JPH073572B2 - Processing method of silver halide color 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, does not use benzyl alcohol, and the color development time is significantly shortened and stabilized. Regarding the processing method.

(Prior Art) In order to enhance the color developability of color photographic light-sensitive materials,
Various developing agent penetrants have been studied, and in particular, a method of adding benzyl alcohol to a color developing solution to accelerate color development is currently widely used in the processing of color photographic light-sensitive materials, especially color paper, because of its large color-promoting effect. Used.

However, when benzyl alcohol is used, its solubility in water is low, and thus diethylene glycol, triethylene glycol, or the like is required as a solvent. However, since these compounds including benzyl alcohol have high pollution load values of BOD and COD, it is preferable to remove benzyl alcohol for the purpose of reducing the pollution load.

Further, even if the solvent is used, it takes time to dissolve benzyl alcohol, and therefore it is preferable not to use benzyl alcohol for the purpose of reducing the preparation work.

Further, when benzyl alcohol is brought into a bleaching bath or a bleach-fixing bath which is a post-bath, it causes the formation of a leuco dye which is a cyan dye, which causes a decrease in color density. Further, since the washing-out speed of the developer component is delayed, the image storability of the processed light-sensitive material may be adversely affected. Therefore, it is preferable not to use benzyl alcohol for the above reasons.

In the conventional color development, it was generally processed in 3 to 4 minutes, but it has been desired that the processing time be shortened due to the recent shortening of delivery time for finishing and reduction of lab work. It was

However, when benzyl alcohol, which is a color-forming accelerator, is removed and the development time is shortened, it is inevitable that the color density is remarkably lowered.

In order to solve this problem, various color development accelerators (for example, U.S. Patent Nos. 2,950,970, 2,515,147, and 2,496,
903, 2,304,925, 4,038,075, 4,119,462
No., British Patents 1,430,998, 1,455,413, JP-A-53-
No. 15831, No. 55-62450, No. 55-62451, No. 55-62452
No. 55-62453, 58-50536, 60-162256,
Even when the compounds described in JP-B-51-12422 and JP-B-55-49728) are used in combination, a sufficient color density has not been obtained.

Also, a method of incorporating a color developing agent (for example, US Pat.
719,492, 3,342,559, 3,342,597, JP-A-56
-6235, 56-16133, 57-97531, 57-8356
Even if the method described in No. 5) is used, color development is slow and fog is generated, and therefore it is not an appropriate method.

Also, a method using a silver chloride emulsion (see, for example, JP-A-58-95).
No. 345, No. 59-232342, No. 60-19140, etc.) is not suitable for practical use due to high fog.

As described above, a method for obtaining a sufficient color image in a short time by using a color developing solution which does not substantially contain benzyl alcohol has not been found.

(Problems to be Solved by the Invention) Therefore, in the present invention, benzyl alcohol is not substantially contained, and fog is small even in a short time processing such as a color development time of 2 minutes 30 seconds or less, and sufficient. The object of the present invention is to provide a processing method capable of obtaining excellent color development.

(Means for Solving Problems) The object of the present invention was achieved by the method described below. That is, (1) a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a reflective support is substantially free of benzyl alcohol and is represented by the following general formula (I). Compound, tetramethylammonium acetate, choline, choline chloride, hydantoic acid, allylamine, aminoguanidine sulphate, o
-Aminobenzoic acid, o-aminobenzyl alcohol, and a color developer containing at least one selected from the group consisting of: a silver halide color photographic light-sensitive material characterized by being processed for 2 minutes and 30 seconds or less. Processing method.

(2) The method for processing a silver halide color photographic light-sensitive material according to (1) above, wherein the silver halide color photographic light-sensitive material contains a magenta coupler represented by the following general formula (II).

It was found to be effectively achieved in.

General formula (I) (R ¹ is an alkyl group having ¹ to 10 carbon atoms,
R ² and R ³ are each a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. ) General formula (II) (In the formula, Rb represents a hydrogen atom or a substituent, Y ₁ represents a group capable of splitting off by a coupling reaction with an oxidized product of an aromatic primary amine developing agent, and Za, Zb or Zc represents a methine group or a substituted methine group. , = N- or -NH-, and a Za-Zb bond and Zb
One of the -Zc bonds is a double bond and the other is a single bond. Next, the general formula (I) will be described in detail.

General formula (I) R ₁ is an alkyl group having ₁ to 10 carbon atoms, preferably an alkyl group having 2 to 5 carbon atoms. R ₂ and R ₃
Are each a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

Specific examples of the case where R _{1 to} R _{3 in} the general formula (I) represent an alkyl group include methyl group, ethyl group, i-propyl group, n
-Hexyl group, cyclohexyl group, decyl group, and the like.

These alkyl groups may be substituted with a chlorine atom, a carboxyl group, an alkoxy group, etc.,
When R ₁ , R ₂ and R ₃ represent an alkyl group, R ₁ and R ₂ , R ₁ and R ₃ ,
R ₂ and R ₃ or R ₁ and R ₂ and R ₃ may be linked to each other to form a ring.

The nitrogen-containing heterocycle may further contain a hetero atom (eg oxygen atom, sulfur atom, etc.).

The compound represented by the general formula (I) is an inorganic acid (for example,
It may take the form of a salt of hydrochloric acid, sulfuric acid, etc.) or an organic acid (eg, oxalic acid, acetic acid, p-toluenesulfonic acid, etc.).

The specific examples of the compounds used in the present invention are shown below,
It is not limited to these.

I-1 Trimethylamine I-2 Diethylamine I-3 Methylamine I-4 Triethylamine I-5 Dipropylamine I-6 Diisopropylamine I-7 Ethylamine I-8 Dimethylamine I-9 6-Aminohexanoic Acid I-10 Glycine I -11 1,1-aminoundeconic acid I-12 L-(+)-cysteine hydrochloride I-13 benzylamine I-14 D, L-serine I-15 morpholine I-16 o-aminobenzyl alcohol I-17 Quinuclidine I-18 Hydroxylethylmorpholine I-19 Tetramethylammonium acetate I-20 Choline I-21 Choline chloride I-22 Hydantoinic acid I-23 Allylamine I-24 Aminoguanidine sulphate I-25 o-Aminobenzoic acid The above compounds and The compound according to claim (1) is an organic compound or a non-organic compound. It may form salts with various acids of the machine.

The amount of these compounds added to the color developing solution is preferably 0.01 g to 20 g, more preferably 0.1 g per color developing solution.
It is from 1g to 10g.

Next, details of the magenta coupler represented by the general formula (II) will be described.

