JPH0531643Y2 - - Google Patents

Description

[Detailed explanation of the idea]

[Industrial Application Field] The present invention relates to a silver halide photographic material.
The present invention can be used as a photosensitive material, for example, by directly exposing an original image containing image information such as text or pictures to a silver halide photographic light-sensitive material, and then performing development processing to obtain a copy image of the original image. can. [Background of the Invention] Many methods and devices for obtaining duplicate images (copies) of documents, books, etc. have been proposed and put into practical use. Typical examples include electrophotographic copying devices and copying devices using silver halide photosensitive materials. However, silver halide photographic materials used for copying have conventionally had thick supports (200~200 mm).
250μ), so it has the disadvantage that light shadows tend to appear when pasted and copied. That is, if an attempt is made to cut and paste the image and make further copies, shadows tend to appear, which is a problem when the copied images are used for typesetting. Furthermore, since the support is thick as described above, when a copy is filed, the volume becomes large and the copy becomes thick and bulky. Furthermore, when retouching or making corrections or additions to the surface of conventional photosensitive materials, it is not possible to write with a pencil or ballpoint pen, which is inconvenient. [Purpose of the invention] The present invention was made to solve the above-mentioned problems.For example, even when filing reports, meeting materials, etc., it does not become thick or bulky, and is easy to file. It is easy to retouch, make corrections, and make additional notes on the surface, and explanations and additions can be written on with a regular pencil or ballpoint pen.Also, the halogenated surface is less likely to cause shadows when pasted and copied. The purpose is to provide silver photographic materials. [Structure and operation of the invention] The silver halide photographic light-sensitive material of the invention has at least one emulsion layer containing internal latent image type silver halide grains and a protective layer on a support, and an original image is directly transferred to the support. It is an internal latent image type direct positive silver halide photographic light-sensitive material for obtaining a copy image of an original image by exposure and processing, and the support has a thickness of 80 mm to 80 mm.
150 μm, the protective layer contains fine particle powder with a particle size of 1 to 10 μm, and the content of the fine particle powder is 0.5 to 5 wt% based on the hydrophilic binder. Achieve the above objectives. According to the present invention, since the support has a thickness of 80 to 150 μm, even if it is used for copying and then filed, it will not become too thick or bulky, and it is possible to obtain a copied image with an appropriate thickness. . Furthermore, since the protective layer contains fine powder, it is possible to write on the surface using various ordinary writing instruments, which is convenient. In the present invention, the protective layer can be formed on the outermost surface of the photosensitive material. The fine particle powder contained in the protective layer is often generally referred to as a matting agent in the art, and therefore, hereinafter, unless otherwise specified, it will be referred to as a matting agent. Matting agents that can be used in the present invention include, for example, crystalline or amorphous silica,
Titanium dioxide, magnesium oxide, calcium carbonate, barium sulfate, barium strontium sulfate, magnesium alumina silicate, silver halide, silicon dioxide, acrylic acid-ethyl acrylate copolymer, acrylic acid-methyl methacrylate copolymer, itaconic acid- Styrene copolymer, maleic acid-methyl methacrylate copolymer, maleic acid-styrene copolymer, acrylic acid-phenyl acrylate copolymer, polymethyl methacrylate, acrylic acid-methacrylic acid-ethyl methacrylate copolymer, polystyrene, Examples include starch, cellulose acetate propionate, etc., and other US Pat.
Examples include compounds described in No. 2992101 and the like, and these can be used alone or in combination of two or more. Colloidal silica may be used in combination with the matting agent. The particle size of the above matte agent has an average particle size of 1 to
It may be 10 μm, preferably 3 to 10 μm. The average particle size here refers to the diameter in the case of spherical particles, and in the case of particles with shapes other than cubic or spherical, the average value of the diameter when the projected image is converted to a circular image of the same area. When the individual grain size is ri and the number is ni, it is defined by the following formula. =Σniri/Σni As a specific measuring method, the method described in Japanese Unexamined Patent Publication No. 59-29243 can be used. In the present invention, the matting agent is dispersed and contained in a protective layer, for example, the protective layer that is the outermost layer of a photosensitive material. Add other additives as necessary to the hydrophilic binder containing the compound, disperse by emulsification dispersion method using shear stress using a high-speed rotating mixer, homogenizer, ultrasonic dispersion, ball mill, etc., and apply by any method. It can be formed by The coating amount of the matting agent is preferably 2.5 to 250 mg per m ² in the protective layer, and more preferably 10 to 50 mg per m ² . Further, the content of the matting agent is 0.5 to 5 wt% based on the hydrophilic binder, more preferably 1 wt%.
