JPH10333294A - Silver halide color photographic sensitively material and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To make it possible to express an intensity difference of exposure amount with the differences of hue and density at the time of imagewise exposure to visible light by spectrally sensitizing with a specified sensitizing dye and expressing the intensity difference of a light source with the differences of the hue and the density. SOLUTION: Silver halide grains in the silver halide emulsion contains at least >=95 mol.% silver chloride and are spectrally sensitized with at least one of the sensitizing dyes represented by the formula and the difference of the light source intensity is expressed with the differences of the hue and the density. The silver halide photographic sensitive material is processed with a color developing solution containing substantially no benzyl alcohol. In the formula, each of R1 and R2 is a 1-6C alkyl or 1-4C substituted alkyl or aralkyl group; each of Z1 and Z2 is a nonmetallic atomic group necessary to form a benzene or naphthalene ring; X1 is an anionic group; and p1 is 1 or 2 and when it is 1, an intermolecular ion is formed.

Description

DETAILED DESCRIPTION OF THE INVENTION

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BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color light-sensitive material having a multi-layer structure and an image forming method. And a method for forming an image.

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2. Description of the Related Art In diagnosis using ME devices such as radiography, medical CT (computer tomography), ultrasonic diagnosis, RI (nuclear medicine), and thermography, an image is displayed on a green CRT and the image is displayed in black and white. Very often, a black-and-white image is produced by exposing a photosensitive material. Since this image is represented only by the density difference, it is difficult to identify a detailed portion. A silver halide color light-sensitive material capable of expressing such an image on a green CRT by a difference in hue and a difference in density is described in JP-A-4-32834. However, there is no description about exposure to other wavelength ranges. A color image is output on a color CRT by performing computer processing, and the color image is exposed to a color photosensitive material to obtain a color image. However, this system is very expensive. Also, silver halide color light-sensitive materials require color development processing, but color developing solutions containing benzyl alcohol are environmentally unfavorable, so recently most color developing solutions do not contain benzyl alcohol. Liquid is used. Therefore, a silver halide color light-sensitive material which can be processed with a color developer containing no benzyl alcohol is preferable.

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SUMMARY OF THE INVENTION A first object of the present invention is to provide a silver halide color light-sensitive material capable of expressing a difference in exposure intensity by a hue and a density difference when imagewise exposed by visible light. An object of the present invention is to provide an image forming method. A second object of the present invention is to provide a silver halide color light-sensitive material and an image forming method which can be processed with a color developer containing substantially no benzyl alcohol.

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An object of the present invention is to provide a silver halide color light-sensitive material having at least two silver halide emulsion layers containing a photosensitive silver halide grain and a coupler on a support. The silver halide grains of the silver halide emulsion are composed of at least 95 mol% or more of silver chloride, and at least one sensitizing dye represented by the following general formula (I) and a sensitizing dye represented by the following general formula (II) At least one of the dyes and the following general formula (III) or (I)
V) are spectrally sensitized with at least one of the sensitizing dyes represented by the formula (V). Each silver halide emulsion has a different sensitivity and contains a coupler which forms a different dye image. And a silver halide photographic light-sensitive material represented by a density difference, and an image forming method in which the silver halide photographic light-sensitive material is developed with a color developer substantially free of benzyl alcohol.

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In the formula, R ₁ and R ₂ each have 1 to 6 carbon atoms.
, An alkyl group having 1 to 4 carbon atoms, an aralkyl group, Z ₁ and Z ₂ each represent a group of nonmetallic atoms necessary for forming a benzene ring and a naphthalene ring, and X ₁ represents an anionic group. P ₁ represents 1 or 2, and when P ₁ is 1, an internal salt is formed.

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In the formula, R ₃ and R ₄ each represent an alkyl group having 1 to 6 carbon atoms which may have a sulfo group as a substituent, A ₁ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, An aryl group, Y ₁ and Y ₂ are a sulfur atom, an oxygen atom,
A selenium atom, an N-R _5, the R ₅ is an alkyl group having 1 to 3 carbon atoms, Z ₃ and Z ₄ each is a benzene ring, a non-metallic atomic group necessary for forming a naphthalene ring, X ₂ is Represents an anionic group. P ₂ represents 1 or 2, and when P ₂ is 1, an internal salt is formed.

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In the formula, R ₆ , R ₇ , R ₈ and R ₉ each represent an alkyl group having 1 to 6 carbon atoms, a substituted alkyl group having 1 to 4 carbon atoms, and an aralkyl group, and A ₂ represents a hydrogen atom and a carbon atom. Z ₁ , Z ₆ , Z _7, and Z ₈ each represent a non-metallic atom group necessary for forming a benzene ring or a naphthalene ring, and Z ₉ forms a 6-membered ring. And X ₃ and X ₄ represent an anionic group. P ₃ and P ₄ represent 1 or 2, and when P ₃ and P ₄ are 1, an inner salt is formed.

In the general formula (I), R ₁ and R _{2 each} have 1 carbon atom.
To 6 alkyl groups (e.g., methyl group, ethyl group, n-
Propyl group, isopropyl group, n-butyl group, isobutyl group, n-hexyl group, isohexyl group, etc.), carbon number 1
To 4 substituted alkyl groups [for example, hydroxylalkyl group (for example, 2-hydroxyethyl group, 3-hydroxypropyl group, 2-hydroxypropyl group, etc.), sulfoalkyl group (for example, 2-sulfoethyl group, 3-sulfopropyl group) Group, 3-sulfobutyl group, 4-sulfobutyl group, etc.), carboxyalkyl group (eg, 2-carboxyethyl group, 3-carboxypropyl group, 3-carboxybutyl group, 4-carboxybutyl group, etc.)], aralkyl group ( For example, a benzyl group or a 2-phenylethyl group). It is preferable that _one of R ₁ and R ₂ is a substituted alkyl group. Z ₁ and Z ₂ represent a substituent (for example, a halogen atom, an alkyl group, an alkoxy group, an aryl group, a cyano group, an alkoxycarbonyl group, a trifluoromethyl group, an alkylsulfonyl group, an alkylsulfamoyl group, an acylamino group, an alkylcarbamoyl Group, acetoxy group, etc.) represents a group of non-metallic atoms necessary for forming a benzene nucleus or a naphthalene nucleus which may have a nucleus. X ₁ represents a commonly used anion group (for example, chloride ion, bromine ion, iodine ion, perchlorate ion, p-toluenesulfonic acid ion, ethyl sulfate ion, etc.). P ₁ represents 1 or 2, and when P ₁ is 1, an internal salt is formed.

In the general formula (II), R ₃ and R ₄ represent an alkyl group having 1 to 6 carbon atoms which may have a sulfo group as a substituent (for example, a methyl group, an ethyl group, an n-propyl group) ,
A ₁ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms (such as an isopropyl group, an n-butyl group, an isobutyl group, an n-hexyl group, a 2-sulfoethyl group, a 3-sulfopropyl group, and a 3-sulfobutyl group). For example, a methyl group, an ethyl group,
Y ₁ and Y ₂ are a sulfur atom, an oxygen atom, a selenium atom, N—R ₅ , and R ₅ is a carbon atom having 1 to 3 carbon atoms. (For example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, etc.). Z ₃ and Z ₄ represent a substituent (for example, a halogen atom, an alkyl group, an alkoxy group,
Aryl group, carbonyl group, alkoxycarbonyl group,
A non-metallic atom group necessary for forming a benzene ring or a naphthalene ring which may have a cyano group or the like. X ₂ represents an anion group (for example, chloride ion, bromine ion, iodine ion, perchlorate ion, p-toluenesulfonic acid ion, ethyl sulfate ion, etc.). P ₂ represents 1 or 2, and when P ₂ is 1, an internal salt is formed.