In the general formula [II], Rb represents a hydrogen atom or a substituent, and Y ₁ represents a hydrogen atom or a group capable of leaving by a coupling reaction with an oxidized product of an aromatic primary amine developer.
Za, Zb and Zc are methine, substituted methine, = N- or-
Representing NH-, one of the Za-Zb bond and the Zb-Zc bond is a double bond and the other is a single bond. When Zb-Zc is a carbon-carbon double bond, it includes the case where it is part of an aromatic ring. It also includes the case where R _b or Y ₁ forms a dimer or higher multimer. Further, when Za, Zb or Zc is a substituted methine, it also includes the case where the substituted methine forms a dimer or higher multimer.

In the general formula [III], a multimer means a compound having two or more groups represented by the general formula [III] in one molecule, and a bis form and a polymer coupler are also included in this. Here, the polymer coupler may be a homopolymer consisting only of a monomer having a portion represented by the general formula [III] (preferably having a vinyl group, hereinafter referred to as vinyl monomer), or an aromatic primary amine developing agent. Copolymers may be made with non-chromogenic, ethylene-like monomers that do not couple with the oxidation products of.

The compound represented by the general formula [III] is a 5-membered ring-5-membered ring condensed nitrogen heterocyclic type coupler, and its coloring mother nucleus shows isoelectronic aromaticity with naphthalene, and is generally called azapentalene. It has a structure. Among the couplers represented by the general formula [III], preferred compounds are 1H-imidazo [1,2-b] pyrazoles and 1H-pyrazolo [1,5-
b] pyrazoles, 1H-pyrazolo [5,1-c] [1,2,4]
Triazoles, 1H-pyrazolo [1,5-b] [1,2,4] triazoles, 1H-pyrazolo [1,5-d] tetrazole and 1H-pyrazolo [1,5-a] benzimidazoles There are general formulas [IV] [V] [VI] [VII] [V
Of these, particularly preferable compounds represented by III] and [IX] are [VI] and [VII].

Substituents R ₇ , R ₈ and R ₉ in the general formulas [IV] to [IX] are hydrogen atom, halogen atom, alkyl group, aryl group, heterocyclic group, cyano group, alkoxy group, aryloxy group, heterocyclic ring. Oxy group, acyloxy group, carbamoyloxy group, silyloxy group, sulfonyloxy group, acylamino group, anilino group, ureido group, imide group, sulfamoylamino group, carbamoylamino group, alkylthio group, arylthio group, heterocyclic thio group, Alkoxycarbonylamino group, aryloxycarbonylamino group,
Represents a sulfonamide group, a carbamoyl group, an acyl group, a sulfamoyl group, a sulfonyl group, a sulfinyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, Y ₁ represents a hydrogen atom, a halogen atom, a carboxy group, or an oxygen atom, a nitrogen atom or a sulfur atom. It represents a group that couples with a carbon at the coupling position via an atom and is coupled off.

R ₇ , R ₈ and R ₉ also include the case where Y ₁ is a divalent group and forms a bis form. Further, when the moiety represented by the general formulas [IV] to [IX] is present in the vinyl monomer, R ₇ , R ₈ or R ₉ represents a mere bond or a linking group, and a general formula The vinyl groups are bonded to the moieties represented by [IV] to [IX].

