JPS6292947A - Processing of silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To reduce consumption of a washing water by incorporating a specific salt of an org. acid to the water-washing bath of the water-washing treatment carried out after a fixing treatment, and by controlling a replenisher for the washing bath to a specific amount. CONSTITUTION:One or more of salts selected among a sodium or a potassium salt of an aminocarboxylic acid, an aminosulfonic acid, a phosphoric acid and a phosphonocarboxylic acid are incorporated into the water-washing bath used after the treatment of a bath having a fixing ability during the processing of the titled material. The amount of the replenisher of the water-washing bath is controlled to 3-50 times of the amount carried in the washing bath from the previous treating bath per an unit area of the sensitive material to be treated. The chelating agent such as the prescribed sodium or potassium salt has not only a bactericidal action against a bacteria but also a stabilizing action for the water-washing solution, and also has an excellent preventing property for a discoloring of a cyan image. Even if the used amount of the water-washing solution is sufficiently controlled as mentioned above in the water-washing treatment, said solution may be stabilized, thereby making it possible to improve in the waste-water treatment and the movement of a developing machine. Thus, the image having a high cyan density and good storage property may be obtd.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a method for developing (hereinafter simply referred to as "processing") a silver halide color photographic light-sensitive material (hereinafter referred to as "color light-sensitive material"), and in particular, to a method for developing a silver halide color photographic light-sensitive material (hereinafter referred to as "color light-sensitive material"). It relates to a treatment method that can significantly reduce the amount of water used in the process.

(Prior art) In recent years, it has been suggested that the amount of water used in the washing process included in the processing of silver halide photographic light-sensitive materials should be reduced due to environmental conservation, water resource, or cost concerns. . For example, the Journal of the Society of Motion Picture and Television Engineers
ty of Motion Picture and T
e1evision Engineers) Volume 64,
“Water Flow Lake in Immersion Washing” on pages 248-253 (May 1955 issue)
of motion picture film (Water)
Flow Rates in Immersion-
Washing of Motion Picture
Fi1m″ Varnish R Goldweiser (S, 17
．． Goldwasser) proposes a method of reducing the amount of washing water by making the washing tank multistage and causing the water to flow countercurrently. Also, U.S. Patent No. 4,336,3
No. 24 proposes a system that saves water by carrying out a stabilization process after a bleach-fixing process without substantially undergoing a water washing process.

These methods are employed in various automatic processors as effective means for saving water.

(Problem to be Solved by the Invention) However, washing water containing iron ions and/or thiosulfate from a bath having a fixing ability (bleach-fixing bath or fixing bath) during processing is extremely undesirable. However, if the amount of water used for washing is significantly reduced, image storage stability deteriorates, and fading of cyan images in particular increases. Furthermore, the residence time of the washing water increases, resulting in the formation of various types of sediments and floating substances, which can adhere to photosensitive materials, clog or stain the filters of automatic processors, etc. , there was a need for improvement as it caused various troubles.

Since the contamination of the washing bath is largely due to bacterial growth, the inventors conducted various studies on compounds that have antibacterial effects and improve photographic performance. It has been found that the above-mentioned conventional drawbacks can be particularly effectively solved when the compound is contained in a washing bath, and the present invention has been achieved.

Therefore, a first object of the present invention is to provide a processing method that can reduce the amount of washing water to a sufficiently small amount after processing with a bath having fixing ability.

A second object of the present invention is to provide a treatment method that can stabilize washing water even if the amount of washing water is sufficiently reduced.

A third object of the present invention is to provide a processing method capable of obtaining images with good preservability even when the amount of water in the washing process performed after processing with a bath having fixing ability is sufficiently reduced.

Furthermore, a fourth object of the present invention is to provide a method for minimizing the amount of washing water used during development of silver halide color photographic materials.

(Means for Solving the Problems) The above-mentioned aspects of the present invention are, in the development processing method for a silver halide color photographic light-sensitive material, a water washing bath following the processing with a bath having a fixing ability performed in the development processing step. contains at least one salt selected from sodium salts or potassium salts of aminocarboxylic acids, aminophosphonic acids, phosphosonic acids, and phosphonocarboxylic acids, and the amount of replenishment of the water washing bath is This was achieved by a method for processing silver halide color photographic materials, which is characterized in that the amount carried over from the previous bath is 3 to 50 times the amount carried over from the previous bath per unit area of the photographic material to be processed.

The bath having the fixing ability described above may be composed of a plurality of baths. That is, the bath having fixing ability may be provided independently after the bleaching bath, may be provided as a bleach-fixing bath, or may be provided as a bleach-fixing bath after the bleaching bath.

After the fixing process or bleach-fixing process, processing processes such as water washing and stabilization are generally performed. Although a simple processing method can be used, the present invention is applicable to a water-saving type washing process that restricts the use of washing water and stably performs the entire development process without special drainage equipment. is particularly effective.

The water washing bath of the present invention contains a chelating agent such as a sodium salt or a potassium salt of aminopolycarboxylic acid, aminopolyphosphonic acid, polyphosphonic acid, phosphonocarboxylic acid, or the like. .

(Function) These chelating agents not only have a bactericidal effect against bacteria and contribute to the stabilization of washing water, but also have the unexpected effect of preventing fading of cyan images by using sodium and potassium salts in particular. effect can be obtained. The effect of preventing fading of cyan dye is small when ammonium salt is used.

Specific examples of chelating agents that can be included in the washing water to achieve the special effects of the present invention are shown below.