In the general formulas (III) and (IV),
R ₆ , R ₇ , R ₈ and R ₉ represent an alkyl group having 1 to 6 carbon atoms (for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an n-hexyl group) , Isohexyl group, etc.), a substituted alkyl group having 1 to 4 carbon atoms [for example, a hydroxylalkyl group (for example, 2-
Hydroxyethyl group, 3-hydroxypropyl group, 2-
Hydroxypropyl group, etc.), sulfoalkyl group (for example, 2-sulfoethyl group, 3-sulfopropyl group, 3-
Sulfobutyl group, 4-sulfobutyl group, etc.), carboxyalkyl group (eg, 2-carboxyethyl group, 3-carboxypropyl group, 3-carboxybutyl group, 4-carboxybutyl group, etc.)], aralkyl group (eg, benzyl group) , 2-phenylethyl group, etc.). R ₆ and R ₇
Is preferred when any one of them is a substituted alkyl group. Similarly, it is preferable that one of R ₈ and R ₉ is a substituted alkyl group. A ₂ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms (eg, a methyl group, an ethyl group, n
-Propyl group, isopropyl group, etc.) and aryl group (for example, phenyl group etc.). Z ₅ , Z ₆ , Z ₇ and Z ₈ represent a substituent (for example, a halogen atom, an alkyl group, an alkoxy group, an aryl group, a cyano group, an alkoxycarbonyl group,
Trifluoromethyl group, alkylsulfonyl group, alkylsulfamoyl group, acylamino group, alkylcarbamoyl group, acetoxy group, etc.), which represents a group of non-metallic atoms necessary for forming a benzene nucleus or a naphthalene nucleus. . Z ₉ represents a nonmetallic atom group necessary for forming a 6-membered ring nucleus which may have a substituent (for example, an alkyl group). X ₃ and X _{4 each} represent a commonly used anion group (for example, chloride ion, bromine ion, iodine ion, perchlorate ion, p-toluenesulfonic acid ion, ethyl sulfate ion, etc.). P ₃ and P ₄ represent 1 or 2, and when P ₃ and P ₄ are 1, an internal salt is formed. Next, specific examples of the sensitizing dye represented by the above general formula are shown, but the present invention is not limited thereto.

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These sensitizing dyes can be purchased from commercial sources, or can be synthesized based on The Cyanine Soybeans and Related Compounds, published by Interscience Publishers, 1964. These sensitizing dyes are used at a concentration of 10 ^-6 to 10 ^-3 mol per mol of silver halide in the silver halide emulsion. When such a sensitizing dye is added to a silver halide emulsion, a method of directly dispersing the sensitizing dye in the silver halide emulsion may be used, or a suitable solvent such as methyl alcohol, ethyl alcohol, A method of dissolving in acetone, N, N-dimethylformamide, ethyl acetate or a mixed solvent thereof, or a solvent containing a surfactant therein, and then adding the resultant solution to a silver halide emulsion may be applied. it can. These sensitizing dyes can be added to a silver halide emulsion during silver halide grain formation or after completion of physical ripening. Preferably, it is added to the silver halide emulsion after completion of physical ripening, before chemical ripening, during chemical ripening, or after chemical ripening. These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used particularly for supersensitization.
Along with the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization. For example, an aminostyryl compound substituted with a nitrogen-containing heterocyclic group (for example, US Pat. Nos. 2,933,390 and 3,933)
No. 635,721), an aromatic organic acid formaldehyde condensate (for example, US Pat.
743,510), cadmium salts, azaindene compounds and the like.

The halogen composition of the silver halide emulsion used in the present invention is such that 95 mol% or more of the silver halide grains are silver chloride, and are composed of silver chlorobromide containing substantially no silver iodide. preferable. Average grain size of silver halide grains (in the case of spherical or spherical particles, the grain diameter,
In the case of a cubic particle, the length of the ridge is defined as the particle size, and is represented by an average based on the projected area. The particle size distribution may be narrow or wide. The silver halide grains may have a regular crystal form such as a cube or an octahedron, or may have an irregular crystal form such as a sphere or a plate, or a composite of these crystal forms. May be. It may consist of a mixture of particles of various crystal forms. Further, an emulsion may be used in which tabular silver halide grains having a diameter of 5 times or more of the thickness thereof occupy 50% or more of the total projected area. The particles may be such that the latent image is mainly formed on the surface, or may be the particles that are mainly formed inside the particle. The silver halide grains may have a layered structure having layers with different halogen compositions on the inside and the outside, or may be joined to silver halide grains having different halogen compositions by epitaxial joining.

In the present invention, the silver halide grains of the silver halide emulsion are those in which a localized layer having a silver bromide content of 30 to 60 mol% is locally epitaxially grown on the surface of the halogen grains, particularly on the corners of the grains. preferable. This localized phase accounts for 0.5 to 5% of the total silver constituting the silver halide grains.
Of silver. The method for producing the epitaxial silver halide grains is described in EP-A-273,430. The silver halide emulsion used in the present invention is a P.I. Glafide
s, Chimie et Physique Pho
tographique (published by PaulMontel,
1967); F. Photograph by Duffin
raphic Emulsion Chemistry
(Published by The Focal Press, 1966
Year), V. L. By Zelikman et al, Ma
King and Coating Photogra
phy Emolsion (The Focal P
Ress Co., 1964) and the like. That is, acid method, neutral method,
Any method such as an ammonia method may be used, and a method of reacting a soluble silver salt with a soluble halogen salt may be any of a forward flow method, a reverse flow method, a double jet method, and a combination thereof.

As one of the simultaneous mixing methods, a method of maintaining a constant pAg in a solution in which silver halide is formed,
A so-called controlled double jet method can also be used. According to this method, a silver halide emulsion having a regular crystal form and a nearly uniform grain size can be obtained. Two or more types of silver halide emulsions formed separately may be used as a mixture. At the time of silver halide grain formation or physical ripening process, cadmium salt, zinc salt, lead salt, thallium salt,
An iridium salt, a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or a complex salt thereof, and the like may coexist. Silver halide emulsions are usually chemically sensitized. For example, a sulfur sensitization method using a compound containing a sulfur capable of reacting with active gelatin or silver (eg, thiosulfate, thioureas, mercapto compounds, rhodanines, etc.), a reducing substance (eg, stannous salt, Reduction sensitization using amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds), noble metal sensitization using noble metal compounds (for example, complex salts of metals such as gold, platinum, iridium, palladium, etc.) alone or in combination Can be used.

