JPH1031274A - Silver halide photographic sensitive material and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material and image forming method capable of obtaining black and white images of a sepia tone even if this photosensitive material is processed with a color developer not contg. benzyl alcohol. SOLUTION: This silver halide photographic sensitive material has at least one layer of silver halide emulsion layers on a base. The silver chloride content of the silver halide particles of the silver halide emulsion layers is >=95mol%. The silver halide emulsion layers contain yellow couplers, magenta couplers and cyan couplers and a* in an L*a*b* color specification system chromaticity diagram is in the range of 0 to +120 and b* is in the range of 0 to +20. This silver halide photographic sensitive material is subjected to development processing by the color developer not substantially contg. the benzyl alcohol.

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 photographic light-sensitive material and an image forming method, and more particularly to a sepia black and white using a dye image which can be processed with a color developer containing substantially no benzyl alcohol. The present invention relates to a photographic material and an image forming method.

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2. Description of the Related Art Normally, a black-and-white photographic image is formed by processing a black-and-white photographic light-sensitive material with a black-and-white developer and forming a black-and-white image with a black image or a sepia-tone black and white image by toning. On the other hand, it is also known to obtain a black-and-white image by adjusting the filter of a multilayer color photographic material using a yellow coupler for a regular photosensitive layer, a magenta coupler for an orthophotosensitive layer, and a cyan coupler for a panchromatic photosensitive layer. However, a black-and-white image using a silver image does not save resources because silver is used for the image. The formation of a black-and-white image using a multilayer color photographic light-sensitive material has a drawback that the tone of each photosensitive layer does not completely match, so that it is difficult to obtain a well-balanced black image from a low density portion to a high density portion. . Further, a color developer using benzyl alcohol is environmentally unfavorable. Further, when a color negative film is used as a negative original, the tone of the negative original cannot be faithfully reproduced unless the photosensitive wavelength range of the color photographic light-sensitive material is in the entire visible range.

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SUMMARY OF THE INVENTION It is a first object of the present invention to recycle silver by forming a sepia black and white image using a dye image. A second object of the present invention is to make it environmentally favorable by processing with a color developer substantially free of benzyl alcohol. A third object of the present invention is to form a well-toned sepia-tone black and white image from a low density portion to a high density portion. A fourth object of the present invention is to form a sepia tone black and white image that faithfully reproduces the tone of a color negative film.

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The object of the present invention is to provide at least one silver halide emulsion layer on a support, wherein the silver halide grains of the silver halide emulsion layer have a silver chloride content of 95 mol. % Or more, the silver halide emulsion layer contains a yellow coupler, a magenta coupler and a cyan coupler, and has a * of 0 in the L * a * b * color system chromaticity diagram.
A silver halide photographic light-sensitive material in which b * is in the range of 0 to +20, 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. Could be achieved.

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.

[0007] As one of the simultaneous mixing methods, a method of keeping pAg constant 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.

[0008] The L * a * b * color system is a color system that is currently most popularly used in all fields to represent the color of an object, and is adopted in JIS (JIS Z 8729). In the present invention, in the L * a * b * color system chromaticity diagram, a * ranges from 0 to +20, and b * ranges from 0 to +2.
A range of 0 is necessary to obtain a sepia tone black and white image. The silver halide emulsion of the present invention comprises at least one sensitizing dye represented by the general formula (I), at least one sensitizing dye represented by the general formula (II), and
It is preferable that at least one of the sensitizing dyes represented by the general formula (III) or (IV) is spectrally sensitized.

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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. Next, specific examples of the sensitizing dye represented by formula (I) will be described.

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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. Next, specific examples of the sensitizing dye represented by the general formula (II) will be described.

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In the general formulas (III) and (IX),
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 q represent 1 or 2, and when P ₃ and q are 1, an inner salt is formed. Next, the general formula (II)
Specific examples of the sensitizing dyes represented by I) and (IV) will be described.

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These sensitizing dyes can be easily synthesized by the method described in Heterocyclic Compounds, Cyanine Soybean and Released Compounds. 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, Acetone, N, N-
A method of dissolving in dimethylformamide, ethyl acetate or a mixed solvent of these, or a solvent containing a surfactant therein, and then adding the resultant to a silver halide emulsion can be applied. 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, aminostyryl compounds substituted with nitrogen-containing heterocyclic groups (for example, compounds described in U.S. Pat. Nos. 2,933,390 and 3,635,721), and aromatic organic acid formaldehyde It may contain condensates (for example, compounds described in U.S. Pat. No. 3,743,510), cadmium salts, azaindene compounds and the like.

