JPH0789212B2 - Processing method of silver halide color photographic light-sensitive material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a development processing (hereinafter simply referred to as “processing”) method of an exposed silver halide color photographic photosensitive material (hereinafter referred to as “color photosensitive material”), In particular, it relates to a rapid processing method with improved desilvering performance.

(Prior Art) Generally, the basic steps of processing a color light-sensitive material are a color developing step and a desilvering step. In the color developing process, the exposed silver halide is reduced by the color developing agent to produce silver, and the oxidized color developing agent is the color developing agent (coupler).
Reacts with to give a dye image. The silver formed here is
In the subsequent desilvering process, it is oxidized by a bleaching agent, further converted into a soluble silver complex by the action of a fixing agent, and dissolved to be removed, whereby only a dye image is formed on the color light-sensitive material.

In addition to the above basic steps, the actual processing includes various auxiliary steps for maintaining the photographic and physical qualities of the image, improving the storability of the image, and the like. For example, a hardening bath, a stopping bath, an image stabilizing bath, a washing bath and the like.

In recent years, there has been a strong demand in the art for speeding up the processing, that is, for shortening the time required for the processing, and in particular, shortening the desilvering process, which accounts for almost half of the processing time, has become a major issue.

In general, as a bleaching agent, red blood salt, dichromate, secondary chloride
Iron, ferric aminopolycarboxylic acid complex salts, persulfates and the like are known.

(Problems to be Solved by the Invention) However, red blood salts and dichromates have pollution problems related to cyanide compounds and hexavalent chromium, and their use requires special treatment equipment. Further, ferric chloride has various problems in practical use due to problems such as generation of iron hydroxide and generation of stains in the subsequent washing step. For persulfate,
Its bleaching action is very weak and has the drawback of requiring a remarkably long bleaching time. In addition, persulfate itself is regulated by the Fire Service Law as a dangerous substance and requires various measures for storage.

Aminopolycarboxylic acid ferric iron complex salts (especially ethylenediaminetetraacetic acid ferric iron complex salt) are the most widely used bleaching agents at present because they have few pollution problems and no storage problems like persulfates. Is. However, the bleaching power of ferric aminopolycarboxylic acid complex is not always sufficient.

Further, it is disclosed in JP-A-6-41145 and 61-47959.
Although 1,2-diaminocyclohexanetetraacetic acid is known, its bleaching power is not always sufficient.

Conventionally, as a means to accelerate the desilvering process, the German patent No. 1
A bleach-fixing solution containing an aminopolycarboxylic acid ferric complex salt and a thiosulfate contained in 866,605 is known. However, in this case,
A ferric aminopolycarboxylic acid complex salt having a weak oxidizing power (bleaching power) is allowed to coexist with a thiosulfate having a reducing power, so that the bleaching power is remarkably weakened, especially for a high-sensitivity and high-silver amount color photographic material for photographing. However, there is a drawback that it is extremely difficult to sufficiently desilver and cannot be put to practical use.

On the other hand, as a method of increasing the bleaching power, a method of adding various bleaching accelerators to a bleaching bath, a bleach-fixing bath or a prebath thereof has been proposed. Such a bleaching accelerator is, for example,
U.S. Pat.No. 3,893,858, British Patent No. 1,138,842, various mercapto compounds as described in JP-A-53-141623, compounds having a disulfide bond as described in JP-A-53-95630, Thiazolidine derivatives as described in JP-A-53-9854, isothiourea derivatives as described in JP-A-53-94927, JP-B-45-850
6, thiourea derivatives as described in JP-A-49-26586, thioamide compounds as described in JP-A-49-42349, and dithiocarbamate salts as described in JP-A-55-26506. , Arylene diamine compounds as described in US Pat. No. 4,552,834.

Although some of these bleaching accelerators certainly show a bleaching promoting effect, they are not practical because they are expensive and have insufficient stability in a bleaching bath. I'm not satisfied with.

Research Disclosure 24023 (April 1984)
JP-A-60-230653 and the like describe treatment methods in which two or more kinds of ferric iron complex salts of various aminopolycarboxylic acids are used in combination, and these methods also have sufficient bleaching promoting effect. It hasn't come out yet.

Therefore, a first object of the present invention is to provide a processing method for rapidly desilvering a color light-sensitive material.

A second object of the present invention is to provide a rapid desilvering method with stable photographic performance.

A third object of the present invention is to provide a rapid desilvering method with less pollution problems.

A fourth object of the present invention is to provide an inexpensive and highly practical rapid desilvering method.

(Means for Solving the Problem) The above object can be achieved by the method described below.

In the method for processing a silver halide color photographic light-sensitive material, the exposed silver halide color photographic light-sensitive material is color-developed and then processed with a processing solution having a bleaching ability. -1) A method for processing a silver halide color photographic light-sensitive material, which comprises a ferric complex salt of an organic chelate compound represented by the formula (1).

General formula (X-1) (In the formula, Y ¹ , Y ² , Y ³ and Y ⁴ may be the same or different and each independently represents a methylene group or an ethylene group, and Z ¹ , Z ² , Z ³ and Z ⁴ may be the same or different. Often independently represent a carboxy group, a phosphono group, a sulfo group or a hydroxy group.The positions of the two substituents on the cyclohexane ring are 1,2-position, 1,3-position, or 1,4-position.
Show in rank. ) As Z ¹ , Z ² , Z ³ and Z ⁴ , a carboxyl group and a hydroxy group are preferable, and a carboxy group is particularly preferable.

Specific examples of the compound represented by formula (X-1) are shown below, but the invention is not limited thereto.

Regarding the compound represented by the general formula (X-1), Keihei Ueno, “Chelate Chemistry”, Vol. 5, Chapter 1 (Nankodo, 1975)
It can be easily synthesized based on the description in the annual publication. Specific synthetic examples of representative compounds are shown below.

