JP2622878B2 - Silver halide photographic material - Google Patents

Description

Description: BACKGROUND OF THE INVENTION The present invention relates to a photographic material having a back layer having improved physical properties, and more particularly, to a back layer having excellent scratch resistance, sliding properties and antistatic properties. A photographic light-sensitive material having

(Prior art) Photosensitive materials are generally cellulose triacetate,
A silver halide photographic emulsion layer and, if necessary, an intermediate layer and a protective layer on one or both of supports such as polyethylene terephthalate, paper or paper coated on both sides with polyethylene terephthalate, or on both sides, The layers are formed by combining various layers of a photographic light-sensitive material such as a filter layer, an antistatic layer, and an anti-halation layer, and generally comprise a hydrophilic binder such as gelatin. As a photographic material having a photographic emulsion coated on both sides of a support, for example, there is a direct X-ray film, but most other photographic materials have a photographic emulsion coated on only one side of the support. ing. Therefore, in the latter case, there is a surface on which the photographic emulsion is not coated, that is, a support surface, which is generally referred to in the art as the "back surface" of a photographic light-sensitive material.

In general, depending on the type of photosensitive material, as a means of improving the photographic or physical quality of the photographic material, an anti-halation layer, an antistatic layer, an anti-adhesion layer, an anti-curl layer, An auxiliary layer such as an overcoat layer is provided.

Since the photographic material has the configuration as described above,
In handling such as winding, rewinding or transporting in the manufacturing process such as coating, drying, processing, shooting, development processing, printing, projection, etc., with various devices, machines, photosensitive materials such as cameras Between contact parts or dust,
Frequently, it is severely adversely affected by contact friction with deposits such as fiber waste.

For example, scratches and abrasions on the surface on the side of the photographic emulsion layer or on the back surface, and deterioration in the driveability of the photosensitive material in a camera or other machine. Of these, the back surface is particularly likely to occur because there are many opportunities for direct contact with various machines. The occurrence of these abrasions is superimposed on the image surface at the time of printing or projection and becomes a serious defect in practical use.

In recent years, the use of photosensitive materials such as high-speed coating, rapid photographing, and rapid processing and the expansion of processing methods, and diversification of use environments such as in a high-temperature and high-humidity atmosphere have been increasing.
Photothermographic materials are subjected to more severe handling than has been conventionally performed, and scratches are more likely to occur. Therefore, there is a demand for a back surface quality that can sufficiently withstand such severe conditions.

Heretofore, as a means for improving the scratch resistance of the back surface of a photographic light-sensitive material, the back surface has been made a sliding surface. For example, by dispersing a slip agent in a binder (cellulose acetate is often used) or applying the slip agent to a support in a solution system with the binder to impart slipperiness to the surface, the scratch is hardly damaged. Specific examples thereof include, for example, polyorganosiloxanes disclosed in JP-A-50-117414, higher fatty acid amides described in JP-A-55-79435, and JP-A-55-126238. The higher fatty acids or esters thereof described therein and the metal salts of higher fatty acids described in US Pat. No. 3,933,516 are known.

(Problems to be Solved by the Invention) However, when the scratch resistance of a photographic light-sensitive material is to be improved by using these known methods, a scratch is hardly caused by providing a slippery surface. However, it is not satisfactory under severe conditions such as a recent high-speed transport process, and often involves the following obstacles.

For example, when silicone is used as a slipping agent for the back layer, the added silicone migrates to the support surface on the side where the photographic emulsion is coated, thereby causing a bad effect at the time of coating the photographic emulsion, resulting in repelling, wetting, etc. Coating properties may be significantly impaired. Silicone, higher fatty acid, polyhydric alcohol ester of higher fatty acid, higher fatty acid amide,
When esters of higher alcohols and the like are used as a slip agent for the back layer, even if they show considerable slipperiness and scratch resistance at the beginning of production, they deteriorate over time (diffusion into the slip agent), The bleeding has disadvantages such as the formation of white powder on the surface of the backing layer, the elution or diffusion of the slipping agent during the development process to lose its effect, and the generation of contamination of the processing solution.

