JPH0555013B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a silver halide photographic material.
The present invention can be used, for example, as a photosensitive material for obtaining a copy image of the original image by directly exposing an original image having image information such as text or pictures onto a silver halide photographic light-sensitive material, and then performing a development process or the like. can. [Background of the Invention] Conventionally, photosensitive materials having a reflective support have a large thickness, which is inconvenient when images are formed on the material, when it is used as a file, pasted on an album, or used for various designs. For this reason, a thin photographic material with a small thickness is desired. However, when a thin photosensitive material is used as a photosensitive material for copying images as described above, it curls during feeding and tends to stick to one of the rollers when being fed between the rollers. The paper often gets wrapped around the paper, causing paper jams, and when it is necessary to pass through a narrow slit during exposure, it is difficult to pass through the narrow slit, resulting in jams. [Object of the Invention] The present invention is a silver halide photographic light-sensitive material with a small thickness, which is less likely to cause curling as described above, and therefore free from various troubles associated with curling, and thus suitable for various uses, For example, an object of the present invention is to provide an advantageous photographic material that can be effectively used as a photosensitive material for copying image formation. [Structure and operation of the invention] As a result of intensive research, the present inventors have found that a silver halide emulsion layer containing a yellow coupler, a silver halide emulsion layer containing a magenta coupler, and a halogen emulsion layer containing a cyan coupler are formed on a reflective support. A silver halide photographic light-sensitive material having a silver halide emulsion layer and a non-light-sensitive layer, and a non-light-sensitive layer on the opposite side of the reflective support from the side having the silver halide emulsion layer, The support has a Taber stiffness of 0.8 to 4.0, and the total amount of hydrophilic colloid on the side having the silver halide emulsion layer provided on the reflective support is 7 to 15 g/ ^m2 , and The amount of total hydrophilic colloid attached to the non-photosensitive layer provided on the side opposite to the side having the silver halide emulsion layer is expressed by weight relative to the total amount of hydrophilic colloid attached on the side having the silver halide emulsion layer. Depending on what is 0.2 to 0.9 times,
It has been found that the above objectives are achieved. In order to obtain a light-sensitive material with a small thickness, it is sufficient to make the support thin, but as a result of various studies, the present inventors found that thin supports have low rigidity, and this is the cause of trouble. We have researched various ways to prevent the above troubles even when using a support with a Taber stiffness of about 0.8 to 4, and have determined the ratio of the hydrophilic binder on the emulsion side to the hydrophilic binder on the opposite side. It has been found that the above objective can be achieved by setting the value to 0.2 to 0.9. In the present invention, the total amount of hydrophilic colloids attached to the non-photosensitive layer on the side opposite to the silver halide emulsion layer is 0.2 to 0.9 by weight relative to the total amount of hydrophilic colloids attached to the emulsion layer side. Although it is twice as much,
More preferably, it is 0.3 to 0.8 times. In this case, in the present invention, the total amount of hydrophilic colloid on the reflective support on the side having the silver halide emulsion layer is 7 to 15 g/m ² . According to the present invention, with the above structure, the emulsion layer side of the light-sensitive material and the opposite side thereof counteract each other in their tendency to curl, and as a result, a state where almost no curl occurs is maintained, and therefore, the inconveniences associated with curling are avoided. resolved. In the present invention, the Taber STIFFNESS of the support is measured using a Taber V-5 Stiffness Measuring Instrument Model 150 B as a measuring instrument.
Taber V-5 Stiffness tester (TABER
INSTRUMENT-A TELEDYNE
COMPANY). It is sufficient that the Taber stiffness falls within the range of 0.8 to 4.0. Note that although the support body generally has different stiffness values in the vertical direction and the horizontal direction, it is sufficient that at least one of the stiffness values is within this range. As the material of the reflective support, various materials can be used as desired, but for example, a reflective support having a water-resistant surface such as polyolefin laminated paper, synthetic paper, etc. is preferably used. A water-resistant surface can be formed by coating a substrate, such as a paper substrate, with a hydrophobic resin, and such hydrophobic resin coating layers can be formed on both sides of the photosensitive material. In an embodiment in which such a water-resistant surface is formed, even when the silver halide photographic light-sensitive material is immersed in a bath used for development processing, it is possible to prevent water from forming on the substrate. Examples of the resin used in the hydrophobic resin coating layer coated on the back surface include polyolefins such as polyethylene, polypropylene, and polybutene, olefins such as ethylene, propylene, and butene, and monomers such as vinyl acetate, vinylidene chloride, and maleic anhydride. (e.g., ethylene-vinyl acetate copolymer, propylene-vinylidene chloride copolymer, propylene-maleic anhydride copolymer, etc.), or polystyrene, polyvinyl chloride, polyacrylate, saturated polyester, polycarbonate, etc. Examples include homopolymers or copolymers such as esters, and blends thereof. The thickness of this hydrophobic resin coating layer is
