JP2543720B2 - Silver halide color-processing method of photographic light-sensitive material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for processing a silver halide color photographic light-sensitive material, and in particular, it exhibits a remarkable color-forming property even when a color developer contains substantially no benzyl alcohol. The present invention relates to a treatment method having a high cost and capable of rapid treatment.

(Prior Art and Problems Thereof) Various methods have been conventionally used in this field in order to increase the developing speed and color developing speed of a color developing solution.

For example, in order for the color developing agent to finally couple with the coupler to form a dye, it is necessary for the color developing agent itself to be incorporated into the coupler-dispersed oil droplets. Various additives are known as additives for promoting In particular, benzyl alcohol is known to have such a large color-promoting effect, has been used for processing various color photographic light-sensitive materials, and is still widely used as an essential component.

Benzyl alcohol is soluble in water to some extent, but its solubility is poor, and diethylene glycol, triethylene glycol, or alkanolamine is widely used to enhance the solubility.

However, these compounds and benzyl alcohol themselves also have a large pollution load when treated as wastewater and have a high BOD value and COD value, and they have the advantage of improving color development or solubility as described above. In view of wastewater treatment, it has been desired to reduce or remove benzyl alcohol.

Furthermore, the solubility of benzyl alcohol is still insufficient even when the above-mentioned solvent such as diethylene glycol is used, which causes a burden on the labor and time for preparing the developer.

Further, if benzyl alcohol is brought into the bleaching bath or bleach-fixing bath which is the subsequent bath together with the developer and accumulates therein, it may cause formation of a leuco body depending on the type of the cyan dye and may lower the color density. I was waking up. It was also found that the accumulation causes insufficient washing out of the developing solution components, especially the color developing agent in the water washing step, resulting in deterioration of image storability due to the residual thereof.

From these viewpoints as well, it is of great significance to reduce or remove benzyl alcohol from a color developing solution.

While color labs are currently facing these problems, there is also a pressing need to shorten processing time in the trend of shortening print delivery times.

However, these requirements cannot be met simultaneously by the conventional techniques, and it is obvious that the color density is remarkably lowered if the developing time is shortened after removing benzyl alcohol from the color developing solution.

On the other hand, conventional yellow couplers are 4-equivalent couplers or JP-A-50-87650, British Patent Nos. 3,369,695 and 3,
Alpha-acyl acetanilides in which one hydrogen atom of the active methylene group described in 408, 194, 3,415,652 and 3,447,928 is substituted with an aryloxy group, a halogen element, a sulfoxy group, an acyloxy group, etc. are known. However, these couplers have insufficient coupling reaction activity. It had a defect such as giving remarkable color fog.

As a yellow coupler which overcomes these drawbacks and has higher activity, one active hydrogen atom of a methylene group described in JP-A-47-26133 and JP-A-56-44420 is prepared by a heterocycle containing a nitrogen atom directly. Substituted couplers are known,
The improvement was recognized as compared with the conventional coupler, but the effect was insufficient.

Further, when a highly active yellow coupler is used, the fog density is generally increased.

Therefore, an object of the present invention is to provide a processing method of a silver halide color photographic light-sensitive material which has a remarkably high color developing property and which is effectively prevented from fogging, even though the color developer contains substantially no benzyl alcohol. To provide.

(Means for Solving Problems) The above object of the present invention comprises at least one silver chlorobromide emulsion or silver chloride emulsion containing 90 to 100 mol% of silver chloride and is represented by the following general formula (I). A silver halide color photographic light-sensitive material containing at least one yellow coupler, which is processed with a color developer containing substantially no benzyl alcohol and no sulfite ion. It has been found to be achieved by the processing method of the light-sensitive material.

General formula [I] (In the formula, R ¹ represents a substituted or unsubstituted tertiary alkyl group or a substituted or unsubstituted aryl group. R ² represents a halogen atom or an alkoxy group. R ³ represents a substituted or unsubstituted alkyl group or It represents a substituted or unsubstituted aryl group, Y ¹ represents a divalent linking group, and X represents a coupling-off group.

As described above, when benzyl alcohol is not substantially contained in the color developing solution, the color developability generally decreases, and therefore it is expected that the use of a coupler having higher activity will be more effective. Although it has been the invention, among the known high activity couplers as described above, particularly among the yellow couplers in which one hydrogen atom of the above-mentioned active methylene group is directly substituted by a heterocycle containing a nitrogen atom, The substituent of the phenylcarbamoyl group in the coupler is represented by --NHCOY ¹ --SO ₂ R ^{3 as in} the coupler of formula (I) of the present invention.
It was found that the coloring property is remarkably improved by increasing the fog density without increasing the fog density.

Hereinafter, the compound of the general formula (I) of the present invention will be described in detail.

In the general formula (I), the tertiary alkyl group represented by R ¹ includes an unsubstituted (eg t-butyl group) and a substituted alkyl group. As the substituent introduced into the above alkyl group, a halogen atom (eg, fluorine, chlorine, bromine, etc.), an alkoxy group (eg, methoxy, ethoxy group, etc.), an aryloxy group (eg, phenoxy group, 4-chlorophenoxy group, etc.) ), An alkylthio group (eg, methylthio, n-butylthio group, etc.), an arylthio group (eg, phenylthio group, etc.), an alkylsulfonyl group (eg, methanesulfonyl group, n-butanesulfonyl group, etc.), an arylsulfonyl group (eg, benzenesulfonyl group, 4-methoxybenzenesulfonyl group etc.), an acylamino group (eg acetylamino group etc.), an amino group (eg diethylamino group) citheno group and the like can be mentioned. The aryl group represented by R ¹ is preferably a phenyl group and may have a substituent. Examples of the substituent of the above aryl group include the same groups as the alkyl group, but in addition to these, an alkyl group (for example, methyl, ethyl, t
-Butyl group, etc.) and the like.

