JPS6134652B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material (hereinafter abbreviated as wash-off light-sensitive material) that forms a wash-off relief image of excellent image quality. Wash-off photosensitive materials are developed using a tanning developing agent to harden only the exposed areas of the photosensitive layer and not the unexposed areas.
This is for forming a so-called relief image in which unexposed areas are removed and exposed areas remain in relief by washing the photosensitive surface after development. Also in wash-off photosensitive materials, it is known to provide an antihalation layer between the support and the photosensitive layer in order to improve the sharpness of the image. The antihalation layer is usually composed of a light-absorbing substance and a binder, and the light-absorbing substance is a dye, pigment, colloidal silver, carbon black, etc., and the binder is a hydrophilic polymer such as gelatin. In wash-off photosensitive materials that have an antihalation layer between the support and the photosensitive layer, upon exposure and development, the tanning developer not only hardens the exposed portion of the photosensitive layer, but also affects the antihalation layer below the photosensitive layer. It diffuses and also hardens the antihalation layer. Therefore, if a water-insoluble dye such as carbon black is used in the antihalation layer, the density of the dye in the antihalation layer is added to the density of the photosensitive layer in the exposed area, so that the density of the image can be extremely high. However, the longer the period from manufacture to use of the wash-off photosensitive material having the above structure, the more apparent fog occurs. Particularly when the antihalation layer contains carbon black as a light absorber, the apparent fog increases significantly due to such storage. This is because when a stored photosensitive material is washed off after being developed with a curable developing agent, part of the antihalation layer containing carbon black sticks to the undercoat layer and cannot be washed away. It's for a reason. For this reason, although the photosensitive material having the above structure has high image density and image sharpness, it has been problematic in practical use. An object of the present invention is to provide a wash-off light-sensitive material that has high image density, excellent image sharpness, and does not increase apparent fog even after a long period of time. The above purpose is to provide a silver halide photographic material in which an undercoat layer, an antihalation layer, and a photosensitive layer containing a tanning developing agent are provided on a support in this order. This was achieved by providing an intermediate layer containing. The subbing layer described above may be applied directly onto the support or may be applied over a matte layer as described in US Pat. No. 4,076,531. The intermediate layer provided in the photosensitive material of the present invention is composed mainly of a hydrophilic polymer. Hydrophilic polymers include gelatin, casein, carboxymethyl cellulose, polyvinyl alcohol, polyvinylpyrrolidone, styrene-maleic anhydride copolymer, condensate of styrene-maleic anhydride copolymer and polyvinyl alcohol, polyacrylate, and ethyl cellulose. etc. In the present invention, a hydrophilic polymer that is hardened by the oxidation product of a developing agent is preferred, and gelatin is preferred. In the manufacturing process, the gelatin used in the above-mentioned intermediate layer is so-called alkali-treated (lime-treated) gelatin that is soaked in an alkaline bath before gelatin extraction, acid-treated gelatin that is soaked in an acid bath, or "Bull.
Any enzyme-treated gelatin as described in "Soc.Sci.Photo.Japan", No. 16, p. 30 (1966) may be used. Further, for the intermediate layer of the light-sensitive material of the present invention, low molecular weight gelatin which is partially hydrolyzed by heating the gelatin in a water bath or by treating it with a proteolytic enzyme can also be used. The gelatin applied to the intermediate layer of the light-sensitive material of the present invention may be partially composed of colloidal albumin, casein, cellulose derivatives such as carboxymethyl cellulose and hydroxyethyl cellulose, sugar derivatives such as agar, sodium alginate, and starch derivatives, if necessary. Synthetic hydrophilic colloids, such as polyvinyl alcohol, polyN-vinylpyrrolidone, polyacrylic acid copolymer, polyacrylamide, or derivatives thereof, can be replaced with partial hydrolysis, etc. In addition, so-called gelatin derivatives, that is, functional groups contained in the molecule. A graft polymer made by treating or modifying an amino group, an imino group, a hydroxyl group, or a carboxyl group with a reagent having one group that can react with them, or by bonding molecular chains of other polymeric substances. May be used instead. In addition to the hydrophilic polymer, surfactants and thickeners commonly used in silver halide emulsion layers can be added to the intermediate layer. A surfactant is added as necessary for purposes such as a coating aid, antistatic properties, and improvement of photographic properties (eg, development acceleration, high contrast, sensitization, etc.). For example, saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/
polypropylene glycol condensates, polyethylene glycol alkyl or alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkyl amines or amides, polyethylene oxide adducts of silicones), glycidol derivatives (e.g. alkenyl succinic polyesters). glycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, nonionic surfactants such as urethanes or ethers; triterpenoid saponins, alkyl carboxylates, alkyl sulfonic acids salts, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkyl phenyl ethers carboxy groups, sulfo groups, such as polyoxyethylene alkyl phosphates, etc.
