GB2090010A - Process for the Development of Photographic Silver Halide Light- sensitive Materials - Google Patents

Abstract

Photographic material comprises a support, at least one silver halide emulsion layer, and a surface layer (e.g. protective layer or back layer) containing acid-processed gelatin (obtained with acid from collagen; pH 4.5-5.3) and optionally other hydrophilic colloids. Development is performed in the presence of compound (which reduces contamination of the surface layer especially in automatic processing) of the formula <IMAGE> R=C7-22 aliphatic, or aryl; R1=H or CH3, R2, R3=C1-4 alkyl, R4, R5=H or C1-4 alkyl, L=-CONH, -SO2NH-, -O-, -S-, -CONH(CH2)1-O-, -SO2NH(CH2)1-O-, <IMAGE> or <IMAGE> where 1=2-5, A=-COO<-> or -SO3<->, m=0 or 1, n and x=0, 1, 2 or 3. 15 such compounds are shown, and synthesis examples. The compound is incorporated in a surface layer in amount of 0.000001-0.001 mol/gram binder or into a developing solution in amount 0.1-10 grams/litre of solution.

Description

SPECIFICATION Process for the Development of Photographic Silver Halide Light-sensitive Materials The present invention relates to photographic silver halide light-sensitive materials (hereinafter referred to more simply as "silver halide light-sensitive materials"), and, more particularly, to silver halide light-sensitive materials containing acid-processed gelatin in a surface layer thereof and to a process for their development.

Silver halide light-sensitive materials comprise, in general, a support, e.g., a plastic film, paper, or polymer-coated paper, at least one silver halide emulsion layer, and, depending on the particular material, other types of layers, such as an intermediate layer, a surface protective layer, a filter layer, an antihalation layer, a back layer, etc., on the support.

Binders which are used to form the layers on the support usually comprise hydrophilic colloids, such as gelatin. Gelatin is ordinarily used as a binder even for the preparation of surface layers, such as a surface protective layer and a back layer. The use of gelatin in the surface layer, however, leads to an increase in the adhesiveness or stickiness of the surface thereof at high humidities, particularly in a high temperature and high humidity atmosphere. Under such conditions, when the surface layer comes into contact with other materials, it readily adheres thereto.

The phenomenon of adhesion can occur between photographic materials themselves or between photographic materials and other materials coming into contact therewith during the production, photographing, processing, projection, or storage of the photographic materials, often causing problems.

In order to solve the problem of adhesion, as is well known in the art, there is employed a method in which fine particles of inorganic substances, e.g., silicon dioxide, silver halide, and titanium dioxide, and organic substances, e.g. polymethyl methacrylate, having a grain size of from about 0.3 y to about 5 #, are introduced into a surface layer to increase the coarseness of the surface thereof, i.e., to perform matting, and thus, to reduce the adhesiveness of the surface layer.The addition of a large amount of matting agent, however, causes various disadvantages; for example, the matting agent aggregates in a coating solution, making it impossible to form a uniform coating layer; the sliding properties are deteriorated, leading to easy scratching of photographic materials; the drivability properties of films in a photographing or projection apparatus are deteriorated; the transparency of images formed is reduced; and the graininess of images increases deteriorating the image.

In order to overcome the above described problems, Japanese Patent Application (OPi) No.

104926/75 (the term "OPI" as used herein refers to a "published unexamined Japanese patent application") discloses a method of incorporating acid-processed gelatin and silicic anhydride colloid into a surface layer, Japanese Patent Application (OPI) No. 137129/75 discloses a method of using acid-processed gelatin in combination with alkali-processed gelatin in a surface layer, Japanese Patent Application (OPI) No. 1 60034/75 discloses a method of incorporating acid-processed gelatin and an organic fluorosurface active agent into a surface layer, and Japanese Patent Application (OPI) No.

6017/76 discloses a method of using acid-processed gelatin and a matting agent in a surface layer.

In high temperature rapid processing in the production or development of silver halide lightsensitive materials, the so-called "reticulation" phenomenon may occur in layers containing gelatin as a binder. In order to prevent such reticulation, Japanese Patent Publication No. 43777/76 discloses a technique of incorporating acid-processed gelatin having a Jelly strength of 250 g or more (as determined with a Bloom type Jelly strength meter according to the PAGI method as described in Shashinyo Gelatin Shikenho, published by Shashinyo Gelatin Shikenho Godo Shingikai, p 5 (1970)) into a surface layer.

As described above, various attempts to improve the physical properties of silver halide lightsensitive materials by the use of acid-processed gelatin have been made.

It has been found, however, that although the use of acid-processed gelatin in a surface layer improves the physical properties, it gives rise to the disadvantage that during the step of development processing, contaminants such as oxidized products of developing agents readily attach to the surface of such silver halide light-sensitive materials. These contaminants attached at the step of development processing seriously deteriorate the image quality after the development processing. In particular, when the silver halide light-sensitive material is processed with an automatic developing machine, the oxidized products of developing agent present on a conveying roller of the automatic developing machine readily attach onto the surface of the silver halide light-sensitive material, significantly deteriorating the image quality.

The principal object of the present invention is to provide silver halide light-sensitive materials having excellent physical properties, such as resistance to adhesion and reticulation, and furthermore which are free from the attachment of contaminants during development processing.

It has now been found that this object can be attained by developing silver halide light-sensitive materials with a surface layer containing acid-processed gelatin as a binder in the presence of compounds represented by formula (I) as shown hereinafter.

The present invention, therefore, comprises a process for developing a silver halide light-sensitive material comprising a support and at least one silver halide light-sensitive emulsion layer on the support wherein a surface layer of the light-sensitive material contains acid-processed gelatin as a binder, and the development is performed in the presence of a compound represented by general formula (I)

wherein R is a saturated or unsatured aliphatic group containing 7 to 22 (and preferably from 8 to 1 5) carbon atoms, or a substituted aryl group; R1 is a hydrogen atom or a methyl group; R2 and R3 are each an alkyl group or a substituted alkyl group (e.g., an alkoxyalkyl group or a hydroxyalkyl group) containing from 1 to 4 carbon atoms; R4 and R5 are each a hydrogen atom or an alkyl group containing from 1 to 4 carbon atoms; ; L is --CONH--,--SO2NH--,--O--,--S--,--CONH(CH2)@--O--,--SO2NH(CH2)@--O--,

m is O or 1; nisO, 1,2,or3; x is 0, 1, 2, or 3; A is --C000 or~So33; and I is an integer of 2 or more (preferably 2 to 5).

Preferred examples of the substituted aryl group R in the formula (I) are represented by the formula (la)

wherein R' is a saturated or unsaturated aliphatic group containing from 7 to 21 carbon atoms, y is O or 1, and n1 is 1 or 2.