More specifically, R ₇ , R ₈ and R ₉ are each a hydrogen atom, a halogen atom (eg, chlorine atom, bromine atom, etc.), an alkyl group (eg, methyl group, propyl group, t-butyl group, trifluoromethyl group, Tridecyl group, 3- (2,4-di-t
-Amylphenoxy) propyl group, 2-dodecyloxyethyl group, 3-phenoxypropyl group, 2-hexylsulfonyl-ethyl group, cyclopentyl group, benzyl group,
Etc.), aryl groups (for example, phenyl group, 4-t-butylphenyl group, 2,4-di-t-amylphenyl group, 4-
Tetradecanamidophenyl group, etc.), heterocyclic group (eg, 2-furyl group, 2-thienyl group, 2-pyrimidinyl group, 2-benzothiazolyl group, etc.), cyano group, alkoxy group (eg, methoxy group, ethoxy group) , 2-methoxyethoxy group, 2-dodecyloxyethoxy group, 2-methanesulfonylethoxy group, etc.), aryloxy group (eg, phenoxy group, 2-methylphenoxy group, 4
-T-butylphenoxy group, etc.), heterocyclic oxy group (eg, 2-benzimidazolyloxy group, etc.), acyloxy group (eg, acetoxy group, hexadecanoyloxy group, etc.), carbamoyloxy group (eg, N
-Phenylcarbamoyloxy group, N-ethylcarbamoyloxy group, etc.), silyloxy group (eg, trimethylsilyloxy group, etc.), sulfonyloxy group (eg, dodecylsulfonyloxy group, etc.), acylamino group (eg, acetamide group) , Benzamide group, tetradecanamide group, α- (2,4-di-t-amylphenoxy) butyramide group, γ- (3-t-butyl-4-hydroxyphenoxy) butyramide group, α- {4- (4 −
Hydroxyphenylsulfonyl) phenoxy} decanamide group, etc.), anilino group (for example, phenylamino group, 2-chloroanilino group, 2-chloro-5-tetradecaneamidoanilino group, 2-chloro-5-dodecyloxycarbonylanilino group) , N-acetylanilino group, 2
-Chloro-5- {α- (3-t-butyl-4-hydroxyphenoxy) dodecanamide} anilino group, etc.), ureido group (eg, phenylureido group, methylureido group, N, N dibutylureido group) Groups, etc.), imide groups (eg, N-succinimide group, 3-benzylhydantoinyl group, 4- (2-ethylhexanoylamino) phthalimide group, etc.), sulfamoylamino groups (eg, N,
N-dipropylsulfamoylamino group, N-methyl-
N-decylsulfamoylamino group, etc., alkylthio group (for example, methylthio group, octylthio group, tetradecylthio group, 2-phenoxyethylthio group, 3-phenoxypropylthio group, 3- (4 -T-butylphenoxy) propylthio group, etc.), an arylthio group (for example,
Phenylthio group, 2-butoxy-5-t-octylphenylthio group, 3-pentadecylphenylthio group, 2-carboxyphenylthio group, 4-tetradecanamidophenylthio group, etc.), heterocyclic thio group (Eg, 2-benzothiazolylthio group, etc.), alkoxycarbonylamino group (eg, methoxycarbonylamino group, tetradecyloxycarbonylamino group, etc.), aryloxycarbonylamino group (eg, phenoxycarbonylamino group) , 2,4-di-tert-butylphenoxycarbonylamino group, etc.), sulfonamide group (for example, methanesulfonamide group, hexadecanesulfonamide group, benzenesulfonamide group, p-toluenesulfonamide group, octadecanesulfone) Amido group, 2-methyloxy-5-t-butylbenze Sulfonamido group, etc.), carbamoyl group (eg, N-ethylcarbamoyl group, N,
N-dibutylcarbamoyl group, N- (2-dodecyloxyethyl) carbamoyl group, N-methyl-N-dodecylcarbamoyl group, N- {3- (2,4-di-tert-amylphenoxy) propyl} carbamoyl group, etc. ), An acyl group (eg, acetyl group, (2,4-di-tert-amylphenoxy) acetyl group, benzoyl group, etc.), a sulfamoyl group (eg, N-ethylsulfamoyl group, N, N
-Dipropylsulfamoyl group, N- (2-dodecyloxyethyl) sulfamoyl group, N-ethyl-N-dodecylsulfamoyl group, N, N-diethylsulfamoyl group, etc., sulfonyl group (for example, Methanesulfonyl group, octanesulfonyl group, benzenesulfonyl group, toluenesulfonyl group, etc.), sulfinyl group (eg,
Octansulfinyl group, dodecylsulfinyl group, phenylsulfinyl group, etc.), alkoxycarbonyl group (eg, methoxycarbonyl group, butyloxycarbonyl group, dodecylcarbonyl group, octadecylcarbonyl group, etc.), aryloxycarbonyl A group (for example, a phenyloxycarbonyl group, 3-pentadecyloxy-
Carbonyl group, etc., and X is a hydrogen atom, a halogen atom (eg, chlorine atom, bromine atom, iodine atom, etc.),
Carboxyl group, or a group linked by an oxygen atom (for example, acetoxy group, propanoyloxy group, benzoyloxy group, 2,4-dichlorobenzoyloxy group, ethoxyoxaloyloxy group, pyrvinyloxy group, cinnamoyloxy group, Phenoxy group, 4-cyanophenoxy group, 4-methanesulfonamide phenoxy group, 4-methanesulfonylphenoxy group, α-naphthoxy group, 3-pentadecylphenoxy group, benzyloxycarbonyloxy group, ethoxy group, 2-cyanoethoxy group, benzyloxy group, 2-phenethyloxy group, 2-phenoxyethoxy group, 5-phenyltetrazolyloxy group, 2-benzothiazolyloxy group, etc.), and a nitrogen atom. Group (for example, benzenesulfonamide group, N-ethyltoluenesulfonamide group Heptafluorobutanamide group, 2,3,4,5,6-pentafluorobenzamide group, octanesulfonamide group, p-cyanophenylureido group, N, N-diethylsulfamoylamino group, 1-piperidyl group, 5,5-Dimethyl-2,4-dioxo-3-oxazolidinyl group, 1-benzyl-ethoxy-3-hydantoinyl group, 2N-1,1-dioxo-3 (2H) -oxo-1,2
-Benzisothiazolyl group, 2-oxo-1,2-dihydro-1-pyridinyl group, imidazolyl group, pyrazolyl group, 3,5-diethyl-1,2,4-triazol-1-yl,
5- or 6-bromo-benzotriazol-1-yl, 5-methyl-1,2,3,4-triazol-1-yl group, benzimidazolyl group, 3-benzyl-1-hydantoinyl group, 1-benzyl- 5-hexadecyloxy-
3-hydantoinyl group, 5-methyl-1-tetrazolyl group, 4-methoxyphenylazo group, 4-pivaloylaminophenylazo group, 2-hydroxy-4-propanoylphenylazo group, etc.), sulfur A group linked by atoms (for example, a phenylthio group, a 2-carboxyphenylthio group,
2-Ketoxy-5-t-octylphenylthio group, 4-
Methanesulfonylphenylthio group, 4-octanesulfonamidophenylthio group, 2-butoxyphenylthio group, 2- (2-hexanesulfonylethyl) -5-tert
-Octylphenylthio group, benzylthio group, 2-cyanoethylthio group, 1-ethoxycarbonyltridecylthio group, 5-phenyl-2,3,4,5-tetrazolylthio group,
2-benzothiazolylthio group, 2-dodecylthio-5-
Thiofenylthio group, 2-phenyl-3-dodecyl-1,
2,4-triazolyl-5-thio group).

When R ₇ , R ₈ , R ₉ or is a divalent group to form a bis derivative, the divalent group may be described in more detail. A substituted or unsubstituted alkylene group (for example, a methylene group, an ethylene group, etc.) , 1,10-decylene _{group, -CH 2 CH 2 -O-CH} 2 CH 2 -,
Etc.) a substituted or unsubstituted phenylene group (eg, 1,4-
Phenylene group, 1,3-phenylene group, -NHCO-R _7, -CONH- group (R ₇ represents a substituted or unsubstituted alkylene group or phenylene group.

When the one represented by the general formulas [IV] to [IX] is in the vinyl monomer, the linking group represented by R ₇ , R ₈ or R ₉ is an alkylene group (a substituted or unsubstituted alkylene group , For example, methylene group, ethylene group, 1,10-decylene group, —CH ₂ CH ₂ OCH ₂ CH ₂ —, etc., phenylene group (substituted or unsubstituted phenylene group, for example, 1,4-phenylene group) , 1,3-phenylene group, -NHCO-, -CONH-, -O-, -OCO- and aralkylene groups (for example, Etc.) and groups that are established by combining those selected from the above.

The vinyl group in the vinyl monomer has the general formula [IV]
In addition to those represented by [IX], it also includes the case of having a substituent. A preferable substituent is a hydrogen atom, a chlorine atom, or a lower alkyl group having 1 to 4 carbon atoms.

Acrylic acid, α is used as the non-color-forming ethylene-like monomer that does not couple with the oxidation product of the aromatic primary amine developer.
-Chloroacrylic acid, α-alacrylic acid (eg, methacrylic acid) and esters or amides derived from these acrylic acids (eg, acrylamide, n-butylacrylamide, t-butylacrylamide, diacetoneacrylamide, methacrylamide) , Methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, t-butyl acrylate, iso-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate And β-hydroxymethacrylate), methylenedibisacrylamide, vinyl esters (eg vinyl acetate, vinyl propionate) And vinyl laurate),
Acrylonitrile, methacrylonitrile, aromatic vinyl compounds (eg, styrene and its derivatives, vinyltoluene, divinylbenzene, vinylacetophenone and sulfostyrene), itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ether ( For example, vinyl ethyl ether), maleic acid, maleic anhydride, maleic acid ester, N-vinyl-2-pyrrolidone, N-vinyl pyridine, and 2- and 4-
Vinyl pyridine and the like. It also includes the case where two or more non-color-forming ethylenically unsaturated monomers used here are used together.

Examples of compounds of the couplers represented by the general formulas [III] to [VIII], synthetic methods, and the like are described in the following documents.

The compound of the general formula [III] is disclosed in JP-A-59-162548, the compound of the general formula [IV] is disclosed in JP-A-60-43659, and the compound of the general formula [V] is disclosed in JP-B-47-27411. , The general formula [V
The compounds of I) are disclosed in JP-A-59-171956 and JP-A-60-172982.
Etc., the compound of the general formula [VII] is described in JP-A-60-33552, and the compound of the general formula [VIII] is described in US Pat.
432 etc., respectively.