Although there are no particular limitations, it is generally preferred to have a thickness of about 15 to 50 μm. Further, the hydrophobic resin layer coated on the side of the substrate (paper or the like) on which the silver halide emulsion layer is provided is preferably formed mainly of polyethylene resin. This polyethylene resin includes a homopolymer of ethylene and a copolymer of ethylene and other components. Other components that can be copolymerized with ethylene include:
For example, α-olefins such as propylene and butene-1, styrene, vinyl compounds such as vinyl stearate, vinyl acetate, acrylic acid, methacrylic acid, and acrylamide, methyl acrylate, ethyl acrylate, methyl methacrylate, and ethyl methacrylate. Examples include esters of vinyl carboxylic acid compounds such as, metal salts of acrylic acid and methacrylic acid, and diene compounds such as butadiene and isoprene. There is no particular restriction on the molecular weight of the polyethylene resin as long as extrusion coating is possible, but polyethylene with a molecular weight in the range of 20,000 to 200,000 is usually used. The polyethylene resin used for the hydrophobic resin coating layer in this case may be any of low density, medium density, and high density polyethylene resins, and these may be used alone or in combination of two or more. Various coatings can be used to apply such a hydrophobic resin onto, for example, a paper substrate to form a hydrophobic resin coating. A particularly common coating method includes extrusion coating. When a hydrophobic resin coating layer is provided to form a water-resistant surface, a light-reflecting substance such as titanium oxide, zinc oxide, calcium carbonate, calcium sulfate, etc. can be added to make the image clearer. These substances may be added alone or in a mixture of two or more, for example, in an amount of about 5 to 25 parts by weight per 100 parts by weight of the resin. Such an opaque layer can be provided, for example, on the surface of the support. When using such a hydrophobic resin layer containing a light-reflecting substance, there is no need to coat it with a baryta layer or the like to impart reflectivity even when a paper base is used. The silver halide photographic light-sensitive material of the present invention comprises a silver halide emulsion layer containing a yellow coupler, a silver halide emulsion layer containing a magenta coupler, a silver halide emulsion layer containing a cyan coupler, and a silver halide emulsion layer containing a cyan coupler on a reflective support. It has a photosensitive layer and a non-photosensitive layer on the side of the reflective support opposite to the side on which the silver halide emulsion layer is provided. The present invention can be applied to any silver halide photographic light-sensitive material using a reflective support, and there are no particular limitations on the field of application. It can be embodied as a photosensitive material for direct positive image formation, a fog-destructive type photosensitive material for direct positive image formation, a reversal color photosensitive material, a silver bleaching type photosensitive material, etc. When embodied as a light-sensitive material for direct positive image formation, one example is a red-sensitive direct positive silver halide emulsion layer containing a cyan coupler and a green-sensitive direct positive silver halide emulsion layer containing a magenta coupler on one side of the support. It has a silver emulsion layer, a yellow filter layer, and a blue-sensitive direct positive silver halide emulsion layer containing a yellow coupler, and can be formed by sequentially coating these layers in the above-mentioned order from the support side. A non-photosensitive layer is formed on the opposite side. The couplers contained in each of the color-sensitive layers mentioned above are yellow dye-forming couplers of the benzoylacetanilide type, pivaloylacetanilide type, or those in which the carbon atom at the coupling position is substituted with a so-called split-off group that can be separated during coupling. Two-equivalent type yellow couplers and the like are useful. As magenta dye-forming couplers, 5-pyrazolone type, pyrazolotriazole type, hyazolinobenzimidazole type, indazolone type couplers, or two-equivalent type magenta couplers having a split-off group are useful. As the cyan dye-forming coupler, phenolic, naphthol, pyrazoquinazolone, or two-equivalent cyan couplers having a split-off group are useful. These dye-forming couplers can be selected arbitrarily;
Furthermore, there are no particular limitations on the method of use, the amount used, etc. In addition, in order to prevent color fading of the dye image due to short wavelength actinic rays, ultraviolet absorbers can be used, such as thiazolidone, benzotriazole,
Examples include acrylonitrile, benzophenone compounds, etc., especially Tinuvin PS, Tinuvin 120, Tinuvin 320, and Tinuvin PS.