When an anionic surfactant such as a higher fatty acid sodium salt or a higher alcohol sulfate ester (sodium salt) is used as a slipping agent for the back layer, the cationic polymer used as the back side antistatic layer is not used. There is a drawback that the antistatic property is significantly impaired.

When a slipping agent is applied to the backing layer, it is usually dissolved or dispersed in an appropriate solvent alone or together with a binder and applied on a support. In this case, when the solvent swells the support, the slipping agent is used. There is a problem that the agent is difficult to stay on the surface because the agent is diffused inside, so that good sliding properties cannot be obtained. For this reason, the amount of the solid content of the slip agent is increased. However, the concentration in the coating solution is increased, so that the slip agent is likely to precipitate and the process is contaminated.

(Object of the Invention) A first object of the present invention is to provide a photographic light-sensitive material having a backing layer which has sufficient scratch resistance even under high-speed transport conditions, has no deterioration over time, and has sufficient scratch resistance even after development processing. Is to provide.

A second object of the present invention is to provide a photographic light-sensitive material having a back layer having improved scratch resistance without impairing the antistatic property and slipperiness of the back layer.

(Means for Solving the Problems) The inventors of the present invention have focused on cellulose derivatives for these objects, and as a result of these studies, these objects show that at least one layer of photosensitive halogen is provided on one side of the support. In a photographic material having a silver halide emulsion layer, 4 to 22
This has been achieved by including cellulose derivatives having from 1 to 3 aliphatic hydrocarbon groups having one carbon atom bonded per glucose unit.

As the above cellulose derivative used in the present invention, those represented by the following general formula (I) are preferably used.

General formula (I) In the formula, X ₁ , X ₂ and X ₃ represent a hydrogen atom and a — (A) _a —R group.

A is (R ₁ represents a hydrogen atom, —CH ₃ , b represents 0 to 10), C
H _{2 c} O- _(c represents 1 to 6), (D represents 1 to 3), a represents 0 or 1. R represents an aliphatic hydrocarbon group having 1 to 22 carbon atoms. X ₁ above,
In X ₂ and X ₃ , those substituted with those having R (degree of substitution) are at least 0.5 or more (preferably 1 to 3) per unit (glucose) of cellulose, and
At least one R is an aliphatic hydrocarbon group having 4 to 22 carbon atoms (preferably an alkyl group having 4 to 18 carbon atoms)
It is.

Next, typical specific examples of the cellulose derivative used in the present invention will be described. (DS means the degree of substitution, but the degree of substitution can be changed arbitrarily.) Cellulose butyrate DS ≒ 3.0 Cellulose caproate DS ≒ 2.9 Cellulose caprylate DS ≒ 2.9 Cellulose caprate DS ≒ 3.0 Cellulose laurate DS ≒ 3.0 Cellulose myristate DS ≒ 2.9 Cellulose palmitate DS ≒ 2.5 Cellulose stearate DS ≒ 2.0 Cellulose behenylate DS ≒ 2.0 Cellulose isostearate DS ≒ 2.5 Cellulose isopalmitate DS ≒ 2.5 Cellulose (palmitate / acetate) DS ≒ 2.0 / 1.0 Cellulose (laurate / acetate) DS ≒ 2.0 / 1.0 Cellulose (isostearate / acetate) DS ≒ 1.5 /
1.5 Hydroxyethyl cellulose (palmitate / acetate) DS 2.0 / 1.0 Hydroxyethyl cellulose (laurate / acetate) DS 2.5 / 0.5 Carboxymethyl cellulose (palmityl ester / acetate) DS 1.0 / 2.0 Cellulose (lauryl ether / acetate) DS 2.0 /
1.0 Poly (oxyethylene) cellulose palmitate DS ≒ 3.
0 Cellulose (palmitate / acetate) DS {1.0 / 2.0 Poly [oxypropylene] cellulose palmitate DS}
3.0 These cellulose derivatives used in the present invention have remarkably improved scratch resistance as compared with conventionally known cellulose acetate esters, as is apparent from the examples described later.
Does not deteriorate over time or after treatment.

