JPH0648370B2 - Silver halide photographic light-sensitive material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material having a dyed hydrophilic colloid layer, which is photochemically inert and is easily decolorized in the course of photographic processing. And / or a silver halide photographic light-sensitive material having a hydrophilic colloid layer containing a dye to be eluted.

(Prior Art) In a silver halide photographic light-sensitive material, a photographic emulsion layer or other layers are often colored for the purpose of absorbing light in a specific wavelength range.

When it is necessary to control the spectral composition of light to be incident on the photographic emulsion layer, a coloring layer is provided on the side of the photographic light-sensitive material farther from the support than the photographic emulsion layer. Such a colored layer is called a filter layer. When there are a plurality of photographic emulsion layers as in a multi-layer color light-sensitive material, the filter layer may be located between them.

Light scattered during or after passing through the photographic emulsion layer may be reflected again at the interface between the emulsion layer and the support or on the surface of the light-sensitive material on the side opposite to the emulsion layer and enter the photographic emulsion layer again. Between the photographic emulsion layer and the support for the purpose of preventing blurring of the image, that is, halation.
Alternatively, a coloring layer is provided on the side of the support opposite to the photographic emulsion layer. Such a colored layer is called an antihalation layer. In the case of a multilayer color light-sensitive material,
An antihalation layer may be placed between the layers.

Decrease in image sharpness due to light scattering in photographic emulsion layer (this phenomenon is generally called irradiation)
Coloring of the photographic emulsion layer is also carried out in order to prevent the above phenomenon.

These layers to be colored are often composed of hydrophilic colloids and therefore for their coloring usually water-soluble dyes are included in the layers. This dye is required to satisfy the following conditions.

(1) It has an appropriate spectral absorption according to the purpose of use.

(2) Photochemically inert. That is, it should not adversely affect the performance of the silver halide photographic emulsion layer in a chemical sense, such as reduction in sensitivity, latent image regression, or fog.

(3) It should not be decolorized or dissolved and removed in the course of photographic processing to leave no harmful coloring on the photographic light-sensitive material after processing.

Many efforts have been made by those skilled in the art to find dyes that meet these conditions, and the dyes listed below are known. For example, British Patent Nos. 506,385 and 1,17
7,429, 1,311,884, 1,33
8,799, 1,385,371, 1,46
7,214, 1,433,102, 1,55
3,516, JP-A-48-85, 130, 49-
114, 420, 55-161, 233, 59
-111,640, 62-273527, U.S. Pat. Nos. 3,247,127, 3,469,985,
Oxonol dyes having a pyrazolone nucleus and a barbituric acid nucleus described in U.S. Pat. No. 4,078,933, U.S. Pat. Nos. 2,533,472, 3,379,533, and British Patent 1,278,621. And other oxonol dyes described in the above publications.

Of these, oxonol dyes having two pyrazolone nuclei have the property of being decolorized in a developer containing sulfite, and are used for dyeing photographic materials as useful dyes with few adverse effects on photographic emulsions. Came.

However, among the dyes belonging to this system, even if it has little effect on the photographic emulsion itself, for the emulsion that has been spectrally sensitized,
It has the drawback of causing a decrease in sensitivity, which is considered to be caused by spectral sensitization to an unnecessary region or desorption of a sensitizing dye.

In addition, there are some that remain after the processing due to the speeding up of the developing processing that has recently been performed. In order to solve this, it has been proposed to use a dye having a high reactivity with sulfite ion, but in this case, the stability in the photographic film is not sufficient, and the density decreases with time, It has the drawback that the desired photographic effect cannot be obtained.

(Problems to be Solved by the Invention) The object of the present invention is, firstly, a silver halide in which a hydrophilic colloid layer is dyed with a novel water-soluble dye which does not adversely affect the photographic characteristics of the silver halide emulsion layer. It is to provide a photographic light-sensitive material.

Secondly, an object of the present invention is to provide a silver halide photographic light-sensitive material in which a hydrophilic colloid layer is dyed with a novel water-soluble dye which is excellent in decolorization by processing.

The third object of the present invention is to provide a silver halide photographic light-sensitive material in which the dyed hydrophilic colloid layer contains a novel water-soluble dye which is stable over time.

Means for Solving the Problems These objects of the present invention are achieved by containing at least one of the dyes represented by formula (I).

General formula (I) In the formula, R represents an alkyl group or an aryl group, and Q represents an aryl group having at least one sulfo group or a carboxyl group. L ₁ , L ₂ and L ₃ represent methine groups and may be different from each other. n represents 0, 1, or 2, and m represents 1, 2, 3 or 4.

Specifically, R in the general formula (I) is an alkyl group (for example, methyl, ethyl, t-butyl, octyl, cyclohexyl, benzyl, etc., preferably having 1 to 13 carbon atoms), an aryl group (for example, phenyl, naphthyl, etc.). 6-carbon
18 is preferred), a substituted aryl group [preferably having 6 to 15 carbon atoms, and the substituent includes a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, etc.), alkyl group (eg, methyl, ethyl, t-butyl, etc.). With 1 to 4 carbon atoms), an alkoxy group (eg, methoxy, ethoxy, etc., preferably with 1 to 4 carbon atoms), a sulfo group (eg o
-Sulfophenyl etc.), carboxyl group (eg o-
Carboxyphenyl, etc.), a cyano group (eg p-cyanophenyl etc.), an amino group (eg p-dimethylamino, p-acetylamino etc.), a hydroxy group (eg p-hydroxyphenyl etc.)].

Q represents an aryl group having at least one sulfo group or carboxyl group (for example, o-sulfophenyl, o-, p-disulfophenyl, p-carboxyphenyl, m-carboxyphenyl, 4-sulfonaphthyl, etc.). , A substituted aryl group [as a substituent, a halogen atom (for example, p
-Chloro-o-sulfophenyl, p-bromo-o-sulfophenyl, o-chloro-p-carboxyphenyl, etc.), alkyl group (for example, o-methyl-p-sulfophenyl, etc., preferably having 1 to 3 carbon atoms). , An alkoxy group (for example, o-methoxy-p-carboxyphenyl, etc., preferably having 1 to 3 carbon atoms). The sulfo group and the carboxyl group are not only free acids but also salts (for example, Na salt,
K salt, ammonium salt, quaternary ammonium salt, etc.) may be formed.

