JPH05297546A - Heat-developable silver halide color photograthic sensitive material and dye image receiving material - Google Patents

Abstract

PURPOSE:To provide the dye image-receiving material high in dye image transferability, improved in film fragility, small in deterioration of sharpness and color mixing due to dye bleeding, and stable in coatability; and the dye image- receiving material good in peelability form the heat-developable photosensitive material and capable of obtaining an image superior in sharpness. CONSTITUTION:The heat-developable silver halide color photographic sensitive material is characterized by containing a support and a photosensitive and heat-developable layer comprising at least photosensitive silver halide, a binder, a reducin agent, and a dye donor forming or releasing a diffusive dye, and a polymer latex emulsion polymerized in a hydrophilic colloid, and the dye image-receiving material is characterized by comprising at least a support and a dye image-receiving material capable of the dye diffused from the photosensitive material and the polymer latex.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-developable silver halide color photographic light-sensitive material and a dye image-receiving material for obtaining an image by heat development.

[0002]

BACKGROUND OF THE INVENTION Photothermographic materials in which a developing process is carried out by heating are known, and those for obtaining a monochrome image and a color image are known. Further, a so-called transfer type photothermographic material is also well known, which transfers an image obtained by heat development from the photosensitive material to the dye image-receiving layer. The heat-developable silver halide color light-sensitive material generally has at least one light-sensitive layer containing a binder, a light-sensitive silver halide emulsion, a dye-donor and a reducing agent on a support, and if necessary, an organic silver salt. And other photographic additives are added.

In the transfer type heat-developable color light-sensitive material, an image-receiving material having an image-receiving layer capable of receiving a dye is used in combination with the light-sensitive material. The present invention relates to such a heat-developable color light-sensitive material and a dye image-receiving material used in combination with it.

In the conventional photothermographic material, JP-A-59-687
No. 30, No. 60-191251, No. 61-210352, No. 62-42153
As described in the publication, a substance existing in the photosensitive layer as a liquid at the heat development temperature (so-called thermal solvent) in order to improve the transfer efficiency of the image dye generated by the heat development and eliminate the transfer unevenness.
We have studied the types and amounts of additives and have improved their performance. However, when a hot solvent which is liquid at room temperature is used, stickiness of the light-sensitive material or sticking between the emulsion surface and the back surface of the light-sensitive material occurs, and JP-A-62-136645,
No. 63-53548, JP-A-1-227150, JP-A-2-863, etc. When a solid thermal solvent at room temperature is used, the brittleness of the film of the photosensitive material is poor. In the transfer process, a crack was formed in the film, and the film was partially missing, causing a failure. In order to solve such a problem, in JP-A-63-163335, a combined use of a solid thermal solvent and a liquid thermal solvent is examined, and in Japanese Patent Application No. 2-156782, the amount of the thermal solvent in the photosensitive material is changed. By adding a high-boiling solvent and / or a polymer latex, the physical properties of the film and the performance of dye transfer are made compatible.

However, even if these techniques are used, the improvement of the brittleness of the film is still insufficient, and the hot solvent and the polymer latex agglomerate during the stagnation of the coating solution, so that a stable coating is carried out. I couldn't. Also, in the image after transfer, so-called sharpness deterioration due to dye bleeding is large, and when a full-color photothermographic material is used, color turbidity due to diffusion of the dye-donor substance between the photosensitive layers is caused during heat development. It happened and the improvement was desired.

On the other hand, investigations for improving the performance of dye image-receiving materials have been continued, and JP-A-60-60643 and 59-1.
Nos. 24332 and 60-19138, in place of the dye image-receiving material having an image-receiving layer made of a thermoplastic hydrophobic polymer as described in Japanese Patent Application No. 02-227460, a hydrophilic binder and a support are provided on a support. By providing a dye image receiving material having a polymer latex, the release property and the transfer property are improved. However, even in this case, the coexistence of the hydrophilic binder and the polymer latex causes bleeding of the dye, which deteriorates the sharpness of the image.

[0007]

The first object of the present invention is to solve the above problems.
The purpose of is to have high transferability of the image dye and excellent brittleness of the film, and deterioration of sharpness and color mixture due to bleeding of the dye are small,
Another object of the present invention is to provide a heat-developable color light-sensitive material capable of stable coating. A second object of the present invention is to provide a dye image-receiving material capable of obtaining an image having excellent releasability from a photothermographic material and excellent sharpness.

[0008]

The above object of the present invention is to emulsify on a support at least a photosensitive silver halide, a binder, a reducing agent, a dye-donor which forms or releases a diffusible dye during thermal development and a hydrophilic colloid. A heat-developable color light-sensitive material containing a polymerized polymer latex, and a dye-image-receiving material containing at least a dye image-receiving substance and a polymer latex emulsion-polymerized in a hydrophilic colloid on a support.

The specific constitution of the present invention will be described in detail below.

The polymer latex emulsion-polymerized in the hydrophilic colloid used in the present invention is obtained as an aqueous dispersion of the polymer. This preparation method includes a method in which a polymerizable monomer and a polymerization agent are added to the hydrophilic colloid to polymerize, and an oligomer is separately synthesized in advance, and then the hydrophilic colloid is added to the hydrophilic colloid. A method of adding this oligomer and, if necessary, a polymerization agent, and further carrying out emulsion polymerization is used.

Monomers for forming the polymers used in the present invention include, for example, substituents containing a suitable active halogen such as halomethylallyl, halomethylcarbonyl, halomethylsulfonyl, haloethylcarbonyl, haloethylsulfonyl groups and the like. And a monomer having Examples thereof include vinylbenzyl chloride, vinylbenzyl bromide, p- (2-chloroethylsulfonylmethyl) styrene, N- (4-chloroethylsulfonylmethylphenyl) acrylamide, vinylchloroacetate, N- (3-chloroacetamidopropyl). ) Methyl acrylamide, N- [3- (3,5-dichloro-1-triazinylamino) -propyl] methacrylamide and the like. In addition, various monomers such as N- [2-ethoxycarbonylmethoxycarbonyl) ethyl] acrylamide having an active ester group, aldehydes such as p-methacryloyloxybenzaldehyde, N-acryloylaziridine, isocyanate ethyl acrylate, etc. Mention may be made of monomers. Examples of other preferable monomers include the compounds described in p34 to p43 of Japanese Patent Application No. 2-156782.

