JPH01207751A - Method for processing silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To make it possible to effect the sufficient desilverization of the title material with rapidity, and to prevent the generation of a stain in the unexposed part of the sensitive material by processing the sensitive material with a bleaching solution or a bleach-fix solution contg. an iron (III) ion of >=0.25mol./l at a treating temp. of >=45 deg.C, and by specifying pH of the bleaching solution or the bleach-fixing solution to 4-6.5. CONSTITUTION:The bleach, the fix or the bleach-fix processing step and then the washing or the stabilizing processing step of the sensitive material are all processed at the treating temp. of >=45 deg.C, preferably >=50 deg.C, further preferably >=60 deg.C. The processing of the sensitive material with a processing solution having bleaching ability is effected with the bleaching solution or the bleach- fixing solution contg. the iron (III) ion of 0.25-1.0mol./l, preferably 0.3-0.8mol./l at the treating temp. of 50-90 deg.C, and pH5.0-6.4, further preferably 5.5-6.3. The color-developing step of the sensitive material is effected with a developer contg. a color developing main agent having a concn. of >=0.2mol./l at the treating temp. of >=45 deg.C. Thus, the sufficient desilverization of the sensitive material, even in case of rapid processing is maintained.

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a method for processing silver halide color photographic materials. More specifically, the present invention relates to a method for processing silver halide color photographic materials (hereinafter sometimes simply referred to as "photosensitive materials") that suppresses the occurrence of staining in unexposed areas during rapid processing. [Background of the Invention] In general, in order to obtain a color image by processing an imagewise exposed light-sensitive material, one step is to remove the generated metallic silver after a color development step, and then wash it with water and stabilize it or stabilize it as an alternative to water washing. A processing step is provided. However, although photosensitive materials are subjected to running processing in automatic developing machines installed in each laboratory,
As part of improving services for users, it is required that the images be processed and returned to the user on the same day they are received, and in recent years, it has become even necessary to return them several hours after receiving the image. The development of rapid processing technology is becoming increasingly urgent. As a result, the processing time, process, and temperature of the current major color photosensitive materials have reached the following levels. That is, the development time for color photographic paper was 8.5 minutes, and the processing temperature was 33.
Color development 3.5 minutes at ℃, bleach fixing 1.5 minutes, washing with water 3.5 minutes
The system technology involved is U.S. Patent No. 582,322 and West German Published Patent No.
S) No. 2,160,872, etc. The development time for color negative film is 3 minutes and 15 seconds for 1 color development, 6 minutes and 30 seconds for bleaching, 4 minutes and 20 seconds for constant M, and 2 minutes and IO seconds for washing.
The dye image stabilizing bath is used for about 1 minute and 05 seconds, and the processing temperature is about 38°C. The system technology included in this is a U.S. defense patent (U.S.
s Defensive Publication)9
10002, JP-A-49-5630 and JP-A-49-12
Fe(III)ED as disclosed in No. 1541
This is a method in which bleaching is performed using a TA complex salt and halide ions, followed by fixing. For color reversal films, a particularly rapid process among general-purpose development processes is the color reversal process for television, which uses persulfates as oxidizing agents and thiol compounds to accelerate bleaching, as disclosed in U.S. Pat. No. 3,707,374. By using this method, the entire process can be completed in about 11 minutes. At this time, the treatment temperature was 41 to 45°C. In addition, a known rapid development process, although not a general one, is the EM25 process (Eastman) for 8mm color films.
(Kodak) for 10 minutes at 52°C, and in order to withstand this high-temperature treatment, it is carried out in a special process that starts with a hardening bath (called pre-hardening), which is the first step of the treatment. As a technology for speeding up the process, speeding up the desilvering process is as follows. The desilvering process may be carried out in two steps, bleaching and fixing, or in one step, which combines bleaching and fixing. The former includes red blood salts, persulfates, ferric chloride, iron (III) organic acid complex salts typified by iron (III) EDTA complex salts, and cobalt (III) EDTA.
Cobalt (
III) A combination of an oxidizing agent such as a complex salt and a silver potential regulator such as an alkali bromide or ammonium bromide is widely used. Among these, Fe(II) is used because of the low pollution of the waste liquid.
I) Those using an aminopolycarboxylic acid complex salt as an oxidizing agent are particularly frequently used. The subsequent fixing step is generally carried out using a fixing solution based on thiosulfate. In the case of one-step processing using a bleach-fix solution, an iron (III) organic acid complex salt, especially an iron (I)
II) A monobath solution consisting of an aminopolycarbon # complex salt and a thiosulfate is widely used. There is also an example of speeding up bleaching and fixing by performing bleaching and fixing in one bath. For example, U.S. Pat. It is disclosed that processing exclusively for color photographic paper is possible. Unicolor (Ur+1calor) is also developing a similar rapid development process for color negatives and photographic paper (
29.5°C, 7 to 11 minutes, for example, "British Journal of Photography-r (British
Journal of Photography)
, January 30, 1970, p. 114). [Problems to be Solved by the Invention] In the above-mentioned prior art, even if the two-step process is used, -
Even in the case of stepwise processing, from the perspective of speeding up general-purpose technology using iron(III) aminopolycarboxylic acid complexes, it is important to note that: ■ Temperature dependence is small and time reduction cannot be expected by raising the temperature; ■ Significant reduction in time due to bleaching accelerators 1) The oxidizing agent and fixing agent concentrations are sufficiently high that even higher concentrations will not contribute to faster bleaching. There are some things that I don't expect too much from. In short, there is a lack of means to increase speed beyond current levels. This problem applies particularly to bleach-fix solutions. This is especially true in a process in which bleach-fixing is carried out immediately after one-color development. In this regard, JP-A-62-2255 provides an image stabilizing bath step directly following the desilvering step. It is proposed that both of these steps be carried out at a temperature of 50°C or higher, but with this technique, staining may occur in unexposed areas, resulting in the apparent whiteness of the photosensitive material being paper, for example. It was found that there are drawbacks that worsen the situation. For example, a p-phenylenediamine derivative is used as a color developing agent in a color developer at a concentration of 0.2 mol/1 or more. Alternatively, it has been found that when the color developing agent is subjected to high temperature treatment at 45° C. or higher, the color developing agent becomes liquefied, which occurs particularly when the color developing solution is stored at high temperature, and becomes large in continuous treatment. Furthermore, it has been found that there is a problem when a cyan coupler is used as a cyan coupler and is combined with a water-washing alternative stabilization treatment at high temperatures. [Object of the Invention] Therefore, the first object of the present invention is to provide a method for processing a silver halide color photographic light-sensitive material, which can not only quickly and sufficiently achieve desilvering but also suppress the occurrence of staining in unexposed areas. The second object of the present invention is to provide
It is an object of the present invention to provide a processing method capable of suppressing the occurrence of staining in unexposed areas, not only in the case of water washing, but also especially when combined with a water washing alternative stabilization treatment. [Structure of the Invention] The processing method of the present invention achieves the above object, after color development,
In a method for processing a silver halide color photographic light-sensitive material, which involves processing with a processing solution having bleaching ability, the processing with the processing solution having bleaching ability is a bleaching solution containing 0.25 mol/l or more of iron (III) ions; 45 by bleach-fix solution
It is characterized in that it is carried out at a processing temperature of 0.degree. C. or higher, and that the pH of the bleaching solution or bleach-fixing solution is 4 to 6.5. In a preferred embodiment of the present invention, (1) the bleaching treatment, the fixing treatment, the bleach-fixing treatment, and the water washing or stabilization treatment performed subsequent to the treatment are all carried out at a processing temperature of 45°C or higher, particularly 50°C or higher, and furthermore 60°C or higher. , ■ Treatment with a treatment solution having bleaching ability produces iron (III) ions of 0.25 to 1.0 mol/concentration,
In particular, the treatment temperature is 50°C to 90°C and the pH is 5 using a bleaching solution or bleach-fixing solution containing 0.3 to 0.8 mol/l.