Examples of the yellow coupler that can be used in the present invention include oil-protected acylacetamide couplers. Specific examples are:
U.S. Pat. Nos. 2,407,210 and 2,875,0
No. 57 and No. 3,265,506. In the present invention, the use of 2-equivalent yellow couplers is described in U.S. Pat. No. 3,408,19.
No. 4, No. 3,447,928, No. 3,933,5
No. 01 and 4,401,752, etc., and an oxygen atom-elimination type yellow coupler described in Japanese Patent Publication No.
No. 8-10739, U.S. Pat. No. 4,022,620
No. 4,326,024, Research Disclosure 18,053 (April 1987), British Patent No. 1,425,020, West German Published Patent No. 2,219,917, No. 2 , 261,361, 2,329,587, and 2,433,812, and the like. α-pivaloylacetanilide-based couplers are characterized by the fastness of coloring dyes, while α-benzoylacetanilide-based couplers are characterized by good coloration.

Examples of the magenta coupler that can be used in the present invention include oil-protected indazolone-based or cyanoacetyl-based couplers, and preferably pyrazoloazole-based couplers such as 5-pyrazolone- and pyrazolotriazole-based couplers. Can be. As the 5-pyrazolone-based coupler, those in which the 3-position is substituted with an arylamino group or an acylamino group are preferable from the viewpoint of the hue and color developing speed of the coloring dye, and specific examples thereof are described in US Pat.
No. 1,082, No. 2,343,703, No. 2,6
No. 00,788, No. 2,908,573, No. 3,
No. 3,152,896 and 3,936,015, and the couplers described in the respective specifications. 2-equivalent 5-pyrazolone couplers are particularly preferred, and the leaving group is US Pat.
A nitrogen atom leaving group described in JP-A-310,619;
An arylthio group described in U.S. Pat. No. 4,351,897 can be mentioned. Further, a 5-pyrazolone-based coupler having a ballast group described in European Patent No. 73,636 is a preferred coupler having high color-forming reactivity. Examples of pyrazoloazole-based couplers include pyrazolo [1,5-b] [1,2,4] triazoles described in European Patent No. 119,860 and US Pat. No. 3,369,897. , The pyrazolotetrazole described in Research Disclosure 24, 220 (June 1984), and the pyrazolopyrazoles described in Research Disclosure 24, 230 (June 1984). Can be mentioned. JP 59
The imidazopyrazoles and pyrazolo [1,5-b] [1,2,4] triazoles described in JP-A-162548 are preferable because they have low yellow side absorption of the coloring dye and high light fastness.

Examples of the cyan coupler which can be used in the present invention include oil-protected naphthol couplers and phenol couplers, and naphthol couplers described in US Pat. No. 2,474,293. Couplers, preferably U.S. Pat. No. 4,052,21
No. 2, No. 4,143,396, No. 4,228,2
No. 33, No. 4,296,200, and high-activity two-equivalent naphthol couplers of the oxygen atom-elimination type described in the respective specifications. Examples of phenol couplers include U.S. Pat. Nos. 2,369,929 and 2,42.
No. 3,730, No. 2,772,162, No. 2,8
And couplers described in each specification such as No. 01,171 and No. 2,895,826.
Cyan couplers which are robust to temperature and humidity are preferred, and phenolic cyan couplers described in U.S. Pat. No. 3,772,022, U.S. Pat. Nos. 2,772,162, 3, 2,5-diacylamino-substituted phenols described in JP-A Nos. 758,308, 4,126,396, and 4,327,137, and JP-A-59-166956. Couplers, U.S. Pat. Nos. 3,446,622 and 4,3
No. 33,999, No. 4,451,559 and No. 4,427,767.
A phenolic coupler having a phenylureido group at the -position and an acylamino group at the 5-position. Next, specific examples of preferred couplers used in the present invention will be described.

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The coupler used in the present invention can be introduced into a silver halide emulsion by various dispersion methods. For example, a solid dispersion method, an alkali dispersion method, preferably a latex dispersion method, more preferably an oil-in-water dispersion method can be used. In the oil-in-water dispersion method, a high-boiling organic solvent having a boiling point of 175 ° C. or higher and a low-boiling auxiliary solvent are dissolved in a single solution or a mixture thereof, and then water or gelatin is dissolved in the presence of a surfactant. Finely dispersed in an aqueous medium such as an aqueous solution. The high boiling point organic solvent is described in U.S. Pat. No. 2,322,027. The dispersion may be accompanied by a phase inversion, and if necessary, the auxiliary solvent can be used for coating after being removed or reduced by distillation, noodle washing, ultrafiltration or the like.

Examples of the high boiling point organic solvent include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, didodecyl phthalate, etc.), esters of phosphoric acid or phosphonic acid (triphenyl phosphate, tricresyl phosphate) ,
2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, trididecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexylphenyl phosphate, benzoic acid ester (2-ethylhexyl benzoate, dodecyl benzoate, 2-ethyloxyl-p-hydroxybenzoate, etc.), amide (diethyldodecaneamide, N-tetradecylpyrrolidone, etc.), alcohol or phenol (isostearyl alcohol, 2,4-di-
t-amylphenol, etc.), aliphatic carboxylic acid esters (dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (N, N-dibutyl-2-butoxy-5-t-) Octylaniline, etc.), and hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.). As the auxiliary solvent, those having a boiling point of about 30 ° C. to about 60 ° C. can be used. Specific examples thereof include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, and 2-ethoxyethyl acetate. And dimethylformamide.

The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in US Pat. No. 4,199,36.
No. 3, West German Published Patent Nos. 2,541,274 and 2,541,230. As the binder or protective colloid that can be used in the emulsion layer or other hydrophilic colloid layers of the photographic light-sensitive material of the present invention, mainly gelatin is used.
For example, gelatin derivatives, albumin, proteins such as casein, ethyl cellulose, cellulose derivatives such as carboxymethyl cellulose, sugar derivatives such as starch derivatives, polyvinyl alcohol, polyacrylic acid, polyacrylamide, mono- or copolymers such as polymethacrylic acid Such hydrophilic polymers can be used.

The emulsion layer and other hydrophilic colloid layers of the photographic light-sensitive material of the present invention may contain various compounds for the purpose of preventing fog during the production process, storage or development processing, or stabilizing photographic performance. Can be added. Examples of the compound include azoles such as nitroindazoles, nitrobenzimidazoles, mercaptothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, mercaptotetrazole (particularly,
-Phenyl-5-mercaptotetrazole), mercaptotriazines, thioketone compounds, azaindenes, for example, triazaindenes and tetraazaindenes (particularly, 4-hydroxy-1,3,3a, 7-tetrazaindene) ), Pentaazaindenes, benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, and many other compounds conventionally known as antifoggants or stabilizers. Of these, particularly preferred are benzotriazoles and nitroindazoles. These compounds may be contained in a processing solution used for the development processing.

The emulsion layer and other hydrophilic colloid layers of the photographic light-sensitive material of the present invention can contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative and the like as a color fogging inhibitor. The emulsion layer and other hydrophilic colloid layers of the photographic light-sensitive material of the present invention may contain an inorganic or organic hardener. Examples of the hardening agent include chromium salts (such as chrome alum), aldehydes (such as formaldehyde and glyoxal), N-methylol compounds, dioxane derivatives, and active vinyl compounds (such as 1,2,5-triacryloyl-hexahydro). -S-triazine, 1,3-
Vinylsulfonyl-2-propanol, etc.), active halogen compounds (e.g., 2,4-dichloro-6-hydroxy-s-triazine, etc.), and mucohalic acids (e.g., mucochloric acid, mucophenoxycyclolic acid, etc.). These hardeners can be used alone or in combination.