Typical examples of compounds represented by the formula (I) are shown below: Compound 1

Compound 2

Compound 3

Compound 4

Compound 5 Compound 6 Compound 7 Compound 8 Compound 9 Compound 10 Compound 11 Compound 12 Compound 13 Compound 14

Compound 15

Preparation Example 1 Synthesis of Compound 1 (1) Preparation of N-dodecyl-N,N-dimethylamine A 2-liter three necked flask equipped with a thermometer, a stirrer, and a dropping funnel was charged with 185 g (1 mol) of dodecylamine and 300 ml of ethanol. After the dissolution of the dodecylamine in the ethanol, 260 ml of 85% formic acid was gradually added dropwise thereto through the dropping funnel while maintaining the temperature at 300C with stirring.After the dropwise addition was completed, 210 ml of 37 wt% formaldehyde was similarly added dropwise thereto. The resulting mixture was stirred at 400C for 1 hour. Then, the flask was placed on a hot water bath, and the mixture was refluxed for about 3 hours until no more carbon dioxide gas was evolved.

After the reflux, a reaction solution was cooled, and a 30% aqueous solution of sodium hydroxide was added little by little to the solution up to basic solution. Then, 400 ml of benzene was added to the solution, and when the resulting mixture was shaken throughly in a separatory funnel and then allowed to stand, it separated into two layers. The upper layer, i.e, the benzene layer, was removed from the flask and dried overnight on potassiuum carbonate. Then the benzoate was distilled away, and the residue was distilled under reduced pressure to obtain 170 g of N-dodecyl-N,N-dimethylamine (b.p.: 9400/1 mmHg; yield: 80%).

(2) Preparation of Compound 1 A 500-ml three necked flask equipped with a thermometer, a stirrer, and a condenser was charged with 106.5 g (0.5 mol) of N-dodecyl-N,N-dimethylamine. An aqueous solution of sodium monochloroacetate, which had been prepared by the method as explained hereinafter, was added thereto, and the mixture was stirred at a temperature of 95 to 10000 for 4 hours on an oil bath. As the reaction proceeded, the reaction solution became gel-like and could not be stirred. At this point, therefore, a small amount of ethanol was added thereto.

The reaction solution was placed in a 1-liter egg-plant type flask, and the water and ethanol was distilled off under reduced pressure. The residue was added to 400 ml of ethanol and dissolved therein, and insoluble by-produced sodium chloride (NaCI) in the ethanol was filtered off. After the ethanol was distilled away, 300 ml of acetone was added to the resulting residue. The mixture was heated in the flask equipped with a condenser to dissolve the residue in the acetone, and the solution was filtered.

When the filtrate was cooled with ice, crystals precipitated.

These crystals were filtered off and dried in a desiccator to obtain 57.1 g of Compound 1. The yield was 42%; the melting point could not be measured because of very high moisture absorption of Compound 1.

(3) Preparation of Sodium Monochloroacetate A solution of 22 g (0.55 mol) of sodium hydroxide in 25 ml of water was added to a solution of 51.7 g (0.55 mol) of monochloroacetic acid in 60 ml of 'water while cooling appropriately so that the temperature did not exceed 500 C. The reaction solution was adjusted to a pH of 6.0 to 7.0.

Preparation Example 2 Synthesis of Compound 2 (1) Preparation of 3-myristylamidopropyl-N,N-dimethylamine A 2-liter three necked flask equipped with a cooling tube was charged with 122.5 g (1.2 mol) of N,N-dimethylamino-propylamine and 123.4 g of acetonitrile. The mixture was cooled with ice with stirring and maintained at a temperature of 1000 or less.

Then, 246.8 g (1 mol) of myristylic acid chloride, which had been prepared by a conventional technique, was added dropwise to the mixture over a period of 1 hour, and the temperature was raised to 600 C. The mixture was stirred for 1 hour at that temperature, and then poured into 2 l of pulverized ice. The precipitated crystals were filtered off and air-dried overnight.

The crystals were recrystallized from acetone to obtain 235 g of 2-myristylamidopropyl-N,Ndimethylamine (m.p.: 45 to 500 C: yield: 75%) (2) Preparation of Compound 2 A mixture of 106 g (0.5 mol) of 3-myristylamidopropyl-N,N-dimethylamine, 47.2 g (10.5 mol) of chloroacetic acid, and 150 g of methanol was placed in a 1-liter three necked flask equipped with a cooling tube, and maintained at a temperature of 1 00C or less by cooling with ice while stirring.

Then, 97 g (0.5 mol) of a 28% methanol solution of sodium methoxide was added dropwise to the above prepared solution over a period of 30 minutes, heated up to 600 C, and stirred for 4 hours at that temperature. The reaction solution was allowed to cool to room temperature, and then precipitated insoluble products were separated by filtration. Subsequently, 1.2 1 of acetone was added to the above separated insoluble products. The precipitated crystals were filtered off, dried, and dissolved in 300 ml of isopropanol by heating. The insoluble portion was separated by filtration while heating and added to 11 of acetone.

After cooling with ice, precipitated crystals were filtered off and dried at a temperature of 50 to 600C to obtain 124 g of Compound 2 (yield: 67%).

Preparation Example 3 Synthesis of Compound 3 (1) Preparation of 3-laurylamidopropyl-N,N-dimethylamine A mixture of 200 g (1 mol) of lauric acid and 122.-49 (i .2 mol) of N,N-dimethylaminopropylamine (b.p.: 1400 C) was placed in a 500-ml flask, and refluxed in a stream of nitrogen (N2) gas at a temperature of 1 000C for 6 hours.

At that temperature, a major portion of the water by-produced by the reaction and excess amine had been removed from the reaction system, and thereafter, they were completely distilled away under reduced pressure.

Then, 600 ml of ethyl acetate was added to the resulting residue, which was dissolved therein by heating. On cooling the solution with ice, white crystals precipitated. These white crystals were filtered off and dried.

When the solution was further concentrated and cooled with ice, crystals again precipitated.

These crystals were separated by filtration, combined together with the firstly precipitated crystals, well mixed, and then dried in a desiccator. Thus, 200 g (yield: 65%) of the desired product was obtained (m.p.: 39 to 400 C; yield: 56 to 65%).

(2) Preparation of Compound 3 A 1-liter eggplant type flask was charged with 190 g (0.67 mol) of 3-laurylamidopropyl-N,Ndimethylamine. An aqueous solution of sodium monochloroacetate, which had been prepared by a method as described hereinafter, and 400 ml of ethyl acetate were added thereto, and the resulting mixture was refluxed at 1 200C for 5 to 6 hours on an oil bath.

After the reflux, the pH of the reaction solution was adjusted to 5.5 to-6.0 by dropwise addition of hydrochloric acid. After the adjustment of the pH, the water and ethanol were distilled away under reduced pressure, and the residue was dried.