Anionic surfactants containing acidic groups such as phospho groups, ethyl sulfate groups, and phosphate ester groups; amino acids;
Aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphoric esters, alkyl betaines,
Ampholytic surfactants such as amine imides and amine oxides; alkyl amine salts, aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridium and imidazolium, and phosphoniums containing aliphatic or heterocyclic rings. Alternatively, cationic surfactants such as sulfonium salts can be used. Specific examples of these surfactants are described in U.S. Pat.
No. 2240472, No. 2831766, No. 3158484, No.
No. 3210191, No. 3294540, No. 3507660, No. 3210191, No. 3294540, No. 3507660, No.
No. 2739891, No. 2823123, No. 3068101, No.
No. 3415649, No. 3666478, No. 3756828, No.
No. 3133816, No. 3441413, No. 3475174, No. 3475174, No. 3441413, No. 3475174, No.
No. 3545974, No. 3726683, No. 3843368, No.
No. 2271623, No. 2288226, No. 2944900, No.
No. 3253919, No. 3671247, No. 3722021, No.
3589906, 3666478, 3574924, British Patent No. 1012495, 1022878, 1179290, British Patent No.
No. 1198450, No. 1397218, No. 1138514, No.
No. 1159825, No. 1374780, No. 1507961, No.
No. 1503218, Belgian Patent No. 731126, West German Patent Application No. OLS 1961638, West German Application No. 2556670, JP-A-Sho
No. 50-117414, No. 50-59025, No. 53-21932,
It is described in No. 52-77135, etc. Examples of thickeners include those made of anionic polymer compounds commonly used in the art, and structurally include vinylbenzenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, acrylic acids, such as methacrylic acid, maleic acid, half ester of maleic acid, phosphoric acid monoester of hydroxyethyl acrylate,
In the side chain, −SO ₃ M, −COOM,

[Formula] means a polymer or copolymer of monomers having a group such as (M:H, metal ion), or a copolymerization of these monomers with other copolymerizable monomers. . Specifically, sodium polyvinylbenzenesulfonate, sodium polyacrylate, and JP-A-51-81123, JP-A-52
Thickeners such as those described in No. 67318 or No. 53-39119 are preferably used. The thickness of the intermediate layer is preferably between 0.05 and 1.45 microns, particularly preferably between 0.1 and 0.8 microns. The photographic emulsion used in the photosensitive layer of the photosensitive material of the present invention contains at least a photosensitive silver halide, a hydrophilic protective colloid, and a tanning developing agent. Silver halide emulsions are usually soluble silver salts (e.g. silver nitrate)
It is made by mixing the solution and a water-soluble halide salt (eg, potassium bromide) solution in the presence of a water-soluble polymer solution such as gelatin. As the silver halide, in addition to silver chloride and silver bromide, mixed silver halides such as chlorobromide, silver iodobromide, and silver chloroiodobromide can be used. The shape of these silver halide grains may be cubic, octahedral, or a mixed crystal form thereof. The particle diameter and average particle size distribution do not need to be particularly limited;
It can be anything. These silver halide grains are produced according to known and commonly used methods. Of course, it is also useful to use the so-called single or double jet method, controlled double jet method, or the like. Furthermore, two or more types of silver halide photographic emulsions formed separately may be mixed. These photographic emulsions are
“The Theory of
Photographic Process” (The Theory of Photographic Process)
It is also described in books such as "Chimie Photographique" by P. Grafikides (Photographic Process), published by Mac Millan, published by Paul Montel (1957), etc. It can be adjusted by various generally accepted methods such as an ammonia method, a neutral method, and an acid method. After forming such silver halide grains, they are washed with water to remove by-product water-soluble salts (for example, potassium nitrate when silver bromide is made using silver nitrate and potassium bromide) from the system. Heat treatment is performed in the presence of chemical sensitizers such as sodium thiosulfate, N-N-N'-trimethylthiourea, monovalent gold thiocyanate chain salts, thiosulfate complexes, stannous chloride, hexamethylenetetramine, etc. Increase sensitivity without coarsening. These general laws are set out above. The above silver halide emulsion can also be chemically sensitized by conventional methods. Chemical sensitizers include
For example, US Patent No. 2399083, US Patent No. 2540085, US Patent No.
