JPH0750326B2 - Processing method of silver halide color photographic light-sensitive material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for processing an exposed silver halide color photographic light-sensitive material (hereinafter referred to as a color light-sensitive material), and in particular, it is sufficiently removed in a short time. The present invention relates to an improved processing method which can be performed by silver, is free from multicolor defects, that is, the reduction (leucoization) of a cyan dye by Fe ²⁺ is difficult to occur, and has excellent photographic properties.

(Prior Art) Generally, the basic steps of processing a color light-sensitive material are a color development step and a desilvering step. In the color developing step, the silver halide exposed by the color developing agent is reduced to produce silver, and the oxidized color developing agent reacts with the color developing agent (coupler) to give a dye image. In the next desilvering process,
The action of an oxidizing agent (commonly called a bleaching agent) oxidizes the silver produced in the color development step, and then it is dissolved by a complexing agent of silver ions, which is commonly called a fixing agent. By passing through this desilvering process, only a dye image is formed on the color light-sensitive material.

The above desilvering step is generally composed of two baths, a bleaching bath containing a bleaching agent and a fixing bath containing a fixing agent. However, a method using one bleach-fixing bath containing a bleaching agent and a fixing agent, a bleaching bath Various methods such as a method of providing a washing step between the fixing bath and the fixing bath are selected according to the light-sensitive material to be processed. However, when bleaching or bleach-fixing processing, when processing a high-sensitivity color light-sensitive material, particularly a color reversal light-sensitive material for photographing and a color negative light-sensitive material for photographing using a high silver content emulsion, desilvering failure is liable to occur and bleaching is long. Since it has time, it is strongly desired to shorten the processing time. Further, the bleach-fixing solution has a drawback that it reduces the cyan dye formed by color development to a leuco dye, impairing the color reproducibility (color restoration property), and development of a desilvering method without such a problem Is desired.

On the other hand, various requirements have been imposed on couplers used in recent color photographic light-sensitive materials. For example, it is excellent in stability, processability, color development, and hue of a color image, and the color image is robust and can be produced by a simple and inexpensive method.

From this point, phenol couplers and naphthol couplers have been conventionally used as cyan couplers. In particular, 1-naphthol couplers have a long-wave absorption maximum (λ _max ) of the formed coloring dye, have little secondary absorption in the green region, and are excellent in color reproduction, and many couplers with excellent coloring properties are found. In addition, since it can be manufactured at low cost, it is widely used in color negative photosensitive materials.

However, even in the development processing of a color light-sensitive material containing these cyan couplers, there is the above-mentioned problem that bleaching takes a long time and the color recovery property is impaired.

[Problems to be solved by the invention]

Therefore, it is an object of the present invention to provide a method for processing a color light-sensitive material which is capable of sufficient desilvering in a short time, has no color restoration defects and has excellent photographic properties.

[Means for solving problems]

As a color light-sensitive material, a specific cyan coupler, that is, a light-sensitive material containing a 1-naphthol-based coupler having a mono-substituted amino group at the 5-position, which is more excellent in color image fastness and color reproducibility than conventional cyan couplers, is treated. The above problems can be solved by selecting and processing the light-sensitive material in a bath having a bleach-fixing ability, and by combining a bleaching bath and a bath having a bleach-fixing ability, the above-mentioned problems can be more effectively solved. I found that

That is, the present invention is a method of processing an exposed silver halide color photographic light-sensitive material, which comprises a step of processing in a bath having a bleach-fixing ability after color development, and the silver halide color photographic light-sensitive material is There is provided a method for processing a silver halide color photographic light-sensitive material characterized by containing at least one cyan dye forming coupler represented by the general formula (I).

The coupler represented by the general formula [I] is also preferably used in combination with the 1-naphthol coupler represented by the following general formula [II] and having an acylamino group at the 2-position.

(In the formula, R ₁ is -CONR ₅ R ₆ , -NHCOR ₅ , -NHCOOR ₇ , -NHSO.
₂ R ₇ , -NHCONR ₅ R ₆ or -NHSO ₂ NR ₅ R ₆ , R ₂ is a group capable of substituting for a naphthol ring, m is an integer of 0 to 3, and R ₃ is -C.
OOR _9, represents a _{-COR 9, -SO 2 R 11,} -CONR 9 R 10 or -SO ₂ NR ₉ R _10. R ₄ represents a substituted or unsubstituted aryl group, and X represents a hydrogen atom or a group capable of splitting off by a coupling reaction with an oxidized product of an aromatic primary amine developing agent. However,
R ₅ and R _{6, which} may be the same or different, each independently represent a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group, and R ₇
Represents an aliphatic group, an aromatic group or a heterocyclic group. Also,
R ₉ , R ₁₀ and R ₁₁ have the same meanings as R ₅ , R ₆ and R ₇ , respectively. In the formula, when m is plural, R _{2 s} may be the same or different and may be bonded to each other to form a ring. R ₂ and R ₃ , or R ₃ and X may be bonded to each other to form a ring. The photosensitive material to be processed in the present invention is characterized by containing a 1-naphthol cyan coupler represented by the above general formula [I]. Incidentally, the aliphatic group in the formula [I] or [II] represents an aliphatic hydrocarbon group (the same applies hereinafter), and includes a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group, It may be substituted or unsubstituted. The aromatic group means a substituted or unsubstituted aryl group, and may be a condensed ring.
The heterocycle means a substituted or unsubstituted monocyclic or condensed ring heterocyclic group.

The substituents in formulas [I] and [II] will be described in detail below.

R ₁ is the group described above, and as R ₅ , R ₆ and R ₇ , an aliphatic group having 1 to 30 carbon atoms, an aromatic group having 6 to 30 carbon atoms, and a heterocyclic group having 2 to 30 carbon atoms are used. Can be mentioned.

R ₂ represents a group capable of substituting on a naphthol ring (including atoms, the same applies hereinafter), and representative examples thereof include halogen atom, hydroxy group, amino group, carboxyl group, sulfonic acid group, cyano group, aromatic group, heterocyclic group. , Carbonamide group, sulfonamide group, carbamoyl group, sulfamoyl group, ureido group, acyl group, acyloxy group, aliphatic oxy group, aromatic oxy group, aliphatic thio group, aromatic thio group, aliphatic sulfonyl group, aromatic Examples thereof include a group sulfonyl group, a sulfamoylamino group, a nitro group and an imide group, and the number of carbon atoms contained in R ₂ is 0 to 30. An example of cyclic R ₂ when m = 2 is a dioxymethylene group.

R ₃ is -COOR ₉ , -COR ₉ , -SO ₂ R ₁₁ , -CONR ₉ R ₁₀ or -SO ₂ NR ₉ R
Represents ₁₀ . Here, R ₉ , R ₁₀ and R ₁₁ are the above R ₅ ,
It has the same meaning as defined in R ₆ and R ₇ .

At R ₁ R ₅ and R ₆ may be bonded to each other to form a nitrogen-containing heterocycle (morpholine ring, piperidine ring, pyrrolidine ring, etc.).

R ₄ is a naphthyl group and a phenyl group having an aliphatic oxy group or a halogen atom at the 2-position [for example, 2-chlorophenyl group, 2-ethoxyphenyl group, 2-propyloxyphenyl group, 2-butyloxyphenyl group, 2-dodecyloxyphenyl group, 2-tetradecyloxyphenyl group,
2- (2-hexyldecyloxy) phenyl group, 2-chloro-5-dodecyloxycarbonylphenyl group and the like] are preferable.

X represents a hydrogen atom or a coupling-off group (including a leaving atom; the same applies hereinafter). A typical example of the coupling-off group is a halogen atom, -OR ₁₅ -SR ₁₅ , -NHCOR ₁₅ , -NHSR ₁₅ , Aromatic azo group having 6-30 carbon atoms, heterocyclic group having 1-30 carbon atoms and linked to the coupling active position of the coupler with a nitrogen atom (succinimide group, phthalimido group, hydantoinyl group, pyrazolyl group, 2- Benzotriazolyl group etc.) and the like. Here, R ₁₅ is an aliphatic group having 1 to 30 carbon atoms, an aromatic group having 6 to 30 carbon atoms, or 2 to 30 carbon atoms.
Represents a heterocyclic group of.