The polymers used in the present invention, including the above examples, are roughly classified into condensation type polymers and unsaturated compound type polymers. Examples of the condensation polymer include polyamide, polypeptide, polyester, polycarbonate, polyanhydride, polyurethane, polyurea and polyether. The unsaturated compound-based polymer is an addition polymer based on a vinyl group, and is a homopolymer of aliphatic hydrocarbon-based, aromatic-based, vinyl alcohol-based, nitrile-based, acrylic-based, methacrylic-based, acrylonitrile-based, halogen-based, etc. And copolymers of these combinations. A specific example of polymer latex is p43 in Japanese Patent Application No. 2-156782.
~ P48 etc. Among the above-mentioned polymer latices, polymer latices having a glass transition temperature (Tg) of 50 ° C. or less are preferably used from the viewpoint of the transferability of the dye. Among them, particularly preferable polymers are polymethyl acrylate, polyethyl acrylate, poly
-n-butyl acrylate, copolymer of ethyl acrylate and acrylic acid, copolymer of vinylidene chloride and butyl acrylate, copolymer of butyl acrylate and acrylic acid, copolymer of vinyl acetate and ethyl acrylate, copolymer of vinyl acetate and butyl acrylate, ethyl acrylate and 2 -Copolymers of acrylamide, copolymers of methyl methacrylate and ethyl acrylate, etc.

The hydrophilic colloid used in the present invention includes cellulose derivatives, polyvinylpyrrolidone,
Polyvinyl alcohol, gelatin derivatives, casein,
Proteins such as zein and glutin, natural or synthetic polymers such as starch and gum arabic can be used alone or in combination of two or more kinds, and among them, a compound such as gelatin which can polymerize a hydrophilic colloid with a polymer is preferably used. Be done.

As the hydrophilic colloid, those such as cellulose derivative, polyvinyl alcohol, polyvinylpyrrolidone, etc. which do not cause the colloid to polymerize with the polymer can be used, or the hydrophilic colloid which polymerizes with the polymer, such as gelatin derivative. Although a compound capable of forming itself as a hydrophilic binder may be used, a gelatin derivative is preferably used.

The emulsion-polymerized polymer latex prepared by using these is prepared by polymerizing a monomer in the presence of a surfactant containing a hydrophilic group, and optionally a polymerizing agent, as described in US Pat. No. 2956884. In the present invention, it is preferable to add and add and to polymerize while vigorously stirring in the presence of a hydrophilic colloid while adjusting the temperature as necessary. Gelatin derivatives are particularly preferred as the hydrophilic colloid. Further, a crosslinking agent of gelatin and a polymer as described in US Pat. Nos. 4,421,847 and 5026632 can be used. As such a crosslinking agent, compounds such as pyridinium carbamoyl, dication ether and carbodiimide are preferably used.

The above-mentioned addition amount of the polymerization agent is preferably 0.5 × 10 ^{−3 to} 1.0, and more preferably 0.5 × 10 ^{−2 to} 0.5 by weight ratio with respect to the hydrophilic colloid.

In the polymer latex of the present invention, general anionic, cationic, nonionic and amphoteric surfactants are used as surfactants during production. These may be used alone or in combination of two or more. The polymer latex used in the present invention has an average molecular weight of 5
It is preferable that the dispersoid has at least 10,000, especially 200,000 to 500,000 polymers. Further, the particle size of the polymer latex can be arbitrarily adjusted depending on the conditions at the time of production (monomer / polymer amount, hydrophilic binder amount, surfactant amount, polymerization temperature, stirring speed, etc.), but the average particle size is preferably 0.01 to 2.0 μm
Is an aqueous dispersion of The amount of the hydrophilic colloid used for emulsion polymerization in the present invention is arbitrary, but in order to efficiently transfer the dye, the mixing ratio is preferably hydrophilic colloid: polymer = 1: 40 to 2: 1. Above all, a more preferable mixing ratio is 1:20 to 1: 1.

When used in a light-sensitive material, the emulsion-polymerized polymer latex used in the present invention can be added to any layer such as an emulsion layer, an intermediate layer and a protective layer containing a photosensitive silver halide. The addition amount thereof is preferably 5 to 400% by weight based on the total amount of the hydrophilic binder of the light-sensitive material. More preferably, it is 20 to 100% by weight. Above all, when added to a layer that does not contain photosensitive silver halide, the same photographic performance can be obtained with a smaller amount than when added to a layer that contains photosensitive silver halide, and the coating solution is stable. It is preferable because it improves the properties.

When the emulsion-polymerized polymer latex of the present invention is used as a dye image-receiving material, the latex of the present invention and, if necessary, a hydrophobic polymer latex or a tertiary polymer having a dye-accepting ability are contained in a hydrophilic binder. To form a dye receiving layer in which a mordant containing a quaternary ammonium group is dispersed. Examples of the hydrophilic binder used in this case include polyvinyl acetate, ethyl cellulose, polyvinyl alcohol, polyvinyl pyrrolidone, gelatin, gelatin derivatives such as phthalated gelatin, cellulose derivatives, proteins, starch, gum arabic, and other synthetic or natural polymers. Examples thereof include substances, which may be used alone or in combination of two or more, and at least one of the hydrophilic binders is required to be hardenable by a hardener, particularly gelatin. It is preferable to use gelatin in combination with a hydrophilic polymer such as polyvinylpyrrolidone or polyvinyl alcohol. The amount of binder used is usually 1 m ^{2 of} support
The amount is 0.05 to 50 g, preferably 0.2 to 20 g. In this case, the addition amount of the emulsion-polymerized polymer latex is 5 to 20 relative to the total amount of the hydrophilic binder of the image receiving material.
0% by weight is preferred. Addition of more than 200% by weight is not preferable because the surface gloss after transfer is significantly deteriorated. 25 to 100
Addition by weight is especially preferred.

