JP3023735B2 - Manufacturing method of photographic material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a photographic material, and more particularly to a method for producing a photographic material having less coating unevenness even when produced using a coating solution having a low gelatin concentration.

[0002]

BACKGROUND OF THE INVENTION Silver halide photographic materials generally contain a hydrophilic binder, photosensitive silver halide grains, and various additives on a support. Generally, in a multilayer color light-sensitive material, a plurality of layers are provided on a support. Therefore, as the layer configuration becomes more complicated, the thickness of the layer made of the hydrophilic binder tends to increase,
In this case, the sharpness, the developing property and the desilvering property, the properties of the film, and the like are likely to decrease.

In a diffusion transfer type photosensitive material that emits a diffusible dye, an increase in film thickness causes undesired problems such as an increase in development time and a decrease in sharpness due to an increase in diffusion distance.

[0004] Therefore, in a multilayer color light-sensitive material, it is a major problem in designing a light-sensitive material, particularly, to reduce the amount of a hydrophilic binder used per layer, usually used gelatin.

However, a problem often arises with respect to the decrease in the amount of gelatin in relation to the viscosity and the set temperature required for a coating solution for stable coating. For example, when the amount of gelatin is reduced, the viscosity of the coating solution is extremely small compared to the viscosity of the coating solution required for stable coating due to the decrease in the gelatin concentration in the coating solution. After coating, the temperature to be set before drying is extremely lowered, so that the setting property is deteriorated, and drying unevenness in the subsequent drying step is likely to occur.

Conventionally, various improvement means have been used to solve such problems.

More specifically, a wide range of thickening agents such as starch, dextran and dextran sulfate, carboxymethylcellulose and cellulose sulfate, and acrylamide, alginic acid, sodium acrylate, polyvinylpyrrolidone and styrene-maleic acid copolymer are contained in the coating solution. Agents have been used.

[0008] However, although such conventional thickeners can certainly provide a certain degree of thickening effect, the thickening effect decreases in the presence of a large amount of polyvalent metal ions,
In order to have a sufficient thickening effect, it is necessary to add a considerable amount of a thickening agent, and therefore, problems such as the coating properties after coating and drying are liable to greatly decrease are likely to occur.

In addition, most of the thickeners used hitherto cannot increase the setting temperature of the coating solution itself, so that the improvement of the coating property is not possible for the coating solution having a relatively low gelatin concentration. Was not very effective.

In order to reduce such a problem, Japanese Patent Laid-Open No.
No. 221736 discloses the use of extracellularly formed polysaccharides in microbial fermentation of glucose, maltose, sucrose or xylose. And one price, two
It is described that a valent and trivalent cation can provide a thickening effect and a setting temperature increasing effect. Gellan gum is described as a particularly preferred polysaccharide. Such gellan gum is actually on the market, for example, commercially available from Kelco, USA under the trade name "Kelcogel".

However, this polysaccharide has a drawback that it requires a dissolution temperature as high as about 90 ° C. or higher, and the adhesiveness to a hydrophilic binder mainly composed of another gelatin is easily deteriorated.

Further, as described in the above specification, the polysaccharide is not only a polyvalent metal ion having two or more valences but also a monovalent cation such as Li ⁺ , Na ⁺ , and K ⁺ which is very common. Has the property that the set temperature is also governed by the anionic surfactants, water-soluble dyes, and other anionic additives usually used when preparing coating solutions for photographic materials. The set temperature is also significantly affected by the cations present, which is a major disadvantage in the design of photographic materials and is an undesirable disadvantage.

JP-A-3-242646 discloses that a natural high molecular polysaccharide derived from red algae is added to a light-sensitive element or a dye-receiving element of a diffusion transfer photographic material to prevent color transfer, improve curling,
It describes improving storage stability and improving the drying load during manufacture. However, the specification does not disclose the effect of thickening the coating solution or increasing the set temperature of the aqueous gelatin solution with a natural high molecular polysaccharide derived from red algae.

JP-A-3-296736 discloses a method for applying a coating solution containing a natural high molecular polysaccharide derived from red algae. There is described a technique of improving the solubility in water by using a specific hydrophilic organic solvent in combination with water and improving the coatability. However, the above specification does not disclose a thickening effect of a coating solution or a setting temperature increasing effect of a natural high molecular polysaccharide derived from red algae.

JP-A No. 4-3055 describes that a high molecular weight polysaccharide derived from red algae is added to a photothermographic material containing a reducible dye-donating compound to obtain a high maximum concentration. I have. However, the specification does not disclose the effect of thickening the coating liquid or the effect of improving the setting temperature by the natural high molecular polysaccharide derived from red algae.

Japanese Patent Application Laid-Open No. 4-116544 discloses a method for producing a coating solution containing a water-soluble polymer such as gelatin which changes sol-gel, which is swollen in advance with water of 5 ° C. or more and 35 ° C. or less and heated. A method for producing a coating solution to be dissolved is described. Further, a natural high molecular polysaccharide derived from red algae is contained as a water-soluble polymer.

According to this production method, it is possible to improve the coating property by reducing the generation of the coating liquid during the preparation of the coating liquid, preventing the generation of a non-uniform gel, and improving the coating property.

However, there is no description in this specification about the effect of increasing the setting temperature or the effect of increasing the setting temperature of the gelatin coating solution by the natural high molecular polysaccharide derived from red algae.

JP-A-4-139447 describes a dye-fixing element containing a natural high-molecular polysaccharide derived from red algae and having a specific layer structure. In this specification, there is no description about the thickening effect of the gelatin-containing coating solution by the natural high molecular polysaccharide derived from red algae or the setting temperature.

JP-A-60-170846 describes that a coating solution containing gelatin, a polysaccharide and an anionic surfactant having a specific structure is used for an image receiving material for silver salt diffusion transfer. As the cation component corresponding to the anionic group of the surfactant, an alkali metal, an alkaline earth metal and the like are described. Many polysaccharides are described, among which carrageenan, a natural high molecular polysaccharide derived from red algae, is described.

However, in the examples, there was no use of a natural high molecular polysaccharide derived from red algae, and there was no effect on the thickening effect of the coating solution or the setting temperature increasing effect by the combination of the specific polysaccharide and the specific cation. Not listed.

[0022]

The object of the present invention is to solve the above-mentioned problems by the first aspect of the present invention.
The purpose of this method is to increase the set temperature of a coating solution containing gelatin, and use a coating solution having good coating solution properties without an extreme increase in the viscosity of the coating solution to form a thin film layer composed of a small amount of gelatin. To provide a silver halide photographic light-sensitive material formed with

It is a second object of the present invention to provide a silver halide photographic light-sensitive material which provides good adhesion between different hydrophilic binder layers.

[0024]

The object of the present invention is to provide a method for producing a photographic material in which a coating solution containing a natural high molecular polysaccharide derived from red algae is coated on a support. The coating solution containing the molecular polysaccharide is K ⁺ , Ca ²⁺ ,
This is achieved by a method for producing a photographic material, wherein the total amount of cations selected from Mg ²⁺ , Zn ²⁺ , Co ³⁺ , and Ni ²⁺ is 10 mmol or more per liter of a coating solution.