The reason for this is that the cellulose derivative used in the present invention, that is, the fatty acid cellulose ester having a hydrocarbon group having 4 or more carbon atoms has a remarkably lower melting point and heat softening point than the cellulose acetate ester, and the carbon number of the fatty acid group It is presumed that the larger the value is, the more excellent the scratch resistance is, and this is attributed to the surface activity behavior due to the long-chain fatty acid group.

The compound represented by the general formula (I) used in the present invention is synthesized by mixing 1 to 3 mol or more of trifluoroacetic anhydride and a fatty acid mixed solution with respect to 1 mol of cellulose or a cellulose derivative (eg, diacetyl cellulose, hydroxycellulose). Aged at 60 ° C for 30-60 minutes. Then add dried cellulose or cellulose derivative to this,
Further, an appropriate amount of methyl chloride or toluene is added as a reaction solvent, and the mixture is reacted at 50 to 55 ° C. for 5 to 7 hours. The reaction solution is poured into 15 volumes of methanol to obtain a precipitate. After the washing, washing with methanol is further repeated to obtain a target fatty acid ester of cellulose. The degree of substitution was determined by NMR and alkali saponification.

 Also, Industrial and Engineering Chemistry43
(3) Fatty acid groups as described in 684. (1951)
It can also be synthesized by the method using chloride and pyridine.
You.

Cellulose derivatives used in the present invention, n-hexane,
hydrocarbons such as n-heptane; alcohols such as methanol and ethanol; ketones such as acetone and methyl ethyl ketone; halogenated hydrocarbons such as methylene chloride and carbon tetrachloride; ethers such as diethyl ether and dioxane; It is used by dissolving it in aromatic hydrocarbons such as toluene.

The amount of the cellulose derivative used in the present invention is 5 to 2000 mg, preferably 10 to 1000 mg per square meter of the back layer.
It is.

The thickness of the backing layer is in the range of 0.005 to 10 μm, preferably in the range of 0.01 to 1 μm.

As the substrate of the support, a cellulose ester film,
A polyester film or the like is used.

As a method for applying or penetrating the layer containing the cellulose derivative used in the present invention, for example, a dipping method as described in US Pat. No. 3,350,026, for example, US Pat.
It can be applied or penetrated from the outside by a method such as an extrusion method as described in 61791, for example, a spray method as described in US Pat. No. 2,674,167.

The cellulose derivative used in the present invention may be used alone, or may be used in combination with another polymer.
The proportion used in combination differs depending on the type of the polymer and is used to the extent that the object of the invention is not hindered.

For example, cellulose triacetate as a polymer,
Cellulose esters such as cellulose diacetate, cellulose acetate maleate, cellulose acetate phthalate, hydroxyalkyl, alkyl cellulose phthalate; formaldehyde and cresol;
Polycondensation polymers such as polycondensates with salicylic acid or oxyphenylacetic acid, or polycondensates with terephthalic acid or isophthalic acid and polyalkylene glycol; single polymers such as acrylic acid, methacrylic acid, styrene carboxylic acid or styrene sulfonic acid Or a copolymer of these monomers or maleic anhydride with a styrene derivative, alkyl acrylate, alkyl methacrylate, vinyl chloride, vinyl acetate, alkyl vinyl ether or acrylonitrile, or a ring-opening half ester or half amide thereof, There are synthetic polymers such as partially hydrolyzed polyvinyl acetate; homopolymers and copolymers obtained from monomers having a polymerizable unsaturated bond such as polyvinyl alcohol.

However, it is not limited to the above as long as it has a film forming ability and is soluble in a solvent.

The layer containing the cellulose derivative or other photographic constituent layers used in the present invention may further contain a slip agent if necessary. As a slipping agent, for example, U.S. Pat.
927, 4,047,958, 3,489,567, UK Patent No. 1,3
No. 13,384, JP-A-60-140341, JP-A-60-140342, JP-A-60-140342
-140343 and a fatty acid amide as described in U.S. Pat.No. 4,275,146, and JP-B-58-33541, JP-A-58-86540, and
Fatty acid esters such as those described in U.S. Pat.
Sulphate salts of aliphatic alcohols as described in U.S. Pat.No. 3,933,516;
It can contain higher fatty acids or metal salts thereof as described in 5-126238.