Gold compounds such as chlorauric acid salts and gold trichloride as shown in No. 2597856 and No. 2597915;
No. 2448060, No. 2540086, No. 2566245, No.
Platinum as shown in Nos. 2566263 and 2598079,
Salts of noble metals such as palladium, iridium, rhodium and ruthenium, US Patent No. 1574944
Sulfur compounds that react with silver salts to form silver sulfide, such as those described in US Pat.
No. 2518698, No. 2521925, No. 2521926,
Examples include stannous salts, amines, and other reducing substances as described in No. 2694637, No. 2983610, and No. 3201254. As the hydrophilic protective colloid for the silver halide emulsion, the compounds described as hydrophilic polymers used in the intermediate layer of the light-sensitive material of the present invention can be used, but gelatin is preferred. The type and manufacturing method of gelatin that can be preferably used are the same as those for gelatin for the intermediate layer, but the protective colloid of the silver halide emulsion and the hydrophilic polymer for the intermediate layer are of exactly the same type of gelatin. may also be different. Examples of the tanning developing agent used in the photosensitive material of the present invention include catechol, 4-phenylcatechol, hydroquinone, pyrogallol, dihydroxybiphenyl, polyhydroxyspirobisindane, and the like.
The descriptions in specifications such as No. 2592368, No. 2685510, No. 3143414, No. 2751295, and No. 3440049 can be referred to. When these tanning developing agents are contained in the photosensitive material, the amount is preferably 0.005 to 1 mol, particularly 0.01 to 0.3 mol, per 1 mol of silver halide in the photosensitive layer. The addition site is preferably the photosensitive layer, but is not limited thereto, and can also be added to other layers such as an antihalation layer and an intermediate layer. As a method of incorporating a tanning developing agent into a sensitive material, in addition to the method of neutralizing and adding an alkaline solution of the compound as described in U.S. Pat. , a method of dissolving and dispersing in a water-soluble organic solvent such as ethylene glycol, dioxane, dimethylformamide, or butyl phthalate, dinonyl phthalate,
Butyl benzoate, diethylhexyl sebatate,
Butyl stearate, dinonyl maleate, tributyl citrate, tricresyl phosphate, dioctyl butyl phosphate, trihexyl phosphate, triotadecyl phosphate, etc. High boiling point organic solvents for coupler dispersion as described in U.S. Pat. No. 3,676,137; Diethyl succinate, dioctyl adipate, 3
- Methods such as dissolving and dispersing in ethyl biphenyl etc. can be used. Furthermore, the surfactants used in dispersing the solution of the tanning developer used in the present invention in the above-mentioned solvent into the hydrophilic protective colloid solution include saponin, sodium alkylsulfosuccinate, and sodium alkylbenzenesulfonate. etc. can also be used. Furthermore, in the photosensitive material of the present invention, by containing at least one compound each represented by the following general formulas (), (), and () in at least one of the photosensitive layer or its hydrophilic colloid layer, A wash-off relief image that is more preferable in terms of photographic characteristics can be obtained. That is, this makes it possible to provide a light-sensitive material containing a developing agent that has strong development activity and whose oxidation product has appropriate curing properties against hydrophilic protective colloids, and which can be used in the photographic emulsion layer or its adjacent layer. It is possible to provide a photosensitive material containing a tanning developing agent that can be stably incorporated into a photosensitive material for a long period of time, and also to significantly suppress hardening of unexposed areas, and to produce cured images with excellent image sharpness and high image density in terms of photographic properties. It is possible to provide a photosensitive material that can be produced. In the formula, R ¹ represents a hydrogen atom or an optionally substituted alkyl group. R ² represents an optionally substituted alkyl group. R ³ represents an alkyl group having 3 to 8 carbon atoms. When R ¹ represents an alkyl group in the general formula (), preferred examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, heptyl group, hexyl group, nonyl group, decyl group, etc. Alkyl groups may be straight chain or branched. Substituents for the above alkyl groups include halogen atoms (chlorine atoms, bromine atoms, etc.), hydroxy groups, carboxy groups, alkoxy groups (preferably alkoxy groups having 1 to 4 carbon atoms), primary, secondary or There are tertiary amino groups, etc. However, among the above-mentioned alkyl groups, substituted or unsubstituted alkyl groups having 1 to 5 carbon atoms are preferred because of