~3wt%. The thickness of the support for the photographic light-sensitive material of the present invention is 80~
It is 150μm. Any support can be used, including reflective supports and transparent supports (e.g. OHP).
However, typical supports include:
Examples include polyethylene terephthalate film, polycarbonate film, polystyrene film, polypropylene film, cellulose acetate film, baryta paper, polyolefin-in laminated paper such as polyethylene, polyethylene terephthalate film kneaded with white pigment, etc., if necessary. . The photographic light-sensitive material of the present invention has at least one silver halide emulsion layer on the support in addition to the above-mentioned protective layer. For example, when a color image is obtained, the support includes a red-sensitive silver halide emulsion layer containing a cyan coupler, a green-sensitive silver halide emulsion layer containing a magenta coupler, an optional yellow filter layer, and It is possible to have a structure having a blue-sensitive silver halide emulsion layer containing a yellow coupler. These layers may be formed by coating in the above-mentioned order from the support side, and the protective layer may be formed on the outermost 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 are useful. As the magenta dye-forming coupler, a 5-pyrazolone type, pyrazolotriazole type, pyrazolinobenzimidazole type, indazolone type, or a two-equivalent type magenta coupler having a split-off group is 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;
Moreover, 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. Of course, it may also be embodied as a black and white photosensitive material. When carrying out the present invention, in addition to the silver halide emulsion layer and protective layer, an intermediate gelatin layer or an antihalation layer may be formed therebelow, if necessary. The silver halide photographic material of the present invention has at least one emulsion layer containing internal latent image type silver halide grains and a protective layer on a support, and is processed by directly exposing the original image to light. This is an internal latent image type direct positive silver halide photographic light-sensitive material for obtaining a copy image of an original image by using the internal latent image type silver halide emulsion. Convergence silver halide emulsion or U.S. Pat. No. 3,206,316;
Silver halide emulsions having internally chemically sensitized silver halide grains as described in US Pat. No. 3,317,322 and US Pat. No. 3,367,778, or US Pat.
Silver halide emulsions having silver halide grains containing polyvalent metal ions as described in No. 3447927 and No. 3531291, or US Pat. No. 3,761,276
A silver halide emulsion in which the grain surface of silver halide grains containing a dopant is weakly chemically sensitized as described in JP-A-50-8524, JP-A-50-8524;
So-called core-shell type silver halide emulsions produced by the lamination method described in JP-A Nos. 38525 and 53-2408, and others described in JP-A-52-156614, JP-A-55-127549, and JP-A-57-79940. Silver halide emulsions and the like 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 has a high 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, and from the viewpoint of developability, silver chloride with a high ratio (70 mol%) is preferred.
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).
Supersensitization) Photographic Science and Engineering
(PSE) Vol. 18, page 4418 (1974). When using internal latent image type silver halide emulsions, 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 impart 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. In addition, examples of nitrogen-containing heterocyclic compounds containing a mercapto group include 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, pyridazine ring, 1,2,3-triazine ring, 1,2,4-triazine ring, 1,3,5-
Triazine rings, etc., and rings in which 2 to 3 of these rings are condensed, such as triazolotriazole rings, diazaindene rings, triazaindene rings, tetrazaindene rings, pentazaindene rings, etc., and phthalazinone rings, indazole rings, etc. Among them, 1-phenyl-5-mercaptotetrazole is particularly preferred. In addition, wetting agents may be used depending on the purpose. Examples of such wetting agents include dihydroxyalkanes, and membrane property improvers include, for example, combinations of alkyl acrylates or alkyl methacrylates with acrylic acid or methacrylic acid. Water-dispersible particulate polymeric substances obtained by emulsion polymerization such as copolymers, styrene-maleic acid copolymers, styrene-maleic anhydride half-alkyl ester copolymers, etc. are suitable, and can be used as coating aids. Examples of these include saponin, polyethylene glycol, lauryl ether, and the like. Other photographic additives include gelatin softeners, surfactants, ultraviolet absorbers, PH regulators, antioxidants, antistatic agents, thickeners, graininess improvers, dyes, mordants, brighteners, and developers. The use of speed modifiers, matting agents, anti-irradiation dyes, etc. is optional. 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. Further, 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. 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. Furthermore, the silver halide photographic material of the present invention is
In addition to the emulsion layer and the protective layer, a filter layer, an intermediate layer, a protective layer,
It is manufactured by coating various photographic constituent layers such as a subbing layer, a backing layer, and 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 process 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 to light. 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 high-intensity light such as flash light for a short time, or to irradiate a weak light. 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, and the type of light source used 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 Although it may be contained in a developer or a processing liquid prior to development, 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. Further, when added to a processing solution such as a developer, the preferred amount is 0.01 to 5 g/, particularly preferably 0.08 to 0.15 g/. 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 compounds described in US Pat. No. 3,227,552; also US Pat.