L ₁ , L ₂ and L ₃ represent a methine group and a substituted methine group [as the substituent, methyl, ethyl, phenyl, benzyl, 2-sulfoethyl and the like]. n represents 0, 1, or 2, and m represents 1, 2, 3 or 4.

In the dye represented by the general formula (I), R is an alkyl group having 1 to 6 carbon atoms, a phenyl group, a substituted phenyl group having 6 to 8 carbon atoms, and Q is phenyl having at least one sulfo group or carboxyl group. A group and a substituted phenyl group having 6 to 8 carbon atoms are preferable.

Next, specific examples of the dye used in the present invention will be shown, but the present invention is not limited thereto.

1. 2. 3. 4. 5. 6. 7. 8. 9. Ten. 11. 12. 13. 14. 15. 16. 17. 18. The method for producing the oxonol dye of the present invention is described in U.S. Pat. No. 2,274,782 and JP-A-62-273527, and the intermediate 2-pyrazolin-5-one is described in JP-A-6-274.
No. 2-273527 or RHWiley, P. Wiley, Heterocyclic Compounds; Pyrazolone, Pyrazolidone And Derivatives (Pyrocyclic Compounds; Py)
razolones, Pyrazolidones and Derivatives) (Interscience Publishers, John Willie and Sons New York 1964) and the like.

When the dye represented by formula (I) is used as a filter dye, an anti-irradiation dye or an antihalation dye, any effective amount can be used,
It is preferably used so that the optical density is in the range of 0.05 to 3.0. The addition time may be any step before coating.

The dye according to the present invention can be dispersed in a hydrophilic colloid layer such as an emulsion layer (intermediate layer, protective layer, antihalation layer, filter layer, etc.) by various known methods.

A method of directly dissolving or dispersing the dye of the present invention in an emulsion layer or a hydrophilic colloid layer, or a method of dissolving or dispersing it in an aqueous solution or a solvent and then using it in the emulsion layer or the hydrophilic colloid layer. Suitable solvents such as methyl alcohol, ethyl alcohol, propyl alcohol, methyl cellosolve, JP-A-48-9715, US Pat.
It can also be added to the emulsion in the form of a solution dissolved in a halogenated alcohol described in No. 6,830, acetone, water, pyridine or the like, or a mixed solvent thereof.

A method in which a hydrophilic polymer having a charge opposite to that of a dye ion coexists in a layer as a mordant, and the dye is localized in a specific layer by interacting with the dye molecule.

The polymer mordant is a polymer having secondary and tertiary amino groups, a polymer having a nitrogen-containing heterocyclic moiety, a polymer having a quaternary cation group, or the like, and a polymer having a molecular weight of 5000 or more is particularly preferably 10,000 or more. .

For example, vinyl pyridine polymers and vinyl pyridinium cationic polymers described in US Pat. No. 2,548,564; vinyl imidazolium cationic polymers disclosed in US Pat. No. 4,124,386; US patents. Polymer mordanting agents disclosed in U.S. Pat. No. 3,958,995 and JP-A-54-115228, which are crosslinkable with gelatin and the like disclosed in U.S. Pat. No. 3,625,694; Water-insoluble mordants disclosed in U.S. Pat. No. 3,898,088; reactive mordants capable of forming a covalent bond with the dyes disclosed in U.S. Pat. No. 4,168,976; British Patent 685. Derived from ethylenically unsaturated compounds having dialkylaminoalkyl ester residues as described in U.S. Pat. Polymer; British Patent 850,281
A product obtained by reaction of a polyvinylalkylketone with aminoguanidine as described in U.S. Pat. No. 3,445,231;
Examples thereof include polymers derived from methyl-1-vinylimidazole.

A method of dissolving a compound using a surfactant.

The useful surfactant may be an oligomer or a polymer.

For details of this polymer, see JP-A-60-15843.
No. 7 (January 2, 1984 by Fuji Photo Film Co., Ltd.)
Application dated 6th day), pages 19 to 27.

Further, a hydrosol of a lipophilic polymer described in JP-B-51-39835 may be added to the hydrophilic colloid dispersion obtained above.

Gelatin is a typical hydrophilic colloid, but any of those conventionally known as those usable for photography can be used.

The silver halide emulsion used in the present invention is preferably silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride.

The silver halide grains used in the present invention have a regular crystal form such as a cube or an octahedron,
Those having an irregular (irregular) crystal form such as a sphere or a plate, or a compound form of these crystal forms. It is also possible to use a mixture of grains having various crystal forms, but it is preferable to use a regular crystal form.

The silver halide grains used in the present invention may have different phases in the inside and the surface layer, or may be composed of a uniform phase. Also, grains in which a latent image is mainly formed on the surface (eg, negative emulsion) may be used, and grains in which the latent image is mainly formed (eg, internal latent image type emulsion, pre-fogged direct reversal type emulsion) May be Preferably, the particles are such that a latent image is mainly formed on the surface.

The silver halide emulsion used in the present invention has a thickness of 0.5 micron or less, preferably 0.3 micron or less and a diameter of preferably 0.6 micron or more, and grains having an average aspect ratio of 5 or more account for 50% or more of the total projected area. Or a statistical variation coefficient (in the distribution represented by the diameter when the projected area is approximated by a circle, the value S / the standard deviation S divided by the diameter) is 20% or less. Dispersed emulsions are preferred. Further, two or more kinds of tabular grain emulsions and monodisperse emulsions may be mixed.

The photographic emulsion used in the present invention is P. grafchides (P.
Glafkides, Chimie er Physique Photographeque (Paul Montel, 1967), GFDuffin, Photographic Emulsion Chemistr
y) (Published by Focal Press, 1966), written by VLZelikman et al., Making and Coating Photographic Emulsion (Published by Focal Press, 1964), etc. It can be prepared using the method described above.

Further, at the time of forming the silver halide grains, in order to control the growth of the grains, as a silver halide solvent, for example, ammonia, rhodan potassium, rhodan ammon, thioether compound (for example, US Pat. Nos. 3,271,157 and 3,574, No. 628, No. 3,704,130, No. 4,297,439, No. 4,276,374, etc.) and thione compounds (for example, JP-A-53-144319).
No. 53-82408, No. 55-77737, etc.), amine compounds (for example, JP-A-54-100717).
No.) etc. can be used.