, 0 to 6.4, especially 5.5 to 6.3,■
In the color development step, the concentration of color developing agent is 0.2 mol/1.
or higher, and/or the treatment temperature is 45°C or higher. [Specific Configuration of the Invention] The present invention will be described in detail below. The bleaching agent used in the processing liquid having bleaching ability of the present invention is:
Aminopolycarboxylic acid iron(III) complex salts are preferred, which are complexes of m-valent iron (ferric) ions and aminopolycarboxylic acids or salts thereof. Representative examples of these aminopolycarboxylic acids and their salts are: [A-1'J Ethylenediaminetetraacetic acid or its salt (salt of ammonium, sodium, potassium, triethanolamine, etc.) [A-2] Trans-1,2-cyclohexanediaminetetraacetic acid or its salt C17) [A-3 ] Dihydroxyethylglycinate or its salt (7J) [A-4 1,3-diaminopropane-2-oltetraacetic acid or its salt CJI) [A-5] 1,3-diaminopropanetetraacetic acid or its salt ( 77) [A-6] 1,2-diaminopropanetetraacetic acid or its salt (Tsuno) [A-7] Diethylenetriaminepentaacetic acid or its salt (11) [A-8] Ethylenediamine diorthohydroxyphenylacetic acid or its salt ( H) [A-9] Hydroxyethylethylenediaminetriacetic acid or its salt (77) EA-10 Ethylenediaminedipropionic acid or its salt (77) [A-11] Ethylenediaminediacetic acid or its salt (17) [A-12 ] Glycol ether diamine tetraacetic acid or its salt (j)) [A-13] Hydroxyethyliminodiacetic acid or its salt (77) [A-14] Nitrilotriacetic acid or its salt CJ
7) [A-15] Nitrilotripropionic acid or its salt (77) [A-16] Triethylenetetraminehexaacetic acid or its salt ()l) [A-171 Ethylenediaminetetrapropionic acid or its salt (I]), etc. can be mentioned. Of course, the present invention is not limited to these exemplified compounds. Among these compounds, A-1, A-2, A-5, A-
6, A-7, and A-12 are preferred. Aminopolycarboxylic acid iron(III) complex salts may be used in the form of complex salts, or iron(III) salts such as ferric sulfate,
An iron (III) ion complex salt may be formed in a solution using ferric chloride, ferric acetate, ferric ammonium sulfate, ferric phosphate, etc. and aminopolycarboxylic acid or its salt. 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, it is possible to use a ferric salt and an aminopolycarboxylic acid to form a complex salt in a solution. In the case of The aminopolycarboxylic acid and the iron complex salt may be used in the form of an ammonium salt, a sodium salt, a potassium salt, or a triethanolamine salt. Two or more types may be used in combination. Further, the bleach-fix solution or bleaching solution containing the above-mentioned iron (III) ion complex may contain metal ion complex salts other than iron, such as cobalt, copper, nickel, and zinc. Bleach-fix solution or bleach solution 11 used in the present invention
The amount of bleach per mol is 0.25 mol or more, preferably 0.25 mol to 3.0 mol, more preferably 0.35 mol to 1.0 mol. In the present invention, examples of the fixing agent include thiosulfates such as sodium thiosulfate, ammonium thiosulfate, and potassium thiosulfate, thiocyanates such as sodium thiocyanate, ammonium thiocyanate, and potassium thiocyanate, thiourea, thioether, and iodine ion. can be used alone or in combination. Here, using iodine ions as a fixing agent means containing 150 g/J1 or more. 150g/! of iodine ions! When containing L or more in a fixer or a bleach-fixer, the contents described in Japanese Patent Publication No. 61-13579, No. 60-10303, No. 52-134433, and No. 52-145029 can be referred to. . The bleaching solution, fixing solution or bleach-fixing solution used in the present invention can contain various additives. For example, a compound having a pyrrolidone nucleus in one molecule structure can be preferably used in the bleach-fix solution of the present invention. The amount added is preferably 1 to 100 g/4Q, more preferably 5 to 50 g/i.
It is stated in No. 1-298499. After margin bleaching and fixing (or bleach-fixing), stabilizing treatment can be performed without washing with water, or washing with water can be performed. In addition to zero or more steps that may be followed by stabilizing treatment, known auxiliary steps such as hardening, neutralization, black-and-white development, reversal, and washing with a small amount of water may be added as necessary. Typical specific examples include the following steps. (1) Color development → bleach fixing → water washing (2) color development → bleach fixing → small amount of water washing → water washing (3) color development → bleach fixing → water washing → stable (4) color development → bleach fixing → stable (5) color development → Bleach fixing → 1st stability → 2nd stability (6)
Color development → bleaching → bleach-fixing → washing (or stabilization) (7) color development → bleaching → fixing → stabilization (8) color development → bleaching → bleach-fixing → washing → stabilization (9) color development → bleaching → bleach-fixing → 1 stable → 2nd stable (10) Color development → bleaching → fixing → 1st stable → 2nd stable (
11) Color development → bleaching → fixing → washing with water → stabilizing (12) color development → washing with a small amount of water → bleaching - washing with a small amount of water → fixing → washing with a small amount of water → washing with water → stabilizing (13) color development → cool white → washing with a small amount of water → fixing → washing with a small amount of water →
Water washing → Stable (4) Black and white development → Water washing (or stabilization) → Reversal → Color development → Bleaching → Fixing → Water washing (or omitted) → Stability Even among these processing steps, the effects of the present invention are more noticeable. In order to achieve this, a processing step having a direct bleach-fixing step subsequent to the color development steps (1), (2), (3), (4) and (5) is more preferred. In the present invention, the bleach-fixing processing time is preferably 10 seconds to 240 seconds, more preferably 20 seconds to 240 seconds.