Subsequently, 1.5 1 of ethanol was added to the residue, which was then dissolved therein by heating. Insoluble sodium chloride and excessive sodium acetate were separated by filtration, and the ethanol was distilled away. Then, about 1. 5 1 of petroleum ether was added to the residue, the resulting mixture was stirred, and then allowed to stand overnight.

The petroleum ether was decanted, and additionally, the solvents were completely distilled away under reduced pressure. The residue was dried to obtain Compound 3 in a light yellowish solid form (yield: 90%).

(3) Preparation of Aqueous Sodium Monochloroacetate Solution A solution of 32 g (0.8 mol) of sodium hydroxide in 30 ml of water was added to a solution of 75.6 g (0.8 mol) of monochloroacetic acid in 70 ml of water while cooling appropriately so that the temperature did not exceed 500 C. The pH of the sodium monochloroacetate solution was adjusted to 9.0-10.0 by adding sodium hydroxide (NaOH).

Example 4 Synthesis of Compound 13 (1) Preparation of -tetradecyl-'-chlorohydrin Ether A 2-liter three necked flask equipped with a stirrer, a reflux condenser, and a thermometer was charged with 1,284 g (6 mol) of tetradecyl alcohol. Then, 2.0 to 2.6 g (0.008 to 0.01 mol) of tin tetrachloride was added thereto as a catalyst. While stirring the mixture thoroughly, 148 g (1.6 mol) of epichlorohydrin was added thereto at once. The mixture was heated, and stirred for 30 minutes at 1 000C and for 2 to 3 hours at 120 to 1300 C. After the reaction, the reaction solution was cooled to 45 to 500C, and a small amount of an aqueous potassium carbonate solution was added thereto. The mixture was then stirred vigorously to decompose the catalyst. Then, anhydrous sodium sulfate was added to dry the solution, and then the solution was separated by filtration. The filtrate thus obtained was subjected to vacuum distillation to obtain the desired product (b.p.: 1 76-1 800C/3 mmHg; yield: 345 g (70% of the theoretical value based on the amount of epichlorohydrin)).

(2) Preparation of Tetraglycidyl Ether A 1-liter three necked flask equipped with a reflux condenser, a stirrer, a thermometer, and a dropping funnel was charged with 343 g (1.12 mol) of chlorohydride diether. While heating at a temperature of 85 to 900C, a 25 to 30% aqueous solution of caustic soda (containing 60 g (1.5 mol) of caustic soda) was added dropwise thereto with vigorous stirring, and thereafter, the mixture was stirred vigorously at a temperature of 95 to 1 000C for 5 hours.

After confirming by the Beilstein flame reaction that the solution contained no chlorine, the solution was cooled to room temperature and was allowed to stand. The solution separated into two layers. The upper layer was separated, diluted with a suitable amount of ether, dried on anhydrous potassium carbonate, and vacuum-distilled to obtain the desired product (b.p.: 1 56-1 6O0C/3 mmHg; yield: 290 g (95% of the theoretical value)).

(3) Preparation of N-(2-hydroxy-3-tetradecyloxypropyl)-N,N-dihydroxyethyl A mixture of 289 g (1.07 mol) of glycidyl ether and 113 g (1.07 mol) of diethanolamine was placed in a 1-liter eggplant type flask, and 300 ml of isopropanol was added thereto. The mixture was refluxed for 3 hours, and then the isopropanol was distilled off.

(4) Preparation of Compound 13 (4-1) Preparation of Sodium Monochloroacetate A solution of 48 g (1.2 mol) of caustic soda in 60 ml of water was grndual.1y added to a solution of 11 3 g (1.2 mol) of monochloroacetate in 80 ml of water while cooling at a temperature of 500C or less to prepare an aqueous solution of sodium monochloroacetate.

(4-2) Preparation of Compound 13 A mixture of 410 g (1.09 mol) of N.-{2-hydrnxy-3-tetradecyloxyprnpyl ] -N,N-dihydrnxyethyl and 113 g (1.2 mol) of monochloroacetate in 80 ml of water was placed in a 1-liter three necked flask equipped with a stirrer and a thermometer, and then 50 ml of dioxane was added thereto. The mixture was stirred at a temperature of 95 to 1000C for 5 hours. Then, the mixture was cooled, washed with petroleum ether, and concentrated to dryness. The solids thus obtained were dissolved in 2 to 2.5 1 of methanol by heating, and insoluble sodium chloride and excessive sodium monochloroacetate were separated by filtration, the methanol was distilled away from the filtrate, and the resulting residue was dried to obtain 450 g of Compound 13 (95% of the theoretical value).

The compound represented by formula (I) as used herein is added to a hydrophilic colloid layer or layers (e.g., a silver halide emulsion layer, a surface protective layer, an intermediate layer, and a back layer), or to a development processing solution. In particular, it is preferred to incorporate the compound into the surface protective layer of the silver halide light-sensitive material.

When the compound represented by the formula (I) is incorporated into the hydrophilic colloid layer, the amount of the compound added is generally from 1.Ox10#to 1.0x10-3 mol, and preferably from 1 Ox 10-5 to 1 Ox 10-4 mol, per gram of binder in the hydrophilic colloid layer.

On the other hand, when the compound is incorporated into the development processing solution, the amount of the compound added is generally from 0.1 to 10 g. and preferably from 0.5 to 3 g, per liter of the development processing solution.

The acid-processed gelatin as used herein is prepared by application of a treatment using hydrochloric acid, for example, in the course of the production thereof from collagen with pigskin, cowbones, or the like as a starting material, and is different from alkali-processed gelatin which is prepared by application of a treatment using lime, for example, which is typically used in the photographic industry.

Methods of production of acid-processed gelatin and alkali-processed gelatin, and their properties are described in detail in Arther Veis, The Macromolecular Chemistry of Gelatin, Academic Press, pp. 187 to 217 (1964). The most significant difference between acid-processed gelatin and alkali-processed gelatin resides in that the isoelectric point of acid-processed gelatin is between pH 6.0 and pH 9.5, whereas that of alkali-processed gelatin is between pH 4.5 and pH 5.3.

Preferably the acid-processed gelatin as used herein has a jelly strength (as determined by the PAGI method by the use of a Bloom type jelly strength meter) of 200 g or more, and preferably from 240 to 300 g.

Examples of the surface layers on the silver halide light-sensitive material as used herein include a a surface protective layer and a back layer. In addition to the acid-processed gelatin, if desired, other hydrophilic colloids such as alkali-processed gelatin, modified gelatin, polyvinyl alcohol and polystyrenesulfonic acid may be incorporated into the surface layer as a binder.

It is preferred, however, that the acid-processed gelatin constitutes at least 80% by weight of the binder contained in the surface layer.

Examples of the silver halide light-sensitive materials as used herein include a color negative film, a color positive film, a color paper, a color reversal film, a black-and-white negative film, an x-ray film, a printing film and microfilm.