In the process of silver halide grain formation or physical ripening,
Cadmium salt, zinc salt, thallium salt, iridium salt or complex salt thereof, rhodium salt or complex salt thereof, iron salt or iron complex salt may be allowed to coexist.

Silver halide emulsions are usually chemically sensitized. For chemical sensitization, for example, H. Freesel (H.Frieser) edition,
Die Grundragen Del Photography Sien Protese Mitt Gilber Halden (Die
Grundlagen der Photographischen Prozesse mit Silbe
rhalogeniden) (Akademissier Ferragus Gezelschact 1968) pp. 675-734 can be used.

That is, a sulfur-sensitizing method using a compound containing sulfur capable of reacting with active gelatin or silver (for example, thiosulfate, thioureas, mercapto compounds, rhodanins); a reducing substance (for example, first tin salt) , Amines, hydrazine derivatives, formamidinesulfinic acid, silane compounds); reduction sensitization methods; noble metal compounds (eg, gold complex salts, complex salts of metals of Group VIII of the periodic table such as Pt, Ir, Pd) The noble metal sensitizing method to be used can be used alone or in combination.

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

The silver halide photographic emulsion of the present invention is a color coupler such as a cyan coupler, a magenta coupler and a yellow coupler.
A coupler and a compound that disperses the coupler may be included.

That is, it may contain a compound capable of forming a color by oxidative coupling with an aromatic primary amine developing agent (for example, a phenylenediamine derivative or an aminophenol derivative) in the color development processing. For example, magenta couplers include 5-pyrazolone couplers, pyrazolobenzimidazole couplers, cyanoacetylcoumarone couplers, pyrazolotriazole couplers, open-chain acylacetonitrile couplers, and the like, and yellow couplers include:
Acylacetamide couplers (for example, benzoylacetanilides, pivaloylacetanilides) and the like, and cyan couplers include naphthol couplers and phenol couplers. These couplers are preferably non-diffusible ones having a hydrophobic group called a ballast group in the molecule. The coupler may be either 4-equivalent or 2-equivalent with respect to silver ion. Further, it may be a colored coupler having a color correcting effect, or a coupler (so-called DIR coupler) which releases a development inhibitor upon development.

In addition to the DIR coupler, a non-coloring DIR coupling compound which is colorless in the product of the coupling reaction and releases a development inhibitor may be contained.

The photographic emulsions of the present invention include, for example, polyalkylene oxide or its derivatives such as ethers, esters and amines, thioether compounds, thiomorpholines, quaternary ammonium salt compounds and urethane derivatives for the purpose of increasing sensitivity, increasing contrast or promoting development. , Urea derivatives, imidazole derivatives, 3-pyrazolidones and the like.

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

The photographic emulsion of the present invention contains various surfactants for various purposes such as coating aid, antistatic property, sliding property improvement, emulsion dispersion, adhesion prevention and photographic property improvement (for example, development acceleration, hardening, sensitization). But it's okay.

Regarding the light-sensitive material of the present invention, with respect to anti-fading agent, hardener, anti-foggant, ultraviolet absorber, protective colloid such as gelatin, and various additives, specifically, Research Disclosure Vol. 176 ( 1978, XII) RD-
17643 and the like.

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

The silver halide photographic light-sensitive material of the present invention includes a color positive film, a color paper, a color negative film, a color reversal film (which may or may not contain a coupler), and a plate-making photographic light-sensitive material (for example, lith film, lith dupe). Films, etc., cathode ray tube display photosensitive materials (eg emulsion X-ray recording photosensitive materials, direct and indirect imaging materials using screens), silver salt diffusion transfer process photosensitive materials, color diffusion transfer Photosensitive material for process, die transfer process
Light-sensitive material, light-sensitive material used in silver dye bleaching method, light-sensitive material for recording printout image, photo-developing printout (Direct
Print image) Photosensitive materials, photothermographic materials, physical development photosensitive materials, and the like.

The exposure for obtaining a photographic image may be performed using a usual method. That is, any of various known light sources such as natural light (sunlight), tungsten lamp, fluorescent lamp, mercury lamp, xenon arc lamp, carbon arc lamp, xenon flash lamp, and cathode ray tube flying spot can be used. The exposure time is usually 1/1000 second to 30 seconds, but exposure shorter than 1/1000 second, for example, 1/10 ⁴ to 1/10 ⁶ seconds using a xenon flash lamp or a cathode ray tube should be used. Exposures longer than 30 seconds can be used. The spectral composition of the light used for exposure can be adjusted with a color filter as needed. Laser light can also be used for the exposure. Also, electron beam, X-ray, γ
It may be exposed by light emitted from a phosphor excited by a ray, an α ray or the like.

For photographic processing of a light-sensitive material produced by using the present invention, for example, Research Disclosur
e) Any known method and known processing solution as described in No. 176, pages 28 to 30 (RD-17643) can be applied. This photographic processing may be either photographic processing for forming a silver image (black and white photographic processing) or photographic processing for forming a dye image (color photographic processing) depending on the purpose. The treatment temperature is usually chosen between 18 and 50 ° C, but it may be below 18 ° C or above 50 ° C.

The color photograph processing method is not particularly limited, and any method can be applied. For example, as a typical example thereof, after exposure, color development, bleach-fixing treatment is performed, and if necessary, further washing with water and stabilization treatment are performed.After exposure, color development, bleaching and fixing treatment are separately performed, A method of further washing with water and stabilizing treatment, if necessary, after exposure, developing with a developer containing a black-and-white developing agent, applying uniform exposure, then performing color development and bleach-fixing treatment, and further washing with water as necessary. , A stabilizing method or after exposure, development with a developing solution containing a black-and-white developing agent, further developing with a color developing solution containing a kasbrush agent (for example, sodium borohydride), and then bleach-fixing processing, There is a method of further washing with water and stabilizing treatment if necessary.