As described above, the aliphatic group in the present invention is saturated / unsaturated,
It may be substituted / unsubstituted, linear / branched / cyclic, and typical examples include a methyl group, an ethyl group, a butyl group, a cyclohexyl group, an allyl group, a propargyl group,
Methoxyethyl group, n-decyl group, n-dodecyl group, n
-Hexadecyl group, trifluoromethyl group, heptafluoropropyl group, dodecyloxypropyl group, 2,4-di-tert-amylphenoxypropyl group, 2,4-di-tert
-Amylphenoxybutyl group and the like are included.

Further, the aromatic group may be substituted or unsubstituted,
Typical examples are phenyl group, tolyl group, 2-tetradecyloxyphenyl group, pentafluorophenyl group,
2-chloro-5-dodecyloxycarbonylphenyl group, 4-chlorophenyl group, 4-cyanophenyl group, 4
-Hydroxyphenyl group and the like are included.

Further, the heterocyclic group may be substituted or unsubstituted,
Typical examples include 2-pyridyl group, 4-pyridyl group,
A 2-furyl group, a 4-thienyl group, a quinolinyl group and the like are included.

Preferred examples of the substituent in the present invention will be described below. R ₁
Is preferably -CONR ₅ R ₆ , and as a specific example, a carbamoyl group,
Ethylcarbamoyl group, morpholinocarbonyl group, dodecylcarbamoyl group, hexadecylcarbamoyl group, decyloxypropyl group, dodecyloxypropyl group, 2,
4-di-tert-amylphenoxypropyl group, 2,4-di-te
Examples include rt-amylphenoxybutyl group.

As for R ₂ and m, m = 0, that is, an unsubstituted one is most preferable, and then R ₂ is a preferable substituent such as a halogen atom, an aliphatic group, a carbonamido group and a sulfonamide group.

Preferred values for R ₃ are shown in parentheses below. -COR ₉
(Formyl group, acetyl group, trifluoroacetyl group, chloroacetyl group, benzoyl group, pentafluorobenzoyl group, p-chlorobenzoyl group, etc.), -COOR ₉
(Methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group, decyloxycarbonyl group, methoxyethoxycarbonyl group, phenoxycarbonyl group, etc.), -SO ₂ R ₁₁ (methanesulfonyl group, ethanesulfonyl group, butanesulfonyl group, hexadecanesulfonyl group) , Benzenesulfonyl group, toluenesulfonyl group, p
-Chlorobenzenesulfonyl group), -CONR ₉ R ₁₀ (N, N
-Dimethylcarbamoyl group, N, N-diethylcarbamoyl group, N, N-dibutylcarbamoyl group, morpholinocarbonyl group, piperidinocarbonyl group, 4-cyanophenylcarbonyl group, 3,4-dichlorophenylcarbamoyl group, 4-methanesulfonyl group Phenylcarbamoyl group), -SO ₂ NR ₉ R ₁₀ (N, N-dimethylsulfamoyl group,
N, N-diethylsulfamoyl group, N, N-dipropylsulfamoyl group, etc.). A particularly preferred R ₃ is -C
OOR _9, a -COR ₉ and -SO ₂ R _11, these -COOR ₉ is more preferred.

Preferred X is a hydrogen atom, a halogen atom, an aliphatic oxy group having 1 to 30 carbon atoms (methoxy group, 2-methanesulfonamidoethoxy group, 2-methanesulfonylethoxy group, carboxymethoxy group, 3-carboxypropyloxy group. , 2-carboxymethylthioethoxy group, 2-methoxyethoxy group, 2-methoxyethylcarbamoylmethoxy group, etc., aromatic oxy group (phenoxy group, 4-
Chlorophenoxy group, 4-methoxyphenoxy group, 4-
tert-octylphenoxy group, 4-carboxyphenoxy group, etc.), heterocyclic thio group (5-phenyl-1,2,3,4-
Tetrazolyl-1-thio group, 5-ethyl-1,2,3,4-tetrazolyl-1-thio group) and aromatic azo group (4-
Dimethylaminophenylazo group, 4-acetamidophenylazo group, 1-naphthylazo group, 2-ethoxycarbonylphenylazo group, 2-methoxycarbonyl-4,5-
Dimethoxyphenylazo group).

R ₄ is a naphthyl group and an aliphatic oxy group at the 2-position or a phenyl group having a halogen atom [for example, 2-chlorophenyl group, 2-ethoxyphenyl group, 2-propyloxyphenyl group, 2-butyloxyphenyl group, 2-dodecyl group]. Oxyphenyl group, 2-tetradecyloxyphenyl group,
2- (2-hexyldecyloxy) phenyl group, 2-chloro-5-dodecyloxycarbonylphenyl group and the like] are preferable.

The coupler represented by the general formula [I] has substituents R ₁ , R ₂ ,
The coupler represented by the general formula [II] at R ₃ or X is divalent or divalent at X or R ₄ , respectively.
You may form the dimer, an oligomer, or the multimer more than it couple | bonded with each other through the group more than the valence. in this case,
The carbon number range shown in each of the above substituents may be out of the range.

When the coupler represented by the general formula [I] or [II] forms a multimer, a homopolymer or copolymer of an addition-polymerizable ethylenically unsaturated compound (cyan color-forming monomer) having a cyan dye-forming coupler residue is used. This is a typical example. In this case, the multimer contains a repeating unit represented by the general formula [IV], and one or more cyan color-forming repeating units represented by the general formula [IV] may be contained in the multimer. It may be a copolymer containing one kind or two or more kinds of color forming ethylene type monomers.

In the formula, R represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a chlorine atom, A represents -CONH-, -COO- or a substituted or unsubstituted phenylene group, and B represents a substituted or unsubstituted alkylene. A group, a phenylene group or an aralkylene group, L is -CONH-, -NHCONH-, -NHCOO-,
-NHCO-, -OCONH-, -NH-, -COO-, -OCO-, -C
O -, - O -, - SO 2 -, - NHSO 2 - or represents a -SO ₂ NH-.
a, b, and c represent 0 or 1. Q represents a cyan coupler residue in which a hydrogen atom other than the hydrogen atom of the hydroxyl group at the 1-position is eliminated from the compounds represented by the general formulas [I] and [II].

As the multimer, a copolymer of a cyan-generating monomer giving a coupler unit of the general formula [IV] and the following non-color-forming ethylene-like monomer is preferable.

As the non-color-forming ethylene-like monomer that does not couple with the oxidation product of the aromatic primary amine developing agent, acrylic acid,
α-Chloroacrylic acid, α-alkylacrylic acid (eg methacrylic acid) Esters or amides derived from these acrylic acids (eg acrylamide, methacrylamide, n-butylacrylamide, t)
-Butyl acrylamide, diacetone acrylamide,
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), vinyl esters (eg vinyl acetate, vinyl propionate and vinyl laurate), acrylonitrile, methacrylonitrile,
Aromatic vinyl compounds (eg styrene and its derivatives such as vinyltoluene, divinylbenzene, vinylacetophenone and sulfostyrene), itaconic acid,
Examples include citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ethers (eg vinyl ethyl ether), maleic acid esters, N-vinyl-2-pyrrolidone, N-vinyl pyridine and 2- and -4-vinyl pyridine.

Particularly preferred are acrylic acid ester, methacrylic acid ester, and maleic acid esters. Two or more kinds of non-color-forming ethylene type monomers used here can be used together. For example, methyl acrylate and butyl acrylate, butyl acrylate and styrene, butyl methacrylate and methacrylic acid, methyl acrylate and diacetone acrylamide, etc. can be used.

As well known in the field of polymer couplers, the ethylenically unsaturated monomer for copolymerization with the vinylic monomer corresponding to the above-mentioned general formula [IV] has physical and / or chemical properties of the copolymer formed. Properties such as solubility, compatibility with the binder of the photographic colloid composition such as gelatin, its softening temperature, flexibility, thermal stability, etc. can be selected to be favorably influenced.

The cyan polymer coupler used in the present invention is obtained by dissolving a lipophilic polymer coupler obtained by polymerization of a vinyl-based monomer which gives a coupler unit represented by the general formula [IV] in an organic solvent in an aqueous gelatin solution. It may be prepared by emulsion-dispersing in the form of latex, or may be prepared by direct emulsion polymerization method.