Hereinafter the construction, light exposure, and development processing of the silver halide light-sensitive material in the present invention are described.

Light-sensitive silver halides which can be used in the silver halide light-sensitive materials of the present invention include silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride.

The grain size distribution may be narrow or broad.

The silver halide particles in the photographic emulsion may be in any of a regular crystal form, e.g., cubic and octahedral forms, an irregular crystal form, e.g., spherical and planar forms, and a composite crystal form thereof. The silver halide may also be a mixture of particles having various crystalline forms.

Each silver halide particle may be composed of an interior phase and a surface phase which are different from each other, or may be composed of a uniform phase. Also, it may be a particle in which a latent image is mainly formed on the surface thereof, or may be a particle in which the latent image is formed in the interior thereof.

In the course of the formation of silver halide particles or the physical ripening thereof, cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or its complex salts, rhodium salts or its complex salts, iron salts or its complex salts, and the like may be present in combination, for the purpose of improving sensitivity, stability during the lapse of time, and high intensity-exposure sensitivity.

Into the silver halide emulsion as used herein can be incorporated various compounds for the purpose of preventing fog during the production, storage, or photographic processing of the lightsensitive material, or of stabilizing the photographic performance thereof.

Compounds which can be used for that purpose include azoles, e.g. benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, and benzimidazoles (particularly nitro- or halogen-substituted compound); heterocyclic mercapto compounds e.g., mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (particularly 1-phenyl-5- mercaptotetrazole), and mercaptopyrimidines; heterocyclic mercapto compounds containing therein water-soluble groups, such as a carboxyl group and a sulfone group; thioketo compounds, e.g.

oxazolinethion; azaindenes, e.g., tetraazaindenes (particularly, 4-hydroxy-substituted (1 ,3,3a,7)tetraazaindenes); benzenethiosulfonic acids; and benzenesulfonic acids. These compounds are known as antifoggants or stabilizers.

The details of such compounds and a method of using them are described, for example, in U.S.

Patents 3,954,474,3,982,947, and 4,021,248, and Japanese Patent Publication No. 28660/77.

Silver halide emulsions are usually subjected to chemical sensitization. For this chemical sensitization, the method described in H. Frieser ed., Die Grundlagen derPhotographischen Prozesse mit Silberhalogeniden, Akademische Verlagsgesellschaft, pp. 675 to 734 (1968) can be used. For example, a sulfur sensitization method using sulfur-containing compounds capable of reacting with active gelatin and silver (e.g., thiosulfates, thioureas, mercapto compounds, and rhodanines), a reduction sensitization method using reducible substances (e.g., stannic salts, amines, hydrazine derivatives, formamazinesulfinic acid, and silane compounds); and a noble metal sensitization method using noble metal compounds (e.g., gold complex salts, and complex salts of Group VIII metals of the Periodic Table, such as Pt, Ir, and Pd) can be used alone or in combination with each other.

The sulfur sensitization method is described in detail, for example, in U.S. Patents 1,574,944, 2,410,689, 2,278,947, 2,728,668, and 3,656,955; the reduction sensitization method, for example, in U.S. Patents 2,983,609, 2,419,974, and 4,054,458; and the noble metal sensitization method, for example, in U.S. Patents 2,399,083, 2,448,060, and British Patent 618,061.

The hydrophilic colloid layer of the silver halide light-sensitive material of the present invention may contain inorganic or organic hardeners. Examples of such hardeners include chromium salts (e.g., chromium alum and chromium acetate), aldehydes (e.g., formaldehyde, glyoxal, and glutaraldehyde), N-methylol compounds (e.g., dimethylol urea, and methyloldimethylhydantoin), dioxane derivatives (e.g., 2,3-dihydroxydioxane), active vinyl compounds (e.g., 1 ,3,5-triacryloyl-hexahydro-s-triazine, and 1 ,3-vinylsulfonol-2-propanol), active halogenated compounds (e.g., 2,4-dichloro-6-hydroxy-s-triazine) and mucohalogenic acids (e.g., mucochloric acid and mucophenoxychloric acid). These compounds may be used alone or in combination with each other.

The photographic emulsion as used herein may be subjected to spectral sensitization with methine dyes, etc. These sensitizing dyes may be used alone or in combination with each other.

Combinations of sensitizing dyes are often used, in particular, for super color sensitization. In combination with such sensitizing dyes, dyes having no spectral sensitization action by themselves, or substances not substantially absorbing visible light, but exhibiting super color sensitization may be incorporated into the photographic emulsion.

Useful sensitizing dyes, combinations of dyes exhibiting super color sensitization, and substances exhibiting super color sensitization are described in Research Disclosure, Vol. 1 76, No.17643, page 23, IV-J (published December 1978).

The photographic emulsion layer or other hydrophilic colloid layers of the silver halide lightsensitive material as used herein may contain various surface active agents for various purposes, for example, for facilitation of coating, prevention of the generation of static electricity, improvements in sliding properties, emulsification and dispersion, prevention of adhesion, and improvements in photographic characteristics (e.g., acceleration of development, increase in contrast, and sensitization).

Surface active agents which can be used for such purposes include nonionic surface active agents, such as saponin (steroid-based), alkyleneoxide derivatives (e.g., polyethylene glycol, condensate of polyethylene glycol and polypropylene glycol, polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitane esters, polyalkylene glycol alkylamines or alkylamides, and polyethylene oxide adducts of silicone), glycidol derivatives (e.g., alkenyl succinic acid polyglyceride and alkylphenol polyglyceride), aliphatic acid esters of polyhydric alcohols, and alkylesters of sugar; anionic surface active agents containing acidic groups, such as a carboxy group, a sulfo group, a phospho group, a sulfate group, and a phosphate group, e.g., alkylcarboxylic acid salts, alkylsulfonic acid salts, alkylbenzenesulfonic acid salts, alkylnaphthalenesulfonic acid salts, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyltaurines, sulfosuccinates, sulfoalkylpolyoxyethylene alkylphenyl ethers, and polyoxyethylene alkyl phosphates; amphoteric surface active agents, such as amino acids, aminoalkylsulfonic acids, aminoalkyl sulfates or phosphates, alkylbetaines, and amineoxides; and cationic surface active agents, such as alkylamine salts, aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts, e.g., pyridium and imidazolium compounds, and aliphatic or heterocyclic ring-containing phosphonium or sulfonium salts.In addition, fluorinated surface active agents can be used.

Suitable examples of such surface active agents are described in U.S. Patents 2,240,472, 2,831,766,3,158,484, 3,294,540, 3,507,660, 2,739,891, 2,823,123,3,41 5,649,3,666,478, 3,756,828,3,133,816, 3,441,413, 3,545,974, 3,726,683, 3,843,368, 2,271,623, 2,944,900, 3,253,919 and 3,589,906, British Patents 1,012,495, 1,022,878, 1,179,290, 1,198,450, 1,397,218, 1,138,514, 1,159,825, 1,507,961 and 1,503,218, Belgian Patent 731,126, West German Patent Application (OLS) No. 1,961,638 and Japanese Patent Applications (OPI) Nos. 117414/75, 59025/75,21922/78.

