JPS6292951A - Method for developing silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To reduce a consumption of a water washing solution by incorporating a specific compd. to a treating bath having a bleaching ability or a previous treating bath, and by supplementing a specific amount of a replenisher to the water-washing bath and/or the stabilizing bath in a desilver step. CONSTITUTION:A 5-membered heterocyclic compd. having >=1 mercapto groups is incorporated to the treating bath having the bleaching ability in the desilver step of the treating step of the sensitive material comprising a color developing, a desilver, a water-washing and/or a stabilizing steps. The amounts of the replenishers for the water-washing bath and/or the stabilizing bath are controlled to 3-50 times of the amount carried in said baths from the previous treating bath per unit area of the sensitive material. By incorporating said heterocyclic ring compd. to the bleaching bath or the bleach-fixing bath, the bleaching ability of said bath is promoted, and the water-washing solution of the following water-washing bath carried in from the previous bath is stabilized, and the decoloring of cyan is prevented, thereby making it possible to reduce sufficiently the used amount of the water-washing solution. Thus, the color photographic sensitive material can be developed, without providing a specific waste water treatment, and the developing treating apparatus can be moved, and a good image is 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
ety of Motion Picture and
“Water Flow Lake in Immersion Washing of Motion Picture Film”, Vol. 64, pp. 248-253 (May 1955 issue)
r Flow Rates in Immersion
-1tjashjng ofMotion P3ctu
re Fi1m' Nis R. Goldweiser (S
, R. Goldwasser) proposes a method of reducing the amount of flushing water by making the flushing tank multistage and causing the water to flow countercurrently. Also, U.S. Patent No. 4,336
．． No. 324 proposes a system that performs stabilization treatment after bleach-fixing treatment without substantially undergoing a water washing step to save water.

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

(Problems to be Solved by the Invention) However, the washing water is very unstable as iron ions and thiosulfates from the bleach-fixing process are brought in during processing, and the amount of washing water can be significantly reduced. If this is done, the residence time of the washing water becomes longer, and various precipitates and floating substances are generated, and these precipitates and floating substances may adhere to the photosensitive materials or clog the filters of automatic processors. or dirt, etc.
There was a need for improvement as this caused various problems.

As a result of intensive research to solve the above-mentioned conventional drawbacks, the present inventors have discovered that when a specific bleach accelerator is used in the bleach-fix solution, the washing water after bleaching can be extremely stabilized. The inventors have also discovered that the cyan fading properties of the resulting images are improved, and have arrived at the present invention.

Therefore, a first object of the present invention is to provide a processing method that can reduce the amount of washing water used after bleach-fixing to a sufficiently small amount.

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 that can obtain good images even when the amount of water in the washing process performed after the bleaching process is sufficiently reduced.

Furthermore, a fourth object of the present invention is to provide a bleach-fix solution that contributes to sufficiently reducing the amount of water used in the washing process performed after the bleach-fix process.

(Means for solving the problem) The above aspects of the present invention include color development, desilvering, water washing and/or
Or, in the development processing step of a silver halide color photographic light-sensitive material consisting of each step of stabilization, at least one of the processing bath having bleaching ability in the desilvering step or its pre-bath has at least one mercapto group. containing a member heterocyclic compound, and the amount added to the washing and/or stabilizing bath is 3 times the amount brought in from the bath per unit area of the photosensitive material.
In the present invention, a processing bath having bleaching ability is a bath that can contribute to bleaching developed silver by containing a bleaching component. Therefore, this bath includes not only a normal bleaching bath but also a bath having bleach-fixing ability.

The treatment bath having bleaching ability may be composed of two or more baths. In this case, the subsequent liquid may be mixed into the front bath in a cascade manner, or conversely, the liquid in the front bath may be caused to flow into the rear bath in a cascade manner. Further, a water washing step (including a small water washing bath in which the amount of washing water is reduced) may be included between each treatment bath having bleaching ability.

The bleaching bath used in the present invention includes red blood salt, dichromate, persulfate, inorganic ferric salt,
Any known salts such as organic acid ferric salts can be selected and used, but they cause less water pollution and metal corrosion.
It is particularly preferable to use a ferric aminopolycarboxylic acid complex salt which has good stability. Aminopolycarboxylic acid 2nd
The iron complex salt is a complex of ferric ion and aminopolycarboxylic acid or a salt thereof.