R ² represents a chlorine atom or an alkoxy group (eg, methoxy, ethoxy, etc.).

The alkyl group represented by R ³ includes an unsubstituted (eg, n-octyl group, n-dodecyl group, n-heptadecyl group etc.) and a substituted alkyl group.

Examples of the substituent introduced into the above alkyl group include the substituent represented by R ¹ .

The aryl group represented by R ³ is preferably a phenyl group,
Includes unsubstituted and substituted phenyl groups.

Examples of the substituent introduced into the phenyl group include the same groups as the alkyl group, but also include an alkyl group (eg, methyl, ethyl group, etc.) and the like.

Y ¹ represents a divalent linking group, and represents an alkylene group, an arylene group, an aralkylene group or a divalent organic group represented by the following general formula [Ia].

-A-V-B- General Formula [Ia] (In the formula, A and B each represent an alkylene group, an arylene group, or an aralkylene group which may have a substituent, and V represents a divalent bridging group. Examples of the substituents of A and B include the same groups as in the case of R ¹ .

Examples of V include oxy, thio, carboxide and sulfonamide groups.

The coupling-off group of X is a coupling-off group capable of releasing a 2-equivalent yellow coupler, preferably a nitrogen-releasing group, and more preferably the following general formula (a), (b) or (c). Represents a group represented.

(In the formula, R ³ and R ⁴ are each a hydrogen atom, a halogen atom carboxylic acid ester group, an amino group, an alkyl group, an alkylthio group, an alkoxy group, an alkylsulfonyl group, an alkylsulfinyl group, a carboxylic acid group, a sulfonic acid group, And represents a substituted or substituted phenyl group or a heterocycle, which may be the same or different.) (W ¹ in the formula Represents a metal atom required to form a 4-membered ring, 5-membered ring, or 6-membered ring. ) More preferably, it is represented by the following formulas (d) to (f).

In the formula, R ⁹ and R ¹⁰ each represent a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group or a hydroxy group. R ¹¹ , R ¹¹ and R ¹³ each represent a hydrogen atom, an alkyl group, an aryl group, an aralkyl group or an acyl group. W ² represents an oxygen or sulfur atom.

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

The yellow coupler represented by formula (I) can be synthesized based on JP-B-56-44420.

Two or more kinds of yellow couplers represented by formula (I) may be used in combination, or other yellow couplers may be used in combination. Benzoyl acetanilide compounds and pivaloyl acetanilide compounds are advantageous as yellow couplers that may be used in combination. Specific examples of yellow couplers that can be used are U.S. Patents 2,875,057 and 3,265,506,
3,408,194, 3,551,155, 3,582,322, 3,
725,072, 3,891,445, West German Patent 1,547,868, West German Published Application 2,219,917, 2,261,361, 2,414,006.
No., British Patent 1,425,020, Japanese Patent Publication No. 51-10783, Japanese Patent Laid-Open No.
47-26133, 48-73147, 51-102636, 50-
No. 6341, No. 50-123342, No. 50-130442, No. 51-21218
No. 7, No. 50-87650, No. 52-82424, No. 52-115219.

Examples of the magenta coupler which can be used in the present invention include oil-protection type indazolone type or cyanoacetyl type, preferably 5-pyrazolone type and pyrazoloazole type couplers such as pyrazolotriazoles. The 5-pyrazolone-based coupler is preferably a coupler in which the 3-position is substituted with an arylamino group or an acylamino group, from the viewpoint of the hue and color density of the color forming dye, and typical examples thereof are U.S. Pat.Nos. 2,311,082 and 2,343,703. ,
No. 2,600,788, No. 2,908,573, No. 3,062,653
No. 3,152,896 and No. 3,936,015. As the leaving group of the 2-equivalent 5-pyrazolone-based coupler, the nitrogen atom leaving group described in US Pat. No. 4,310,619 or the arylthio group described in US Pat. No. 4,351,897 is preferable. Further, the 5-pyrazolone-based coupler having a ballast group described in EP 73,636 provides a high color density.

As the pyrazoloazole-based coupler, US Pat.
369,879 pyrazolobenzimidazoles, preferably pyrazolo [5,1-c] [1,2,4] triazoles described in US Pat. No. 3,725,067, Research Disclosure 24220 (June 1984). Pyrazolotetrazoles and Research Disclosure 24 described
The pyrazolopyrazoles described in 230 (June 1984) can be mentioned. The imidazo [1,2-b] pyrazoles described in European Patent No. 119,741 are preferable in view of less yellow sub-absorption of the color forming dye and light fastness, and European Patent No. 119,8
The pyrazolo [1,5-b] [1,2,4] triazole described in No. 60 is particularly preferable.