Further, if necessary, a matting agent can be added. The matting agents include silica, inorganic compounds such as strontium barium sulfate, and organic polymers such as polymethyl methacrylate and polystyrene.
Fine particles of 01 to 10μ are preferred.

The photographic light-sensitive material of the present invention can be used as an antistatic agent in photographic constituent layers such as a photographic emulsion layer and a back layer, for example, as described in U.S. Pat. Nos. 2,725,297, 2,972,535 and 2,972,536.
Nos. 2,972,537, 2,972,538, 3,033,679,
3,072,484, 3,262,807, 3,525,621, 3,6
15,531, 3,630,743, 3,653,906, 3,655,38
4, 3,655,386, and British Patent 1,222,154,
No. 1,235,075, hydrophilic polymers such as those described in U.S. Pat.Nos. 2,973,263 and 2,976,148, for example, U.S. Pat.Nos. 2,584,362 and 2,591,590. Biguanide compounds such as those described in U.S. Pat.No.2,639,234
No. 2,649,372, 3,201,251, sulfonic acid type anion compounds as described in 3,457,076,
For example, phosphate esters and quaternary ammonium salts as described in U.S. Patent Nos. 3,317,344 and 3,514,291 can be used, for example, U.S. Patent Nos. 2,882,157 and 2,982,651,
3,399,995, 3,549,369, 3,564,043, 4,1
A cationic compound as described in U.S. Pat.No. 26,467, for example, a nonionic compound as described in U.S. Pat.
No. 6,268, etc., amphoteric compounds, for example, U.S. Pat.No. 2,647,836 and the like complex compounds, for example, U.S. Pat.No. 2,717,834, U.S. Pat.
Organic salts as described in 5,387 and the like can be included.

 The photographic light-sensitive material of the present invention will be described in more detail.

The silver halide emulsion usable in the present invention may be any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride. From the viewpoint of rapid processing, an emulsion having a silver chloride content of 95 mol% or more is preferred.

The silver halide grains in the photographic emulsion layer may have regular crystals such as cubic or octahedral, or irregular (irregula) such as spherical or tabular.
r) It may have a crystal form or a compound form of these crystal forms. It may consist of a mixture of particles of different crystal forms.

The silver halide grains may have different phases between the inside and the surface layer or may consist of a uniform phase. Also, grains whose latent image is mainly formed on the surface (eg, a negative emulsion) may be formed, and grains whose main image is mainly formed inside the grains (eg, an internal latent image type emulsion, a directly fogged emulsion which has been previously fogged) May be used.

The silver halide emulsion used in the present invention has a thickness of 0.5 μm or less, preferably 0.3 μm or less and a diameter of preferably 0.6 μm or more, and grains having an average aspect ratio of 5 or more account for 50% or more of the total projected area. Tabular grains that occupy may be used. It is preferred to use tabular emulsion grains having an aspect ratio of 5 or more in combination with the filter dye of the present invention in order to provide a silver halide color photographic light-sensitive material having remarkably excellent sharpness and color reproducibility. For details of tabular emulsions and their use, see RESEARCH DISCLOSURE, Item 22534, p.20 to p.58 (Ja
n., 1983), and Item 22530, pp. 237-240 (May, 1985).

Further, the silver halide emulsion used in the present invention may be a monodispersed emulsion in which grains having a grain size within ± 40% of the tabular grain size account for 95% or more of the number of grains.

The photographic emulsion used in the present invention is Chimie er Physique Photogroheque by P. Glafkides.
(Paul Montell, 1967), GFDuffin, Photograpic Emulsion Chemistry
(Focal Press, 1966), VLZelikman et al., Making and Coating Photographic Emulsion
and Coating Photographic Emulsion) (Focal Press, 1964).