Of these surface active agents, anionic surface active agents having a sulfo group are particularly preferred.

The photographic emulsion layer of the silver halide light-sensitive material of the present invention may contain color-forming couplers, i.e., compounds capable of forming color through oxidative coupling with aromatic primary amine developers (e.g., phenylenediamine derivatives and aminophenol derivatives) at the color development processing. Couplers which can be used include magenta couplers, such as a 5-pyrazolone coupler, a pyrazoloneimidazole coupler, a cyanoacetylcumarone coupler, and a closed acylacetonitrile coupler, yellow couplers, such as an acylacetamido coupler (e.g., benzoylacetoanilides and pivaloylacetoanilides), and cyan couplers, such as a naphthol coupler, and a phenol coupler. Of these couplers, those non-diffusing type couplers containing a hydrophobic group (called a ballast group) in the molecule are preferred.Any of 4equivalent and 2-equivalent couplers can be used. Colored couplers having the color correction effect, or couplers releasing a development inhibitor upon development (so-called DIR couplers) can be used.

In addition to such DIR couplers, non-color-forming DIR coupling compounds producing a colorless product as a consequence of the coupling reaction and releasing a development inhibitor can be used.

Suitable examples of magenta couplers are described in U.S. Patents 2,600,788, 2,983,608, 3,062,653, 3,127,269, 3,311,476,3,419,391, 3,519,429,3,558,319, 3,582,322, 3,615,506, 3,834,908, 3,891,445, West German Patent 1,810,464, West German Patent Application (OLS) Nos.

2,408,665,2,417,945, 2,418,959, and 2,424,467, Japanese Patent Publication No. 6031/65 and Japanese Patent Applications (OPI) Nos. 20826/76, 58922/77, 129538/74, 74027/74, 159336/75, 42121/77, 74028/74, 60233/75,26541/76, and 55122/78.

Suitable examples of yellow couplers are described in U.S. Patents 2,875,057, 3,265,506, 3,408,194,3,551,155, 3,582,322,3,725,072, 3,891,445, West German Patent 1,547,868, West German Patent Application (OLS) Nos.2,219,917,2,261,361,2,414,006, British Patent 1,425,020, Japanese Patent Publication No. 10783/76 and Japanese Patent Application (OPI) Nos. 26132/72, 73147/73, 102636/76, 6431/75, 123342/75, 130442/75,21827/76, 87650/75, 82424/77, 115219/77.

Suitable examples of cyan couplers are described in U.S. Patents 2,369,929, 2,434,272, 2,474,293, 2,521,908, 2,895,826, 3,034,892, 3,311,476, 3,458,31 5, 3,476,563, 3,583,971, 3,591,383, 3,767,411, 4,004,929, West German Patent Application (OLS) Nos. 2,414,830, 2,454,329 and Japanese Patent Applications (OPI) Nos. 59838/73, 26034/76, 5055/73, 146828/76, 69624/77, 90932/77.

Colored couplers which can be used are described in U.S. Patents 3,476,560, 2,521,908, 3,034,892, Japanese Patent Publication Nos. 2016/69,22335/63, 11304/77,32461/69, Japanese Patent Application (OPI) Nos. 26034/76, 42121/77, and West German Patent Application (OLS) No.

2,418,959.

DIR couplers which can be used are described in U.S. Patents 3,227,554, 3,617,291, 3,701,783, 3,790,384, 3,632,345, West German Patent Application (OLS) Nos. 2,414,006, 2,454,301, 2,454,329, British Patent 953,454, Japanese Patent Application (OPI) Nos. 69624/77, 122335/74, and Japanese Patent Publication No. 16141/76.

In addition to DIR couplers, the light-sensitive material may contain therein other compounds releasing a development inhibitor upon development, as noted above. The compounds described in, for example, U.S. Patents 3,297,445, 3,379,529, West German Patent Application (OLS) No. 2,417,914 and Japanese Patent Application (OPI) Nos. 15271/77 and 9116/78 can be used.

These couplers are incorporated into the silver halide emulsion layer by known techniques, for example, by the method described in U.S. Patent 2,322,027. For example, the coupler is dissolved in phthalic acid alkyl esters (e.g., dibutyl phthalate and dioctyl phthalate), phosphoric acid esters (e.g., diphenyl phosphate, triphenyl, phosphate, tricresyl phosphate, and dioctylbutyl phosphate), citric acid esters (e.g., tributyl acetylcitrate), benzoic acid esters (e.g., octyl benzoate), alkylamides (e.g., diethyllaurylamide), aliphatic acid esters (e.g., dibutoxyethyl succinate and dioctyl azelate), trimesic acid esters (e.g., tributyl trimesiate), or the like, or in organic solvents having a boiling point of about 300C to 1 5O0C, such as lower alkyl acetates, e.g., ethyl acetate and butyl acetate, ethyl propionate, sec-butyl alcohol, methyl isobutyl keton, #-ethoxyethyl acetate, and methyl cellosolve acetate, and then dispersed in a hydrophillic colloid. The above described high boiling point organic solvents and low boiling point organic solvents may also be used in admixture with each other.

Also, a method of dispersion using the polymeric substances described in Japanese Patent Publication No. 39853/76 and Japanese Patent Application (OPI) No. 59943/76 can be used.

In the case of couplers having an acidic group, e.g., a carboxylic acid and a sulfonic acid, they are introduced into the hydrophilic colloid in the form of an alkalline aqueous solution.

If necessary, matting agents, such as silicon oxide and polymethyl methacrylate fine particles (having a grain size of 1 to 10 #), and lubricants, such as colloidal silica, can be incorporated into the surface layer of the silver halide light-sensitive material of the present invention.

In the practice of the present invention, known fading-preventing agents, such as hydroquinone derivatives, gallic acid derivatives, p-alkoxyphenols, p-oxyphenol derivatives, and bisphenols, can be used in combination. Color image stabilizers as used herein can be used alone or as a mixture comprising two or more thereof.

Suitable examples of hydroquinone derivatives are described in U.S. Patents 2,360,290, 2,418,613, 2,675,314, 2,710,197, 2,704,713, 2,728,659,2,732,300, 2,735,765, 2,710,801, 2,816,028 and British Patent 1,363,921.

Suitable examples of gallic acid derivatives are described in U.S. Patents 3,457,079, 3,069,262, etc.

Suitable examples of p-alkoxyphenols are described in U.S. Patents 2,735,765, 3,698,909, Japanese Patent Publication Nos. 20977/74 and 6623/77.