U.S. Pat.No. 3,451, for a method of emulsifying and dispersing a lipophilic polymer coupler in the form of a latex in an aqueous gelatin solution.
820, U.S. Pat.No. 4,080,211 for emulsion polymerization,
The method described in U.S. Pat. No. 3,370,952 can be used.

The specific examples of the couplers represented by formula (I) are shown below, but the couplers used in the present invention are not limited to these. In the following structural formula, (t) C ₅ H ₁₁ is -C (CH
₃ ) ₂ C ₂ H ₅ and (t) C ₈ H ₁₇ represent -C (CH ₃ ) ₂ CH ₂ C (CH ₃ ) ₃ , respectively.

Specific examples of the coupler represented by the general formula [II] are shown below.

The coupler represented by the general formula [I] is disclosed in Japanese Patent Application No. 59-93605.
No. 59-264277 and No. 59-268135.

The coupler represented by the general formula [II] is a US Pat.
3488193, JP-A-48-15529, 50-117422, 52-1
No. 8315, No. 52-90932, No. 53-52423, No. 54-48237,
54-66129, 55-32071, 55-65957, 55-105
226, 56-1938, 56-12643, 56-27147,
It is synthesized by the method described in 56-126832 and 58-95346.

The coupler of the present invention and other couplers which can be used in combination can be introduced into the light-sensitive material by various known dispersion methods, for example, solid dispersion method, alkali dispersion method, preferably latex dispersion method, more preferably oil-in-water dispersion method. Can be mentioned as a typical example. In the oil-in-water dispersion method, the boiling point is 175.
After being dissolved in either a single solution of a high-boiling point organic solvent having a temperature of not lower than 0 ° C. or a so-called auxiliary solvent having a low boiling point, or a mixed solution thereof, it is finely dispersed in an aqueous medium such as water or an aqueous gelatin solution in the presence of a surfactant. Examples of high boiling organic solvents are described in US Pat. No. 2,322,027 and the like. The dispersion may be accompanied by phase inversion, and if necessary, the auxiliary solvent may be distilled,
It may be used for application after being removed or reduced by noodle washing or ultrafiltration.

Specific examples of the high boiling point organic solvent include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate,
Di-2-ethylhexyl phthalate, decyl phthalate, etc.), esters of phosphoric acid or phosphonic acid (trifel phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate) , Tributoxyethyl phosphate, trichloropropyl phosphate, di-
2-ethylhexylpheninephosphonate, etc., benzoic acid esters (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), amides (diethyldodecane amide, N-tethyladecylpyrrolidone, etc.), alcohols Or phenols (isostearyl alcohol,
2,4-di-tert-amylphenol, etc.), aliphatic carboxylic acid esters (dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (N, N-dibutyl-2) -Butoxy-5-tert-octylaniline), hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.) and the like. The auxiliary solvent has a boiling point of about 30 ° C or higher, preferably 50 ° C.
An organic solvent having a temperature of about 160 ° C. or lower can be used, and typical examples are ethyl acetate, butyl acetate, ethyl propionate,
Methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide and the like can be mentioned.

The steps of the latex dispersion method, effects, and specific examples of the latex for impregnation are described in US Pat. No. 4,199,363, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.

In the present invention, various color couplers can be used in combination, Research Disclosure, December 1978, 1764
Representative examples are the cyan, magenta and yellow dye-forming couplers described in Section 3VII-D and the patent cited in 18717, November 1979. It is preferable that these couplers have resistance to diffusion by introducing a ballast group or by polymerizing a dimer or more.
It may be an equivalent coupler or a two equivalent coupler. A coupler in which the dye formed is diffused to improve the graininess, and a DIR coupler which releases a development inhibitor along with the coupling reaction to bring about an edge effect or an interlayer effect can also be used.

The yellow coupler that can be used in combination with the present invention releases at an oxygen atom or a nitrogen atom. α-Pyvirol or α-benzoylacetanilide based couplers are preferred.
Particularly preferred specific examples of these two-equivalent couplers are oxygen atom-releasing yellow couplers described in U.S. Pat.
No. 4,314,023, JP-B-58-10739, JP-A-50-13
No. 2926, West German Application Publication No. 2,219,917, No. 2,261,361
No. 2,329,587, No. 2,433,812 and the like, nitrogen atom-releasing yellow couplers described in JP-A No. 2,329,587 and No. 2,433,812 are typical examples. Examples of magenta couplers include 5-pyrazolone-based couplers, pyrazolo [5,1-c] (1,2,4] triazoles described in U.S. Pat.No. 3,725,067, or hirazolo [5] described in European Patent 119,860. , 1-b] [1,
2,4] triazole can be used. A magenta coupler having two equivalents with a leaving group bonded to the coupling active position with a nitrogen atom or a sulfur atom is also preferable.

The cyan coupler of the present invention and the above-mentioned dye image forming coupler (main coupler) which can be used in combination usually have 16 to 32 carbon atoms.
The high-boiling organic solvent such as phthalic acid ester or phosphoric acid ester is used together with an organic solvent such as ethyl acetate, if necessary, and the emulsion is dispersed in an aqueous medium for use. The standard amount of the main coupler used is preferably 0.01 to 0.5 mol for the yellow coupler, 0.003 to 0.3 mol for the magenta coupler, and 0.002 to 0.3 mol for the cyan coupler per mol of the light-sensitive silver halide.

In the photographic emulsion layer of the photographic light-sensitive material of the present invention, any silver halide of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used. 30 is preferred
It contains less than mol% of silver iodide. It is silver iodobromide or silver iodochlorobromide. Particularly preferred is silver iodobromide containing 2 to 25 mol% silver iodide.

The shape of silver halide grains in a photographic emulsion is not particularly limited, and may be wavy regular grains having regular crystal bodies such as cubes, octahedra and tetradecahedrons, or spherical grains. It may have an irregular crystal form, a crystal defect such as a crystal face, or a composite form thereof.

The grain size of the silver halide may be fine grains of 0.1 micron or less, large grains having a projected area diameter of up to 10 microns, a monodisperse emulsion having a narrow distribution, or a polydisperse emulsion having a wide distribution.

Two or more kinds of silver halide emulsions formed separately may be mixed and used.

Further, tabular grains having an aspect ratio of 5 or more can be used in the present invention. Tabular grains are described in Cleve, Photography Theory and Pract.
ice (1930), p. 131; Gatov, Photographic Science and Engineering (Gutoff, Photogr
aphic Science and Engineering) Volume 14, pp. 248-257 (1970); U.S. Pat. Nos. 4,434,226 and 4,414,310,
It can be easily prepared by the method described in U.S. Pat. No. 4,434,048 and British Patent No. 2,112,157. The use of tabular grains has advantages such as an increase in covering power and an increase in color sensitization efficiency by a sensitizing dye, which is described in detail in US Pat. No. 4,434,226 cited above.

The crystal structure may be uniform or may have different halogen compositions inside and outside, and the layered structure may be eliminated. These emulsion grains are described in British Patent No. 1,027,146.
U.S. Pat. Nos. 3,505,068, 4,444,877, and Japanese Patent Application No. 58-248469. Further, silver halides having different compositions may be joined by epitaxial joining, or may be joined with compounds other than silver halide such as silver rhodanide and lead oxide.

The photographic emulsion used in the present invention may be spectrally sensitized with a known photographic sensitizing dye. In addition, a known antifoggant or stabilizer may be used for the purpose of preventing fogging during the production, storage or photographic processing of the light-sensitive material, or stabilizing the performance. For specific examples and usages thereof, U.S. Pat.Nos. 3,954,474, 3,982,947, Japanese Patent Publication No. 52-28660
Issue, Research Disclosure 17643 (December 1978)
Mon) VIA or VIM, and Barr, "Stabilization of silver halide photographic emulsions," Focal Press, Inc. (EJBirr, Stabili
zation of Photographic Silver Halide Emulsions ″, F
ocal Press, 1974) etc.

The light-sensitive material of the present invention may contain hydroquinones, aminophenols, sulfonamidephenols and the like as color fog preventing agents or color mixing preventing agents. Various anti-fading agents can be used in the light-sensitive material of the present invention,
There are organic inhibitors such as 5-hydroxycoumarans and spirochromans, and metal complex inhibitors represented by bis- (N, N-dialkyldithiocarbamate) nickel complexes.