No. 3718470, No. 3719494, No. 3734738 and No.
Heterocyclic quaternary nitrogen compounds described in US Pat. No. 3,759,901 and the like; and acylhydrazinophenylthioureas described in US Pat. Also,
These fogging agents can also be used in combination.
For example, Research 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. The internal latent image type silver halide photographic light-sensitive material of the present invention generally forms a positive image directly by exposing the entire surface to light after imagewise exposure or by developing it in the presence of a fogging agent. Any development processing method can be adopted as the development processing method for the photosensitive material.
Preferred is a surface development treatment 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 the original image is formed by subjecting an exposed silver halide photographic light-sensitive material to processing using a processing solution having development processing and fixing ability. The above-mentioned development processing includes not only color development processing but also 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 black-and-white developer used in the development process is the so-called black-and-white first developer used in the processing of color photographic light-sensitive materials, or the black-and-white developer used in the processing of black-and-white photographic light-sensitive materials. Various well-known additives can be included. Typical additives include developing agents such as 1-phenyl-3-pyrazolidone, metol and hydroquinone, preservatives such as sulfites, accelerators consisting of alkalis such as sodium hydroxide, sodium carbonate and potassium carbonate, and odors. Inorganic or organic inhibitors such as potassium chloride, 2-methylbenzimidazole, methylbenzthiazole, water softeners such as borisonic acid salts, surface overdevelopment inhibitors consisting of trace amounts of iodides and mercapto compounds, etc. can be mentioned. In the present invention, the first
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
Use at a concentration of ~15g. As an aminophenol developer, for example, 0
-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, examples of particularly useful compounds include N,N
-diethyl-p-phenylenediamine hydrochloride, N
-methyl-p-phenylenediamine hydrochloride, N,
N-dimethyl-p-phenylenediamine hydrochloride,
2-amino-5-(N-ethyl-N-dodecylamino)-toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate, 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 usually 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,
Optionally, water softeners, thickeners, and the like may also be included. The pH value of this color developer is usually 7 or more, most commonly about 10 to about 13. The fixing solution when 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] Cyhydroxyethylglycine citric acid (or tartaric acid) [9] Ethyl etherdiaminetetraacetic acid [10] Glycol etherdiaminetetraacetic acid [11] Ethylenediaminetetrapropionic acid [12] Phenylene Diaminetetraacetic 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] Cyclohexanediamine 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, it is particularly desirable to include rehalogenating agents such as alkali halides or ammonium halides, such as potassium bromide, sodium bromide, sodium chloride, and ammonium bromide, metal salts, chelating agents, and the like. In addition, PH buffering agents such as borates, oxalates, acetates, carbonates, and phosphates, alkylamines, polyethylene oxides, and other substances known to be commonly added to bleaching solutions may be added as appropriate. . 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 addition, in order to increase the activity of the bleach-fix solution, air or oxygen may be blown into the bleach-fix solution 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 the treatment with a treatment liquid having fixing ability, a normal water washing treatment may be performed, but particularly when implementing the present invention, it is preferable to perform a stabilization treatment that does not substantially include a water 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 photosensitive material is preferably to immerse the silver halide photographic material in the bath in the same way as with general processing solutions. It may be applied to the emulsion surface of the silver halide photographic light-sensitive material, both sides of the conveyance leader, and the conveyance belt, or it may be sprayed by spraying 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 agent include isothiazoline type, benzisothiazoline type, thiapendazole type and the like. Furthermore, as metal salts, 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 optical 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, and acetic acid. , or PH adjusters such as sodium hydroxide, sodium acetate, and 