Examples of the dye-donor substances used in the photothermographic material of the present invention include, for example, JP-A Nos. 61-61157 and 61-611.
No. 58, No. 62-44738, No. 62-129850, No. 62-129851,
No. 62-129852, No. 62-169158, couplers forming diffusible dyes described in Japanese Patent Application No. 1-200859, for example, leuco dyes described in JP-A No. 61-88254, U.S. Pat. 95
Azo dyes described in No. 7, or U.S. Patent Nos. 4,463,079, 4,
439,513, JP-A-59-60434, 59-65839, 59-71
046, 59-87450, 59-123837, 59-124329
No. 59-165054, No. 59-165055, etc. In particular, a compound that forms a diffusible dye by a coupling reaction is preferable. For example, JP-A-2-863, page 9, lower left column 2
It is represented by the general formula (a) in the line.

Among them, a polymer coupler having a polymer chain having a repeating unit derived from a monomer represented by the general formula (b) described in the same publication, page 9, lower right column, line 8 is preferable.

Examples of positive type dye-donor substances include:
JP 59-55430, 59-165054, 59-154445,
59-116655, 59-124327, 59-152440, 64-13
There are compounds described in each publication such as No. 546.

The above dye-providing substances may be used alone or in combination of two or more.

The photothermographic material of the present invention is, for example,
A dye-donor substance is contained in a microcapsule together with the polymerizable compound described in JP-A-2-293753 and JP-A-2-308162, and the resulting compound is thermally developed to image-wise the polymerization reaction of the polymerizable compound. Alternatively, it can also be applied to a photothermographic material of a type in which the microcapsules are cured in the reverse image to change the diffusivity of the dye-donor substance to the image receiving layer to form an image.

As the photosensitive silver halide used in the photothermographic material of the present invention, those known in the art can be used, for example, silver chloride, silver bromide, silver iodobromide, silver chlorobromide. Alternatively, silver chloroiodobromide can be used.

The silver halide may have a uniform composition from the inside to the surface of the grain, or may be a silver halide whose composition changes continuously or stepwise inside and on the surface.

The silver halide may have a tabular shape, a cubic shape, a spherical shape, an octahedron, a dodecahedron, a tetrahedron, or the like having a clear crystal habit or not.

Further, for example, US Pat.
20,613, 3,271,257, 3,317,322, 3,511,62
No. 2, No. 3,531,291, No. 3,447,927, No. 3,761,266,
The internal latent image type silver halide emulsions described in JP-A-3,703,584, JP-A-3736,140, JP-A-3,761,276, JP-A-52-15661 and JP-A-55-127549 can also be used.

The photosensitive silver halide can be added with a metal ion species such as iridium, gold, rhodium, iron and lead in the form of a suitable salt in the grain forming step.

The grain size of the above-mentioned photosensitive silver halide emulsion is about 0.
The thickness is 02 to 2 μm, preferably about 0.05 to 0.5 μm.

In the present invention, as a method for preparing a photosensitive silver halide, a photosensitive silver salt-forming component such as a water-soluble halide is allowed to coexist with an organic silver salt described below, and a part of the organic silver salt is subjected to photosensitive halogenation. It can also be formed by converting a part of silver.

The photosensitive silver halide emulsion is prepared by chemically sensitizing the surface of silver halide grains with a known sensitizer (eg, active gelatin, inorganic sulfur, sodium thiosulfate, thiourea dioxide, sodium chloroaurate). It is also possible to carry out chemical sensitization in the presence of a nitrogen-containing heterocyclic compound or a mercapto group-containing heterocyclic compound.

Further, the light-sensitive silver halide can be spectrally sensitized to blue, green, red and near-infrared light by a known spectral sensitizing dye such as cyanine and merocyanine used in ordinary photography.

These sensitizing dyes are used in an amount of 1 μmol to 1 mol, preferably 10 μmol to 0.1 mol, per mol of silver halide.
Can be added at any time during the formation of silver halide grains, the removal of soluble salts, before the start of chemical sensitization, at the time of chemical sensitization, or after the end of chemical sensitization.

In the photothermographic material of the present invention, known organic silver salts can be used for the purpose of increasing sensitivity and improving developability.

The organic silver salt that can be used in the present invention is
For example, JP-B-43-4921, JP-A-49-52626, and JP-A-52-14
1222, 53-36224, 53-37626, 53-36224,
53-37610 and other publications and U.S. Patent 3,330,633,
No. 3,794,496, No. 4,105,451, etc., silver salts of long-chain aliphatic carboxylic acids and silver salts of carboxylic acids having a heterocycle (for example, silver behenate, α- (1-phenyltetrazolethio)). Silver acetate), Japanese Patent Publication No. 44-26582, No. 45-
No. 12700, No. 45-18416, No. 45-22815, JP-A-52-1373
No. 21, No. 58-118638, No. 58-118639, U.S. Pat.
Examples thereof include silver salts of compounds having an imino group described in JP-A No. 274 and the like, acetylene silver described in JP-A No. 61-249044, and the like.

Particularly, a silver salt of a compound having an imino group is preferable, and for example, a silver salt of benzotriazole and its derivative (for example, silver benzotriazole, silver 5-methylbenzotriazole, etc.) is particularly preferable.

The above organic silver salts can be used alone or in combination of two or more kinds. These are prepared in a hydrophilic colloid aqueous solution such as gelatin, and soluble salts are removed and used as they are. Alternatively, the organic silver salt can be isolated and mechanically pulverized and dispersed into solid fine particles for use.