326, 327, 328 (all manufactured by Ciba Geigy)
It is advantageous to use them alone or in combination. When carrying out the present invention, in addition to the above-mentioned red, green, and blue color-sensitive layers and the non-photosensitive layer on the opposite side, a protective layer, an intermediate gelatin layer, or an antihalation layer underneath is formed as necessary. You may. When a direct positive image-forming silver halide emulsion is used in the light-sensitive material of the invention, for example, an internal latent image type silver halide emulsion can be used as the emulsion. For example, so-called convergence silver halide emulsions by the conversion method described in U.S. Pat. No. 2,592,250, or internally chemically sensitized silver halide grains as described in U.S. Pat. or a silver halide emulsion having silver halide grains containing polyvalent metal ions as described in U.S. Pat. No. 3,271,157, U.S. Pat. No. 3,447,927 and U.S. Pat. Silver halide emulsions whose grain surfaces are weakly chemically sensitized containing dopants described in JP-A-50-8524, JP-A-50-38525 and JP-A-53
- So-called core-shell type silver halide emulsions made by the lamination method described in No. 2408, and other JP-A-52
Silver halide emulsions described in No. 156614, No. 55-127549, and No. 57-79940 can be used. In this case, it is particularly preferable that the internal latent image type silver halide be made of layered grains. Such silver halide can be produced in the same manner as ordinary laminated silver halide. For example, JP-A No. 50-8524, JP-A No. 50-38525, JP-A No. 53-
As described in No. 60222, No. 55-1524, and U.S. Pat. No. 3,206,313, silver chloride grains are formed, bromide is added thereto to convert them into silver bromide grains, and halide is further laminated by adding silver nitrate; Examples include a method in which silver iodobromide grains are produced in a state with little excess halogen, and then silver chloride and silver bromide are sequentially laminated. The composition of the silver halide grains inside the laminated type and core-shell type is high in silver bromide content (60-
(100 mol%) silver iodobromochloride grains are suitable. The composition of the silver halide layered on the outside is preferably silver chlorobromide, with a high silver chloride ratio (70 mol%) from the viewpoint of developability.
above) is desirable. The grain size of silver halide is 0.2~
Particles of 1.7μ can be used, and those with a narrow particle size distribution are preferable when high contrast is required, and those with a wide particle size distribution are preferable when low contrast is required. Various photographic additives can be added to the internal latent image type silver halide emulsion. For example, optical sensitizers that can be used include cyanines, merocyanines, trinuclear or tetranuclear merocyanines, trinuclear or tetranuclear cyanines, styryls, holobolacyanines, hemicyanines, oxonols, and hemioxonols. Examples include nols and the like. Internal latent image type silver halide emulsions can be supersensitized. Regarding the method of supersensitization, see, for example, ``Review of the mechanism of supersensitization,'' Review of Supersensitization.
-sensitization) Photographic Science and Engineering (Photographic
Science and Engineering) (PSE) Vol.18, No.
4418 (1974). When internal latent image type silver halide emulsions are used, the emulsions contain stabilizers that are commonly used, such as compounds with azaindene rings, in order to keep the surface sensitivity as low as possible and to give lower minimum density and more stable properties. and a heterocyclic compound having a mercapto group. Examples of compounds having an azaindene ring include 4-hydroxy-6-methyl-1,3,3a-7
-Tetrazaindene is preferred. Among the heterocyclic compounds having a mercapto group, nitrogen-containing heterocyclic compounds include a pyrazole ring, 1,2,4-triazole ring, 1,2,3-triazole ring, 1,
3,4-thiadiazole ring, 1,2,3-thiadiazole ring, 1,2,4-thiadiazole ring,
1,2,5-thiadiazole ring, 1,2,3,4
-tetrazole ring, pyritazine ring, 1,2,3-
triazine ring, 1,2,4-triazine ring, 1,
3,5-triazine ring, etc., and further these rings are 2
~3 fused rings, such as a triazolotriazole ring, a diazaindene ring, a triazaindene ring,
Examples include a tetrazaindene ring, a pentazaindene ring, a phthalazinone ring, an indazole ring, and 1-phenyl-5-mercaptotetrazole is particularly preferred. In addition, wetting agents are used depending on the purpose. Examples of such wetting agents include dihydroxyalkanes, and examples of improving film properties include, for example, combinations of alkyl acrylates or alkyl methacrylates with acrylic acid or methacrylic acid. copolymer, styrene-maleic acid copolymer,
Water-dispersible fine particulate polymeric substances obtained by emulsion polymerization such as styrene maleic anhydride half alkyl ester copolymer are suitable, and examples of coating aids include saponin, polyethylene glycol, lauryl ether, etc. can be mentioned. Other photographic additives include gelatin plasticizers, surfactants, ultraviolet absorbers, PH adjusters, antioxidants,
It is optional to use antistatic agents, thickeners, graininess improvers, dyes, mordants, brighteners, development rate regulators, matting agents, anti-irradiation dyes, and the like. The silver halide photographic material of the present invention may contain appropriate gelatin (including oxidized gelatin) and its derivatives depending on the purpose. Preferred gelatin derivatives include, for example, acylated gelatin, guanidylated gelatin, carbamylated gelatin, cyanoethanolated gelatin,
Examples include esterified gelatin. Such gelatins can also be used in the non-photosensitive layer (layer opposite to the emulsion layer) of the present invention. Furthermore, in the silver halide photographic material of the present invention, the hydrophilic colloid layer may contain other hydrophilic binders in addition to gelatin. This hydrophilic binder can be added to photographic constituent layers such as an emulsion layer, an intermediate layer, a protective layer, a filter layer, and a backing layer depending on the purpose. It is possible to contain agents, lubricants, etc. Such gelatins and binders can also be used in the non-photosensitive layer (layer on the side opposite to the emulsion layer) of the present invention. Further, the photographic constituent layers of the light-sensitive material of the present invention can be hardened with any suitable hardening agent. Preferred hardening agents include chromium salts, zirconium salts, aldehyde hardeners such as formaldehyde and mucohalogen acids, halotriazine hardeners, polyepoxy compounds, ethyleneimine hardeners, vinyl sulfone hardeners, and acryloyl hardeners. can be mentioned. Further, the silver halide photographic material of the present invention is