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 to improve processing effects. It is optional to add various additives for improvement and expansion. The above compounds and other additives can be added as a concentrated liquid to a 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 stages are treated in a shorter time, and the later stages are treated in a shorter time. It is preferable that the processing time be longer. When implementing the present invention, washing with water before and after stabilization processing may not be necessary, but rinsing with a small amount of water within a short period of time, surface cleaning with a sponge, stabilization of images, and cleaning of silver halide photographic light-sensitive materials are possible. Providing a treatment tank for adjusting surface properties is optional. Examples of the agent for stabilizing the image and adjusting the surface properties of the silver halide photographic light-sensitive material include activators such as formalin and its derivatives, siloxane derivatives, polyethylene oxide compounds, and quaternary salts. When implementing 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. Furthermore, 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. Each emulsion was prepared as follows, and a sample of a silver halide photographic light-sensitive material was manufactured. The following 9 layers from the red-sensitive emulsion layer to the protective layer were deposited on surface-treated 114 μ thick polyethylene laminated paper (consisting of 21 g of polyethylene containing 15 wt% titanium oxide, 75 g of inner paper, and 21 g/ ^m2 of polyethylene). It was coated and dried using a simultaneous coating method. Red-sensitive emulsion layer (first layer) A 2.0% inert gelatin solution was maintained at 50°C, and the following solutions A and B were simultaneously added and poured over 3 minutes while stirring. After 10 minutes, the following solution C was added by injection over a period of 3 minutes. After aging for 40 minutes, excess salt was removed by a precipitation washing method, and then the following solutions D and E were added to form a layer of silver chlorobromide consisting of 95 mol% AgCl and 5 mol% AgBr on the surface. Excess water-soluble salts were removed again by the precipitation washing method, and a small amount of gelatin was added and dispersed.

[Table] This silver halide emulsion was then added with a sensitizing dye [D-
1] and sensitizing dye [D-4], a liquid containing 2,5-dioctylhydroquinone protected and dispersed with dibutyl phthalate and cyan coupler [CC-1], 4-hydroxy-6-methyl-1,3,
3a,7-tetrazaindene, 1-phenyl-5
-Add appropriate amounts of mercaptotetrazole, gelatin, and coating aid [S-1]. Coated silver amount 0.4g/m ²
It was applied so that First intermediate layer (second layer) 2,5- dispersed in dioctyl phthalate
Dioctylhydroquinone and ultraviolet absorber Tinuvin 328 (manufactured by Ciba Geigy), coating aid [S-1
Prepare a gelatin solution containing Tinuvin 328
It was applied at a concentration of 0.15 g/m ² . Green-sensitive emulsion layer (third layer) Silver halide grains were prepared in the same manner as the red-sensitive emulsion. In addition to this, sensitizing dye [D-2], 2,5-dioctylhydroquinone protected and dispersed with dibutyl phthalate, and magenta coupler [MC
-1], 4-hydroxy-6-methyl-
Add appropriate amounts of 1,3,3a,7-tetrazaindene, 1-phenyl-5-mercaptotetrazole, gelatin, and coating aid [S-2]. Coated silver amount
It was applied at a concentration of 0.4 g/m ² . 2nd intermediate layer (4th layer) The same formulation as the 1st intermediate layer with the same amount of Tinuvin 328 applied.
It was set to 0.2g/ ^m2 . 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)
2,5-dioctylhydroquinone liquid dispersed in yellow colloidal silver and dioctyl phthalate, coating aid [S-2] and hardening agent [H-1]
(added just before coating), coated silver amount 0.15g/
It was applied so that it was ² m2. Third intermediate layer (6th layer) Same formulation as the first intermediate layer, coating amount of Tinuvin 328
It was applied at a concentration of 0.15 g/m ² . Blue-sensitive emulsion layer (7th layer) A 1.5% inert gelatin solution was kept at 60° C. and while stirring, the following solutions A and B were simultaneously added and injected over 15 minutes. After 15 minutes, inject the following solution C over 2 minutes, and after 1 minute, add Hypo equivalent to 3 mg/Ag, and then inject for 40 minutes.
Aged for minutes. When sampled and analyzed for composition, it was silver chlorobromoiodide consisting of 4 mol% of AgCl, 96 mol% of AgBr, and 2 mol% of AgI. After removing excess salt by precipitation and washing with water, the following solutions D and E were added to give 97 mol% AgCl and 3 mol% AgBr.
After laminating the surface layer, excess salt was removed again by precipitation and water washing, and gelatin for dispersion was added.