Cyan couplers that can be used in the present invention include oil-protection type naphthol-based and phenol-based couplers, naphthol-based couplers described in U.S. Pat.No. 2,474,293, preferably U.S. Pat.Nos. 4,052,212, 4,146,396, and No. 4,228,233 and No. 4,296,200
As a representative example, the oxygen atom-releasing two-equivalent naphthol-based couplers described in JP-A No. 1994-242242 can be mentioned. Further, specific examples of the phenol-based coupler are described in U.S. Patents 2,369,929 and 2,80.
1,171, 2,772,162, 2,895,826 and the like. Cyan couplers which are fast against humidity and temperature are preferably used in the present invention, and typical examples thereof include a phenol system having an alkyl group of ethyl group or more at the meta position of the phenol nucleus described in U.S. Pat.No. 3,772,002. Cyan coupler, U.S. Pat.Nos. 2,772,162, 3,758,308, 4,126,396, 4,334,011,
No. 4,327,173, West German Patent Publication No. 3,329,729 and Japanese Patent Application No. 58-42671, and 2,5-diacylamino-substituted phenol couplers and U.S. Pat.No. 3,446,622.
Nos. 4,333,999, 4,451,559 and 4,42
Nos. 7,767 and the like include phenolic couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position.

The graininess can be improved by using a coupler in which the color forming dye has an appropriate diffusibility. Such dye-diffusing couplers are described in U.S. Patent No. 4,366,237 and British Patent No.
Specific examples of magenta couplers are described in 2,125,570, and specific examples of yellow, magenta or cyan couplers are described in EP 96,570 and German Offenlegungsschrift 3,234,533.

The dye-forming coupler and the above-mentioned special coupler may form a dimer or higher polymer. Typical examples of polymerized dye forming couplers are described in US Pat. Nos. 3,451,820 and 4,080,211. Specific examples of polymerized magenta couplers are described in British Patent No. 2,102,173 and U.S. Patent No. 4,367,282.

The various couplers used in the present invention can be used in combination of two or more kinds in the same layer of the light-sensitive layer in order to satisfy the properties required for the light-sensitive material, and the same compound can be used in two or more different layers. Can also be introduced.

The standard amount of the color coupler used is in the range of 0.001 to 1 mol per mol of the photosensitive silver halide,
Preferably 0.01 to 0.5 moles for yellow couplers,
It is 0.003 to 0.3 mol for the magenta coupler and 0.002 to 0.3 mol for the cyan coupler.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods. Examples of the high boiling point organic solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027. Further, the steps of the latex dispersion method, effects, specific examples of latex for impregnation are described in U.S. Pat.
363, West German Patent Application (OLS) Nos. 2,541,274 and
No. 2,541,230.

The silver halide emulsion of the light-sensitive material used in the present invention is
A silver chlorobromide emulsion or a silver chloride emulsion containing 90 to 100 mol% of silver chloride.

The silver halide grains used in the present invention may have different phases in the inside and the surface layer, may have a multi-phase structure having a junction structure, or may have a uniform phase as a whole. Moreover, they may be mixed.

The average grain size distribution of the silver halide grains used in the present invention may be either narrow or wide. However, the value obtained by dividing the standard deviation value in the grain size distribution curve of the silver halide emulsion by the average grain size (fluctuation) Rate) within 20%, particularly preferably 15
It is preferred to use so-called monodisperse silver halide emulsions within the range of% in the present invention. Further, in order to satisfy the target gradation of the light-sensitive material, two or more kinds of monodisperse silver halide emulsions having different grain sizes in the emulsion layers having substantially the same color sensitivity (the above-mentioned monodispersity is the same). Those having a variation rate are preferable) can be mixed in the same layer or multilayer-coated in different layers. Further, two or more kinds of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion may be used as a mixture or as a mixture.

The silver halide grains used in the present invention have a regular shape such as a cube, an octahedron, a rhodohedron and a tetradecahedron.
It may be a compound having various crystalline forms or a coexisting thereof, may have an irregular crystalline form such as a spherical shape, or may be a composite form of these crystalline forms. Further, tabular grains may be used, and in particular, an emulsion in which tabular grains having a length / thickness ratio value of 5 to 8 or 8 or more account for 50% or more of the total projected area of grains may be used. It may be an emulsion composed of a mixture of these various crystal forms.

These various emulsions may be either a surface latent image type in which a latent image is mainly formed on the surface or an internal latent image type in which a latent image is formed inside a grain.

The photographic emulsion used in the present invention is RESEARCH DISCLOSUR.
It can be prepared using the method described in E vol.170 Item No.17643 (I, II, III) (1978.12).

The emulsion used in the present invention is usually one that has been physically ripened, chemically ripened and spectrally sensitized. Additives used in such processes are Research Dista Roger Vol. 176, No. 17643 (December 1978) and Vol. 187, N.
No. 18716 (November, 1979), the relevant places are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and the locations described in the table below are shown.

The photographic light-sensitive material used in the present invention is applied to a commonly used plastic film (cellulose nitrate, cellulose acetate, polyethylene terephthalate, etc.), a flexible support such as paper or a rigid support such as glass. . For details on the support and coating method, see RESE
ARCH DISCLOSURE Volume 176 Item 17643 Item XV (p.27) XVII
Section (p.28) (December 1978 issue).

In the present invention, a reflective support is preferably used.

The "reflective support" is one which enhances the reflectivity and makes the dye image formed on the silver halide emulsion layer clear, and such a reflective support includes titanium oxide, zinc oxide, Examples include those coated with a hydrophobic resin containing a light reflecting substance such as calcium carbonate and calcium sulfate dispersed therein, and those using a hydrophobic resin containing a light reflecting substance dispersed therein as a support.