Representative examples of these aminopolycarboxylic acids and their salts include: A-1 Ethylenediaminetetraacetic acid A-2 Ethylenediaminetetraacetic acid disodium salt A-3 Ethylenediaminetetraacetic acid nimonium salt A-4 Ethylenediaminetetraacetic acid (trimethylammonium ) A-5 Ethylenediaminetetraacetic acid tetrapotassium salt A-6 Ethylenediaminetetraacetic acid tetrasodium salt A-7 Ethylenediaminetetraacetic acid disodium salt A-8 Diethylenetriaminepentaacetic acid A-9 Diethylenetriaminepentaacetic acid pentasodium salt A-10 Ethylenediamine-N- (β-oxyethyl)
-N, N', N' -Triacetic acid A-11 ethylenediamine-N-(β-oxyethyl) N, N', N'
-Pentanoic acid trisodium salt A-12 ethylenediamine-N-(β-oxyethyl)
-N, N', N' -Pentanoic acid triammonium salt A-13 Propylenediaminetetraacetic acid A-14 Propylenediaminetetraacetic acid disodium salt A-15 Nitrilotriacetic acid A-16 Nitrilopentazoic acid trisodium salt A- 17 Cyclohexanediaminetetraacetic acid A-18 Cyclohexanediaminetetraacetic acid disodium salt A-19 Iminoniacetic acid A-20 Dihydroxyethylglycine A-21 Ethyl etherdiaminetetraacetic acid A-22 Glycol etherdiaminetetraacetic acid A-23 Ethylenediaminetetrapropionic acid, etc. However, the present invention is not limited to these exemplified compounds.

Among these compounds, especially A-1 to A-3, A-8
, A-17 are preferred.

Aminopolycarboxylic acid ferric complex salts may be used in the form of complex salts, or may be used in the form of ferric salts, such as ferric sulfate, ferric chloride,
A ferric ion complex salt may be formed in a solution using ferric nitrate, ferric ammonium sulfate, ferric phosphate, etc. and aminopolycarboxylic acid.

When used in the form of a complex salt, one type of complex salt or two or more types of complex salts may be used.

On the other hand, when forming a complex salt in a solution using a ferric salt and an aminopolycarboxylic acid, one or more types of ferric salts may be used. Furthermore, one type or two or more types of aminopolycarboxylic acids may be used. In any case, the aminopolycarboxylic acid may be used in excess of the amount required to form the ferric ion complex.

As the above ferric ion complex, cobalt other than iron,
A metal ion complex salt such as copper may also be contained.

In addition to bleaching agents and the above-mentioned compounds, the bleaching baths of the present invention contain bromides (to be explained in more detail below), such as potassium bromide, sodium bromide, ammonium bromide, or chlorides, such as potassium chloride, chloride, etc. Rehalogenating agents such as sodium, ammonium chloride, etc. can be included. In addition, pH of nitrates such as sodium nitrate and ammonium nitrate, boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, etc.
One or more inorganic acids, organic acids and their salts having buffering capacity, as well as thiosulfates such as sodium thiosulfate, ammonium thiosulfate, sodium ammonium thiosulfate, potassium thiosulfate, sodium thiocyanate, ammonium thiocyanate, thiocyanic acid. It may contain a compound having a fixing ability such as thiocyanate such as potassium, thiourea, thioether, etc.

In the present invention, the treatment bath having bleaching ability may further contain various additives. For example, it may contain sulfites such as sodium sulfite and ammonium sulfite, various antifoaming agents, or surfactants, iodides such as potassium iodide, sodium iodide, ammonium iodide, and hydroxylamine, It is also possible to contain hydrazine or a bisulfite adduct of an aldehyde compound.

Regarding the processing solution having bleaching ability used in the present invention, the bleaching agent is used in an amount of 0.05 mol to 1 mol, preferably 0.1 mol to 0.5 mol, per 1β of the processing solution. Further, the pH of the treatment liquid is 4.0 to 9.0, especially 5.0 when used.
It is preferably 0 to 8.0. In addition, when using a fixing agent, 0.3 mol to 3 mol per 11 processing liquids,
Preferably it is used in an amount of 0.5 mol to 2.5 mol.