In forming the silver halide grains, in order to control the growth of the grains, as a silver halide solvent, for example, ammonia, rodankari, rodanammon, thioether compound (for example, US Pat. Nos. 3,271,157 and 3,574,6
No. 28, No. 3,704,130, No. 4,297,439, No. 4,276,
No. 374) and thione compounds (for example, JP-A-53-144319).
No. 53-82408, No. 55-7777), amine compounds (for example, JP-A-54-100717).

In the course of silver halide grain formation or physical ripening, a cadmium salt, a zinc salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt may be coexisted.

Silver halide emulsions are usually chemically sensitized. For chemical sensitization, for example, H. Frieser,
Die Grundlagen del Fotografischen Ipsenze Mitsut Silberhalogeniden (Die
Grundlagen der Photographischen Prozesse mit Silbe
rhalogeniden) (Academia serrata 1968), pages 675 to 734.

That is, a sulfur sensitization method using a compound containing a sulfur capable of reacting with active gelatin or silver (eg, thiosulfate, thioureas, mercapto compounds, rhodanines); a reducing substance (eg, stannous tin salt, Reduction sensitization method using amines, hydrazine derivatives, formamidinesulfinic acid, silane compounds); noble metal compounds (for example, gold complex salts and complex salts of Group VIII metals such as Pt, Ir and Pd). The noble metal sensitization method used can be used alone or in combination.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the production process, storage or photographic processing of the light-sensitive material, or stabilizing photographic performance. That is, azoles such as benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (particularly nitro- or halogen-substituted); heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzothiazoles, mercapto Benzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), mercaptopyrimidines; the above heterocyclic mercapto compounds having a water-soluble group such as a carboxyl group or a sulfone group; thioketo compounds such as Oxazolinethione; azaindenes such as tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a, 7) tetraazaindenes); benzenethiosulfonic acids; Zensurufuin acid; can be added to many of the compounds known to the antifoggants or stabilizers, such as.

Various color couplers can be used in the present invention, and specific examples are described in the patents described in the above-mentioned Research Disclosure (RD) No. 17643, VII-CG. As the dye-forming coupler, a coupler which provides the three primary colors of the subtractive color method (that is, yellow, magenta and cyan) by color development is important. Specific examples of the diffusion-resistant 4-equivalent or 2-equivalent coupler are described in RD17643, VII-
In addition to the couplers described in the patents described in sections C and D, the following can be preferably used in the present invention.

Typical examples of the yellow coupler that can be used include known oxygen atom-eliminable yellow couplers and nitrogen atom-eliminable yellow couplers. α-
Pivaloyl acetanilide couplers are excellent in the fastness of coloring dyes, especially in light fastness, while α-benzoylacetanilide couplers provide high color density.

Magenta couplers that can be used in the present invention include hydrophobic 5-pyrazolone and pyrazoloazole couplers having a ballast group. As the 5-pyrazolone coupler, a coupler in which the 3-position is substituted with an arylamino group or an acylamino group is preferable from the viewpoint of the hue and color density of the coloring dye.

Cyan couplers usable in the present invention include hydrophobic and non-diffusible naphthol-based and phenol-based couplers, preferably a two-equivalent naphthol-based coupler of an oxygen atom-elimination type. Couplers capable of forming a cyan dye which is robust to humidity and temperature are preferably used. Typical examples thereof include an alkyl group having an ethyl group or more at the meta-position of the phenol nucleus described in U.S. Pat.No. 3,772,002. And a 2,5-diacylamino-substituted phenolic coupler, a phenolic coupler having a phenylureido group at the 2-position and an acylamino group at the 5-position, and the like.

Granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Such couplers are specific examples of magenta couplers in U.S. Pat.No. 4,366,237 and the like, and yellow in European Patent No. 96,570 and the like.
Specific examples of magenta or cyan couplers are described.

Dye-forming couplers and the above-mentioned special couplers may form polymers of dimers or more. Typical examples of polymerized dye-forming couplers are described in U.S. Pat. No. 3,451,820. Specific examples of the polymerized magenta coupler are described in U.S. Pat. No. 4,367,282.