The color developing solution used in the present invention may contain a known aromatic primary amine color developing agent. A preferred example is a p-phenylenediamine derivative, and representative examples thereof 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 4-amino-3-methyl -N-ethyl-N-
[Β- (Methanesulfonamido) ethyl] -aniline 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 Among the above p-phenylenediamine derivatives, 4-amino-3-methyl-N-ethyl-N- [β- is particularly preferable.
(Methanesulfonamido) ethyl] -aniline (Exemplary Compound D-6).

Further, these p-phenylenediamine derivatives may be salts such as sulfates, hydrochlorides, sulfites and p-toluenesulfonates. The amount of the aromatic primary amine developing agent to be used is preferably about 0.1 g to about 20 g, more preferably about 0.5 g to about 10 g, per developer.

If necessary, any development accelerator can be added to the color developing solution. However, the color developing solution of the present invention does not substantially contain benzyl alcohol from the viewpoints of pollution, solution preparation and fog prevention. Here, the term "substantially free of benzyl alcohol" means color developer 1
Per benzyl alcohol means less than 2 ml. Preferably, it contains no benzyl alcohol.

Further, the color developing solution of the present invention comprises sodium sulfite,
It does not contain sulfite ions such as potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite and potassium metasulfite, and carbonyl sulfite adducts.

Further, as a compound that directly preserves the color developing agent, various hydroxylamines, hydroxamic acids described in Japanese Patent Application No. 61-186559, hydrazines and hydrazides described in 61-170756, 61-188742 and Same as 61-203253
No. 61-188741, α-hydroxyketones and α-aminoketones, and / or 61
It is preferable to add various saccharides described in -180616.
Further, in combination with the above compounds, Japanese Patent Application Nos.
-166674, 61-165621, 61-164515, 61-
170789 and 61-168159 monoamines and the like,
61-173595, 61-164515, diamines described in 61-186560 and the like, polyamines described in 61-165621 and 61-169789, polyamines described in 61-1888619, Nitroxy radicals described in No. 61-197760, No. 61
-186561 and 61-197419 alcohols,
It is preferable to use the oximes described in 61-198987 and the tertiary amines described in 61-265149. Other preservatives include various metals described in JP-A-57-44148 and 57-53749, salicylic acids described in JP-A-59-180588, and alkanolamines described in JP-A-54-3532. Polyethyleneimines described in JP-A-56-94349, aromatic polyhydroxy compounds described in U.S. Pat. No. 3,746,544 and the like may be contained, if desired. In particular, aromatic polyhydroxy compounds, triethanolamine, and Japanese Patent Application No. 61-26
Addition of the compounds described in 4159 is preferred. The color developing solution used in the present invention preferably has a pH of 9 to 12, more preferably 9 to 11.0, and the color developing solution may contain compounds of other known 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, valine salt , Proline salt, trishydroxyaminomethane salt, lysine salt and the like can be used. In particular, carbonates, phosphates, tetraborate and hydroxybenzoates are highly soluble and have a high pH of 9.0 or above.
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, potassium borate, sodium tetraborate (borax), tetraborate Potassium acid, sodium O-hydroxybenzoate (sodium salicylate), potassium O-hydroxybenzoate, 5-
Sodium sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate)
And so on. However, the invention is not limited to these compounds.

The amount of the buffer added to the color developer is 0.1 mol /
It is preferably at least above, and particularly preferably 0.1 mol / to 0.4 mol /. In addition, as a precipitation inhibitor of calcium and magnesium in the color developer,
Alternatively, various chelating agents can be used to improve 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-56-97347 and JP-B-56-393.
Organic phosphonic acids described in 59 and West German Patent 2,227,639, JP-A-52-102726, JP-A-53-42730, and JP-A-54-12112.
No. 7, No. 55-126241 and No. 55-65956, and other phosphonocarboxylic acids described in JP-A Nos. 58-195845 and 58-
Examples thereof include compounds described in 203440 and Japanese Patent Publication No. 53-40900. Specific examples are shown below, but the present invention is not limited thereto.

-Nitrilotriacetic acid-Diethylenetriaminepentaacetic 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-nitrilotripropionic acid- 1,2-diaminopropanetetraacetic acid-hydroxyethyliminodiacetic acid-glycol ether diamine tetraacetic acid-hydroxyethylenediamine triacetic acid-ethylenediamine orthohydroxy Phenylacetic 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 chelating agents may be used in combination of two or more if necessary. good. 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.

Other development accelerators include Japanese Patent Publication No. 37-16088 and No. 3
7-5987, 38-7826, 44-12380, 45-9019
Thioether compounds disclosed in U.S. Pat. No. 3,813,247 and US Pat. No. 3,813,247; p-phenylenediamine compounds disclosed in JP-A-52-49829 and JP-A-50-15554;
-137726, JP-B-44-30074, JP-A-56-156826 and JP-A-52-43429, and the like, quaternary ammonium salts, U.S. Patents 2,494,903, 3,128,182, and 4,23.
0,796, 3,253,919, Japanese Patent Publication No. 41-11431, U.S. Patent Nos. 2,482,546, 2,596,926 and 3,582,346, etc., amine compounds described in Japanese Patent Publication Nos. 37-16088, 42-2.
No. 5201, U.S. Pat.No. 3,128,183, JP-B-41-11431,
No. 42-23883 and U.S. Pat.No. 3,532,501, polyalkylene oxides and other 1-phenyl-3
-Pyrazolidones, imidazoles, etc. can be added as required.