10, CH2PO3H2N-
CH2PO3H2 CH2PO3H2 11, CH2PO3H2 CH2PO3H2 The amount of the sodium salt or potassium salt of aminopolycarboxylic acid used in the present invention added to the washing water is lXl0 4~
lXl0 Imol/litre, preferably 5X10-4~2
X 10-2 mol/I! , particularly preferably lXl0-
3~lXl0-2 mol/I! It is. If it is less than 10-4 mol/l, the addition of these chelating agents has no effect, and if it is more than 10-1 mol/l, salts may precipitate on the film surface of the photosensitive material after drying. This is undesirable because it causes problems such as scum adhering to the hack surface or emulsion surface and furthermore, an increase in yellow stain.

Various compounds can be added to the washing process of the present invention for the purpose of preventing precipitation and stabilizing the washing water. For example, disinfectants and anti-inflammatory agents that prevent the growth of various bacteria, algae, or molds (e.g., Journal of Antibacterial and Antifungal Agents (J, 8nLibact)).

Antifung, 8 gents) 11th
Vol., N6, 5, pp. 207-223 (1983) and compounds described in Hiroshi Horiguchi's "Chemistry of Antibacterial and Antifungal"), metal salts such as magnesium salts and aluminum salts, alkali metals and Ammonium salts, surfactants for preventing drying load and unevenness, etc. can be added as necessary. Also, Photographic Science and Engineering Magazine by West (
Phot, Sci, Eng,), Volume 6, 344-3
Compounds described on page 59 (1965) may also be added. Examples of fungicides that can be used in combination include thiazole, isothiazole, halogenated phenol, sulfanilamide, and benzotriazole.

The washing process may be carried out in multiple directions using two or more tanks (for example, 2 to 9 tanks) to save washing water. Furthermore, instead of the water washing step, a multistage countercurrent stabilization treatment step as described in JP-A-57-8543 may be performed. Various compounds may be added to this water washing bath for the purpose of stabilizing the image, and various other additives such as surfactants, fluorescent brighteners, hardeners, etc. may also be used. Alternatively, two or more different target compounds may be used in combination.

Furthermore, in the case of color photosensitive materials for photography, the normally performed post-fixing (rinsing with water and stabilization) process can be replaced with the washing process (water-saving treatment) of the present invention. At this time, the magenta coupler is 2
In the case of equivalent amounts, formalin in the stabilizing bath may be removed.

In the color light-sensitive material processed in the present invention, silver bromide,
Any silver halide such as silver iodobromide, silver chlorobromide, silver chloroiodobromide, silver chloride, and silver chloroiodide may be used, but silver iodobromide is preferable for high-sensitivity light-sensitive materials.

In the case of silver iodobromide, the silver iodide content is usually 40 mol% or less, preferably 20 mol% or less. Photosensitive materials particularly suitable for processing in the present invention are those with a high silver content, about 3 or more grams per square meter, preferably 4.0 grams per square meter.
The above is a color photosensitive material for photography weighing up to about 12 g.

The above-mentioned silver halide grains may be so-called regular grains having a regular crystal structure such as a cube, octahedron, or dodecahedron, or may have an irregular crystal shape such as a spherical shape, or may have a twin crystal shape. It may be one with crystal defects such as planes, or a composite form thereof. Mixtures of particles of various crystalline forms may also be used.

The grain size of the silver halide mentioned above may be fine grains of about 0.1 micron or less, large grains with a projected area diameter of about 10 microns, monodispersed emulsions with a narrow distribution, or polydisperse emulsions with a wide distribution. A dispersed emulsion may also be used.

Further, tabular grains having an aspect ratio of 5 or more may be used in the above emulsion layer.

The crystal structure of the emulsion grains described above may be uniform, the inside and outside may have different silver halide compositions, or they may have a layered structure. These emulsion grains are described in British Patent No. 2,027,146, US Patent No. 3,505.
No. 068, No. 4,444.877 and JP-A No. 1986-1
No. 4333, etc. Further, silver halides having different compositions may be bonded by epitaxial bonding, or compounds other than silver halide such as silver rhodan or lead oxide may be bonded.

The above-mentioned emulsion may be of a surface latent image type in which a latent image is mainly formed on the surface, an internal latent image type in which a latent image is formed inside the grains, or a type in which a latent image is formed both on the surface and inside the grains.

The silver halide photographic emulsion of the color light-sensitive material used in the present invention can be produced using any known method, for example, Research Disclosure, 1768, 17643 (
December 1978), pp. 22-23 \ “■, Emulsion preparation and
Types)” and volume 187, 11h18716
(November 1976), p. 648.

The photographic emulsion used in the color light-sensitive material used in the present invention is described in "Physics and Chemistry of Photography" by Glufkides, published by Beaumontel (P., Glufkides, Chimiee).
t Physique Photographique
, Paul Montel.

1967), Photo Emulsion Chemistry J1 by Duffin, published by Focal Press (G, F, Duffin, Phot
graphicEmulsion Chemistry
y (Focal Press, 1966)), "Manufacture and Coating of Photographic Emulsions" by Zelikman et al., published by Focal Press (V, L, Zelikman et al.
,+Making and Coating Photo
graphic emulsion.

(Focal Press, 1964), etc. can be suitably prepared.

Photo emulsion m! II! ! If necessary, various silver halide solvents (for example, ammonia, rhodankali, or U.S. Pat.
No. 0, No. 53-82408, No. 53-144319, No. 54-100717 or No. 54-15582
Thioethers and thione compounds described in No. 8 etc.) can also be used.