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. Hereinafter, specific examples of the coupler used in the present invention are shown.

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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.
In the silver halide photographic light-sensitive material of the present invention, in order to obtain a hue of a sepia tone, a preferable usage amount of a yellow coupler (Y), a magenta coupler (M) and a cyan coupler (C) is a molar ratio of Y: M: C = 2 to 3: 1: 1.5 to 2.5
It is.

Examples of the high boiling organic solvent include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, didodecyl phthalate, etc.), and phosphoric acid or phosphonic acid esters (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. Other exemplified compounds can be synthesized in the same manner as described above. 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 fogging 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. In the emulsion layer and other hydrophilic colloid layers of the photographic light-sensitive material of the present invention,
Hydroquinone derivatives, aminophenol derivatives, gallic acid derivatives, ascorbic acid derivatives, and the like can be contained as color fog inhibitors.

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 glyogizal), 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 (eg, 2,4-dichloro-6-hydroxy-s-triazine, etc.), mucohalic acids (eg, mucochloric acid, mucophenoxycyclolic acid, etc.) These hardeners can be used alone or in combination. The emulsion layer and the other hydrophilic colloid layer of the photographic light-sensitive material of the present invention may contain 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, sensitization, etc. ), Etc., for various purposes. Examples of the surfactant include saponin, alkylene oxide derivatives (polyethylene glycol, polyethylene glycol alkyl ethers, etc.), glycidol derivatives (alkenyl succinic acid polyglyceride, alkylphenol polyglyceride, etc.), fatty acid esters of polyhydric alcohols,
Nonionic surfactants such as alkyl esters of sugars, alkyl carboxylate, alkyl sulphates, carboxy groups such as alkyl phosphates, sulfo groups,
Anionic surfactants having acidic groups such as sulfate groups and phosphate groups, amphoteric surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates and phosphate esters, and aliphatic or aromatic surfactants. Cationic surfactants such as quaternary ammonium salts or heterocyclic quaternary ammonium salts can be mentioned.

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 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 photographic light-sensitive material of the present invention, an anti-fading agent can be used in the emulsion layer and other hydrophilic colloid layers, and the anti-fading agent can be used alone or in combination of two or more. Examples of the discoloration inhibitor include, for example, JP-A-59-12
Phenols or phenyl ether compounds described in JP-A-5732, metal complexes described in JP-A-60-97353, hindered amines or hindered phenol compounds described in JP-A-62-115157, Examples thereof include metal complexes described in Japanese Unexamined Patent Publication No. 61-140941. 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 silver halide photographic light-sensitive material of the present invention can form a black-and-white image by exposing from a black-and-white negative film or from a color negative film. The color developer that can be used in the present invention is preferably an alkaline aqueous solution mainly containing an aromatic primary amine developing agent. 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. Color developers include carbonates, pH buffers such as borates and phosphates, bromides,
Antifoggants such as iodides and organic antifoggants can be included. If necessary, a water softener, a sulfite of an alkali metal, a development accelerator such as diethylene glycol, polyethylene glycol, a quaternary ammonium salt, an amine, a competing coupler, a fogging agent such as sodium boron hydride, 1-phenyl Auxiliary developing agents such as -3-pyrazolidone, viscosity-imparting agents, US Pat. No. 4,082,7
It may contain a polycarboxylic acid-based chelating agent described in JP-A No. 23, an antioxidant described in West German Patent Application 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.

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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. Liquid I Deionized water 1,000 ml Sodium chloride 4.0 g Inert gelatin 30 g Citric acid 2.4 g Liquid II 1,3-dimethyl-2-imidazolidinthione (1% aqueous solution) 2 ml Liquid III Deionized water 200 ml Sodium chloride 13.6 g Odor Potassium bromide 0.28 g IV solution Deionized water 200 ml Silver nitrate 40 g V solution Deionized water 400 ml Sodium chloride 27.25 g Potassium bromide 0.56 g VI solution Deionized water 400 ml Silver nitrate 80 g

After dissolving solution I at 55 ° C.,
The solution was added, and after 1 minute, Solution III and Solution IV were added simultaneously 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.
0. Next, the temperature was raised to 55 ° C., sodium thiosulfate was added, and after optimal chemical sensitization,
The solution was cooled to 0 ° C, and sensitizing dye I-3 was added thereto per mole of silver.
^Is 1 × 10 ^-4 mol, and sensitizing dye II-20 is 1.3 × 10 4
^-4 mol and 4 × 10 ^-5 mol of sensitizing dye IV-10 were added. 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.