In a preferred aspect of the present invention, the natural polymer polysaccharide derived from red algae is a natural polymer polysaccharide selected from kappa carrageenan, iota carrageenan, lambda carrageenan, and furceleran. cations contained per 10 mmol or ^{more, K +, Ca 2+, Mg} 2+, wherein the coating liquid contains that a cation selected from ^{Zn 2+ K +, Ca 2+,} Mg 2+, Zn
The total amount of cations selected from ^{2+ is 20} to 200 mmol per liter of the coating solution. The coating solution containing the natural high molecular polysaccharide derived from the red algae further contains gelatin, and the gelatin concentration is 1%. ~
6% by weight The weight ratio of the natural polymer polysaccharide derived from red algae to gelatin in the coating liquid containing the natural polymer polysaccharide derived from the red algae is in the range of 0.02 to 0.4. Can be

Hereinafter, the present invention will be described specifically.

The natural high molecular polysaccharides derived from red algae used in the present invention are all polysaccharides extracted and purified from red algae, and are described in detail in "Food Industry" Vol. 31 (1988) 21. Page. Specific examples of natural high molecular polysaccharides derived from red algae include agar, κ-carrageenan, λ-carrageenan, ι-carrageenan, and phaceleran.In the present invention, particularly, κ-carrageenan , Λ-carrageenan, and ι-carrageenan are preferred. Among them, iota-carrageenan and κ-carrageenan are particularly preferred, and most preferably, iota-carrageenan.

The above natural macromolecular polysaccharides derived from red algae may be used alone in a single coating solution or in combination of two or more. Especially when using κ-carrageenan,
It is preferable to use λ-carrageenan from the viewpoint of the film properties of the photographic material.

In this case, the ratio of κ-carrageenan to λ-carrageenan is in the range of 2: 8 to 9: 1 by weight.
Preferably 4: 6 to 8: 2, particularly preferably 5: 5
The range is 7: 3.

The concentration of the natural high molecular polysaccharide derived from red algae in the coating solution is generally from 0.02 to 5%, preferably from 0.02 to 5%.
It is 0.05 to 2%, particularly preferably 0.1 to 1%.

The preferred range varies depending on the type and concentration of gelatin and other water-soluble polymers in the coating solution used, and is not unique, but the coating solution is substantially derived from gelatin and red algae. When only the natural high molecular polysaccharide is used as the binder, the range is preferably used when the gelatin concentration is usually 1 to 6%.

When the gelatin concentration is higher than this, a lower concentration of natural high molecular weight polysaccharide derived from red algae is used.

When the coating solution containing the natural high molecular weight polysaccharide derived from red algae contains gelatin, the weight ratio of the natural high molecular weight polysaccharide derived from red algae to gelatin is as follows.
It is preferably in the range of 0.02 to 0.4.

The coating solution containing the natural high molecular polysaccharide derived from red algae of the present invention preferably further contains gelatin. If the concentration of gelatin is not using a natural high molecular polysaccharide derived from red algae, generally 2 to 10% is used from the viscosity of the coating solution and the setting property of the coating solution.
Since the set temperature rises, it can be used stably even at a lower gelatin concentration. Specifically, a coating solution of about 1% can be used. The upper limit of the gelatin concentration is not particularly limited, but is generally determined by the viscosity of the coating solution, and is usually 8% or less, preferably 6% or less.

The above-mentioned gelatin may be basically any kind as long as it is usually used for photography.
Alkali-treated gelatin or acid-treated gelatin can be used. Further, a so-called derivative gelatin in which amino groups of gelatin are completely or partially blocked can also be used. In this case, all of the gelatin contained in the coating solution containing the natural high molecular polysaccharide derived from red algae may be derivative gelatin, or a part thereof may be derivative gelatin.

Gelatin has a weight average molecular weight of about 10,000.
Those having a size of from 00 to 200,000 are preferably used. In particular, those having a number average molecular weight of 500,000 or more are particularly preferably 10% by weight or less of the whole gelatin.

As the derivative gelatin, a derivative gelatin in which the amino group of the gelatin is blocked is preferable, and examples thereof include isocyanate addition, acylation, and deamination. Preferred derivative gelatin is gelatin obtained by adding gelatin and phenyl isocyanate, alkyl isocyanate, or the like, or gelatin obtained by reacting an acid anhydride such as phthalic anhydride or an acid chloride such as phthalic chloride. The blocking ratio of the amino group of gelatin is 70% or more of the amino group, preferably 80% or more, particularly preferably 90% or more.
% Or more.

The above-mentioned coating solution containing a natural high molecular polysaccharide derived from red algae can contain other water-soluble polymers in addition to gelatin. Specifically, cellulose, cellulose derivatives such as carboxymethyl cellulose and cellulose sulfate, starch, dextrin, alginic acid,
Natural polymers such as gum arabic and pullulan, polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene glycol, water-soluble polyvinyl butyral, water-soluble polyester, polyacrylic acid, and vinyl monomers having a carboxyl group or a sulfonic acid group described in JP-A-62-245260 Examples thereof include homopolymers and synthetic polymers such as copolymers having these vinyl monomers as repeating units, and these may be used alone or in combination of two or more.

Particularly preferred water-soluble polymers are gelatin, gelatin derivatives, polyvinyl pyrrolidone, polyvinyl alcohol, polyethylene glycol, water-soluble polyvinyl butyral, and the above-mentioned vinyl monomers having a carboxyl group or a sulfonic acid group alone or copolymer.

Further, as the water-soluble polymer, polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol, water-soluble polyvinyl butyral, and the above-mentioned vinyl monomer having a carboxyl group or a sulfonic acid group alone or copolymer are not less than 5% with respect to water at room temperature. Those having solubility are preferable, and those having a number average molecular weight of preferably about 6,000 to 500,000 are used.

In the present invention, the coating solution containing a natural high molecular polysaccharide derived from red algae is K ⁺ , Ca ²⁺ , M
It is necessary that the total amount of cations selected from g ²⁺ , Zn ²⁺ , Co ³⁺ , and Ni ²⁺ be 10 mmol or more per liter of the coating solution.

When such a cation is present in the coating solution in an amount less than the amount of the present invention, it is necessary to increase the concentration of the natural high molecular weight polysaccharide derived from red algae in order to achieve a sufficient rise in set temperature. And thus causes a significant increase in the viscosity of the coating solution. As a result, it becomes difficult to obtain good coating properties.

The presence of such a cation may increase the set temperature of the natural polysaccharide derived from red algae, but may decrease the viscosity of the coating solution, and may increase the cation concentration and the natural polysaccharide derived from the red algae. The concentration is appropriately optimized from this viewpoint.

When the concentration of the above cation is below the range of the present invention, it is necessary to add an unnecessarily large amount of natural high molecular weight polysaccharide derived from red algae to gelatin. The hardened gelatin film tends to be insufficient. In particular, K ⁺ , Ca ²⁺ ,
The sum of the cations selected from Mg ²⁺ and Zn ²⁺ is the coating solution 1
When the amount is 20 to 200 mmol per liter, the photographic performance is not adversely affected, and furthermore, the use of the minimum necessary natural polymer polysaccharide derived from red algae does not increase the viscosity of the extra coating solution. The set temperature can be greatly increased.

Next, the photographic material of the present invention will be described.
The present invention can be applied to any photographic material having a hydrophilic binder.

More specifically, a black-and-white photographic light-sensitive material or a color photographic light-sensitive material containing silver halide, a light-sensitive element or a dye-receiving element of a silver halide diffusion transfer material, a heat-developable silver halide photographic light-sensitive material, Dye image-receiving materials for heat-developable photographic materials, and photographic materials using various silver halides, such as photosensitive elements and image-receiving materials for silver salt diffusion transfer photographic materials, are preferably used. In particular, heat-developable silver halide photographic light-sensitive materials that are not wet-processed and their dye-receiving materials are
It is particularly preferable because it is necessary to reduce the amount of the hydrophilic binder in order to increase the diffusibility of the dye.