their excellent solubility and photographic performance. Preferred examples of the alkyl group represented by R ² in the general formula () are the same as the preferred examples of R in the general formula (), but alkyl groups having 2 to 5 carbon atoms are preferable because they have excellent solubility and photographic performance. A group is more preferable, and an alkyl group having 3 carbon atoms is especially preferable. The alkyl group represented by R ³ in the general formula () may be linear or branched and preferably has 3 to 8 carbon atoms. Specifically, they include propyl group, butyl group, hexyl group, octyl group, etc. Among these, particularly preferred alkyl groups are those having 4 to 6 carbon atoms. Specific compounds suitable for the present invention are shown in detail in Japanese Patent Application No. 100593/1983. The compound represented by the general formula () is
It can be easily produced by a method similar to the synthesis method of polyhydroxy-spiro-bis-indane described in No. 3440049 (1969), but the rearrangement to polyhydroxy-spiro-bis-indane is suppressed as much as possible, In order to obtain a high yield of polyhydroxy-spiro-bis-chroman, it is important to keep the reaction temperature as low as possible, and specifically, it is preferable to carry out the reaction temperature at 100°C or lower, especially at 80°C or lower. is preferred. The compound represented by the general formula () is widely used as an antioxidant added to fats and oils and butter. In the compound represented by the general formula (), the linear alkyl group-substituted product can be synthesized by a catalytic reduction method using the corresponding acyl product in the presence of a nickel or palladium catalyst or the like. The branched alkyl group-substituted product can be synthesized using catechol and an olefin corresponding to the desired substituent using sulfuric acid, hydrochloric acid, an ion exchange resin, activated clay, or the like as a catalyst. These compounds can be stably contained in photographic materials or processing solutions. Moreover, it shows good development activity for silver halide exposed to light and has an excellent hardening action for hydrophilic protective colloids, especially gelatin. That is, the gelatin or photosensitive film cured using the compounds of the general formula (), general formula (), and general formula () used in the present invention has extremely high dissolution resistance to alkaline solutions. Furthermore, the compounds of general formula (), general formula (), and general formula () used in the present invention do not interact with other photographic additives that coexist, such as antifoggants, and therefore are not compatible with other photographic additives. The effect of additives is not reduced and the developing and curing activity of the developing agent is not lost. In order to disperse the compounds of general formula (), general formula () and general formula () of the present invention in a silver halide emulsion layer or its adjacent layer, US Pat.
As described in No. 3440049, other methods for neutralizing alkaline solutions of the compound include dichlorohexanone, acetone, methoxyethanol, ethoxyethanol, ethylene glycol, dioxane,
A method of dissolving and dispersing in a water-soluble organic solvent such as dimethylformamide, or butyl phthalate,
Dinonyl phthalate, butyl benzoate, diethylhexyl sebatate, butyl stearate, dinonyl maleate, tributyl citrate, tricresyl phosphate, dioctyl butyl phosphate, trihexyl phosphate, triotadecyl phosphate, etc. Listed in US Patent No. 3,676,137 A method of dissolving and dispersing the coupler in a high-boiling organic solvent for dispersing the coupler, diethyl conicate, dioctyl adidinate, 3-ethylpifhenyl, etc., as described above, can be used. Furthermore, saponin, sodium alkylsulfosuccinate, and sodium alkylbenzenesulfonate can be used as a surfactant when dispersing a solution of the curable developer used in the present invention in the above-mentioned solvent into a hydrophilic protective colloid solution. etc. can also be used. The compound represented by the general formula () of the present invention is preferably added in an amount of 0.01 to 1 mol/mol Ag, particularly preferably 0.02 to 0.3 mol/mol Ag, to the light-sensitive material. The compound represented by the general formula () is preferably added to the light-sensitive material in an amount of 0.005 to 0.1 mol/mol Ag, particularly preferably 0.01 to 0.1 mol/mol Ag. The compound represented by the general formula () is preferably added to the light-sensitive material in an amount of 0.01 mol to 1 mol/mol Ag, particularly preferably 0.03 mol to 0.3 mol/mol Ag. A typical example of the hydrophilic protective colloid in the silver halide photosensitive layer used in the photosensitive material of the present invention is gelatin. Other examples include casein, carboxymethyl cellulose, polyvinyl alcohol, polyvinylpyrrolidone, styrene-maleic anhydride copolymer, condensate of styrene-maleic anhydride copolymer and polyvinyl alcohol, polyacrylate, ethylcellulose, etc., but the present invention is not limited to this. The silver halide emulsion layer can also contain antifoggants, polymer latexes, surfactants, chemical sensitizers, spectral sensitizing dyes, etc., but these additives are subject to research.・Research Disclosure