Further, JP-A-58-42045, JP-A-59-214854 and JP-A-59-177.
553, 59-177554, and 59-177557 and the like highly colored ballast groups, the general formula [III] ~ [V
It applies to any of the compounds of III].

Specific examples of the pyrazoloazole-based coupler used in the present invention are shown below, but the invention is not limited thereto.

These couplers are generally used in an amount of 2 × 10 ⁻³ to 5 × 10 ⁻¹ mol, preferably 1 × 10 ⁻² mol per mol of silver in the emulsion layer.
Mol to 5 × 10 ^-1 mol.

The couplers and the like can be used in combination of two or more kinds in the same layer in order to satisfy the characteristics required for the light-sensitive material, and it is of course possible to add the same compound to two or more different layers.

To introduce the coupler into the silver halide emulsion layer, known methods such as the method described in US Pat. No. 2,322,027 are used. For example, phthalic acid alkyl ester (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid ester (diphenyl phosphonate, triphenyl phosphonate, tricresyl phosphonate, dioctyl butyl phosphonate), citric acid ester (eg acetyl) Tributyl citrate), benzoic acid esters (eg octyl benzoate), alkylamides (eg diethyllaurylamide), fatty acid esters (eg dibutoxyethyl succinate, diethyl azelate), trimesic acid esters (eg tributyl trimesate)
Or an organic solvent having a boiling point of about 30 ° C. to 150 ° C., for example, lower alkyl acetate such as ethyl acetate and butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate,
After being dissolved in methyl cellosolve acetate or the like, it is dispersed in a hydrophilic colloid. The high boiling point organic solvent and the low boiling point organic solvent may be mixed and used.

The "reflective support" that can be used in the present invention is one that enhances the reflectivity and makes the dye image formed on the silver halide emulsion layer clear, and such a reflective support has an oxidation property on the support. Examples include those coated with a hydrophobic resin containing a light reflecting substance such as titanium, zinc oxide, calcium carbonate and calcium sulfate dispersed therein, and those using a hydrophobic resin containing a light reflecting substance dispersed therein as a support. For example, baryta paper, polyethylene-coated paper, polypropylene-based synthetic paper, a transparent support provided with a reflective layer or in combination with a reflective material, such as a glass plate, polyethylene terephthalate, polyester film such as cellulose triacetate or cellulose nitrate, Polyamide film, Polycarbonate film,
There are polystyrene films and the like, and these supports can be appropriately selected depending on the purpose of use.

The color developer used in the present invention contains substantially no benzyl alcohol. Not containing substantially 2.0m
It has a benzyl alcohol concentration of 1 / l or less, and preferably contains no benzyl alcohol.

The color development time is 2 minutes 30 seconds or less, preferably 20 seconds to 2 minutes 30 seconds, and more preferably 40 seconds to 2 minutes 00 seconds. The term "color development time" as used herein refers to the time from the contact of the light-sensitive material with the color developing solution to the contact with the processing solution of the next bath, and includes so-called moving time.

The color developing solution used for the development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. As the color developing agent, a p-phenylenediamine compound is preferably used, and a typical example thereof is 3-methyl-4-amino-N, N-
Diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxylethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4 -Amino-N-ethyl-N-β-methoxyethylaniline and their sulfates, hydrochlorides or p-toluenesulfonates, etc. may be mentioned.

The color developer used in the present invention preferably has a pH of 9 to 1.
2, more preferably from 9 to 11.0, and the color developing solution may contain other known developing solution component compounds.

For example, caustic soda, caustic potash, sodium carbonate, potash carbonate, tertiary sodium phosphate, third alkaline buffer and pH buffering agent
Potassium phosphate, potassium metaborate, borax, etc. are used alone or in combination. Further, for the purpose of giving a buffering ability, convenience of preparation, or increasing ionic strength, further, disodium hydrogen phosphate or potassium, potassium dihydrogen phosphate or sodium, sodium bicarbonate or potassium, boric acid, etc. , Various salts such as alkali nitrate, alkali sulfate and the like are used.

In addition, various chelating agents can be used in the color developing solution to prevent precipitation of calcium and magnesium. Examples thereof include polyphosphates, aminopolycarboxylic acids, phosphonocarboxylic acids, aminopolyphosphonic acids, 1-hydroxyalkylidene-1,1-diphosphonic acids and the like.

If necessary, any development accelerator can be added to the car developer. For example, U.S. Patent No. 2,648,604, Japanese Patent Publication No.44-9503
No. 3, U.S. Pat. No. 3,171,247, various pyrimidium compounds and other cationic compounds, cationic dyes such as phenosafranine, neutral salts such as thallium nitrate and potassium nitrate, JP-B-44-9304, U.S. Pat. , 53
3,990, 2,531,832, 2,950,970, 2,577,127
Polyethylene glycol and its derivatives described in No. 3, nonionic compounds such as polythioethers, US Pat.
The thioether compounds described in No. 242 may be used.

Further, a sulfite salt represented by sodium sulfite, potassium sulfite, potassium bisulfite, sodium bisulfite, or the like, which is usually used as a preservative, can be added if necessary. The addition amount is preferably as small as possible if the homeostasis can be maintained, 0 to
5 g / l, more preferably about 0 to 3 g / l.

Further, hydroxylamines may be added as a preservative. Hydroxylamines include hydroxylamine, N, N-dimethylhydroxylamine, N, N-diethylhydroxylamine, N, N-di (methoxyethyl) hydroxylamine, etc., which form salts with various acids. You can do it. The amount of these hydroxylamines added is preferably as small as possible so long as the preservability is maintained, and is 0 to 10 g, preferably 0 to 6 g, per 1 color developer.

In the present invention, an optional antifoggant can be added to the color developer, if necessary. As the antifoggant, alkali metal halides such as potassium bromide, sodium chloride and potassium iodide and organic antifoggants can be used.
Two or more kinds of these antifoggants may be used in combination, but if fog is prevented, the addition amount thereof is preferably small.

Examples of the organic antifoggant include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2 -Thiazolylmethyl-benzimidazole, nitrogen-containing heterocyclic compounds such as hydroxyazaindolizine and mercapto-substituted heterocyclic compounds such as 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzimidazole and 2-mercaptobenzothiazole, and further thiosalicylic acid Such mercapto-substituted aromatic compounds can be used. Particularly preferred are nitrogen-containing heterocyclic compounds. These antifoggants may be eluted from the color light-sensitive material during processing and accumulated in the color developing solution.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed at the same time as the fixing process, or may be performed individually. Examples of the bleaching agent include compounds of polyvalent metals such as iron (III), cobalt (III), chromium (VI), and copper (II), peracids, quinones, nitro compounds, and the like. Phelicyanide as a typical bleaching agent; dichromate; organic complex salt of iron (III) or cobalt (III),
For example, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, and 1,3-diamino-2-propanoltetraacetic acid, or complex salts of organic acids such as citric acid, tartaric acid, and malic acid; persulfates; manganic acid. Salt; nitrosophenol and the like can be used. Of these, the following bleaching agents are preferred.