Synthesis Example 1 Synthesis of Compound X- (3) To a mixed solvent of 200 ml of ethanol and 100 ml of water, 148 g of sodium chloroacetate salt, 40 g of 1,3-bis (aminomethyl) cyclohexane and a small amount of phenolphthalein were added. The reaction temperature was set so as not to exceed 70 ° C., and the pH was adjusted by adding an aqueous sodium hydroxide solution (45 g of sodium hydroxide dissolved in 80 ml of water) so as to maintain the pale red color of phenolphthalein. After heating under reflux for a further 1 hour, the mixture was allowed to cool and 106 ml of concentrated hydrochloric acid and 700 ml of ethanol were added. The crystals formed were collected by filtration, washed thoroughly with water, and 1000 ml of water and 1000 ml of ethanol.
Compound X- was obtained by recrystallization from a mixed solvent of ml.
(3) was obtained.

Collected 75 g (yield 71%), melting point 128 ° C. (decomposition) In the present invention, a processing solution having a bleaching ability is a processing solution capable of bleaching (oxidizing) silver produced in the developing step, and usually bleaching It includes both a solution (bleaching bath) and a bleach-fixing solution (bleach-fixing bath).

In the present invention, the amount of the bleaching agent contained in the processing solution having a bleaching ability is 0.05 mol to 1 mol per one. When the processing solution having a bleaching ability is a bleaching solution, it is preferably 0.1 mol to 1 mol, and particularly preferably 0.2 mol to 0.5 mol per one. When the processing solution having a bleaching ability is a bleach-fixing solution, it is preferably 0.05 mol to 0.5 mol per unit, and particularly 0.1 mol.
Molar to 0.3 molar is preferred.

In the present invention, the organic chelate compound represented by the general formula (X-1) may be used in the form of a ferric complex salt, or a ferric salt such as ferric sulfate or ferric chloride. Ferric nitrate,
You may form a ferric complex ion in a solution using ferric ammonium sulfate, ferric phosphate, etc. and this organic chelate compound. When used in the form of complex salt, one kind of complex salt may be used, or two or more kinds of complex salt may be used. On the other hand, when a complex salt is formed in a solution using a ferric salt and the organic chelate compound of the present invention, the ferric salt is
You may use 2 or more types. Further, one kind or two or more kinds of the organic chelate compound of the present invention may be used. Further, in any case, the organic chelate compound of the present invention may be used in an excess amount to form a complex salt with ferric ion.

Further, the ferric complex salt of the organic chelate compound of the present invention and a known ferric aminopolycarboxylic acid complex salt may be used in combination. Examples of the aminopolycarboxylic acid compound that can be used in combination with the organic chelate compound of the present invention include B-1 ethylenediaminetetraacetic acid B-2 ethylenediaminetetraacetic acid disodium salt B-3 ethylenediaminetetraacetic acid diammonium salt B-4 ethylenediaminetetraacetic acid tetra ( (Trimethylammonium) salt B-5 ethylenediaminetetraacetic acid tetrapotassium salt B-6 ethylenediaminetetraacetic acid tetrasodium salt B-7 ethylenediaminetetraacetic acid trisodium salt B-8 diethylenetriaminepentaacetic acid B-9 diethylenetriaminepentaacetic acid sodium salt B-10 ethylenediamine -N- (β-oxyethyl)
-N, N ', N'-triacetic acid B-11 ethylenediamine-N- (β-oxyethyl)
-N, N ', N'-Triacetic acid trisodium salt B-12 Ethylenediamine-N- (β-oxyethyl)
-N, N ', N'-triacetic acid triammonium salt B-13 1,2-diaminopropane tetraacetic acid B-14 1,2-diaminopropane tetraacetic acid disodium salt B-15 nitrilotriacetic acid B-16 nitrilotriacetic acid tri Sodium salt B-17 1,2-Diaminocyclohexanetetraacetic acid B-18 1,2-Diaminocyclohexanetetraacetic acid disodium salt B-19 Iminodiacetic acid B-20 Dihydroxyethylglycine B-21 Ethyletherdiaminetetraacetic acid B-22 Glycol Ether diamine tetraacetic acid B-23 ethylenediamine tetrapropionic acid B-24 1,3 diaminopropane tetraacetic acid and the like can be mentioned. The ferric complex salt of the organic chelate compound of the present invention and the ferric aminopolycarboxylic acid complex salt may be used in combination of one type each, or 2 types each.
You may use together more than one kind.

Further, the ferric iron complex salt of the organic chelate compound of the present invention and the above aminopolycarboxylic acid compound may be used in combination.

When the organic chelate compound of the present invention and the aminopolycarboxylic acid compound are used in combination, the ratio is 1/10 to 10/1 in terms of molar ratio.
Is preferable, and particularly preferably 1/5 to 5/1.

A compound known as a fixing agent can be added to the processing solution having a bleaching ability of the present invention. For example, thiosulfates such as sodium thiosulfate, ammonium thiosulfate, sodium ammonium thiosulfate and potassium thiosulfate,
Sodium thiocyanate, ammonium thiocyanate,
Thiocyanates such as potassium thiocyanate, thiourea, thioether and the like can be used. The addition amount of these fixing agents is preferably 3 mol or less per one, and particularly preferably 0.
5 to 2 mol is preferred.

A compound conventionally known as a bleaching accelerator can be added to the processing solution having a bleaching ability of the present invention. Such bleach accelerators are described, for example, in U.S. Patent No. 3,893,85.
No. 8, German Patent No. 1,290,812, JP-A-53
-95630, Research Disclosure No. 17129
Compounds having a mercapto group or disulfide group described in JP-A No. 1978 (July 1978), thiazolidine derivatives described in JP-A-50-140129, thiourea derivatives described in US Pat. No. 3,706,561, The iodides described in JP-A-58-16235, the polyethylene oxides described in German Patent 2,748,430, and the polyamine compounds described in JP-B-45-8836 can be used. Particularly preferred are the compounds described in JP-A-61-75352. These bleaching accelerators can also be used by adding them to the pre-bath of the processing solution having the bleaching ability of the present invention.