A water-soluble bromide can also be added to the treatment bath having bleaching capabilities. Here, water-soluble bromide is a compound that releases bromide ions when dissolved in a bleach bath or bleach-fix bath.
Specifically, alkali total bromides such as potassium bromide, sodium bromide, and lithium bromide, ammonium bromide, hydrobromic acid, and alkaline earth metals such as magnesium bromide, calcium bromide, and strontium bromide. Examples include bromide and the like. Among these water-soluble bromides, ammonium bromide is particularly preferred.

The amount of these water-soluble bromides added is 0.5 to 1°3 mol/
1, particularly preferably 0.7 to 1.3 mol/β.

It is known that various bleach accelerators are added to the treatment bath having bleaching ability and its pre-bath used in the present invention.

Bleach accelerators include, for example, bromide ions, iodide ions, U.S. Pat.
No. 506, No. 49-26586, JP-A-53-327
No. 35, No. 53-36233 and No. 53-3701
Thiourea compounds as shown in No. 6; JP-A-53-
No. 124424, No. 53-95631, No. 53-57
No. 831, No. 53-32736, No. 53-65732
No. 54-52534, and U.S. Patent No. 3.89.
Thiol compounds as shown in JP-A-49-596.44, JP-A-50-140129, etc.
No. 53-28426, No. 53-141623, No. 5
Heterocyclic compounds described in JP-A No. 3-104232 and JP-A No. 54-35727, etc.;
5-25064 and 55-26506, tertiary amines described in JP-A-48-84440, thiocarbamoyls described in JP-A-49-42349, etc. It is being

However, in the present invention, in particular at least one
It is necessary to contain a 5-membered heterocyclic compound having 1 [1 mercapto group.

When the above-mentioned heterocyclic compound is added as a bleach accelerator, it not only accelerates the bleaching ability of the bleach bath or bleach-fix bath (but also the subsequent It has been found that the completely unexpected effect of stabilizing the washing water (described below) in the washing bath and improving the fading of cyan can be obtained.

That is, even if conventionally known bleaching accelerators other than those mentioned above are used, the effects of the present invention cannot be obtained.

Next, as specific examples of the above-mentioned five-membered heterocyclic compound that can be used in the present invention, the following can be mentioned.

(1) N-N (2) N-N E■] U □ Engineering □ Next, after the treatment bath with bleaching ability, treatment steps such as water washing and stabilization are generally performed; Although it is also possible to use a simple processing method such as performing only a stabilization treatment without providing a substantial washing step, the present invention limits the use of washing water and allows development without special drainage equipment. It is particularly effective for use in water-saving washing processes to stably carry out all processing steps.

In the washing process of the present invention, various known compounds may be added for the purpose of preventing precipitation and stabilizing the washing water. for example,
Chelating agents such as inorganic phosphoric acid, aminopolycarboxylic acid, and organic phosphonic acid; bactericidal agents and anti-inflammatory agents that prevent the growth of various bacteria, algae, and molds (for example, Journal of
Antibacterial and Antifung Agency (J, Antibact, Antifung)
.

Agents) vol, 11. Na3. p, 207-2
23 (1983) and compounds described in Hiroshi Horiguchi's "Chemistry of Antibacterial and Antifungal"), metal salts such as magnesium salts and aluminum salts, alkali metal and ammonium salts, or dry substances, A surfactant or the like may be added as necessary to prevent unevenness. Or Photo, Science and Engineering magazine by West.
g,).

Compounds described in Vol. 6, pp. 344-359 (1965), etc. may be added. In the washing process, in which the addition of a chelating agent or a bactericidal anti-spill agent is particularly effective, washing may be performed in multiple stages of 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-5'1-8543 may be performed. Various compounds are added to this stabilizing bath for the purpose of stabilizing images. Various buffers (e.g. borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, ammonia water, Typical examples include monocarboxylic acids, dicarboxylic acids, polycarboxylic acids, etc.) and aldehydes such as formalin.

In addition, chelating agents (inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphonic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.), fungicides (thiazole type, isothiazole type, halogenated phenol, sulfanilamide, benzotriazole) etc).

Various additives such as surfactants, fluorescent brighteners, and hardeners may be used, and two or more compounds for the same or different purposes may be used in combination.

In addition, as a membrane pHII preparation after treatment, ammonium chloride,
It is preferable to add various ammonium salts such as ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate in order to improve image storage stability.

Furthermore, in the case of color photosensitive materials for photography, the normally performed post-fixing (washing-stabilization) process can be replaced with the above-mentioned stabilization process and water-washing process (water-saving process). At this time, if the amount of magenta coupler is 2 equivalents, formalin in the stabilizing bath may be removed.