The reducing agent used in the photothermographic material of the present invention is selected from those conventionally known for photothermographic materials depending on the developing mechanism and the dye formation / release mechanism. The reducing agent referred to herein also includes a reducing agent precursor that releases the reducing agent during thermal development.

Examples of the reducing agent that can be used in the present invention include US Pat. Nos. 3,351,286 and 3,761,270,
3,764,328, 3,342,599, 3,719,492, Research Disclosure 12,146, 15,108
No. 15,127, and JP-A-56-27132, 53-135628.
No. 57-79035 p-phenylenediamine-based and, and p- aminophenol-based developing agent, phosphoric acid amide phenol-based developing agent, sulfonamide aniline-based developing agent, and hydrazone-based developing agent, phenols, sulfone Amidophenols, polyhydroxybenzenes,
There are naphthols, hydroxybisnaphthyls, methylenebisphenols, ascorbic acids, 1-aryl-3-pyrazolidones, hydrazones, and precursors of the above various reducing agents.

The dye-providing substance may also serve as the reducing agent.

A particularly preferred reducing agent is JP-A-56-146133.
No. 62-227141 and N- (p-N ', N'-dialkylamino) phenylsulfamate and derivatives thereof,
Specific examples thereof include the compounds described in JP-A-2-863, page 7, lower left column, line 6 to page 8, lower right column.

A thermal solvent can be used in the photothermographic material of the present invention for the purpose of accelerating the transfer of dye and other purposes. The thermal solvent is a compound that has a function of liquefying during thermal development and promoting thermal development and thermal transfer of a dye, and is preferably in a solid state at room temperature.

Examples of the thermal solvent that can be used in the present invention include US Pat. Nos. 3,347,675, 3,667,959, and 3,347,675.
438,776, 3,666,477, Research Disclosure No. 17,643, JP-A-51-19525, 53-24829, 5
3-60223, 58-118640, 58-198038, 59-2295
No. 56, No. 59-68730, No. 59-84236, No. 60-191251,
No. 60-232547, No. 60-14241, No. 61-52643, No. 62-78
554, 62-42153, 62-44737, 63-53548,
63-161446, JP-A 1-224751, 2-863, 2-12
Examples thereof include the compounds described in each publication such as 0739 and 2-123354. Specifically, urea derivatives (urea, dimethylurea, phenylurea, etc.), amide derivatives (eg, acetamide, stearylamide, p-toluamide, p-propanoyloxyethoxybenzamide, etc.), sulfonamide derivatives (eg, p-toluene). Sulfonamide etc.) and polyhydric alcohols (eg 1,6 hexanediol, pentaerythritol, polyethylene glycol etc.) are preferably used.

The above-mentioned thermal solvent can be added to any layer such as a photosensitive silver halide emulsion layer, an intermediate layer, a protective layer, or an image receiving layer of an image receiving material. Wt% to 500 wt%, more preferably 20 wt% to 2
It is 00% by weight.

The binder used in the photothermographic material of the present invention includes, for example, preferable combinations of the binders described in JP-A-2-863, page 10, upper right column, line 14 to lower left column, line 10. Can be used. Particularly preferred binders are gelatin, polyvinylpyrrolidone and combinations thereof.

In addition to the above, various additives can be added to the photothermographic material of the present invention, if necessary.

Examples of the development accelerator include, for example, JP-A-59-177.
550, 59-111636, 59-124333, 61-72233
No. 61-236548, JP-A 1-152454, JP-A 61-1596.
No. 42, JP-A-1-104645 and Japanese Patent Application No. 1-110767, or a development accelerator releasing compound, or a metal ion having an electronegativity of 4 or more described in JP-A-1-104645 can also be used. ..

Examples of the antifoggant include US Pat.
645,739, higher fatty acids, secondary mercury salts described in JP-B-47-11113, N-halides described in JP-A-51-47419, US Pat. No. 3,700,457, JP-A-51- Fifty
No. 725, Japanese Patent Application No. 1-69994, mercapto compound-releasing compounds described in 1-104271; arylsulfonic acid described in JP-A-49-125016; lithium carboxylate described in 51-47419; British Patent 1,455,271 and oxidizers described in JP-A-50-101019, sulfinic acids and thiosulfonic acids described in 53-19825, thiouracils described in 51-3223, sulfur described in 51-26019, sulfur, No. 51-42529, No. 51-811
No. 24, and No. 55-93149, disulfides and polysulfides, No. 51-57435, rosins or diterpenes, No. 51-104338, polymer acids having a carboxyl group or a sulfonic acid group, U.S. Pat. Thiazolythion described in 4,138,265, JP-A-54-51821 and JP-A-55-142,331.
No. 3, U.S. Pat. No. 4,137,079, triazoles, JP-A-55-140883, thiosulfinic acid esters, JP-A-59-46641, 59-57233, and 59-57234.
-Or tri-halide, a thiol compound described in JP-A-59-111636, a hydroquinone derivative described in JP-A-60-198540 and 60-227255, and a hydrophilic group described in JP-A-62-78554 Antifoggants, polymer antifoggants described in JP-A No. 62-121452, anti-foggants having a ballast group described in JP-A No. 62-123456, and colorless couplers described in JP-A No. 1-161239. Be done.

Examples of the base precursor include, for example, JP-A Nos. 56-130745, 59-157637, 59-166943 and 59-59.
180537, 59-174830, 59-195237, 62-10824
No. 9, No. 62-174745, No. 62-187847, No. 63-97942,
The compounds and base-releasing techniques described in JP-A-63-96159 and JP-A-1-68746 are cited.

Various known photographic additives other than those described above can be used in the photothermographic material of the present invention. Examples thereof include antihalation dyes, antiirradiation dyes, colloidal silver, optical brighteners, A hardening agent, an antistatic agent, a surfactant, an inorganic or organic matting agent, an anti-fading agent, an ultraviolet absorber, an antifungal agent, a white background color tone adjusting agent and the like can be contained. For example, RD (Research
Disclosure) Nos. 17029, No. 29963, JP-A Nos. 62-135825, and 64-13546.