An ultraviolet absorber such as benzotriazole may be used in combination with the light-sensitive material of the present invention, and typical examples thereof are described in Research Disclosure 24239 (June 1984). The light-sensitive material of the present invention may also contain a water-soluble dye in the hydrophilic colloid layer for the purpose of filter dye, prevention of irradiation or halation and other purposes.

As the binder for the photographic light-sensitive layer or the back layer of the present invention, gelatin, modified gelatin, synthetic hydrophilic polymer and the like can be used. In addition, a hardener such as a vinyl sulfone derivative may be contained in any hydrophilic cotoid layer,
Furthermore, a vinyl polymer containing a sulfinate in the side chain may be used as a hardening accelerator.

The light-sensitive material of the present invention contains one or more surfactants for various purposes such as coating aid, antistatic property, slipperiness improvement, emulsion dispersion, adhesion prevention and photographic property improvement (for example, acceleration of phenomenon, hardening, sensitization). But it is okay.

In the light-sensitive material of the present invention, in addition to the above-mentioned additives, various stabilizers, stain inhibitors, phenomenon agents or precursors thereof,
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 1976).

The present invention can be preferably applied to a high-speed photographic color film having at least two emulsion layers having the same color sensitivity and different sensitivities on a support. The order of layer arrangement is typically a red-sensitive layer, a green-sensitive layer and a blue-sensitive layer in order from the support side,
The inversion layer arrangement may be such that the high-sensitivity layer is sandwiched between emulsion layers having different color sensitivities.

In the processing method of the present invention, a light-sensitive material containing at least one naphthol-based coupler represented by the above general formula [I] or [II] is exposed, then color-developed by a known method, and optionally washed with water. Then, it is treated with a bath having a bleach-fixing ability. Here, a bath having a bleach-fixing ability (hereinafter referred to as a bleach-fixing bath) means a bath containing a bleaching agent and a fixing agent in one bath. Known bleaching agents include bleaching agents such as iron (III), cobalt (II
I), chromium (IV), compounds of polyvalent metals such as copper (II) (eg ferricyanide), peracids, quinones, nitroso compounds; dichromates; iron (III) or cobalt (III) Organic complex salts (for example, aminopolycarboxylic vinegars such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, complex salts of aminopolyphosphonic acid, phosphonocarboxylic acid and organic phosphonic acid) or organic acids such as citric acid, tartaric acid and malic acid; Persulfate; hydrogen peroxide; permanganate and the like can be used. Of these, organic complex salts of iron (III) and persulfates are preferable from the viewpoint of rapid treatment and environmental pollution. The aminopolycarboxylic acids or aminopolyphosphonic acids or salts thereof useful for forming organic complex salts of iron (III) are listed: ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediamine-N- (β-oxyethyl) -N , N ′,
N'-triacetic acid, 1,2-diaminopropanetetraacetic acid, triethylenetetraminehexaacetic acid, 1,3-diaminopropanetetraacetic acid, nitrilotriacetic acid, nitrilotripropionic acid, cyclohexanediaminetetraacetic acid, 1,3-diamino-2 -Propanol tetraacetic acid, methyliminodiacetic acid, iminodiacetic acid, hydroxyliminodiacetic acid, dihydroxyethylglycine ethyl ether diamine tetraacetic acid, glycol ether diamine tetraacetic acid, ethylenediamine tetrapropionic acid, ethylenediamine dipropionacetic acid, phenylenediamine tetraacetic acid, 2- Phosphonobtan-1,2,4-triacetic acid, 1,3-diaminopropanol-N, N, N ', N'-tetramethylenephosphonic acid, ethylenediamine-N, N, N', N'-tetramethylenephosphonic acid, 1,3-Propylenediamine-N, N, N ', N'-tetramethylenephos Examples include phosphonic acid, 1-hydroxyethylidene-1,1'-diphosphonic acid, and the like.

Among these compounds, iron (III) complex salts of ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 1,2-diaminopropanetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, and iminodiacetic acid can be used. It is preferred because of its high bleaching power. Further, in the present invention, these bleaching agents may be used in combination.

In the present invention, the amount of bleaching agent per bleach-fixing solution is 0.
The amount is 04 mol to 1.0 mol, preferably 0.08 mol to 0.5 mol.

Examples of the fixing agent contained in the bleach-fixing bath include thiosulfates such as sodium thiosulfate, ammonium thiosulfate, sodium ammonium thiosulfate and potassium thiosulfate, thiocyanates such as sodium thiocyanate, ammonium thiocyanate and potassium thiocyanate, Thiourea, thioether and the like can be used. The amount of these fixing agents is 0.3 to 4 mol, preferably 0.5 to 3 mol, per 1 bleach-fixing solution. Also, these fixing agents may be used in combination.

In the present invention, the above-mentioned bleach-fixing bath is basically used, but if a bleaching bath is provided before the bleach-fixing bath, a further excellent effect can be obtained. Here, the bleaching bath means a bath containing the bleaching agent but not the fixing agent.

In addition to the above bleaching agent and fixing agent, the bleach-fixing solution according to the present invention may contain various additives as required. Also, the bleaching bath may contain the following additives.

For example, sulfite salts such as sodium sulfite and ammonium sulfite, and pH adjusting agents such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, acetic acid, and sodium acetate, either alone or in combination of two or more. Can be included. In addition, various antifoaming agents, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid and the like, one or more inorganic acids and organic acids having a pH buffering capacity, and these. It is possible to add additives known to use a bleaching solution such as the salt of 1 above.

In the present invention, the amount of the bleaching agent per bleaching solution is 0.1 mol to 1 mol, preferably 0.2 mol to 0.5 mol. The pH of the bleaching solution is preferably 4.0 to 8.0 when used.

Further, the present inventors have found that in the treatment method of the present invention, in the bleaching bath, at least one bleaching accelerator or surfactant selected from a compound having a mercapto group or a disulfide bond, an isothiourea derivative and a thiazolidine derivative. Or an alkali metal halide such as potassium iodide, potassium bromide or ammonium bromide, ammonium halide, and further hydroxylamine, hydrazine, or a bisulfite adduct of an aldehyde compound.

The pH of the bleach-fixing solution according to the present invention is 5-8, preferably 6-7.5.

In the present invention, the bleaching time is preferably 20 seconds to 4 minutes, and when the bleaching accelerator of the general formulas (V) to (XIII) described later is used, it is more preferably 20 seconds to 2 minutes. When is not used, it is more preferably 1 minute to 4 minutes.

The bleach-fixing time is preferably 20 seconds to 15 minutes, more preferably 30 seconds to 10 minutes.

In the present invention, a washing step may be provided between the bleaching bath and the bleach-fixing bath. Further, the effect of the present invention is not impaired at all even if the washing process is a small amount of washing bath in which the amount of supplied water is extremely reduced. Further, the bleach-fixing bath may be divided into two or more baths, and it is particularly preferable that a countercurrent cascade pipe is provided from the rear bath to the front bath.

In the present invention, a replenisher is preferably introduced into the bleach-fix bath. At this time, the replenisher is a solution containing necessary components (for example, a bleaching agent and a fixing agent).

Furthermore, the overflow solution of the bleaching bath can be introduced into the bleach-fixing solution as the processing is carried out. Here, the overflow solution refers to a used bleach solution that has flowed out of the bleaching bath as a result of adding the bleach replenishing solution to the bleaching bath.

By this method, the bleaching agent component in the bleach-fixing bath can be maintained by the introduction of the overflow solution from the bleaching bath of the pre-bath, and therefore a very economical treatment can be performed.

In recent years, from the viewpoint of environmental pollution prevention, it has been desired to reduce the amount of photographic processing waste liquid having high biochemical oxygen demand (BOD) and chemical oxygen demand (COD). The reduction in volume allows for economical processing with low recovery processing costs.

In the method in which the replenisher is introduced into the bleach-fixing solution as described above, the overflow solution from the bleaching bath which has been conventionally discharged is introduced into the bleach-fixing bath and is replenished in the bleach-fixing bath. It can also serve as a medium for diluting the components to the preferred concentrations. Therefore, the solution to be replenished in the bleach-fixing bath may remain in a concentrated state, and the effect that the amount of waste liquid generated as a result can be reduced can be obtained.