Further, in the present invention, the amount of replenishment to the washing and/or stabilizing bath is 3 to 50 times the amount brought in from the previous bath per unit area of the photosensitive material. If it is less than 3 times, cyan fading will worsen, and if it is more than 50 times, the content of the pre-bath components will decrease, making it impossible to improve the liquid stability of the water washing and/or stabilizing bath.

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. The photosensitive materials particularly amenable to processing in the present invention are photosensitive materials 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, Vol. 176, 17643 (
December 1978), pp. 22-23, '1. Emulsion manufacturing (
Emulsion preparation and T
ypes)” and Volume 187, 11h18716 (19
(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 Paul Montell.
t Physique Photographique
, Paul Montel.

1967), Duffin, “Photographic Emulsion Chemistry”, Focal Press, CG, 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
rapic emulsion.

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

For the preparation of photographic emulsions, various silver halide solvents (for example, ammonia, rhodankali, or -144319, 54
It is also possible to use thioethers and 1,000-ion compounds described in No. 100717 or No. 51-155828.

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 having an average grain diameter of 0.25 to 2 microns and at least 95% by weight or at least 95% by number of silver halide grains within the range of ±20% of the average grain diameter may be used.

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. Additives used in such processes are listed in the aforementioned Research Disclosure No. 17643.
(December 1978) and Tokimaru 18716 (1979)
(November 2013), 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.

1 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 Anti-fog agent Pages 24-25 Page 649 Right column and stabilizer 6 Light absorber, fu Page 25-26 649 Right column ~
Ilter dye 650 left hand UV absorber 7 stain inhibitor page 25 right column 650 left to right (8) dye image stabilizer 25 page 9 hardener page 26 651 left hand column 10
Binder 26 pages Same as above 11
Plasticizer, lubricant Page 27 650 Right column 12
Coating aid, surface Pages 26-27 Same as above Activator 13 - 270i As the yellow coupler used in the color photosensitive material used in the present invention, hydrophobic acylacetamide couplers having a ballast group are representative. Examples include: Specific examples include U.S. Patent No. 2,407.210, U.S. Patent No. 2,875,
No. 057 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.
．． 408.194, 3.447.928, 3,933,501, 4,022,620, etc. or Japanese Patent Publication No. 58-10739 , U.S. Patent No. 4,401,
No. 752, No. 4,326,024, RD18053
(April 1979), British Patent No. 1,425,020
No. 2,219,917, West German Application No. 2.2
No. 61,361, No. 2.329,587 and No. 2
, 433.812 and the like 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.
Same No. 2,343.703, Same No. 2,600,788, Same No. 2,908,573, Same 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) Triazoles, pyrazolotetrazoles described in Research Disclosure FF124220 (June 1984) and JP-A-60-33552 and Research Disclosure 2
4230 (June 1984) and JP-A-60-43
Examples include the pyrazolopyrazoles described in No. 659.

Imidazo [1], which is described in U.S. Pat.
゜2-b] Preferred are pyrazoles, as described in European Patent No. 119
．． Pyrazolo (1,5-b) [1,2
, 4)) Riazole are particularly preferred.

In the processing method of the present invention, when a photosensitive material using the following general formulas (X) and (XI) is used as a cyan coupler, the gradation of the cyan image is not particularly softened, and the cyan color is restored. This is preferable because it gives good results.

General formula (X) II 1 In the formula, R1, R2 and R4 represent a substituted or unsubstituted aliphatic hydrocarbon group, aryl group or heterocyclic group, and R3 and R6 are hydrogen atoms, halogen atoms, substituted or unsubstituted Is it an aliphatic group, an aryl group, an 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 Z2 represent a hydrogen atom or a group capable of being separated during an oxidative coupling reaction with a developing agent. n represents 0 or 1. 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. 4,327.1'73, West German Patent (OLS) No. 3,329.729 and European Patent No. 1
The 2°5-diacyl aminophenol coupler described in No. 21,365 and the like falls under this category.

♂l (,t) C3HI + N Another type of cyan coupler suitable for application of the present 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. 1.2, No. 4,146゜396, No. 4,228
Typical examples include the oxygen atom elimination 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 Research Disclosure 1k176 mentioned above.
43.4-0.

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, magenta 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 camping are also preferably used in the present invention.