Ethylenediaminetetraacetic acid iron (III) salt Diethylenetriaminetetraacetic acid iron (III) salt Methyliminodiacetic acid iron (III) salt Cyclohexanediaminetetraacetic acid iron (III) salt 1,3-diaminopropanetetraacetic acid iron (III) salt Bleaching solution and bleach fixing The pH of the liquid is preferably 3 to 9, more preferably 4 to 8. In order to adjust the pH, various acids such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid and citric acid, and alkalis such as caustic soda and ammonia may be added if necessary.

If necessary, various accelerators may be used in combination with the bleaching solution and the bleach-fixing solution.

After the bleach-fixing process or the fixing process, a washing process is usually performed. Various known compounds may be added to the water washing step for the purpose of preventing precipitation and saving water. For example, in order to prevent precipitation, water softeners such as inorganic phosphoric acid, aminopolycarboxylic acid, and organic phosphoric acid, bactericides and antifungal agents that prevent the generation of various bacteria, algae, and molds, magnesium salts and aluminum. A hardening agent typified by a salt, or a surfactant for preventing drying load and unevenness can be added if necessary. Or West, Photographik Science and Engineering (LEWest, Phot.Sci.Eng.), Volume 6, 344-359
The compounds described in page (1965) and the like may be added. It is particularly effective to add a chelating agent or an antifungal agent.

Further, in order to improve the stability of the wash water, it is also an effective means to use ion-exchanged water in which calcium and magnesium ions are reduced to 3 ppm or less.

In the water washing step, it is general to carry out countercurrent water washing of two or more tanks to save water. Furthermore, instead of the washing step, it is disclosed in
You may implement the multistage countercurrent stabilization processing process as described in 8543. Various compounds are added to the stabilizing bath for the purpose of stabilizing the image. For example, adjust the membrane pH (eg pH3
~ 8) various buffering agents (for example, borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, ammonia water, monocarboxylic acid, dicarboxylic acid, polycarboxylic acid) Typical examples include formalin and the like). In addition, water softener (inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.), bactericide (benzisothiazolinone, irithiazolone, 4-thiazolinebenzimidazole), if necessary. , Halogenated phenols, etc.), surfactants, fluorescent brighteners, hardeners and the like, and two or more kinds 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.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and accelerating the processing. For incorporation, it is preferable to use various precursors of color developing agents.

The silver halide color light-sensitive material of the present invention may contain various 1-phenyl-3-pyrazolidones in order to accelerate color development, if necessary. Typical compounds are JP-A-58-50534, JP-A-58-50535 and JP-A-58-11.
It is described in No. 5438.

The various treatment liquids in the present invention are used at 10 ° C to 50 ° C. A temperature of 33 ° C to 38 ° C is standard, but it is possible to raise the temperature to accelerate the treatment and shorten the treatment time, and conversely to lower the temperature to improve the image quality and improve the stability of the treatment liquid. it can. Further, in order to save silver in the light-sensitive material, processing using cobalt intensification or hydrogen peroxide intensification described in West German Patent No. 2,226,770 or US Pat. No. 3,674,499 may be performed.

If necessary, a heater, a temperature sensor, a liquid level sensor, a circulation pump, a filter, a floating pig, a squeegee, etc. may be provided in each treatment bath.

Known silver halide emulsions are used in the emulsion layer of the silver halide photographic light-sensitive material of the present invention.

The silver halide preferably used in the present invention is silver bromide, silver chlorobromide and silver chloride substantially free of silver iodide,
Preferred is silver chlorobromide containing 2-99 mol% of silver chloride. In order to obtain an emulsion having sufficient sensitivity without increasing fog, the silver bromide content is preferably 20 mol% or more, but when it is particularly rapid, it is 20 mol% or less, or 10 mol% or less. It may be preferable to use less than or equal to mol%.
Decreasing the silver bromide content not only improves the development speed, but also reduces the accumulation of bromine ions in the developing solution when the photosensitive material containing it is run in the processing solution, and the developing solution itself is high. It becomes active and highly preferred for rapid processing. The silver halide grains 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. For example, in the case of silver chlorobromide grains having different phases, it may be a grain having a nucleus or a single layer or a plurality of layers richer in silver bromide than the average halogen composition. Further, it may be a grain having a nucleus rich in silver chloride from the average halogen composition or a single or plural layers in the grain. The average grain size of silver halide grains (in the case of spherical grains or grains close to spheres, the average grain size based on the projected area with the grain size as the grain size in the case of cubic grains) is 2μ or less. 0.1 μ or more is preferable, but 1 μ or less and 0.15 μ or more is particularly preferable. The particle size distribution may be narrow or wide. A so-called monodisperse silver halide emulsion having a narrow grain size distribution in which 90% or more, particularly 95% or more of all grains fall within the average grain size ± 40% in terms of number of grains or weight can be used in the present invention. . 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 an emulsion layer having substantially the same color sensitivity are mixed in the same layer or different layers. Can be applied in multiple layers. Further, two or more kinds of polydisperse silver halide emulsions or a combination of monodisperse emulsions and polydisperse emulsions can be mixed or laminated and used.

The silver halide grains used in the present invention may have a regular crystal such as a cube, an octahedron, a dodecahedron and a tetradecahedron, and an irregular shape such as a sphere. It may have an (irregular) crystal form, or may have a composite form of these crystal forms. Further, tabular grains may be used, and particularly, an emulsion in which tabular grains having a length / thickness ratio value of 5 or more, particularly 8 or more account for 50% or more of all projection plane species of the grain 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 which forms a latent image mainly on the surface or an internal latent image type which is formed inside the grain.

The photographic emulsion used in the present invention is Chimie by P. Glafkides.
et Physique Photographique (published by Paul Montel, 1967
), GF Duffin Photographic Emulsion Chemistry
(Focal Press, 1966) By VL Zelikman et al Making a
nd Coating Photographic Emulsion (Focal Press, 1
964) and the like. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and a method of reacting a soluble silver salt and a soluble halogen salt may be a one-sided mixing method, a simultaneous mixing method or a combination thereof. Good. A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. A conversion method in which a halogen salt is added to form a more sparingly soluble silver halide can also be used, as one form of the simultaneous mixing method, a method of keeping pAg constant in a liquid phase in which silver halide is produced, That is, the so-called controlled double jet method can also be used. According to this method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained.

