JPH117101A - Silver halide photographic sensitive material and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the silver halide photographic sensitive material high in whiteness by incorporating an ultraviolet absorber in one of protective layers located on the side of the support and a fluorescent whitening agent mordant in one of the protective layers farthest from the support. SOLUTION: The silver halide emulsion layer contains silver halide grains having a silver chloride content of >=95 mol% and yellow, magenta, and cyan couplers, and the protective layer on the side of the support contains the ultraviolet absorber and the one farthest apart from the support contains the fluorescent whitening agent mordant. The preferable ultraviolet absorber is embodied by a compound represented by the formula in which R1 is an H or halogen atom or an alkyl, aryl, or alkoxy group or the like; and each of R2 and R3 is an alkyl or aryl or alkoxy group or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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 method having high whiteness.
The present invention also relates to a silver halide photographic light-sensitive material for printing excellent in light color fastness and an image forming method.

[0002]

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. or,
It is also known to use a yellow coupler, a magenta coupler and a cyan coupler together in a photosensitive layer to obtain a black-and-white image based on a dye image (for example, see JP-A-6-505).
580). When a black-and-white image is formed from a conventional silver image, development processing is performed using a black-and-white developing agent such as hydroquinone or methol, but there are few laboratories and photo shops capable of performing this development processing. On the other hand, in the current processing of color paper, it is general to perform processing with a color developer substantially not containing benzyl alcohol. Processing machines suitable for this processing are widely used in laboratories, photo shops, and the like, and black-and-white image forming materials applicable to this processing are preferable. However, in a photosensitive material which obtains a black-and-white image from the dye image, the image is formed by a dye, and the yellow coupler which is most easily faded by light is closer to the surface than a multilayer color paper which is usually commercially available. Therefore, there is a disadvantage that fading due to light easily occurs.

[0003] In order to reduce the fading due to the light, a silver halide color photographic light-sensitive material for printing is
It is known to use UV absorbers. However, since the UV absorber is not white in itself but rather yellow, the use of many UV absorbers to enhance the stabilization of the dye image reduces the fading of the dye image, but the white background is slightly yellow. A problem of being carried. In order to increase the whiteness, a method of increasing the apparent whiteness by leaving a fluorescent whitening agent in a print layer after development has been used. For example, a water-soluble optical brightener is added to a developer,
It is known to use a fluorescent brightener mordant in an emulsion layer, a layer containing an ultraviolet absorber, a protective layer and the like of a silver halide color photographic material. However, in order to obtain a white background having a sufficient whiteness, a large amount of a fluorescent whitening agent mordant must be used, and therefore, the development of the hydrophilic colloid layer such as an emulsion layer or an intermediate layer is suppressed. There have been problems such as a decrease in the film thickness or unevenness on the surface.

[0004]

SUMMARY OF THE INVENTION A first object of the present invention is to provide a color developer which is substantially free of benzyl alcohol, whereby a black-and-white image can be formed from a dye image. An object of the present invention is to provide a silver halide photographic light-sensitive material. A second object of the present invention is to
It is an object of the present invention to provide a silver halide photographic light-sensitive material which can form a black-and-white image of a dye image by processing with a color developer containing substantially no benzyl alcohol and has improved light fastness. A third object of the present invention is to provide a high whiteness image forming method capable of forming a black-and-white image by a dye image by processing with a color developer containing substantially no benzyl alcohol. . A fourth object of the present invention is to provide an image forming method which can form a black-and-white image by a dye image by processing with a color developer containing substantially no benzyl alcohol, and has improved light fastness. That is.

[0005]

An object of the present invention is to provide a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support and at least two protective layers on the silver halide emulsion layer. In the material, the silver halide content of the silver halide grains in the silver halide emulsion layer is 95 mol% or more, and the silver halide emulsion layer comprises a yellow coupler,
It contains a magenta coupler and a cyan coupler, among the protective layers, the protective layer located on the support side contains an ultraviolet absorber, and the fluorescent brightener mordant in the protective layer located farthest from the support. And an image forming method in which this silver halide photographic light-sensitive material is developed with a color developer substantially free of benzyl alcohol. Preferred examples of the ultraviolet absorber that can be used in the present invention include a compound represented by the following general formula (I).