The treatment liquid having a bleaching ability of the present invention includes, in addition to the bleaching agent and the above compounds, bromides such as potassium bromide, sodium bromide, ammonium bromide or chlorides such as potassium chloride, sodium chloride and ammonium chloride. Rehalogenating agents can be included. In addition, 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,
Has a pH buffering capacity for sodium citrate, tartaric acid, etc. 1
Additives known to be used in ordinary bleaching solutions such as one or more kinds of inorganic acids, organic acids and salts thereof can be added.

Further, all the additives that can be added to the bleach-fixing solution, such as sulfite, bisulfite, various buffers and chelating agents, can be added.

The pH of the bleaching treatment solution of the present invention is preferably 4.0 to 8.0.

The processing solution having a bleaching ability of the present invention may be used as a bleaching bath or a bleach-fixing bath.

Further, it may be used as a bleach-bleach-fixing bath as described in JP-A-61-75352. The processing bath having a bleaching ability of the present invention may be provided immediately after the color developing bath, or a washing bath or an intermediate bath may be provided between the two.

The processing temperature and processing time of the processing solution having a bleaching ability of the present invention differ depending on the type of photographic material to be processed, the composition of the processing solution, etc., but usually about 20 to 60 ° C., preferably about 6 minutes or less.

In the processing method of the present invention, the color developing solution used for color development processing is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. As the color developing agent, a p-phenylenediamine compound is preferably used. Typical examples of p-phenylenediamine compounds are 3-methyl-4-amino-N, N-diethylaniline and 3-methyl-4-amino-N-ethyl-N.
-Β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N
-Β-methoxyethylaniline and sulfates thereof,
Hydrochloride, phosphate or p-toluenesulfonate,
Examples thereof include tetraphenyl borate and p- (t-octyl) benzene sulfonate.

Further, the concentration of the developing agent and pH of the color developing solution are very important factors for shortening the color developing time. In the present invention, the developing agent is used in a concentration of about 1.0 g to about 15 g per color developing solution,
More preferably, about 3.0 g to about 8.0 g per color developer.
Use at the concentration of. The pH of the color developing solution is usually 9 or higher, and most preferably about 9.5 to about 12.0.

The processing temperature of the color developer in the processing method of the present invention is
20 ° C to 50 ° C is preferable.

Further, in the present invention, various development accelerators may be used together if necessary.

As a development accelerator, benzyl alcohol, US Patent 2,
648,604, JP-B-44-9503, various pyrimidium compounds represented by U.S. Pat.No. 3,171,247, other cationic compounds, cationic dyes such as phenosafranin, neutral salts such as thallium nitrate and potassium nitrate, JP-B-
44-9304, U.S. Patents 2,533,990, 2,531,832, and
Polyethylene glycol and its derivatives described in 2,950,970 and 2,577,127, nonionic compounds such as polythioethers, and thioether compounds described in US Pat. No. 3,201,242 may be used.

In the color developing step in the processing method of the present invention, various antifoggants may be used in combination for the purpose of preventing development fog. As the antifoggant in these developing steps, alkali metal halides such as potassium bromide, sodium bromide and potassium iodide, and organic antifoggants are preferable. Examples of the organic antifoggants include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-
Nitrogen-containing heterocyclic compounds such as nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiozolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, hydroxyazaindolizine and 1-phenyl-5-mercaptotetrazole, 2-mercaptobenz A mercapto-substituted heterocyclic compound such as imidazole and 2-mercaptobenzothiazole, and a mercapto-substituted aromatic compound such as thiosalicylic acid can be used. These antifoggants include those that are eluted from the color light-sensitive material into the developing solution during processing.

In addition, the color developer in the processing method of the present invention is a pH buffering agent such as an alkali metal carbonate, borate or phosphate; hydroxylamine, triethanolamine, West German Patent Application (OLS) No. 2,622,950. Preservatives such as the compounds mentioned, sulfites or bisulfites; organic solvents such as diethylene glycol; dye-forming couplers;
Competitive couplers such as citrazinic acid, J acid, H acid; nucleating agents such as sodium boron hydride; co-developers such as 1-phenyl-3-pyrazolidone; tackifiers;
Ethylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, N-hydroxymethylethylenediaminediacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, and JP-A-58
No. 18170 (1979), aminopolycarboxylic acids typified by the compounds described in JP-A-195845, 1-hydroxyethylidene-1,1'-diphosphonic acid, and the like.
May)), aminophosphonic acids such as organic phosphonic acid, aminotris (methylenephosphonic acid), and ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid, JP-A Nos. 52-102726 and 53. -42730, 54-121127, 55-4
No. 024, No. 55-4025, No. 55-126241, No. 55-65955,
No. 55-65956, and Research Disclosure N
A chelating agent such as phosphonocarboxylic acid described in No. 18170 (May, 1979) can be contained.

If necessary, the color developing bath may be divided into two or more baths, and the color developing replenisher may be replenished from the frontmost bath or the last bath to shorten the developing time or the replenishing amount.

The processing method of the present invention can also be used for color reversal processing. In the present invention, as the black and white developing solution used at this time, what is commonly known as a black and white first developing solution used for reversal processing of a color photographic light-sensitive material or one used for processing a black-and-white light-sensitive material can be used. Further, various well-known additives which are generally added to the black and white developer can be contained.

Typical additives include a developing agent such as 1-phenyl-3-pyrazolidone, metol and hydroquinone, a preservative such as sulfite, and an accelerator composed of an alkali such as sodium hydroxide, sodium carbonate or potassium carbonate. , Potassium bromide, 2-methylbenzimidazole,
Inorganic or organic inhibitors such as methylbenzthiazole, water softeners such as polyphosphates, trace amounts of iodides, and development inhibitors composed of mercapto compounds can be mentioned.