In the process of silver halide grain formation or physical ripening,
Cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or its complex salt, rhodium salt or its complex salt, iron salt or iron complex salt may coexist.

The silver halide emulsion is usually used for coating after physical ripening, desalting and chemical ripening after grain formation.

Known silver halide solvents (e.g., ammonia, rodancali or U.S. Pat. No. 3,271,157, JP-A-51-12360).
JP-A-53-82408, JP-A-53-144319, JP-A-5
4-100717 or thioethers and thione compounds described in JP-A No. 54-155828, etc. are precipitated, physically aged,
It can be used in chemical aging. In order to remove the soluble silver salt from the emulsion after physical ripening, the Nudel washing, the flocculation precipitation method, the ultrafiltration method and the like are used.

The silver halide emulsion used in the present invention is a compound containing sulfur capable of reacting with active gelatin or silver (for example, thiosulfate,
Sulfur sensitization method using thioureas, mercapto compounds, rhodanines); Reduction sensitization method using reducing substances (eg, primary tin salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds); A noble metal sensitization method using a metal compound (for example, a complex salt of a metal of Group VIII of the Periodic Table such as Pt, Ir, Pd, Rh, and Fe in addition to a complex salt of gold) can be used alone or in combination.

The photographic emulsion used in the present invention is spectrally sensitized with a photographic sensitizing dye. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes.

These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used especially for the purpose of supersensitization.

Along with the sensitizing dye, a dye that does not have a spectral sensitizing effect by itself, a substance that does not substantially absorb visible light, or a substance that exhibits supersensitization may be included in the emulsion. For example, nitrogen-containing heterocyclic ring-substituted aminostilbene compounds (e.g., those described in U.S. Pat.Nos. 2,933,390 and 3,635,721), aromatic organic acid formaldehyde condensates (e.g., those described in U.S. Patent 3,743,510) ), Cadmium salt, azaindene compound and the like.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the production process of the light-sensitive material, during storage or during photographic processing, or stabilizing photographic performance.

Various color couplers can be used in the present invention. Useful color couplers are cyan, magenta and yellow color couplers, typical examples of which are naphthol or phenol compounds, prazolone or pyrazoloazole compounds and open chain or heterocyclic ketomethylene compounds. Specific examples of these cyan, magenta and yellow couplers that can be used in the present invention include Research Disclosure (RD) 17643 (1978, 1
(Feb.) Section VII-D and the patent cited in 18717 (November 1979).

The color coupler incorporated in the light-sensitive material preferably has a ballast group or is polymerized to be diffusion resistant. The coating amount of silver can be reduced in the case of a two-equivalent color coupler in which a coupling active position is substituted with a leaving group, rather than a four-equivalent color coupler in which a hydrogen atom is present. It is also possible to use a coupler in which the color-forming dye has an appropriate diffusibility, a non-color-forming coupler, or a DIR coupler which releases a development inhibitor with a coupling reaction or a coupler which releases a development accelerator.

A typical example of the yellow coupler that can be used in the present invention is an oil protect type acylacetamide coupler. A specific example is U.S. Pat. No. 2,407,21.
No. 0, No. 2,875,057 and No. 3,265,506. In the present invention, it is preferable to use a 2-equivalent yellow coupler, and U.S. Pat.Nos. 3,408,194 and 3,447,9.
No. 28, No. 3,933,501 and No. 4,022,620 oxygen atom desorption type yellow couplers or Japanese Patent Publication No. 58-10739, U.S. Patent No. 4,401,752, No. 4,326,
No. 024, RD18053 (April 1979), British Patent No. 1,425,020
Representative examples thereof include nitrogen atom-releasing yellow couplers described in West German Application Publication Nos. 2,219,917, 2,261,361, 2,329,587, and 2,433,812. α-pivaloyl acetanilide type couplers are excellent in fastness of color forming dyes, especially light fastness, while α
-The benzoylacetanilide type coupler provides a high color density.

Cyan couplers that can be used in the present invention include oil-protected naphthol-based and phenol-based couplers, and naphthol-based couplers described in U.S. Pat.No. 2,474,293, preferably U.S. Pat.No. 4,052,212.
Representative examples are the oxygen atom-elimination type two-equivalent naphthol couplers described in 4,146,396, 4,228,233 and 4,296,200. Further, specific examples of phenol-based couplers include U.S. Pat. Nos. 2,369,929 and 2,801,1.
No. 71, No. 2,772,162, No. 2,895,826 and the like. Cyan couplers that 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 higher at the meta position of the phenol nucleus described in US Pat. No. 3,772,002. Cyan coupler, U.S. Pat.
3,758,308, 4,126,396, 4,334,011, 4,327,173, West German Patent Publication 3,329,729 and Japanese Patent Application No. 58-42671, and 2,5-diacylamino-substituted phenol couplers and U.S. Patents. Third 3,446,622
Nos. 4,333,999, 4,451,559 and 4,42
No. 7,767, and the like, phenol couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position, and the like.

A coupler in which the color forming dye has an appropriate diffusibility can be used in combination. Such couplers are described in U.S. Pat.
Specific examples of magenta couplers are described in 237 and British Patent No. 2,125,570, and specific examples of yellow, magenta or cyan couplers are described in European Patent No. 96,570 and West German Patent Application No. 3,234,533.

The dye-forming coupler and the above-mentioned special coupler may form a dimer or higher polymer except for the coupler in which the color-forming dye has diffusibility. Typical examples of polymerized dye forming couplers are U.S. Pat. Nos. 3,451,820 and 4,080,2.
It is described in No. 11. Specific examples of polymerized magenta couplers are described in British Patent No. 2,102,173 and U.S. Patent No. 4,3.
No. 67,282.

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

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods, and examples thereof include a solid dispersion method, an alkali dispersion method, preferably a latex dispersion method, and more preferably an oil-in-water dispersion method. be able to. In the oil-in-water dispersion method, a high-boiling point organic solvent having a boiling point of 175 ° C. or higher and a low-boiling point so-called auxiliary solvent are dissolved in a single liquid or a mixed liquid of both, and then water or gelatin is added in the presence of a surfactant. Finely dispersed in an aqueous medium such as an aqueous solution. Examples of high boiling organic solvents are described in U.S. Pat.No. 2,322,027
No. etc.

The standard amount of color coupler used is in the range of 0.001 to 1 mole per mole of light-sensitive silver halide, preferably 0.01 to 0.5 mole for yellow coupler, 0.03 to 0.3 mole for magenta coupler, and cyan coupler for cyan coupler. It is 0.002 to 0.3 mol.

The light-sensitive material produced by using the present invention is, as a color antifoggant or color mixing inhibitor, a hydroquinone derivative, an aminophenol derivative, an amine, a gallic acid derivative, a catechol derivative, an ascorbic acid derivative, a colorless coupler, a sulfonamidephenol. You may contain a derivative etc.