[0006]

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In the formula, R ₁ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkenyl group, a nitro group or a hydroxyl group, and R ₂ and R ₃ represent an alkyl group, an aryl group, Represents an alkoxy group or an aryloxy group. Representative specific examples of the ultraviolet absorbent represented by the general formula (I) which is liquid at ordinary temperature are shown below, but the present invention is not limited thereto.

[0008]

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[0009]

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[0010]

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[0011]

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[0012]

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[0013]

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The liquid ultraviolet absorber represented by the general formula (I) may be added in combination of two or more kinds. In addition, the liquid and the ultraviolet absorber represented by the general formula (I) which is solid at normal temperature can be used in combination. Typical specific examples of the solid-state ultraviolet absorber represented by the general formula (I) are shown below, but the invention is not limited thereto.

[0015]

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[0016]

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[0017]

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[0018]

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[0019]

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[0020]

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[0021]

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The above ultraviolet absorber is disclosed in JP-B-36-10.
No. 466, No. 42-26187, No. 48-41572
And US Patent Nos. 3,754,919 and 4,220,711.
The ultraviolet absorbent represented by the general formula (I) is dissolved in a high-boiling organic solvent, if necessary, in combination with a low-boiling solvent, and finely dispersed in a hydrophilic binder such as an aqueous gelatin solution using a surfactant. I do. When an ultraviolet absorber which is liquid at normal temperature is used, it may be used in combination with a high-boiling organic solvent, but it is more preferable not to use a high-boiling organic solvent. The finely dispersed emulsified dispersion may be added to a hydrophilic binder. The amount of the ultraviolet absorber represented by the general formula (I) is preferably 0.01 to 1 part by weight per 1 part by weight of the binder. Binder coating amount of the protective layer containing the ultraviolet absorber, 1 m ² per 100~1000mg are preferred.

The fluorescent whitening agent mordants used in the present invention are described in JP-B-43-13498 and JP-B-43-22882, US Pat. Nos. 3,052,544 and 3,663.
No. 6,470, No. 3,167,429, No. 3,1
Nos. 68,403 and 3,252,801, etc., N-vinylpyrrolidone-based polymers,
U.S. Pat. Nos. 2,448,507 and 2,448,5
Nos. 08 and 2,721,852, pyridine-based polymers described in U.S. Pat.
For example, morpholine-based polymers described in US Pat. No. 332, oxazolidine-based polymers described in US Pat. No. 3,006,762, and polyvinyl alcohol-based polymers can be used. In particular, poly-N-vinylpyrrolidone having the structure of the following repeating unit,
Alternatively, a copolymer derived from N-vinylpyrrolidone and an ethylenically unsaturated monomer is preferred.

[0024]

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In this case, the average molecular weight of the poly-N-vinylpyrrolidone or N-vinylpyrrolidone copolymer is not particularly limited, but usually about 3000 to several tens of thousands is used. When an N-vinylpyrrolidone copolymer is used, it may be a random polymer or a block polymer. Further, the copolymerization ratio is usually a molecular ratio of 1: 0.25 to N-vinylpyrrolidone and an ethylenically unsaturated monomer.
It is about 1: 4. Examples of the comonomer unit suitably used for the copolymer include the following.

[0026]

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[0027]

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[0028] In the above (i) ~ (vi), R 4 and R ₅ each represent a hydrogen atom or an alkyl group, R _6, R
₇ and R ₉ each represent a hydrogen atom or an alkyl group;
₈ represents an alkylene group. The fluorescent whitening agent mordant of the present invention is preferably contained in an amount of 0.01 to 1 part by weight per 1 part by weight of the binder. The coating amount of the binder of the protective layer containing the optical brightener mordant of the present invention is 100 to 1 m ^2.
1000 mg is preferred.