The present invention also relates to a photosensitive photographic material containing no silver halide other than the above-mentioned silver halide photographic material,
Further, the present invention can be applied to a recording material of a sublimation type thermal transfer material, an image receiving element, and the like as long as the material contains a hydrophilic binder.

The photographic material of the present invention is usually obtained by coating a coating solution containing a natural high molecular polysaccharide derived from red algae on a support. It may be one coated with a plurality of contained coating liquids. Further, it may be coated on a support together with a coating solution containing no natural high molecular polysaccharide derived from red algae. here,
Coating on a support does not only mean that a coating solution containing a natural high molecular polysaccharide derived from red algae is applied on the support without interposing any other layer between them. Layer (for example, a hydrophilic // hydrophobic subbing layer containing no natural high molecular polysaccharide derived from red algae, a photosensitive layer containing no natural high molecular polysaccharide derived from red algae, etc.)
May be applied.

The layer containing the natural polysaccharide derived from the red algae may be a photosensitive layer, a non-photosensitive layer (for example, an undercoat layer,
Intermediate layer, protective layer, etc.), but can also be used as a so-called back layer opposite to the photographic layer.

Next, a method of preparing a coating solution containing a natural high molecular polysaccharide derived from red algae of the present invention and a coating solution used for coating each of the other layers on a support will be described. .

The procedure for preparing the above coating solution is as follows: gelatin,
A water-soluble polymer, a water-soluble polymer component such as a natural high-molecular polysaccharide derived from red algae are all mixed, and the mixture is swollen with water at room temperature as usual, and dissolved by heating (for example, 60 to 70 ° C). Is preferable, and a method in which necessary additives are added before, during or after cooling to the temperature of the coating solution and coating is performed, or the above gelatin, a natural high molecular polysaccharide derived from red algae, and if necessary, There is a method in which each aqueous solution of the water-soluble polymer to be used is heated and dissolved in advance, and these are mixed. The viscosity of the coating liquid is preferably usually 40
At 4 to 80 centipoise (cp), more preferably 6
~ 50cp.

When a plurality of coating solutions including the above-mentioned coating solutions are coated on a support of a silver halide photographic light-sensitive material, a conventionally known coating method can be applied, such as curtain coating, air knife coating, dip coating, or the like. Reverse roll coating, bead coating, extrusion coating and the like can be applied.

In the application, all the constituent layers may be simultaneously applied in multiple layers simultaneously, or may be applied in two or more divided applications. After coating on the support, the coating solution is gelled and then heated and dried as needed.

As the support of the photographic light-sensitive material of the present invention,
A paper support, a transparent or reflective plastic support such as polypropylene, polyethylene terephthalate, or cellulose acetate can be used.

Particularly, in the case of a silver halide photographic light-sensitive material comprising a paper support, a hydrophobic polymer layer such as polyethylene, polypropylene, polystyrene, polyphenylene ether or the like having a thickness of 2 μm or more is provided between the paper support and the hydrophilic binder. It is preferable to provide such an arrangement because it is effective in preventing chips when cutting with a cutter or the like.

At this time, it is preferable that the surface of the support and / or the surface of the hydrophobic polymer layer be subjected to activation treatment such as corona discharge.

Hereinafter, other constitutions of the photographic material of the present invention will be described by taking as an example a case where the present invention is a silver halide photographic material.

When the present invention is applied to a silver halide photographic light-sensitive material, conventionally known photosensitive silver halides can be used, for example, silver chloride, silver bromide, silver iodobromide, and the like. Silver chlorobromide and silver chloroiodobromide can be used.

The silver halide may have a uniform composition from the inside to the surface of the grain, or may have a continuous or stepwise changing composition between the inside and the surface.

The shape of the silver halide may be one having a distinct crystal habit such as tabular, cubic, spherical, octahedral, dodecahedral, or tetrahedral, or the like.

Further, for example, US Pat. No. 2,592,250,
3,220,613, 3,271,257, 3,317,322, 3,51
1,622, 3,531,291, 3,447,927, 3,761,266
Nos. 3,703,584, 3,736,140, 3,761,276,
Internal latent image type silver halide emulsions described in JP-A-52-15661 and JP-A-55-127549 can also be used.

At the grain formation stage of the photosensitive silver halide, metal ion species such as iridium, gold, rhodium, iron and lead can be added in a suitable salt form.

The particle size of the photosensitive silver halide emulsion is about 0.5.
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 later, and a part of the organic silver salt is subjected to the photosensitive halide. It can also be formed by converting to 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, etc.). And chemical sensitization can be performed in the presence of a nitrogen-containing heterocyclic compound or a mercapto group-containing heterocyclic compound.

Further, the photosensitive silver halide can be subjected to spectral sensitization to blue, green, red, and near-infrared light with 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 1 mol of silver halide.
It can be added at the time of forming silver halide grains, at the time of removing soluble salts, before the start of chemical sensitization, at the time of chemical sensitization, or after the end of chemical sensitization.

The hydrophilic binder layer of the silver halide photographic light-sensitive material is preferably hardened with a known inorganic or organic photographic hardener. Preferred hardeners are vinyl sulfone hardeners and active halogen releasing hardeners.

The silver halide photographic light-sensitive material of the present invention is applicable to black-and-white or color photographic light-sensitive materials. It can also be applied to wet processing (color negative film, color reversal film, color photographic paper, direct reversal color photographic paper, black and white photographic paper, black and white film, etc.), silver salt diffusion transfer method, color diffusion transfer method, It can be applied to any of thermal development (black and white, color).

When the silver halide photographic light-sensitive material of the present invention is applied to a color photographic light-sensitive material, two or four equivalents of known photographic color couplers are used. Specifically, acylamide-type active methylene compounds, pyrazolone compounds, pyrazoloazole compounds, naphthol compounds, and phenol compounds are used. These couplers are usually added by emulsifying and dispersing them in a hydrophilic binder such as gelatin together with a high boiling point organic solvent, a hydroquinone derivative as an anti-stain agent used as required, and an image preservability improver.

Various photographic additives to be added to the silver halide photographic light-sensitive material of the present invention are described in, for example, Research Disclosure, No. 17643, pp. 23-8.

Next, a photothermographic material having a particularly great effect of the present invention will be described.

When the light-sensitive material of the present invention is a heat-developable light-sensitive material, the dye-providing substance to be used may be, for example, that described in
61-61157, 61-61158, 62-44738, 62-12985
No. 0, No. 62-129851, No. 62-129852, No. 62-169158,
Couplers that form diffusible dyes described in Japanese Patent Application No. 1-200859, such as leuco dyes described in JP-A-61-88254, azo dyes described in U.S. Pat.No. 4,235,957, or U.S. Pat. No. 4,439,513, JP-A-59-60434
Nos. 59-65839, 59-71046, 59-87450, 5
9-123837, 59-124329, 59-165054, 59-180
No. 548 and No. 59-165055. Particularly preferred are compounds that form a diffusible dye by a coupling reaction,
For example, it is represented by the general formula (A) in the lower left column, second line, page 9 of JP-A-2-863.

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

Examples of the positive dye-providing substance include:
JP-A-59-55430, JP-A-59-165054, JP-A-59-154445,
59-116655, 59-124327, 59-152440, 59-18
There are compounds described in respective publications such as No. 0548 and No. 64-13546.

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

The photothermographic material of the present invention comprises a dye-providing substance in a microcapsule together with a polymerizable compound described in, for example, JP-A-2-93753 and JP-A-2-308162. By heat development, a polymerization reaction of the polymerizable compound is caused in an image-like or reverse-image-like manner, the microcapsules are hardened, and the diffusivity of the dye-donor substance into the image receiving layer is changed to form an image. It can also be applied to developed photosensitive materials.