The processing method of the present invention comprises the processing steps such as color development, bleaching and bleach-fixing described above. Here, after the bleach-fixing step, a treatment step such as washing and stabilization is generally carried out. However, after the bleach-fixing step, the stabilizing treatment can be easily carried out without substantially washing with water. Treatment methods can also be used.

The washing water used in the washing step may contain known additives, if necessary. For example, water softeners such as inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid, bactericides and antifungal agents that prevent the growth of various bacteria and algae (eg, isothiazolone, organochlorine bactericides, benzotriazole, etc.) , A drying load, and a surfactant for preventing unevenness can be used. Or LE
West, “Water Quality Criteria”, Phot.Sci.and Eng.,
The compounds described in vol. 9, No. 6, pages 344 to 359 (1965) and the like can also be used.

If necessary, the washing step may be performed using two or more tanks, and the washing water may be reduced (for example, 1 / m ² or less) as multi-step countercurrent washing (for example, 2 to 9 steps). .

As the stabilizing solution used in the stabilizing step, a processing solution for stabilizing the dye image is used. For example, a liquid having a buffering capacity of pH 3 to 6, a liquid containing an aldehyde (for example, formalin), and the like can be used. In the stabilizing solution, if necessary, an ammonium compound, Bi, a metal compound such as Al,
A fluorescent whitening agent, a chelating agent (for example, 1-hydroxyethylidene-1,1-diphosphonic acid), a bactericidal agent, an antifungal agent, a hardener, a surfactant and the like can be used.

In addition, the stabilization step may be performed using two or more tanks if necessary, and multi-stage countercurrent stabilization (for example, 2 to 9 steps) reduces the stabilizing solution (for example, 1 / m ² or less), Furthermore,
The water washing step can be omitted.

As the water used in these washing step or stabilizing step, in addition to tap water, Ca such as ion exchange resin,
Water, halogen, deionized to a Mg concentration of 5 mg / l or less,
You may use the water sterilized by the ultraviolet sterilization lamp etc.

The present invention can be applied to various color light-sensitive materials. Typical examples include color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers.

The silver halide emulsion used in the present invention can be prepared by the method described in Research Disclosure, vol. 176, Item No. 17643, item [I].

Any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used in the silver halide color photographic light-sensitive material used in the present invention.

The silver halide grains in the photographic emulsion may be so-called regular grains having regular crystal bodies such as cubes, octahedra and tetradecahedrons, and those having an irregular crystal shape such as spheres, It may have a crystal defect such as a twin plane or a composite form thereof.

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

Monodisperse emulsions are silver halide grains having an average grain diameter of greater than about 0.1 micron, at least about 95
Emulsions are typically such that the weight percentage is within ± 40% of the average grain diameter. An average particle diameter of about 0.25 to 2 microns, at least about 95% by weight or at least about 95% in quantity
An emulsion in which the above silver halide grains are within the range of average grain diameter ± 20% can be used in the present invention.

The crystal structure may be uniform, may have different halogen compositions inside and outside, or may have a layered structure. These emulsion grains are described in British Patent No. 1,027,146,
U.S. Pat.Nos. 3,505,068, 4,444,877 and JP-A-60
-143331 etc. Further, silver halides having different compositions may be joined by epitaxial joining.

By using tabular grains in the silver halide photographic emulsion used in the present invention, improvement in sensitivity including improvement in color sensitizing efficiency by a sensitizing dye, improvement in relation between sensitivity and graininess, improvement in sharpness, development progress It is possible to improve the sex, the covering power, and the crossover. Here, the tabular silver halide grains have a diameter / thickness ratio of 5 or more, for example, more than 8, or 5 or more and 8 or more.
There are the following:

The tabular halogen composition is preferably silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodobromide, silver chloride or silver iodochloride. Silver iodobromide is particularly preferred for use in 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, more preferably 15 mol% or less.
It is not more than mol%. Further, silver chlorobromide and silver bromide are particularly preferable for the photosensitive material for printing.

The tabular grains may have a uniform halogen composition or may have two or more phases having different halogen compositions. For example, when silver iodobromide is used, the tabular silver iodobromide grains having a layered structure composed of a plurality of phases each having a different iodide content can be used. JP-A-58-113928 and JP-A-59-99433 disclose preferable examples of the halogen composition of tabular silver halide grains and the distribution of halogen within the grains.

The preferred use of tabular silver halide grains in the present invention is Research Disclosure No. 22534.
(January 1983) and No. 25330 (May 1985), for example, a use method based on the relationship between tabular grain thickness and optical properties is disclosed.

Next, a silver halide solvent is useful for promoting the ripening of silver halide grain formation. For example, it is known to have excess halogen ions present in the reactor to accelerate aging. As ripening agents other than halogen ions, ammonia or amine compounds, thiocyanate salts such as alkali metal thiocyanate salts, especially sodium and potassium thiocyanate salts, and ammonium thiocyanate salts can be used. Using a thiocyanate ripening agent is US Patent No. 2,222,264,
Teachings can be found in Nos. 2,448,534 and 3,320,069.
Also U.S. Pat.Nos. 3,271,157, 3,574,628 and 3,
Conventional thioether ripening agents as described in 737,313 can also be used. Alternatively, JP-A-53-82408
It is also possible to use a thione compound as disclosed in No. 53-144319.

The properties of the silver halide grains can be controlled by allowing various compounds to be present during the silver halide precipitation formation process. For example, by allowing compounds such as copper, iridium, lead, bismuth, cadmium, zinc, (chalcogen compounds such as sulfur, selenium and tellurium), gold and compounds of Group VIII noble metals to be present during the silver halide precipitation process. The properties of silver halide can be controlled.