When a conventional bleaching bath is mixed with the fixing bath, the cyan dye is leucoized and the photographic performance is significantly impaired.Therefore, a washing process is usually provided between the bleaching bath and the fixing bath to prevent the mixture. It is considered to be extremely unfavorable to be mixed in the fixing solution, and the present invention in which an overflow solution of a bleaching bath is mixed with a fixing agent to form a bleach-fixing bath is completely different from the conventional wisdom. .

In the present invention, the amount of the bleaching bath overflow liquid introduced into the bleach-fixing bath and the amount of the fixing agent-containing liquid to be replenished to the bleach-fixing bath at the same time are set according to the concentrations of the bleaching agent and the fixing agent in the bleach-fixing bath. Can be set within the above range, and can be variously set depending on the concentration of the bleaching agent in the overflow solution to be introduced and the concentration of the fixing agent to be replenished, but preferably 150 ml to 900 ml per 1 m ² of the light-sensitive material.

In the replenisher for the bleach-fixing bath in the present invention, known fixing agents such as ammonium thiosulfate and sodium thiosulfate, and additives that can be added to the fixing solution such as sulfite, bisulfite, various buffers and chelating agents. Can all be added. The concentration of each component in these replenishing solutions can be set so that when it is mixed with the overflow solution of the bleaching bath and diluted, it becomes a concentration necessary as a bleach-fixing solution, and it is usually higher than the case of replenishing in the fixing bath. Can also be enriched. As a result, the amount of liquid discharged is also reduced, and the burden of recovery processing can be reduced.

The concentration of the fixing agent contained in the replenisher for the bleach-fixing bath is preferably 0.5 to 4 mol / l, more preferably 1 to 3
Mol / l, and the pH of the replenisher is preferably 6-10, 7
Up to 9 are more preferable. Further, ferric aminopolycarboxylic acid complex salts, ammonium halides such as ammonium bromide, sodium bromide and sodium iodide, and alkali metal halides may be added.

In the present invention, in order to introduce the overflow solution of the bleaching bath into the bleach-fixing bath, the overflow tube of the bleaching bath may be directly connected to the bleach-fixing bath so that the overflow solution directly enters the bleach-fixing bath. Alternatively, the overflow solution may be once stored outside the tank and mixed with the solution containing the fixing agent and then transferred into the bleach-fixing bath or separately from the fixing agent.

In the present invention, the bleaching accelerator that can be contained in the bleaching bath or the bleach-fixing bath is selected from compounds having a mercapto group or a disulphide bond, thiazolidine derivatives, thiourea derivatives and isothiourea derivatives. Any compound having a bleaching promoting effect may be used, but those represented by the following general formulas [V] to [XII] are preferable.

General formula [V] In the formula, R ₂₁ and R ₂₂ may be the same or different, and a hydrogen atom,
A substituted or unsubstituted lower alkyl group (preferably having a carbon number of 1 to 5, particularly preferably a methyl group, an ethyl group or a propyl group) or an acyl group (preferably having a carbon number of 1 to 3, such as an acetyl group or a propionyl group); , N is 1 to 3
Is an integer.

R ₂₁ and R ₂₂ may combine with each other to form a ring.

As R ₂₁ and R ₂₂ , a substituted or unsubstituted lower alkyl group is particularly preferable.

Here, examples of the substituent that R ₂₁ and R ₂₂ have include a hydroxyl group, a carboxyl group, a sulfo group, and an amino group.

General formula [VI] In the formula, R ₂₃ and R ₂₄ have the same meanings as R ₂₁ and R _{22 in} the general formula [V]. n is an integer of 1 to 3.

R ₂₃ and R ₂₄ may combine with each other to form a ring.

As R ₂₃ and R ₂₄ , a substituted or unsubstituted lower alkyl group is particularly preferable.

Here, examples of the substituent that R ₂₃ and R ₂₄ have include a hydroxyl group, a carboxyl group, a sulfo group, and an amino group.

General formula (VII) General formula (VIII) General formula (IX) In the formula, R ₂₅ represents a hydrogen atom, a halogen atom, (for example, a chlorine atom, a bromine atom, etc.), an amino group, a substituted or unsubstituted lower alkyl group (preferably having a carbon number of 1 to 5, especially a methyl group, an ethyl group, Propyl group is preferred), an amino group having an alkyl group (methylamino group, ethylamino group,
Dimethylamino group, diethylamino group, etc.).

Here, as the substituent which R ₂₅ has, a hydroxyl group,
A carboxyl group, a sulfo group, an amino group etc. can be mentioned.

General formula (X) In the formula, R ₂₆ and R ₂₇ may be the same or different and each is a hydrogen atom or an alkyl group which may have a substituent (preferably a lower alkyl group such as a methyl group, an ethyl group or a propyl group), A phenyl group which may have a substituent or a heterocyclic group which may have a substituent (more specifically, a heterocycle containing at least one hetero atom such as a nitrogen atom, an oxygen atom, a sulfur atom) Group, for example, a pyridine ring, a thiophene ring, a thiazolidine ring, a benzoxazole ring, a benzotriazole ring, a thiazole ring, an imidazole ring, etc., and R ₂₆ is a hydrogen atom or a lower alkyl group which may have a substituent (for example, Methyl group, ethyl group, etc., preferably having 1 to 3 carbon atoms.

Here, examples of the substituents possessed by R _{26 to} R ₂₈ include a hydroxyl group, a carboxyl group, a sulfo group, an amino group, and a lower alkyl group.

R ₂₉ represents a hydrogen atom or a carboxyl group.

General formula (XI) In the formula, R ₃₀ , R ₃₁ , and R ₃₂ may be the same or different and each represents a hydrogen atom or a lower alkyl group (eg, methyl group, ethyl group, etc., preferably 1 to 3 carbon atoms).

R ₃₀ and R ₃₁ or R ₃₂ may combine with each other to form a ring.

X is a substituent (eg, a lower alkyl group such as a methyl group,
It represents an amino group, a sulfo group, a sulfonic acid group or a carboxyl group which may have an alkoxyalkyl group such as an acetoxymethyl group.

R _{30 to} R ₃₂ are particularly preferably a hydrogen atom, a methyl group or an ethyl group, and X is preferably an amino group or a dialkylamino group.

General formula (XII) In the formula, R ₄₁ and R ₄₂ represent a hydrogen atom, a hydroxyl group, a substituted or unsubstituted amino group, a carboxy group, a sulfo group or a substituted or unsubstituted alkyl group, and R ₄₃ and R ₄₄ represent a hydrogen atom, a substituted or unsubstituted It represents a substituted alkyl group or a substituted or unsubstituted acyl group, and R ₄₃ and R ₄₄ may be linked to form a ring. M represents a hydrogen atom, an alkali metal atom or an ammonium group, and n represents an integer of 2 to 5.

General formula (XIII) In the formula, X represents N or C—R, and R, R ₅₁ , R ₅₂ and
R ₅₃ represents a hydrogen atom, a halogen atom, an amino group, a hydroxyl group, a carboxy group, a sulfo group or a substituted or unsubstituted alkyl group, and R ₅₄ and R ₅₅ represent a hydrogen atom, a substituted or unsubstituted alkyl group or an acyl group. Represent, R ₅₄ and R ₅₅
May be linked together to form a ring. However, neither R ₅₄ nor R ₅₅ is a hydrogen atom. n represents an integer of 0 to 5.

Preferred specific examples of the compounds represented by formulas (V) to (XIII) are shown below.

Although any of the above compounds can be synthesized by a known method, particularly for the compound of the general formula (V), US Pat.
5,954, G. Schwarzenbach et al., Helv. Chi.
m.Acta.), 38 , 1147 (19555), RO Clinton et al., Journal of American Chemical Society (ROClinton et al., J.Am.Chem.SOC.), 70 , 950 (19).
48) and compounds of general formula (VI) are disclosed in JP-A-53-95630.
JP-A Nos. 54-52534 and JP-A Nos. 51-68568 and 51-70763 for compounds of the general formula (IX). Same as 53-50169
Japanese Patent Publication No. 53-985.
No. 4, Japanese Patent Application No. 58-88938, and for compounds of the general formula (XI), JP-A No. 53-94927, general formula (XII)
Compound of Advanced in heterocyclic
Chemistry (Advanced in Heterocyclic Chemistr
y), 9 , 165 to 209 (1968), can be easily synthesized by alkylation of 2,5-dimercapto-1,3,4-thiadiazole, and is represented by the general formula (XIII). The compound is A. Wall, W. Marckwald, Berichte (A. Wohl, W. Marckwald, Ber), 22 , 568 (1889), M. Freund, Berichte (M. Freund, Ber.), 29 , 2483 ( 189
6), APT Airson et al., Journal of Chemical Society (APTEasson et al., J. Chem. Soc.), 193 .
2 , 1806 and RG Johns et al., Journal of American Chemical Society (RG Jones et al., J. Am. Che
m.Soc., 71 , 4000 (1949)) and the like.