In the present invention, any antifoggant can be added if necessary. As the antifoggant, alkali metal halides such as sodium chloride, potassium bromide and potassium iodide and organic antifoggants can be used. Examples of the organic antifoggant include benzotriazole and 6-
Nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-
Representative examples thereof include nitrogen-containing heterocyclic compounds such as thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine and adenine.

Further, various surfactants such as alkylsulfonic acid, arylphosphonic acid, aliphatic carboxylic acid, and aromatic carboxylic acid may be added as needed.

The processing temperature of the color developing solution of the present invention is 20 to 50 ° C, preferably 30 to 40 ° C. The processing time is 20 seconds to 5 minutes, preferably 30 seconds to 2 minutes. The smaller the replenishment amount, the better,
It is 20 to 600 ml, preferably 50 to 300 ml per 1 m ^{2 of the} light-sensitive material. More preferably, it is 100 ml to 200 ml.

Next, the bleaching solution, the bleach-fixing solution and the fixing solution used in the present invention will be described.

As the bleaching agent used in the bleaching solution or the bleach-fixing solution used in the present invention, any bleaching agent can be used, but especially organic complex salts of iron (III) (for example, aminopolyamines such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid). Carboxylic acids, aminopolyphosphonic acids, complex salts such as phosphonocarboxylic acids and organic phosphonic acids) or organic acids such as citric acid, tartaric acid, malic acid; persulfates; hydrogen peroxide and the like are preferable.

Of these, organic complex salts of iron (III) are particularly preferable from the viewpoint of rapid processing and prevention of environmental pollution. Furthermore, aminopolycarboxylic acid iron (III) complex salts are preferable. Aminopolycarboxylic acids useful for forming organic complex salts of iron (III),
Listed as aminopolyphosphonic acids, or organic phosphonic acids or salts thereof, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1,3-diaminopropanetetraacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiamino acid. Acetic acid, iminodiacetic acid, glycol ether diamine tetraacetic acid, etc. can be mentioned. These compounds are sodium,
Any of potassium, lithium or ammonium salt may be used. Among these compounds, ethylenediaminetetraacetic acid,
Iron (III) complex salts of diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 1,3-diaminopropanetetraacetic acid and methyliminodiacetic acid are preferred because of their high bleaching power.

These ferric ion complex salts may be used in the form of complex salts, and ferric salts such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, ferric phosphate. And a chelating agent such as aminopolycarboxylic acid, aminopolyphosphonic acid or phosphonocarboxylic acid may be used to form a ferric ion complex salt in a solution. In addition, the chelating agent may be used in excess of forming a 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
It is 0.50 mol /.

The bleaching solution, the bleach-fixing solution and / or the pre-bath of these,
Various compounds can be used as the bleaching accelerator.
For example, U.S. Pat. No. 3,893,858, German Patent No.
1,290,812, JP-A-53-95630, Research Disclosure, etc., 17129 (July 1978 issue), compounds having a mercapto group or a disulfide bond, JP-B-45-8506, JP-A-SHO No. 52-20832, No. 53-3
2735, U.S. Pat. No. 3,706,561 and the like, thiourea compounds, and halides such as iodine and bromine ions are preferable because of their excellent bleaching power.

In addition, the bleach-fixing solution used in the present invention includes bromide (eg, potassium bromide, sodium bromide, ammonium bromide) or chloride (eg, potassium chloride, sodium chloride, ammonium chloride) or iodide (eg,
A rehalogenating agent such as ammonium iodide) may 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 alkali metal or ammonium salts thereof, or corrosion inhibitors such as ammonium nitrate and guanidine Etc. can be added.

The bleach-fixing solution or the fixing agent used in the fixing solution according to the present invention includes known fixing agents, that is, thiosulfates such as sodium thiosulfate and ammonium thiosulfate; thiocyanates such as sodium thiocyanate and ammonium thiocyanate; ethylene. Bisthioglycolic acid, 3,6-dithia-1,8
A thioether compound such as octanediol and a water-soluble silver halide solubilizer such as thioureas, and these may be used alone or in admixture 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 ammonium thiosulfate as the thiosulfate. The amount of fixer per 1 is 0.
It is preferably 3 to 2 mol, more preferably 0.5 to 1.0 mol. The pH range of bleach-fixing solution or fixing solution is 3-10
Is preferable, and 5-9 is particularly preferable.

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

The bleach-fixing solution or the fixing solution according to the present invention may be a sulfite (for example, sodium sulfite, potassium sulfite,
Ammonium sulfite, etc.), bisulfite (eg, ammonium bisulfite, sodium bisulfite, potassium bisulfite, etc.), metabisulfite (eg, potassium metabisulfite, sodium methyl bisulfite, ammonium metabisulfite, etc.) ) And the like, which contains a sulfite ion-releasing compound. These compounds are converted to sulfite ions by about 0.02
˜0.50 mol / content is preferred, and more preferably 0.04 to 0.40 mol / content.

As a preservative, it is common to add sulfite,
In addition, ascorbic acid, carbonyl bisulfite adduct, sulfinic acids described in Japanese Patent Application No. 62-142941, or carbonyl compounds may be added.