You can refer to the description in Vol. 176, pages 22-29 (December 1978). The antihalation layer used in the photosensitive material of the present invention preferably uses a binder that is hardened by the oxidation product of the developing agent, similar to the binder used in the photosensitive layer, etc., and the light absorbing material is carbon black or colloidal silver. and Research Disclosure magazine 17643 (1978
The dyes described in the December issue of 2010 can be used. If the above-mentioned binder is used in the antihalation layer, the antihalation layer under the exposed emulsion layer will be cured together with the photosensitive layer and will not be removed by processing, but the antihalation layer below the exposure level in the unexposed areas will be cured by processing. It is removed along with the photosensitive layer. Therefore, there is no need for the light-absorbing substance in the antihalation layer to be decolorized by development or to be eluted into a processing solution. Rather, image density can be further increased if the light-absorbing substance in the antihalation layer remains in the exposed area even after development. Therefore, the light-absorbing substance in the antihalation layer is preferably one such as carbon black or colloidal silver, which is not bleached by ordinary black-and-white processing solutions and does not dissolve into the processing solution, in order to increase the image density. In particular, carbon black is preferable since it fully exhibits the effects of the present invention. The thickness of the antihalation layer is preferably from 0.05 to 1.45 microns, particularly preferably from 0.2 to 0.9 microns. The combined thickness of the antihalation layer and the intermediate layer is preferably 0.1 to 1.5 microns, particularly preferably 0.3 to 1.0 microns. The support used in the photosensitive material of the present invention may be a hard support such as glass, metal, or ceramic, or a flexible support, depending on the purpose, as long as it is a flat material that does not undergo significant dimensional changes during processing. It may be a support. Typical flexible supports include cellulose nitrate film, cellulose acetate film, cellulose acetate butylate film, cellulose acetate propionate film, polystyrene film, polyethylene terephthalate film, which are usually used in photographic materials. Polycarbonate film, other laminates of these, glass, paper coated with baryta, α-
Olefin polymers, especially polyethylene, polypropylene, ethylenebutene copolymers, etc. with 2 carbon atoms
Paper coated or laminated with α-olefin polymer of ~10, as described in Japanese Patent Publication No. 19068/1983. By roughening the surface, it improves adhesion with other polymeric substances, There are also plastic films that have improved printability. These supports are selected to be transparent or opaque depending on the purpose of the photosensitive material. In addition, when the material is transparent, it is not only colorless and transparent, but also dye-pigment can be added to make it colored and transparent. This has been done in the past with X-ray films and is also known in J.SMPTE 67 296 (1958). Opaque supports include those that are inherently opaque such as paper, transparent films to which dyes and pigments such as titanium oxide are added, or plastic films that have been surface-treated by the method described in Japanese Patent Publication No. 19068-1983. Furthermore, it also includes paper, plastic film, etc. that have been made completely light-shielding by adding carbon black dye or the like. When the adhesive strength between the support and the photosensitive layer or intermediate layer is insufficient, a layer having adhesive properties to either of them is provided as an undercoat layer. Further, in order to further improve the adhesion, the surface of the support may be subjected to preliminary treatment such as corona discharge, ultraviolet irradiation, flame treatment, etc. A matte layer may be provided on one or both sides of the support used in the photosensitive material of the present invention. The matting agent used in the matting layer is fine particles of a water-insoluble organic or inorganic compound with an average particle diameter of 0.2μ to 10μ, particularly preferably 0.3μ to 5μ.