Also, as a monodispersed emulsion, silver halide grains having an average grain diameter of more than about 0.1 micron, at least 95
Emulsions in which the weight percent is within ±40% of the average grain diameter are typical. Emulsions may be used in which the average grain diameter is 0.25''2 microns and at least 95% by weight or at least 95% of the silver halide grains are within ±20% of the average grain diameter.

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

The emulsion used is usually one that has been subjected to physical ripening, chemical ripening, and spectral sensitization. The additive used in such a process is the aforementioned Research Disclosure Magnetic 17643.
(December 1978) and N118716 (197
(November 1999), and the relevant parts are summarized in the table below. Other known photographic additives are also listed in the two Research Disclosures mentioned above, and are listed in the table below.

l Chemical sensitizer page 23 page 648 right column 2
Sensitivity enhancer Same as above 3 Spectral sensitizer, pages 23-24 Page 648 right column ~ Super sensitizer Page 649 right column 4 Color enhancer
Page 24 5 Antifogging agent Pages 24-25 Page 649 Right column and stabilizer 6 Light absorber, F Page 25-26 Page 649 Right column ~
Ilter dye 650 left column UV absorber 7 stain inhibitor page 25 right column 650 left to right column 8 dye image stabilizer page 25 9 hardener page 26 651 left column lO
Binder Page 26 Same as above 11 Plasticizer, lubricant Page 27 650 Right column 12 Coating aid, surface Pages 26-27 Same as above Activator 13 Stick 27N - Same as above Yellow coupler used in the color photosensitive material used in the present invention Typical examples include hydrophobic acylacetamide couplers having a ballast group. Specific examples thereof include U.S. Patent Nos. 2,407.210 and 2.8.
75. (Described in No. 157 and No. 3,265.506, etc.)

For the processing method of the present invention, the use of two-equivalent yellow couplers is preferred, representative examples of which are U.S. Pat.
, No. 408,194, No. 3,447.928, No. 3,933,501, No. 4.022.620, etc., or Japanese Patent Publication No. 10739/1983. No. 4,401, U.S. Pat.
No. 752, No. 4.326,024, RD18053
(April 1979), British Patent No. 1,425.020
No., West German Application Publication No. 2,219,917, No. 2.2
61.361, 2,329.587 and 2
, 433, 812, etc. can be mentioned. α-pivaloylacetanilide couplers have excellent color fastness, especially light fastness, while α-benzoylacetanilide couplers provide high color density.

Examples of magenta couplers include hydrophobic indacylon- or cyanoacetyl-based couplers having a ballast group, preferably 5-pyrazolone- and pyrazoloazole-based couplers. The 5-pyrazolone coupler is preferably a coupler in which the 3-position is substituted with an arylamino group or an acylamino group from the viewpoint of the hue and color density of the coloring dye, and typical examples thereof include U.S. Pat.
No. 2,343,703, No. 2,600,788, No. 2,908.573, No. 3,062.653
No. 3,152,896 and No. 3.936.0
It is described in No. 15, etc.

Particularly preferred as the leaving group for the 2-equivalent 5-pyrazolone coupler are the nitrogen atom leaving group described in U.S. Pat. No. 4,310,619 or the arylthio group described in U.S. Pat. No. 4,351,897. Also European Patent No. 73,6
The 5-pyrazolone coupler having a ballast group described in No. 46 provides high color density. Examples of pyrazoloazole couplers include pyrazolobenzimidazoles described in U.S. Pat. No. 3,061,432, preferably pyrazolo(5,
1-c) (1,2,4)t-lyazoles, research
Disclosure m24220 (June 1984) and pyrazolotetrazoles described in JP-A-60-33552 and Research Disclosure 24230
(June 1984) and pyrazolobirazoles described in JP-A-60-43659. Imidazo[1°2-b] described in U.S. Pat.
] Preferred are pyrazoles, as described in European Patent No. 119.860.
Pyrazolo CI, 5-b) (1,2,4
) I-lyazole is particularly preferred.

In the processing method of the present invention, when a photosensitive material using the following general formulas (X) and (Xl) as a cyan coupler is used, the gradation of the cyan image is not particularly softened and the cyan image density is high. This is preferable because it provides the following.

General formula (X)! 2 In the formula, R1, R2, and R4 represent a substituted or unsubstituted aliphatic hydrocarbon group, a ring group, or a heterocyclic group, and R3 and R6 represent a hydrogen atom, a halogen atom, or a substituted or unsubstituted aliphatic group. group, aryl group, acylamino group,
R3 represents a group of nonmetallic atoms that together with R2 form a nitrogen-containing 5- or 6-membered ring.

R5 represents an alkyl group which may be substituted, and Zl and Zl represent a hydrogen atom or a group capable of being separated during an oxidative camping reaction with a developing agent. n represents O or l. Specific examples of cyan couplers represented by general formula (X) or (XI) are listed below, but even more specific examples include the phenolic coupler described in U.S. Patent No. 3,772°002, No. 2,772,162, No. 3,75
8゜308, same No. 4,126,396, same No. 4゜3
34.011, OLS No. 4,327.173, West German Patent (OLS) No. 3,329,729 and European Patent No. 12
The 2°5-diacyl aminophenol coupler described in No. 1.365 and the like falls under this category.

Another type of cyan coupler suitable for use with this invention is a 5-amide substituted naphthol coupler. Specific examples include Japanese Patent Application No. 59-93605 and Japanese Patent Application No. 264277.
No. 268135.

An example of the compound is shown below.

Cyan couplers that can be used in combination with the above cyan couplers include the naphthol couplers described in U.S. Pat. No. 2,474,293, preferably U.S. Pat. No. 4,052,2.
No. 12, No. 4,146゜396, No. 4,228,
Typical examples include the oxygen atom M type 2-equivalent naphthol couplers described in No. 233 and No. 4,296.200.