In the photothermographic material of the present invention, known organic silver salts can be used for the purpose of increasing sensitivity and improving developability. Organic silver salts that can be used in the present invention include, for example, JP-B-43-4921, JP-A-49-52626,
2-141222, 53-36224, 53-37626, 53-36224
Nos. 53-37610 and U.S. Pat.
Nos. 3,794,496 and 4,105,451, etc., silver salts of long-chain aliphatic carboxylic acids and silver salts of carboxylic acids having a heterocyclic ring (for example, silver behenate, α- (1-phenyltetrazole) Thio) silver acetate, etc.), JP-B-44-26582,
No. 45-12700, No. 45-18416, No. 45-22815, JP 52
-137321, 58-118638, 58-118639, U.S. Patent
Examples thereof include silver salts of compounds having an imino group described in JP-A Nos. 4,123,274 and acetylene silver described in JP-A-61-249044.

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

The above-mentioned organic silver salts can be used alone or in combination of two or more. These are prepared in an aqueous solution of hydrophilic colloid such as gelatin, and are used as they are after removing soluble salts. In addition, 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 by a developing mechanism and a dye formation / release mechanism. The reducing agent referred to herein includes a reducing agent precursor that releases the reducing agent during thermal development.

Examples of the reducing agent which can be used in the present invention include, for example, US Pat. Nos. 3,351,286 and 3,761,270,
3,764,328, 3,342,599, 3,719,492, Research Disclosure 12,146, 15,10
No. 8, No. 15,127, and JP-A-56-27132, No. 53-135628
No. 57-79035, p-phenylenediamine and p-aminophenol developing agents, phosphoramidophenol developing agents, sulfonamidoaniline developing agents, and hydrazone developing agents, phenols, sulfone Amidophenols, polyhydroxybenzenes,
There are naphthols, hydroxybisnaphthyls, methylenebisphenols, ascorbic acids, 1-aryl-3-pyrazolidones, hydrazones, and precursors of the above various reducing agents. Further, the dye-providing substance can also serve as a reducing agent.

Particularly preferred reducing agents are described in JP-A-56-146133.
And N- (pN ', N'-dialkylamino) phenylsulfamate and derivatives thereof described in JP-A No. 62-227141, specifically, page 7, lower left column, line 6 in JP-A No. 2-863. To page 8, the lower right column.

In the photothermographic material of the present invention, a thermal solvent can be used for the purpose of accelerating the transfer of a dye and other purposes. The thermal solvent is a compound which is liquefied during thermal development and has an action of promoting thermal development and thermal transfer of a dye, and is preferably in a solid state at normal temperature.

Examples of the thermal solvent which can be used in the present invention include, for example, US Pat. Nos. 3,347,675, 3,667,959,
438,776, 3,666,477, Research Disclosure No. 17,643, JP-A-51-19525, 53-24829,
53-60223, 58-118640, 58-198038, 59-229
556, 59-68730, 59-84236, 60-191251,
No. 60-232547, No. 60-14241, No. 61-52643, No. 62-78
No. 554, No. 62-42153, No. 62-44737, No. 63-53548,
No. 63-161446, JP-A No. 1-224751, No. 2-863, No. 2-12
Compounds described in each gazette such as 0739 and 2-123354 are exemplified.

Specifically, urea derivatives (urea, dimethylurea, phenylurea, etc.), amide derivatives (eg, acetamido, stearylamide, p-toluamide, p-propanoyloxyethoxybenzamide, etc.), and sulfonamide derivatives (eg, P-toluenesulfonamide and the like, and polyhydric alcohols (for example, 1,6 hexanediol, pentaerythritol, polyethylene glycol and the like) are preferably used. In particular, the effect of the present invention is great when the thermal solvent is contained in the form of solid fine particles.

The above-mentioned thermal solvent can be added to any layer such as a light-sensitive silver halide emulsion layer, an intermediate layer, a protective layer, or an image receiving layer of an image receiving material. 10% to 500% by weight, more preferably 20% by weight
~ 200% by weight.

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

As the development accelerator, for example, JP-A-59-177
No. 550, No. 59-111636, No. 59-124333, No. 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 can also use the development accelerator-releasing compound, or metal ions having an electronegativity of 4 or more described in JP-A-1-104645.

As the antifoggant, for example, US Pat.
No. 3,645,739, higher fatty acids,
No. 11113, mercury salt described in JP-A-51-47419.
-Halide, U.S. Pat.No. 3,700,457, JP-A-51-50
No. 725, Japanese Patent Application Nos. 1-69994 and 1-104271, mercapto compound-releasing compounds described, arylsulfonic acids described in JP-A-49-125016, lithium carboxylate described in JP-A-51-47419, UK Patent No. 1,455,271 and JP-A-50-1010
Oxidizing agents described in No. 19, sulfinic acids and thiosulfonic acids described in 53-19825, thiouracils described in 51-3,223, sulfur described in 51-26019, 51-42529, 51-81124.
And disulfides and polysulfides described in JP-A-55-93149, rosin or diterpenes described in JP-A-51-57435, polymer acids having a carboxyl group or a sulfonic acid group described in JP-A-51-104338, and US Pat. No. 4,138,265. Thiazolythion, JP-A-54-51821, JP-A-55-142,331
No., triazoles described in U.S. Pat.No.4,137,079, thiosulfinic acid esters described in JP-A-55-140883,
JP-A-59-46641, JP-A-59-57233, di- or tri-halides described in JP-A-59-57234, thiol compounds described in JP-A-59-111636, JP-A-60-198540 and JP-A-60-1985- Hydroquinone derivatives described in 227255, antifoggants having a hydrophilic group described in JP-A-62-78554, polymer antifoggants described in JP-A-62-121452, ballasts described in JP-A-62-123456 Antifoggants having a group, and colorless couplers described in JP-A-1-61239.

Examples of the base precursor include those described in JP-A-56-130745, JP-A-59-157637, JP-A-59-166943 and JP-A-59-18.
0537, 59-174830, 59-195237, 62-108249
No. 62-174745, No. 62-187847, No. 63-97942, No.
63-96159, JP-A-1-68746 and the like, and the compounds or base releasing technologies described in each publication.

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, fluorescent brighteners, It may contain 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 color tone adjusting agent and the like. These are described, for example, in RD (Research Disclosure) Nos. 17029 and 29,963,
These are described in JP-A-62-135825 and JP-A-64-13546.

In particular, halogen-substituted heterocyclic compounds described in JP-A-63-144350, compounds having a specific rate of reaction with anisidine described in JP-A-3-223852, especially alkyl halides Kind, and furthermore,
It is particularly preferable to include a substance capable of absorbing contaminants described in JP-A-2-44356 in the photosensitive layer.

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

As the support used in the photothermographic material of the present invention, for example, the supports described in JP-A No. 2-863, page 12, upper left column, line 15 to upper right column, first line can be used.
Preferably, a polyethylene terephthalate support or a paper support such as cast coated paper or baryta paper is used.

The heat-developable light-sensitive material of the present invention preferably contains (a) a photosensitive silver halide emulsion, (b) a reducing agent, (c) a binder, and further contains (d) organic silver. When it is a color light-sensitive material, it further contains (e) a dye-providing substance.
These may be contained in a single photographic component layer, or may be added separately in two or more layers.