The emulsion layer and other hydrophilic colloid layers of the photographic light-sensitive material of the present invention may comprise a coating aid, an antistatic agent, an improvement in slipperiness, an emulsification dispersion, an adhesion prevention and an improvement in photographic properties (for example,
A surfactant may be contained for various purposes such as development acceleration, high contrast, sensitization, etc.). Examples of the surfactant include saponins, alkylene oxide derivatives (polyethylene glycol, polyethylene glycol alkyl ethers, etc.), glycidol derivatives (alkenyl succinic acid polyglycerides, alkylphenol polyglycerides, etc.), fatty acid esters of polyhydric alcohols, and sugars. Nonionic surfactants such as alkyl esters, anions having an acidic group such as carboxy group, sulfo group, sulfate group, phosphate group such as alkyl carboxylate, alkyl sulfate, alkyl phosphate, etc. Amphoteric surfactants, amino acids, aminoalkylsulfonic acids, amphoteric surfactants such as aminoalkylsulfuric acid or phosphate esters, aliphatic or aromatic quaternary ammonium salts, or heterocyclic quaternary ammonium salts Etc. It can be exemplified emissions surfactant.

The emulsion layer and other hydrophilic colloid layers of the photographic light-sensitive material of the present invention may contain a dispersion of a water-soluble or poorly-soluble synthetic polymer for the purpose of improving dimensional stability and the like. For example, alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate, (meth) acrylamide, vinyl ester, glycidin (meth) acrylate, acrylonitrile, styrene, etc., alone or in combination, or acrylic acid, methacrylic acid, It can be used in combination with a polymer having a combination of α, β-unsaturated dicarboxylic acid, styrenesulfonic acid and the like as a monomer component. Other hydrophilic colloid layers other than the silver halide emulsion layer in the present invention include a surface protective layer, a filter layer, an antihalation layer, and an antistatic layer. A hydrophilic colloid layer such as a surface protective layer may contain a matting agent for the purpose of preventing adhesion and improving the surface condition. As matting agents, US Pat. Nos. 2,701,245 and 2,992,101
No. 4,142,894, No. 4,396,70
Fine particles such as polymethyl methacrylate homopolymers, copolymers of methyl methacrylate and methacrylic acid, starch, silica, and magnesium oxide described in the specifications of No. 6 can be used. The surface protective layer includes a silicone compound described in each of U.S. Pat. Nos. 3,489,576 and 4,047,958.
No. 23139, colloidal silica, paraffin wax, higher fatty acid esters and the like can be added.

The photographic light-sensitive material of the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, U.S. Patent Nos. 3,533,794 and 4,236,013
Benzotriazoles substituted with an aryl group described in U.S. Pat. No. 4,195,999 described in Japanese Patent Publication No. 51-6540 and European Patent No. 57,160. Butadiene described, U.S. Pat. Nos. 3,705,805 and 3,70
7,375, cinnamic acid esters described in the specifications of US Pat. No. 3,215,230 and British Patent No. 1,321,355, benzophenones described in the specifications of US Pat. Polymer compounds having an ultraviolet absorbing group described in the specifications of 3,761,272 and 4,431,726 can be used. U.S. Pat. Nos. 3,499,762 and 3,700,455
UV-absorbing optical brighteners described in the above-mentioned specifications may be used.

The photographic light-sensitive material of the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as prevention of irradiation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes,
Cyanine dyes and azo dyes are included. Among them, oxonol dyes, hemioxonol dyes and merocyanine dyes are useful. In the emulsion layer and other hydrophilic colloid layers of the photographic light-sensitive material of the present invention, polyols such as trimethylolpropane, pentanediol, butanediol, ethylene glycol and glycerin can be used as plasticizers. Further, a fluorescent whitening agent, a development accelerator, a pH adjuster, a thickener, an antistatic agent and the like can be added to the emulsion layer and other hydrophilic colloid layers.

The support used in the photographic light-sensitive material of the present invention may be a film made of a synthetic polymer such as cellulose triacetate, cellulose diacetate, nitrocellulose, polystyrene, polyethylene terephthalate, polycarbonate, etc., baryta paper, or α-olefin binder. Paper (eg, polyethylene, polypropylene) or the like, or synthetic paper or the like can be used. The support may be colored using a dye or a pigment. When such a support is used for a reflective material, it is preferable to add a white pigment to the support or the laminate layer. Examples of the white pigment include titanium dioxide, barium sulfate, zinc oxide, zinc sulfide, calcium carbonate, antimony trioxide, silica white, alumina white, and titanium phosphate. In particular, titanium dioxide, barium sulfate, and zinc oxide are useful. The surface of these supports is
In general, an undercoating treatment is performed to improve the adhesion to a photographic emulsion. The surface of the support may be subjected to a treatment such as corona discharge or ultraviolet irradiation before or after the undercoating treatment. When these supports are used for a reflective material, a hydrophilic colloid layer containing a white pigment at a high density is further provided between the support and the emulsion layer to improve whiteness and sharpness of a photographic image. Can be. In the photographic light-sensitive material of the present invention, when a synthetic resin film kneaded with a white pigment is used, in addition to the improvement of smoothness, gloss, and sharpness, a photographic image excellent in saturation, depiction of a dark portion, and the like can be obtained. . In this case, polyethylene terephthalate and cellulose acetate are particularly useful as synthetic resin films, and barium sulfate and titanium oxide are particularly useful as white pigments.

The color developer which can be used in the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine developing agent as a main component. As a developing agent, 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-methanesulfonamidoethylaniline, 4-amino-3-methyl-N-ethyl-N-β-methoxyethylaniline and the like can be mentioned. The color developer is
PH buffers such as carbonates, borates and phosphates, and antifoggants such as bromides, iodides and organic antifoggants can be included. Also, if necessary, a water softener,
Alkali metal sulfites, diethylene glycol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, competitive couplers, fogging agents such as sodium boron hydride, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity Granting agent, US Patent No. 4,08
It may contain a polycarboxylic acid-based chelating agent described in US Pat. No. 2,723, an antioxidant described in West German Patent Publication No. 2,622,950, and the like. The fact that benzyl alcohol is not substantially contained in the developer means that even if benzyl alcohol is contained in the developer, it is not more than 5 ml / l. More preferably, it does not contain benzyl alcohol.

The silver halide photographic light-sensitive material of the present invention is usually subjected to bleaching after color development. The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. As the bleaching agent, for example, compounds of polyvalent metals such as iron (III), cobalt (III), chromium (VI), and copper (II), peracids, quinones, and nitroso compounds are used. For example, ferricyanide, dichromate, an organic acid salt of iron (III) or cobalt (III), for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, 1,3
-Aminopolycarboxylic acids such as -diamino-2-propanoltetraacetic acid or complex salts of organic acids such as citric acid, tartaric acid and malic acid, persulfates, manganates, nitrosophenols and the like can be used. Of these, sodium ethylene (III) ethylenediaminetetraacetate and ammonium (III) ethylenediaminetetraacetate are particularly useful. The iron (III) complex salt of ethylenediaminetetraacetate is useful both in an independent bleaching solution and in a single-bath bleach-fixing solution. After the color development or the bleach-fixing process, a water washing process may be performed. Color development can be performed at any temperature between 18 ° C and 55 ° C. Preferably, it is performed at 30 ° C. or higher, particularly preferably at 35 ° C. or higher. The time required for development is in the range of about 1 minute 30 seconds to about 20 seconds, and a shorter one is preferred. For continuous development processing, liquid replenishment is preferable, and 100 ml or more, preferably 160 ml to 330 ml of liquid is replenished per square meter of processing area. Bleaching and fixing can be carried out at any temperature between 18 ° C. and 50 ° C., preferably 30 ° C. or higher. When the temperature is set to 35 ° C. or more, the processing time can be reduced to one minute or less, and the replenishing amount of the liquid can be reduced. The time required for rinsing after color development or bleach-fixing is usually within 1 minute, and processing can be performed within 1 minute using a stabilizing bath.