A period of 150 seconds to 150 seconds is appropriate. When bleaching and fixing are performed separately, the bleaching time is preferably 10 seconds to 90 seconds, more preferably 20 seconds to 8 seconds.
0 seconds, and the fixing process is preferably 10 seconds to 200 seconds,
More preferably, it is 20 seconds to 150 seconds. The aromatic primary amine color developing agent used in the color developing solution used before processing with the processing solution having bleaching ability of the present invention may be any of the known aromatic primary amine color developing agents that are widely used in various color photographic processes. Included. These developers include aminophenol and p-phenylenediamine derivatives. These compounds are generally used in the form of salts, such as hydrochlorides or sulfates, since they are more stable than in the free state. Additionally, these compounds are generally used at a concentration of about 0.1 g to about 30 g per 1 fL of color developer, more preferably about 1 g to about 15 g per 1M. In the color developing step of the present invention, the concentration of the color developing agent is 0.2.
mol/i or more, and/or the treatment temperature is 45
It is preferable that the temperature is at least ℃. Examples of aminophenol-based developers preferably used in the present invention include 0-aminophenol, p-aminophenol, 5-amino-2-oxytoluene, 2-amino-3-oxytoluene, and 2-oxy-3-oxytoluene. Amino
Includes 1,4-dimethylbenzene and the like. A particularly useful aromatic primary amine color developer is N. It is an N-dialkyl-p-phenylenediamine compound, and the alkyl group and phenyl group may be substituted or unsubstituted.Among them, a particularly useful compound is N,N-diethyl-p- Phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, N,N-dimethyl-p-phenylenediamine hydrochloride, 2-amino-5-(N-ethyl-N-dodecylamino)-toluene, N- Ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-amitsuaniline sulfate, N-ethyl-N-β-hydroxyethylaminoaniline, 4-amino-3-methyl-N,N-diethylaniline, 4 -amino-N-(2-methoxyethyl)-N-
Examples include ethyl-3-methylaniline-p-toluenesulfonate. The present invention works effectively when the paraphenylenediamine color developing agent is mixed into the bleach-fix solution of the present invention. The alkaline color developing solution used before the treatment with the processing solution having bleaching ability of the present invention contains, in addition to the above-mentioned aromatic primary amine color developing agent, various types of color developing solutions that are usually added to color developing solutions. Component 1 For example, alkaline agents such as sodium hydroxide, sodium carbonate, potassium carbonate, alkali metal sulfites, alkali metal bisulfites, alkali metal thiocyanates, alkali metal halides, benzyl alcohol, diethylenetriaminepentaacetic acid, 1-hydroxyethylene Water softeners and thickeners such as -1,1-diphosphonic acid may optionally be included. The pH of these color developing solutions is 1, usually 7 or more. Processing times for zero color development, most commonly from about 10 to about 13, are preferably from 5 seconds to 180 seconds, more preferably from 10 to 180 seconds.
seconds to 120 seconds. The treatment temperature is preferably 30°C or higher, more preferably 45°C to 70°C, especially 50°C to 70°C.
It is. As described above, in the processing method of the present invention, it is preferable to perform one-color development followed by bleach-fixing, and after bleach-fixing, washing with water or stabilization treatment in place of water washing may be performed, followed by ordinary stabilization treatment. In the present invention, "treatment with a stabilizing solution as an alternative to water washing" refers to a stabilizing treatment that is performed immediately after treatment with a processing solution that has a fixing ability and does not substantially require a washing treatment. The processing liquid used in the treatment is called a washing alternative stabilizing solution, and the treatment tank is a washing alternative stabilizing bath (tank) or a stabilizing bath (
It is called a tank). In the present invention, the water washing alternative stabilizing tank may be one tank, but it is preferably 2 to 3 tanks, and preferably 9 tanks or less at most. That is, if the replenishment amount is the same, the more tanks, the more tanks. The lower the contaminant concentration in the final washing alternative stabilization bath. As described above, the treatment with the water-washing substitute stabilizing solution of the present invention is carried out once after the treatment with the treatment solution having fixing ability. Compounds preferably used in the water-washing alternative stabilizer in the present invention include chelating agents having a chelate stability constant of 8 or more for iron ions, and these are preferably used to achieve the objects of the present invention. Here, the chelate stability constants are: L, G, 5ille
N. A. E. Martell°, “5tabili
ty (:instants of Me-talio
n Complexes”, The Ch.
e+5ical 5ocjety, London
(1964), S., Chaberek-A., E.M.
'Organic Sequeste' by arte11
ring Agents'', Wiley (1959)
etc. means a commonly known constant. Examples of chelating agents having a chelate stability constant of 8 or more for iron ions that are preferably used in the water washing alternative stabilizer of the present invention include organic carboxylic acid chelating agents, organic phosphoric acid chelating agents, inorganic phosphoric acid chelating agents, polyhydroxy compounds, etc. can be mentioned. Note that the above-mentioned iron ion means ferric ion (Fe 2 *). Specific examples of compounds of chelating agents having a chelate stability constant of 8 or more with ferric ions include, but are not limited to, the following compounds: ethylenediamine diorthohydroxyphenylacetic acid, Diaminopropane tetraacetic acid, nitrilotriacetic acid, hydroxyethylenediaminetriacetic acid, dihydroxyethylglycine, ethylenediaminediacetic acid, ethylenediaminenibropionic acid, iminodiacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, diaminopropanoltetraacetic acid, transcyclohexanediaminetetraacetic acid Acetic acid, glycol ether diamine tetraacetic acid, ethylenediaminetetrakismethylenephosphonic acid, nitrilotrimethylenephosphonic acid, l-hydroxyethylidene-1,1-diphosphonic acid, 1,1-diphosphonoethane-2-carboxylic acid, 2-phosphonobutane-1, Examples include 2,4-tricarboxylic acid, 1-hydroxy-1-phosphonopropane-1,2,3-)licarboxylic acid, catechol-3,5-diphosphonic acid, sodium pyrophosphate, sodium tetrapolyphosphate, and sodium hexametaphosphate. and particularly preferably diethylenetriaminepentaacetic acid, nitrilotriacetic acid, nitrilotrimethylenephosphonic acid, 1-hydroxyethylidene-1,
1-diphosphonic acid and the like, among which 1-hydroxyethylidene-1,1-diphosphonic acid is most preferably used. The amount of the above chelating agent used is 0 per water washing alternative stabilizer ift.