These various additives can be appropriately added not only to the photosensitive layer but also to any constituent layer such as an intermediate layer, an undercoat layer, a protective layer or a backing layer.

As the support used in the photothermographic material of the invention, for example, the supports described in JP-A-2-863, page 12, upper left column, line 15 to upper right column, line 1 can be used. .. Preferably, a polyethylene terephthalate support or a paper support such as cast coated paper or baryta paper is used.

The photothermographic material of the present invention comprises (a) a photosensitive silver halide emulsion, (b) a reducing agent, (c) a binder,
It is preferable to contain (d) a dye-providing substance and further contain (e) organic silver. These may be contained in a single photographic constituent layer, or may be added by dividing them into two or more layers.

It is also possible to provide two or more photosensitive layers having substantially the same color sensitivity to form a low sensitivity layer and a high sensitivity layer, respectively.

When the photothermographic material of the present invention is used as a full-color recording material, it usually has three photosensitive layers having different color sensitivities, and in each photosensitive layer dyes having different hues are formed by thermal development. Or is released. In this case, generally, the yellow dye (Y) is added to the blue photosensitive layer (B),
The green photosensitive layer (G) is combined with the magenta dye (M), and the red photosensitive layer (R) is combined with the cyan dye (C), but the present invention is not limited thereto, and any combination is possible. is there. Specifically, (BC)-(GM)-
(R-Y), (infrared photosensitivity-C)-(G-Y)-(R-
Combinations such as M) are also possible. The layer structure of each layer is arbitrary, and R-G-B, G-R-B, and
Layer arrangements such as R-G-infrared and G-R-infrared are possible.

In addition to the photosensitive layer, the photothermographic material of the present invention may optionally be provided with a non-photosensitive layer such as an undercoat layer, an intermediate layer, a protective layer, a filter layer, a backing layer and a release layer. ..

The light-sensitive portion of the present invention is used in combination with an image-receiving material. In this case, the image-receiving material is composed of a support and an image-receiving layer having a dye-receiving ability provided thereon. The image-receiving layer is roughly classified into a case where the binder constituting the image-receiving layer has a dye receiving ability and a case where a mordant capable of receiving the dye is contained in the binder. When the binder has a dye-accepting ability, the substance preferably used is preferably one formed of a polymer having a glass transition temperature of about 40 ° C. or higher and about 250 ° C. or lower. Specifically, “Polymer Handbook Second Edition” (Joy Brand Wrap, EH Inmargat), John Willie & Sons Publishing {Polymer Handbook 2nd. Ed. (J. Brandrup, EHImme
Synthetic polymers having a glass transition temperature of about 40 ° C. or higher described in “John Wily & Sons” by rgut) are useful. Generally, those having a molecular weight of about 2,000 to 200,000 are useful. These polymers alone 2
One or more kinds may be used in combination, and a copolymerizable polymer having two or more kinds of repeating units may be used.

Specifically, JP-A-2-863, page 14, upper left column 1
The polymers described from the 4th line to the 14th line in the upper right column can be used including the preferable polymers.

Further, in the image receiving material in which the image receiving layer contains a mordant in the binder, a polymer containing a tertiary amine or a quaternary ammonium salt is preferably used as the mordant. For example, US Pat. 64-64
Examples thereof include compounds described in Japanese Patent No. 13546. As the binder used for holding these mordants, hydrophilic binders such as gelatin and polyvinyl alcohol are preferably used.

A dye receiving layer obtained by dispersing a hydrophobic polymer latex having dye receiving ability in a hydrophilic binder in a form similar to the image receiving layer having the mordant in the binder can also be used in the present invention.

The image-receiving material may be provided with a single image-receiving layer on the support, or may be coated with a plurality of constituent layers, in which case all of them are dye image-receiving layers. Alternatively, only a part of the constituent layers can be the image receiving layer.

When the image-receiving material has a support separately from the image-receiving layer, the support of the image-receiving material may be either a transparent support or a reflective support. The support described in column 15 line to lower right column 8 line,
It can be used by selecting from a reflective support having a second type diffuse reflectance.

The photothermographic material of the present invention includes RD (Research Disclosure) 15108, JP-A-57-198458,
It is also possible to use a so-called mono-sheet type photothermographic material in which a photosensitive layer and an image receiving layer are previously laminated on the same support as described in JP-A-57-207250 and JP-A-61-80148.

Various known additives can be added to the image receiving material. Examples of such additives include stain inhibitors, ultraviolet absorbers, optical brighteners, image stabilizers, development accelerators, antifoggants, pH regulators (acid and acid precursors, base precursors, etc.), heat Solvents, organic fluorine compounds, oil droplets, surfactants, hardeners, matting agents, various metal ions and the like can be mentioned.

In any case, the combination of the light-sensitive material and the image-receiving material according to the constitution of the present invention is preferable.

The photothermographic material of the present invention can be exposed by known exposure means suitable for the color sensitivity of the photosensitive material.

As the exposure light source which can be used, those described in JP-A-2-863, page 12, lower left column, lines 13 to 16 can be used, preferably a laser light source, CR
T light source and LED are used. Also, a light source in which a semiconductor laser and an SHG element (second harmonic generation element) are combined can be used.

As for the exposure time, one screen is exposed once or
Or, it depends on the digital exposure for each pixel,
In the former case, it is usually 0.001 seconds to 10 seconds, and in the latter case, it is performed in the range of 10 ^-8 to 10 ^-2 seconds per pixel.

Upon exposure, the color temperature of the exposure light source can be adjusted by using a color filter, if necessary, and scanning exposure can also be performed with a laser or the like.