The silver halide photographic 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 used in the present invention is a color developer containing substantially no benzyl alcohol and containing a fluorescent whitening agent. 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 color developer used in the present invention contains a water-soluble fluorescent whitening agent. Various known water-soluble fluorescent whitening agents can be used. Among them, preferred optical brighteners are shown below. 1 Diaminostilbene represented by the following general formula (II)

[0030]

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In the formula, R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ each represent a hydrogen atom, a hydroxyl group, a halogen atom, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylamino group, an arylno group, a sulfone group ( A metal salt), a carboxyl group (including a metal salt) and the like. R
₁₄ and R ₁₅ each represent a sulfone group (including a metal salt), a carboxyl group (including a metal salt), and the like. Such diaminostilbene compounds are disclosed in US Pat. No. 2,933,3.
No. 90, etc. 2 Thiophene represented by the following general formula (III)

[0032]

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Wherein R ₁₆ , R ₁₇ , R ₁₈ , R ₁₉ , R ₂₀ , R
₂₁ , R ₂₂ and R ₂₃ each represent a hydrogen atom or a carbon atom 1
Represents an alkyl group of 5 or less. R ₂₄ and R ₂₅ each represent a hydrogen atom or an alkyl or aryl group having 15 or less carbon atoms. Such a thiophene compound is described in Japanese Patent Publication No. 45-24068. 3 Coumarins represented by the following general formula (IV)

[0034]

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In the formula, R ₂₆ is an alkyl group, an amino group or the like;
₂₇ represents an aryl group, an arylamino group or the like. 4 Anthracene 5 Terphenyl 6 Tetraphenylbutadiene 7 Quinoxaline Next, specific examples of these optical brighteners will be shown.

[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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These fluorescent whitening agents are usually added to a color developer at about 0.1 to 10 g / l. The color developer used in the present invention is an alkaline aqueous solution mainly containing an aromatic primary amine developing agent. Examples of the developing agent include 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. Color developers are pH buffers such as carbonates, borates and phosphates,
Antifoggants such as bromide, iodide and organic antifoggants can be included. Also, if necessary, water softener, alkali metal sulfite, diethylene glycol,
Development accelerators such as polyethylene glycol, quaternary ammonium salts and amines, competing couplers, fogging agents such as sodium boron hydride, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity improvers, U.S. Pat. 0
It may contain a polycarboxylic acid chelating agent described in U.S. Pat. No. 82,723, an antioxidant described in West German Patent Application No. 2,622,950, and the like.

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 not only deteriorated by light, heat or humidity, but also deteriorated and faded by mold during storage. 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.

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 of the ammonia method and the like may be used, and the method of reacting the soluble silver salt with the 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 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.

The silver halide emulsion of the present invention comprises at least one sensitizing dye represented by the general formula (V), at least one sensitizing dye represented by the general formula (VI),
It is preferable to spectrally sensitize at least one of the sensitizing dyes represented by the general formulas (VII) and (VIII).

[0049]

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In the general formula (V), R ₃₁ and R _{32 each} represent an alkyl group having 1 to 6 carbon atoms (for example, a methyl group, an ethyl group,
-Propyl group, isopropyl group, n-butyl group, isobutyl group, n-hexyl group, isohexyl group, etc., substituted alkyl group having 1 to 4 carbon atoms [for example, hydroxylalkyl group (for example, 2-hydroxyethyl group, 3 -Hydroxypropyl group, 2-hydroxypropyl group, etc.), sulfoalkyl group (eg, 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.]] and aralkyl groups (eg, benzyl group, 2-phenylethyl group, etc.). It is preferred that one of R ₃₁ and R ₃₂ is a substituted alkyl group. Z ₁ and Z _{2 each} represent a substituent (for example, a halogen atom, an alkyl group, an alkoxy group, an aryl group,
Necessary for forming a benzene nucleus or naphthalene nucleus which may have a cyano group, an alkoxycarbonyl group, a trifluoromethyl group, an alkylsulfonyl group, an alkylsulfamoyl group, an acylamino group, an alkylcarbamoyl group, an acetoxy group, etc. Represents a non-metallic atomic group. 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.