In addition to the matting agent content on the side opposite to the emulsion layer and color-sensitive layer on the support, as described above, a filter layer, an intermediate layer, a protective layer, a subbing layer, a backing layer,
It is manufactured by coating various photographic constituent layers such as an antihalation layer. As a coating method, dip coating, air doctor coating, extrusion coating, slide hopper coating, curtain flow coating, etc. can be used. In the present invention, when directly forming a positive image using an internal latent image type silver halide photographic light-sensitive material, the main step is to transfer the internal latent image type silver halide photographic light-sensitive material, which has not been fogged in advance, to the internal latent image type silver halide photographic light-sensitive material after image exposure. It is common to perform surface development after or while performing fogging treatment. The fogging treatment can be carried out by providing uniform exposure over the entire surface or by using a fogging agent. In this case, uniform exposure over the entire surface is performed by immersing or moistening the image-exposed internal latent image type silver halide photographic light-sensitive material in a developer or other aqueous solution, and then uniformly exposing the entire surface. is preferred.
The light source used here may be any light within the sensitive wavelength range of the internal latent image type silver halide photographic light-sensitive material, and it is also possible to irradiate with high-intensity light such as flash light for a short period of time, or with a weak Light may be irradiated for a long time. The time for uniform exposure over the entire surface can be varied over a wide range depending on the internal latent image type silver halide photographic light-sensitive material, the processing conditions, the type of light source used, etc. so as to ultimately obtain the best positive image. Further, a wide variety of compounds can be used as the above-mentioned fogging agent, and this fogging agent only needs to be present during the development process, for example, in an internal latent image type silver halide photographic light-sensitive material such as a silver halide emulsion layer, or It may be contained in a liquid or a processing liquid prior to development processing, but it is preferably contained in an internal latent image type silver halide photographic light-sensitive material (particularly preferably in a silver halide emulsion layer). The amount used can vary widely depending on the purpose, and the preferred amount is 1 to 1,500 mg, particularly preferably 10 to 1,000 mg per mole of silver halide when added to a silver halide emulsion layer. It is. In addition, when added to a processing solution such as a developer, the preferred amount of addition is 0.01 to 5 g/, particularly preferably
It is 0.08-0.15g/. Such fogging agents include, for example, hydrazines described in US Pat. No. 2,563,785 and US Pat. No. 2,588,982, or
Hydrazide or hydrazone compound described in US Pat. No. 3,227,552: Also, US Pat.
Heterocyclic quaternary nitrogen compounds described in US Pat. No. 3,719,494, US No. 3,734,738, and US Pat. Further, these fogging agents can also be used in combination. For example, research disclosure
Disclosure) No. 15162 describes the use of a non-adsorption type fogging agent in combination with an adsorption type fogging agent, which can also be applied to the present invention. Specific examples of useful fogging agents include hydrazine hydrochloride, phenylhydrazine hydrochloride, 4-methylphenylhydrazine hydrochloride, 1-formyl-2-
(4-methylphenyl)hydrazine, 1-acetyl-2-phenylhydrazine, 1-acetyl-2
-(4-acetamidophenyl)hydrazine, 1
-methylsulfonyl-2-phenylhydrazine, 1-benzoyl-2-phenylhydrazine,
Examples include hydrazine compounds such as 1-methylsulfonyl-2-(3-phenylsulfonamidophenyl)hydrazine and formaldehyde phenylhydrazine. When the present invention is applied to an internal latent image type silver halide photographic light-sensitive material, a positive image is directly formed by exposing the entire surface of the material after image exposure or developing it in the presence of a fogging agent. Any developing method may be employed as the developing method for the photosensitive material, preferably a surface developing method. This surface development processing method means processing with a developer substantially free of silver halide solvent. In the present invention, a positive image (developed image) corresponding to an original image is formed by subjecting an exposed silver halide photographic light-sensitive material to development treatment and treatment with a processing liquid having fixing ability. The above-mentioned development processing includes, in addition to color development processing, a combination of black-and-white development and color development, such as in reversal color processing. It also includes full-surface exposure or development in the presence of a fogging agent, such as in the processing of internal latent image type silver halide photographic materials. The first compound used in the color development process in the present invention
Aromatic amino color developing agents include various types that are widely used in various color photographic processes. These developers include aminophenol and p-phenylenediamine derivatives. Since these compounds are more stable in the free state, they are generally used in the form of salts, such as hydrochlorides or sulfates. In addition, these compounds are generally used at a concentration of about 0.1 g to about 30 g per color developer,
More preferably, about 1 g per color developer 1
Use at a concentration of ~15g. Examples of aminophenol-based developers include o
-aminophenol, p-aminophenol, 5
-amino-2-oxy-toluene, 2-amino-
Included are 3-oxy-toluene, 2-oxy-3-amino-1,4-dimethyl-benzene, and the like. Particularly useful primary aromatic amino color developers are N,N-dialkyl-p-phenylenediamine compounds, and the alkyl and phenyl groups may be substituted or unsubstituted.