As DIR couplers that release development inhibitors, the patented couplers described in the aforementioned Research Disclosure M17643, Items 1 to F 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 U.S. 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, extrafiltration, etc. 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 agent 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. Developer drug! Specific examples of the 7-cursor include indoaniline compounds described in U.S. Pat. No. 3,342,597,
Research Disclosure No. 3゜342.599, Research Disclosure No. 14850 (August 1976) and Research Disclosure No. 1515
Schiff base type compound described in No. 9 (November 1976),
Aldol compound described in No. 13924, U.S. Patent No. 3
, 719.492, JP-A-53-1
There is a urethane compound described in No. 35628, and
No. 6-6235, No. 56-16133, No. 56-59
No. 232, No. 56-67842, No. 56-83734
No. 56-83735, No. 56-83736, No. 56-8973' 5, No. 56-81837, No. 5
No. 6-54430, No. 56-106241, No. 56-
No. 107236, No. 57-97531, and No. 57-
Various salt-type precursors described in US Pat. No. 83,565 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-pyrazolidones 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. 58-50534, No. 58-50535, No. 58-115438, etc.

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Aminophenol compounds are also useful as color developing agents, but p-phenylenediamine compounds are preferably used, representative examples of which are 3-methyl-4-amino-N, N-diethylaniline, 3-methyl -4-amino-N-ethyl-N-
β-hydroxylethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N
-β-methoxyethylaniline and their sulfates,
Examples include hydrochloride, phosphate or p-1-luenesulfonate, tetraphenylborate, p-(t-octyl)benzenesulfonate, 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 〇-aminophenol, p-aminephenol, 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 (
(1966) (L, F, A, Mason.

“Photographic Processing
Chemistry'', FocalPress) 2
Those described in pages 26 to 229, U.S. Pat. No. 2,193.015, U.S. Pat. If necessary, two or more color developing agents may be used in combination.

The color developer contains pH buffering agents 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 No. 2622950, sulfites or bisulfites; organic solvents such as diethylene glycol; benzyl alcohol, polyethylene glycol, quaternary ammonium salts, amines,
Development accelerators such as thiocyanate, 3,6-thiaoctane-1,8-diol; dye-forming couplers; competitive couplers; nucleating agents such as thorium boron hydride;
Auxiliary developers such as 1-phenyl-3-pyrazolidone; tackifying agents; ethylenediaminetetraacetic acid, nitrilotriacetic acid,
Aminopolycarboxylic acids represented by cyclohexanediaminetetraacetic acid, iminodiacetic acid, N-hydroxymethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, and the compounds described in JP-A-58-195845, etc., ■-hydroxy Ethylidene-1.1'-diphosphonic acid, organic phosphonic acid described in Research Disclosure 18170 (May 1979), aminotris (methylenephosphonic acid), ethylenediamine-N,N,N', N"-tetramethylene Aminophosphonic acid such as phosphonic acid, JP-A-52-1027
No. 26, No. 53-42730, No. 54-121127
No. 55-4024, No. 55-4025, No. 55
-126241, 55-65955, 55-6
No. 5956, and Research Disclosure 18
170 (May 1979).

Color developing agents are generally used in amounts of about 0.00% per color development g1z.
A concentration of 1 g to about 30 g, more preferably color developer 1
Use a concentration of about 1 g to about 15 g per e. 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 includes known black and white developers such as dihydroxybenzenes such as hydroquinone and hydroquinone monosulfonate, 3-birapritones such as -phenyl-3-pyrazolidone, and aminophenols such as N-methyl-p-aminephenol. Drugs can be used alone or in combination.

The bleaching step and fixing step after color development are as described above.

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.

In the washing process, for the purpose of preventing sedimentation 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, fungicides and anti-puff agents that prevent the growth of various groupers, algae, and molds (for example, Journal of Antibacterial and Antibacterial Unfjungar Agents (
J, Antibact, Antffung, Ag
ents) vol, 11. No, 5゜p207~223
(1983) and the compounds described in "Chemistry of Antibacterial and Antifungal" by Hiroshi Horiguchi), metal salts such as magnesium salts and aluminum salts, alkali metal and ammonium salts, or Photographic by Wes L-・Science and Engineering Magazine (Ph.
ot, Sci.

Compounds described in J. Eng., Volume 6, pp. 344-359 (1965) may also be added. It is particularly effective to add chelating agents, fungicides, and anti-piping agents.