A known anti-fading agent can be used in the light-sensitive material of the present invention. Hydroquinones as organic anti-fading agents,
6-hydroxychromans, 5-hydroxycoumarans, spirochromans, p-alkoxyphenols,
Hindered phenols centered on bisphenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines and ether or ester derivatives obtained by silylating and alkylating the phenolic hydroxyl groups of these compounds As a representative example. Further, a metal complex represented by (bissalicylaldoximato) nickel complex and (bis-N, N-dialkyldithiocarbamato) nickel complex can also be used.

To prevent deterioration of the yellow dye image due to heat, humidity and light,
Compounds having both hindered amine and hindered phenol partial structures in the same molecule, as described in US Pat. No. 4,268,593, give good results. In order to prevent deterioration of the magenta dye image, especially deterioration due to light,
The spiroindanes described in JP-A-56-159644 and the hydroquinone diether- or monoether-substituted chromanes described in JP-A-55-89835 give preferable results.

In the light-sensitive material of the present invention, an ultraviolet absorber can be added to the hydrophilic colloid layer.

The light-sensitive material of the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as prevention of irradiation or halation.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material of the present invention may contain a stilbene-based, triazine-based, oxazole-based or coumarin-based brightening agent.
Water-soluble ones may be used, and water-insoluble whitening agents may be used in the form of dispersion.

As the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used.

In addition to general-purpose lime-processed gelatin, acid-processed gelatin and Bull.Soc.Sci.Phot.Japan, No.16, p.30 (19
The enzyme-treated gelatin as described in 66) may be used, and a hydrolyzate or oxygen hydrolyzate of gelatin may also be used.

In the light-sensitive material of the present invention, any hydrophilic colloid layer constituting the photographic light-sensitive layer or the back layer may contain an inorganic or organic hardener.

In the light-sensitive material of the present invention, in addition to the above-mentioned additives, various stabilizers, stain inhibitors, developers or their precursors,
A development accelerator or its precursor, a lubricant, a mordant, a matting agent, an antistatic agent, a plasticizer, or other various additives useful for a photographic light-sensitive material may be added. Typical examples of these additives are Research Disclosure 17643 (1
December 978) and 18716 (November 1979).

The invention is applicable to multilayer multicolor photographic materials having at least two different spectral sensitivities on the support. Multilayer natural color photographic materials are usually a red-sensitive emulsion layer, a green-sensitive emulsion layer, a
And at least one blue-sensitive emulsion layer. The order of these layers can be arbitrarily selected as required. Each of the above emulsion layers may be composed of two or more emulsion layers having different sensitivities, and a non-photosensitive layer may be present between two or more emulsion layers having the same sensitivity.

The light-sensitive material according to the present invention, in addition to the silver halide emulsion layer,
Protective layer, intermediate layer, filter layer, anti-halation layer,
It is preferable to appropriately provide an auxiliary layer such as a back layer.

(Examples) Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited thereto.

[Example 1] On a paper support laminated on both sides with polyethylene, multi-layer color photographic printing papers (a) to (e) having different layer constitutions shown in Table A with different magenta couplers were prepared. The coating liquid was prepared as follows.

Preparation of coating solution for the first layer Yellow coupler (a) 19.1 g and color image stabilizer (b) 4.4
To g, 27.2 ml of ethyl acetate and 7.9 ml of solvent (c) were added and dissolved, and this solution was emulsified and dispersed in 185 ml of 10% gelatin aqueous solution containing 8 ml of 10% sodium dodecylbenzenesulfonate. On the other hand, the following blue-sensitive sensitizing dyes were added to a silver chlorobromide emulsion (containing 80 mol% of silver bromide and 70 g / Kg of Ag) per mol of silver chlorobromide.
90 g of a blue-sensitive emulsion was prepared by adding 0 × 10 ^-4 mol.
The emulsified dispersion and the emulsion were mixed and dissolved, the gelatin concentration was adjusted so that the composition shown in Table A was obtained, and the coating solution for the first layer was prepared.

The coating solutions for the second to seventh layers were also prepared in the same manner as the coating solution for the first layer. As the gelatin hardening agent for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used.

The following were used as the spectral sensitizer for each emulsion.

Blue-sensitive emulsion layer (7.0 × 10 ^-4 mol added per mol of silver halide) Green-sensitive emulsion layer (4.0 × 10 ^-4 mol added per mol of silver halide) (7.0 × 10 ^-5 mol added per mol of silver halide) Red-sensitive emulsion layer (Addition of 1.0 × 10 ⁻⁴ mol per mol of silver halide) The following dye was used as an anti-irradiation dye in each emulsion layer.

Structural formulas of compounds such as couplers used in this example are as follows.

(J) Solvent (isoC ₉ H ₁₈ O ₃ P = O The magenta couplers used are as follows.

Sample B (The coating amount of the third layer was 0.35 g / m ² .

Sample B Sample C Exemplified Compound M-42 Sample D Exemplified Compound M-43 Sample E Exemplified Compound M-45 Next, each of samples I to E was measured by a sensitometer (Fuji Photo Film Co., Ltd.).
And a stepwise exposure for sensitometry through blue, green, and red filters using an FWH type light source (color temperature: 3200 ° K). The exposure at this time was performed so that the exposure amount was 250 CMS with an exposure time of 0.5 seconds.

The exposed photosensitive material was processed in the following processing steps.

(Processing process) (Temperature) (Time) Color development process 38 ℃ 2'00 "Bleach fixing process 38 ℃ 1'00" Water washing process 24-33 ℃ 1'00 "Drying process 80 ℃ 50" Is the street.

As for the color developers, the formulation A containing benzyl alcohol and the formulation B not containing benzyl alcohol were used.

Further, the formulations in which various compounds of the general formula (I) shown in Table 1 were added to the formulations A and B were designated as C to J, respectively.

The formulation of the bleach-fix solution is shown below.

(Bleaching fixer formulation) Ammonium thiosulfate (54wt%) 150ml Na ₂ SO ₃ 15g NH ₄ [Fe (III) (EDTA)] 55g EDTA ・ 2Na 4g Add water to a total volume of 1000ml (pH 6.9) Table 1 shows the results of measuring the minimum and maximum densities of the obtained magenta dyes with a Macbeth densitometer by treating the samples with the developer formulations A to J, respectively.

When the compound of the present invention was added in the presence of benzyl alcohol (Nos. 3 to 6), it was found that remarkable magenta fog was generated. However, when it is added to a color developer containing no benzyl alcohol (No. 7-1
0), no fog is generated, and sufficient color development is exhibited.
Further, it can be seen that when the magenta coupler represented by the general formula (II) is used, it exhibits more excellent color developability. Also, when the time of the color developing step was shortened to 1 minute, almost the same result as above was obtained.