Among them, particularly useful compounds include N,N-
Diethyl-p-phenylenediamine hydrochloride, N-
Methyl-p-phenylenediamine hydrochloride, NN
-dimethyl-p-phenylenediamine hydrochloride, 2
-Amino-5-(N-ethyl-N-dodecylamino)-toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline hydrochloride, N-ethyl-N-β- Hydroxyethylaminoaniline, 4-amino-methyl-
N,N-diethylaniline, 4-amino-N-
Examples include (2-methoxyethyl)-N-ethyl-3-methylaniline-p-toluenesulfonate. In addition to the first aromatic amino color developer, the alkaline color developer that can be used in the present invention further contains various components that are normally added to color developers, such as sodium hydroxide, sodium carbonate, and potassium carbonate. Alkaline agents such as alkali metal bisulfites, alkali metal thiocyanates, alkali metal halides, benzyl alcohol,
Water softeners, thickeners, and the like may optionally be included. The pH value of this color developer is usually 7 or more, most commonly about 10 to about 13. The fixing solution used in carrying out the present invention is a processing solution containing a soluble complexing agent that is solubilized as a silver halide complex salt, and includes not only a general fixing solution but also a bleach-fixing solution, a single-bath development fixing solution, Although a single-bath development bleach-fix solution is also included, a bleach-fix solution is preferred. Soluble complexing agents include, for example, potassium thiosulfate,
Typical examples include thiosulfates such as sodium thiosulfate and ammonium thiosulfate, thiocyanates such as potassium thiocyanate, sodium thiocyanate, and ammonium thiocyanate, thiourea, thioether, and high concentrations of bromide and iodide. However, it is particularly desirable to contain thiosulfate in terms of stabilization of dye images over time, chemical stability, and ability to form soluble complexes with silver halide. After color development processing, processing is performed with a processing liquid having fixing ability. In color processing, if the processing liquid having fixing ability is a fixing liquid, bleaching processing is performed before that. A metal complex salt of an organic acid is used as a bleaching agent in the bleach solution or bleach-fix solution used in the bleaching process, and the metal complex salt is
It has the effect of oxidizing the metallic silver produced during development and converting it into silver halide, and at the same time coloring the uncolored areas of the coloring agent. Its structure is based on aminopolycarboxylic acid or organic acids such as oxalic acid and citric acid. Coordinated with metal ions such as iron, cobalt, and copper. The most preferred organic acids used to form such metal complexes of organic acids include:
Examples include polycarboxylic acids and aminopolycarboxylic acids. These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts. Specific representative examples of these include the following. [1] Ethylenediaminetetraacetic acid [2] Diethylenetriaminepentaacetic acid [3] Ethylenediamine-N-(β-oxyethyl)-N,N',N'-triacetic acid [4] Propylenediaminetetraacetic acid [5] Nitrilotriacetic acid [6] Cyclohexanediaminetetraacetic acid [7] Iminodiacetic acid [8] Dihydroxyethylglycine citric acid (or tartaric acid) [9] Ethyl etherdiaminetetraacetic acid [10] Glycol etherdiaminetetraacetic acid [11] Ethylenediaminetetrapropionic acid [12] Phenylene diamine Tetraacetic acid [13] Ethylenediaminetetraacetic acid disodium salt [14] Ethylenediaminetetraacetic acid tetra(trimethylammonium) salt [15] Ethylenediaminetetraacetic acid tetrasodium salt [16] Diethylenetriaminepentaacetic acid pentasodium salt [17] Ethylenediamine-N-(β -oxyethyl)-N,N'-N'-triacetic acid sodium salt [18] Propylene diamine tetraacetic acid sodium salt [19] Nitrilotriacetic acid sodium salt [20] Cyclohexane diamine tetraacetic acid sodium salt The bleaching solution used is as described above. In addition to containing metal complex salts of organic acids such as the following as bleaching agents, various additives may also be included. As additives, in particular alkali halides or ammonium halides,
For example, it is desirable to contain a halogenating agent such as potassium bromide, sodium bromide, sodium chloride, ammonium bromide, a metal salt, a chelating agent, and the like. Also borates, oxalates, acetates, carbonates,
PH buffering agents such as phosphates, alkylamines, polyethylene oxides, and other substances known to be added to ordinary bleaching solutions can be appropriately added. Furthermore, the fixing solution and bleach-fixing solution contain sulfites such as ammonium sulfite, potassium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite, sodium metabisulfite, and boric acid. Borax, sodium hydroxide, potassium hydroxide,