Specifically, the components (a), (b), (c), and (d) are added to one layer, and (e) is added to a layer adjacent thereto, or ( It is also possible to add a), (c), (d) and (e) to a single layer and (b) to another layer.

Further, the photosensitive layer having substantially the same color sensitivity can be composed of two or more photosensitive layers.
Each may be a low-sensitivity layer and a high-sensitivity layer.

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 a dye having a different hue is formed in each photosensitive layer by thermal development. Or released. in this case,
Generally, the yellow dye (Y) is added to the blue photosensitive layer (B).
However, the magenta dye (M) is combined with the green photosensitive layer (G), and the cyan dye (C) is combined with the red photosensitive layer (R). However, the present invention is not limited thereto, and any combination may be used. It is possible. Specifically, (BC)-(GM)-(R
-Y), (infrared-sensitive -C)-(GY)-(RM)
Are also possible.

The layer structure of each layer is arbitrary, and R, G, B, R, G and B infrared rays, and G
Layer arrangements such as infrared are possible.

The photothermographic material of the present invention can optionally have 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, in addition to the photosensitive layer. .

When the photothermographic material of the present invention is of a transfer type, an image receiving material is preferably used. The image receiving material is
It is composed of a support and an image receiving layer having a dye receiving ability provided thereon. The support itself can also serve as an image receiving layer having a dye receiving ability.

The image-receiving layer is roughly classified into a case where the binder constituting the image-receiving layer itself has a dye-receiving ability, and a case where a mordant capable of receiving a dye is contained in the binder.

When the binder has a dye-accepting ability, the substance preferably used has a glass transition temperature of about 40 ° C. or higher,
It is preferably formed of a polymer having a temperature of about 250 ° C. or lower. Specifically, “Polymer Handbook Second Edition” (edited by Joy Brandrup, E.H. (J. Brandrup, E.
H. Immergut) Synthetic polymers having a glass transition temperature of about 40 ° C. or higher described in John Wiley & Sons｝ are useful, and generally, the molecular weight of the polymer is 2,000 to 2
About 00,000 is useful. These polymers may be used alone or in combination of two or more, or may be copolymerizable polymers having two or more types of repeating units.

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

In the image receiving material in which the image receiving layer contains a mordant in a binder, a polymer containing a tertiary amine or a quaternary ammonium salt is preferably used as the mordant. For example, US Pat. No. 3,709,690 and US Pat. JP 6
And the compounds described in JP-A No. 4-13546. Also,
As a binder used to hold these mordants, for example, a hydrophilic binder such as gelatin or polyvinyl alcohol is preferably used.

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

The image receiving material of the present invention may have a single image receiving layer provided on a support, or may have a plurality of constituent layers coated thereon. It may be an image receiving layer, or only a part of the constituent layers may be an 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, and is described in JP-A-2-863, page 14, lower left column. 1
The support described in line 5 to line 8 in the lower right column,
It can be used by selecting from a reflective support having seed diffuse reflection properties.

The photothermographic material of the present invention is disclosed in RD (Research Disclosure) No. 15,108, JP-A-57-198458.
Nos. 57-207250, 61-80148, etc., so-called mono-sheet type photothermographic materials in which the photosensitive layer and the image receiving layer are preliminarily laminated on the same support. .

Various known additives can be added to the image receiving member of the present invention. Such additives include, for example, antifouling agents, ultraviolet absorbers, fluorescent whitening agents, image stabilizers, development accelerators, antifoggants, pH regulators (acid and acid precursors, base precursors, etc.), heat Examples thereof include solvents, organic fluorine compounds, oil droplets, surfactants, hardeners, matting agents, and various metal ions.

The natural high molecular polysaccharide derived from red algae of the present invention can be used in any layer of the hydrophilic binder-containing layer of the photothermographic material and the dye image-receiving material.

[0113]

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

Example 1 The present invention will be described below with reference to examples, but embodiments of the present invention are not limited thereto.

A coating solution was prepared as follows to prepare a multilayer silver halide color photographic light-sensitive material 1 having the constitution shown in Table 1.

First Layer Coating Solution Yellow coupler (Y-1) 26.7 g, dye image stabilizer (ST-1) 10.0 g, dye image stabilizer (ST-2) 6.
60 ml of ethyl acetate was added to and dissolved in 67 g, 0.67 g of the additive (HQ-1) and 6.67 g of the high boiling point organic solvent (DNP), and this solution was dissolved in 6% containing 7 ml of a 20% surfactant (SU-1).
A 220 μl aqueous gelatin solution was emulsified and dispersed using an ultrasonic homogenizer to prepare a yellow coupler dispersion. This dispersion was mixed with a blue-sensitive silver halide emulsion (containing 8.68 g of silver) prepared under the following conditions to prepare a first layer coating solution.

The coating liquids for the second to seventh layers were prepared in the same manner as the coating liquid for the first layer.

Further, as a coating aid, a surfactant (S
U-2) and (ST-3) were added to adjust the surface tension.

Tables 1 and 2 show the gelatin concentrations of the coating solutions of the first to seventh layers and the wet film thickness (μm) at the time of coating.

[0120]

[Table 1]

[0121]

[Table 2]

[0122]

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[0123]

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[0124]

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[0125]

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[0126]

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(Method for Preparing Blue-Sensitive Silver Halide Emulsion) 40
(A) in 1000 ml of a 2% aqueous gelatin solution kept at
Solution) and (solution B) were added simultaneously over 30 minutes while controlling pAg = 6.5 and pH = 3.0, and the following (solution C) and (solution D) were further controlled while controlling pAg = 7.3 and pH = 5.5. Co-addition took 180 minutes. At this time, the control of pAg is described in JP-A-59-454.
PH was controlled using an aqueous solution of sulfuric acid or sodium hydroxide.

(Solution A) Sodium chloride 3.42 g Potassium bromide 0.03 g Water was added to 200 ml (Solution B) Silver nitrate 10 g Water was added to 200 ml (Solution C) Sodium chloride 102.7 g Potassium bromide 1.0 g Water was added to 600 ml (D solution) 300 g of silver nitrate was added and 600 ml of water was added. After completion of the addition, desalting was performed using a 5% aqueous solution of Demol N and 20% aqueous solution of magnesium sulfate manufactured by Kao Atlas Co., Ltd. A monodispersed cubic emulsion EMP-1 having a diameter of 0.85 μm, a coefficient of variation (σ / r) = 0.07, and a silver chloride content of 99.5 mol% was obtained.

The emulsion EMP-1 was chemically ripened at 50 ° C. for 90 minutes using the following compound to obtain a blue-sensitive silver halide emulsion (Em-B).

Sodium thiosulfate 0.8 mg / mol AgX chloroauric acid 0.5 mg / mol AgX stabilizer STAB-1 6 × 10 ^-4 mol / mol AgX sensitizing dye BS-1 4 × 10 ^-4 mol / mol AgX sensitization Dye-sensitive dye BS-2 1 × 10 ^-4 mol / mol AgX (Preparation method of green-sensitive silver halide emulsion) (solution A) and (B
Liquid) and the addition time of (Liquid C) and (Liquid D) in the same manner as EMP-1 except that the average particle size was 0.53 μm.
m, a coefficient of variation (σ / r) = 0.08, and a monodispersed cubic emulsion EMP-2 having a silver chloride content of 99.5 mol% was obtained.

The following compounds were used for EMP-2.
Chemical ripening was performed at 120 ° C. for 120 minutes to obtain a green-sensitive silver halide emulsion (Em-G).