The photothermographic material of the present invention is preferably 70 to 200 ° C., more preferably 90 to 170 ° C., preferably 1 to 180 seconds, more preferably 2 to 2 after imagewise exposure or at the same time as exposure. It is heat-developed for 120 seconds to form a dye image. The transfer of the diffusible dye to the image-receiving material may be performed simultaneously with the heat-development by bringing the image-receiving layer surface of the image-receiving material into close contact with the photosensitive layer side of the photosensitive material during the heat-development. The dye may be transferred by bringing it into close contact with the material, and further, after supplying water, the photosensitive material and the image receiving material may be brought into close contact with each other. In addition, the photosensitive material is preheated in the range of 70 to 160 ° C. before exposure, or disclosed in JP-A-60-143338 and 61-16-16.
As described in No. 2041, immediately before development, at least one of the light-sensitive material and the image-receiving material can be preheated in the temperature range of 80 to 120 ° C.

When the heat-developable light-sensitive material of the present invention is heat-developed, known heating means can be applied. For example, JP-A-2-863, page 13, upper left column, lines 12 to 19 The described method, the method by far infrared heating, etc. can be used.

The heating pattern at the time of heat development is not particularly limited, a method of performing at a constant temperature, a method of performing high temperature in the initial stage of development and a low temperature in the latter half of development, or vice versa,
Further, any method such as a method of changing the temperature region in three or more steps or a method of continuously changing the temperature can be used.

[0074]

EXAMPLES The effects of the present invention will be specifically illustrated by the following examples.

Example 1. [Preparation of Polymer Latex Dispersion (1-1)] Vinyl chloride (188 g), ethyl acrylate (700 g), sodium di (2-ethylhexyl) sulfosuccinate (10 g), potassium persulfate (0.6 g) and distilled water ( 1800g) under nitrogen atmosphere 60
The polymer latex dispersion liquid (1-1) was prepared by vigorously stirring at 60 ° C. for 60 minutes.

[Preparation of Polymer Latex Dispersion (1-2) Emulsion Polymerized in Gelatin] In the preparation of polymer latex dispersion (1-1), a 3% ossein gelatin aqueous solution ( 1800 g) was used to prepare a polymer latex dispersion (1-2) emulsion-polymerized in gelatin in the same manner.

[Preparation of Polymer Latex Dispersion (1-3) Emulsion Polymerized in Gelatin] Hydroxyl hydroxide 1- (4) was used as a crosslinking agent in the preparation of polymer latex dispersion (1-2) emulsion polymerized in gelatin. -Morpholinocarbonyl) -4
-(2-Sulfoethyl) pyridinium inner salt (3.0 g) was added, and emulsion polymerization was carried out in gelatin in the same manner to prepare a polymer latex dispersion (1-3).

[Preparation of Polymer Latex Dispersion (2-1)] In the preparation of polymer latex dispersion (1-1), the monomers used were changed to methyl methacrylate (50 g) and ethyl acrylate (950 g). Was similarly prepared to prepare a polymer latex dispersion (2-1).

[Preparation of Polymer Latex Dispersion Liquid (2-2) Emulsion Polymerized in Gelatin] In the preparation of the polymer latex dispersion liquid (2-1), a 3% ossein gelatin aqueous solution (instead of distilled water (1800 g) ( 1800 g) was used to prepare a polymer latex dispersion (2-2) emulsion-polymerized in gelatin in the same manner.

[Preparation of Polymer Latex Dispersion (2-3) Emulsion Polymerized in Gelatin] Hydroxyl hydroxide 1- (4) was used as a crosslinking agent in the preparation of polymer latex dispersion (2-2) emulsion polymerized in gelatin. -Morpholinocarbonyl) -4
-(2-Sulfoethyl) pyridinium inner salt (3.0 g) was added, and a polymer latex dispersion liquid (2-3) emulsion-polymerized in gelatin was prepared in the same manner.

[Preparation of Polymer Latex Dispersion (2-4) Emulsion Polymerized in Gelatin] In the preparation of polymer latex dispersion (2-2), 6% ossein was used instead of 3% ossein gelatin aqueous solution (1800 g). In gelatin aqueous solution
(1800 g) was used to prepare a polymer latex dispersion liquid (2-4) emulsion-polymerized in gelatin in the same manner.

[Preparation of Polymer Latex Dispersion (2-5) Emulsion Polymerized in Gelatin] In preparation of polymer latex dispersion (2-3) emulsion polymerized in gelatin, sodium di (2-ethylhexyl) sulfosuccinate was prepared. The amount used was increased to 20 g, and the polymer latex dispersion liquid (2-5) emulsion-polymerized in gelatin was prepared in the same manner.

[Preparation of Polymer Latex Dispersion (3-1)] Styrene (104 g), ethyl acrylate (600 g), butyl acrylate (425 g), sodium dodecylbenzenesulfonate (8 g), ammonium persulfate (3 g) and Distilled water (1
(800 g) was vigorously stirred at 60 ° C. for 80 minutes in a nitrogen atmosphere to prepare a polymer latex dispersion (3-1).

[Preparation of Polymer Latex Dispersion (3-2) Emulsion Polymerized in Gelatin] In the preparation of polymer latex dispersion (3-1), 3% ossein gelatin aqueous solution (instead of distilled water (1800 g) ( 1800 g) was used to prepare a polymer latex dispersion (3-2) emulsion-polymerized in gelatin in the same manner.

[Preparation of Polymer Latex Dispersion Liquid (3-3) Emulsion Polymerized in Gelatin] In the preparation of the polymer latex dispersion liquid emulsion (3-2) emulsion polymerized in gelatin, 1- (4) hydroxide was used as a crosslinking agent. -Morpholinocarbonyl) -4
-(2-Sulfoethyl) pyridinium inner salt (3.0 g) was added, and a polymer latex dispersion liquid (3-3) emulsion-polymerized in gelatin was prepared in the same manner.

[Preparation of Photosensitive Silver Halide Emulsion] At 50 ° C., a mixed aqueous solution of potassium iodide and potassium bromide (Liquid A) and an aqueous solution of ammoniacal silver nitrate (Liquid B) were added to an ossein gelatin aqueous solution at pH and pAg. Is added by the double jet method while controlling the addition rate so that
When 80% was added, a silver halide emulsion prepared by adding a solution C in which K ₃ IrCl ₆ was dissolved in a NaCl aqueous solution was spectrally sensitized and shown in Table 1. Each blue-sensitive silver halide emulsion was prepared.