It can contain one or more PH buffers consisting of various salts such as sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide. When processing is carried out while replenishing the bleach-fixing solution (bath) with a bleach-fixing replenisher, the bleach-fixing solution (bath) may contain thiosulfate, thiocyanate, sulfite, etc. These salts may be added to the replenisher to replenish the processing solution (bath). In order to increase the activity of the bleach-fix solution, air or oxygen may be blown into the bleach-fix bath and the bleach-fix replenisher storage tank, if desired, or a suitable oxidizing agent, such as peroxide, may be added. Hydrogen, bromate, persulfate, etc. may be added as appropriate. After treatment with a treatment liquid having fixing ability, a normal water washing treatment may be performed, but particularly when carrying out the present invention, it is preferable to perform a stabilization treatment that does not substantially include a post-washing step. Stabilization treatment that does not substantially include a water washing process is
Immediately after treatment with a treatment solution that has fixing ability, stabilization treatment is performed using a single tank or multiple tank countercurrent method, etc., but other than general water washing such as rinsing, auxiliary water washing, and known water washing accelerator baths, etc. It may also include a treatment step. In the stabilization treatment process, the method of bringing the stabilizing solution into contact with the silver halide photographic material is preferably to immerse the silver halide photographic material in the same bath as with general processing solutions, but it is preferable to immerse the silver halide photographic material in the bath, but it is preferable to use a sponge, synthetic fiber cloth, etc. It may be applied to the emulsion surface of the silver halide photographic material, both sides of the transport leader, and the transport belt by means of a method such as the above, or it may be sprayed by a spray method or the like. The case where a stabilizing bath by the immersion method is used will be mainly explained below. It is preferable that the stabilizing liquid contains a chelating agent having a chelate stability constant of 6 or more with respect to iron ions. Examples of the chelating agent having a chelate stability constant of 6 or more for iron ions include organic carboxylic acid chelating agents, organic phosphoric acid chelating agents, inorganic phosphoric acid chelating agents, polyhydroxy compounds, and the like.
Note that the above-mentioned iron ion means ferric ion (Fe ³⁺ ). Specific examples of chelating agents having a chelate stability constant of 6 or more with ferric ions include diethylenetriaminepentaacetic acid, nitrilotriacetic acid,
-hydroxyethylidene-1,1-diphosphonic acid and the like. The amount of the above chelating agent used is per stabilizing solution.
It ranges from 0.01 to 50g, preferably from 0.05 to 20g. Furthermore, preferable compounds to be added to the stabilizing liquid include anti-bacterial agents, water-soluble metal salts, ammonium compounds, and the like. Examples of the above-mentioned antibacterial agents include inthiazoline type, benzisothiazoline type, thiapendazole type and the like. Furthermore, examples of metal salts include Ba, Ca, Ce, Co,
In, La, Mn, Ni, Pb, Sn, Zn, Ti, Zr, Mg,
It is a metal salt of Al or Sr, and can be supplied as an inorganic salt such as a halide, hydroxide, sulfate, carbonate, phosphate, or acetate, or as a water-soluble chelating agent. The amount used is 1×10 ^-4 to 1× per stabilizing liquid.
10 ^-1 mol, preferably 4 x 10 ^-4 to 2
×10 ^-2 mol, more preferably 8 × 10 ^-4 to 1 × 10 ^-2
It is in the molar range. The amount of the above compound added to the stabilizing solution is 0.01 to 50 g per stabilizing solution,
Preferably it is in the range of 0.05 to 20g. In addition to the above compounds, the stabilizing liquid also contains fluorescent brighteners, organic sulfur compounds, onium salts, hardeners, quaternary salts, water droplet prevention agents such as polyethylene oxide derivatives, siloxane derivatives, boric acid, citric acid, phosphoric acid, Acetic acid, or sodium hydroxide, sodium acetate,
Various additives to improve and extend processing effects, such as PH buffering agents such as potassium citrate, organic solvents such as methanol, ethanol, and dimethyl sulfoxide, dispersants such as ethylene glycol and polyethylene glycol, and other color tone adjusting agents. Adding is optional. The above compounds and other additives can be added as a concentrated liquid to the stabilization tank, or
Alternatively, the above compounds and other additives are added to the stabilizing liquid supplied to the stabilizing tank, and this is used as a supply liquid for the stabilizing liquid, or halogenated by adding it to the pre-bath of the stabilizing treatment process. There are various methods such as including it in a silver photographic light-sensitive material and making it exist in a stabilizing tank, but any method of addition may be used. As for the method of supplying the stabilizing liquid in the stabilization treatment step, when a multi-tank countercurrent system is used, it is preferable to supply the stabilizing liquid to the rear bath and overflow from the front bath. The preferred pH value of the treatment liquid in the stabilizing bath is PH4 to 8. Further, the pH can be adjusted using the above-mentioned pH adjusting agent. The treatment temperature during stabilization treatment is, for example, 20℃.