The colored dye is deteriorated and faded by mold during storage, in addition to being deteriorated by light, heat or humidity. The cyan dye is particularly susceptible to deterioration by mold, and it is preferable to use a fungicide. A specific example of a fungicide is disclosed in
Examples thereof include 2-thiazolylbenzimidazoles described in JP-A-7-157244. The fungicide may be incorporated in the silver halide photographic material,
It may be added from the outside in the development processing step, and can be added in any step as long as it coexists with the processed photosensitive material.

[0081]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below based on embodiments. Example 1 A silver halide emulsion was prepared according to the following formulation. Solution I Deionized water 1,000 ml Sodium chloride 4.0 g Inert gelatin 30 g Citric acid 2.4 g Solution II Solution 1,3-dimethyl-2-imidazolidinthione (1% aqueous solution) 2 ml

Liquid III Deionized water 200 ml Sodium chloride ag Potassium bromide bg IV liquid Deionized water 200 ml Silver nitrate 40 g V liquid Deionized water 400 ml Sodium chloride c g Potassium bromide d g VI liquid Deionized water 400 ml Silver nitrate 80 g , A to d are shown in Table 1.

[0083]

[Table 1]

After dissolving solution I at 55 ° C.,
The solution was added, and one minute later, solution III and solution IV were simultaneously added over 20 minutes. After aging for 10 minutes, Solution V and Solution VI were simultaneously added over 30 minutes.
Aged for minutes. After completion of the physical ripening of each emulsion, excess salts were removed by the method described in Example 1 of U.S. Pat. No. 2,613,928. To each emulsion thus obtained, water and gelatin were added to redissolve, and the pH was adjusted to 6.
Adjusted to zero. Next, the temperature was raised to 55 ° C., sodium thiosulfate was added, and after optimal chemical sensitization,
After cooling to 0 ° C., a sensitizing dye was added as shown in Table 2. After standing for 20 minutes, 50 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added as a stabilizer per mol of silver halide.

[0085]

[Table 2]

[0086]

[Table 3]

[0087]

Embedded image

A coupler dispersion was prepared as follows. After dissolving the coupler in dibutyl phthalate and ethyl acetate, in the presence of a surfactant, added to an aqueous gelatin solution,
Fine dispersion was performed using an ultrasonic homogenizer. As shown in Table 3, the first layer (lowest layer) to the fourth layer
Layers (top layer) were simultaneously coated, and samples 1 to 6 were applied as shown in Table 4.
Was prepared. Immediately before coating, 1,2-bis- (α-vinylsulfonylacetamide) was used as a hardening agent in each layer.
Ethane was added at 15 mg / g of gelatin.

[0089]

[Table 4]

High-boiling solvent A: diheptyl phthalate Color-mixing inhibitor A: 2,5-di-tert-octylhydroquinone High-boiling solvent B: dibutyl phthalate

[0091]

[Table 5]

The sample thus prepared was exposed through an optical wedge using a sensitometer for sensitometry (light source color temperature: 3200 K), processed by the following color development, bleach-fixing and water washing, and dried. Processing process Processing temperature Processing time Color development 35 ° C 45 seconds Bleaching and fixing 35 ° C 45 seconds Rinse 35 ° C 90 seconds

Color developer 4-amino-3-methyl-N-ethyl-N- (β-methylsulfonamidoethyl) aniline sesquisulfate monohydrate 6.1 g triethanolamine 8.2 g nitrilotriacetic acid 1.5 g 1-hydroxyethylidene-1,1'-diphosphonic acid (60% aqueous solution) 1.6 g Potassium hydroxide 4.2 g Tivanol SFP 0.8 g Potassium carbonate 0.9 g N, N-diethylhydroxylamine 4.0 g Water And adjusted to pH 10.10 by adding 10% sulfuric acid or a 20% aqueous potassium hydroxide solution. Cibaanol SFP is a fluorescent whitening agent manufactured by Ciba-Geigy Actien Geselshaft.

Bleaching-fixing solution Sodium ferric ethylenediaminetetraacetate monohydrate 48.0 g Disodium ethylenediaminetetraacetate dihydrate 24.0 g Ammonium thiosulfate (70% aqueous solution) 148 ml Sodium bisulfite (anhydrous) 15.0 g Water Was adjusted to 1 l, and the pH was adjusted to 6.10 by adding 25% aqueous ammonia or 90% acetic acid.

Washing solution methanol 4.0 ml p-hydroxybenzoic acid-n-butyl ester 0.01 g thiabendazole 0.10 g ethylene glycol 6.0 ml Water is added to make 1 liter. pH was 7.45.

The image of the optical wedge thus obtained was measured with a Macbeth densitometer TR944 using a blue filter and a green filter. The reciprocal of the exposure at the density of fog +0.6 was calculated for the densities of yellow and magenta, and the result was taken as the sensitivity. Sample No. 4 with a yellow sensitivity of 100
The relative sensitivities of yellow and magenta of each sample were determined. Further, the maximum densities of yellow and magenta were determined.
Table 5 shows the obtained results. Note that the white color is the color of the polyethylene-coated paper and indicates that there is no coloring pigment,
Indicates that the measurement could not be performed.

[0097]

[Table 6]

From the results shown in Table 5, Samples 4 and 6 of the present invention were
It can be seen that the hue differs depending on the difference in exposure intensity, and that a sufficient density can be obtained even when processed with a color developer containing no benzyl alcohol. Example 2 Sensitizing dyes were added to emulsions Em-1 to Em-3 of Example 1 per mol of silver as shown in Table 6, and 4-hydroxy-6-methyl-1,3 was used as a stabilizer. , 3a, 7-Tetrazaindene was added in an amount of 50 mg per mol of silver halide.

[0099]

[Table 7]

Samples 7 to 10 were prepared as shown in Table 8 by simultaneously coating the first layer (lowest layer) to the seventh layer (top layer) as shown in Table 7 on polyethylene-coated paper. Immediately before coating, 1,2-bis- (α-vinylsulfonylacetamido) ethane was added to each layer as a hardener at a rate of 1 / g of gelatin.
5 mg was added.

[0101]

[Table 8]

[0102]

[Table 9]

[0103]

Embedded image

[0104]

Embedded image

[0105]

Embedded image

The fluorine-based surfactant was manufactured by Dainippon Ink and Chemicals, Inc., trade name: F-120 (potassium N-perfluorooctylsulfonyl-Nn-propylglycine).
The silicone oil used was KF-410 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.).