[0087]

[Table 1]

[0088]

[Chemical 1]

[Preparation of benzotriazole silver emulsion] 50 ° C.
Ammoniacal silver nitrate aqueous solution and benzotriazole aqueous solution are added and mixed in 10% aqueous solution of phenylcarbamoyl gelatin by the double jet method, and after the addition is completed, the pH of the solution is reduced with sulfuric acid to cause aggregation / desalting to thereby form needle crystals ( Width 0.1
˜0.2 μm, length 0.5-2.0 μm).

[Preparation of heat-developable color photosensitive material] Thickness 160
A heat-developable color light-sensitive material (1) having the layer structure shown below was prepared on a photographic baryter paper support having a thickness of μm.

The added amount of each material is shown in the amount per 1 m ² of the heat-developable color light-sensitive material.

The addition amounts of the photosensitive silver halide emulsion and the benzotriazole silver emulsion are expressed in terms of silver.

[Layer constitution of heat-developable color light-sensitive material] Subbing layer Polyphenylene ether resin 2.0 g Polystyrene resin 1.5 g Antifoggant-1 0.7 g First layer (red light-sensitive layer) benzotriazole silver emulsion 0.4 g Dye donating material ( 3) 1.5g Red-sensitive silver halide emulsion 0.40g Gelatin 1.0g Polyvinylpyrrolidone (K-90) 0.02g DAP-1 0.1g Thermal solvent-1 1.2g 1,10-Diiododecane 0.09g Polyethylene glycol (MW = 2,000) 0.15g Antifoggant-2 0.02g Anti-irradiation dye-2 0.02g Tricresylphosphate 0.4g Hardener-1 0.05g Second layer (intermediate layer) gelatin 0.8g Thermal solvent-1 0.3g Polyvinylpyrrolidone (K -90) 0.08g Reducing agent precursor-1 0.86g Diisodecyl phthalate 0.08g UV absorber-1 0.1g Zinc sulfate 0.4g Hardener-1 0.05g Third layer (green photosensitive layer) benzotriazole silver emulsion 0.4g Dye Donor ( 2) 0.6g Green light-sensitive silver halide emulsion 0.36g Gelatin 1.0g Polyvinylpyrrolidone (K-90) 0.02g DAP-1 0.1g Thermal solvent-1 1.2g 1,10-diiododecane 0.09g Polyethylene glycol (MW = 2,000) 0.15g Antifoggant-2 0.03g Anti-irradiation dye-1 0.03g Tricresyl phosphate 0.3g Hardener-1 0.05g Fourth layer (intermediate layer) gelatin 0.8g Thermal solvent-1 0.3g Polyvinylpyrrolidone (K -90) 0.08g Diisodecyl phthalate 0.08g Yellow filter dye-1 0.4g UV absorber-1 0.1g Zinc sulfate 0.4g Hardener-1 0.05g Fifth layer (blue photosensitive layer) benzotriazole silver emulsion 0.6g Dye Donor (1) 1.3g Blue-sensitive silver halide emulsion 0.61g Gelatin 1.4g Polyvinylpyrrolidone (K-90) 0.03g DAP-1 0.2g Thermal solvent-1 1.4g 1,10-diiododecane 0.09g Polyethylene glycol (MW = 2,000) 0.22g Antifoggant -2 0.03g Tricresyl phosphate 0.3g Hardener-1 0.04g 6th layer (protective layer) Gelatin 0.4g Polyvinylpyrrolidone (K-90) 0.03g Reducing agent precursor-1 0.66g Diisodecyl phthalate 0.04g UV absorption Agent-1 0.2g Zinc sulfate 0.1g Hardener-1 0.05g Silica powder 0.1g Antifoggant-2 0.01g In each layer, surfactant S-1 was used as a coating aid.

In preparation of the heat-developable color light-sensitive material (1), polymer latex dispersions were further added as shown in Tables 2 and 3 to prepare heat-developable color light-sensitive materials (2) to (26).

[0095]

[Chemical 2]

[0096]

[Chemical 3]

[0097]

[Chemical 4]

[0098]

[Chemical 5]

[0099]

[Table 2]

[0100]

[Table 3]

The addition amount is the total amount of the polymer latex solid content of each addition layer and represents the amount per 1 m ² of the heat-developable color light-sensitive material. Each of the obtained samples was subjected to the conditions of 35 ° C. and 60% relative humidity for 4 days. It was preserved and hardened.

[Preparation of dye image receiving material (A)] Thickness 180 μm
A polyvinyl chloride layer containing a compound as described below was coated as an image-receiving layer on the photographic baryter paper support of Example 1 to prepare a dye image-receiving material (A).

Polyvinyl chloride (average degree of polymerization: about 900) 12 g Image stabilizer-1 0.8 g Image stabilizer-2 0.2 g Image stabilizer-3 0.2 g Image stabilizer-4 0.3 g Image stabilizer-5 0.1 g Image Stabilizer-6 0.2g Di- (2-ethylhexyl) phthalate 1.0g Tricresyl phosphate 0.5g

[0104]

[Chemical 6]

Sample N of the obtained heat-developable color light-sensitive material
o. The following items of 1 to No. 26 were evaluated. The evaluation results are shown in Tables 4 and 5.

[Evaluation of Photographic Performance] Obtained Sample Nos. 1 to 1
Twenty-six heat-developable color light-sensitive materials were exposed to white light of 1600 CMS through a step wedge, and heat-developed at 145 ° C. for 70 seconds by superimposing the dye-image-receiving material (A). After thermal development, the light-sensitive material and the image receiving material were peeled off to obtain a transferred image on the image receiving material.