The washing process is a multi-stage countercurrent washing with two or more tanks (e.g. 2 to 9 tanks).
You can also reduce the amount of water used for washing. Furthermore, instead of the water washing step, a multistage countercurrent stabilization treatment step as described in JP-A-57-8543 may be performed. In that case, various compounds are added to the stabilizing bath for the purpose of stabilizing the image.

For example, various buffers (e.g. borate, metaborate, borax,
Typical examples include phosphates, carbonates, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acids, dicarboxylic acids, polycarboxylic acids, etc.) and aldehydes such as formalin. In addition, chelating agents (inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphonic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.), fungicides (thiazole type, isothiazole type, halogenated phenol, sulfanilamide, benzotriazole, etc.) ), surfactants, fluorescent whitening agents, hardeners, and other various additives may be used, and two or more compounds for the same or different purposes may be used in combination. In addition, the film p after treatment
Ammonium chloride, ammonium nitrate,
Various ammonium salts such as ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate can also be added.

In addition, for color photosensitive materials for photography, after bleaching and fixing (washing -
The stabilization step can also be replaced with the above-mentioned stabilization step and water washing step (water saving treatment).

At this time, if the amount of magenta coupler is 2 equivalents, formalin in the stabilizing bath may be removed.

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 higher temperatures can be used to accelerate processing and shorten processing time, or lower temperatures can be used to improve image quality and stability of the processing solution. I can do it. In addition, West German Patent No. 2゜226.770 or U.S. Patent No. 3 is used to save silver on photosensitive materials.
, 674,499 may be performed using cobalt intensification or hydrogen peroxide intensification.

Each processing time can be shorter than the standard time if necessary, within a reasonable range, 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 F7 pipes, various squeegees, etc., as necessary.

The present invention can be applied to various color photosensitive materials. Typical examples include color negative film for general use or movies, color reversal film for slides or television, color paper, color positive film, and color reversal paper. The present invention also relates to Research Disclosure 17123 (July 1978).
It can also be used in black-and-white light-sensitive materials using a mixture of three color couplers as described in J.

(Effects of the Invention) According to the present invention, since the amount of washing water used can be sufficiently reduced, development of silver halide color photographic materials can be easily carried out even in places without special waste water facilities. It is also possible to move the developing processor. Furthermore, since the washing water is stabilized, the resulting images are also extremely good.

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto.

(Example) Example 1゜Color negative film HR-10 manufactured by Fuji Photo Film
After imagewise exposure of 0 (24 shots), the film was continuously processed in the following processing steps using Fuji Photo Negative Processor Nocer FP-500 (manufactured by Fuji Photo Film ■).

Tank refilling work 1,
°day 6 - (m1/upper color development process 3"15" 38°C soil 0.3°c21ff
i45 Bleach-fixing process■ 2゛00'' 38℃±3℃
IH-bleach-fixing process ■ 3゛15” 38°C
±3℃ 13ff 39Water wash ■
1゛30" 33℃±3℃ 8β -Water wash ■ 2'OO' 33℃±3
℃ 8β 20-- Engineering 40"
38°C±3°C 13ff 39 The washing process was a two-stage countercurrent washing from washing (①) to washing (②). Further, in the bleach-fixing step, FP-500 was modified so that the flow was carried out in two stages, from the bleach-fixing bath (1) to the bleach-fixing bath (2).

In addition, the amount of processing liquid brought in from each type of front tank is 24 shots per 1
It was about 2 ml per bottle.

The prescriptions for each tank fluid and each replenisher are shown below.

<Color developer> L) Alternating or directing Sodium pentadentate nitrilotriacetate 1. Og 1.1. g Sodium sulfite 4.0g 4.4g Sodium carbonate 30.0g 32.0g Potassium bromide
1.4g 0.7g Hydroxylamine sulfate 2.4g 2.6g4-(
N-ethyl-N-β-hydroxyethylamino)-2-methylaniline sulfate 4. 5g 5. Add 0g water 16 1 dipH10,
0010,05 Bleach-fix solution> Mata Z Kyu 1 full solution ethylenediaminetetraacetic acid ferric ammonium salt 80. Og 90.0g Ethylenediaminetetraacetic acid disodium dihydrate 5. Og 6.0g Sodium sulfite 10.0g 15.0g Ammonium thiosulfate aqueous solution (70%) 250.0g 270.0
g Bleach accelerator (listed in Table 1) I Xl[12M 1
．． Add 0X1rf2M water 1.
O401,0A pH7,06,8 Wash with water> Add 0.4g of ethylenediaminetetraacetic acid disodium dihydrate to 0.4g of water 1. ON 1.0βpH7.0
7.0 Stabilizing liquid〉 Formalin 8. 0ml 8. 0
ml dry well (total ± 4.0ml 4.
0ml photographic film side) Add water and process 40 rolls of color negative film per day under the above conditions.
The treatment was carried out for several days. Table 1 shows the number of days until floating matter and precipitates appeared in the washing tank (2) and the washing tank (2). Similarly, Table 1 also shows the results when various compounds were added to the bleach-fix solution (tank solution and replenisher solution).