Further, a buffer, an optical brightener, a chelating agent, an antifoaming agent, a fungicide, and the like may be added as necessary.

The shorter the processing time of the desilvering process in the present invention, the more remarkable the effect of the present invention, and the desilvering process time is 2 minutes or less, more preferably 1 minute or less.

The silver halide color photographic light-sensitive material used in the present invention is generally washed with water and / or stabilized after desilvering such as fixing or bleach-fixing.

The amount of rinsing water in the rinsing process varies widely depending on the characteristics of the light-sensitive material (for example, depending on the material used such as couplers) and application, the rinsing water temperature, the number of rinsing tanks (number of stages), the replenishment method such as countercurrent and forward flow, and various other conditions. Can be set. Among these, the relationship between the number of flush tanks and the water volume in the multi-stage countercurrent system is described in the Journal of the Society of Motion Picture and Television Engineers (Journa
l of the Society of Motion Picture and Television
Engineers) 64, pp. 248-253 (May 1955 issue). Usually, the number of stages in the multi-stage countercurrent system is preferably 2 to 6, and particularly preferably 2 to 4.

According to the multi-stage countercurrent method, the amount of washing water can be greatly reduced,
For example, 1 or less, preferably 0.5 or less per 1 m ^{2 of the} light-sensitive material is possible, and the effect of the present invention is remarkable, but bacteria are propagated due to the increase in the residence time of water in the tank, and the suspended matter generated is the light-sensitive material. Problems such as adherence to
In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, the method of reducing calcium and magnesium described in Japanese Patent Application No. 131632/1986 can be used very effectively. Further, the isothiazolone compounds and siabendazoles described in JP-A-57-8542, 61-12
Chlorinated germicides such as chlorinated sodium isocyanurate described in No. 0145, benzotriazole described in Japanese Patent Application No. 60-105487, copper ions and others Hiroshi Horiguchi, "Chemistry of Antibacterial and Antifungal Agents", edited by Hygiene Engineering Society The sterilizing agents described in "Sterilization, Sterilization, and Antifungal Technologies of Microorganisms" and "Encyclopedia of Antibacterial and Antifungal Agents" edited by Japan Society for Antibacterial and Antifungal Agents can be used.

Further, for washing water, a surfactant as a draining agent and a chelating agent typified by EDTA as a water softener can be used.

It is also possible to carry out treatment with the stabilizing solution directly after the above washing step or without going through the washing step. A compound having an image stabilizing function is added to the stabilizing solution. For example, an aldehyde compound typified by formalin or a film suitable for stabilizing a dye is used.
Examples thereof include buffering agents for adjusting the pH and ammonium compounds. Further, in order to prevent the growth of bacteria in the liquid and impart fungicidal properties to the processed photosensitive material, the above-mentioned various bactericides and fungicides can be used.

Further, a surfactant, an optical brightener and a hardener may be added. In the processing of the light-sensitive material of the present invention, when the stabilization is directly carried out without a water washing step, the method disclosed in JP-A-57-
8543, 58-14834, 59-184343, 60-22034
No. 5, No. 60-238832, No. 60-239784, No. 60-239749
All known methods described in Nos. 61-4054 and 61-118749 can be used.

In addition, it is also a preferred embodiment to use a chelating agent such as 1-hydroxyethylidene-1,1-diphosphonic acid or ethylenediaminetetramethylenephosphonic acid, or a magnesium or bismuth compound.

In addition, the stabilizing solution has a multi-stage counter-current system as well as the washing water, so that the amount of water is greatly increased (1 or less, more preferably 0.5 or less).
You can do the following). Replenishment of washing water or stabilizing solution may be continuous or intermittent. In the latter case, the processing is performed according to the processing amount or at regular time intervals.

The pH of the washing step or stabilizing step of the present invention is 4-10, preferably 5-8. Temperature is the application of the photosensitive material
Although it can be set variously depending on the characteristics and the like, it is generally 15 to 45 ° C, preferably 20 to 40 ° C. The time can be set arbitrarily, but the shorter the effect of the present invention is more remarkable, preferably 30 seconds to
It is 2 minutes, more preferably 30 seconds to 1 minute 30 seconds. The smaller the replenishment amount, the more preferable from the viewpoint of running cost, reduction of discharge amount, handleability, and the like, and the effect of the present invention is great.

The specific amount of replenishment is 0.5 to 50 times, preferably 3 to 40 times the carry-in amount per unit area from the pre-bath.

The liquid used in the washing and / or stabilizing step can be used in the previous step. As an example of this, the overflow of the washing water reduced by the multi-stage countercurrent method is caused to flow into a bleach-fix bath preceding the bath, and the bleach-fix bath is replenished with a concentrated solution to reduce the amount of waste liquid.

In the present invention, the total time of the bleach-fixing step and the washing or stabilizing step is preferably 3 minutes or less.

The method of the present invention can be applied to any processing step using a color developer. For example, it can be applied to the processing of color paper, color reversal paper, color direct positive light-sensitive material, color positive film, color negative film, color reversal film, etc. Application is preferred.

(Example) Hereinafter, the present invention will be illustrated by examples.

Example 1 Single-layer color photographic papers I-A to I-L having the following layer structure were prepared by changing the yellow coupler and halogen composition on a paper support laminated on both sides with polyethylene.