In the present invention, in order to correct unnecessary absorption of coloring dyes, it is preferable to use a colored coupler together with the color negative light-sensitive material for photographing to perform masking. The colored coupler is the aforementioned Research Disclosure Na176.
43, Sections ■-G.

Granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Such a coupler is
U.S. Patent No. 4,366.237 and British Patent No. 2,1
Specific examples of magenta couplers are given in European Patent No. 96,570 and German Published Application No. 3,234.
No. 533 describes specific examples of yellow, mazenk or cyan couplers.

The dye-forming couplers and the above-mentioned special couplers may form dimers or higher polymers. A typical example of a polymerized dye-forming coupler is U.S. Pat. No. 3,451.820.
No. 4,080,211. Specific examples of polymerized magenta couplers are described in British Patent No. 2,
No. 102,173 and U.S. Pat. No. 4,367.282.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention.

DIR couplers that release development inhibitors are the aforementioned Research Disclosure 11kL'l 7643, ■~F.
The patented couplers described in Section 1 are useful.

The purpose of the present invention can be achieved by using the cyan coupler of the present invention in an amount of 0.002 to 0.5 mol per mol of photosensitive silver halide in the layer to be introduced.

The couplers used in the present invention and the couplers that can be used in combination can be introduced into the light-sensitive material by various known dispersion methods.
For example, typical examples include a solid dispersion method, an alkali dispersion method, preferably a latex dispersion method, and more preferably an oil-in-water dispersion method. In the oil-in-water dispersion method, after dissolving either a high-boiling point organic solvent with a boiling point of 175°C or higher and a low-boiling point so-called auxiliary solvent alone or in a quicksand mixture, water or gelatin is added in the presence of a surfactant. Finely dispersed in aqueous catalysts such as aqueous solutions. Examples of high boiling point organic solvents are described in US Pat. No. 2,322,027 and others. Dispersion may be accompanied by phase inversion, and if necessary, the auxiliary solvent may be removed or reduced by distillation, noodle washing, ultrafiltration, or the like before use for coating.

The photosensitive material used in the present invention contains hydroquinone derivatives, aminophenol derivatives, amines, gallic acid derivatives, catechol derivatives, ascorbic acid derivatives, colorless couplers, sulfonamide phenol derivatives, etc. as color fogging inhibitors or color mixing inhibitors. May be contained.

Various anti-fading agents can be used in the photosensitive material used in the present invention. Organic antifading agents include hydroquinones, 6-hydroxychromans, 5-hydroxychromans, spirochromans, p-alkoxyphenols, hindered phenols mainly including bisphenols, gallic acid derivatives, and methylenedioxybenzenes. Typical examples include aminophenols, hindered phenols, and ether or ester derivatives obtained by silylating or alkylating the phenolic hydroxyl group of each of these compounds. Further, metal complexes represented by (bissalicylaldoximado)nickel complex and (bis-N,N-dialkyldithiocarbamado)nickel complex, etc. can also be used.

The silver halide color light-sensitive material of the present invention may contain a color developing drug or a precursor thereof for the purpose of simplifying and speeding up processing. Precursors are preferable for inclusion in the light-sensitive material because they increase the stability of the photosensitive material. Specific examples of developer precursors include, for example, U.S. Pat.
, 342,597, Research Disclosure No. 14850 (August 1976), and Research Disclosure No. 15159.
Schiff base-type compounds described in No. 13924 (November 1976), aldol compounds described in No. 13924, U.S. Pat.
Gold salt complex described in No. 719,492, JP-A-53-13
There are urethane compounds described in No. 5628, and
-6235, 56-16133, 56-592
No. 32, No. 56-67842, No. 56-83734, No. 56-83735, No. 56-83736, No. 5
No. 6-89735, No. 56-81837, No. 56-5
No. 4430, No. 56-106241, No. 56-107
No. 236, No. 57-97531, and No. 57-835
Various salt-type precursors described in No. 65 and the like can also be used in the present invention.

The silver halide color light-sensitive material of the present invention may contain various 1-phenyl-3-virazolidones in order to promote color development.
No. 4339, No. 57-144547, No. 57-211
No. 147, No. 58-50532, No. 58-50536
No. 58-50533, No. 5 B-50534,
It is described in No. 58-50535 and No. 58-115438.

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous fg solution containing an aromatic primary amine color developing agent as a main component. Aminephenol compounds are also useful as color developing agents, but p-
Phenyldiamine compounds are preferably used, typical examples of which include 3-methyl-4-amino-N, N-diethylaniline, and 3-methyl-4-amino-N-ethyl-N.
-β-hydroxylethylaniline, 3-methyl-4-
Amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-
Examples include N-β-methoxyethylaniline and their sulfates, hydrochlorides, phosphates, p-toluenesulfonates, tetraphenylborates, p-(t-octyl)henzensulfonates, and the like. These diamines are generally more stable in their salt form than in their free state, and are therefore preferably used.

Examples of aminophenol derivatives include O-aminophenol, p-aminophenol, 4-amino-2-
These include methylphenol, 2-amino-3-methylphenol, 2-oxy-3-amino-1,4-dimethylbenzene, and the like.

In addition, "Photographic Ink Processing Chemistry" by F. A. Meson, Focal Press (
19jt 6th year) (L, F, 8, Mason + “Pho
tographic Processing Chem
istry", FocalPress) 226-2
29 pages, U.S. Patent No. 2,193.015, U.S. Patent No. 2,59
2,364, JP-A No. 48-64933, etc. may be used. If necessary, two or more color developing agents may be used in combination.