The aromatic primary amine type color developing agents used in the color developing solution in the present invention include known ones widely used in various color photographic processes. These developing agents include aminophenol-based and p-phenylenediamine-based derivatives. A preferred example is a p-phenylenediamine derivative, and representative examples are shown below, but the invention is not limited thereto.

D-1 N, N-diethyl-p-phenylenediamine D-2 2-amino-5-diethylaminotoluene D-3 2-amino-5- (N-ethyl-N-laurylamino) toluene D-4 4- [ N-ethyl-N- (β-hydroxyethyl) amino] aniline D-5 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline D-6 N-ethyl-N- ( β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline D-7 N- (2-amino-5-diethylaminophenylethyl) methanesulfonamide D-8 N, N-dimethyl-p-phenylenediamine D- 9 4-amino-3-methyl-N-ethyl-N-methoxyethylaniline D-10 4-amino-3-methyl-N-ethyl-N-β
-Ethoxyethylaniline D-11 4-amino-3-methyl-N-ethyl-N-β
-Butoxyethylaniline Further, these p-phenylenediamine derivatives may be salts such as sulfates, hydrochlorides, sulfites and p-toluenesulfonates. The above compounds are described in US Pat.
No. 3,015, No. 2,552,241, No. 2,56
6,271, 2,592,364, 3,65
6,950, 3,698,525 and the like. The amount of the aromatic primary amine color developing agent used is about 0.1 g to about 20 g, and more preferably about 0.1 g per 1 developing solution.
The concentration is from 5 g to about 10 g.

The color developer used in the present invention may contain hydroxylamines as is well known.

Hydroxylamines are more commonly used in the form of water-soluble acid salts, although they can be used in the free amine form in color developers. Common examples of such salts are sulfates, oxalates, chlorides, phosphates, carbonates, acetates and the like. The hydroxylamines may be substituted or unsubstituted, and the nitrogen atom of the hydroxylamines may be substituted with an alkyl group.

Addition amount of hydroxylamine is 0g per 1 color developer
It is preferably from 10 to 10 g, more preferably from 0 to 5 g. If the stability of the color developer is maintained, it is preferable that the addition amount be small.

Further, it is preferable that the preservative contains a sulfite salt such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite, potassium metasulfite, or a carbonyl sulfite adduct. The addition amount of these is preferably from 0 g to 20 g /, more preferably from 0 g to 5 g /, and if the stability of the color developer is maintained, the smaller amount is preferable.

Other preservatives include JP-A Nos. 52-49828, 56-47038, 56-32140, and 59-.
160142 and aromatic polyhydroxy compounds described in US Pat. No. 3,746,544; US Pat.
03 and British Patent 1,306,176; hydroxyacetones; JP-A-52-143020 and JP-A-53-89425; α-aminocarbonyl compounds; JP-A-57-44148 and 57-5374.
Various metals as described in JP-A No. 9-102727;
Various saccharides described in No. 52-27638; hydroxamic acids described in No. 52-27638; α, α′-described in No. 59-160141.
Dicarbonyl compounds; salicylic acids described in No. 59-180588; alkanolamines described in No. 54-3532; poly (alkyleneimines) described in No. 56-94349; gluconic acid derivatives described in No. 56-75647, etc. Can be raised. Two or more kinds of these preservatives may be used in combination, if necessary. In particular, addition of 4,5-dihydroxy-m-benzenedisulfonic acid, poly (ethyleneimine), triethanolamine and the like is preferable.

The color developer used in the present invention preferably has a pH of 9 to
12, more preferably 9 to 11, and the color developing solution may contain other known compounds as developing solution components.

In order to maintain the above pH, it is preferable to use various buffers. As the buffer, carbonate, phosphate, borate, tetraborate, hydroxybenzoate, glycine salt,
N, N dimethylglycine salt, leucine salt, norleucine salt, guanine salt, 3,4-dihydroxyphenylalanine salt, alanine salt, aminobutyrate, 2-amino-2-methyl-1,3-propanediol salt, parin salt, Proline salt, trishydroxyaminomethane salt, lysine salt and the like can be used. In particular, carbonates, phosphates, tetraborate salts, and hydroxybenzoates have high solubility and pH of 9.0 or higher.
It is particularly preferable to use these buffers because they have excellent buffering ability in the H region, have no adverse effect on photographic performance (fog, etc.) even when added to a color developing solution, and are inexpensive.

Specific examples of these buffers include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, boric acid. Potassium, sodium tetraborate (borax), potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate) ), Potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate), and the like. However, the present invention is not limited to these compounds.

The amount of the buffering agent added to the color developing solution is preferably 0.1 mol / or more, particularly 0.1 mol / to 0.4 mol /
Is particularly preferable.

In addition, various chelating agents can be used in the color developing solution as a precipitation preventing agent for calcium and magnesium, or for improving the stability of the color developing solution.

The chelating agent is preferably an organic acid compound, for example, aminopolycarboxylic acids described in JP-B-48-030496 and 44-30232, JP-A-56-9734.
7, Japanese Patent Publication No. 56-39359 and West German Patent 2,2
Organic phosphonic acids described in 27,639, JP-A-52-
No. 102726, No. 53-42730, No. 54-12
1127, 55-126241 and 55-6.
Examples thereof include phosphonocarboxylic acids described in JP-A-5956 and other compounds described in JP-A-58-195845, JP-A-58-203440 and JP-B-53-40900. Specific examples are shown below, but the present invention is not limited thereto.

-Nitrilotriacetic acid-Diethyleneaminopentaacetic acid-Ethylenediaminetetraacetic acid-Triethylenetetraminehexaacetic acid-N, N, N-trimethylenephosphonic acid-Ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid-1, 3-Diamino-2-propanol-4acetic acid, transcyclohexanediaminetetraacetic acid, nitrilotriapropionic acid, 1,2-diaminopropanetetraacetic acid, hydroxyethyliminodiacetic acid, glycol ether amine tetraacetic acid, hydroxyethylenediamine triacetic acid, ethylenediamine ortho Hydroxyphenylacetic acid 2-phosphonobutane-1,2,4-tricarboxylic acid 1-hydroxyethane-1,1-diphosphonic acid N, N'-bis (2-hydroxybenzyl) ethylenediamine-N, N'-diacetic acid These sharp Doo agent may be used in combination of two or more if necessary. The amount of these chelating agents added may be an amount sufficient to block the metal ions in the color developing solution. For example, it is about 0.1 g to 10 g per one.