-50°C, preferably 25°C - 40°C. In addition, from the viewpoint of rapid processing, the shorter the treatment time, the better, but it is usually 20 seconds to 5 minutes, most preferably 30 seconds to 2 minutes.In a multi-vessel countercurrent system, the earlier the earlier the treatment, the shorter the treatment time, and the later It is preferable that the processing time is longer. When carrying out the present invention, washing with water may not be necessary before and after stabilization processing, but rinsing with a small amount of water within a short period of time, surface cleaning with a sponge, stabilization of images, and silver halide photographic material may be carried out. It is optional to provide a treatment layer for adjusting the surface properties of the material. Examples of agents for stabilizing the image and adjusting the surface properties of the silver halide photographic material include activators such as formalin and its derivatives, siloxane derivatives, polyethylene oxide compounds, and quaternary salts. In carrying out the present invention, it is optional to provide additional processing steps in addition to the processing steps described above. Further, silver may be recovered by a known method not only from the above-mentioned stabilizing solution but also from a processing solution containing a soluble silver complex salt such as a fixing solution or a bleach-fixing solution. Further, if the above-mentioned stabilization treatment is carried out, a water washing process is substantially unnecessary, and therefore there is no need for piping equipment for water washing processing, and there is an advantage that the apparatus itself can be easily installed at any location. [Examples] Examples of the present invention will be described in detail below, but the present invention is not limited to these embodiments. A sample was prepared as follows. A gelatin solution having the following composition was applied to the back side (that is, the transparent polyethylene layer side) of a surface-treated polyethylene laminate paper having a Taber stiffness of 2.1 and dried. The coating amount was as shown in Table 1 for each sample. (Gelatin liquid) Gelatin S-2 S-3 NaCl 100g 1g 0.2g 0.5g In addition, nine emulsion layers as shown below were provided on the surface (on the side of the white polyethylene layer containing titanium oxide) to directly produce a positive color photosensitive material. did. Similarly, by changing the support, Taber stiffness was 1.8.
The same layer as above was applied to a surface-treated polypropylene synthetic paper (manufactured by Oji Yuka Synthetic Paper Co., Ltd.).
I also prepared a shaped one. (Emulsion layer, etc.) Preparation of emulsion S 750 ml of a 2.0% inert gelatin solution was kept at 50°C, and the following solutions A1 and B were added simultaneously while stirring, and injected over 3 minutes. After aging for 25 minutes, excess salt was removed by precipitation and water washing, followed by redispersion, and liquid C1 and liquid D1 were added. After 10 minutes, excess water-soluble salt was removed again, and a small amount of gelatin was added to disperse the silver halide particles. Preparation of Emulsion L 750 ml of a 1.5% inert gelatin solution was kept at 60°C, and while stirring, solutions A2 and B were added simultaneously and injected over 15 minutes. After aging for 40 minutes, excess salt was removed by precipitation and washing, followed by redispersion, 10 mg of hypo was added, and then liquid C2 and liquid D2 were added. After 10 minutes, excess water-soluble salt was removed again, and a small amount of gelatin was added to disperse the silver halide particles. Preparation of Emulsion M 750 ml of a 2.0% inert gelatin solution was kept at 50°C, and the following solutions A3 and B were added simultaneously while stirring and injected over 5 minutes. After aging for 25 minutes, excess salt was removed by precipitation and washing, followed by redispersion, and liquid C1 and liquid D2 were added. After 10 minutes, remove excess water-soluble salts again.