The color developer contains pHy buffers such as alkali metal carbonates, borates or phosphates; development inhibitors or antifoggants such as bromides, iodides, benzimidazoles, benzothiazoles or mercapto compounds. preservatives such as hydroxylamine, triethanolamine, compounds described in OLS 2622950, sulfites or bisulfites; organic solvents such as diethylene glycol; benzyl alcohol, polyethylene glycol, quaternary Development accelerators such as ammonium salts, amines, thiocyanates, 3,6-thiaoctane-1,8-diol; dye-forming couplers; competitive couplers; nucleating agents such as sodium boron hydride; 1
Auxiliary developers such as phenyl-3-pyrazolidone; viscosity-imparting agents; ethylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, N-hydroxymethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid and,
Aminopolycarboxylic acids typified by the compounds described in JP-A-58-195845, 1-hydroxyethylidene-1,1'-diphosphonic acid, organic phosphones described in Research Disclosure 18170 (May 1979) acids, aminophosphonic acids such as aminotris (methylenephosphonic acid), ethylenediamine-N, N, N', N'-tetramethylenephosphonic acid, JP-A-52-102
No. 726, No. 53-42730, No. 54-12112
No. 7, No. 55-4024, No. 55-4025, No. 5
No. 5-126241, No. 55-65955, No. 55-
No. 65956, and Research Disclosure 1
8170 (May 1979).

The color developing agent is generally used at a concentration of about 0.00% per 11 parts of the color developer.
1 g to about 30 g, more preferably color developer 1
It is used at a concentration of about 1 g to about 15 g per portion. Further, the pH of the color developing solution is usually 7 or more, and most commonly used at a pH of about 9 to about 13.

In the development process for reversal color photosensitive materials, black and white development is usually performed followed by color development. This black and white developer contains known compounds such as dihydroxyhenzenes such as hydroquinone and hydroquinone monosulfonate, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol. Black and white developers can be used alone or in combination.

After color development, the photographic emulsion layer is usually bleached.

The bleaching process may be carried out simultaneously with the fixing process in a single bath bleach-fixing process (Prinx), or may be carried out separately. Furthermore, in order to speed up the processing, a bleaching treatment followed by a bleach-fixing treatment may be used. Examples of bleaching agents used in bleaching or bleach-fixing include compounds of polyvalent metals such as iron (■), cobalt (■), chromium (■), and copper (■) (for example, ferricyanide compounds), peracids, Quinones, nitroso compounds; dichromate; iron (I[[) or cobalt (I
II) organic complex salts (for example, complex salts of aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, and organic phosphonic acid) or citric acid, tartaric acid,
Organic acids such as malic acid; persulfates; hydrogen peroxide; permanganates and the like can be used. Of these, iron (II
I) Organic complex salts and persulfates are preferred from the viewpoint of rapid processing and environmental pollution. Aminopolycarboxylic acids or aminopolyphosphonic acids or salts thereof useful for forming iron(III) organic complexes include: ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediamine-N-(β-oxyethyl)-N , N
',N'-triacetic acid, 1,2-diaminopropanetetraacetic acid, triethylenetetraminehexaacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, dil-lilotripropionic acid, cyclohexanediaminetetraacetic acid, ■,3-diaminor 2-Propatol tetraacetic acid, acetic acid methyliminodiacetic acid, iminodiacetic acid, hydroxyl iminodiacetic acid, dihydroxyethylglycine ethyl ether diamine tetraacetic acid, glycol ether diamine tetraacetic acid, ethylenediaminetetrapropionic acid, ethylenediamineniprobionic acid, phenylenediaminetetraacetic acid, 2- Phosphonobutane-1,2,4-triacetic acid, ■,3-diaminopropanol-N,N,N'.

No -tetramethylenephosphonic acid, ethylenediamine-N,N,N", No -tetramethylenephosphonic acid, 1.3-propylenediamine-N,N,N', N'-tetramethylenephosphonic 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, and methyliminodiacetic acid are preferred because they have a high bleaching edge.

The iron (I [ , ferric phosphate, etc.) and a chelating agent (aminopolycarboxylic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.) may be reacted in a solution to form a ferric ion complex salt. When forming a complex salt in a solution, one or both of the ferric salt and the chelating agent may be used in combination of two or more. In either case of forming a pre-formed complex salt or forming a complex salt, the chelating agent may be used in an amount greater than the stoichiometric amount. The bleaching solution or bleach-fixing solution containing the above-mentioned ferric ion complex may contain gold mud ions other than iron such as cobalt and copper, complex salts thereof, or hydrogen peroxide.

Persulfates for bleaching or bleach-fixing that can be used in the present invention include alkali metal persulfates such as potassium persulfate and sodium persulfate, or ammonium persulfate.

Bleach or bleach-fix solutions may contain bromides (e.g., potassium bromide, sodium bromide, ammonium bromide) or chlorides (
Rehalogenating agents such as potassium chloride, sodium chloride, ammonium chloride) or iodides (eg ammonium iodide) can be included. Boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, as required
One or more inorganic acids and organic acids having pH buffering capacity such as citric acid, sodium citrate, and tartaric acid, and their alkali metal or ammonium salts, or ammonium nitrate;
Corrosion inhibitors such as guanidine can be added.