If necessary, any development accelerator can be added to the color developing solution.

Examples of the development accelerator include benzyl alcohol, Japanese Patent Publication Nos. 37-16088, 37-5987, and 38-7.
826, 44-12380, 45-9019, and thioether compounds described in U.S. Pat. No. 3,813,247; JP-A-52-49829 and 50-;
15-554, p-phenylenediamine compounds, JP-A-50-137726, JP-B-44-300
74, JP-A-56-156826 and JP-A-52-4.
Quaternary ammonium salts described in 3429 and the like; p-aminophenols described in US Pat. Nos. 2,610,122 and 4,119,462; US Pat.
No. 903, No. 3,128,182, No. 4,230,7
No. 96, No. 3,253,919, Japanese Patent Publication No. 41-114
31, US Pat. Nos. 2,482,546 and 2,59
Amine compounds described in JP-A-6,926 and JP-A-3,582,346; JP-B-37-16088, JP-A-42-
No. 25201, U.S. Pat. No. 3,128,183, Japanese Patent Publication Nos. 41-11431 and 42-23883, and U.S. Pat. No. 3,532,501, and other polyalkylene oxides, and 1-phenyl-3-pyrazolidone. , Hydrazines, mesoionic compounds, thione compounds, imidazoles, etc. can be added as necessary. Especially thioether compounds and 1-phenyl-
The 3-pyrazolidones are preferred.

If desired, any antifoggant can be added to the color developer of the present invention. Potassium bromide as an antifoggant,
Alkali metal halides such as sodium chloride and potassium iodide and organic antifoggants can be used. Examples of the organic antifoggant include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chlorobenzotriazole, 2-thiazolylbenzimidazole, 2 A nitrogen-containing heterocyclic compound such as thiazolylmethylbenzimidazole, a mercapto-substituted heterocyclic compound such as 2-mercaptobenzimidazole and 2-mercaptobenzothiazole, adenine,
Furthermore, mercapto-substituted aromatic compounds such as thiosalicylic acid can be used. These antifoggants may be eluted from the silver halide color photographic light-sensitive material during processing and accumulated in the color developer, but from the viewpoint of reducing the emission amount,
It is preferable that the amount of these accumulated is small.

The color developer of the present invention preferably contains a fluorescent whitening agent. Examples of the fluorescent whitening agent include 4,4-diamino-2,
2'-Disulfostilbene compounds are preferred. The amount added is 0 to 5 g / preferably 0.1 g to 2 g /.

If necessary, various surfactants such as alkylphosphonic acid, arylphosphonic acid, aliphatic carboxylic acid and aromatic carboxylic acid may be added.

The processing temperature of the color developing solution in the present invention is 30 to 50 ° C.
Is preferable, and more preferably 33 to 42 ° C. The replenishing amount is 30 to 2000 m per 1 m ² of the light-sensitive material,
It is preferably 30 to 1500 m. From the viewpoint of reducing the amount of waste liquid, it is preferable that the replenishment amount of these is small.

A ferric ion complex salt is generally used as the bleaching agent in the bleaching solution or the bleach-fixing solution used in the present invention.
The ferric ion complex salt is a complex of ferric ion and a chelating agent such as aminopolycarboxylic acid, aminopolyphosphonic acid or salts thereof. The aminopolycarboxylic acid salt or aminopolyphosphonic acid salt is a salt of aminopolycarboxylic acid or aminopolyphosphonic acid with an alkali metal, ammonium, or a water-soluble amine. The alkali metal is sodium, potassium, lithium or the like, and the water-soluble amine is an alkylamine such as methylamine, diethylamine, triethylamine or butylamine, a finger-ring amine such as cyclohexylamine, an aniline or m-.
Aryl amines such as toluidine and heterocyclic amines such as pyridine, morpholine and piperidine.

Typical examples of these chelating agents such as aminopolycarboxylic acid and aminopolyphosphonic acid or salts thereof are ethylenediaminetetraacetic acid, ethylenediaminetetraacetic acid disodium salt, ethylenediaminetetraacetic acid diammonium salt, ethylenediaminetetraacetic acid tetra (trimethylammonium) salt, ethylenediamine. Tetraacetic acid tetrapotassium salt Ethylenediaminetetraacetic acid tetrasodium salt Ethylenediaminetetraacetic acid trisodium salt Diethylenetriaminepentaacetic acid Diethylenetriaminepentaacetic acid pentasodium salt Ethylenediamine-N- (β-oxyethyl) -N,
N ', N'-triacetic acid ethylenediamine-N- (β-oxyethyl) -N,
N ', N'-triacetic acid trisodium salt ethylenediamine-N- (β-oxyethyl) -N,
N ', N'-Triacetic acid triammonium salt Propylenediaminetetraacetic acid Propylenediaminetetraacetic acid disodium salt Nitrilotriacetic acid Nitrilotriacetic acid trisodium salt Cyclohexanediaminetetraacetic acid Cyclohexanediaminetetraacetic acid disodium salt Iminodiacetic acid dihydroxyethylglycine Ethyletherdiaminetetraacetic acid salt Glycol ether diamine tetraacetic acid Ethylene diamine tetrapropionic acid Phenylenediamine tetraacetic acid 1,3-diaminopropanol-N, N, N ', N'-
Tetramethylenephosphonic acid Ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid 1,3-Propylenediamine-N, N, N', N'-tetramethylenephosphonic acid, etc., but of course It is not limited to these exemplified compounds.

The ferric ion complex salt may be used in the form of a complex salt.
Iron salts, such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, ferric phosphate, etc., and chelating agents for aminopolycarboxylic acids, aminopolyphosphonic acids, phosphonocarboxylic acids, etc. And may be used to form a ferric ion complex salt in the solution. When used in the form of a complex salt, one type of complex salt may be used, or two or more types of complex salt may be used. On the other hand, when a complex salt is formed in a solution by using a ferric salt and a chelating agent, one or more ferric salts may be used. Furthermore, one or more chelating agents may be used. Also, in either case,
The chelating agent may be used in excess to form the ferric ion complex salt. Among the iron complexes, aminopolycarboxylic acid iron complexes are preferable, and the addition amount thereof is 0.01 to 1.0 mol /, preferably 0.05 to 0.50 mol /.