Sodium thiosulfate 1.5 mg / mol AgX chloroauric acid 1.0 mg / mol AgX stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye BS-1 4 × 10 ⁻⁴ mol / mol AgX (red Method for preparing photosensitive silver halide emulsions) (solution A) and (B)
Liquid) and the addition time of (liquid C) and (liquid D) in the same manner as in EMP-1 except that the average particle size was 0.50 μm.
m, a coefficient of variation (σ / r) = 0.08, and a monodispersed cubic emulsion EMP-3 having a silver chloride content of 99.5 mol% was obtained.

EMP-3 was reacted with the following compound at 60
At 90 ° C. for 90 minutes to obtain a red-sensitive silver halide emulsion (E
mR).

Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX stabilizer STAB-1 6 × 10 ^-4 mol / mol AgX sensitizing dye BS-1 1 × 10 ^-4 mol / mol AgX

[0135]

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On the other hand, coating solutions of the color photographic light-sensitive materials-2 to 8 were prepared in the same manner as described above, except that the coating solution of the color photographic light-sensitive material-1 was changed as follows.

(Color photographic light-sensitive material-2) In the color photographic light-sensitive material-1, a coating solution in which the gelatin content of the first layer was 70% by weight of the gelatin of the first layer of the color photographic light-sensitive material-1 was used. Created. That is, when the wet film thickness was prepared in the same manner as in the color photographic light-sensitive material-1, the amount of gelatin added was adjusted to 70%.

(Color Photographic Material-3) In the color photographic material-2, κ-carrageenan was added to the coating solution of the first layer in an amount of 5% by weight based on gelatin. The method of adding κ-carrageenan was to simultaneously swell with pure water at room temperature at the same time as gelatin powder and then heat to 60 to 65 ° C. to dissolve.

(Color Photographic Material-4) In Color Photographic Material-3, NaSO ₄ was added to the coating solution of the first layer so that Na ⁺ was 50 mmol per liter of the coating solution.

(Color Photographic Material-5) In the color photographic material-3, K ₂ SO ₄ was added to the coating solution of the first layer so that K ⁺ was 20 mmol per liter of the coating solution.

(Color Photographic Material-6) In Color Photographic Material-3, Mg ₂ SO ₄ was added to the coating solution of the first layer so that Mg ²⁺ was 20 mmol per liter of the coating solution.

(Color Photographic Material-7) In Color Photographic Material-3, ZnSO ₄ was added to the coating solution of the first layer so that Zn ²⁺ was 20 mmol per liter of the coating solution.

(Color Photographic Material-8) In the color photographic material-3, K ₂ SO ₄ and MgSO ₄ were added to the coating solution of the first layer.
K ⁺ was added so as to be 5 mmol per liter of the coating solution, and Mg ²⁺ was added so as to be 5 mmol per liter of the coating solution.

The content of each ion of K ⁺ , Ca ²⁺ , Mg ²⁺ , Zn ²⁺ , Co ²⁺ , and Ni ²⁺ contained in the coating solution of the first layer of each photographic light-sensitive material was analyzed. As a result, the results shown in Table 3 were obtained.

Next, each coating solution was kept at 40 ° C., the viscosity of the coating solution was measured, and the freezing point of the coating solution was examined using this coating solution according to the Paggy method. Table 3 shows the obtained results.

[0146]

[Table 3]

From the results shown in Table 3, it can be seen that the viscosity of the coating solution of the first layer for the color photographic material-2 in which the gelatin concentration was lowered was lowered, and particularly the coagulation temperature of the coating solution was lowered remarkably. On the other hand, it can be seen that the coating liquid-3 to which κ-carrageenan is added has a remarkable rise in the viscosity of the coating liquid but a small rise in the freezing point. In addition, Na ⁺ ion
The coating liquid added 50 mmol per liter also has viscosity,
The freezing point is hardly affected.

On the other hand, in Coating Solutions 5 to 8 containing the cation of the present invention in an amount within the range of the present invention, although the viscosity of the Coating Solution tends to decrease rather than that of Coating Solution-3,
It can be seen that the freezing point is significantly increased.

Example 2 Silver halide photographic light-sensitive materials-1 to 1 prepared in Example-1
8 was laminated on one side of a 170 g / m ² paper support with polyethylene (thickness 25 μm), and a polyethylene layer containing titanium oxide was coated on the other side. Using the coating solution prepared in Example 1, simultaneous application was performed to prepare multilayer color photographic light-sensitive materials-1 to 8.

The application was performed with the wet film thickness shown in Table 1.
Immediately before coating, (H-1) was used as a hardener in the second and fourth layers.
And (H-2) was added to the seventh layer.

The obtained silver halide photographic light-sensitive material was
Stored at 40 ° C., 50-60% relative humidity for 7 days.

Next, each sample was subjected to uniform exposure (exposure was carried out under the condition that almost neutral gray having a reflection density of about 1.0 was obtained after the development processing).

Then, it was processed in the following processing steps.

[0154] step Temperature Time color development 35.0 ± 0.3 ° C. 45 seconds blix 35.0 ± 0.5 ° C. 45 seconds stabilized 30 to 34 ° C. 90 sec Drying 60-80 ° C. 60 seconds color developer pure 800ml Triethanolamine 10 g N , N-Diethylhydroxylamine 5g Potassium bromide 0.02g Potassium chloride 2g Potassium sulfite 0.3g 1-Hydroxyethylidene-1,1-diphosphonic acid 1.0g Ethylenediaminetetraacetic acid 1.0g Catechol-3,5-diphosphonic acid disodium 1.0g N -Ethyl-N-β methanesulfonamide Ethyl-3-methyl-4-aminoaniline sulfate 4.5 g Optical brightener (4,4'-diaminostilbene sulfonic acid derivative) 1.0 g Potassium carbonate 27 g Adjust to 1 l and adjust to pH = 10.10.

Bleaching / fixing solution Ethylenediaminetetraacetic acid ammonium ferric ammonium dihydrate 60 g Ethylenediaminetetraacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 ml Ammonium sulfite (40% aqueous solution) 27.5 ml Water was added to make a total volume of 1 l. Or adjust to pH = 5.7 with glacial acetic acid.

Stabilizing solution 5-chloro-2-methyl-4-isothiazolin-3-one 1.0 g ethylene glycol 1.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 2.0 g ethylenediaminetetraacetic acid 1.0 g ammonium hydroxide (20 % Aqueous solution) 3.0 g Optical brightener (4,4'-diaminostilbene sulfonic acid derivative) 1.5 g Water is added to make up to 1 liter, and the pH is adjusted to 7.0 with sulfuric acid or potassium hydroxide.

The obtained sample was visually judged to evaluate applicability. Table 4 shows the results. In the table, .largecircle. Indicates a state without any step unevenness, .DELTA. Indicates a level in which some step unevenness is recognized but is practically acceptable, and X indicates a level in which the step unevenness is severe.

Further, the above photographic material was subjected to 20 ° C. and 20% relative humidity.
, And the tape was stuck on the emulsion surface and peeled off vigorously to examine the interlayer adhesion. Table 4 shows the results.

In the table, ○ indicates that the emulsion layer was not peeled at all, Δ indicates that the emulsion layer was partially peeled, and x indicates that the emulsion layer was peeled over almost the entire surface.

[0160]

[Table 4]

From the results in Table 4, it can be seen that the photographic material of the present invention has good coatability because the viscosity of the coating solution and the coagulation temperature are maintained in appropriate ranges, and also has good adhesion to the emulsion layer. You can see that there is.