The amount of the compound having a mercapto group or disulfide bond in the molecule, the thiazoline derivative or the isothiourea derivative, which is added to the liquid having the bleaching ability, depends on the kind of the photographic material to be processed, the processing temperature, and the intended processing. 1 × 10 per treatment liquid, depending on time etc.
^-5 to 10 ^-1 mol is suitable, preferably 1 x 10 ^{-4 to} 5 x
It is 10 ^-2 mol.

To add these compounds to the treatment liquid, it is common to dissolve them in water, an alkali organic acid organic solvent or the like in advance, and add them directly as a powder to the bleaching bath. There is no effect on the bleaching promoting effect.

In the treatment method of the present invention, it is possible to use a simple treatment method in which after the treatment in the bleaching can bathing, only washing is performed, or conversely, only stabilizing treatment is performed without providing a substantial washing step.

In the washing process, for the purpose of preventing precipitation and stabilizing the washing water,
Various known compounds may be added. For example, chelating agents such as inorganic phosphoric acid, aminopolycarboxylic acid, and organic phosphonic acid, bactericides and antifungal agents that prevent the generation of various bacteria, algae, and molds (for example, Journal of Antibacterial and Anti-Fungal Agents (J.Antibact.Antifung.Agents) vol.11, No.5, p207-
223 (1983) and compounds described in Hiroshi Horiguchi's "Chemistry of Microbiosis Control", metal salts represented by magnesium salts and aluminum salts, alkali metal and ammonium salts, or drying load and unevenness. A surfactant or the like for prevention can be added if necessary. Or West Photographic Science and Engineering Magazine (Phot.Sci.Eng.), Volume 6, 3
The compounds described on pages 44 to 359 (1965) and the like may be added. It is particularly effective to add a chelating agent or a bactericide / antifungal agent.

The water washing step is performed by multi-stage countercurrent water washing of two or more tanks (for example, 2-9
It is also possible to reduce the amount of washing water by using a tank). Further, instead of the washing step, a multistage countercurrent stabilization treatment step as described in JP-A-57-8543 may be carried out. Various compounds are added to the stabilizing bath for the purpose of stabilizing the image. For example membrane pH
Buffers (eg, borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, ammonia water, monocarboxylic acid, etc.) for adjusting (for example, pH 3 to 8) Representative examples include aldehydes such as dicarboxylic acid and polycarboxylic acid used in combination) and formalin. Other chelating agents (inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphonic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.), bactericidal agents (thiazole-based, isothiazole-based, halogenated phenol, sulfanilamide, benzotriazole, etc.) ), Various additives such as surfactants, optical brighteners and hardeners may be used, 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 in order to improve the image storability.

Further, in the case of the color photosensitive material for photographing, the (washing-stabilizing) step after fixing which is usually performed can be replaced with the above-mentioned stabilizing step and the washing step (water saving processing). At this time, if the magenta coupler is 2 equivalents, the formalin in the stabilizing bath may be removed.

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. In order to save photographic 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.

In addition, each processing time can be shortened from the standard time within a range that does not cause any trouble in order to accelerate the processing.

The silver halide color photographic material used in the present invention may contain a color developing agent or a precursor thereof for the purpose of simplifying and accelerating the processing. For incorporation, a precursor is preferable because it improves the stability of the photographic material. Specific examples of the developer precursor include, for example, indoaniline compounds described in US Pat. No. 3,342,597, No. 3,342,599, Research Disclosure 1
No. 4850 (August 1976) and No. 15159 (November 1976)
Schiff base type compounds described, aldol compounds described in the same 13924, metal salt complexes described in US Patent No. 3,719,492,
There are urethane compounds described in JP-A-53-135628, JP-A-56-6235, JP-A-56-16133, JP-A-56-59232, and JP-A-56-67.
No. 842, No. 56-83734, No. 56-83735, No. 56-83736,
56-89735, 56-81837, 56-54430, 56-106
241, 56-107236, 57-97531 and 57-83565
The various salt type precursors described in US Pat.

The silver halide color photographic material used in the present invention includes
To promote color development, various 1-phenyl-3-
Pyrazolidones may be incorporated. Typical compounds are JP-A Nos. 56-64339, 57-144547, 57-211147, and
58-50532, 58-50536, 58-50533, 58-50534
No. 58-50535 and No. 58-115438.

Further, in the case of continuous processing, a constant finish can be obtained by using a replenisher for each processing solution to prevent fluctuations in the liquid composition. The replenishment amount can be reduced to half or less than the standard replenishment amount for cost reduction.

If necessary, a heater, a temperature sensor, a liquid level sensor, a circulation pump, a filter, various floating pigs, various squeegees, etc. may be provided in each processing bath.

The present invention can be applied to various color light-sensitive materials. Typical examples include color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers. The present invention also relates to Research Disclosure 17123 (July 1978).
It is also applicable to a black and white light-sensitive material using a mixture of three-color couplers described in (Mon.). Of these, it is particularly preferable to apply to a color negative film.

Example 1 On a triacetyl cellulose film support, a multi-layer color negative film sample consisting of each layer having the composition shown below was prepared.

1st layer: Antihalation layer Gelatin layer containing black colloidal silver 2nd layer: Intermediate layer Gelatin layer containing emulsified dispersion of 2,5-di-t-octylhydroquinone 3rd layer: Low sensitivity red sensitive emulsion layer Odor Silver halide emulsion (silver iodide: 5 mol%): Silver coating amount: 1.6 g / m ² Sensitizing dye I: 6 mol per mol of silver 6 × 10 ^-4 mol Sensitizing dye II :: 1 mol of silver To 1.5 × 10 ^-4 mol Coupler (listed in Table-1) …… 0.04 mol to 1 mol silver EX-1 …… 0.003 mol to 1 mol silver Coupler EX-2 …… 1 mol silver To 0.0006 mol 4th layer; high-sensitivity red-sensitive emulsion layer Silver iodobromide emulsion (silver iodide; 10 mol%) ... Silver coating amount 1.4 g / m ² Sensitizing dye I ......... to 1 mol of silver 3 × 10 ⁻⁴ mol Sensitizing dye II: 1.2 × 10 ⁻⁴ mol coupler for 1 mol of silver (shown in Table 1): 0.02 mol for 1 mol of silver Coupler EX-1: 1 silver 0.0016 moles per mole Fifth layer; the same sixth layer and the intermediate layer a second layer; Low speed green-sensitive emulsion layer Monodisperse silver iodobromide emulsion (silver iodide: 4 mol%) ... coating amount of silver 1.2g
/ m ² Sensitizing dye III ………… 3 × 10 ^-4 mol for 1 mol silver sensitizing dye IV ………… 1 × 10 ^-4 mol for 1 mol silver Coupler EX-3 …… 1 mol silver To 0.05 mol Coupler EX-4 ... 0.008 mol to 1 mol silver Coupler EX-2 ... 0.0015 mol to 1 mol silver 7th layer; high-sensitivity green acid emulsion layer Silver iodobromide emulsion (iodine Silver halide: 10 mol%) Coating silver amount 1.3 g / m ² Sensitizing dye III ………… 2.5 × 10 ⁻⁴ mol for 1 mol of silver Sensitizing dye IV ………… 0.8 × for 1 mol of silver 10 ^-4 mol Coupler EX-5 ...... 0.017 mol per 1 mol silver Coupler EX-4 ...... 0.003 mol per 1 mol silver Coupler EX-6 ...... 0.003 mol per 1 mol silver 8th layer; Yellow filter layer Gelatin layer containing yellow colloidal silver and emulsified dispersion of 2,5-di-t-octylhydroquinone in aqueous gelatin solution Ninth layer; low sensitivity blue emulsion layer Silver iodobromide emulsion (silver iodide; 6 mol%) Coated silver amount 0.7 g / m ² Coupler EX-7 ...... Ag 0.015 mol 10th layer against 0.25 mole coupler EX-2 ...... 1 mol of silver relative to the molar; high-speed blue-sensitive emulsion layer Silver iodobromide (Silver iodide; 6 mol%) Coating amount 0.6 g / m ² Coupler EX-7: 0.06 mol per 1 mol of silver 11th layer; 1st protective layer Silver iodobromide (1 mol of silver iodide %, Average particle size 0.07μ) ... Coating silver amount 0.5g Gelatin layer containing emulsified dispersion of UV absorber UV-1 12th layer; 2nd protective layer Gelatin layer containing trimethylmethanoacrylate particles (diameter about 1.5μ) Apply.