If necessary, a bleaching accelerator can be used in the bleaching solution or the bleach-fixing solution. Specific examples of useful bleaching accelerators include U.S. Pat. No. 3,893,858, West German Patents 1,290,812, 2,059,988, and JP-A-53-32736, 53-53. 57831, 3
No. 7418, No. 53-65732, No. 53-7262
No. 3, No. 53-95630, No. 53-95631,
No. 53-104232, No. 53-124424, No. 53-141623, No. 53-28426, Research Disclosure No. 17129 (July 1978).
Compounds having a mercapto group or a disulfide group described in JP-A-50-140129; JP-B-45-8506 and JP-A-52
-20832, 53-32735, U.S. Pat. No. 3,706,561; thiourea derivatives; West German Patent 1,127,715; JP 58-16235; Iodides; West German. Patent Nos. 966,410 and 2,
Polyethylene oxides described in 748,430;
Polyamine compounds described in JP-B-45-8836; Others, JP-A-49-42434 and JP-A-49-59644
No. 53-94927, No. 54-35727, No. 55-26506 and No. 58-163940, and iodine, bromine ion and the like. Among them, a compound having a mercapto group or a disulfide group is preferable from the viewpoint of a large accelerating effect, and particularly, US Pat. No. 3,893,858 and West German Patent 1,290,
The compounds described in JP-A No. 812 and JP-A-53-95630 are preferable.

In addition, the bleaching solution or bleach-fixing solution of the present invention contains bromide (eg potassium bromide, sodium bromide, ammonium bromide) or chloride (eg potassium chloride, sodium chloride, ammonium chloride) or iodide (eg iodide). Ammonium) rehalogenating agents can be included. Boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, if necessary
One or more inorganic acids having a pH buffering ability such as phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, organic acids and their alkali metal or ammonium salts, and further ammonium nitrate, guanidine, etc. Corrosion inhibitors can be added.

The bleach-fixing solution of the present invention or the fixing agent used in the fixing solution is
Known fixing agents, that is, thiosulfates such as sodium thiosulfate and ammonium thiosulfate; thiocyanates such as sodium thiocyanate and ammonium thiocyanate; ethylenebisthioglycolic acid, 3,6-dithia-1,8-octanediol, etc. Water-soluble silver halide solubilizers such as thioether compounds and thioureas, and these can be used alone or in combination of two or more. Further, a special bleach-fixing solution containing a combination of a fixing agent described in JP-A-55-155354 and a large amount of a halide such as potassium iodide can be used. In the present invention, it is preferable to use thiosulfate, particularly ammonium thiosulfate.

The amount of the fixing agent per 1 is preferably 0.3 to 2 mol,
More preferably, it is in the range of 0.5 to 1.0 mol.

The pH range of the bleach-fixing solution or the fixing solution in the present invention is 3 to 1
0 is preferable, and 4-9 is particularly preferable. When the pH is lower than this, desilvering property is improved, but deterioration of the liquid and leuco conversion of the cyan dye are promoted. On the other hand, if the pH is higher than this, desilvering is delayed and stain is likely to occur.

To adjust the pH, hydrochloric acid, sulfuric acid, nitric acid, acetic acid (glacial acetic acid), bicarbonate, ammonia, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, etc. can be added if necessary. .

Further, the bleach-fixing solution may contain various other fluorescent whitening agents, defoaming agents or surfactants, polyvinylpyrrolidone, organic solvents such as methanol.

The bleach-fixing solution and the fixing solution of the present invention include a sulfite (eg, sodium sulfite, potassium sulfite, ammonium sulfite, etc.), a bisulfite (eg, ammonium bisulfite, sodium bisulfite, potassium bisulfite, etc.) as a preservative. , A metabisulfite (for example, potassium metabisulfite), sodium metabisulfite, ammonium metabisulfite, and the like, and a sulfite ion-releasing compound.
These compounds are about 0.02-0.50 in terms of sulfite ion.
It is preferable that it is contained per mol, more preferably 0.
It is 04 to 0.40 mol /.

As a preservative, it is common to add sulfite, but in addition, ascorbic acid and carbonyl bisulfite adduct,
Alternatively, a carbonyl compound or the like may be added.

Further, a buffering agent, a fluorescent whitening agent, a chelating agent, an antifungal agent and the like may be added if necessary.

Next, the water washing step of the present invention will be described. In the present invention, a simple treatment method such as performing only a so-called "stabilization treatment" may be used without providing a substantial water washing step in place of the usual "water washing treatment". As described above, the “water washing treatment” in the present invention is used in a broad sense as described above.

The rinsing water amount of the present invention is difficult to define because it depends on the number of multi-stage countercurrent rinsing baths and the amount of the pre-bath component of the light-sensitive material introduced, but in the present invention, the bleach-fix solution component in the final rinsing bath is It may be 1 × 10 ⁻⁴ or less. Eg 3
About 1,000 per 1 m ² of light-sensitive material when washing in counter-current water
It is preferable to use m or more, more preferably 500
It is 0 m or more. In the case of water-saving treatment, photosensitive material 1
It is recommended to use 100 to 1000 m per m ² .

The washing temperature is 15 ° C to 45 ° C, more preferably 20 ° C to 3
It is 5 ° C.

In the washing process, for the purpose of preventing precipitation and stabilizing the washing water,
Various known compounds may be added. For example, chelating agents such as inorganic phosphoric acid, aminopolycarboxylic acid, and organic phosphonic acid, bactericides and antifungal agents that prevent the generation of various bacteria, algae, and molds (for example, "Journal of Antibacterial・ Anti-Fungal Ages "(J.Antibact.Antifung.Agents) Vol.11, No.5,
p207 to 223 (1983), and Hiroshi Horiguchi, "Antibacterial and Antifungal Chemistry" (Sankyo Publishing, 1982).
Compounds described in, metal salts represented by magnesium salts and aluminum salts, alkali metal and aluminum salts,
Alternatively, a surfactant or the like for preventing drying load or unevenness can be added as necessary. Or West, “Photographic Science and Engineering Magazine (Phot.Sci.Eng.), Volume 6, 344-
You may add the compound as described in page 359 (1965) etc.