[0051]

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In the general formula (VI), R ₃₃ and R ₃₄ 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) , Isopropyl group, n-butyl group, isobutyl group, n
-Hexyl group, 2-sulfoethyl group, 3-sulfopropyl group, 3-sulfobutyl group, etc., A ₁ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms (eg, a methyl group, an ethyl group, an n-propyl group) , An isopropyl group or the like), an aryl group (for example, a phenyl group or the like), Y ₁ and Y ₂ are a sulfur atom,
Oxygen atom, a selenium atom, an N-R _35, R ₃₅ is 1 to carbon atoms
3 represents an alkyl group (for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, etc.). Z ₃ and Z ₄ form a benzene ring or a naphthalene ring which may have a substituent (eg, a halogen atom, an alkyl group, an alkoxy group, an aryl group, a carbonyl group, an alkoxycarbonyl group, a cyano group, etc.) Represents a group of nonmetallic atoms required for 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.

[0053]

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[0054]

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In the general formulas (VII) and (VIII), R ₃₆ , R ₃₇ , R ₃₈ and R ₃₉ 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). Group, n-butyl group, isobutyl group, n
-Hexyl group, isohexyl group, etc.), a substituted alkyl group having 1 to 4 carbon atoms [eg, a hydroxylalkyl group (eg, a 2-hydroxyethyl group, a 3-hydroxypropyl group, a 2-hydroxypropyl group, etc.), a sulfoalkyl group] (For example, 2-sulfoethyl group, 3-sulfopropyl group, 3-sulfobutyl group, 4-sulfobutyl group, etc.), carboxyalkyl group (for example, 2-carboxyethyl group, 3-carboxypropyl group, 3-carboxybutyl group, 4-carboxybutyl group etc.]] and aralkyl groups (for example, benzyl group, 2-phenylethyl group etc.).
It is preferred that one of R ₃₆ and R ₃₇ is a substituted alkyl group. Similarly, it is preferable that one of R ₃₈ and R ₃₉ is a substituted alkyl group. A ₂ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms (for example, a methyl group,
Represents an ethyl group, an n-propyl group, an isopropyl group and the like; and an aryl group (eg a phenyl group and the like). Z ₅ , Z ₆ , Z
₇ and Z ₈ are substituents (for example, halogen atom, alkyl group, alkoxy group, aryl group, cyano group, alkoxycarbonyl group, trifluoromethyl group, alkylsulfonyl group, alkylsulfamoyl group, acylamino group,
A non-metallic atomic group necessary for forming a benzene nucleus or a naphthalene nucleus which may have an alkylcarbamoyl group or an acetoxy group. 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.

Specific examples of the sensitizing dye represented by the above general formula are described in Japanese Patent Application No. 8-192965. 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, In acetone, N, N-dimethylformamide, ethyl acetate or a mixed solvent thereof, or
A method of dissolving them in a solvent containing a surfactant and then adding them 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, an aminostyryl compound substituted with a nitrogen-containing heterocyclic group (for example,
U.S. Pat. Nos. 2,933,390 and 3,635,7
No. 21), an aromatic organic acid formaldehyde condensate (for example, US Pat. No. 3,743,5).
No. 10), 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 which 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 little yellow sub-absorption of the coloring dye and have 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. Specific examples of preferred couplers to be used in the present invention are described in Japanese Patent Application No. Hei.
192965.

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, the yellow coupler (Y), the magenta coupler (M) and the cyan coupler (C) are preferably used in a molar ratio of Y: M: C = 2.
４4: 1: 2 to 4.