Couplers that release a photographically useful residue upon coupling can also be preferably used in the present invention. As the DIR coupler releasing a development inhibitor, the couplers of the patents described in the aforementioned RD17643, VII-F are useful.

In the light-sensitive material of the present invention, a coupler which releases a nucleating agent or a development accelerator or a precursor thereof in an image-like manner during development can be used. Specific examples of such compounds are described in British Patent Nos. 2,097,140 and 2,131,188.

The photographic emulsion of the present invention may be used for the purpose of increasing sensitivity, increasing contrast, or accelerating development, for example, a polyalkylene oxide or a derivative thereof such as ether, ester, or amine;
It may contain thioether compounds, thiomorpholins, quaternary ammonium salt compounds, urethane derivatives, urea derivatives, imidazole derivatives, 3-pyrazolidones, and the like.

In the silver halide photographic emulsion of the present invention, known water-soluble dyes other than the dyes disclosed in the present invention (for example, oxonol dyes; hemioxonol dyes and merocyanine dyes) are used as filter dyes or for various purposes such as prevention of irradiation. May be used in combination. The spectral sensitizer may be used in combination with known cyanine dyes, merocyanine dyes, and hemicyanine dyes other than the dyes shown in the present invention.

The photographic emulsion of the present invention contains various surfactants for various purposes such as coating aids, antistatic, improving slipperiness, emulsifying and dispersing, preventing adhesion and improving photographic properties (for example, development acceleration, high contrast, sensitization). May be.

Further, the light-sensitive material of the present invention includes a discoloration inhibitor, a hardener, a color fogging inhibitor, an ultraviolet absorber, a protective colloid such as gelatin, and various additives.
643 etc.

The finished emulsion is coated on a suitable support such as baryta paper, resin coated paper, synthetic paper, triacetate film, polyethylene terephthalate film, other plastic base or glass plate.

The silver halide photographic light-sensitive material of the present invention includes a color positive film, a color paper, a color negative film,
Color reversal (may or may not include a coupler), photographic material for plate making (eg, lith film, lith de-up film, etc.), photographic material for cathode ray tube display (eg, photographic material for emulsion X-ray recording) , Materials for direct and indirect photography using a screen), photosensitive materials for a silver salt diffusion transfer process, photosensitive materials for a color diffusion transfer process, and a die transfer process are described in RD-17643. Any of the known methods and known processing solutions as described can be applied. The processing temperature is usually selected between 18 and 50 ° C, but may be lower than 18 ° C or higher than 50 ° C. Particularly when applied to a color photographic process comprising a developing process for forming a dye image, a favorable effect can be exhibited.

The color developer generally comprises an alkaline aqueous solution containing a color developing agent. Color developing agents are known primary aromatic amine developers such as phenylenediamines (for example, 4
-Amino-N, N-diethylaniline, 3-methyl-4-
Amino-N, N-diethylaniline, 4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4 -Amino-N-ethyl-N-
β-methanesulfamidoethylaniline, 4-amino-
3-methyl-N-ethyl-N-β-methoxyethylaniline) can be used.

In addition, LFA Messon's "Photograph Processing Chemistry", published by the Focal Press (1966)
226-229, U.S. Pat.Nos. 2,193,015 and 2,592,364
And those described in JP-A-48-64933.

Developers also include pH buffers such as alkali metal sulfites, bisulfites, carbonates, borates, and phosphates,
It may contain a development inhibitor such as bromide, iodide, and an organic antifoggant or an antifoggant. If necessary, water softeners, preservatives such as hydroxylamine, benzyl alcohol, organic solvents such as diethylene glycol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers,
Competitive coupler, fogging agent such as sodium boron hydride, auxiliary developing agent such as 1-phenyl-3-pyrazolidone, viscosity-imparting agent, polycarboxylic acid chelating agent described in U.S. Pat. No. 4,083,723, West German publication (OLS) 2,622,950
May be contained.