Furthermore, the present invention is particularly effective in the case of adding a chelating agent, a bactericidal agent, and an antibacterial agent to the washing water to significantly reduce the amount of washing water by multistage countercurrent washing with two or more tanks. Further, it is also particularly effective when a multistage countercurrent stabilization treatment step (so-called stabilization treatment) as described in JP-A-57-8543 is carried out instead of the usual water washing step. In these cases, the bleach-fixing component in the final bath may be 5 × 10 ^-2 or less, preferably 1 × 10 ^-2 or less.

Various compounds are added to the stabilizing bath for the purpose of stabilizing the image. For example, adjust the membrane pH. (For example, pH 3-8
Buffers (eg borate, metaborate, borax, phosphate, carbonate, potassium hydroxide,
Representative examples include aldehydes such as sodium hydroxide, aqueous ammonia, monocarboxylic acids, dicarboxylic acids, polycarboxylic acids, etc.) and formalin. Other chelating agents (inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphonic acid, aminopolyphosphonic acid,
Phosphonocarboxylic acid, etc.), bactericides (thiazole-based, isothiazole-based, halogenated phenols, sulfanilamide, benzotriazole, etc.), surfactants, fluorescent brighteners, hardeners and other additives are used. Alternatively, two or more of the same or different target compounds may be used in combination.

Further, it is preferable to add various ammonium salts such as ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate as a film pH adjuster after the treatment in order to improve the image storability.

When the amount of washing water is significantly reduced as described above, it is preferable to allow a part or all of the overflow liquid of washing water to flow into a bleach-fixing bath or a stabilizing bath which is a pre-bath for the purpose of reducing the amount of drainage.

In this treatment step, a constant finish can be obtained by using a replenisher of each treatment solution to prevent the composition of the solution from changing during continuous processing. The replenishment amount can be reduced to half or less than the standard replenishment amount for cost reduction.

If necessary, a heater, a temperature sensor, a liquid level sensor, a circulation pump, a filter, various floating pigs, various squeegees, nitrogen stirring, air stirring and the like may be provided in each treatment bath.

Color photographic processing is a process that uses a color developer,
It can be applied to any processing step. For example, it can be applied to the processing of color paper, color reversal paper, color positive film, color negative film, color reversal film and the like.

(Example) Next, the present invention will be described in more detail based on examples.

Example 1 A multilayer color print sample (1) having the following layer structure was prepared on a paper support laminated on both sides with polyethylene.

Layer composition The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). However, the silver halide emulsion is the coating amount in terms of silver.

Support Polyethylene laminated paper [Polyethylene on the first layer side contains a white pigment (TiO ₂ ) and a bluish dye (ultraviolet). ] First layer (blue-sensitive silver halide emulsion layer) Monodispersed salt to which spectral sensitizer (Sen-1) was added Silver bromide emulsion (EM-1) 0.16 Spectral sensitizer (Sen-1) Added monodisperse salt Silver bromide emulsion (EM-2) 0.10 Antifoggant (Cpd-1) 0.004 Gelatin 1.83 Yellow coupler (ExY) 0.83 Color image stabilizer (Cpd-2) 0 0.03 Polymer (Cpd-3) 0.08 Solvent (Solv-1 and Solv-2 volume ratio 1: 1) 0.35 Hardener (Hd) 0.02 Second layer (color mixing prevention layer) Gelatin 1.25 Color mixing inhibitor (Cpd-4) 0.04 Solvent (Solv-3 and Solv-4 volume ratio 1: 1) 0.20 Hardener (Hd) 0.02 Third layer (green sensitive silver halide emulsion layer) Monodispersed silver chlorobromide emulsion (E-E to which spectral sensitizer (Sen-2,3) was added -3) 0.05 Monodispersed silver chlorobromide emulsion (EM-4) with addition of spectral sensitizer (Sen-2, 3) 0.11 Antifoggant (Cpd-5) 0.001 Gelatin 1. 79 Magenta Coupler (ExM) 0.32 Color Image Stabilizer (Cpd-6) 0.20 Color Image Stabilizer (Cpd-7) 0.03 Color Image Stabilizer (Cpd-8) 0.03 Solvent (Solv-3) And Solv-5 Volume ratio 1: 2) 0.65 Hardener (Hd) 0.01 Fourth layer (UV absorbing layer) Gelatin 1.58 UV absorber (UV-1 / 2/3 molar ratio 1: 4) : 4) 0.62 Color mixing inhibitor (Cpd-4) 0.05 Solvent (Solv-6) 0.34 Dye (Dy-1) 0.005 Dye (Dy-2) 0.015 Hardener (Hd) 0.01 Fifth layer (red-sensitive silver halide emulsion layer) Spectral sensitizer (Sen-4,5) Added monodispersed silver chlorobromide emulsion (EM-5) 0.07 Monodispersed silver chlorobromide emulsion (EM-6) 0.15 Spectral sensitizer (Sen-4,5) added 0.15 Antifoggant Agent (Cpd-9) 0.0002 Gelatin 1.34 Cyan coupler (ExC-1) 0.15 Cyan coupler (ExC-2) 0.18 UV absorber (UV-1 / 3/4 molar ratio 1: 3: 3) 0.17 Polymer (Cpd-3) 0.33 Solvent (Solv-1) 0.23 Hardener (Hd) 0.01 Sixth layer (UV absorbing layer) Gelatin 0.53 UV absorbing agent (UV- 1/2/3 molar ratio 1: 4: 4) 0.21 solvent (Solv-6) 0.08 hardener (Hd) 0.01 seventh layer (protective layer) gelatin 1.33 acrylic alcohol of polyvinyl alcohol Modified copolymer (Modification degree 17%) 0.17 Liquid paraffin 0.03 The details of the silver halide emulsion used in the above sample are shown in Table 1.