Example 3 [Preparation of Photosensitive Silver Halide Emulsion] In a 5% ossein gelatin aqueous solution kept at 50 ° C., a mixed solution of KI and KBr and an ammoniacal silver nitrate aqueous solution were kept at a constant pH and pAg. ,
The addition was performed by the double jet method while controlling the addition rate, and when the addition was completed at 80%, a solution of K ₃ IrCl ₆ dissolved in an aqueous NaCl solution was added in an amount of 10 ^-6 mol per mol of silver halide. After completion of the addition of the silver halide solution and an aqueous solution of a halide, desalting was performed according to a conventional method to prepare a silver halide emulsion for blue light sensitivity. Similarly, at different temperatures, green and red light-sensitive silver halide emulsions were prepared.

The silver halide emulsion thus obtained was chemically and spectrally sensitized to obtain blue, green and red-sensitive silver halide emulsions.

The used photosensitive silver halide emulsion (AgBr
I) is shown below.

Item Blue photosensitive Green photosensitive Red photosensitive Halogen composition (Br mol%) 98 98 98 Particle shape Cubic crystal Cubic crystal Cubic crystal Average particle size * 1 0.30 μm 0.19 μm 0.19 μm Particle size distribution * 2 0.15 0.13 0.13 Surface chemical sensitization * 3 S + Au S S stabilizer * 4 ST-1 ST-1 ST-1 Sensitizing dye BSD-1 GSD-1 RSD-1 * 1 Spherical equivalent diameter * 2 Particle size distribution = (particle Diameter distribution standard deviation) / (average particle size) * 3 S + Au; gold-sulfur sensitization S with sodium thiosulfate and potassium chloroaurate; sulfur sensitization with sodium thiosulfate * 4 ST-1; 4-hydroxy-6- Methyl-1,3,3a, 7-tetrazaindene Each chemical sensitization is performed in the presence of each sensitizing dye,
After the completion of the chemical sensitization, the above-mentioned stabilizer ST-1 (1 g per mol of silver halide) and 1 mmol of the following antibacterial agent were added.

The above three types of photosensitive silver halide emulsions each contained 45 g of ossein gelatin per mole of silver halide, and were finished to 1200 cc per mole of silver halide.

[Preparation of silver benzotriazole emulsion] 58 ° C.
In a 7% aqueous solution of phenylcarbamoyl gelatin kept in water, a 1N aqueous solution of ammoniacal silver nitrate and an aqueous solution of benzotriazole (each mole of benzotriazole per mole) were added.
(Containing 0.2 moles of ammonia). The addition time is 72 minutes. At this time, the pAg was kept constant at 9.2. After completion of the addition, the pH of the solution was lowered to cause aggregation and desalting to obtain a needle-like crystalline silver benzotriazole dispersion (silver benzotriazole microcrystals having a width of about 0.1 to 0.4 μm and a length of about 0.1 to 0.4 μm.
0.5-3 μm).

The silver benzotriazole contains 41 g of phenylcarbamoyl gelatin per mole of silver. The amount of the dispersion per mole of silver was 760 cc.

[Preparation of Dye Donor Dispersion] Using the dye donors (1), (2) and (3), three kinds of dye donor dispersions were prepared by the following dispersion procedure.

[Dispersion procedure] 100 g of a dye-providing substance and 300 g of ethyl acetate were dissolved by heating (solution A), and 900 cc of a 3% ossein gelatin aqueous solution (solution B) (provided that the following surfactant was used)
1 contained 6 g), and emulsified and dispersed by a high-speed homogenizer. Ethyl acetate was removed under reduced pressure to adjust the total amount to 1000 cc.

[Preparation of Coating Solution for Photothermographic Material-101] Coating solution for red-sensitive layer (first layer); gelatin concentration = 4.0% red-sensitive silver halide emulsion 78.5 cc benzotriazole silver emulsion 92.3 cc fog Inhibitor-1 aqueous solution (1%) 6.5cc 5% Surfactant (SU-2) aqueous solution (containing 40% methanol) 12cc Dye donor (3) dispersion 343.3cc polyethylene glycol (average molecular weight = 2000) 16g 20% Gelatin aqueous solution 114 cc 10% polyvinylpyrrolidone (K-15) aqueous solution 21.7 cc pure water 250.7 cc Hardener-1 (3% aqueous solution, containing 40% ethanol) 65 cc Coating solution for first intermediate layer (second layer); gelatin concentration = 4.0% 20% gelatin aqueous solution 200cc color developing agent precursor aqueous solution (20%) 200cc 5% surfactant (SU-2) 8cc polyethylene glycol (average molecular weight = 2000) 8g 10% polyvinylpyrrolidone (K-15) aqueous solution 40cc pure Water 464cc dura Agent-1 (3% aqueous solution, as described above) 80cc coating solution for green photosensitive layer (third layer); gelatin concentration = 4.0% green photosensitive silver halide emulsion 112.2cc silver benzotriazole emulsion 67.5cc antifoggant-1 aqueous solution (1%) 9.6cc 5% surfactant (SU-2) aqueous solution (above) 17cc dye-donating substance (2) dispersion 255cc polyethylene glycol (average molecular weight = 2000) 16g 20% gelatin aqueous solution 126.3cc 10% polyvinylpyrrolidone ( K-15) aqueous solution 20 cc pure water 326.5 cc hardener-1 (3% aqueous solution, as described above) 50 cc coating solution for the second intermediate layer (fourth layer); gelatin concentration = 4.0% yellow filter dye-1 dispersion 200 cc 20 % Aqueous gelatin solution 200cc color developing agent precursor aqueous solution (20%) 200cc 5% surfactant (SU-2) 16cc polyethylene glycol (average molecular weight = 2000) 8g 10% polyvinylpyrrolidone (K-15) aqueous solution 40cc pure water 256cc hard film Agent-1 (3% aqueous solution, 40 80cc Blue photosensitive layer coating solution (5th layer); Gelatin concentration = 4.0% Blue photosensitive silver halide emulsion 134.6cc Benzotriazole silver emulsion 71cc Antifoggant-1 aqueous solution (1%) 8.6cc 5 % Surfactant SU-2 aqueous solution (above) 20 cc Dye-donating substance (1) dispersion 490 cc polyethylene glycol (average molecular weight = 2000) 14 g 20% gelatin aqueous solution 64.5 cc 10% polyvinylpyrrolidone (K-15) aqueous solution 20 cc pure water 127.3 cc Hardener-1 (3% aqueous solution, above) 50cc Coating solution for protective layer (6th layer); Gelatin concentration = 4.0% 20% gelatin aqueous solution 200cc Color developing agent precursor aqueous solution (20%) 200cc polyethylene glycol (average molecular weight) = 2000) 8g 10% polyvinylpyrrolidone (K-15) aqueous solution 40cc 5% surfactant SU-2 aqueous solution (above) 28cc pure water 444cc hardener-1 (3% aqueous solution, containing 40% ethanol) 80cc or less Referred to as the structural formula of additives

[0172]

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[0173]

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The hardener of each layer was added to the coating solution immediately before coating.

The coating liquid for each of the first to sixth layers was p
H was adjusted to 5.8 ± 0.1 (10% solution of sulfuric acid or NaOH was used).

On the other hand, in the coating solution for the photothermographic material-101, the gelatin of the first layer and the gelatin of the third layer were respectively 60% of the gelatin amount of the photothermographic material-101, and the gelatin amount of the fifth layer was Was reduced to 70% to prepare a coating solution for photothermographic material-102 in the same manner as described above. However, for gelatin, the amount of the 20% gelatin aqueous solution used in preparing each coating solution was 32.2 cc (first layer) and 46.4 cc (third layer), respectively.
And 12.0 cc (fifth layer), and the decrease in the liquid volume due to this reduction was increased by adding pure water, and the total liquid volume was the same.