The pH of the developer is preferably 8 or more, and more preferably 9 or more. Further, the concentration of sulfite or bisulfite in the developer is preferably 10 ^-3 mol / liter or more, more preferably 10 ^-3 mol / liter.
More than ^-2 mol / liter is more preferable.

The fixing solution or the bleach-fixing solution preferably contains a sulfite or a bisulfite.

Bleaching solutions, bleach-fixing solutions and their prebaths may contain compounds already known as bleaching accelerators, for example, US Pat.
No. 8, German Patent No. 1290812, No. 2059988
JP-A-53-32736, JP-A-53-57831, JP-A-37418, JP-A-53-65732 and JP-A-53-72623.
No. 53-95630, No. 53-95631, No. 53-10
No. 4232, No. 53-124424, No. 53-141623, No. 53-28426, Compounds having a mercapto group or a disulfide group described in Research Disclosure No. 17129, JP-A-50- Thiazolidine derivatives as described in 140129, JP-B-45-8506,
JP-A-52-20832, JP-A-53-32735, the thiourea derivative described in U.S. Pat.No. 3,706,561, German Patent No. 1127715, and the thiourea derivative described in JP-A-58-16235. Compounds, polyethylene oxides described in German Patent Nos. 966410 and 2748430, JP-B-45-88
No. 36, polyamine compounds described in JP-A-49-42434.
JP-A-49-59644, JP-A-53-94927 and JP-A-54
JP-A-35727, JP-A-55-26506, and JP-A-58-163940 can also be used in combination.

The processing method of the present invention comprises the above-described processing steps such as color development, bleaching and fixing. Here, after the fixing step or the bleach-fixing step, processing steps such as water washing and stabilization are generally performed. However, only the water washing step is performed or, conversely, a substantial water washing step is provided. Alternatively, a simple processing method such as performing only the stabilization processing step can be used.

As the stabilizing solution used in the stabilizing step, a processing solution that stabilizes the dye image is used. For example, a solution having a buffer capacity of pH 3 to 6, a solution containing an aldehyde (for example, formalin), or the like can be used. As the stabilizing solution, a fluorescent whitening agent, a chelating agent, a bactericide, a sunscreen, a hardener, a surfactant and the like can be used as necessary.

In addition, the stabilization step may be performed using two or more tanks as necessary, and multi-stage countercurrent stabilization (for example, 2 to 9 stages)
As a result, the stabilizing solution can be saved, and the washing step can be omitted.

Known additives can be added to the washing water used in the washing step, if necessary. For example, chelating agents such as inorganic phosphoric acid, aminopolycarboxylic acid, and organic phosphoric acid, disinfectants or deterrents for preventing the growth of various bacteria and algae, hardening agents such as magnesium salts and aluminum salts, drying loads, unevenness A surfactant or the like can be used to prevent the occurrence of blemishes. Or LEWest, “Water Quali
ty Criteria "Photograph Science and Engineering (Phot.Sci.and Eng.), vol.9 No.6
The compounds described in pages 344 to 359 (1965) can also be used.

The rinsing step may be performed using two or more tubs as necessary, and the rinsing water may be reduced by multi-stage countercurrent rinsing (for example, 2 to 9 tiers).

(Examples) Hereinafter, the present invention will be described in more detail by way of examples, but embodiments of the present invention are not limited thereto.

Example 1 The following coating composition containing the cellulose derivative shown in Table 1 was applied on a cellulose triacetate film so as to have a coating composition of 50 ml / m ² , and dried at 80 ° C. for 5 minutes to prepare four kinds of samples.

<Coating composition> Cellulose derivative (shown in Table 1) 0.6 g methylene chloride 60 ml n-hexane 240 ml The obtained four kinds of samples were examined for dynamic friction coefficient and scratch resistance by the following methods. The results are shown in Table 1.

(Dynamic friction coefficient)

Using a steel ball with a diameter of 5 mm manufactured by Toyo Baldwin,
The measurement was carried out under the conditions of a load of 10 g and a speed of 10 m / min.

(Scratch resistance)

Using a Shinto-18 type Heidon-18 measuring instrument,
Scratching with a continuous load of 0 to 100 g with a diamond needle of 0.025 mmR,
The evaluation was made based on the load at which the scratches started to be seen by transmitted light.