Silver halide emulsions are usually chemically sensitized. Chemical sensitization by The James, TH Theory
The Theory of the Photograph, 4th edition, published by Macmillan, 1977 (The Theory of the Photograph
ic Process, 4th ed, Macmillan, 1977) 67-76, using active gelatin. Further, it can be carried out using sulfur, selenium, tellurium, gold, platinum, palladium, iridium or a combination of a plurality of these sensitizers. Chemical sensitization is optimally performed in the presence of gold and thiocyanate compounds or in U.S. Pat.
No. 711, No. 4,266,018 and No. 4,054,457 sulfur-containing compound or hypo, described in No. 4, thiourea compounds,
It is carried out in the presence of a sulfur-containing compound such as a rhodanine compound. It is also possible to carry out chemical sensitization in the presence of a chemical sensitization aid. As the chemical sensitization aid used, compounds such as azaindene, azapyridazine, and azapyrimidine which are known to suppress fog and increase sensitivity in the process of chemical sensitization are used.

The silver halide photographic emulsion used in the present invention may be spectrally sensitized with methine dyes and the like. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes.

These sensitizing dyes may be used alone or in combination thereof, and the combination of sensitizing dyes is often used especially for the purpose of supersensitization. Along with the sensitizing dye, a dye having no spectral sensitizing effect itself or a substance which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion.

As these dyes, those described in Research Disclosure, vol.176, Item No.17643, IV (December 1978) can be used.

The spectral sensitization of the silver halide emulsion used in the present invention can be carried out at any stage of emulsion preparation.

Generally, a spectral sensitizing dye is added to a chemically sensitized emulsion before coating. U.S. Pat. No. 4,425,426 and the like disclose a method of adding to an emulsion before or during the start of chemical sensitization. In addition, a method of adding a spectral sensitizing dye to an emulsion before the formation of silver halide grains is completed is described in US Pat.
735,766, U.S. Patent 3,628,960, U.S. Patent 4,183,756
And U.S. Pat. No. 4,225,666. Particularly in U.S. Pat.Nos. 4,183,756 and 4,225,666, a spectral sensitizing dye is added to an emulsion after the formation of stable nuclei for silver halide grain formation to increase photographic sensitivity and spectral sensitizing dye by silver halide grains. It is disclosed that there are advantages such as enhanced adsorption of

In the photographic emulsion layer of the photographic light-sensitive material of the present invention, for the purpose of increasing sensitivity, increasing contrast, or promoting development, for example, polyalkylene oxide or its derivative such as ether, ester, amine, thioether compound, thiomorpholine, quaternary ammonium salt compound. , A urethane derivative, a urea derivative, an imidazole derivative, and 3-pyrazolidones.

In the silver halide photographic emulsion used in the present invention, for the purpose of preventing fog during the manufacturing process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance,
Various compounds can be included. That is, azoles, for example, benzothiazolium, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazole. , Benzotriazole, nitrobenzotriazoles, mercaptotetrazole (particularly 1-phenyl-5-mercaptotetrazole), etc .; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes, for example triazaindenes , Tetraazaindenes (especially 4-hydroxy substituted (1,3,3a,
7) Tetraazaindenes), pentaazaindenes, etc .; Add many compounds known as antifoggants or stabilizers such as benzenethiosulphonic acid, benzenesulphonic acid, benzenesulphonic acid amide, etc. You can

Various color couplers can be used in the present invention, specific examples of which are described in the patents described in Research Disclosure (RD) No. 17643, VII-CG. As the dye-forming coupler, a coupler that gives the three primary colors of the subtractive color method (that is, yellow, magenta, and cyan) by color development is important, and specific examples of the diffusion-resistant, 4-equivalent or 2-equivalent coupler are the above-mentioned RD17643, VII-
In addition to the couplers described in the patents described in the sections C and D,
The following can be preferably used in the present invention.

Typical examples of usable yellow couplers include known oxygen atom-releasing yellow couplers and nitrogen atom-releasing yellow couplers. The α-pivaloyl acetanilide type couplers are excellent in the fastness of color forming dyes, especially the light fastness, while the α-benzoyl acetanilide type couplers can obtain a high color density.

Examples of magenta couplers that can be used in the present invention include hydrophobic 5-pyrazolone and pyrazoloazole couplers having a ballast group. The 5-pyrazolone-based coupler is preferably a coupler in which the 3-position is substituted with an arylamino group or an acylamino group, from the viewpoint of the hue and color density of the color forming dye.

The cyan couplers that can be used in the present invention include hydrophobic and diffusion resistant naphthol-type and phenol-type couplers, and oxygen atom desorption-type two-equivalent naphthol-type couplers are preferred as typical examples. Couplers that can form a cyan dye that is robust against humidity and temperature are
It is preferably used, and a typical example thereof is US Pat.
No. 3,772,002, a phenolic cyan coupler having an ethyl group or higher alkyl group at the meta-position of the phenolic nucleus, 2,5-diacylamino-substituted phenolic coupler, a phenylureido group at the 2-position and a 5-position. Examples thereof include phenol-based couplers having an acylamino group, and 5-amidonaphthol-based cyan couplers described in European Patent No. 161,626A.

The graininess can be improved by using a coupler in which the color forming dye has an appropriate diffusibility. Such couplers are
Specific examples of magenta couplers are described in US Pat. No. 4,366,237, and specific examples of yellow, magenta or cyan couplers are described in European Patent No. 96,570.

The dye-forming coupler and the above-mentioned special coupler may form a polymer of a duplex or more. Typical examples of polymerized dye forming couplers are described in US Pat. No. 3,451,820. Specific examples of the polymerized magenta coupler are described in US Pat. No. 4,367,282 and the like.