[0107]

[Table 10]

The sample thus produced was exposed and developed in the same manner as in Example 1. The image of the obtained optical wedge was measured with a Macbeth densitometer TR944 by applying a blue filter, a green filter, and a red filter. For the densities of yellow, magenta, and cyan, the reciprocal of the exposure amount at a density of fog + 0.6 was calculated and used as the sensitivity.
The relative sensitivity of each sample was determined with the yellow sensitivity of Sample No. 9 as 100. Further, the maximum densities of yellow, magenta and cyan were determined. The results obtained are shown in FIG. In addition,
The white color is the color of the polyethylene-coated paper, indicating that there is no coloring dye, and-indicates that measurement could not be performed.

[0109]

[Table 11]

[0110]

[Table 12]

From the results shown in Tables 9 and 10, Samples 9 and 10 of the present invention have different hues due to the difference in exposure intensity, and sufficient density and sensitivity can be obtained even when processed with a color developer containing no benzyl alcohol. You can see that.

[0112]

According to the silver halide color light-sensitive material of the present invention, an image exposed to light including blue light, green light and red light can be represented by a difference in hue and a difference in density. Further, according to the present invention, a silver halide color light-sensitive material having high sensitivity and high color density can be obtained even when processed with a color developer containing no benzyl alcohol.

────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] August 5, 1997

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Name of invention

[Correction method] Change

[Correction contents]

Patent application title: Silver halide color light-sensitive material and image
Image forming method

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] Claims

[Correction method] Change

[Correction contents]

[Claims]

Embedded image In the formula, R ₁ and R ₂ each represent an alkyl group having 1 to 6 carbon atoms, a substituted alkyl group having 1 to 4 carbon atoms, and an aralkyl group;
Z ₁ and Z ₂ each represent a group of nonmetallic atoms necessary to form a benzene ring and a naphthalene ring, and X ₁ represents an anionic group. P ₁ represents 1 or 2, and when P ₁ is 1, an internal salt is formed.

Embedded image In the formula, R ₃ and R ₄ each represent an alkyl group having 1 to 6 carbon atoms which may have a sulfo group as a substituent, and A ₁ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an aryl group. , Y
₁ and Y ₂ are a sulfur atom, an oxygen atom, a selenium atom,
NR ₅ , R ₅ represents an alkyl group having 1 to 3 carbon atoms, Z ₃ and Z ₄ each represent a group of nonmetallic atoms necessary for forming a benzene ring and a naphthalene ring, and X ₂ represents an anionic group. Represent. P ₂
Represents 1 or 2, and when P ₂ is 1, an internal salt is formed.

Embedded image

Embedded image In the formula, R ₆ , R ₇ , R ₈ and R ₉ each represent an alkyl group having 1 to 6 carbon atoms, a substituted alkyl group having 1 to 4 carbon atoms, and an aralkyl group, A ₂ represents a hydrogen atom, and 1 to 3 carbon atoms. An alkyl group of
An aryl group, Z ₅ , Z ₆ , Z ₇ and Z ₈ each represent a non-metallic atomic group necessary for forming a benzene ring and a naphthalene ring, and Z ₉ represents an atomic group necessary for forming a 6-membered ring. X ₃ and X ₄ represent an anionic group. P ₃ and P ₄ represent 1 or 2, and when P ₃ and P ₄ are 1, an inner salt is formed.

Embedded image In the formula, R ₁ and R ₂ each represent an alkyl group having 1 to 6 carbon atoms, a substituted alkyl group having 1 to 4 carbon atoms, and an aralkyl group;
Z ₁ and Z ₂ each represent a group of nonmetallic atoms necessary to form a benzene ring and a naphthalene ring, and X ₁ represents an anionic group. P ₁ represents 1 or 2, and when P ₁ is 1, an internal salt is formed.

Embedded image In the formula, R ₃ and R ₄ each represent an alkyl group having 1 to 6 carbon atoms which may have a sulfo group as a substituent, and A ₁ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an aryl group. , Y
₁ and Y ₂ are a sulfur atom, an oxygen atom, a selenium atom,
NR ₅ , R ₅ represents an alkyl group having 1 to 3 carbon atoms, Z ₃ and Z ₄ each represent a nonmetallic atom group necessary for forming a benzene ring and a naphthalene ring, and X ₂ represents an anionic group. Represent. P ₂
Represents 1 or 2, and when P ₂ is 1, an internal salt is formed.

Embedded image

Embedded image In the formula, R ₆ , R ₇ , R ₈ and R ₉ each represent an alkyl group having 1 to 6 carbon atoms, a substituted alkyl group having 1 to 4 carbon atoms, and an aralkyl group, A ₂ represents a hydrogen atom, and 1 to 3 carbon atoms. An alkyl group of
An aryl group, Z ₅ , Z ₆ , Z ₇ and Z ₈ each represent a non-metallic atomic group necessary for forming a benzene ring and a naphthalene ring, and Z ₉ represents an atomic group necessary for forming a 6-membered ring. X ₃ and X ₄ represent an anionic group. P ₃ and P ₄ represent 1 or 2, and when P ₃ and P ₄ are 1, an inner salt is formed.

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0004

[Correction method] Change

[Correction contents]

[0004]

An object of the present invention is to provide a silver halide color light-sensitive material having at least two silver halide emulsion layers containing a photosensitive silver halide grain and a coupler on a support. The silver halide grains of the silver halide emulsion are composed of at least 95 mol% or more of silver chloride, and at least one sensitizing dye represented by the following general formula (I) and a sensitizing dye represented by the following general formula (II) At least one of the dyes and the following general formula (III) or (I)
V) are spectrally sensitized with at least one of the sensitizing dyes represented by the formula (V). Each silver halide emulsion has a different sensitivity and contains a coupler which forms a different dye image. It can be achieved with a silver halide color photographic <br/> light material represented by density difference, and the image forming method of developing a silver halide color light-sensitive material with a color developer containing no benzyl alcohol substantially Was.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0041

[Correction method] Change

[Correction contents]

These sensitizing dyes can be purchased commercially, or can be synthesized based on The Cyanine Soybeans and Related Compounds, published by Interscience Publishers, 1964. These sensitizing dyes are used at a concentration of 10 ^-6 to 10 ^-3 mol per mol of silver halide in the silver halide emulsion. When such a sensitizing dye is added to a silver halide emulsion, a method of directly dispersing the sensitizing dye in the silver halide emulsion may be used, or a suitable solvent such as methyl alcohol, ethyl alcohol, A method of dissolving in acetone, N, N-dimethylformamide, ethyl acetate or a mixed solvent thereof, or a solvent containing a surfactant therein, and then adding the resultant solution to a silver halide emulsion may be applied. it can. These sensitizing dyes can be added to a silver halide emulsion during silver halide grain formation or after completion of physical ripening. Preferably, it is added to the silver halide emulsion after completion of physical ripening, before chemical ripening, during chemical ripening, or after chemical ripening. These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used particularly for supersensitization.
Along with the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization. For example, an aminostyryl compound substituted with a nitrogen-containing heterocyclic group (for example, US Pat. Nos. 2,933,390 and 3,933)
No. 635,721), an aromatic organic acid formaldehyde condensate (for example, US Pat.
743,510), cadmium salts, azaindene compounds and the like.