The coating solution is prepared by mixing and dissolving an emulsion, various chemicals, and an emulsified dispersion of a coupler. The respective preparation methods are described below.

Preparation of coupler emulsion 0.025 mol of yellow coupler and color image stabilizer (Cpd-
1) 4.4 g of ethyl acetate 27.2 cc and solvent (Solv-1) 7.
Add 7 cc and dissolve, and 185 cc of 10% gelatin aqueous solution containing 8 cc of 10% sodium dodecylbenzene sulfonate.
Emulsified and dispersed.

Next, the method for preparing the emulsion will be described.

Blue-sensitive emulsion (1 liquid) (2 solutions) Sulfuric acid (1N) 24cc (3 solutions) The following compound A (1%) 3cc (4 solutions) (5 liquids) (6 liquids) (7 liquids) (Liquid 1) was heated to 76 ° C., and (Liquid 2) and (Liquid 3) were added.

Then, (4 solution) and (5 solution) were added simultaneously spending 10 minutes.

After another 10 minutes, (6 solution) and (7 solution) were added simultaneously spending 35 minutes. Five minutes after the addition, the temperature was lowered and the mixture was desalted. Water and dispersed gelatin were added to adjust the pH to 6.3 to obtain a monodisperse cubic silver chloride emulsion having an average grain size of 1.1 μm and a coefficient of variation (standard deviation divided by the average grain size: s / d) of 0.10.

To this emulsion was added the following blue spectral sensitizing dye (S-1)
A 0.6% solution was added to cc, and 0.05 μg of AgBr ultrafine grain emulsion was added at a ratio of 0.5 mol% to the host AgCl emulsion, and the mixture was aged at 58 ° C. for 10 minutes. Thereafter, sodium thiosulfate was added, the chemical sensitization was optimally performed, and a stabilizer (Stb-1) was added at 10 ^-4 mol / mol Ag.

Similarly, a part of NaCl in the 1st, 4th, and 6th liquid is KBr.
To prepare blue-sensitive emulsions having different halogen compositions.

The following layers were provided as protective layers on each blue-sensitive emulsion layer.

As a hardener for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used.

The following experiment was conducted to examine the photographic characteristics of these coated samples.

First, a gradation exposure for sensitometry was applied to the coated sample using a sensitometer (FWH type manufactured by Fuji Photo Film Co., Ltd., color temperature of light source: 3200 ° K). The exposure at this time was performed so that the exposure amount was 250 CMS with an exposure time of 1/10 second. The above material was processed in the following processing steps.

However, the composition of the color developing solution was changed as shown in Table 1 (Processes I to V). Processing process temperature Time Color development 35 ℃ 45 seconds Bleach fixing 30-36 ℃ 45 seconds Stable 30-37 ℃ 20 seconds Stable 30-37 ℃ 20 seconds Stable 30-37 ℃ 20 seconds Stable 30-37 ℃ 30 seconds Dry 70 85 ℃ 60 seconds (stabilized → 4 tank countercurrent method) The composition of each processing solution is as follows.

Color developer Benzyl alcohol See Table 1 Sodium sulfite See 〃 Ethylenediaminetetraacetic acid 2.0 g Triethanolamine 8.0 g Sodium chloride 1.4 g Potassium carbonate 25 g N-ethyl-N- (β-methanesulfonamidoethyl)
-3-Methyl-4-aminoaniline sulfate 5.0 g N, N-diethylhydroxylamine 4.2 g 5,6-dihydroxybenzene-1,2,4-trisulfonic acid 0.
3 g Fluorescent whitening agent (4,4'-diaminostilbene 2.0 g Add water 1000 ml pH (25 ° C) 10.10 Bleach-fix solution Water 400 ml Ammonium thiosulfate (70%) 100 ml Sodium sulfite 18 g Ethyne diamine Iron (III) ammonium tetraacetate 55
g Ethylenediaminetetraacetic acid disodium 3 g Glacial acetic acid 8 g Water was added to 1000 ml pH (25 ° C) 5.5 Stabilizing solution 1-Hydroxyethylidene-1,1-diphosphonic acid (60
%) 2.0 g Bismuth chloride 1.0 g 5-Chloro-2-methyl-4-isothiazolin-3-one 0.02 g 2-Methyl-4-isothiazolin-3-one 0.01 g Ammonia water (28%) 2.0 ml Water was added. The results of measuring 1000 ml pH (25 ° C) 7.0 D _min (minimum concentration) and D _max (maximum concentration) with a Macbeth densitometer are also shown in Table 1.

 However, the yellow couplers used are as follows.

Y-3 No. 11 (shown by the above compound number) Y-4 No. 12 (shown by the above compound number) From Table 1, using the yellow coupler of the present invention (I
-F) to L), and when processed with a color developing solution containing substantially no benzyl alcohol (Processes IV and V), excellent photographic characteristics having a small D _min and a large D _max can be obtained. In particular, the effect is that when the sulfite ion is not contained (treatment V), the Cl content of the emulsion is 90 mol% or more (IF,
G, J, K) is remarkable.

Example 2 As shown in Table 2, the first layer (bottom layer) to the seventh layer of the double-sided polyethylene laminated paper treated by corona discharge machining
Layers (uppermost layer) are sequentially formed by coating, and color photographic paper sample II-
A was produced. Preparation of the coating solution for each layer is as follows.
The details of the structural formulas, such as the coupler and the color image stabilizer, used in the coating solution will be described later.