Example 2 In Example 1, the addition amount of each compound of the present invention was 9.0 g.
With / l, the same processing as in Example 1 is performed and the same effect as in Example 1 is obtained.

Example 3 A multilayer color photographic paper was prepared on a paper support laminated on both sides with polyethylene. The coating liquid was prepared as follows.

Preparation of coating liquid for the first layer: 19.1 g of yellow coupler (a) and 4.4 of a color-increasing stabilizer (b)
To g, 27.2 ml of ethyl acetate and 7.9 ml of solvent (c) were added and dissolved, and this solution was emulsified and dispersed in 185 ml of 10% gelatin aqueous solution containing 8 ml of 10% sodium dodecylbenzenesulfonate. On the other hand, the following blue-sensitive sensitizing dyes were added to a silver chlorobromide emulsion (containing 1.0 mol% of silver bromide and 70 g / Kg of Ag) per mol of silver chlorobromide.
90 g of a blue-sensitive emulsion was prepared by adding 0 × 10 ^-4 mol.
The emulsified dispersion was mixed and dissolved, the gelatin concentration was adjusted so that the composition shown in Table B was obtained, and the coating solution for the first layer was prepared.

The coating solutions for the second to seventh layers were also prepared in the same manner as the coating solution for the first layer. As the gelatin hardening agent for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used.

The following were used as the spectral sensitizer for each emulsion.

Blue-sensitive emulsion layer (5.0 × 10 ^-4 mol added per mol of silver halide) Green-sensitive emulsion layer (4.0 × 10 ^-4 mol added per mol of silver halide) (7.0 × 10 ^-5 mol added per mol of silver halide) Red-sensitive emulsion layer (Addition of 0.9 × 10 ⁻⁴ mol per mol of silver halide) The following dye was used as the anti-irradiation dye in each emulsion layer.

Green sensitive emulsion layer Red-sensitive emulsion layer: Structural formulas of compounds such as couplers used in this example are as follows.

(A) Yellow coupler (F) Color image stabilizer The color photographic paper obtained as described above was subjected to wedge-shaped exposure and then processed in the following processing steps.

Treatment process Temperature Time Color development (35 ℃) See Table 2 Bleaching and fixing (35 ℃) 45 seconds Rinse 1 (35 ℃) 20 seconds Rinse 2 (35 ℃) 20 seconds Rinse 3 (35 ℃) 20 seconds Dry (80 ℃ ) 60 seconds Each liquid used is as follows.

Color developer Triethanolamine 10g N, N-diethylhydroxylamine 4g Sodium sulfite 0.2g Potassium carbonate 30g EDTA ・ 2Na ・ 2H ₂ O 2g Potassium bromide 0.01g 4-Amino-3-methyl-N-ethyl-N- [ β- (methanesulfonamido) ethyl] -aniline, sulfate 5.0 g Fluorescent brightener (4,4′-diamino-stilbene type, Ciba Geigy) UVITEX CK) 3.0 g Compound of the present invention Table 2 Add water 1000 ml pH 10.20 Bleach-fix solution EDTA Fe (III) NH ₄・ 2H ₂ O 60 g EDTA ・ 2Na ・ 2H ₂ O 4 g Ammonium thiosulfate (70%) 120 ml Sodium sulfite 16 g Glacial acetic acid 7 g Water 1000 ml pH 5.5 ( Rinse solution) 1-Hydroxyethylidene-1,1'-diphosphonic acid (60
%) 1.6 ml Bismuth chloride 0.35 g Polyvinylpyrrolidone 0.25 g Ammonia water (26%) 2.5 ml Nitrilotriacetic acid ・ 3Na 1.0 g EDTA ・ 4H 0.5 g Sodium sulfite 1.0 g 5-Chloro-2-methyl-4-isothiazoline-3- On 50 mg formalin (37%) 0.1 ml water was added to 1000 ml pH 7.0 The Dmin and Dmax of the obtained sample were measured with a McBell densitometer and the results are shown in Table 2.

Based on the present invention (Nos. 15 to 17), fog was low and sufficient color development was obtained, whereas the presence of benzyl alcohol caused high fog (Nos. 12, 18, 19, 20, 2).
1) In the absence of the accelerator of the present invention, the color developability decreases. (No. 22), [Example 4] Instead of I-10 (glycine) in Example 3 and Table 2, compound I-4, choline, DL-serine and hydroxyethylmorpholine were used to carry out individual experiments. Even in the same manner as in Example 3, when the compound of the present invention was contained, excellent photographic characteristics were exhibited.

(Effects of the Invention) In addition to the compound represented by the general formula (I), the above-mentioned compounds such as tetramethylammonium acetate, choline, choline chloride, hydantoic acid and the like caused remarkable fog when used in a general color developing solution. However, when benzyl alcohol was not present and the development time was short as in the present invention, excellent color forming property and development accelerating effect were exhibited. Especially, it was remarkable in the light-sensitive material containing the magenta coupler represented by the general formula (II).

Further, since the compound of the present invention is not so low in water solubility as benzyl alcohol, it is preferable in that the auxiliary solvent such as diethylene glycol is unnecessary or can be greatly reduced.

Further, among the compounds of the present invention, the compounds represented by the general formula (I) and the like are preferable from the viewpoint of improving the stability of the developing solution.

Claims (2)

[Claims] 1. A silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a reflective support.
A compound which is substantially free of benzyl alcohol and is represented by the following general formula (I), tetramethylammonium acetate, choline, choline chloride, hydantoic acid, allylamine, aminoguanidine sulphate,
o-aminobenzoic acid, o-aminobenzyl alcohol,
A method for processing a silver halide color photographic light-sensitive material, which comprises processing with a color developing solution containing at least one selected from the above for a time of 2 minutes and 30 seconds or less. General formula (I) (R ¹ is an alkyl group having ¹ to 10 carbon atoms, an alkyl group substituted with a chlorine atom, a carboxyalkyl group or an alkoxyalkyl group, and R ² and R ³ are each a hydrogen atom, or 1 to An alkyl group having 10 carbon atoms, an alkyl group substituted with a chlorine atom, a carboxyalkyl group or an alkoxyalkyl group, R ¹ to
When R ³ represents an alkyl group, they may be linked to each other to form a ring. ) 2. The silver halide color photographic light-sensitive material described above,
A method for processing a silver halide color photographic light-sensitive material according to claim (1), which contains a magenta coupler represented by the following general formula (II). General formula (II) (In the formula, Rb represents a hydrogen atom or a substituent, Y ₁ represents a group capable of leaving by a coupling reaction with an oxidized product of an aromatic primary amine developing agent, and Za, Zb or Zc represents a methine group or a substituted methine group. , = N- or -NH-, and a Za-Zb bond and Zb
One of the -Zc bonds is a double bond and the other is a single bond. )