Examples of the high boiling organic solvent include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, didodecyl phthalate, etc.), and 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, benzoate (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, and specific examples thereof include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, and 2-hexanone. Ethoxyethyl acetate, dimethylformamide and the like can be mentioned. 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,
363, West German Patent Publication 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 layer of the photographic light-sensitive material of the present invention, mainly gelatin is used. In addition, for example, gelatin derivatives, albumin, casein Such as proteins, ethyl cellulose, cellulose derivatives such as carboxymethyl cellulose, sugar derivatives such as starch derivatives,
A hydrophilic polymer such as a homopolymer or a copolymer such as polyvinyl alcohol, polyacrylic acid, polyacrylamide, and polymethacrylic acid 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. 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 the 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, alkyl (meth) acrylamide, vinyl ester, glycidin (meth) acrylate, acrylonitrile, styrene, etc., alone or in combination, or acrylic and methacrylic acid , Α, β-unsaturated dicarboxylic acid, styrenesulfonic acid and the like can be used in combination with a polymer having 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,
Examples include 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, U.S. Pat.
No. 2,101, No. 4,142,894, No. 4,3
Fine particles such as polymethyl methacrylate homopolymers, copolymers of methyl methacrylate and methacrylic acid, starch, silica, and magnesium oxide described in each of the specifications of JP-A-96,706 can be used. In addition, U.S. Pat. No. 3,489,576 and U.S. Pat.
7,958, colloidal silica described in JP-B-56-23139, other paraffin waxes, 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 a hydrophilic colloid layer other than the protective layer.
For example, US Patent Nos. 3,533,794 and 4,2
Benzotriazoles substituted with aryl groups described in JP-A-36,013, JP-B-51-6540, and EP-A-57,160.
Butadiene described in U.S. Pat. No. 4,195,999, cinnamic esters described in U.S. Pat. Nos. 3,705,805 and 3,707,375, U.S. Pat. Benzophenones described in the specifications of Patent No. 3,215,230 and British Patent No. 1,321,355, and specifications of U.S. Patent Nos. 3,761,272 and 4,431,726. Polymer compounds having an ultraviolet absorbing group described in the publication can be used. U.S. Pat. Nos. 3,499,762 and 3,700,45
The ultraviolet-absorbing fluorescent whitening agents described in each of the specifications of No. 5 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.

As the support used in the photographic light-sensitive material of the present invention, 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.

[0069]

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

Solution III Deionized water 200 ml Sodium chloride ag Potassium bromide bg Solution IV Deionized water 200 ml Silver nitrate 40 g

Solution V Deionized water 400 ml Sodium chloride c g Potassium bromide dg VI solution Deionized water 400 ml Silver nitrate 80 g The values of ad are shown in Table 1.

[0072]

[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 50. Next, the temperature was adjusted to 55 ° C., sodium thiosulfate was added, and after optimal chemical sensitization, the sensitizing dye A was added in an amount of 1 × 10 ⁻⁴ mol per mol of silver. 1.3 × 10 ^-4 mol of sensitizing dye B and 4 sensitizing dye C
× 10 ^-5 mol was added. After standing for 20 minutes, 4-hydroxy-6-methyl-1,3,3a, 7-
50 mg of tetrazaindene per mole of silver halide
Was added.

[0074]

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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 2, the first layer (lowest layer) to the third layer
Layers (top layer) were simultaneously coated, and samples 1 to 9 were applied as shown in Table 3.
It was created. 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.

[0077]

[Table 2]

[0078]

[Table 3]

The fluorosurfactant A was manufactured by Dainippon Ink and Chemicals, Inc., trade name: F-120 (potassium N-perfluorooctylsulfonyl-Nn-propylglycine), and the silicone oil was manufactured by Shin-Etsu Chemical Co., Ltd. Co., Ltd., trade name KF-410 was used. Other additives are as follows. High boiling point solvent A: diheptyl phthalate High boiling point solvent B: dibutyl phthalate Color mixture inhibitor A: 2,5-di-tert-octyl hydroquinone

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The thus-prepared sample was exposed to a light wedge according to the sensitometry method, subjected to color development, bleach-fixing and water washing according to the following processing methods, dried, and then subjected to black-and-white density measurement using a Macbeth densitometer RD918. Was measured to determine fog, sensitivity and maximum density. Table 4 shows the obtained results. The sensitivity is a value obtained by multiplying the value of the reciprocal of the exposure amount logE for obtaining a density of fog +0.6 by 100, and the relative sensitivity is a relative sensitivity when the sensitivity of the sample 6 is set to 100. 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 fluorescent whitening agent (W-10) 0.8 g potassium carbonate 0.9 g N, N- Diethylhydroxylamine 4.0 g Water was added to make 1 l, and pH was adjusted to 10.10 by adding 10% sulfuric acid or 20% potassium hydroxide aqueous solution.

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.