As can be seen from Table 1, No. 1 to No. 3 have scratch resistance and No. 4 are excellent in small dynamic friction coefficient.

Example 2 The following coating composition was applied on a cellulose triacetate film so as to be 50 ml / m ² , and dried at 80 ° C. for 5 minutes.

<Coating composition> Cellulose dipalmitate (degree of substitution: about 1.7) 0.6 g SiO ₂ fine particles (average particle size: 0.1 μ) 120 mg methylene chloride 150 ml cyclohexanone 60 ml acetone 90 ml The obtained sample was treated in the same manner as in Example 1. As a result, the coefficient of dynamic friction was 0.22, and the scratch resistance was 52 g, which was excellent.

Example 3 An indirect radiographic emulsion of 9% by weight of gelatin and 9% by weight of silver halide was applied to the opposite side of the photographic support No. 1 obtained in Example 1 to prepare a photographic light-sensitive material. The surface and the back surface were brought into contact with each other and stored at room temperature for 3 months, but no effect on sensitivity and fog was observed.

Example 4 The following first layer composition was applied on a cellulose triacetate film to a concentration of 15 ml / m ² and dried at 70 ° C. for 3 minutes.

[Composition for the first layer] Hydrophilic polymer (described below) 35 g ethylene glycol 270 ml methanol 6000 ml acetone (hydrophilic polymer) ^* 4000 ml * Dissolve 0.1% by weight of polymer in 1% by weight
The NSP / C (viscosity number) measured at 0 C was 0.12.

The hydrophilic polymer was 50 mg / m ² .

On the first layer, the following second layer compositions 1 to 4 were applied in a concentration of 25 ml / m ² and dried at 100 ° C. for 3 minutes to obtain a photographic support 1
~ 4.

<Composition-1 for second layer> Cellulose (palmitate / acetate) [degree of substitution about 1.
5 / 1.5] 86 g SiO ₂ fine particles (average particle size 0.1 μm) 7 g acetone 8500 ml methanol 1500 ml <composition for second layer-2> stearic acid 17 g cellulose (palmitate / acetate) [degree of substitution about 1.
5 / 1.5] 86 g SiO ₂ fine particles (average particle diameter 0.1 μ) 7 g acetone 8500 ml methanol 1500 ml <Composition for second layer-3> Diacetyl cellulose 86 g SiO ₂ fine particles (average particle diameter 0.1 μ) 7 g acetone 8500 ml methanol 1500 ml Two-layer composition-4> Stearic acid 17 g Diacetyl cellulose 86 g SiO ₂ fine particles (average particle size 0.1 μm) 7 g Acetone 8500 ml Methanol 1500 ml These samples were examined for kinetic friction coefficient, scratch resistance and surface resistivity. The dynamic friction coefficient and the scratch resistance were evaluated in the same manner as in Example 1.

Surface resistivity is 30% RH, JIS K-6911-1 circular electrode
979 based on TR-8601 manufactured by Takeda Riken Co., Ltd.

 Table 2 shows the above results.

As can be seen from Table 2, the result of No. 1 of the present invention is very excellent in the flaw resistance although the dynamic friction coefficient is higher than that of No. 4 of the comparative example.

Further, No. 1 did not show any deterioration in scratch resistance even after one year storage.

In No. 2 of the present invention, the dynamic friction coefficient is reduced (slipperiness is improved)
And a substantial improvement in scratch resistance was observed.

Also, the surface resistivity of Nos. 1 and 2 of the present invention had almost no effect as compared with the conventional Nos. 3 and 4.

Claims (1)

(57) [Claims] 1. A support having at least one photosensitive silver halide emulsion layer on one side and at least one photosensitive silver halide emulsion layer on the other side.
A photographic light-sensitive material having a backing layer comprising a cellulose derivative in which an aliphatic hydrocarbon group having 4 to 22 carbon atoms is bonded to the backing layer in an amount of 1 to 3 per glucose unit. Photosensitive material