It is up to μ. Examples of organic compounds include:
Examples of water-dispersible vinyl polymers include polymethyl acrylate, polymethyl methacrylate, polyacrylonitrile, acrylonitrile-α-methylstyrene copolymer, polystyrene, styrene-divinylbenzene copolymer, polyvinyl acetate, polyethylene carbonate, polytetrafluoro Examples of cellulose derivatives such as ethylene include methyl cellulose, ethyl cellulose, cellulose acetate, cellulose acetate propionate, and nitrocellulose. Examples of starch derivatives include carboxy starch, carboxy nitrophenyl starch, urea-formaldehyde-starch reactants, etc. Gelatin hardened with a known hardening agent, hardened gelatin hardened with coacervate to form microcapsule hollow particles, etc. can be preferably used alone or in combination. As examples of inorganic compounds, silicon dioxide, titanium dioxide, magnesium dioxide, aluminum dioxide, barium sulfate, calcium carbonate, silver chloride desensitized by a known method, silver bromide, glass, etc. can be preferably used. The above-mentioned matting agents can be used by mixing different types of substances as necessary. To form a hematite layer on a hydrophobic support, the binder may be dissolved in a solvent, a matting agent may be added thereto, dispersed using an attritor, sand grinder, homomixer, ball mill, etc., and applied to the support. The solvent used is acetone,
Ketones such as methyl ethyl ketone, cyclohexanone, etc.; Esters such as ethyl acetate, propyl acetate, butyl acetate; Ethers such as dioxane, tetrahydrofuran; Alcohols such as methanol, ethanol, propanol, butanol, diacetone alcohol; Chlorides such as methylene chloride, ethylene chloride, propylene chloride, etc.; Phenols such as phenol, cresol, resorcin, etc.; Methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, dimethyl formamide; etc. alone or in combination of two or more. Can be used. There is no problem in adding coating aids, crosslinking agents, whitening agents, etc. to the matte layer. Titanium oxide (0.1-0.5μ) is preferred as the whitening agent. The coating amount of titanium oxide is 0.03~3g/ ^m2 , especially 0.05~2g/m2.
Preferably, it is ^m2 . The matte layer may be applied directly to the support, or a subbing layer may be provided on the support and the matte layer may be applied thereon. As a binder, the undercoat layer for applying the pine layer may contain nitrocellulose, cellulose diacetate, cellulose ester, polyester, styrene-butadiene copolymer, vinylidene chloride copolymer, alone or in combination. It is applied using an organic solvent such as methanol, acetone, or methyl ethyl ketone. The undercoat layer may contain a PET swelling agent such as gresol, p-chlorophenol, resorcinol, etc., if necessary. For the application of the matte layer, ordinary coating methods such as clavier coating, extrusion coating, dip coating, bar coating, and roller bead coating can be used. The drying temperature is preferably 50 to 140°C, and the drying time is preferably 30 seconds to 10 minutes. The amount of matting agent applied is 1 to 20 per square meter.
g, especially preferably 3 to 10 g. The amount of polymethyl methacrylate applied is preferably 1 to 10 g, particularly 2 to 5 g per square meter. The amount of nitrocellulose applied is preferably 0.5 to 10 g, particularly 1 to 5 g per square meter. The undercoat layer on a support having a matte layer usually consists of a binder such as gelatin or nitrocellulose as a main component. It is preferable to contain an inorganic or organic hardening agent for this purpose. Examples include chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, cultaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.) ), activated vinyl compound (1,3,5-triacryloyl-hexahydro-s-triazine,
bis(vinylsulfonyl) methyl ether, vinyl sulfone compounds described in JP-A-54-73871, etc.), active halogen compounds (2,4-dichloro-6-hydroxy-s-triane, etc.), mucohalogen acids (mucochlor acid, mucophenoxychloric acid, etc.), isoxazoles, dialdehyde starch, 2-chloro-6-hydroxytriazinylated gelatin, polyamide epichlorohydrin resin, etc. can be used alone or in combination. Specific examples include U.S. Patent No. 1870354 and
No. 2080019, No. 2726162, No. 2870013, No. 2080019, No. 2726162, No. 2870013, No.
No. 2983611, No. 2992109, No. 3047394, No.
No. 3057723, No. 3103437, No. 3321313, No.
No. 3325287, No. 3362827, No. 3539644, No. 3325287, No. 3362827, No. 3539644, No.
3543292, British Patent No. 676628, British Patent No. 825544, British Patent No.
No. 1270578, No. 2002529A, German patent 872153
No. 1090427, Special Publication No. 3467133, No. 46-1872
No. 49-26580, etc. Among these, preferable hardening agents are aldehydes (for example, formaldehyde, glyoxal, etc.),
N-methylol compounds (such as dimethylol urea), polyamide epirrolhydrin resins as described in Japanese Patent Publication No. 49-26580, or hydroxyl in the main chain as described in Japanese Patent Publication No. 54-73871. Vinyl sulfone compounds having a substituted group are preferred. Particularly preferred are polyamide epichlorohydrin resins and vinyl sulfone compounds whose main chains are substituted with hydroxyl groups. The undercoat layer may contain cresol, p-chlorophenol, resorcinol salicylic acid, etc., if necessary. The binders for these matte layers, undercoat layers, etc., as well as antihalation layers, photosensitive layers, etc.