The coating liquid for the first layer was prepared as follows. That is, a mixture of 200 g of yellow coupler, 93.3 g of anti-fading agent, 10 g of high boiling point solvent (p) and 5 g of solvent (q) and 600 ml of ethyl acetate as an auxiliary solvent was heated and dissolved at 60 ° C.,
The mixture was mixed with 3,300 ml of a 5% gelatin aqueous solution containing 330 ml of a 5% aqueous solution of alkanol B (trade name, alkylnaphthalene sulfonate, manufactured by DuPont). Next, this liquid was emulsified using a colloid mill to prepare a coupler dispersion. Ethyl acetate was distilled off from the dispersion under reduced pressure to give a sensitizing dye for a blue-sensitive emulsion layer and 1-methyl-2-mercapto-5-.
Emulsion 1,4 with acetylamino-1,3,4-triazole
Add to 00g (including 96.7g as Ag, 170g gelatin),
Further, 2,600 g of a 10% gelatin aqueous solution was added to prepare a coating solution. The coating liquids for the second to seventh layers were prepared according to the composition shown in Table 2 according to the first layer.

The following sensitizing dyes were used in each emulsion layer.

Blue-sensitive emulsion layer; Anhydro-5-methoxy-5'-methyl-3,3'-disulfopropylselenacyanine hydroxide Green sensitive emulsion layer; Anhydro-9-ethyl-5,5'-diphenyl-3,3 ' -Disulfoethyloxacarbocyanine hydroxide red-sensitive emulsion layer; 3,3'-diethyl-5-methoxy-9,9 '
-(2,2-dimethyl-1,3-propano) thiazicarbocyanine iodide The following compounds were used as stabilizers for each emulsion layer.

1-methyl-2-mercapto-5-acetylamino-
1,3,4-Triazole The following substances were used as anti-irradiation dyes.

4- (3-carboxy-5-hydroxy-4- (3-
(3-Carboxy-5-oxo-1- (4-sulfonatophenyl) -2-pyrazolin-4-ylidene) -1-propenyl-1-pyrazolyl) benzenesulfonate-di-potassium salt N, N '-( 4,8-dihydroxy-9,10-dioxo-3,7
-Disulfonatoanthracene-1,5-diyl) bis (aminomethanesulfonate) -tetrasodium salt Also, 1,2-bis (vinylsulfonyl) ethane was used as a hardening agent.

 The couplers used are as follows.

Next, the yellow coupler of Sample II-A was replaced with the following II-B-
Samples II-B, II-C, II- in equimolar substitution with II-G
D, II-E, II-F and II-G were prepared.

II-E Coupler No. 6 of the present invention (indicated by the above compound number) II-F Coupler No. 11 of the present invention (indicated by the above compound number) II-G Coupler No. 12 of the present invention (in the above compound number) Numbered) Continuous exposure (running test) until the above light-sensitive materials II-A to II-G are imagewise exposed and replenished with twice the tank capacity of color development in the following processing steps using a paper processor. I went.

The composition of each processing solution is as follows.

Bleach-fixing solution (same as tank solution and replenisher) Water 400 ml Ammonium thiosulfate (70%) 100 ml Sodium sulfite 17 g Ethylenediaminetetraacetic acid iron (III) ammonium 55
g Ethylenediaminetetraacetic acid disodium 5 g Glacial acetic acid 9 g Water added 1000 ml pH (25 ° C) 5.40 Stabilizer (same as tank solution and replenisher) Formalin (37%) 0.1 g Formalin-sulfite adduct 0.7 g 5 -Chloro-2-methyl-4-isothiazolin-3-one 0.02 g 2-Methyl-4-isothiazolin-3-one 0.01 g Copper sulfate 0.005 g Add water to 1000 ml pH (25 ℃) 4.0 Add to each running solution. In contrast, wedge-shaped post-exposure sample II
Table 3 shows the results obtained by treating -A to II-G and measuring the yellow density D _min and D _max .

According to the present invention, sufficiently excellent photographic characteristics with a small D _{min and a} large D _max were obtained.

Example 3 The same test was carried out by using the yellow couplers of Nos. 1, 2, 4, 9, 16 and 21 of the present invention instead of the yellow coupler used in the sample II-E of Example 2, respectively. Similarly, excellent photographic performance with a small D _{min and a} large D _max was obtained.

Example 4 A running test was conducted in the same manner as in Example 2 except that triethanolamine in the color developer of Example 2 was changed to the compound below and diethylhydroxylamine was changed to the compound below. was gotten.

(Effect of the Invention) According to the method of the present invention, it is possible to remarkably improve the color developability and effectively suppress the fogging, even though the color developing solution contains substantially no benzyl alcohol.

Claims (1)

(57) [Claims] 1. A silver halide containing at least one silver chlorobromide emulsion or silver chloride emulsion containing 90 to 100 mol% of silver chloride and containing at least one yellow coupler represented by the following general formula (I). Color photographic light-sensitive material
A method for processing a silver halide color photographic light-sensitive material, which comprises processing with a color developer containing substantially no benzyl alcohol and containing no sulfite ion. General formula (I) (In the formula, R ¹ represents a tertiary alkyl group or an aryl group. R ² represents a halogen atom or an alkoxy group. R ³
Represents an alkyl group or an aryl group. Y ¹ represents a divalent linking group. X represents a coupling-off group. )