Suitable examples of p-oxyphenol derivatives are described in U.S. Patents 3,432,300, 3,573,050, 3,574,627, 3,764,337 and Japanese Patent Application (OPI) Nos. 35633/77, 147434/77, and 152225/77.

Suitable examples of bisphenols are described in U.S. Patent 3,700,455.

The silver halide light-sensitive material of the present invention may contain ultraviolet absorbers in the hydrophilic colloid thereof. Examples of such ultraviolet absorbers include aryl groupsubstituted benzotriazole compounds, 4-thiazolidone compounds, benzophenone compounds, cinnamic acid ester compounds, butadiene compounds, benzoxazole compounds, and furthermore, ultraviolet ray-absorbing polymers. These ultraviolet absorbers may be fixed in the above described hydrophilic colloid layer. In addition, the silver halide light-sensitive material may contain hydroquinone derivatives, aminophenol derivatives, gallic acid derivatives, ascorbic acid derivatives, and the like as anti-stain agents.

The silver halide light-sensitive material of the present invention can contain dispersions of water-insoluble or water-sparingly soluble synthetic polymers in the photographic emulsion layer and other hydrophilic colloid layer thereof for the purpose of improving the dimensional stability. Synthetic polymers which can be used for that purpose include homo- and co-polymers of alkyl acrylate or methacrylate, alkoxyalkyl acrylate or methacrylate, glycidyl acrylate or methacrylate, acrylamide or methacrylamide, vinyl esters (e.g., vinyl acetate), acrylonitrile, olefins, styrene, etc., and copolymers of the above monomers and acrylic acid, methacrylic acid, a,#-unsaturated dicarboxylic acids, hydroxyalkyl acrylate or methacrylate, sulfoalkyl acrylate or methacrylate, styrenesulfonic acid, and the like.

In addition, the silver halide light-sensitive material may contain stilbene-based, triazine-based, oxazole-based, cumarine-based, or like brighteners. These brighteners may be water-soluble, or waterinsoluble brighteners may be used in the form of a dispersion.

Useful supports for the production of the silver halide light-sensitive material of the present invention include films of semi-synthetic and synthetic polymers, such as cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, and polycarbonate, and a baryta layer or a-olefin polymer (e.g., polyethylene, polypropylene, and an ethylene-butene copolymer)-coated or laminated paper. These supports may be colored with dyes and pigments. Also, they may be colored black for the purpose of shielding the light. The surface of the support is generally subjected to a subbing treatment to improve the adhesion to the photographic emulsion layer and so forth. Before or after the subbing treatment, the surface of the support may be subjected to corona discharge, irradiation with ultraviolet rays, flame treatment, and so forth.

In preparing the silver halide light-sensitive material of the present invention, the hydrophilic colloid layers such as a photographic emulsion layer can be coated on the support or another layer by various known techniques, e.g., dip coating, roller coating, curtain coating, and extrusion coating. The methods described in U.S. Patents 2,681,294,2,761,791, and 3,526,528 can be advantageously used in the present invention.

The silver halide light-sensitive material of the present invention is exposed to light by conventional techniques to obtain photographic images. For this light-exposure, any of known light sources, e.g., natural light (sunlight), a tungsten lamp, a fluorescent lamp, a mercury lamp, a xenon arc lamp, a carbon arc lamp, a xenon flash lamp, and a cathode ray tube flying spot can be used. The exposure time may be, of course, within the range of from 1/1,000 second to 1 second, which is typically employed for photographic cameras. Light-exposure for shorter than 1/1,000 second, for example, light-exposure for 1/104 second to 1/108 second by the use of a xenon flash lamp or cathode ray tube, can be used. In addition, light-exposure for longer than 1 second can be used.If necessary, the spectral composition of the light used for the light-exposure can be controlled by the user of a color filter. The light-exposure can be performed by the use of a laser. Also, the light generated from a fluorescent material activated by electron rays, x-rays, y-rays, a-rays, and the like can be used.

In the development processing of the silver halide light-sensitive material of the present invention, any of the known methods and processing solutions as described, for example, in Research Disclosure, No. 176, pp. 28 to 30, No.17643 can be used. This photographic processing may be any of photographic processing to form silver images (a black-and-white photographic processing) and a photographic processing to form dye images (a color photographic processing). The processing temperature is usually selected from the range of from 1 80C to 50 C, but it may be lower than 1 80C or higher than 50 C.

Developers for use in the black-and-white photographic processing can contain known developing agents. Developing agents which can be used include dihydroxybenzenes (e.g., hydroquinone),3-pyrazolidones (e.g., 1-phenyl-3-pyrazolidone), and aminophenols (e.g., N-methyl-pamino phenol). These developing agents can be used alone or in combination with each other. In addition to the developing agent, the developer generally contains other known additives, such as a preservative, an alkali agent, a pH buffer, and an antifoggant, and, if necessary, may contain a dissolution aid, a color controller, a development accelerator, a surface active agent, a defoaming agent, a water-softening agent, a hardener, and a tackifier.

A photographic processing of the so-called "lith" type can be applied to the photographic emulsion of the present invention. The term "light type development processing" is used herein to indicate a development processing in which for photographic reproduction of line images, or for photographic reproduction of half-tone images by means of dots, dihydroxybenzenes are usually used as developing agents, and the development is performed at a low concentration of sulfite ions. This procesing described in detail in Mason, Photographic Processing Chemistry, pp. 163 to 165 (1966).

As a specific type of development processing, there may be employed a method in which the developing agent is contained in the light-sensitive material, for example, the emulsion layer, and the development is performed by processing the light-sensitive material in an aqueous alkali solution.

Hydrophobic developing agents can be incorporated into the emulsion layer by various techniques as described, for example, in U.S. Patent 2,739,890, British Patent 813,253, and West German Patent 1,547,763. This development processing may be performed in combination with a silver salt stabilization treatment using thiocyanic acid salts.

Conventional fixer compositions can be used in the present invention. Fixing agents which can be used include thiosulfuric acid salts and thiocyanic acid salts. In addition, organic sulfur compounds which are known to have the effect of fixing as a fixing agent can be used. The fixer may contain watersoluble aluminum salts as hardeners.

Formation of dye images can be performed by conventional techniques, such as a negativepositive method (as described, for example, in Journal of the Society of Motion Picture and Television Engineers, Vol. 61, pup 667 to 701 (1953)), a color reversal method in which a negative silver image is formed by developing with a developer containing therein a black and white developing agent, and then is subjected to at least one uniform light-exposure or another appropriate fog treatment, and subsequently, color development is performed to obtain a dye positive image, and a silver dye breach method in which a photographic emulsion layer containing dye is exposed imagewise to light, then developed to form a silver image, and the silver image thus formed is used as a bleach catalyst to bleach the dye.