Preferably, it is cured by oxidation products of the developing agent. The developing treatment of the photosensitive material of the present invention is characterized in that the developing bath is an alkaline activator bath, but the other steps can be carried out as usual. The PH of the activator is selected to be in the range of about 7 to 14, preferably PH12 to PH14. The temperature of the activator treatment is preferably in the range of 5 to 30°C, particularly preferably 13 to 20°C. The activator used in the present invention is basically a general black and white developer from which the developing agent has been removed. As the PH buffer for the activator, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium or potassium tertiary phosphate, potassium metaphosate, borax, etc. are used alone or in combination. In addition, for the purpose of providing buffering capacity, for convenience in preparation, or to increase ionic strength, additional additives such as disodium or potassium hydrogen phosphate, sodium or potassium dihydrogen phosphate, sodium or potassium bicarbonate, Various salts such as acids, alkali nitrates, and alkali sulfates can be used. Further, an appropriate amount of a fog suppressant can also be included. These include inorganic halide compounds and known organic antifoggants. Typical examples of this inorganic halide compound are bromides such as sodium bromide, potassium bromide, or ammonium bromide;
An iodide such as potassium iodide or sodium iodide. On the other hand, examples of organic antifoggants include 6-nitrobenzindazole described in U.S. Pat. No. 2,496,940, U.S. Pat. No. 2,497,917, and U.S. Pat.
5-nitrobenzimidazole, as described in the Journal of the Photographic Society of Japan, Vol. 11, p. 48 (1948), as well as diaminophenazine and o-phenylenediamine, as well as mercaptobenzimidazole, methylbenzthiazole, and mercaptobenzoxazole. ,
Examples include heterocyclic compounds represented by thiouracil, 5-methylbenztriazole, and the compound described in Japanese Patent Publication No. 46-41675. In addition, antifoggants listed in "Science Photography Handbook" Volume 2, page 119 (Maruzen, published in 1959) can also be used. For surface layer development adjustment, Japanese Patent Publication No. 46-19039, No. 45
Development inhibitors known from No.-6149, US Pat. No. 3,295,976, etc. can also be used. In addition, ammonium chloride, potassium chloride, sodium chloride, etc. can be added as necessary. Further, if necessary, any development accelerator can be added in combination. Among these are U.S. Patent 2648604
Various pyridinium compounds and other cationic compounds represented by Japanese Patent Publication No. 44-9503 and U.S. Patent No. 3,671,247, cationic pigments such as phenosaffron, neutral salts such as thallium nitrate and potassium nitrate, and Japanese Patent Publication No. 44-9504. No., U.S. Patent No. 2533990
Nonionic compounds such as polyethylene glycol and its derivatives, polythioethers, etc., described in No. 2531832, No. 295070, and No. 2577127,
-9509, Belgian Patent No. 682862, organic solvents, organic amines, ethanolamine, ethylenediamine, diethanolamine, etc. In addition, “Photographic Processing Chemistry” by LFAMason
"Processing Chemistry" pp. 40-43 (Focal
Press-London 1966). Also, sodium sulfite, potassium sulfite, potassium bisulfite, and sodium bisulfite can be added. Furthermore, polyphosphoric acid compounds represented by sodium hexametaphosphate, sodium tetrapolyphosphate, sodium tripolyphosphate, or potassium salts of the above polyphosphoric acids, ethylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, N-( Aminopolycarboxylic acids such as hydroxymethyl)ethylenediaminetriacetic acid and diethylenetriaminepentaacetic acid can be used as water softeners. The amount added varies depending on the hardness of the water, but is usually between 0.5 and
Can be used at around 10g/. Other calcium and magnesium suppressants can also be used. These are "Belgisches Chmiches" by J. Willems.