Couplers that release a photographically useful residue upon coupling are also preferably used in the present invention. As the DIR coupler releasing the development inhibitor, the couplers of the patents described in the above-mentioned RD17643, VII to F are useful.

In the light-sensitive material of the present invention, a coupler capable of releasing a nucleating agent or a development accelerator or a precursor thereof imagewise during development can be used. Specific examples of such compounds are described in British Patent Nos. 2,097,140 and 2,131,188. In addition, DIR described in JP-A-60-185950
Redox compound-releasing couplers, couplers which release dyes that recolor after separation described in EP 173,302A, and the like can be used.

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

The light-sensitive material used in the present invention is, as a color antifoggant or color mixing inhibitor, a hydroquinone derivative, an aminophenol derivative, an amine, a gallic acid derivative, a catechol derivative, an ascorbic acid derivative, a colorless coupler, a sulfonamide phenol derivative, etc. May be included.

A known anti-fading agent can be used in the light-sensitive material used in the present invention. Known anti-fading agents include hydroquinones, 6-hydroxychromans, 5-hydroxycoumarans, spirochromans, p-alkoxyphenols, hindered phenols centering on bisphenols, gallic acid derivatives, and methylenediene. Representative examples include oxybenzenes, aminophenols, hindered amines, and ether or ester derivatives obtained by silylating or alkylating the phenolic hydroxyl groups of these compounds. Further, a metal complex represented by a (bissalicylaldoximato) nickel complex and a (bis-N, N-dialkyldithiocarbamato) nickel complex can also be used.

In the light-sensitive material used in the present invention, an ultraviolet absorber can be added to the hydrophilic colloid layer. For example, benzotriazoles substituted with an aryl group described in U.S. Pat.No. 3,553,794, and European Patent 57,160, butadienes described in U.S. Pat.No. 4,450,229, and cinnamon described in U.S. Pat.No. 3,705,805. Acid esters, benzophenones described in U.S. Pat. No. 3,215,530, and polymer compounds having an ultraviolet absorbing residue as described in U.S. Pat. No. 3,761,272 can be used. The UV-absorbing fluorescent brighteners described in US Pat. No. 3,499,762 may also be used. Typical examples of the ultraviolet absorber are described in RD24239 (June 1984) and the like.

The light-sensitive material used in the present invention comprises one or more surfactants for various purposes such as coating aid, antistatic property, sliding property improvement, emulsion dispersion, adhesion prevention and photographic property improvement (for example, development acceleration, contrast enhancement, sensitization). May be included.

The light-sensitive material used in the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as prevention of irradiation or halation. As such dyes, oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, anthraquinone dyes, and azo dyes are preferably used. In addition to these, cyanine dyes, azomethine dyes, triazolemethane dyes, and phthalocyanine dyes are also useful. The oil-soluble dye can be emulsified by the oil-in-water dispersion method and added to the hydrophilic colloid layer.

In the light-sensitive material used in the present invention, various methods such as an oil-in-water dispersion method, a latex dispersion method, a solid dispersion method and an alkali dispersion method can be used to introduce a lipophilic compound such as a photographic coupler into the hydrophilic organic colloid layer. A method can be used, and a preferable method can be appropriately selected depending on the chemical structure and physicochemical properties of the compound to be introduced.

(Examples) Hereinafter, the present invention will be described in more detail by showing specific examples of the present invention. However, the present invention is not limited to the following examples.

Example 1 On a subbed cellulose triacetate film support,
A multilayer color photographic light-sensitive material 101 was produced by applying each layer having the following composition in multiple layers.

(Photosensitive Layer Composition) The numbers corresponding to the respective components indicate the coating amount expressed in g / m ² unit, and for silver halide, the coating amount in terms of silver. However, for the sensitizing dye and the coupler, the coating amount is shown in mol unit per mol of silver halide in the same layer.