The color developer is generally composed of an alkaline aqueous solution containing a color developing agent. Color developing agents which can be used are known primary aromatic amine developers, such as phenylenediamines (e.g., 4-amino-N,N-diethylaniline, 3-methyl-4-amino-N,N- diethylaniline, 4-a mi no-N-ethyl-N-P-hyd roxyethyla ni line, 3-methyl-4-a mi no-N-ethyl-N-P- hydroxyethylaniline,3-methyl-4-amino-N-ethyl-N-p-methanesulfoamidoethylaniline, and 4-amino-3 methyI-N-ethyl-N-#-methoxyethylaniline). In addition, those compounds described in L. F. A. Mason, Photographic Processing Chemistry, Focal Press, pp. 226 to 229 (1 966), U.S. Patents 2,193,01 5, 2,592,364 and Japanese Patent Application (OPI) No. 64933/73 can also be used.

The color developer can further contain a pH buffer, a development inhibitor, an antifoggant, etc.

If desired, it may contain a water-softening agent, a preservative, an organic solvent, a development accelerator, a dye-forming coupler, a competitive coupler, a fogging agent, an auxiliary developer, a tackifier, a polycarboxylic acid-based chelating agent, an antioxidant, and the like.

Examples of such additives are described in Research Disclosure, No.17643, and in U.S. Patent 4,083,723 and West German Patent Application (OLS) No. 2,622,950.

The photographic emulsion layer after color development is usually subjected to a bleach processing. The bleach processing may be performed simultaneously with a fix processing, or separately therefrom. Bleaching agents which can be used include compounds of polyvalent metals, e.g., iron (III), cobalt (III), chromium (VI), and copper (II), peracids, quinones, and nitroso compounds.

For example, ferricyanide compounds, dichromic acid salts, organic complex salts of iron (III) and cobalt (III), such as complex salts of aminopolycarboxylic acids (e.g., ethylenediaminetetraacetic acid, nitrotriacetic acid, and 1 ,3-diamino-2-propanoltetraacetic acid), or organic acids (e.g., citric acid, tartaric acid, and malic acid), persulfuric acid salts, permanganic acid salts, nitrosophenol, and the like can be used. Of these compounds, potassium ferricyanide, iron (III) sodium ethylenediaminetetraacetate, and iron (III) ammonium ethyleneidiaminetetraacetate are particularly useful.

Ethylenediaminetetraacetic acid iron (III) complex salts are useful both in an independent bleaching solution and in a combined bleaching and fixing solution.

To the bleaching solution or bleach-fixing solution can be added the bleach accelerators described in U.S. Patents 3,042,520, 3,241 966, Japanese Patent Publication Nos. 8506/70, 8836/70, etc. the thiol compounds described in Japanese Patent Application (OPI) No. 65732/78, and other various additives.

The silver halide light-sensitive material as used herein may be processed with a developer which is replenished or maintained by the methods described in Japanese Patent Applications (OPI) Nos.

84636/76, 119934/77,46732/78, 9626/79, 19741/79,37731/79, 1048/81 and 1049/81 and Japanese Patent Application No. 1 02962/79.

The bleach-fixing solution for use in the processing of the silver halide light-sensitive material may be reproduced by the methods described in Japanese Patent Applications (OPI) Nos. 781/71, 49437/73, 18191/73, 145231/75, 18541/76, 19535/76, 144620/76, and Japanese Patent Publication No.23178/76 Some of the major advantages of the present invention are: (1) In the steps of coating and drying a coating solution to form a hydrophilic colloid layer in the course of the production of a silver halide light-sensitive material, even though rapid drying is performed, for example, drying is performed under the conditions that the equilibrium water content is attained in 3 minutes or less, and especially 2 minutes or less, reticulation does not occur.Furthermore, even though development is performed by the use of an automatic developing machine, deterioration of image quality resulting from the attachment of contaminants, composed mainly of oxidized products of developing agent onto the surface of the light-sensitive material does not occur.

(2) A siliver halide light-sensitive material is obtained which is sufficiently prevented from adhering to other materials, and which is free from attachment of contaminants at the step of development processing.

(3) Since a silver halide light-sensitive material having excellent physical properties (e.g., reticulation and prevention of adhesion) can be obtained even though rapid drying is performed, and furthermore, the attachment of contaminants during processing steps does not occur, the production and development of the light-sensitive material can be carried out very quickly.

The following example is provided to illustrate the invention in greater detail, but the invention is not limited thereto.

Example On a polyethylene double-laminated paper were coated a 1 st layer (lowermost layer) to a 5th layer as described in Table 1, and, in different samples, various 6th layers (uppermost layer) having different compositions as shown in Table 2 were used to prepare various color light-sensitive materials.

A coating solution for the preparation of the 1 st layer was prepared as follows: One hundred grams of a yellow coupler (*6) was dissolved in a mixture of 100 ml of dibutyl phthalate and 200 ml of ethyl acetate, and the solution was emulsified and dispersed in 800 g of a 10% aqueous gelatin solution containing 80 ml of a 1% aqueous solution of sodium dodecylbenzene sulfonate. The emulsion thus prepared was then mixed with 1,450 g (70 g as Ag) of a blue-sensitive silver chlorobromide emulsion (Br: 80 mol%) to obtain the desired coating solution.

The other coating solutions containing appropriate corresponding couplers were prepared in the same manner as above.

These coating solutions were coated by an extrusion coating method and dried quickly. The time required to reach the equilibrium water content was about 1.5 minutes.

Each light-sensitive material thus prepared was exposed to blue light, green light and red light (in such a manner that the density of color formed after development was 1.0), and then, was processed with an automatic developing machine according to the processing steps shown below: Processing Steps Temperature ( C) Time (minutes) Developer 33 3.5 Bleach-fixer 33 1.5 Water-washing 28-35 3 The composition of each processing solution was as follows:: Developer Benzyl alcohol 15 ml Diethylene glycol 8 ml Ethylenediaminetetraacetic acid 5g Sodium sulfite 2g Anhydrous potassium carbonate 30 g Hydroxylamine sulfuric acid salt 3g Potassium bromide 0.6 g 4-Amino-N-ethyl-N-(/3-methanesulfonamidoethyl)-m-toluidine 2/3 sulfuric acid salt monohydrate 5g (adjusted to pH 10.20) Water to make 1 liter Bleachjixer Ethylenediaminetetraacetic acid 2g Iron (III) ethylenediaminetetraacetate ~ 40 g Sodium sulfite 5g Ammonium thiosulfate 70 g Water to make 1 liter The automatic developing machine used for the above processing was a Fuji Color Sheet Roll Processor PSR-2040 (produced by Fuji Photo Film Co., Ltd.; "Fuji" is a registered Trade Mark).

Furthermore, after a processing bath was placed in the automatic developing machine, color paper commercially available was processed for several days, and then, each light-sensitive material was developed in a state wherein a conveying roller of the automatic developing machine was dirty.