The appropriate amount of bleaching agent per 1β of bleaching solution is 0.1 to 2 mol, and the preferred pH range of the bleaching solution is 0.5 to 8.0 in the case of ferric ion complex salt, especially aminopolcarboxylic acid. , 4.0 to 7.0 in the case of ferric ion complex salts of aminopolyphosphonic acid, phosphonocarboxylic acid, and organic phosphonic acid. In the case of persulfate, 0.1 to 2 mol/! p at 1 degree of
The range of H is preferably 1 to 5.

The fixing agent used for fixing or bleach-fixing is a known fixing agent. (1) Thiosulfates such as sulfur thiosulfate and ammonium thiosulfate; thiocyanates such as sulfur thiocyanate and ammonium thiocyanate. ; Water-soluble silver halide solubilizers such as ethylene bisthioglycolic acid, thioether compounds such as 3,6-cythia-1,8-octanediol, and thioureas; one type or a mixture of two or more of these is used. can be used. Furthermore, in the bleach-fixing process, a special bleach-fix solution consisting of a combination of a fixing agent and a large amount of a halide such as potassium iodide as described in JP-A-55-155354 can also be used.

In the case of fixing or bleach-fixing, the fixing agent b1 degree is 0°2~
4 mol/β is desirable, and in the bleach-fixing process, the range of 0.1 to 2 mol of the ferric ion complex salt and 0.2 to 4 mol of the fixing agent is desirable per 11 of the bleach-fix solution. Furthermore, p)-1 of the fixing and bleaching solution is usually preferably 4.0 to 9.0, particularly preferably 5.0 to 8.0.

In addition to the above-mentioned additives that can be added to the bleach solution, the fixer or bleach-fix solution may contain preservatives such as sulfites (e.g., sodium sulfite, potassium sulfite, ammonium sulfite), bisulfites, hydroxylamine, hydrazine,
A bisulfite adduct of an aldehyde compound (eg, acetaldehyde sodium bisulfite), etc. can be included.

Furthermore, various fluorescent brighteners, antifoaming agents, surfactants,
Organic solvents such as polyvinylpyrrolidone and methanol can be contained.

A bleach accelerator may be used in the bleaching solution, bleach-fixing solution, and their prebaths, if necessary.

Specific examples of useful bleach accelerators are described in U.S. Pat. No. 3,893,858, German Pat.
, No. 290,812, No. 2,059°988, JP-A No. 53-32736, No. 53-57831, No. 374
No. 18, No. 53-65732, No. 5.3-72623
No. 53-95630, No. 53-95631, No. 53-104232, No. 53-124424, No. 5
Compounds having a mercapto group or disulfide group as described in No. 3-141623, No. 53-28426, Research Disclosure No. 17129 (July 1978), etc.; as described in JP-A-50-140129; Thiazoline derivative; Japanese Patent Publication No. 45-8506,
1,000 urea derivatives described in JP-A-52-20832, JP-A-53-32735, and U.S. Pat. No. 3,706-561; West German Patent No. 1,127,715, JP-A-58-16
Iodides described in West German Patent No. 23; polyethylene oxides described in West German Patent No. 966.410 and West German Patent No. 2,748,430; polyamine compounds described in Japanese Patent Publication No. 45-Sen 8836; and others
．． No. 9-42434, No. 49-59644, No. 53-
No. 94927, No. 54-35727, No. 55-265
Compounds described in No. 06 and No. 5B-163940 and iodine and bromine ions can also be used. Among these, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large promoting effect, and are particularly preferred as described in U.S. Pat. No. 3,893,85.
No. 8, West German Patent No. 1,290,812, Japanese Unexamined Patent Publication No. 1983-
The compounds described in No. 95630 are preferred.

After the fixing process or bleach-fixing process, processing processes such as water washing and stabilization are generally performed. Simple processing methods can also be used.

The water washing treatment in the present invention is as described above.

Various processing solutions in the present invention are used at 10°C to 50°C. A temperature of 33°C to 38°C is standard, but higher temperatures can be used to accelerate the processing and shorten the processing time.
Conversely, it is possible to improve the image quality and the stability of the processing solution by lowering the temperature. In addition, West German Patent No. 2゜226.770 or U.S. Patent No. 3,67 is used to save silver on photosensitive materials.
Treatments using cobalt intensification or hydrogen peroxide intensification as described in U.S. Pat. No. 4,499 or monobath development bleach-fixing as described in U.S. Pat. No. 3,923.511 may be carried out.

Each processing time can be made shorter than the standard time within a reasonable range, if necessary, in order to speed up the process.

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

Each treatment bath may be provided with a heater, a temperature sensor, a liquid level sensor, a circulation pump, a filter, various floating pigs, various squeegees, etc., as necessary.

(Effects of the Invention) According to the present invention, even if the amount of washing water used during washing treatment is sufficiently reduced, the washing water can be stabilized.
This also greatly improves wastewater treatment and the movement of developing machines. The resulting image has a high cyan density and has good storage stability.

Example 1 A multilayer color photosensitive material sample was prepared on a triacetyl cellulose film support, each layer having the composition shown below.