A small amount of gelatin was added to disperse the silver halide grains. A1 liquid pure water NaCl NH ₄ Br KI 2000ml 35g (60mol%) 109.6g (80mol%) 0.8g (0.5mol%) A2 liquid pure water NaCl NH ₄ Br KI 1000ml 26.3g (103mol%) 109.6g ( 80 mol%) 0.8g (0.5 mol%) A3 liquid pure water NaCl KBr 1000ml 38.8g 12g B liquid pure water AgNO ₃ 1200ml 170g C1 liquid pure water NaCl NH ₄ Br 1000ml 60g (103 mol%) 6.9g (5.0 mol% ) C2 liquid pure water NaCl 1000ml 31・6g D1 liquid pure water NaCl AgHO ₃ 1000ml 70g D2 liquid pure water AgNo ₃ 1000ml 80g Add sensitizing dyes, couplers, etc. to these three types of emulsions as shown below for multilayer color sensitization. Created the material. Red-sensitive emulsion layer (first layer) Sensitizing dye [D
-3], [D-4], stabilizer [T-1], [T-2],
Surfactant [S-2], further dibutyl phthalate,
A protected dispersed coupler solution containing ethyl acetate, surfactant [S-2], 2,5-dioctylhydroquinone, and cyan couplers [CC-1] and [CC-2] was added. Add gelatin and make emulsion S: Emulsion M 5:
5 (weight ratio) and coated silver amount 0.4g/
m ² , and the applied gelatin amount is 1.8 g/m ² . First intermediate layer (second layer) A gelatin solution containing a protect-dispersed solution containing dioctyl phthalate, 2,5-dioctylhydroquinone, the ultraviolet absorber Tinuvin 328 (manufactured by Ciba Geigy), and a surfactant [S-1]. Prepared tinuvin coating amount 0.15g/m ² , gelatin coating amount 1.08
Apply so that it is g/m ² . Green-sensitive emulsion layer (third layer) Sensitizing dye [D-2], stabilizers [T-1], [T-2], surfactant [S-2] for emulsion S and emulsion M
Add dibutyl phthalate, ethyl acetate,
A protect-dispersed coupler solution containing 2,5-dioctylhydroquinone, surfactant [S-1], and magenta coupler [MC-1] was added. Add gelatin, further add hardener [H-1], and mix emulsion S: emulsion M at a ratio of 5:5 (weight ratio), silver coating amount 0.43 g/m ² , gelatin coating amount
Apply at a concentration of 1.5g/ ^m2 . 2nd intermediate layer (4th layer) Same formulation as the 1st intermediate layer, coating amount of Tinuvin 328 0.2
g/m ² , gelatin coating amount is 0.7 g/m ² . Yellow filter layer (5th layer) Created by oxidation in an alkaline weak reducing agent (weak reducing agent removed by noodle water washing method after neutralization)
yellow colloidal silver and dioctyl phthalate,
Protect dispersion liquid containing ethyl acetate, surfactant [S-1], 2,5-dioctylhydroquinone, surfactant [S-2] and hardening agent [H-
1] and coated so that the coating amount of colloidal silver is 0.15 g/m ² and the coating amount of gelatin is 1.0 g/m ² . Third intermediate layer (sixth layer) Same as the first intermediate layer. Blue-sensitive emulsion layer (7th layer) Sensitizing dye [D
-1], stabilizers [T-1], [T-3], surfactant [S-2], dibutyl phthalate, ethyl acetate, 2,5-dioctylhydroquinone, surfactant [S-1], and Yellow coupler [Y-1]
Protect dispersed coupler solution containing Add gelatin, further add hardener [H-1], and mix emulsion L: emulsion M at a ratio of 5:5 (weight ratio), silver coating amount 0.55 g/m ² and gelatin coating amount.
Apply at a coating density of 1.7g/ ^m2 . Third intermediate layer (eighth layer) Prepare a gelatin solution containing dioctyl phthalate, 2,5-dioctylhydroquinone, ultraviolet absorber Tinuvin 328, and surfactant [S-1] in which protection is dispersed, and coat the tinuvin in an amount of 0.5 g. / ^m2 ,
Apply gelatin at a coating amount of 0.9 g/m ² . Protective layer (9th layer) A gelatin solution containing colloidal silica, coating aid [S-2], hardener [H-2], and [H-3] was used so that the gelatin coating amount was 0.8 g/ ^m2. Apply. [D-1] [D-2] [D-3] [D-4] [T-1] [T-2] [T-3] [S-1] [S-2] [S-3] [H-1] [H-2] [H-3] [YC-1] [MC-1] [CC-1] [CC-2]

【table】

〔Effect of the invention〕

As mentioned above, the silver halide photographic light-sensitive material of the present invention has a small thickness and does not easily curl, and therefore does not suffer from various troubles associated with curling, and can therefore be effectively used for various purposes.

[Brief explanation of the drawing]

FIG. 1 is a schematic sectional view showing an example of an image forming apparatus that can use the photosensitive material of the present invention. FIG. 2 is a schematic diagram for explaining the curl measurement method. FIG. 3 is a partially enlarged view of the device of FIG. 1. 1... Image forming apparatus main body, 3... Image exposure section,
11...Paper feed section, 12...Photosensitive material (sample), 1
3...Transporting section, 22...Cutting member, 24...Photo processing section, 30...Drying section.

Claims (1)

[Claims] 1. A silver halide emulsion layer containing a yellow coupler, a silver halide emulsion layer containing a magenta coupler, a silver halide emulsion layer containing a cyan coupler, and a non-photosensitive layer are formed on a reflective support. and a non-photosensitive layer on the side of the reflective support opposite to the side having the silver halide emulsion layer, wherein the reflective support has a Taber stiffness of 0.8 to 4.0. , and the amount of total hydrophilic colloid on the side having the silver halide emulsion layer provided on the reflective support is 7 to 15 g/m ² , and the side opposite to the side having the silver halide emulsion layer The total amount of hydrophilic colloids attached to the non-photosensitive layer provided on the layer is 0.2 to 0.9 times by weight the total amount of hydrophilic colloids attached to the side having the silver halide emulsion layer. Silver halide photographic material.