After the development processing, the degree of contamination of the surface of the lightsensitive material due to the attachment of contaminants thereonto, and the formation of reticulation were visually observed. The results are shown in Table 2.

Table 1 5th Layer (red-sensitive layer) Containing 300 mg/m2 (calculated as Ag) of a silver chlorobromide emulsion (Br: 50 mol%), 1,000 mg/m2 of gelatin, 400 mg/m2 of a cyan coupler (&num;1), and 200 mg/m2 of a coupler solvent (&num;2).

4th Layer (intermediate layer) Containing 1,200 mg/m2 of gelatin, 1,000 mg/m2 of an ultraviolet absorber (&num;3), and 250 mg/m2 of an ultraviolet absorber solvent (&num;2).

3rd Layer (green-sensitive layer) Containing 290 mg/m2 (calculated as Ag) of a silver chlorobromide emulsion (Br: 50 mol%), 1,000 mg/m2 of gelatin, 200 mg/m2 of a Magenta coupler (&num;4), and 200 mg/m2 of a coupler solvent (&num;5).

2nd Layer (intermediate layer) 1,000 mg/m2 of gelatin.

1 sot Layer (blue-sensitive layer) Containing 400 mg/m2 (calculated as Ag) of a silver chlorobromide emulsion (Br: 80 mol%), 1,200 mg/m2 of gelatin, 300 mg/m2 of a yellow coupler (&num;6), and 1 50 mg/m2 of a coupler solvent (#7).

Support Polyethylene double-laminated paper support &num;1 Coupler: 2- [ a-(2,4-di-tert-pentylphenoxy)butaneamido-4,6-dichloro-5-methylphenol &num;2 Solvent: dibutyl phthalate &num;3 Ultraviolet absorber: 2-(2-hydroxy-3-sec-butyl-5-tert-butylphenyl)benzotriazole &num;4 Coupler: 1 -(2,4,6-trichlorophenyl)-3-(2-chloro-5-tetradecaneamido)anilino-2-pyrazolin-5-on &num;5 Solvent: tricresyl phosphate &num;6 Coupler: &alpha;-pivaroyl-&alpha;-(2,4-dioxo-5,5'- dimethyloxazolizin-3-yl)-2-chloro-5- [ &alpha;-(2,4-di-tert- pentylphenoxy)-butaneamido]acetoanilide &num;7 Solvent: dioctylbutyl phosphate Table 2 Results Composition of Uppermost Layer * 1 Degree of Sample SurfaceActive Formation of Contamination No.Gelatin Agent *4 Reticulation during Processing alkali-processed gelatin *2 ~ formed not attached 2 acid-processed gelatin *3 -- not formed attached 3 do saponin do do 4 do B*5 do do 5 do C*6 do do 6 do D*7 do do 7 do F*8 do do 8 (the present invention) do Compound 3 of the do not attached present invention 9 (the present invention) do Compound 2 of the do do present invention *1 In all samples, the uppermost layer further contained a sodium salt of 2,4-dichloro-6-hydroxy- S-triazine, and 6.2x 10-5 mol/m2 of the compound represented by the formula:

*2 Isoelectric point: pH 5.0, 1.0 g/m2 *3 isoelectric point: pH 7.0, 1.0 g/m2 *4 6.2X10-5 mol/m2 *5 C12H25-O+CH2CH2O#0H

*8 C12H25-OSO3Na As is apparent from Table 2, in the case of Sample 1, in which alkali-processed gelatin was used as a binder for the uppermost layer, the attachment of contaminants during the development processing did not occur, but the formation of reticulation resulting from the rapid drying of the coating solution after the coating thereof was observed. Thus, the silver halide light-sensitive material of Sample 1 was not suitable for practical use.

On the other hand, in the case of Samples 8 and 9, in which acid-processed gelatin was used in combination with the compounds of the invention, the formation of reticulation and the attachment of contaminants during processing were not observed. Thus, they exhibited excellent performance.

Claims (16)

Claims

1. A process of developing a silver halide photographic light-sensitive material comprising a support and at least one silver halide light-sensitive emulsion layer on the support, wherein a surface layer of the light-sensitive material contains acid-processed gelatin as a binder, and the development is performed in the presence of a compound represented by the general formula::

wherein R is a saturated or unsaturated aliphatic group containing from 7 to 22 carbon atoms, or a substituted aryl group; R, is a hydrogen atom or a methyl group; R2 and R3 are each an alkyl group or substituted alkyl group containing from 1 to 4 carbon atoms; R4 and R5 are each a hydrogen atom or an alkyl group containing from 1 to 4 carbon atoms; L is --CONH--,--SO2NH--, --OO--, --S--,--CONH(CH2)@--O--,--SO2NH(CH2)@--O--,

m is O or 1; nisO, 1,2or3; xis 0, 1,2or3; A is~COOE' or --SO3#; and / is an integer of 2 or more.

2. A process as claimed in Claim 1, wherein R is a saturated or unsaturated aliphatic group containing from 8 to 15 carbon atoms.

3. A process as claimed in Claim 1 or 2, wherein / is an integer of 2 to 5.

4. A process as claimed in Claim 1 or 2 or 3, wherein R is a substituted aryl group represented by the formula (ia)

wherein R' is a saturated or unsaturated aliphatic group containing from 7 to 21 carbon atoms, y is O or 1, and n, is 1 or 2.

5. A process as claimed in Claim 1, wherein said compound is any of Compounds 1 to 1 5 shown hereinbefore.

6. A process as claimed in any of Claims 1 to 5, wherein the compound represented by formula (I) is incorporated in a hydrophilic colloid layer of the silver halide light-sensitive material.

7. A process as claimed in Claim 6, wherein the compound represented by formula (I) is incorporated in a surface layer.

8. A process as claimed in Claim 7, wherein said surface layer is a surface protective layer.

9. A process as claimed in any of Claims 6 to 8, wherein the compound represented by formula (I) is incorporated in an amount of from 1.0 to 10-6 to 1 Ox 10-3 mol per gram of binder in the layer.

10. A process as claimed in Claim 9, wherein said amount is from 1.Ox 10-5 to 1.Ox 10-4 mol per gram of binder.

11. A process as claimed in Claim 7, substantially as hereinbefore described with reference to Sample 8 or 9 of the Example.

12. A process as claimed in any of Claims 1 to 5, wherein the compound represented by formula (I) is incorporated in a development processing solution in which the development is performed.

13. A process as claimed in Claim 12, wherein the compound is incorporated in the development processing solution in an amount of from 0.1 to 10 grams per litre of development processing solution.

14. A process as claimed in Claim 13, wherein said amount is from 0.5 to 3 g per litre.

15. A light-sensitive silver halide photographic material as defined in any of Claims 1 to 10.

16. A light-sensitive silver halide photographic material as claimed in Claim 15, substantially as hereinbefore described with reference to Sample 8 or 9 of the Example.