1st layer; antihalation layer; black gelatin layer containing colloidal silver; 2nd layer; intermediate layer; 2. Gelatin layer containing an emulsified dispersion of 5-di-t-octylhydroquinone; 3rd layer; low-sensitivity red-sensitive emulsion layer; Silveride emulsion (iodide #H: 5 mol%)...silver coating amount 1,
6g/rrr Sensitizing dye I...6X10-5 moles per mole of silver Sensitizing dye ■...1.5XIO- per mole of silver
5 mole coupler EX-1: 0.04 mole per mole of silver Coupler EX-2: 0.003 mole per mole of silver
Molar coupler EX-3...0.000 per mole of silver
6 mol 4th layer: Highly sensitive red-sensitive emulsion layer Silver iodobromide emulsion (silver iodide; 10 mol %)...Silver coating amount
1. 4g/rrr
Sensitizing dye summer...3xto- for 1 mole of silver! 5
Molar sensitizing dye ■...1.2XlO- per mole of silver
5 mole coupler EX-4...0.02 moles per 1 mole of silver Coupler EX-2...0.001 per mole of silver
6 mol No. 51'ii; 6th layer same as the 2nd intermediate layer; Low-sensitivity green-sensitive emulsion layer Monodisperse silver iodobromide emulsion (silver iodide; 4 mol %)...Silver coating amount 1.2 g/I Sensitizing dye...
・3x1o- per mole of silver! 5 mol sensitizing dye■...1Xl0-5 mol per 1 mol of silver Coupler EX-5...0.05 mol per 1 mol of silver Coupler EX-6...iJN per 1 mol Teo,
ooa mole coupler EX-3...0.0OL per mole of silver
5 mol 7th layer: High-sensitivity green-sensitive emulsion layer Silver iodobromide emulsion (silver iodide; 10 mol %)...Silver coating amount
1.3g/rd sensitizing dye...
...2.5X10-5 moles per mole of silver sensitizing dye ■...0.8X10-5 per mole of silver
5 mole coupler EX-7...0.017 per mole of silver
Molar coupler EX-6...0.003 per mole of silver
Molar coupler EX-8...0.003 per mole of silver
Mole 8th layer: Yellow filter layer Yellow colloidal silver and 2,5-di-t- in gelatin aqueous solution
9th gelatin layer containing an emulsified dispersion of octylhydroquinone; low-sensitivity blue-sensitive emulsion layer silver iodobromide emulsion (silver iodide; 6 mol %)...silver coating amount 0.
7g/n (Coupler EX-9... 0.25 mol per 1 mol of silver Coupler EX-3... 0.01 mol per 1 mol of silver)
5 mol 10th layer: Highly sensitive blue-sensitive emulsion layer Silver iodobromide (silver iodide; 6 mol %)...Silver coating amount 0.6 g
/m Coupler EX-9...0.06 mol per mol of silver 11th layer; First protective layer silver iodobromide (silver iodide 1 mol%, average grain size 0.07μ)...
・Amount of silver applied: 0.5g Ultraviolet absorber UV
12th gelatin layer containing the emulsified dispersion of -1; second protective layer coated with a gelatin layer containing trimethylmethanoacrylate particles (diameter 1° 5 μm).

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

The compounds used to prepare the samples are as follows.

Sensitizing dye I; anhydro-5,5°-dichloro-3,
3°-di(γ-sulfopropyl)-9-ethyl-thiacarbocyanine hydroxide pyridinium salt sensitizing dye 4'-5''-dibenzothiacarbocyanine hydroxide/triethylamine salt sensitizing dye ■: Anhydro-9-ethyl-5,5-dichloro-3,3°-di(γ-sulfopropyl)oxycarbocyanine/sodium salt enhancement Mysterious Sutra ■: Anhydro 5
．． 6. 5°, 6°-tetrachloro-1,1′-diethyl-3,3″-di(β-[β-(γ-sulfopropyl)ethoxy]ethyl)imidazolocarbocyanine hydroxide sodium salt (t (0 0-11 X--2 H
2) 2NHCOCH2SO2CE (=C) 12σV-/x7 y #7/J (ratio of y) After cutting the color photosensitive material thus prepared into 35 m/ml↑J, it was photographed outdoors as a standard subject. Photographs were taken and the following processing was performed using an automatic processor.

Table 1 - Treatment process (temperature 38°C)
Knee color development 3 minutes 15 seconds 18ff 38ml
Bleach 6 minutes 30 seconds 36β 18m! Fixation 3
Minutes 15 seconds 18/! 33mj! Washing ■ 1 minute 30 seconds 9β - Washing ■ 1 minute 30 seconds 9
ff 27mA-40'l 9j! 3
3m7! *: Per 1 m length of photosensitive material 35 m/m In the above processing steps, water washing (■) and (2) were performed using a countercurrent water washing method from ■ to ■. Next, the composition of each treatment liquid will be described. In addition, two types of washing liquids of the present invention and four types of comparative examples were used.

(Color developer) Mother solution (g) Replenisher (g) Diethylene 1.Ol.1-triaminepentaacetic acid 1-hydroxy 2.0 2.2 Ethylidene
-1゜1-diphosphonic acid sodium sulfite 4.0 4.4 Potassium carbonate 30.0 32.0 Potassium bromide 1,
4 0.7 potassium iodide 1.3mg
-Hydroxyamine 2.4 2.64-(N-
Add ethyl-4,55,O N-β-hydroxyethylamine)-2-methylaniline sulfate solution if INpt-i
10.00 10.05 (Bleach night) Mother liquor (g) Replenishment/fL (g) Ethylenediamine 100 110 Tetraacetic acid 2nd
Iron ammonium salt ethylenediamine 4 10 11 acetic acid disodium salt ammonia water 7rr+j! 5mf
f Ammonium nitrate 10.0 12.0g Ammonium bromide 150 170 Add water
Ifl lN pH 6,05,8 (Fixer) Mother liquor (g) Replenisher (g) Ethylenediamine tetra 1.0 1.2 Acetate disodium salt Sodium sulfite 4.0 5.0 Sodium bisulfite 4.6 5.8 Ammonium thiosulfate Aqueous solution (70%) 175mff 200m7
! Add water to 11pH6
,66,6 (stable solution) Mother liquor (g) ? +Li solution (g) Formalin (37% w/v) 2. 0mff 3.0mf
f polyoxyethylene 0.3 0.45-p-monononylphenyl ether (average ff1 degree io) add water
ll (Washing liquid) The number of ingredients contained in the washing liquid 11 is as shown in Table 2.

(Ill L, EDTA in the table is ethylenediaminetetraacetic acid.

Using A in Table 2 as the water/8 liquid, and using an automatic developing machine with the tank capacity listed in Table IG, the photographed color photosensitive material (35 m /
m width) was treated continuously for 20 days at a rate of 50 m per day. After continuous treatment for 20 days, using a tank light source and adjusting the filter C color temperature to 4800"K,
The color photosensitive material subjected to wedge exposure of 0 CMS was processed and used as a test material.

Next, the washing liquid was sequentially changed to B, C, D, E, and F in Table 2, and the same treatment as that for the washing liquid was performed to obtain a test sample.

Each of the above samples was stored at 80° C. for 9 days, and the fading of the cyan dye was investigated. The results are shown in Table 3.

Table 3 Fading test results (80°C for 9 days) A (comparative example) -0,18 B (comparative example) -0,25 C (comparative example) -0,17 D (comparative example) -0,17 E (real invention) -0,08F (present invention)
-0,09 As shown in Table 3, the ammonium salt of EDTA increases the fading of the cyan dye, and the calcium salt and lithium salt have no effect, but the EDTA glue of the present invention - thorium salt and potassium salt increase the fading of the cyan dye. It can be seen that this significantly reduces

Example 2 The color photosensitive material prepared in Example 1 was photographed in the same manner as in Example 1, and subjected to the following processing using an automatic processor.

Table 4 Treatment process (temperature 38°C) Ij! -11-J Odor 1 Separate use-1-Li S Otsu 2” Amount-Supplementary, Tenp-Color development 3 minutes 15 seconds l Q N 3
8ml bleach 1 minute 00 seconds 4A 13m
ff Bleach fixing 3 minutes 15 seconds 10ρ 27m1 water washing ■ 40 seconds 4! - Wash with water ■ 1 minute O
O seconds 412 27 rn j! Brown 40
'4i1! 18 mN In the above treatment steps, water washing (■) and (2) were carried out in a countercurrent water washing system from (■) to (2).

Also, the overflow solution accompanying replenishment of the bleaching solution was introduced into the bleach-fixing solution.

The composition of each treatment solution is listed below. In addition, three types of washing liquids according to the present invention and three types other than those according to the present invention (ratio examples) were used.

(color developer) Both the mother liquor and the replenisher were the same as in Example 1.

(Bleach solution) Common to mother liquor and replenisher (g) Ammonium bromide 100 Ethylenediamine 120 Tetraacetic acid ferric ammonium salt Ethylenediamine tetra 10.0 Disodium acetate salt Ammonium nitrate 10.0 Bleach accelerator below 2.0 Aqueous ammonia
Add 17.0 ml of water and prepare lJ p I-16.5: (Bleach-fix solution) Mother liquor (g) Replenisher (g) Ammonium bromide 50.0 -Ethylenediaminetetra 50.0 -Ferric acetate ammonium salt Ethylenediaminetetra 5.0 1. Og acetic acid sodium acetate ammonium hydrochloride 5.0 - Bleach accelerator below 1.0 - H3 cH3
Sodium sulfite 12.0 20.0 Ammonium thiosulfate aqueous solution (70%) 240m42 400mA Ammonium 10.0mj! Add water IA II! pH7
,38,0 (Stable solution) Both the mother liquor and the replenisher were the same as in Example 1.

(Washing liquid) The ingredients contained per 1β of the washing liquid are as shown in Table 5.

First, using G in Table 5 and an automatic processor having the tank capacity listed in Table 1, the photographed color photosensitive material (3
The treatment was continued for 20 days at a rate of 20 m per day. After the continuous treatment for 20 days, test samples were obtained in the same manner as in Example 1. Next, add the washing liquid to 11, I, in Table 5.
Test samples were obtained in the same manner by changing to J, then L.

For each sample thus obtained, the fading of the cyan dye when stored at 80° C. for 9 days and the state of the washing solution at the end of each treatment are shown in Table 6.

Table 6 Fading test results (80°C, 9 days) and liquid observation results Washing liquid Discoloration of cyan dye Liquid (at N41.2) G -0,23 Cloudy H-0,30 Clean O η juice -1 -- 1-0, 24 A lot of muddy ■Power 1 “1 gun generated J
-0,22 Cloudy Hikin 11 2 pt-Order-K -0,07 Clean one shot■ L -0,09 Clean one-II As seen from Table 6, the water washing bath of the present invention fades the cyan dye. At the same time, it has the effect of keeping the liquid clean. It is clear from Comparative Example IXJ that this effect is not common to sodium salts of weak acids, and is a unique effect of the present invention.

Claims (1)

[Claims] In the development processing method for silver halide color photographic light-sensitive materials, the water washing bath that follows the processing with a bath having fixing ability carried out in the development processing step includes an aminocarboxylic acid, an aminocarboxylic acid,
It contains at least one salt selected from sodium salts or potassium salts of aminophosphonic acid, phosphonic acid, and phosphonocarboxylic acid, and the replenishment amount of the water washing bath is equal to or greater than the unit of photosensitive material to be processed. A method for processing a silver halide color photographic material, characterized in that the amount brought in from the previous bath is 3 to 50 times per area.