[0090]

[Table 4]

From the results shown in Table 4, the samples 6, 7 and 8
Nos. 8 and 9 show that sufficient photographic properties can be obtained even when processed with a color developer containing no benzyl alcohol. The image of each sample obtained in this way is 30,0
After irradiating with a xenon fade meter of 00 lux for 300 hours, the change rate of the image density 1.0 of each sample was measured by using a Macbeth densitometer TR944, and the image remaining rate was determined. Separately, the unexposed film was processed by the above-described developing method, and the fluorescence intensity was measured using an excitation light having a wavelength of 400 nm using an 850 type spectrofluorometer manufactured by Hitachi, Ltd. Note that the fluorescence intensity was expressed as relative fluorescence intensity with the fluorescence intensity of sample 1 as 1. The gloss was measured using a gloss meter manufactured by Tokyo Denshoku Co., Ltd., and the sweating phenomenon was also observed. Table 5 shows the results.

[0092]

[Table 5]

From the results shown in Table 5, the samples 6, 7 and 8
8 and 9 show that there is no image remaining ratio, whiteness (relative fluorescence intensity), glossiness and sweating phenomenon, as compared with the comparative sample.
It turns out that all items are excellent.

[0094]

According to the silver halide photographic light-sensitive material and the image forming method of the present invention, high whiteness and excellent light fastness are obtained
By processing with a color developer containing substantially no benzyl alcohol, a black and white image based on a dye image can be obtained.

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03C 7/407 G03C 7/407 (72) Inventor Yoshiro Hayabuchi 1-24-40 Minamihara, Hiratsuka-shi, Kanagawa Oriental Photo Industry (72) Inventor Katsuyuki Arasawa 1-24-40 Minamihara, Hiratsuka-shi, Kanagawa Prefecture Oriental Photo Industry Co., Ltd.

Claims (6)

[Claims] 1. A silver halide emulsion layer on a support and at least two silver halide emulsion layers on the silver halide emulsion layer.
In a silver halide photographic material having a protective layer, the silver halide emulsion layer has a silver chloride content of 95 mol% or more, and the silver halide emulsion layer comprises a yellow coupler, a magenta Containing a coupler and a cyan coupler, among the protective layers, includes an ultraviolet absorber in the protective layer located on the support side, and a fluorescent whitening agent mordant in the protective layer located farthest from the support. A silver halide photographic light-sensitive material characterized by containing: 2. The silver halide photographic material according to claim 1, wherein the ultraviolet absorbent is a compound represented by the following general formula (I). Embedded image In the formula, R ₁ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkenyl group, a nitro group, a hydroxyl group, and R ₂ and R ₃ represent an alkyl group, an aryl group, an alkoxy group, Represents an aryloxy group. 3. The silver halide according to claim 1, wherein the optical brightener mordant is poly-N-vinylpyrrolidone or a copolymer derived from N-vinylpyrrolidone and an ethylenically unsaturated monomer. Photosensitive material. 4. At least one silver halide emulsion layer on a support and at least two silver halide emulsion layers on the silver halide emulsion layer
In a method for processing a silver halide photographic material having a protective layer, the silver halide emulsion layer has a silver chloride content of 95 mol% or more, and the silver halide emulsion layer has A coupler, a magenta coupler and a cyan coupler, among the protective layers, an ultraviolet absorber in a protective layer located on the support side, and a fluorescent brightening in a protective layer located farthest from the support. An image forming method comprising developing a silver halide photographic light-sensitive material containing a mordant with a color developer containing substantially no benzyl alcohol and containing a fluorescent whitening agent. 5. The image forming method according to claim 4, wherein the ultraviolet absorbent is a compound represented by the following general formula (I). Embedded image In the formula, R ₁ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkenyl group, a nitro group, a hydroxyl group, and R ₂ and R ₃ represent an alkyl group, an aryl group, an alkoxy group, Represents an aryloxy group. 6. The image forming method according to claim 4, wherein the fluorescent whitening agent mordant is poly-N-vinylpyrrolidone or a copolymer derived from N-vinylpyrrolidone and an ethylenically unsaturated monomer. .