(Sen-1) 6 × 10 ⁻⁴ mol / Ag mol (Sen-2) 4 × 10 ⁻⁴ mol / Ag mol (Sen-3) 8 × 10 ⁻⁵ mol / Ag mol (Sen-4) 1.8 × 10 ^-4 mol / Ag mol (Sen-5) 3 × 10 ⁻³ mol / Ag mol (ExY) (ExM) (ExC-1) (ExC-2) (Hd) (Cpd-1) (Cpd-2) (Cpd-3) (Cpd-4) (Cpd-5) (Cpd-6) (Cpd-7) (Cpd-8) (Cpd-9) (UV-1) (UV-2) (UV-3) (UV-4) (Solv-1) (Solv-2) O = POC ₉ H ₁₉ (iso)) ₃ (Solv-3) (Solv-4) (Solv-5) (Solv-6) (Dy-1) (Dy-2) Samples (2) to (7) in which the dye of the fourth layer was changed from the above samples
Was produced. The composition is shown in Table 2.

For samples (1) to (8), the stability of the dye in the film and the exposure humidity dependence were investigated. For the stability of the dye,
Evaluation was made based on the residual rate of the dye after left for 2 weeks at -80%. The exposure humidity dependency is 25 ° C-55% and 25 ° C.
After exposure under the condition of -85% C, the following processing was carried out to evaluate the relative sensitivity at an optical density of 1.0 for a blue-sensitive silver halide emulsion layer having a large change. The evaluation results are shown in Table 3.

The composition of each treatment liquid is as follows.

Color developer Bleach-fix solution As can be seen in Table 3, samples using the dyes of the invention
(2) to (8) have excellent stability in the film, and 25 ℃ -55%
The relative sensitivity is high, and there is little decrease in sensitivity at 25 ° C-85%.

Example-2 A sample (9) having the following layer structure was prepared in the same manner as in Example-1.

First layer (blue-sensitive silver halide emulsion layer) Monodisperse salt to which spectral sensitizer (Sen-6) was added Silver bromide emulsion (EM-7) 0.27 Gelatin 1.86 Yellow coupler (ExY) 0. 82 Solvent (Solv-4) 0.35 Hardener (Hd) 0.02 Second layer (color mixing prevention layer) Gelatin 0.99 Color mixing inhibitor (Cpd-4) 0.06 Solvent (Solv-3 and Solv- 4 Volume ratio 1: 1) 0.12 Hardener (Hd) 0.02 Third layer (green sensitive silver halide emulsion layer) Spectral sensitizer (Sen-7,3) Silver halide emulsion (EM-8) 0.45 Gelatin 1.24 Magenta coupler (ExM) 0.35 Color image stabilizer (Cpd-6) 0.20 Color image stabilizer (Cpd-7) 0.03 Color image stabilizer Agent (Cpd-8) 0.03 Solvent (Solv-3 and Solv-5) Form Product ratio 1: 2) 0.65 Hardener (Hd) 0.01 Fourth layer (UV absorbing layer) Gelatin 1.58 UV absorber (UV-1 / 2/3 molar ratio 1: 4: 4) 0 .62 Color mixing inhibitor (Cpd-4) 0.05 Solvent (Solv-6) 0.34 Dye (Dy-1) 0.005 Dye (Dy-2) 0.015 Hardener (Hd) 0.01th Five layers (red-sensitive silver halide emulsion layer) Monodispersed silver chlorobromide emulsion (EM-9) 0.20 Gelatin 0.92 Cyan coupler (ExC-) with spectral sensitizer (Sen-4,5) added 3) 0.15 Cyan coupler (ExC-4) 0.18 Ultraviolet absorber (UV-1 / 3/4 molar ratio 1: 3: 3) 0.17 Solvent (Solv-4) 0.20 Hardener ( Hd) 0.01 Sixth layer (UV absorbing layer) Gelatin 0.53 UV absorber (UV-1 / 2 / 3 Molar ratio 1: 4: 4) 0.21 Solvent (Solv-6) 0.08 Hardener (Hd) 0.01 Seventh layer (protective layer) Gelatin 1.33 Acrylic modified copolymer of polyvinyl alcohol (Modification degree: 17%) 0.17 Liquid paraffin 0.03 Table 4 shows the details of the silver halide emulsion used in the above sample.

(Sen-6) (Sen-7) (ExC-3) (ExC-4) From the above sample, samples (10) to (1) in which the dye of the fourth layer was changed
6) was produced. The composition is shown in Table 5.

Samples (9) to (16) were examined for stability of dye in the film and exposure humidity dependence. For the stability of the dye,
The residual rate of the dye after standing for 2 weeks at 5 ° C-80% was evaluated. The exposure humidity dependence is 25 ° C-55% and 2
After exposing under the condition of 5 ° C-85%, the following treatment is performed,
The relative sensitivity at an optical density of 1.0 was evaluated for a blue-sensitive silver halide emulsion layer having a large change. The evaluation results are shown in Table 6.

(A three-tank countercurrent flow system from rinse to → was used.) The composition of each processing solution is as follows.

Color developer Bleach-fix solution Rinse solution Ion-exchanged water (3pp each for calcium and magnesium
m or less) As is clear from Table 6, samples (1
0) to (16) have excellent stability in the film, and 25 ° C-55%
The relative sensitivity is high, and there is little decrease in sensitivity at 25 ° C-85%.

(Effects of the Invention) According to the present invention, a silver halide having a hydrophilic colloid layer containing a novel dye that is decolorized and eluted during photographic processing and does not adversely affect the photographic characteristics of a photographic emulsion, particularly the spectral sensitization property. A photographic light-sensitive material can be obtained.

Further, according to the present invention, it is possible to obtain a silver halide photographic light-sensitive material having excellent stability over time and small exposure dependence.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP 63-244034 (JP, A) JP 63-264745 (JP, A) JP 50-147712 (JP, A) JP 50- 145125 (JP, A) JP 63-139949 (JP, A) JP 64-541 (JP, A) JP 63-231445 (JP, A) JP-B 2-16505 (JP, B2)

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material containing at least one compound represented by the following general formula (I). (I) In the formula, R represents an alkyl group or an aryl group, and Q represents an aryl group having at least one sulfo group or a carboxyl group. L ₁ , L ₂ and L ₃ represent methine groups and may be different from each other. n represents 0, 1, or 2, and m
Represents 1, 2, 3 or 4.