(Sample 101) First layer: antihalation layer Black colloidal silver ...... Silver 0.18 gelatin ...... 0.40 Second layer: Intermediate layer 2,5-di-t-pentadecylhydroquinone ...... 0.18 Coupler C-1 ...... 0.07 Coupler C-3 ...... 0.02 UV absorber U-1 ...... 0.08 UV absorber U-2 ...... 0.08 Organic solvent HBS-1 ...... 0.10 Organic solvent HBS-2 ...... 0.02 Gelatin ...... 1.04 Third layer; 1st Red-sensitive emulsion layer Silver iodobromide emulsion (silver iodide 6 mol%, average grain size 0.8 μm) ...... Silver 0.50 Sensitizing dye IX ...... 6.9 × 10 ^-5 Sensitizing dye II ・ ・ ・ 1.8 × 10 ^-5 Sensitizing dye III …… 3.1 × 10 ^-4 Sensitizing dye IV …… 4.0 × 10 ^-5 Coupler C-2 …… 0.146 Organic solvent HBS-1 …… 0.40 Coupler C-10 …… 0.008 Gelatin …… 1.20 4th layer Second red-sensitive emulsion layer Silver iodobromide emulsion (5 mol% silver iodide, average grain size 0.85 μm) …… Silver 1.15 Sensitizing dye IX …… 5.1 × 10 ^-5 Sensitizing dye II …… 1.4 × 10 ^{-5-sensitized} color III ...... 2.3 × 10 ^-4 Sensitizing dye IV ...... 3.0 × 10 ^-5 coupler C-2 ...... 0.060 Coupler C-3 ...... 0.008 Coupler C-10 ...... 0.004 organic solvent HBS-2 ...... 0.40 Gelatin ... … 1.50 Fifth layer; third red-sensitive emulsion layer Silver iodobromide emulsion (silver iodide 10 mol%, average grain size 1.5 μm) …… Silver 1.50 Sensitizing dye IX …… 5.4 × 10 ^-5 Sensitizing dye II …… 1.4 × 10 ^-5 Sensitizing dye III …… 2.4 × 10 ^-4 Sensitizing dye IV …… 3.1 × 10 ^-5 Coupler C-5 …… 0.012 Coupler C-3 …… 0.003 Coupler C-4 …… 0.004 Organic solvent HBS-1 0.32 Gelatin 1.63 6th layer; Intermediate layer Gelatin 1.06 7th layer; 1st green emulsion layer Silver iodobromide emulsion (6 mol% silver iodide, average grain size 0.8 μm) ) Silver 0.35 Sensitizing dye V …… 3.0 × 10 ^-5 Sensitizing dye VI …… 1.0 × 10 ^-4 Sensitizing dye VII …… 3.8 × 10 ^-4 Coupler C-6 …… 0.120 Coupler C-1… … 0.021 Coupler C-7 …… 0.030 Coupler C-8 …… 0.025 Organic solvent HBS-1 ...... 0.20 Gelatin ...... 0.70 Eighth layer; Second green emulsion layer Silver iodobromide emulsion (silver iodide 5 mol%, average grain size 0.85 µm) ...... Silver 0.75 Sensitizing dye V …… 2.1 × 10 ^-5 Sensitizing dye VI …… 7.0 × 10 ^-5 Sensitizing dye VII …… 2.6 × 10 ^-4 Coupler C-6 …… 0.021 Coupler C-8 …… 0.004 Coupler C-1 …… 0.002 Coupler C-7 0.003 Organic solvent HBS-1 0.15 Gelatin 0.80 9th layer; 3rd green sensitive emulsion layer Silver iodobromide emulsion (silver iodide 10 mol%, average grain size 1.2 μm) Silver 1.80 Sensitizing dye V …… 3.5 × 10 ^-5 Sensitizing dye VI …… 8.0 × 10 ^-5 Sensitizing dye VII …… 3.0 × 10 ^-4 Coupler C-6 …… 0.011 Coupler C-1 …… 0.001 Organic Solvent HBS-2: 0.69 Gelatin: 1.74 10th layer; Yellow filter layer: Yellow colloidal silver: Silver 0.05 2,5-di-t-pentadecylhydroquinone: 0.03 Gelatin: 0.95 11th layer; 1 blue-sensitive emulsion layer Silver iodobromide emulsion (silver iodide 6 mol%, average particle size 0.6 .mu.m) ...... silver 0.24 Sensitizing dye VIII ...... 3.5 × 10 ^-4 coupler C-9 ...... 0.27 Coupler C-8 …… 0.005 Organic solvent HBS-1 …… 0.28 Gelatin …… 1.28 12th layer; 2nd blue emulsion layer Silver iodobromide emulsion (silver iodide 10 mol%, average grain size 1.0 μm) …… Silver 0.45 Sensitization Dye VIII: 2.1 × 10 ^-4 Coupler C-9: 0.098 Organic solvent HBS-1: 0.03 Gelatin: 0.46 13th layer: 3rd blue-sensitive emulsion layer Silver iodobromide emulsion (silver iodide 10 mol% , Average particle diameter 1.8 μm) Silver 0.77 Sensitizing dye VIII 2.2 × 10 ^-4 Coupler C-9 0.036 Organic solvent HBS-1 0.07 Gelatin 0.69 14th layer; 1st protective layer Iodine Silver bromide (silver iodide 1 mol%, average particle size 0.07 μm) ...... Silver 0.5 UV absorber U-1 ...... 0.11 UV absorber U-2 ...... 0.17 Organic solvent HBS-1 ...... 0.90 Gelatin ...... 0.95 15th layer; 2nd Protective layer Polymethylmethacrylate particles (diameter about 1.5 μm) …… 0.54 S-1 …… 0.15 S-2 …… 0.05 Gelatin …… 0.72 In addition to the above composition, each layer contains gelatin hardener H-1 and surface active agent. The agent was added.

The chemical structural formulas or chemical names of the compounds used in the above examples are shown below.

HBS-1 Tricresyl Phosphate HBS-2 Dibutyl Phthalate In the multilayer color photographic light-sensitive material prepared as described above,
Color temperature of 4800 ° K with a filter using a tungsten light source
After the exposure was adjusted to 25 CMS, it was processed at 38 ° C. according to the following processing steps.

Process liquid composition used in the time between the color developing 3 min 15 sec Bleaching 3 minutes Fixing 3 min 15 sec Washing 1 min 30 sec Stabilization 45 seconds processing as engineering is as follows.

Color developer Diethylenetriaminepentaacetic acid 1.0g 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0g Sodium sulfite 4.0g Potassium carbonate 30.0g Potassium bromide 1.4g Potassium iodide 1.3mg Hydroxylamine sulfate 2.4g 4- (N- Ethyl-N-β-hydroxyethylamino)
-2-Methylaniline sulfate 4.5g Water added 1.0l pH10.0 Bleaching solution Bleaching agent (compounds listed in Table 1) 0.5 mol Chelate compound (same as above) 0.05 mol Ammonium bromide 150g Ammonium nitrate 10g Water added 1.0 l pH6.0 Here, the chelate compound represents the same organic acid as the ferric ammonium salt of the organic acid used for the bleaching agent.

Fixing solution Ethylenediaminetetraacetic acid disodium salt 1.0g Sodium sulfite 4.0g Ammonium thiosulfate aqueous solution (70wt%) 250.0ml Sodium bisulfite 4.6g Water was added 1.0l pH6.6 Water washing solution Ethylenediaminetetraacetic acid disodium salt 0.4g Water was added 1000 ml pH 7.5 Stabilizer Formalin (40 wt% aqueous solution) 2.0 ml Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization: approx. 10) 0.3 g Water-added 1000 ml About Fluorescent X
The amount of residual silver in the highest color density portion was measured by line analysis.
The results are shown in Table 1.