In addition to the above composition, a gelatin hardening agent H-1 and a surfactant were added to each layer.

Compounds used to make samples Sensitizing dye I: Anhydro-5,5'-dichloro-3,3'-di-
(Γ-Sulfopropyl) -9-ethyl-thiacarbocyanine hydroxide / pyridinium salt Sensitizing dye II: anhydro-9-ethyl-3,3′-di- (γ
-Sulfopropyl) -4,5,4'-5'-dibenzothiacarbocyanine hydroxide triethylamine salt Sensitizing dye III: anhydro-9-ethyl-5,5'-dichloro-3,3'-di- ( γ-Sulfopropyl) oxacarbocyanine sodium salt Sensitizing dye IV: Anhydro-5,6,5 ′, 6′-tetrachloro-
1,1'-diethyl-3,3'-di- (β- [β- (γ-sulfopropyl) ethoxy] ethylimidazolocarbocyanine hydroxide sodium salt _{H-1 CH 2 = CH-} SO 2 -CH 2 -CONH- (CH 2) 2 NHCOCH 2 SO 2 CH = CH 2 Tungsten light source was used for the color light-sensitive material prepared in this way, and the color temperature was adjusted to 4800 ° K with a filter.
After giving a wedge exposure of S, follow the process steps below 3
Development processing was performed at 8 ° C.

Color development 3 minutes 15 seconds Bleach fixing Processing time shown in Table-1 Washing 1 minute 40 seconds Stability 40 seconds The composition of the processing solution used in each step above is as follows.

<Color developer> Diethylenetriamine pentaacetic acid 1.0g 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0g Sodium sulfite 4.0g Potassium carbonate 30.0g Potassium bromide 1.4g Potassium iodide 1.3mg Hydroxylamine sulfate 2.4g 4- ( N-ethyl-N-β-hydroxylethylamino) -2-methylaniline sulphate 4.5g Water added 1 pH 10.00 <bleach fixer> Ethylenediaminetetraacetic acid ferric ammonium salt 80.0g Ethylenediaminetetraacetic acid disodium salt 5.0 g Sodium sulfite 12.0 g Ammonium thiosulfate 240 ml Aqueous solution (70%) Ammonia water (28%) 10.0 ml Add water 1 pH pH shown in Table 1 <Stabilizer> Formalin (37% W / V) 2.0 ml Polyoxyethylene -P-Monononyl phenyl ether (average degree of polymerization 10) 0.3g Water was added 1 The gradation of each sample that had been subjected to the above treatment was examined. It was

Fuji Photo Film Co., Ltd. Fuji Color Process CN-16 treatment (color development 3 minutes 15 seconds, bleaching 6 minutes 30 seconds, water washing 2 minutes 10 seconds, fixing 4 minutes 20 seconds, water washing 3 minutes 15)
Second, stabilization treatment for 1 minute and 5 seconds, and then dried. The processing temperature was set at 38 ° C.), and the gradation was examined in the same manner, and the results were compared with the results of each processing step.

The comparison result is the characteristic value of each process and the standard process (CN-16 process)
Table 1 shows the difference in the characteristic values of. Therefore, Table-1
The numerical value of the gradation of is far from 0, the deviation from the standard processing is large, and the photographic property is poor.

Here, the gradation is determined by the following method.

Gradation: Based on the exposure amount that increases 0.2 from the minimum density in the standard processed sample, the density value at this exposure amount for each processed sample and the density value at the point where the exposure amount which is logarithmically 1.5 is added to the exposure value The difference was taken as the gradation.

In Table-1, Comparative Compounds A, B and C are the following cyan dye forming couplers.

As is clear from Table-1, when the pH of the bleach-fixing solution is lowered, the conventional cyan dye-forming couplers are sample Nos. 5 and 6.
As can be seen from the above, the gradation of the R layer is lowered, but when the cyan dye-forming couplers of the present invention (general formulas I and II) are combined, excellent photographic properties can be obtained without cyanation of the cyan dye. Recognize.

Example 2 Ethylenediamine 4 in bleaching solution and bleach-fixing solution of Example 1
The same treatment as in Example 1 was performed except that the ferric ammonium acetate was replaced with diethylenetriamine pentaacetic acid ferric ammonium salt. The results were the same as in Example 1.

Example 3 The color light-sensitive material of Example 1 was exposed to light in the same manner as in Example and processed in the following processing steps.

Color development 3 minutes 15 seconds Bleach fixing 4 minutes Washing with water 1 minute 40 seconds Stability 40 seconds The composition of the processing solution used for each processing step is as follows.

<Color developer> Same as in Example 1 <Bleaching fixer> Ethylenediaminetetraacetic acid ammonium ferric acid 80.0 g Ethylenediaminetetraacetic acid disodium salt 5.0 g Sodium sulfite 12.0 g Ammonium thiosulfate aqueous solution (70%) 240 ml Ammonia water (28%) 10.0 ml Bleach Accelerator ^* 1 × 10 ⁻² mol Water was added 1 pH pH shown in Table 2 Compound VI- (1) was used as a bleach accelerator.

<Stabilizer> Same as in Example 1.

As in the case of Example 1, the gradation of each sample subjected to the above-mentioned treatment is shown in Table-2 with the difference from the value of standard treatment.

As is clear from Table 2, even if a bleaching accelerator is added and the bleach-fixing time is shortened, combination of the cyan dye-forming couplers of the present invention (general formulas I and II) does not lead to leuco cyanation and is excellent. It can be seen that the sex is obtained.

Further, when the same test was conducted by changing to the bleaching accelerators VII- (2) and VIII- (2), the same result was obtained.

Example 4 Example 1 except that the composition of the bleach-fix solution was changed as follows.
The same process was performed.

The results are shown in Table-3.

As is clear from Table 3, even if the Fe ²⁺ concentration in the bleach-fix solution is high, the same effect as in Example 1 can be obtained.

<Bleach-fixing solution> ethylenediaminetetraacetic acid ferric ammonium salt 64.0g ethylenediaminetetraacetic acid ferrous ammonium salt 16.0g ethylenediaminetetraacetic acid disodium salt 5.0g sodium sulfite 12.0g ammonium thiosulfate aqueous solution (70%) 240ml ammonia water (28% ) Addition of 11 ml water 1 pH pH shown in Table 3 The bleach-fix solution is a solution assuming a running state.

Example 5 Processing was carried out in the same manner as in Example 1 except that a bleaching bath having the following composition was provided in front of the bleach-fixing bath and the processing was carried out under the conditions shown in Table-4. The results are summarized in Table-4.

<Bleach> Ethylenediaminetetraacetic acid ferric ammonium salt 120g Ethylenediaminetetraacetic acid disodium salt 10.0g Ammonia water (28%) 17.0ml Ammonium nitrate 10.0g Ammonium bromide 100g Water is added 1 pH 6.5 As is clear from Table-4, the desilvering time was 4 minutes (bleaching 1 minute
30 seconds, bleach-fixing 2 minutes and 30 seconds)
As shown in No. 2, the gradation of the R layer is lowered, but when the cyan dye-forming couplers of the present invention (general formulas I and II) are combined, desilvering property and no leuco formation of the cyan dye are excellent. The photographic quality can be secured.

Example 6 The same procedure as in Example 5 was carried out except that diethylenetriaminepentaacetic acid ferric ammonium salt was replaced with ethylenediaminetetraacetic acid ferric ammonium salt in the bleaching solution and the bleach-fixing solution. The results were the same as in Example 5.

Example 7 The color light-sensitive material of Example 1 was exposed in the same manner as in Example 1 and processed in the following processing steps.