For the obtained dye image, a reflection densitometer P
The density was measured using DA65 [manufactured by Konica Corporation] to obtain the maximum density (Dmax) and the minimum density (Dmin).

Further, the interference filter KL63 (Toshiba Corp.)
Of 1600 CMS, followed by the same heat development treatment, and the resulting yellow image was subjected to density measurement using a reflection densitometer PDA65 to obtain a blue reflection density of 1.0. Calculate the ratio of green reflection density,
The color turbidity was evaluated by using this as a measure of the color turbidity of magenta for the yellow image.

Furthermore, the step wedge is replaced with a sharpness chart wedge, and the interference filter KL54 [Toshiba Corp.
Manufactured by the company] and exposed to green light of 1600 CMS, and then subjected to the same heat development treatment, and the obtained magenta sharpness chart pattern is microdensitometer PDM5
AR [manufactured by Konica Corporation] was used to measure the concentration and 5 line pair
Sharpness was evaluated by the MTF value (%) in mm / mm.

[Evaluation of brittleness of film of heat-developable color light-sensitive material] In a room air-conditioned at a temperature of 25 ° C and a relative humidity of 20%, each of the heat-developable color light-sensitive materials (1) to (26) was rolled by a rolling cutter. It was cut into a size of 10 cm x 10 cm. Table 4 shows the degree of collapse of the film of the photosensitive material at this time.
It evaluated by the evaluation criteria as shown in. Furthermore, temperature 25 ℃,
Similar evaluation was performed in a room air-conditioned at a relative humidity of 60%.

[Evaluation of stagnation stability of coating solution] 500 cc of the coating solution obtained by removing the hardening agent-1 from the coating solution used for preparing the heat-developable color photosensitive materials (1) to (26) was prepared separately,
This was left to stand still for 1 to 5 hours while being kept warm at 40 ° C.
When this coating solution was filtered using a 30 μm mesh filter cloth having a surface area of 20 cm ² , the permeability of the filter cloth decreased and the stagnation time when aggregates were observed on the filter cloth was evaluated as a measure of coating solution stability. went.

[0112]

[Table 4]

[0113]

[Table 5]

[0114]

[Table 6]

[0115]

[Table 7]

[0116]

[Table 8]

[0117]

[Table 9]

[0118]

[Table 10]

From the results shown in Tables 5 to 10, in the heat-developable color light-sensitive material of the present invention, the transferability of the image dye is excellent and the brittleness of the film is excellent, and the deterioration of the sharpness and the color mixture due to the bleeding of the dye occur. It can be seen that it has a small and stable coating property.

Example 2. [Preparation of Dye Image Receiving Material (1)] A dye image receiving material (1) was prepared by coating a dye image receiving layer having the following composition on a 160 μm thick photographic baryta paper.

The addition amount of each material is shown by the coating amount per 1 m ² of the dye image receiving material.

Gelatin 4g Dye mordant -18g Image stabilizer -1 0.8g Image stabilizer -2 0.3g Image stabilizer -4 0.7g Image stabilizer -6 0.5g Polyvinyl chloride latex 10g Hardener -1 0.02g

[0123]

[Chemical 7]

Then, as shown in Tables 11 and 12, the dye was prepared in the same manner as in the preparation of the dye image-receiving material (1) except that the amount of gelatin was adjusted and the polymer latex described in Example 1 was added. Image receiving materials (2) to (24) were produced.

Before use, the dye image-receiving materials (1) to (24) were stored under the conditions of 35 ° C. and 60% relative humidity for 2 days and hardened.

[0126]

[Table 11]

[0127]

[Table 12]

[Evaluation of Dye Image Receiving Material] The heat developable color light-sensitive materials (1) and (8) prepared in Example 1 were exposed to the sharp chart wedge and the green light of the interference filter KL54 to obtain the dye image receiving material. Overlay with (1) to (24)
Thermal development was performed at 145 ° C. for 75 seconds. After the developed sample was allowed to cool to room temperature, the light-sensitive material and the image-receiving material were peeled off, and the peelability was evaluated. For the magenta-colored sharpness chart pattern obtained after peeling, a microdensitometer P
DM5AR [manufactured by Konica Corporation] was used to measure the concentration and Dmi
The sharpness was evaluated by n, Dmax and MTF value (%) at 5 line pair / mm.

The peelability was evaluated on the basis of the following criteria by treating 10 sheets in succession.

◯: It can be easily peeled, and the photosensitive layer is not attached to the image-receiving layer at the edge of the light-sensitive material. Δ: Peeling can be performed relatively easily, but smooth peeling can be performed inside. None, or a part of the photosensitive layer adhered to the image receiving layer at the end The evaluation results are shown in Tables 13 to 16.

[0131]

[Table 13]

[0132]

[Table 14]

[0133]

[Table 15]

[0134]

[Table 16]

From the above results, when the polymer latex emulsion-polymerized in the hydrophilic binder of the present invention is used as the dye image receiving material, it is possible to improve the sharpness without deteriorating the releasability. Recognize.

[0136]

INDUSTRIAL APPLICABILITY According to the present invention, a heat-developable silver halide color photograph which has a high transferability of an image dye, has improved brittleness of a film, has less deterioration of sharpness due to dye bleeding, and has a small color mixture and enables stable coating. It has been possible to provide a dye image-receiving material which is excellent in peelability from a light-sensitive material and a heat-developable light-sensitive material and which is capable of obtaining an image having excellent sharpness.

Claims (2)

[Claims] 1. A support containing at least a photosensitive silver halide, a binder, a reducing agent, a dye-providing substance that forms or releases a diffusible dye during thermal development, and a polymer latex emulsion-polymerized in a hydrophilic colloid. A heat-developable silver halide color photographic light-sensitive material. 2. A dye image receiving material capable of receiving a dye to be diffusion-transferred from a heat developable silver halide color photographic light-sensitive material containing at least a dye image receiving material and a polymer latex emulsion-polymerized in a hydrophilic colloid on a support. .