[Table] This silver halide emulsion contains sensitizing dye [D-3],
Liquid containing yellow coupler [YC-1] dispersed with dioctyl phthalate, 2-mercaptobenzothiazole, 4-hydroxy-6-methyl-
1,3,3a,7-tetrazaindei, gelatin,
Using a solution containing a coating aid [S-3] and a hardening agent [H-2] (added immediately before coating), the amount of silver coated was 0.5 g/m ²
It was applied so that 4th intermediate layer (8th layer) Same as the 1st intermediate layer, Tinuvin 328 coating amount 0.3g/
It was applied so that it was ² m2. However, a hardener [H-2] was added immediately before coating. Protective layer (9th layer) Amorphous silica with an average particle size of 3 μm (content ratio is shown in Table 1 below), coating aid [S-3], hardening agent [H-2] and [H -3] (added immediately before coating) was used to coat gelatin so that the coating amount was 1.0 g/ ^m2.In this way, as shown in Table 1, the amount of silica relative to gelatin was 0% (sample 1). (Comparative example), 1% (Sample 2. Present invention), 3% (Sample 3.
(this invention) and 9% (Sample 4. This invention). In addition, as a comparative example with different support thicknesses,
A sample was also prepared in which each of the above layers was applied on a 230 μ thick polyethylene laminated paper (consisting of 27 g of polyethylene containing 15 wt% titanium oxide, 160 g of inner paper, and 30 g/ ^m2 of polyethylene) (Sample 5. The silica content was 0). ). Cyan coupler [CC-1] Magellan coupler [MC-1] Yellow coupler [YC-1] Sensitizing dye [D-1] Sensitizing dye [D-2] Sensitizing dye [D-3] Sensitizing dye [D-4] Coating aid [S-1] Coating aid [S-2] Coating aid [S-3] Hardener [H-1] Hardener [H-2] Hardener [H-3] The obtained sample was tested using the image forming apparatus shown in FIG. Incidentally, FIG. 1 is a schematic cross-sectional view showing an example of an image forming apparatus that can use the photosensitive material of the present invention. , photo processing section 24
and a drying section 30. The image exposure section 3 includes a light source 4, a first reflection mirror 5, a second reflection mirror 6, a third reflection mirror 7, a lens 8,
It consists of a fourth reflecting mirror 9 and a fifth reflecting mirror 10. The light source 4 is provided with a slit, and a light source with no uneven light distribution particularly in the axial direction is preferably used. In this example, a rod-shaped halogen lamp (200 W) with a slit width of 10 mm is used, and a ground glass is provided on the light exit surface to eliminate uneven light distribution. An original image (not shown) placed on a transparent platen glass 2 is slit-exposed by a light source 4, and as the light source 4 scans and moves, the reflected light from the original screen, that is, the optical image, is reflected by a first reflecting mirror 5, Silver halide is moving from the exposure opening 23 in synchronization with the scanning movement of the light source 4 via the second reflecting mirror 6, the third reflecting mirror 7, the lens 8, the fourth reflecting mirror 9, and the fifth reflecting mirror 10. The photosensitive material 12 is sequentially exposed. In this way, a light image corresponding to the original image is exposed onto the silver halide photographic light-sensitive material 12. Note that the first reflecting mirror 5, the second reflecting mirror 6, and the third reflecting mirror 7 move in accordance with the scanning movement of the light source 4. In addition, a lens 8, a fourth reflective mirror 9, and a fifth reflective mirror 1
0 remains stationary during exposure, but when changing magnification, it moves to a predetermined position corresponding to the magnification ratio prior to exposure in order to change the optical distance. On the other hand, the silver halide photographic light-sensitive material 12, which is a sample according to this example, is formed into a roll shape, and the dark box 1
It is housed within 2'. The silver halide photographic material 12 pulled out from the dark box 12' is conveyed within the conveying section 13 by a series of pressure-contact rotating roller pairs 14, 14' to 21, 21'. By the way, silver halide photographic material 1, which has been in roll form until now,
2 is cut into a desired size by a cutting member 22 provided in the conveyance path. Therefore, after being cut, the silver halide photographic material 12 is conveyed in the form of a sheet. As the cutting member 22,
For example, the cutter blade is silver halide photographic light-sensitive material 1.