As is clear from Table 1, when the exemplified compound of the present invention was used as an organic chelate compound for a bleaching agent, a preferable image having a small residual silver amount was obtained.

On the other hand, when the comparative compound is used, the amount of residual silver is large and it is found that a preferable image cannot be obtained.

Example 2 The multilayer color photographic light-sensitive material prepared in Example 1 was used in Example 1.
Exposure was carried out in the same manner as above, and treatment was carried out at 38 ° C. according to the following steps.

Processing process time Color development 3 minutes 15 seconds Bleaching 45 seconds Bleaching fixing 2 minutes 30 seconds Water washing 1 minute 30 seconds Stabilization 45 seconds The composition of the processing solution used for processing is the color developing solution and stabilizing solution It has the same composition as 1. Other treatment liquid compositions are as follows.

Bleaching solution Bleaching agent (compounds listed in Table 2) 0.5 mol Chelating compound (same as above) 0.05 mol Ammonium bromide 150 g Ammonium nitrate 10 g Water added 1 pH 6.0 Bleach-fixing solution Bleaching agent (same as bleaching solution) 0.3 mol Chelating compound (Same as above) 0.05 mol Sodium sulfite 15g Ammonium thiosulfate aqueous solution (70wt%) 250ml Add water 1 pH 7.0 In bleaching solution and bleach-fixing solution, chelate compound is the same as ferric ammonium salt of organic acid used as bleaching agent. Represents an organic acid.

Washing solution 2-Methyl-4-isothiazolin-3-one 3 mg 5-Chloro-2-methyl-4-isothiazolin-3-one 6 mg Ethylene glycol 1.5 ml 1000 ml of water was added to the processed photographic material The residual silver amount in the highest density part was measured by. The results are shown in Table 2.

As shown in Table 2, when the exemplified compound of the present invention was used as an organic chelate compound for a bleaching agent, a preferable image having a small residual silver amount was obtained.

Example 3 The multilayer color photographic light-sensitive material prepared in Example 1 was cut into a roll film having a width of 35 m / m and exposed imagewise, and then 30 m a day.
Fuji Photo Film Co., Ltd. FP350 automatic developing machine was partially modified, and continuously processed for 1 month (processing temperature 38 ° C.). The specifications of the developing machine and the processing steps were as follows.

Engineering more processing time Tank capacity Replenishment rate ^* Color development 3 min 15 sec 10l 38 ml Bleach 45 seconds 4l 18 ml bleach-fixing 2'30 10l 27 ml washing 40 seconds 4l - washing 1 min 00 sec 4l 27 ml stable 40 seconds 4l 18 ml the treatment process In, the replenishment amount ^* represents the replenishment amount per 1 m of 35 m / m width roll film. The washing with water was a countercurrent washing method from to. Further, the overflow solution accompanying the replenishment of the bleaching solution was introduced into the bleach-fixing solution.

The composition of each treatment liquid is as follows.

Color developer Bleach (same as tank solution and replenisher) Ammonium bromide 100g Bleach (compounds listed in Table 3) 0.06mol Ethylenediaminetetraacetic acid ferric ammonium salt 96g Ethylenediaminetetraacetic acid disodium salt 10.0g Ammonium nitrate 10.0g Bleach accelerator 2.0g Ammonia water 17ml Add water 1 pH 6.5 Bleach-fixer Rinsing solution (tank solution and replenisher are the same) "Demineralized water" was used.

Here, "demineralized water" refers to ordinary tap water using an ethion exchange resin (manufactured by Mitsubishi Kasei Co., Ltd., trade name Diaion SK-1B), and the calcium and magnesium concentrations in the liquid are water 1
It was processed so that it would be 5 mg or less per unit.

Stabilizer The exposed photosensitive material was processed in the same manner as in Example 1 using each processing solution after continuous processing, and the amount of residual silver in the highest density portion was measured by fluorescent X-ray analysis. The results are shown in Table 3.

As is clear from Table 3, when the organic chelate compound for the bleaching agent of the present invention is used, a preferable image having a small amount of residual silver, a high cyan density after the processing and a small color returning defect can be obtained. It was

Example 4 The same procedure as in Example 1 was carried out except that the composition of the bleaching solution in Example 1 was changed as follows.

Bleaching solution Bleach A (compounds listed in Table 4) 0.17 mol Bleach B (same as above) 0.33 mol Chelate compound (same as above) 0.05 mol Ammonium bromide 150 g Ammonium nitrate 10 g Water 1 pH 6.0 where chelate compound is bleached The same organic acid as the ferric ammonium salt of organic acid used in the agent B was used.

The results obtained are shown in Table 4.

As is apparent from Table 4, a sufficient bleaching effect was obtained even when the ferric ammonium salt of ethylenediaminetetraacetic acid and the compound of the present invention were used together as a bleaching agent.

(Effects of the Invention) According to the present invention, a color sensitive material having high sensitivity and high silver content could be sufficiently desilvered in a short time without impairing photographic properties. Further, when continuously treated by the method of the present invention,
A good photographic image can be obtained with a small amount of replenishment, and as a result, the amount of waste liquid can be reduced.

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Claims (1)

[Claims] 1. A method of processing a silver halide color photographic light-sensitive material, which comprises subjecting an exposed silver halide color photographic light-sensitive material to color development and then treating it with a processing solution having a bleaching ability. The following general formula (X-1)
A method of processing a silver halide color photographic light-sensitive material, comprising a ferric iron complex salt of an organic chelate compound represented by: General formula (X-1) (In the formula, Y ¹ , Y ² , Y ³ and Y ⁴ each independently represent a methylene group or an ethylene group, and Z ¹ , Z ² , Z ³ and Z ⁴ are each independently a carboxy group, a phosphono group or a sulfo group. Or a hydroxy group. The positions of the two substituents on the cyclohexane ring are 1,2-position, 1,3-position, or
Expressed in 1,4-position. )