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.

The above silver halide emulsion and coupler dispersion were
Mix and make polyethylene coated paper so that
Three layers were simultaneously coated on the top. Top protective layer Gelatin 1.0g / m^Two UV absorbing layer UV absorbing agent A 0.15g / m^Two UV absorber B 0.20 g / m^Two High boiling point solvent 0.2g / m^Two Gelatin 0.6g / m^Two Silver halide emulsion layer Silver halide emulsion Silver 0.7 g / m^Two Coupler High boiling point solvent 1g / m^Two Gelatin 1.5g / m^Two Anti-irradiation dye A 0.03 g / m^Two Anti-irradiation dye B 0.03 g / m^Two  Tinuvin 144 0.01 g / m^Two Support polyethylene coated paper

Table 1 shows the couplers used and the amounts used. Other additives are as follows. High boiling point solvent n-dibutyl phthalate

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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 washing with water, 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 20% potassium hydroxide aqueous solution. In addition,
CIVANOL SFP is a fluorescent whitening agent manufactured by Ciba-Geigy Actien Gesellschaft.

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 And adjusted to pH 6.10 with 25% aqueous ammonia or 90% acetic acid.

Washing liquid 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 obtained in this way was measured for black and white density using a Macbeth densitometer, and the portion having a density of 1 was measured using SZT- # 80 manufactured by Nippon Denshoku Industries Co., Ltd.
The a * and b * values in the L * a * b * color system were measured.
Table 1 shows the obtained results.

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[Table 1]

From the results shown in Table 1, the samples 4, 5, and 6 according to the present invention were obtained.
Means that a * in the L * a * b * color system is 0 to + even when processed with a color developer substantially containing no benzyl alcohol.
It can be seen that a sample in the range of 20 and b * in the range of 0 to +20 has a sepia hue.

The silver halide photographic light-sensitive material of the present invention comprises:
Even when processed with a color developer containing substantially no benzyl alcohol, a * is 0 to +2 in the L * a * b * color system chromaticity diagram using yellow, magenta and cyan couplers.
By setting the range of 0 and b * in the range of 0 to +20, a sepia tone black and white image can be obtained.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Yoshiro Hayabuchi 1-24-40 Minamihara, Hiratsuka-shi, Kanagawa Prefecture Inside Oriental Photo Industry Co., Ltd. (72) Inventor Hisako Nakamura 1-24-24 Minamihara, Hiratsuka-shi, Kanagawa Prefecture No. 40 Oriental Photo Industry Co., Ltd.

Claims (4)

[Claims] 1. A silver halide photographic material having at least one silver halide emulsion layer on a support,
The silver halide grains of the silver halide emulsion layer have a silver chloride content of 95 mol% or more, and the silver halide emulsion layer has
It contains a yellow coupler, a magenta coupler and a cyan coupler, and has a * in the L * a * b * color system chromaticity diagram.
Is in the range of 0 to +20, and b * is in the range of 0 to +20. 2. A yellow coupler, a magenta coupler and a cyan coupler in a molar ratio of 2-3: 1: 1.5-2.
5. The silver halide photographic light-sensitive material according to claim 1, wherein 3. A silver halide emulsion having at least one silver halide emulsion layer on a support, wherein the silver halide grains of the silver halide emulsion layer have a silver chloride content of 95 mol% or more. The layer contains a yellow coupler, a magenta coupler, and a cyan coupler, and a * in the L * a * b * color system chromaticity diagram ranges from 0 to +20, and b * ranges from 0 to +2.
An image forming method comprising developing a silver halide photographic material having a range of 0 with a color developer substantially containing no benzyl alcohol. 4. A yellow coupler, a magenta coupler and a cyan coupler in a molar ratio of 2-3: 1: 1.5-2.
The image forming method according to claim 3, wherein