Incidentally, the first layer of the photothermographic material-101 to
The content of Co ³⁺ , Ni ²⁺ , Zn ²⁺ in the coating solution of the sixth layer is determined by the coating solution 1
All were less than 0.1 mmol per liter.

Further, the concentrations of K ⁺ , Ca ²⁺ , and Mg ²⁺ in the coating solutions of the first to sixth layers of the photothermographic material-101 were as shown in Table 5.

[0180]

[Table 5]

Next, in the photothermographic material-102, a water-soluble polymer and a cation shown in Table 6 were added to the first, third, and fifth layers.

[0182]

[Table 6]

The cation was added as an aqueous solution of K ₂ SO ₄ , MgSO ₄ , Ca (NO ₃ ) ₂ .

The amount of the water-soluble polymer added is a weight ratio to gelatin. The cation addition amount is mmol per liter of the coating solution. The addition amounts of the water-soluble polymer and the cation in the first, third and fifth layers are all the same.

The first and third layers of the photothermographic material-102
In the preparation of the coating solution for the layer and the fifth layer, when the amount of gelatin is reduced, without decreasing the gelatin concentration, the coating solution was prepared to be 4.0% for each of the photothermographic materials-117. Was prepared.

First and second layers of photothermographic materials-101 to 117
The coating liquid viscosity and the freezing point of each coating liquid of the layer and the third layer were determined by the method described in Example 1, and the results shown in Table 7 were obtained.

[0187]

[Table 7]

From the results in Table 7, it can be seen that the photothermographic material-117, which does not reduce the gelatin concentration and does not lower the gelatin concentration in order to maintain the solidification point, has a high coating solution viscosity, making it difficult to apply multiple layers simultaneously.

On the other hand, the coating solution containing a natural high molecular polysaccharide derived from red algae and containing the cation of the present invention, even in a low gelatin concentration as in Example 1,
It can be seen that it has a good coating solution viscosity and has a moderately high coagulation temperature. In particular, κ-carrageenan and ι-carrageenan are preferable.

On the other hand, when Kelcogel produced by the microbial fermentation method is used, although the effect of sufficiently improving the coagulation temperature is recognized, the viscosity increases significantly, making it difficult to apply with a gelatin-containing coating solution. easy. In particular, in a multilayer simultaneous application system, such a remarkable thickening is a serious problem for the multilayer simultaneous application.

Example 4 [Preparation of photothermographic material] Using the coating solution prepared in Example 3, the following undercoat layer was coated on a baryta paper support, and the The first to sixth layers were simultaneously coated with the coating solution described in No. 3 to prepare photothermographic materials-101 to 117. However, the photothermographic materials -115 and 116 could not be applied.

Subbing layer Polyphenylene ether 2.0 g Polystyrene 2.0 g CD trapping agent 1.0 g The obtained photothermographic material was subjected to heating at 40 ° C. and a relative humidity of 50 to 60%.
Stored for a day and cured.

[Preparation of Image Receiving Material] An image receiving layer having the following composition was coated on the same baryta paper support as used for preparing the photothermographic material to prepare image receiving material-1. .

(The amount of addition is shown per 1 m ² of the image receiving material) Polycarbonate (average molecular weight: 20,000) 12 g Image stabilizer-1 1.1 g Image stabilizer-2 0.3 g Image stabilizer-3 0.5 g CD trapping agent 0.8g Hot solvent-B 2.0g

[0195]

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[Evaluation of Photothermographic Material] The obtained photothermographic material was stored at 23 ° C. and a relative humidity of 20% and 55%, and was uniformly exposed (the reflection density after dye transfer to the image receiving material was about 1%). Exposure conditions that give a neutral gray)
Heat development for 0 seconds, then superimpose on the image receiving material for 1
The dye image was transferred by pressing and heating at 30 ° C. for 30 seconds. After cooling, the image receiving material was peeled off from the photothermographic material, the transferred image on the image receiving layer surface was visually observed, and the coatability was examined in the same manner as in Example-1. Further, the photothermographic material and the dye image-receiving material were peeled off in a thermostat at 60 ° C. (The peeling property was lowered at a constant temperature. That is, the adhesion between the emulsion layer or the undercoat layer of the photosensitive layer film was poor. This causes a phenomenon in which some layers on the photosensitive layer side adhere to the surface of the image receiving layer when the photosensitive material is separated from the image receiving material.)

Table 8 shows the results of the peelability test and the application properties.
Shown in The peelability was as follows: ○: no photosensitive layer adhered to the image receiving layer surface △: photosensitive layer adhered to the edge of the image receiving layer surface ×: adhered to almost the entire surface of the image receiving layer, or the photosensitive layer could not be peeled .

[0198]

[Table 8]

From the results shown in Table 8, the photothermographic material of the present invention was obtained.
It can be seen that -104, 107, 108, 110, 112 and 114 can obtain good coating properties and releasability even if the gelatin is reduced. Particularly, κ-carrageenan and ι-carrageenan are preferable.

Example -5 In the photothermographic material -107 prepared in Example 3, the cation was changed from K ⁺ to Zn ²⁺ or Ca ²⁺ , and the photothermographic material was used in the same manner as the photothermographic material -107. Example-
By repeating the tests of Example 3 and Example 4, it was confirmed that the effect of the present invention, that is, the freezing point of the coating solution could be increased within an appropriate range without significantly increasing the viscosity of the coating solution.

[0201]

According to the present invention, it is possible to increase the set temperature of a coating solution containing gelatin, and to use a coating solution having good coating solution physical properties without accompanied by an extreme increase in viscosity of the coating solution. It was possible to provide a silver halide photographic light-sensitive material which formed a thin film layer made of gelatin and gave good adhesion between different hydrophilic binder layers.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁷ , DB name) G03C 1/04 G03C 1/498 502 G03C 8/40 505

Claims (6)

(57) [Claims] 1. A method for producing a photographic material, wherein a coating solution containing a natural high molecular polysaccharide derived from a red algae is coated on a support, wherein the coating solution contains a natural high molecular polysaccharide derived from the red algae. The liquid is K ⁺ , Ca ²⁺ , Mg ²⁺ , Zn ²⁺ , Co
^A method for producing a photographic material, wherein the total amount of cations selected from ³⁺ and Ni ²⁺ is 10 mmol or more per liter of a coating solution. 2. The photographic material according to claim 1, wherein the natural high molecular weight polysaccharide derived from red algae is a natural high molecular weight polysaccharide selected from kappa carrageenan, iota carrageenan, lambda carrageenan, and furceleran. Manufacturing method. 3. The method according to claim 2, wherein the cation contained in the coating solution in an amount of 10 mmol or more per liter is K ⁺ , Ca ²⁺ , Mg ²⁺ , Z.
3. The method according to claim 2, wherein the cation is a cation selected from n < ²⁺ >. 4. The K ⁺ , Ca ²⁺ , M contained in the coating solution
4. The method according to claim 3, wherein the total amount of cations selected from g2 ⁺ and Zn2 ^{+ is 20} to 200 mmol per liter of the coating solution. 5. The coating solution containing a natural high molecular polysaccharide derived from red algae further contains gelatin, and the concentration of the gelatin is 1 to 6% by weight. How to make photographic materials. 6. The weight ratio of the natural high molecular weight polysaccharide derived from the red algae to the gelatin of the coating solution containing the natural high molecular weight polysaccharide derived from the red algae is in the range of 0.02 to 0.4. A method for producing a photographic material according to claim 5.