Industry” 21, P325 (1956) and 23, P1105
(1958). Next, preferred embodiments of the present invention will be listed. 1. A light-sensitive material as claimed in the claims in which the binder of the antihalation layer and the silver halide emulsion layer substantially comprises gelatin. 2. The photosensitive material described in embodiments 1 to 3, in which the antihalation layer contains carbon black. 3. The photosensitive material as claimed in the claims, wherein the intermediate layer between the undercoat layer and the antihalation layer has a thickness of 0.05 to 1.45 microns. 4. The photosensitive material as claimed in the claims, wherein the combined thickness of the antihalation layer and the intermediate layer is 0.1 to 1.5 microns. 5 Claims or embodiments 1 to 4 in which the undercoat layer contains an aldehyde (for example, formaldehyde, glyoxal, etc.), an N-methylol compound (for example, dimethylol urea, etc.), or a polyamide epichlorohydrin resin
Photosensitive materials listed in section. 6. A photosensitive material according to the claims, which contains at least one compound each represented by the general formulas (), (), and () in at least one layer thereof. 7. A photosensitive material as described in Claims or Embodiments 1 to 6, which has a matte layer on a support. The present invention will be explained in more detail by describing examples below. Example Samples A and B were prepared by the following method. Sample A An emulsion containing 60 g of gelatin and 1.1 mol of silver bromide (30 mol % silver bromide) in 760 g of water was prepared. The average grain size of the silver chlorobromide was 0.4 microns. After removing soluble salts from this emulsion in a conventional manner, it was chemically sensitized by adding sodium thiosulfate. The following substances were added to this raw emulsion. Saponin 6 aqueous solution 20g Dispersion (a) prepared by the following method 500g Composition (a-1) and composition (a-2) having the following composition were mixed and stirred vigorously to form a dispersion.
I chose (a).

【table】 A composition for an antihalation layer having the following composition was also prepared. Gelatin 40g Carbon black 15g Water 1 A composition for an intermediate layer having the following composition was also prepared. Gelatin 40g Water 1 Preparation of a support with a matte layer Add a solution of the following composition to a biaxially stretched and crystallized polyethylene terephthalate film with a thickness of 100μ.
g/m ² and dried at 120°C for 5 minutes. Cellulose acetate 0.4wt% Nitrocellulose 0.4 Acetone 50 Resorcinol 6.2 Methaninol 43 Next, 50g of matting agent dispersion having the following composition
m ² coated and dried at 120°C for 10 minutes. Polymethyl methacrylate (trade name Sumipex B-LG) 9 wt% Diacetone alcohol 15 Acetone 50 Methanol 11 Nilocellulose (Daicel.RS1/2) 2.5 Silicon oxide (average size 1.5μ) 12 Titanium oxide (average size 0.3μ) 0.5 Next, 10 g/m ² of the following solution was applied as an undercoat on the mat layer and dried at 120° C. for 10 minutes. Gelatin 1 wt% Polyamide epichlorohydrin resin described in Japanese Patent Publication No. 49-26580 0.02 Nitrocellulose 0.5 Water 2 Acetic acid 2 Methanol 63.48 Acetone 30 First, on a support having a matte layer undercoated as above, an intermediate layer was prepared. The composition was applied so that the gelatin coating amount was 0.4 g/m ² , and then the composition for the antihalation layer was applied so that the gelatin coating amount was 0.4 g/m 2 .
It was applied as per 0.4 g/m ² . At this time, the obtained film thicknesses were 0.4 μm for the intermediate layer and 0.4 μm for the antihalation layer. On top of that, put a photosensitive layer with an amount of silver of 3g/
Coat it to a thickness of m ² and dry it as sample A. Sample B A sample was prepared in exactly the same manner as Sample A, except that no intermediate layer was applied and the following composition was applied as an antihalation layer on the undercoat layer so that the coating amount of gelatin was 0.8 g/m ² I made it. This is designated as sample B. At this time, the film thickness of the antihalation layer was 0.8 μm. Test Samples A and B were subjected to forced aging to perform a preservability test. For forced aging, the samples were left in an environment of 50°C and 70% relative humidity for 1 and 3 days. After that, each sample, including samples that were not subjected to forced aging, was immersed in an activator solution (PH13.8) with the following composition without exposure.
The sample was immersed for 10 seconds at 20°C, and then the emulsion surface was wiped with a sponge in warm water at 40°C to determine whether an antihalation layer remained on the sample surface. Activator treatment liquid Potassium carbonate 25 g Potassium hydroxide 7 g Potassium sulfite 1 g Potassium bromide 0.1 g Water 1 The obtained results are shown in Table-1. As can be seen from Table 1, in Sample B, which does not have an intermediate layer, the carbon of the antihalation layer remains on the unexposed areas of the photosensitive surface over time, and the surface is clean and the apparent fog (optical density of the unexposed areas) is reduced. On the other hand, sample A having an intermediate layer had a clean surface with no carbon remaining even after aging.

【table】

Claims (1)

[Claims] 1 In a silver halide photographic light-sensitive material in which an undercoat layer, an antihalation layer, and a photosensitive layer containing a tanning developing agent are provided in this order on a support, an intermediate layer containing gelatin is provided between the undercoat layer and the antihalation layer. 1. A silver halide photographic material forming a wash-off relief image.