[Procedure amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0071

[Correction method] Change

[Correction contents]

The emulsion layer and other hydrophilic colloid layers of the color light-sensitive material of the present invention may contain various compounds for the purpose of preventing fog during the production process, storage or development, or stabilizing photographic performance. Can be added.
Examples of the compound include azoles such as nitroindazoles, nitrobenzimidazoles, mercaptothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, and mercaptotetrazole (especially,
1-phenyl-5-mercaptotetrazole, etc., mercaptotriazines, thioketone compounds, azaindenes, for example, triazaindenes, tetraazaindenes (particularly, 4-hydroxy-1,3,3a, 7-tetrazain And pentaazaindenes, benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, and many other compounds conventionally known as antifoggants or stabilizers. Particularly preferred among these are benzotriazoles,
Nitroindazoles. These compounds may be contained in a processing solution used for the development processing.

[Procedure amendment 6]

[Document name to be amended] Statement

[Correction target item name] 0072

[Correction method] Change

[Correction contents]

The emulsion layer and other hydrophilic colloid layers of the color light-sensitive material of the present invention can contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, etc. as a color fogging inhibitor. The emulsion layer and other hydrophilic colloid layers of the color light-sensitive material of the present invention can contain an inorganic or organic hardener. Hardening agents include, for example, chromium salts (such as chrome alum), aldehydes (formaldehyde,
Gliogizar etc.), N-methylol compounds, dioxane derivatives, active vinyl compounds (e.g., 1,2,5-triacryloyl-hexahydro-s-triazine, 1,
3-vinylsulfonyl-2-propanol, etc.), active halogen compounds (eg, 2,4-dichloro-6-hydroxy-s-triazine, etc.), and mucohalic acids (eg, mucochloric acid, mucophenoxycyclolic acid, etc.). These hardeners can be used alone or in combination.

[Procedure amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0073

[Correction method] Change

[Correction contents]

The emulsion layer and other hydrophilic colloid layers of the color light-sensitive material of the present invention may comprise a coating aid, an antistatic agent, an improvement in slipperiness, an emulsification / dispersion, an adhesion prevention and an improvement in photographic properties (eg, development acceleration, high contrast A surfactant may be contained for various purposes such as sensitization. As a surfactant,
For example, nonions such as saponins, alkylene oxide derivatives (polyethylene glycol, polyethylene glycol alkyl ethers, etc.), glycidol derivatives (alkenyl succinic acid polyglycerides, alkylphenol polyglycerides, etc.), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc. Anionic surfactants having an acidic group such as a carboxy group, a sulfo group, a sulfate group, and a phosphate group such as a surfactant, an alkyl carboxylate, an alkyl sulfate, an alkyl phosphate, and an amino acid. Surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphoric acid esters, and cationic surfactants such as aliphatic or aromatic quaternary ammonium salts, or heterocyclic quaternary ammonium salts Raise the agent Rukoto can.

[Procedure amendment 8]

[Document name to be amended] Statement

[Correction target item name]

[Correction method] Change

[Correction contents]

The emulsion layer and other hydrophilic colloid layers of the color light-sensitive material of the present invention may contain a dispersion of a water-soluble or poorly-soluble synthetic polymer for the purpose of improving dimensional stability and the like. For example, alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate, (meth) acrylamide, vinyl ester, glycidin (meth) acrylate, acrylonitrile, styrene, etc., alone or in combination, or acrylic acid, methacrylic acid, It can be used in combination with a polymer having a combination of α, β-unsaturated dicarboxylic acid, styrenesulfonic acid and the like as a monomer component. Other hydrophilic colloid layers other than the silver halide emulsion layer in the present invention include a surface protective layer, a filter layer, an antihalation layer, and an antistatic layer. A hydrophilic colloid layer such as a surface protective layer may contain a matting agent for the purpose of preventing adhesion and improving the surface condition. As matting agents, US Pat. Nos. 2,701,245 and 2,992,101
No. 4,142,894, No. 4,396,70
Fine particles such as polymethyl methacrylate homopolymers, copolymers of methyl methacrylate and methacrylic acid, starch, silica, and magnesium oxide described in the specifications of No. 6 can be used. The surface protective layer includes a silicone compound described in each of U.S. Pat. Nos. 3,489,576 and 4,047,958.
No. 23139, colloidal silica, paraffin wax, higher fatty acid esters and the like can be added.

[Procedure amendment 9]

[Document name to be amended] Statement

[Correction target item name] 0075

[Correction method] Change

[Correction contents]

The color light-sensitive material of the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, U.S. Patent Nos. 3,533,794 and 4,236,01
No. 3, benzotriazoles substituted with aryl groups described in, for example, Japanese Patent Publication No. 51-6540 and European Patent No. 57,160, U.S. Pat. No. 4,195,999. Butadiene described in US Pat. Nos. 3,705,805 and 3,70
7,375, cinnamic acid esters described in the specifications of US Pat. No. 3,215,230 and British Patent No. 1,321,355, benzophenones described in the specifications of US Pat. Polymer compounds having an ultraviolet absorbing group described in the specifications of 3,761,272 and 4,431,726 can be used. U.S. Pat. Nos. 3,499,762 and 3,700,455
UV-absorbing optical brighteners described in the above-mentioned specifications may be used.

[Procedure amendment 10]

[Document name to be amended] Statement

[Correction target item name] 0076

[Correction method] Change

[Correction contents]

The color photographic material of the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as prevention of irradiation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes, hemioxonol dyes and merocyanine dyes are useful. In the emulsion layer and other hydrophilic colloid layers of the photographic light-sensitive material of the present invention, polyols such as trimethylolpropane, pentanediol, butanediol, ethylene glycol and glycerin can be used as plasticizers. Further, the emulsion layer and other hydrophilic colloid layers may contain a fluorescent whitening agent, a development accelerator,
Adjusters, thickeners, antistatic agents and the like can be added.

[Procedure amendment 11]

[Document name to be amended] Statement

[Correction target item name] 0077

[Correction method] Change

[Correction contents]

The support used in the color light-sensitive material of the present invention may be a film made of a synthetic polymer such as cellulose triacetate, cellulose diacetate, nitrocellulose, polystyrene, polyethylene terephthalate, polycarbonate, etc., baryta paper, or α-olefin binder. Paper (eg, polyethylene, polypropylene) or the like, or synthetic paper or the like can be used. The support may be colored using a dye or a pigment. When such a support is used for a reflective material, it is preferable to add a white pigment to the support or the laminate layer. Examples of the white pigment include titanium dioxide, barium sulfate, zinc oxide, zinc sulfide, calcium carbonate, antimony trioxide, silica white, alumina white, and titanium phosphate. In particular, titanium dioxide, barium sulfate, and zinc oxide are useful. The surface of these supports is
In general, an undercoating treatment is performed to improve the adhesion to a photographic emulsion. The surface of the support may be subjected to a treatment such as corona discharge or ultraviolet irradiation before or after the undercoating treatment. When these supports are used for a reflective material, a hydrophilic colloid layer containing a white pigment at a high density is further provided between the support and the emulsion layer to improve whiteness and sharpness of a photographic image. Can be. In the color light-sensitive material of the present invention, when a synthetic resin film kneaded with a white pigment is used, in addition to the improvement of smoothness, glossiness and sharpness, a photographic image excellent in saturation, depiction of a dark portion, etc. can be obtained. . In this case, polyethylene terephthalate and cellulose acetate are particularly useful as synthetic resin films, and barium sulfate and titanium oxide are particularly useful as white pigments.