There are various types of cutter blades, such as one that cuts while moving across two sides in the width direction, and one that cuts the silver halide photographic material at once by lowering the cutter blade horizontally to 12 sides. There is no particular limitation on the member as long as it can cut the silver oxide photographic light-sensitive material 12. Of course, silver halide photographic material 1
As 2, a sheet-like material may be used instead of a roll-like material. When a sheet-like material is used, the cutting member 22 does not need to be provided. The silver halide photographic light-sensitive material 12 thus cut into sheets is exposed to the light image of the original image at the exposure opening 23 while moving in synchronization with the scanning movement of the light source 4, as described above. In this embodiment, the silver halide photographic material 12 is cut before exposure, but it may be cut after exposure. Silver halide photographic material 12 that has been exposed
is sent to the next photo processing section 24. The photographic processing section 24 subjects the exposed silver halide photographic light-sensitive material 12 to photographic processing to form a developed image corresponding to the original image. In this embodiment, the photo processing section 24
consists of four processing tanks, namely a developing processing tank 25, a bleaching and fixing processing tank 26, and stabilizing tanks 27 and 28. The stabilizing tanks 27 and 28 are of a two-tank countercurrent type. Further, the light source 29 is for providing fog exposure during development processing when, for example, an internal latent image type silver halide photographic material is used as the silver halide photographic material 12. The exposed silver halide photographic material 12 is processed in each processing tank for a predetermined time in the photographic processing section 24, then sent to the drying section 30, dried, and discharged from the apparatus. In the figure, 31 is a waste liquid storage section, and 32 is a replenishment liquid storage section. (In this embodiment, the mirror is configured with five mirrors, but the image exposure unit 3 can be made more compact by using three or one mirror, for example). Using the above-mentioned apparatus, a sample was loaded into the magazine 12' and subjected to transportation, exposure, and development processing. The specific photographic processing conditions in this example are as follows. Processing process (processing temperature and processing time) [1] Immersion (color developer) 38℃ 8 seconds [2] Fog exposure 10 seconds at 1 lux [3] Color development 38℃ 2 minutes [4] Bleach-fixing 35℃ 60 seconds [5] Stabilization treatment 25-30℃ 1 minute 30 seconds [6] Drying 75-80℃ 1 minute Processing solution composition (color developer) Benzyl alcohol 10ml Ethylene glycol 15ml Potassium sulfite 2.0g Potassium bromide 1.5g Sodium chloride 0.2g Potassium carbonate 30.0g Hydroxylamine sulfate 3.0g Polyphosphoric acid (TPPS) 2.5g 3-Methyl-4-amino-N-ethyl-N-
(β-methanesulfonamidoethyl)-aniline sulfate 5.5g Fluorescent brightener (4,4'-diaminostilbenzsulfonic acid derivative) 1.0g Potassium hydroxide 2.0g Add water to bring the total amount to 1, pH 10.20 Adjust to. (Bleach-fix solution) Ferric ammonium ethylenediaminetetraacetic acid dihydrate 60g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% solution) 100ml Ammonium sulfite (40% solution) 27.5ml Adjust the pH to 7.1 with potassium carbonate or glacial acetic acid and water Add to make the total amount 1. (Stabilizing liquid) 5-chloro-2-methyl-4-isothiazolin-3-one 1.0g Ethylene glycol 10g 1-hydroxyethylidene-1,1'-diphosphonic acid 2.5g Bismuth chloride 0.2g Magnesium chloride 0.1g Ammonium hydroxide (28% aqueous solution) 2.0g Sodium nitrilotriacetate 1.0g Add water to bring the total volume to 1, and adjust the pH to 7.0 with ammonium hydroxide or acetic acid. Note that the stabilization treatment was carried out using a two-tank liquid-direction method as described above.

[Effect of idea]

As mentioned above, the silver halide photographic light-sensitive material of the present invention does not increase in thickness or volume even when it is filed, and it is easy to file, and it is easy to retouch the surface and write additional corrections. It has the advantage that it can be written on with a regular pencil or ballpoint pen, and there is little risk of shadows appearing even if it is pasted and copied.

[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. 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)

[Scope of utility model registration request] The support has at least one emulsion layer containing internal latent image type silver halide grains and a protective layer, and has an internal latent image layer for obtaining a copied image of the original image by directly exposing the original image and processing it. In the image-type direct positive silver halide photographic light-sensitive material, the support has a thickness of 80 to 150 μm, and the protective layer has a grain size of 1
1. An internal latent image type direct positive silver halide photographic light-sensitive material, which contains fine particle powder of ~10 μm, and the content of the fine particle powder is 0.5 to 5 wt% based on the hydrophilic binder.