In addition, sensitometrically exposed color negative film HR
-100 (Fuji Photo Film-'!A) was treated with the solution after 60 days of processing, and then the concentration was measured through blue, green, and red filters. After aging this sample at 80°C for 9 days, the concentration was measured again and the cyan concentration (θ = 1.5) was determined.
The residual rate of cyan concentration was determined. The results are shown in Table 1.

Table 1 Sample Bleach accelerator Days Cyan concentration
] 72' %■-1 Blank 12 10 70 Comparative Example 1
-2 To comparison compound 12 10 72
〃1-3 〃B12 10 6
8 ”1-4 Compound of the present invention (2) 60 or more 60 or more 92
Present invention 1-5 〃(4) 60 or more 60 or more
9゜1-6 〃(6) 50 45
85 〃1-7 〃(7) 50
45 84 〃1-8 〃(9)
50 45 831-9 〃(12)
55 50 88 〃1-10
〃(16) 50 45 86
”1-11 〃(18) 50 45
87 〃1-12 〃(20)
50 4, 86〃Comparative compound A H Comparative compound B As is clear from Table 1, when the bleach accelerator of the present invention is included in the bleach-fix solution, when the photosensitive material is continuously processed, the subsequent washing water is It can be seen that the stability is significantly improved and the fading of cyan is also improved. In particular, it can be seen that compounds (2) and (4) have excellent effects.

Example 2 The same experiment as in Example 1 was carried out except that the bleach-fix solution was changed to the following formulation, and the same results as in Example 1 were obtained.

<Bleach-fix solution> 12ii Ferric ammonium salt of diethylenetriaminepentaacetate 100.0g 110.0gDiethylenetriaminepentaacetic acid ammonium disulfite 5.0g 6.0gSodium sulfite 15.0'g 20.0g
Ammonium thiosulfate aqueous solution (70%) 270.0ml 300
．． 0ml bleach accelerator (same as Table 1) 1x112M 1.1x
1 (add 12M water 1.0#
1.0ρpH7,57,0 Example 3゜Fuji Photo Film @Ren's Color Negative Film HR-10
After imagewise exposure of 0 (24 shots), the images were continuously processed using the following processing steps using Fujicolor Negative Processor FP-500.

Tank capacity/portion 07'-(ml Color development process 3'15" 38℃±0.3℃ 2
H45 bleaching process 1°00” 38℃±3℃ 18β
20 Bleach-fixing process 3°15” 38℃±3℃
18j! 39 water wash ■ 1'30
' 33℃± 3℃ 86 -Water washing ■ 2'OO'' 33℃± 3℃ 8
E2040' 38°C±3°C 13f 39 The washing process was a two-stage countercurrent washing from washing (①) to washing (②).

In addition, the amount of processing liquid brought in from each type of front tank is 24 shots per 1
The volume was approximately 2 ml per bottle.

The prescriptions for each tank fluid and each replenisher are shown below.