[Procedure amendment 12]

[Document name to be amended] Statement

[Correction target item name] 0079

[Correction method] Change

[Correction contents]

The silver halide color light-sensitive material of the present invention comprises
After color development, it is usually bleached. The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. As the bleaching agent, for example, compounds of polyvalent metals such as iron (III), cobalt (III), chromium (VI), and copper (II), peracids, quinones, and nitroso compounds are used. For example, ferricyanide, dichromate, an organic acid salt of iron (III) or cobalt (III), for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, 1,3
-Aminopolycarboxylic acids such as -diamino-2-propanoltetraacetic acid or complex salts of organic acids such as citric acid, tartaric acid and malic acid, persulfates, manganates, nitrosophenols and the like can be used. Of these, sodium ethylene (III) ethylenediaminetetraacetate and ammonium (III) ethylenediaminetetraacetate are particularly useful. The iron (III) complex salt of ethylenediaminetetraacetate is useful both in an independent bleaching solution and in a single-bath bleach-fixing solution. After the color development or the bleach-fixing process, a water washing process may be performed. Color development can be performed at any temperature between 18 ° C and 55 ° C. Preferably, it is performed at 30 ° C. or higher, particularly preferably at 35 ° C. or higher. The time required for development is in the range of about 1 minute 30 seconds to about 20 seconds, and a shorter one is preferred. For continuous development processing, liquid replenishment is preferable, and 100 ml or more, preferably 160 ml to 330 ml of liquid is replenished per square meter of processing area. Bleaching and fixing can be carried out at any temperature between 18 ° C. and 50 ° C., preferably 30 ° C. or higher. When the temperature is set to 35 ° C. or more, the processing time can be reduced to one minute or less, and the replenishing amount of the liquid can be reduced. The time required for rinsing after color development or bleach-fixing is usually within 1 minute, and processing can be performed within 1 minute using a stabilizing bath.

──────────────────────────────────────────────────の Continuing on the front page (51) Int.Cl. ⁶ Identification symbol FI G03C 7/20 G03C 7/20 7/407 7/407 (72) Inventor Yoshiro Hayabuchi 1-24-1, Minamihara, Hiratsuka-shi, Kanagawa No. 40 Oriental Photo Industry Co., Ltd.

Claims (2)

[Claims] 1. A silver halide color light-sensitive material having at least two silver halide emulsion layers containing at least photosensitive silver halide grains and a coupler on a support,
The silver halide grains of the silver halide emulsion are composed of at least 95 mol% or more of silver chloride, and at least one sensitizing dye represented by the following general formula (I);
It is spectrally sensitized with at least one kind of sensitizing dye represented by I) and at least one kind of sensitizing dye represented by the following general formula (III) or (IV). A silver halide photographic light-sensitive material containing different couplers for forming different dye images, wherein the difference in intensity of the light source is represented by the hue and the density difference. Embedded image In the formula, R ₁ and R ₂ each represent an alkyl group having 1 to 6 carbon atoms, a substituted alkyl group having 1 to 4 carbon atoms, and an aralkyl group;
Z ₁ and Z ₂ each represent a group of nonmetallic atoms necessary to form a benzene ring and a naphthalene ring, and X ₁ represents an anionic group. P ₁ represents 1 or 2, and when P ₁ is 1, an internal salt is formed. Embedded image In the formula, R ₃ and R ₄ each represent an alkyl group having 1 to 6 carbon atoms which may have a sulfo group as a substituent, and A ₁ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an aryl group. , Y
₁ and Y ₂ are a sulfur atom, an oxygen atom, a selenium atom,
NR ₅ , R ₅ represents an alkyl group having 1 to 3 carbon atoms, Z ₃ and Z ₄ each represent a nonmetallic atom group necessary for forming a benzene ring and a naphthalene ring, and X ₂ represents an anionic group. Represent. P ₂
Represents 1 or 2, and when P ₂ is 1, an internal salt is formed. Embedded image Embedded image In the formula, R ₆ , R ₇ , R ₈ and R ₉ each represent an alkyl group having 1 to 6 carbon atoms, a substituted alkyl group having 1 to 4 carbon atoms, and an aralkyl group, A ₂ represents a hydrogen atom, and 1 to 3 carbon atoms. An alkyl group of
An aryl group, Z ₅ , Z ₆ , Z ₇ and Z ₈ each represent a non-metallic atomic group necessary for forming a benzene ring and a naphthalene ring, and Z ₉ represents an atomic group necessary for forming a 6-membered ring. X ₃ and X ₄ represent an anionic group. P ₃ and P ₄ represent 1 or 2, and when P ₃ and P ₄ are 1, an inner salt is formed. 2. A support having at least two silver halide emulsion layers containing at least photosensitive silver halide grains and a coupler, wherein the silver halide grains of the silver halide emulsion are at least 95 mol% or more. At least one sensitizing dye represented by the following general formula (I), at least one sensitizing dye represented by the following general formula (II) and the following general formula (III) or (IV) Are sensitized by at least one of the sensitizing dyes represented by, each silver halide emulsion has a different sensitivity, and each contains a coupler that forms a different dye image, and the difference in light source intensity is determined by the hue and density. An image forming method comprising developing a silver halide photographic light-sensitive material represented by the difference with a color developer substantially containing no benzyl alcohol. Embedded image In the formula, R ₁ and R ₂ each represent an alkyl group having 1 to 6 carbon atoms, a substituted alkyl group having 1 to 4 carbon atoms, and an aralkyl group;
Z ₁ and Z ₂ each represent a group of nonmetallic atoms necessary to form a benzene ring and a naphthalene ring, and X ₁ represents an anionic group. P ₁ represents 1 or 2, and when P ₁ is 1, an internal salt is formed. Embedded image In the formula, R ₃ and R ₄ each represent an alkyl group having 1 to 6 carbon atoms which may have a sulfo group as a substituent, and A ₁ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an aryl group. , Y
₁ and Y ₂ are a sulfur atom, an oxygen atom, a selenium atom,
NR ₅ , R ₅ represents an alkyl group having 1 to 3 carbon atoms, Z ₃ and Z ₄ each represent a nonmetallic atom group necessary for forming a benzene ring and a naphthalene ring, and X ₂ represents an anionic group. Represent. P ₂
Represents 1 or 2, and when P ₂ is 1, an internal salt is formed. Embedded image Embedded image In the formula, R ₆ , R ₇ , R ₈ and R ₉ each represent an alkyl group having 1 to 6 carbon atoms, a substituted alkyl group having 1 to 4 carbon atoms, and an aralkyl group, A ₂ represents a hydrogen atom, and 1 to 3 carbon atoms. An alkyl group of
An aryl group, Z ₅ , Z ₆ , Z ₇ and Z ₈ each represent a non-metallic atomic group necessary for forming a benzene ring and a naphthalene ring, and Z ₉ represents an atomic group necessary for forming a 6-membered ring. X ₃ and X ₄ represent an anionic group. P ₃ and P ₄ represent 1 or 2, and when P ₃ and P ₄ are 1, an inner salt is formed.