Color development 3 minutes 15 seconds Bleaching 50 seconds Bleaching fixing 2 minutes 30 seconds Water washing 1 minute 40 seconds Stability 40 seconds The composition of the processing solution used for the above steps is as follows.

<Color developer> The same as in Example 1.

<Bleach> ethylenediaminetetraacetic acid ferric ammonium salt 120g disodium ethylenediaminetetraacetate salt 10.0g ammonia solution 17.0ml nitrate 10.0g ammonium bromide 100 g (1.02 mol) bleaching accelerator VI- (1) 5 × 10 ^-3 mol Add water 1 pH 6.5 <bleach-fixing solution> Ethylenediaminetetraacetic acid ferric ammonium salt 50.0g Ethylenediaminetetraacetic acid disodium salt 5.0g Sodium sulfite 12.0g Ammonium thiosulfate aqueous solution (70%) 240ml Ammonia water (28%) 10.0ml Ammonium bromide 40 g pH 7.3 <Stabilizer> Same as in Example 1.

For each sample that has been subjected to the above processing, check the gradation,
Further, the amount of silver remaining in the highest density portion was measured by fluorescent X-ray analysis.

The results are shown in Table-5.

As is clear from Table 5, when a bleaching accelerator is added to the bleaching solution, the bleaching time can be further shortened and the gradation of the R layer is not lowered. Further, the same test was carried out by changing the bleaching agent to VII- (2) and VIII- (2), and the desilvering property was VI- (1).
However, the gradation of the R layer did not deteriorate.

Example 8 The same treatment as in Example 7 was carried out except that the composition of the bleaching solution was changed as follows. The results were the same as in Example 7.

<Bleach> Ethylenediaminetetraacetic acid ferric ammonium salt 120g Ethylenediaminetetraacetic acid disodium salt 12g Ammonia water (28%) 10ml Sodium sulfite 2g Ammonium thiosulfate aqueous solution (70%) 10ml Ammonium nitrate 11g Ammonium bromide 100g Bleach accelerator (IV) -(1) 5 × 10 ⁻³ mol of water was added to give 1 pH 6.4 Example 9 The same treatments as in Example 4 were carried out except that the compositions of the bleaching solution and the bleach-fixing solution were changed as follows. The results are shown in Table-6. As is clear from Table-6, even if the Fe ²⁺ concentration in the bleaching solution and the bleach-fixing solution is high, the same effect as in Example 4 can be obtained (the desilvering property is good and the cyan dye is not leucoized). ).

<Bleach> Ethylenediaminetetraacetic acid ferric ammonium salt 102g Ethylenediaminetetraacetic acid ferrous ammonium salt 18.0g Ethylenediaminetetraacetic acid disodium salt 10.0g Ammonia water (28%) 18.0ml Ammonium nitrate 10.0g Ammonium bromide 100g Add water 1 pH (25 ° C) 6.5 <bleach-fixing solution> Ethylenediaminetetraacetic acid ferric ammonium salt 35.0g Ethylenediaminetetraacetic acid ferrous ammonium salt 15.0g Ethylenediaminetetraacetic acid disodium salt 5.0g Sodium sulfite 12.0g Ammonium thiosulfate aqueous solution (70% ) 240 ml Ammonia water (28%) 11.0 ml Water is added for 1 pH (25 ° C) 7.3 The above bleaching solution and bleach-fixing solution are solutions assuming a running state.

Example 10 The coupler EX-1 of the multilayer color negative film of Example 1 was used as EX.
A multilayer color negative film sample was prepared in the same manner as in Example 1 except that it was changed to -10, and the same processing as in Example 1 was carried out, and the same results as in Example 1 were obtained.

Example 11 The same process as in Example 5 was carried out except that the same sample as the multilayer color negative film sample used in Example 10 was used, and the same result as in Example 5 was obtained.

Example 12 Ethylenediaminetetraacetic acid second in bleach-fix solution of Example 1
Iron ammonium salt is equimolar to cyclohexanediamine 4
The same treatment as in Example 1 was performed except that the ferric acetate ammonium salt was replaced. The results are shown in Table-7.

As is clear from Table-7, it can be seen that the same effects as in Example 1 can be obtained in this example as well.

Example 13 Except that the ethylenediaminetetraacetic acid ferric ammonium salt in the bleaching solution and the bleach-fixing solution of Example 5 was replaced with an equimolar amount of cyclohexanediaminetetraacetic acid ferric ammonium salt.
The same process as in Example 5 was performed. The results are shown in Table-8.

As is apparent from Table-8, it can be seen that the same effects as in Example 5 can be obtained in this example as well.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Abe Abe, 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture, Fuji Photo Film Co., Ltd. (56) References JP-A-58-50532 (JP, A) JP-A-58-115438 ( JP, A) JP 61-41145 (JP, A) JP 61-50142 (JP, A)

Claims (5)

[Claims] 1. A method of processing an exposed silver halide color photographic light-sensitive material, comprising a step of processing in a bath having a bleach-fixing ability after color development, and the silver halide color photographic light-sensitive material is A method for processing a silver halide color photographic light-sensitive material, which comprises at least one cyan dye forming coupler represented by the formula [I]. (In the formula, R ₁ is -CONR ₅ R ₆ , -NHCOR ₅ , -NHCOOR ₇ , -NHSO.
₂ R ₇ , -NHCONR ₅ R ₆ or -NHSO ₂ NR ₅ R ₆ , R ₂ is a group capable of substituting for a naphthol ring, m is an integer of 0 to 3, and R ₃ is -C.
_{OOR 9, -COR 9, -SO 2} R 11, a -CONR ₉ R ₁₀ or -SO ₂ NR ₉ R _10,
X represents a hydrogen atom or a group capable of splitting off by a coupling reaction with an oxidized product of an aromatic primary amine developing agent. However, R ₅ and R ₆ may be the same or different and independently represent a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group, and R ₇ represents an aliphatic group, an aromatic group or a heterocyclic group. Represent.
Further, R ₉ , R ₁₀ and R ₁₁ have the same meanings as R ₅ , R ₆ and R ₇ , respectively. In the formula, when m is plural, R _{2 s} may be the same or different and may be bonded to each other to form a ring. R ₂ and R ₃ , or R ₃ and X may be bonded to each other to form a ring.) 2. A bath having a bleach-fixing ability is at least one selected from the group consisting of a compound having a mercapto group or a disulfide bond, an isothiourea derivative and a thiazolidine derivative.
A processing method according to claim (1) containing a bleaching accelerator. 3. A method of processing an exposed silver halide color photographic light-sensitive material, comprising a step of processing in a bleaching bath and a bath having a bleach-fixing ability after color development, wherein the silver halide color photographic light-sensitive material is A method for processing a silver halide color photographic light-sensitive material, which comprises at least one cyan dye forming coupler represented by the following general formula [I]. (In the formula, R ₁ is -CONR ₅ R ₆ , -NHCOR ₅ , -NHCOOR ₇ , -NHSO.
₂ R ₇ , -NHCONR ₅ R ₆ or -NHSO ₂ NR ₅ R ₆ , R ₂ is a group capable of substituting for a naphthol ring, m is an integer of 0 to 3, and R ₃ is -C.
_{OOR 9, -COR 9, -SO 2} R 11, a -CONR ₉ R ₁₀ or -SO ₂ NR ₉ R _10,
X represents a hydrogen atom or a group capable of splitting off by a coupling reaction with an oxidized product of an aromatic primary amine developing agent. However, R ₅ and R ₆ may be the same or different and independently represent a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group, and R ₇ represents an aliphatic group, an aromatic group or a heterocyclic group. Represent.
Further, R ₉ , R ₁₀ and R ₁₁ have the same meanings as R ₅ , R ₆ and R ₇ , respectively. In the formula, when m is plural, R _{2 s} may be the same or different and may be bonded to each other to form a ring. R ₂ and R ₃ , or R ₃ and X may be bonded to each other to form a ring.) 4. A bath having a bleach-fixing ability is a fixing bath,
The processing method according to claim (3), wherein the bleach-fixing bath is formed by moistening the bleaching solution from the bleaching bath in the previous step. 5. A bath having a bleach-fixing ability is at least one selected from the group consisting of a compound having a mercapto group or a disulfide bond, an isothiourea derivative and a thiazolidine derivative.
A processing method according to claim (3) containing a bleach accelerating agent.