Color developer> 1) Sodium nitrilotriacetate 1. Og 1.1g Sodium sulfite 4.0g 4.4g Sodium carbonate 30.0g 32. Qg potassium bromide
1.4g 0.7g Hydroxylamine sulfate 2.4g 2.6g4-(
N=ethyl-N-β-hydroxyethylamino)-2-methylaniline sulfate 4- 5g Add 5.0g water if 1 βpH 10,
0010,05 Bleaching solution> Ammonium bromide 160.0g 176.0g
Ammonia aqua regia (28χ) 25.0g 15
．． 0g ethylenediamine-tetraacetic acid sodium iron salt 130. Og 143.0g glacial acetic acid 14. 0ml 14.
Add 0ml water IN 1ff
pH 6, O 5, 7 Bleach-fix solution> Taresi solution Box J ethylenediaminetetraacetic acid ferric ammonium salt 80.0g 100.0g ethylenediaminetetraacetic acid disodium dihydrate 5. Og 6.0g
Ammonium sulfite 15.0g 20.0g
Sodium thiosulfate aqueous solution (70%) 250.0g 270.0
g Bleach accelerator (listed in Table 3) 1 xt'M 1.
Add 1 x + ff2M water 1.0!
1.01 pH 7,06,8 Wash with water Add 0.4g of disodium ethylenediaminetetraacetate 0.4g of water 1. O401,0NpH7,07,
0 <Stabilizer> L1 Bunshin 1 Gorami Formalin 8. 0ml 8. 0
ml Drywell (Fuji Photo Film@Mei) 4. 0ml 4.
After adding 0 ml of water, 40 color negative films were processed per day under the above conditions for 60 days. Table 3 shows the number of days until floating matter and precipitates appeared in the washing tank (2) and the washing tank (2). Similarly, Table 3 also shows the results when various compounds were added to the bleach-fix solution (tank solution and replenisher solution).

Note that the O mark in the table indicates that no R, free substances, or precipitates were generated even after 60 days of treatment.

In addition, sensitometrically exposed color negative film J (
After treating R-100 (manufactured by Fuji Photo Film ■) with the solution after 60 days of treatment, the concentration was measured through blue, green, and red filters. After aging this sample at 80°C for 9 days, the concentration was measured again and the cyan concentration (θ=1..5
) was calculated. The results are shown in Table 3.

Table 3 Sample Bleach accelerator Days Cyan concentration NQ
y1y'2 %3-1
Blank 14 12 72 Comparative example 3-2 Comparative compound C141272 3-3 #D 14 12 703-4 Compound of the present invention (2) ○ 0 93 Invention 3-5 〃(4) ○ 0 903-
6” (5) 45 40 86
3-8 〃(9) 45 40 833
-9 〃(11) 45 40 853
-10 〃(13) 45 40 83
3-11 〃(17) 50 40 8
73-12 〃(18) 45 40
863-13 〃19 45 40 8
6 Comparative Compound C Comparative Compound D H2N -C-C-N H2 S As is clear from Table 3, when the bleach accelerator of the present invention is included in the bleach-fix solution, even if the photosensitive material is continuously processed, It can be seen that the stability of the subsequent washing water is significantly improved and the fading of cyan color is also improved.

Example 4 In Example 3, instead of HR100, VRloo (manufactured by Eastman Kodanok) exposed to sensotometry was used to determine the residual rate of cyan concentration after 9 days at 80°C. was treated in exactly the same manner as in Example 3, but it was found that when the bleach-accelerating material of the present invention was included in the bleach-fix solution, cyan fading was improved even at VRl of 00.

Example 5゜Table 4 shows the replenishment amount of water washing performed in sample hole 3-4 in Example 3.
An experiment was carried out in exactly the same manner as in Example 3, except for the following variables, and the number of days until floating matter and sediment appeared in the washing tanks (■) and (■) and cyan fading were determined in the same manner as in Example 3. .

The results are shown in Table 4. (The amount brought in from the pre-bath is 2
4 shots (approximately 2ml per bottle)
・-4 Sample replenishment amount Days Cyan concentration (m
11 pieces) Survival rate <X> Magnetic 7°
2 7°-172 4-1460 or more 60 or more 68 Comparative example 4-2 10 90
Present invention 4-5.100 50 40
944-6 150 9 17
94゛1 From the results in Table 4, it can be seen that the ratio of the replenishment amount to the amount brought in from the prebath was outside the scope of the present invention (
4-1, 4-6), there is almost no stabilizing effect of the washing water (Sample 4-6), or cyan fading worsens (Sample 4-1).
) has been proven to be effective.

Claims (1)

[Claims] In the development processing step of a silver halide color photographic light-sensitive material, which consists of each step of color development, desilvering, water washing and/or stabilization, at least one of the processing bath having bleaching ability in the desilvering step or its pre-bath, Contains a 5-membered heterocyclic compound having at least one mercapto group, and the amount added to the washing and/or stabilizing bath is 3 to 50 times the amount brought in from the bath per unit area of the photosensitive material. A method for developing a silver halide color photographic material, characterized in that: