-called monosheet type photothermographic material in which a photosensitive layer and an image-receiving layer are formed on the same support, as described in the above publication.

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

Various additives used in the photographic field can be used in the protective layer. The additives include various matting agents, colloidal silica, shearing agents, organic fluoro compounds (especially fluorine surfactants), antistatic agents, ultraviolet absorbers,
High-boiling organic solvents, antioxidants, hydroquinone derivatives,
Polymer latex, surfactants (including polymeric surfactants), hardeners (including polymeric hardeners), organic silver salt particles, non-photosensitive silver halide particles, antifoggants, development accelerators, etc. can be mentioned.

Regarding these additives, please refer to RD (Research Tisfroger Magazine) Vol. 170. June 1978 No.
, 17 (5 lower +-: 1., . [Examples] Examples of the present invention will be described below. However, as a matter of course, the present invention is not limited to the examples.

Example 1 A silver iodobromide emulsion, a dispersion of an organic silver salt and a thermal solvent, a dye-providing substance dispersion, and a reducing agent dispersion were prepared in the following manner.

In this example, first, using these, photosensitive material sample size 1
It was created. An image receiving member was also created. The amount added is
Unless otherwise specified, the amounts are expressed per 1 nf of photosensitive material and image receiving member (the same applies in each table).

■Preparation of silver iodobromide emulsion at 50°C, JP-A No. 57-92523, No. 57
Using the mixing agitator shown in the specification of -92524,
This is an aqueous solution containing 11.6 g of potassium iodide and 131 g of potassium bromide in solution (A) in which 20 g of ossein gelatin, 1000 g of distilled water, and ammonia are dissolved (
B) Liquid 500@! and 500 @ of solution (C), which is an aqueous solution containing 1 mole of silver nitrate and ammonia! and p at the same time
Ag was added while keeping it constant.

The shape and size of the emulsion grains to be prepared are determined by pH, pAg and B.
Adjustment was made by controlling the addition rates of liquid and liquid C. In this way, a core emulsion with a silver iodide content of 7 mol %, regular octahedral grains, and an average grain size of 0.25 μm was prepared.

Next, by coating a shell of silver halide with a silver iodide content of 1 mol % in the same manner as in the method described in -F, a core/shell type grain with a regular octahedron and an average grain size of 0.3 μm was formed. A silver emulsion was prepared (monodispersity was 9%). The emulsion thus prepared was washed with water and desalted.

■Preparation of photosensitive silver halide dispersion The following components were added to the silver iodobromide emulsion 70-- prepared as described above, and chemical sensitization and spectral sensitization were carried out to form a red-sensitive photosensitive halide. A silver emulsion dispersion was prepared.

(a) Preparation of red-sensitive silver iodobromide emulsion The above silver iodobromide emulsion 700 @/4-
Hydroxy-6-methyl-1.3.3a, 7tetrazaindene 0.4g gelatin
32 g Sodium thiosulfate 10 mg The following sensitizing dye (a) 1% methanol solution 80 @l Distilled water 1200 at Sensitizing dye (a) ■Preparation of organic silver salt dispersion Dissolve silver hensitriazole and silver nitrate in a water-alcohol mixed solvent. 28.8 g of 5-methylhensitriazole silver obtained by the reaction in a poly(N-vinylpyrrolidone)
6.0 g, and 0.6 5-methylbenzo l-lyazole
5 g was dispersed in an alumina ball mill and the pH was adjusted to 6.0 to give 200 mff.

■Preparation of thermal solvent dispersion Add 025 g of the following thermal solvent to 100 mj of a 0.5% polyvinylpyrrolidone aqueous solution! Dispersed in an alumina bow mill,
It was set to 120mff.

Thermal solvent - ■ ■ Thermal solvent - Preparation of organic silver dispersion 25 g of thermal solvent - (p-methylhenzamide), 6.
3g of silver 5-methylhensitriazole, and 0.3g
5-methylhensitriazole was dispersed in a 1% polyvinylpyrrolidone aqueous solution (130 mj2) using an alumina ball mill to obtain a solution of 150 f2.

(1) Preparation of dye-providing substance dispersion-1 20.0 g of the above (Cpm 1), which is the dye-providing substance of the present invention, 0.5 g of the following compound (ST-1), and (SC-1) 1.
2g was dissolved in 100mf of ethyl acetate and 115ml of di(2-ethylhexyl)phthalate, and
C (manufactured by DuPont) 5% by weight aqueous solution 124m! ! ,, Phenylcarbamoylated gelatin (manufactured by Rousslow) 30.
After mixing with 720 mff of gelatin aqueous solution containing 5 g and dispersing with an ultrasonic homogenizer, and distilling off ethyl acetate,
The pH was adjusted to 6.0 to 795 mff to obtain a dye-providing substance dispersion 1.

(ST-1) Reducing agent-1 (SC 1) ■ Preparation of reducing agent solution 20.0 g of reducing agent-1 below, 3.3 g of reducing agent-2,
0.50 g of the following fluorine-based surfactant-1 was dissolved in water to obtain βH6.0 to obtain a reducing agent solution of 250 mff1.

Surfactant-1 NaOxS cll COOC00CIIz (CF
zCFz)■ Cl1z C00CIlz (CFzCFz)nl!
(m) Preparation of light-sensitive material Using the organic silver salt dispersion, red-sensitive silver halide emulsion, dye-providing substance dispersion and reducing agent solution prepared above, a color light-sensitive material was obtained as follows.

0.5 g/n of hensitriazole silver (1.2 g/n of dye-donor, 0.6 g/n of reducing agent, red-sensitive halogenated material) on a 180 μm thick transparent polyethylene terephthalate support with latex undercoat. silver 0.81
g A g 7m, heat solvent 4.0g, gelatin 2.0g
, phenylcarbamoylated gelatin (0.5 g, n=2 or 3)) and polyvinylpyrrolidone (K-30) 0.5 g to prepare a photosensitive material-1.

■Preparation of image receiving member The following compound (TP-1), (AC
-1) by coating a polyvinyl chloride layer (image-receiving layer) containing
An image receiving member was produced.

(TP-1) HOCtlzCtlzSCH□Cll2SC1l□CI
+2011 0.2 g/po The obtained photosensitive material was exposed to red light through a step wedge, overlapped with an image receiving member, and thermally developed at 150° C. for 60 seconds.

Reflection density of the obtained image for blue light, green light, and red light (maximum density <Dmax> and minimum density <Dmin
> was measured. The results are shown in Table 1 below.

As can be seen from Table 1, it was possible to obtain a substantially black image with sufficient maximum density and low fog.

Furthermore, the image obtained in this example is composed of a black pigment formed by a reaction between pigments, and has sufficient immobility.
It had excellent storage stability.

Furthermore, as shown in this example, there is only one type of dye component (red dye) in the dye-donating substance that exists in the photosensitive material before exposure, and this has a filter effect only on blue to green light. Since there is no red light, there is no desensitization due to light absorption of the dye-donating substance when exposed to red light. On the other hand, in the conventional photosensitive material described in JP-A No. 60-162251, the dye-donating substance absorbs light in the entire visible light range, so it exhibits significant desensitization to red exposure. It was something that would happen.

Example-2 Example-1 photosensitive material-1 except that the dye-providing substance of the present invention in Example-1 was changed to Cpm5 and Cpm-7
Photosensitive materials 2 and 3 were prepared in the same manner as above.

The photosensitive materials 2 and 3 obtained were exposed and developed in the same manner as in Example 2 to obtain substantially black transferred images with maximum density and fog shown in Table 1.

It can be seen that the effect of the present invention is also recognized in Photosensitive Material 2.3.

Example-3 Example-1 photosensitive + A material-1 except that red-sensitive silver halide was changed to infrared-sensitive silver halide in Example-1.
Photosensitive material-4 was prepared in the same manner as above. The obtained photosensitive material-4 was exposed to infrared light and then thermally developed in the same manner as in Example-1 to obtain transferred images having the densities shown in Tables 1 to 1. It can be seen that the effect of the present invention is also recognized for Photosensitive Material-4.

Incidentally, infrared-sensitive silver halide was prepared according to the following procedure.

(b) Preparation of infrared-sensitive silver iodobromide emulsion The above silver iodobromide emulsion 70-4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 0.6 g The following sensitizing dye ( b)
Methanol 0.1% solution 8〇 - Following sensitizing dye (c) methanol 0.05% solution 4〇 - Sodium thiosulfate 20■ Ion exchange water 1200 m7 Comparative example-1 Dye-donor of the present invention for photosensitive material-1 Comparative photosensitive material-5 was prepared by adding the following three yellow, magenta, and cyan couplers instead of Cpm-1, and using the same procedures as photosensitive material-1 except for that. The amount of each coupler applied is as follows.

Yellow coupler 0.75g/■f mazen coupler-0.42g /r+? Cyan coupler 1.1 g/rrr Furthermore, Comparative Photosensitive Material-6 was prepared in the same manner as Comparative Photosensitive Material-5 except that the amount of the compound shown below in Comparative Photosensitive Material-5 was changed as follows. Puco.

Hen's triadur silver 1, 25g/boro reducing agent
1.5g/red-sensitive silver halide
2.0gAg/rd heat treatment
10 g/n Igelatin 5.0 g Phenylcarbamoylated gelatin 1.25 g/rd Polyvinylpyrrolidone 1.25 g/rd The obtained comparative photosensitive materials-5 and 6 were subjected to the same exposure and development as in Example-1. Obtained black cyan coupler 1h (C11□ C-IJ-i- (B A )-y- 0NH y : 60% by weight (BΔ is n-butyl acrylate-1-0) Magenta coupler 3 Examples-1 to 4 , as understood from Evaluation Table 1 of Comparative Example 1, the photosensitive materials 1 to 4 according to the present invention obtained in Examples 1 to 4, silver halide, organic silver salt, thermal solvent, and reducing agent Comparative photosensitive material-5, in which the amounts of binder and the like applied were the same, could not obtain sufficient density.On the other hand, in photosensitive material-6, in which the amounts of these substances were increased by 2.5 times, the photosensitive material according to the present invention - An image with Dmax close to 1 to 4 can be obtained, but with increased fog.

That is, from the above-mentioned Examples and Comparative Examples, if the photosensitive material of the present invention is used, a substantially black image with high density and low capri can be obtained without increasing the amount of materials (silver compound, reducing agent, etc.) attached. It is clear that it can be done.

〔Effect of the invention〕

As mentioned above, the heat-developable photosensitive material of the present invention is capable of forming a substantially black or gray dye image, and even if the amount of silver and the amount of additives such as reducing agents are reduced, sufficient images can be obtained. This makes it possible to make the photosensitive layer thinner, thereby improving dye transferability and sharpness. It has the advantage that it can be configured to be written by light without loss of sensitivity and can also be configured to improve image preservation.

Claims (1)

[Scope of Claims] 1. A heat-developable photosensitive material comprising at least a photosensitive silver halide, a reducing agent, a binder, and a dye-providing substance represented by the following general formula (1) on a support. General formula (1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, A represents a coupler moiety that can form a dye by a coupling reaction with an oxidized form of a reducing agent, and L represents A
represents a divalent bonding group bonded to A at the active point of the coupler site, and B represents the general formula (1) during thermal development.
represents a ballast group having a molecular size or shape capable of rendering the dye-donor represented by substantially immobile, and Dye represents a dye moiety. n represents 1, 2 or 3, and a part of the coupler part represented by A may also serve as part of a dye part represented by Dye. Furthermore, the maximum absorption wavelength in the visible part of the dye moiety represented by Dye and the maximum absorption wavelength in the visible part of the dye formed by the coupling reaction between the coupler part represented by A and the oxidized form of the reducing agent are They differ by 50 nm or more.