．． 01-50g is preferable, more preferably 0.05-50g
It is in the range of 20g. Furthermore, as a compound to be added to the water washing alternative stabilizing liquid of the present invention,
Ammonium compounds are particularly preferred. These are supplied by ammonium salts of various inorganic compounds, including ammonium hydroxide, ammonium bromide, ammonium carbonate, ammonium chloride, ammonium hypophosphite, ammonium phosphate, ammonium phosphite, and fluoride. Ammonium, acidic ammonium fluoride, ammonium fluoroborate, ammonium arsenate, ammonium bicarbonate, ammonium hydrogen fluoride, ammonium hydrogen sulfate, ammonium sulfate, ammonium iodide, ammonium nitrate, ammonium pentaborate, ammonium acetate, ammonium adipate, tricarboxylic laurate Ammonium acid, ammonium benzoate, ammonium carbamate, ammonium citrate, ammonium diethyldithiocarbamate, ammonium formate, ammonium hydrogen malate, ammonium hydrogen oxalate, ammonium phthalate, ammonium hydrogen tartrate, ammonium thiosulfate, ammonium sulfite, ethylenediaminetetraacetic acid Ammonium, ferric ammonium ethylenediaminetetraacetate, ammonium lactate, ammonium malate, ammonium maleate, ammonium oxalate, ammonium phthalate, ammonium picrin, ammonium pyrrolidine dithiocarbamate, ammonium salicylate, ammonium chelate, ammonium sulfanilate, These include ammonium tartrate, ammonium thioglycolate, and 2,4.6-dolinitrophenolammonium. Among these ammonium compounds, ammonium thiosulfate is particularly preferred in achieving the effects of the present invention. The amount of ammonium compound added is 1. OX 10-' or more is preferable, more preferably stable liquid 11490.001
~5.0 mol, more preferably 0.002 mol
~1.0 mol. Further, it is desirable that the washing substitute stabilizing solution in the present invention contains sulfite within a range that does not contradict the purpose of the present invention, that is, within a range that does not cause the generation of bacteria. In the present invention, the sulfite to be contained in the water washing substitute stabilizing solution may be one that releases sulfite ions. Any organic or inorganic substance may be used, but inorganic salts are preferable, and specific preferred compounds include sodium sulfite, potassium sulfite, ammonium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, sodium metabisulfite, Potassium metabisulfite, ammonium metabisulfite and hydrosulfide, sodium cartaraldehyde bisbisulfite, sodium succinic aldehyde bisbisulfite, and the like. The above-mentioned sulfite is contained in the water washing alternative stabilizing solution at least 1
Preferably, a reasonable amount of 10-' mol/l is added, more preferably from 5 x 10-' mol/l.
1. The amount of OX to be added is 10-' mol/l. Although it may be added directly to the washing substitute stabilizing solution, it is preferable to add it to the washing substitute stabilizing replenishing solution. The water-washing substitute stabilizer used in the present invention desirably contains an anti-pyre agent, which can further improve sulfurization prevention and image preservability. Preferable anti-healing agents to be added to the stabilizer of the present invention include sorbic acid, benzoic acid compounds, phenol compounds, thiazole compounds, lysine compounds, guanidine compounds,
Carbamate compounds, triazole compounds, morpholine compounds, quaternary phosphonium compounds, ammonium compounds, urea compounds, isoxazole compounds,
propatoolamine compounds, sulfamide compounds,
These are pyronone compounds and amino compounds. The benzoic acid compounds include salicylic acid, hydroxybenzoic acid, and ester compounds of hydroxybenzoic acid such as methyl ester, ethyl ester, propyl ester, butyl ester, etc., but preferably n-butyl ester and isobutyl ester of hydroxybenzoic acid. ester, propyl ester, and salicylic acid, and more preferably a mixture of the three hydroxybenzoic acid esters. A phenolic compound is a compound that may have a halogen atom, a nitro group, a hydroxyl group, a carboxylic acid group, an amino group, an alkyl group (especially an alkyl group with C1 to C6), or a phenyl group as a substituent. , preferably ortho-phenylphenol and ortho-cyclohexylphenol, nitrophenol, chlorophenol, cresol, guaiacol, aminophenol, phenol and the like. The thiazole compound is a compound having a nitrogen atom and a sulfur atom in a five-membered ring, and is preferably 1,2-benzisothiazolin 3-one, 2-methyl-4-isothiazolin 3-one, or 2-octyl-4-isothiazolin. 3-one, 5-chloro-2-methyl-4-isothiacyli-3-one, 2-(4-thiazolyl)benzimidazole. Specifically, pyridine-based compounds include 2,6-dimethylpyridine, 2,4,6-drimethylpyridine, radium-2
-Pyridinethiol-1-oxide and the like, preferably radium-2-pyridinethiol-1-oxide. Specifically, guanidine compounds include cyclohexidine,
Examples include polyhexamethylene biguanidine hydrochloride, dodecylguanidine salt, etc., and dodecylguanidine and its salts are preferred. Specific examples of carbamate compounds include methyl-1-(butylcarbamoyl)-2-benzimidazole carbamate and methylimidazole carbamate. Specific examples of morpholine compounds include 4-(3-nitrobutyl)morpholine and 4-(3-nitrobutyl)morpholine. Quaternary phosphonium compounds include tetraalkylphosphonium salts, tetraalkoxyphosphonium salts, etc.
Preferred are tetraalkylphosphonium salts, and more specific preferred compounds are tri-n-butyl-tetradecylphosphonium chlorite and triphenyl-nitrophenylphosphonium chloride. Specific examples of quaternary ammonium compounds include benzalkonium salts, benzethonium salts, tetraalkylammonium salts, alkylpyridium salts, and more specifically dodecyldimethylbenzylammonium chlorite,
Examples include dodecyldimethylammonium chloride and laurylpyridinium chloride. Specifically, the urea-based compounds include N-(3,4-dichlorophenyl)-N”-(4-chlorophenyl)urea, N-(
Examples include 3-trifluoromethyl)-N'-(4-chlorophenyl)urea. Specific examples of isoxazole compounds include 3-hydroxy-5-methyl-isoxazole. Proptool amino compounds include n-proptools and isoproptools, specifically DL-2-benzylamino-1-proptool, 3-diethylamino-
1-propanol, 2-dimethylamino-2-methyl-
1-propatur, 3-amino-1-propatur, idopropaturamine, diisopropaturamine, N
, N-dimethyl-isopropanolamine, and the like. Specifically, the sulfamide-based compounds include O-nitrobenzenesulfamide, p-aminobenzenesulfamide, fluorinated sulfamide, 4-chloro-3,5-dinitrobenzenesulfamide, and α-amino-p-toluenesulfamide. Famide, sulfanilamide, acetosulfaguanidine, sulfathiazole, sulfadiazine, sulfamethacine, sulfamethacine, sulfaine oxazole, homosulfamine, sulfamidine, sulfaguanidine, sulfamethizole, sulfapyrazine, phthalisosulfathiazole, succinyl Examples include sulfathiazole. Specific examples of pyronone compounds include dehydroacetic acid and the like. A specific example of the amino acid compound is N-lauryl-β-alanine. Specific examples of triazole compounds include 2-aminotriazole, benzotriazole, and 5-methyl-benzotriazole. Among the above-mentioned anti-spill agents, compounds preferably used in the present invention are thiazole compounds, sulfamide compounds, and pyronone compounds. The amount of anti-piping agent added to the stabilizing solution is 0 per 1L of stabilizing solution.
．． It is preferable to use it in the range of 001 to 30g,
More preferably, it is used in a range of 0.003 to 5 g. The pH of the stabilizer used in the present invention is not particularly limited, but is preferably in the range of pH 0.5 to 12.0, more preferably in the range of pH 5.0 to 9.0, particularly preferably in the range of pH 6, It ranges from 0 to 9.0. The replenishment amount of the stabilizer of the present invention is 93.
000m1 or less is preferable, more preferably 500mA
or less, particularly preferably 50tjL to 500mfL
is within the range of The stabilizing solution in the present invention preferably contains a metal salt in combination with a chelating agent. Such metal salts include Ba, Ca, Ce, G
o, In. La, Mn, Ni, Bi, Pb, Sn, Z
Metal salts of n, Ti, Zr, Mg, An or S, including halides, hydroxides, sulfates, carbonates,
It can be supplied as an inorganic salt such as phosphate or acetate or as a water-soluble chelating agent. The usage amount is per liter of stabilizer IX
It ranges from 1 G'''4 to 1X10-'' moles, preferably from 4x10-' to 2X10-'' moles. Further, in the present invention, other compounds that can be added to the water washing substitute stabilizer include organic acid salts (citric acid, acetic acid, succinic acid, oxalic acid, benzoic acid, etc.), pHll buffer agents (phosphoric acid,
borates, hydrochloric acid, sulfuric acid, etc.) or surfactants, but the amount of these compounds added is necessary to maintain the pH of the water washing alternative stabilizing solution according to the present invention and to maintain the stability of color photographic images during storage. Any compound may be used in any combination as long as it does not adversely affect the formation of precipitates. The treatment temperature for stabilization treatment is not limited, but is 45℃.
or higher, more preferably 50°C or higher, particularly preferably 60°C or higher, and the upper limit is 90°C in view of the physical properties of the emulsion.
From the viewpoint of rapid processing, the treatment time is preferably as short as possible, but it is usually 3 seconds to 10 minutes, most preferably 5 seconds to 2 minutes. It is preferable that the treatment be carried out in a short time and that the treatment time in the subsequent tank be long. In particular, it is desirable to perform the treatment sequentially with a treatment time 20% to 50% longer than in the previous tank. After the stabilization treatment according to the present invention, no water rinsing treatment is required at all, but rinsing by rinsing with a small amount of water within a very short time, surface cleaning, etc. can be optionally performed as necessary. In the stabilization treatment process according to the present invention, when using a multi-tank counter current system, it is preferable to supply the stabilizing solution as an alternative to water washing in the stabilization treatment process, preferably by supplying it to the rear bath and allowing it to overflow from the front bath. You can also do it. In addition, the above compounds can be added as a concentrated liquid to the stabilization tank, or the above compounds and other additives may be added to the washing alternative stabilizing solution supplied to the stabilizing tank, and this can be added as a washing alternative stabilizing solution. There are various methods for adding the stabilizer, such as using it as a supply liquid for the liquid, but any method of addition may be used.Furthermore, the stable liquid of the present invention can be treated with an ion exchange resin and reused. Next, the photosensitive material to be processed in the present invention will be explained. The photosensitive material is manufactured using an internal development method (U.S. Pat. No. 2,376.679, U.S. Pat.
1,171), as well as external development systems in which the coupler is contained in the developer (see U.S. Pat. Nos. 2,252,718, 2,592,243, and 2,590,970). Any couplers generally known in the art can be used. For example, cyan couplers include those based on a naphthol or phenol structure and which form an indoaniline dye upon coupling. Listed. As a magenta coupler, 5-
Those having a pyrazolone ring as a skeleton structure and those based on pyrazoleazole, yellow couplers such as benzoylacetanilide, bivalylacetanilide, and acylacedoanilite structures having an active methylene ring and having a substituent at the coupling position. You can use either one with or without one. Thus, as the coupler, both the so-called 2-equivalent type coupler and the 4-equivalent type coupler can be applied. In the present invention, when a photosensitive material containing a cyan coupler having the following structural formula is used and processed with a bleach solution or a bleach-fix solution of less than 9114, the cyan dye becomes leuco. can be prevented. In the present invention, particularly useful cyan couplers include the cyan couplers shown in the following binding margins [C-1] to [C-3] in order to better achieve the effects of the present invention. General formula [C-1] In the Funai formula, one of R and R1 is a hydrogen atom, the other is a linear or branched alkyl group having at least 2 to 12 carbon atoms, and X is a hydrogen atom or an aromatic group. It represents a group that can be separated by a coupling reaction with an oxidized form of a primary-amino color developing agent, and R2 represents a ballast group. -Tsuriyo [C-2] 01 is expressed by the general formula [C-3] OI+, where Y is -COR, -C0NHCOR, or -C0NHCOR4 (however, R
4 represents an alkyl group, alkenyl group, cycloalkyl group, aryl group or heterocyclic group, RS is a hydrogen atom,
An alkyl group, an alkenyl group, a cycloalkyl group, an aryl group or a heterocyclic group; R4 and R5 may be bonded to each other to form a 5- to 6-membered heterocycle. )
R1 represents a ballast group, and 2 represents a hydrogen atom or a group that can be separated by a coupling reaction with an oxidized product of an aromatic primary amino color developing agent. A preferable cyan coupler is the above-mentioned binding margin % formula.The binding margin [C-1] will be further explained. In the present invention, the linear or branched alkyl group having 2 to 12 carbon atoms represented by R1 and R in the above-mentioned - binding margin [C-1] is 1
For example, ethyl group, propyl group, butyl group. In the general formula [C-1], the ballast group represented by R2 provides sufficient bulk to the coupler to prevent the coupler from being substantially dispersed from the layer to which it is applied into other layers. Typical ballast groups have a total carbon number of 8 to 32.
Examples include an alkyl group or an aryl group, preferably having a total number of carbon atoms of 13 to 28. These alkyl groups and aryl groups may have a substituent, and examples of the substituent for this aryl group include 1, for example, an alkyl group and an aryl group. Alkoxy group, allyloxy group, carboxy group. Examples include acyl group, ester group, hydroxy group, cyano group, nitro group, carbamoyl group, carbonamido group, alkylthio group, arylthio group, sulfonyl group, sulfonamide group, sulfamoyl group, and halogen, and substituents for alkyl group include Examples include the substituents listed above for the aryl group except for the alkyl group. Preferable examples of the ballast group include the following formula: Preferred substituents include alkyl groups, hydroxyl groups, halogen atoms, alkylsulfonamide groups, and the most preferred are branched alkyl groups such as t-butyl groups. The group capable of leaving on coupling with the oxidized color developing agent defined by X in the above-mentioned margin [C-1] determines the number of equivalents of the coupler and , which influences the reactivity of the coupling. Typical examples include halogens such as chlorine and fluorine, aryloxy groups, substituted or unsubstituted alkoxy groups, acyloxy groups, sulfonamide groups, arylthio groups, heteroylthio groups, heteroyloxy groups, sulfonyloxy groups, and carbamoyloxy groups. Examples include groups. More specific examples include JP-A-50-10135 and JP-A-50-12033.
No. 4, No. 50-130414, No. 54-48237, No. 51-146828, No. 54-14736, No. 47-37425, No. 50-123341, No. 58
-95345, Japanese Patent Publication No. 48-36894, U.S. Pat.
, 227, 551 and the like. Next, the cyan coupler indicated by the binding margin [C-2] or [C-3] will be explained. Said - Tsuzuri allowance [C-
2] and [C-3], Y is a group represented by -COR4°-CONHCOR, or -CON)ISO2R4. Here, R4 is an alkyl group, preferably an alkyl group having 1 to 20 carbon atoms (for example, methyl, ethyl, t-butyl, dodecyl, etc.), an alkenyl group, preferably an alkenyl group having 2 to 20 carbon atoms (for example, allyl group, heptadecenyl group, etc.), cycloalkyl group, preferably one with a 5- to 7-membered ring (e.g., cyclohexyl, etc.)1.
Aryl groups (e.g., phenyl, tolyl, naphthyl, etc.), heterocyclic groups, preferably 5- to 6-membered heterocyclic groups containing 1 to 4 nitrogen atoms, # atoms, or sulfur atoms (e.g., furyl group, thienyl group, benzothiazolyl group, etc.). Rs represents a hydrogen atom or a group represented by R4. R4 and Rs may be bonded to each other to form a 5- to 6-membered heterocycle. Note that any substituent can be introduced into R2 and R:l, for example, a group having 1 to 1 carbon atoms.
10 alkyl groups (e.g. methyl, i-propyl, i-
butyl, t-butyl, t-octyl, etc.), aryl group (
For example, phenyl, naphthyl, etc.), halogen atoms (fluorine, chlorine, bromine, etc.), cyano, nitro, sulfonamide groups (for example, methanesulfonamide, butanesulfonamide, p-toluenesulfonamide, etc.), sulfamoyl groups (for example, methylsulfonamide, etc.), moyl, phenylsulfamoyl, etc.), sulfonyl groups (e.g. methanesulfonyl, p-
toluenesulfonyl, etc.), fluorosulfonyl groups, carbamoyl groups (e.g., dimethylcarbamoyl, phenylcarbamoyl, etc.), oxycarbonyl groups (e.g., ethoxycarbonyl, phenoxycarbonyl, etc.), acyl groups (e.g., acetyl, benzoyl, etc.), heterocyclic groups (e.g., pyridyl). pyrazolyl group, etc.), an alkoxy group, an aryloxy group, an acyloxy group, and the like. General formula [C-2] and binding margin [C-3] Smell "C, R
, 3 represents a cyan coupler represented by the general formulas [C-2] and -C-3 and a ballast group necessary to impart diffusion resistance to the cyan dye formed from the cyan coupler. , preferably an alkyl group, an aryl group, or a heterocyclic group having 4 to 30 carbon atoms. Examples include linear or branched alkyl groups (e.g. t-butyl, n-octyl, t-octyl, n-dodecyl, etc.), alkenyl groups, cycloalkyl groups, 5- or 6-membered heterocyclic groups, etc. . In the general formulas [C-21 and C-3], 2 represents a hydrogen atom or a group that can be separated during the coupling reaction of a color developing agent with an oxidizing product. For example, a halogen atom (such as chlorine, bromine, fluorine, etc.), substituted or unsubstituted alkoxy groups, aryloxy groups, heterocyclic oxy groups, acyloxy groups, carbamoyloxy groups, sulfonyloxy groups, alkylthio groups, arylthio groups, heterocyclic thio groups,
Examples include sulfonamide groups, and more specific examples include U.S. Pat.
No. 425, Japanese Patent Publication No. 48-36894, Japanese Patent Publication No. 1977-1
No. 0135, No. 50-117422, No. 50-130
No. 441, No. 51-108841, No. 50-1203
No. 43, No. 52-18315, No. 53-105226
No. 54-14736, No. 54-48237, No. 55-32071, No. 55-65957, No. 56-
No. 1938, No. 56-12643, No. 56-2714
No. 7, No. 59-146050, No. 59-166956
No. 60-24547, No. 60-35731, No. 80-37557, and the like. In the present invention, the following - binding margin [C-4], [C-5]
Or, a cyan coupler represented by [C-6] is more preferable from the viewpoint of achieving the object of the present invention. - Binding allowance [C-4] I - Binding allowance [C-5] OI+ General formula [C-6] r4 In general formula [C-4], R34 is a substituted or unsubstituted aryl group (particularly preferably phenyl When the aryl group has a substituent, the substituent is -8
OtR3t, halogen atom (fluorine, bromine, chlorine, etc.), -CF2, -NO□, -CN, -C
OR3? , -C0OR, -3OJRsy,
At least one substituent selected from is included. Here, R3? is an alkyl group, preferably having 1 or more carbon atoms
20 alkyl groups (e.g. methyl, ethyl, tert-
butyl, dodecyl groups, etc.), alkenyl groups, preferably alkenyl groups having 2 to 20 carbon atoms (allyl groups, heptadecenyl groups, etc.), cycloalkyl groups, preferably 5- to 7-membered ring groups (such as cyclohexyl), aryl represents a group (for example, phenyl group, tolyl group, naphthyl group, etc.), and Ro is a hydrogen atom or R3? It is a group represented by - A preferable compound of the cyan coupler of the present invention represented by [C-4] is one in which R37 is a substituted or unsubstituted phenyl group, and the substituent to the phenyl group is cyano, nitro, -5OJis (1119 is an alkyl group), a halogen atom, or trifluoromethyl. In general formulas [C-5] and [C-6], R35, R
3G is an alkyl group, preferably an alkyl group having 1 to 20 carbon atoms (for example, methyl, ethyl, tert-butyl,
dodecyl groups, etc.), alkenyl groups, preferably alkenyl groups having 2 to 20 carbon atoms (allyl groups, oleyl groups, etc.),
A cycloalkyl group, preferably a 5- to 7-membered ring group (e.g., cyclohexyl, etc.), an aryl group (e.g., phenyl group, tolyl group, naphthyl group, etc.), a heterocyclic group (e.g., one or more nitrogen, oxygen, or sulfur atoms) 5 members including 4 pieces ~
A 6-membered heterocycle is preferred, and examples thereof include furyl group, thienyl group, benzothiazolyl group, and the like. ) represents. Said R3? , R351 and - binding margin [C-5] and [C
83% of -6], fhs can further introduce any substituent, and specifically, a substituent such as that which can be introduced into R8. As a substituent, a halogen atom (chlorine atom, fluorine atom, etc.) is particularly preferable. - In binding margins [C-4], [C-5] and [C-6], 2 and R3 have the same meanings as in - binding margins [C-2] and [C-3], respectively. A preferable example of the ballast group represented by R3 is a group represented by the following ballast margin [C-7]. General formula [C-73 In the formula, J represents an oxygen atom, a sulfur atom, or a sulfonyl group, represents an integer from 0 to 4, the sentence represents 0 or l, and when K is 2 or more, two or more are present. R41 may be the same or different. 140 represents a linear or branched alkylene group having 1 to 20 carbon atoms, and a substituted alkylene group such as an aryl group; R
41 represents a monovalent group, preferably a hydrogen atom, a halogen atom (e.g. chromium, bromine), an alkyl group, preferably a linear or branched alkyl group having 1 to 20 carbon atoms (e.g. methyl, t-butyl, t-butyl, - pentyl, t-octyl, dodecyl, pentadecyl, benzyl, phenethyl, etc.), aryl group (e.g. phenyl group), heterocyclic group (preferably nitrogen-containing heterocyclic group), alkoxy group, preferably straight chain or branched alkoxy groups having 1 to 20 carbon atoms (e.g., methoxy, ethoxy, E-butyloxy, octyloxy, decyloxy, dodecyloxy, etc.), aryloxy groups (e.g., phenoxy), hydroxy groups, acetoxy groups, preferably alkyl carbonyloxy group,
Arylcarbonyloxy group (e.g. acetoxy group,
benzoyloxy group), carboxy, alkyloxycarbonyl group, preferably a linear or branched alkylcarbonyl group having 1 to 20 carbon atoms, preferably a phenoxycarbonyl group, an alkylthio group, preferably an acyl group having 1 to 20 carbon atoms, preferably is a linear or branched alkylcarbonyl group having 1 to 20 carbon atoms, an acylamino group, preferably a linear or branched alkylcarboxamide group having 1 to 20 carbon atoms, a benzenecarboxamide group, a sulfonamide group, preferably a carbon number A linear or branched alkylsulfonamide group having 1 to 20 carbon atoms, a benzenesulfonamide group, a carbamoyl group, preferably a linear or branched alkylaminocarbonyl group having 1 to 20 carbon atoms, a phenylaminocarbonyl group, a sulfamoyl group, preferably It represents a linear or branched alkylaminosulfonyl group or phenylaminosulfonyl group having 1 to 20 carbon atoms. Synthesis methods of the cyan couplers shown in the above-mentioned - binding margins [C-1] to [C-3] and specific exemplified compounds are described in Japanese Patent Application No. 6
No. 1-92655, pages 76 to 124, and cyan couplers (CC-1) to (CC-28) and 98 to 12 shown in pages 81 to 85 of the same specification.
Cyan couplers (C-1) to (C-10) shown on page 3
0) is given as a specific example. The silver halide emulsions that can be used in the present invention are of all kinds, including silver chloroiodide, silver iodobromide, and silver chloroiodobromide, which contain silver iodide in an amount of 0.5 mol% or more. Silver halide containing 0.5 mol % or more of silver iodide, especially silver iodobromide containing 0.5 mol% or more of silver iodide, is also effective. Further, it may be a tabular silver halide emulsion or a core/shell emulsion. As protective colloids for these silver halide, in addition to natural products such as gelatin, synthetically obtained colloids may be used. A variety of materials can be used. Silver halide emulsions include stabilizers,
Common photographic additives such as sensitizers, hardeners, sensitizing dyes, and surfactants may also be included. Photosensitive materials used in the present invention include color negative films, color vapors, color transfer films, color reversal papers, etc. Photosensitive materials that are applicable to processing systems that have a color development process (including activator treatment) and a bleach-fixing process. Any material can be used, but photographic color negative film and color vapor are most preferred. [Effects of the Invention] According to the present invention, not only can desilvering be accomplished quickly and sufficiently, but also the occurrence of staining in unexposed areas can be suppressed. In addition, the occurrence of staining in unexposed areas can be suppressed not only when washing with water but also especially when combined with a stabilization treatment as an alternative to washing with water. [Examples] Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto. In addition, in all the examples below, the amount added in the silver halide color photographic light-sensitive material is per 1 m'',
Silver halide and colloidal silver are shown in terms of silver. Example 1 The following layers were sequentially coated on a cellulose triacetate support to prepare a multilayer color photographic material sample. 1st layer: antihalation layer (HC layer) 0.16g/r
Antihalation layer consisting of rf black colloidal silver and 1.4 g/m'' gelatin. Second layer 2 subbing layers (10 layers) Subbing layer consisting of 1.9 g/m'' gelatin. Third layer: Red-sensitive silver halide emulsion layer (R layer) The silver halide used in this layer is as follows. Silver iodobromide containing 5.5 mol% of Agl with an average grain size of 0.
5JL Kaku monodisperse spherical particles and monodisperse spherical particles containing 5.0 mol % of Agl and having an average particle size of 1.0 l were added in a ratio of 1=1 (the amount of coating was Silver amount: 1.87g/
Go). Each of the above silver halide emulsion layers was color sensitized to red sensitivity, and 0.2 mol 1 mol A of the following cyan coupler (C-1)
g and %0.0006 mole 1 mole Ag of the following colored cyan coupler (CC-1) was mixed with tricresyl phosphate (
A red-sensitive silver halide emulsion layer containing a dispersion in which an inhibitor is dissolved in methanol (hereinafter referred to as TCP) and emulsified and dispersed in an aqueous solution containing gelatin. 4th layer: Intermediate layer (2G layer) with 0.14 g/ln' of 2.5-di-t-butylhydroquinone. 0.07g/ln' dibutyl phthalate (hereinafter referred to as DB
The middle layer consists of P). Fifth layer: Green-sensitive silver halide emulsion layer (G layer) The silver halide used in this layer is as follows. Silver iodobromide containing 6.0 mol% of Agl with an average grain size of 0.
Monodisperse spherical particles of 4ILm (coating amount is 1.52 in terms of silver amount)
g/m'''). Each of the above silver halide emulsions was color sensitized to green sensitivity, and the following magenta coupler (M-1) was mixed with 0.15 mol 1 mol Ag and 0.015 mol 1 mol Ag. A green-sensitive silver halide emulsion layer containing a dispersion obtained by emulsifying and dispersing TCP in which the following colored magenta coupler (CM-1) is dissolved in an aqueous solution containing gelatin. 6th layer: 0.3 g/rn' Yellow colloidal silver, 0.
Yellow filter layer containing 0.11 g/rn' DBP and 2.1 g/rrf gelatin in which 22 g antifouling agent (2,5-di-t-octylhydroquinone) was dissolved. 7th layer: Low-speed blue-sensitive silver halide emulsion layer (8 layers) The silver halide used in this layer is as follows. Monodisperse spherical particles with an average grain size of 0.5 layer m containing 5.5 mol% of Agl (coating amount is 0.56 g/m'' in silver amount). The above silver halide emulsion was color sensitized to blue sensitivity. Things and 0
．． 29 mol 1 mol Ag of the following yellow coupler (Y-1
) dissolved in TCP and emulsified and dispersed in an aqueous solution containing gelatin. 8th layer: Highly sensitive blue-sensitive silver halide emulsion (8 layers) Same as the 7th layer, except that the silver halide grains contain 6 mol% of Agl and have an average grain size of 1. Monodisperse spherical particles of Ogm are used (coating amount is 0.48 g/m'' silver). 9th layer: Protective layer (3G layer) Protective layer containing 0.9 g/m'' gelatin. Each layer contains the above-mentioned In addition, gelatin hardeners (1,2-bisvinylsulfonylethane and 2,4-dichloro-6-hydroquinone s-) riazine sodium salt) and surfactants were included.Coupler etc. used in each layer were as follows. It is as shown below: Cyan coupler (CN-101) 1-hydroxy-4-4[4-(1-hydroxy-8-
acetamido-3,6-disulfo-2-naphthylazo)
phenoxy]-N-[δ-(2,4-di-t-amylphenoxy)butyl 1-2-naphthamide disodium salt magenta coupler (M-1) 1-(2,4,6-trichlorophenyl)- 3-([α
-(2,4-di-t-amylphenoxy-acetamido]benzamide)-3-pyrazolone colored magenta coupler (CM-1) 1-(2,4,
6-trichlorophenyl)-4-(1-naphthylazo)
-3-(2-chloro-5-octadecenylsuccinimide anilino)-5-pyrazolone yellow coupler (Y-1) α-[4-(1-benzyl-2-phenyl-3,5-dioxo-1 ,2,4-triaziridinyl-α-pivaloyl-2-chloro-5-

[γ-(2,4-di-t-amylphenoxy)butanamide]acetanilide Each sample was exposed to light (16 CMS) through a wedge and processed through the following processing steps to obtain a dye image. Processing process Color development 50 seconds (65℃) drying
Drying *1: The bleach-fixing processing time is changed in 20 second increments,
Table 3 shows the time at which desilvering was completed (the time at which the amount of residual silver became 1.0 mg/100 crn' or less in fluorescent X-ray silver amount analysis). The composition of the treatment liquid used in each treatment step is as follows. [Color developer] (CD) [Bleach-fix solution] (BF) [Stabilizer J (ST) For the sample obtained by processing, the cyanstein concentration was determined using an optical densitometer (PDA-65 manufactured by Konica). measure,
The results are shown in Table 1. In addition, the maximum density of the cyan dye after the treatment was measured, and the maximum cyan density after the color restoring treatment described below was also measured, and the maximum cyan density restoring rate was determined and shown in Table 2. Recoloring treatment: Treated with diethylenetriaminepentaacetic acid iron ammonium salt 100g/l, pH 8.0 for 3 minutes at 35°C, washed with water, dried, and measured. Table 1 Table 2 Table 3 From Tables 1 and 2, 0.25 mol of iron (III) ion is added to the bleach-fix solution in order to suppress the generation of cyanstein in unexposed areas and maintain good color reversibility. /Contains more than 45℃
When the above treatment is performed, it is found that pH 4 to 6.5 is extremely preferable. Furthermore, Table 3 shows that according to the conditions of the present invention, good desilvering properties can be maintained even during rapid treatment. Example 2 The same procedure as in Example 1 was carried out except for the following changes. Processing process Color development 1 minute 30 seconds (50℃) Zero 1 drift
White 1 minute 30 seconds Processing temperature changes as shown in Table 4 Bleach fixing 3 minutes (60℃) Drying
Drying book 1: The overflow solution of the bleaching solution was all allowed to flow into the next bleach-fixing solution. The composition of the treatment liquid used in each treatment step is as follows. [Color developer] (CD) Tank solution and replenisher, same composition [Bleach tank solution] (BL) [Bleach replenisher] (BL) [Bleach-fix tank solution] (BF) [Bleach-fix replenisher] (BF) [Stabilizing liquid] (ST) Tank liquid and replenishing liquid, same composition (Note 2: Manufactured by Rohm & Haas) However, the replenishment amount of each processing liquid is CD: 10ml/100
cm", BL is 4ml 7100cm", BF is 7cm/10ffcrn", S T t) < 15mJ
L/100c. Table 4 From Table 4, the occurrence of cyan stain in the unexposed area was suppressed,
In order to maintain good recolorability, iron (II) is added to the bleach-fix solution.
I) When containing 0.25 mol/IL or more of ions and processing at 45° C. or higher, it is found that pH 4 to 6.5 is extremely preferable. Example 3 A photosensitive material was prepared by sequentially coating the following layers on a polyethylene coated paper support from the support side. Note that polyethylene coated paper has an average molecular weight of 10
0,000. 200 parts by weight of polyethylene with a density of 0.95 and an average molecular weight of 2,000. 6.8% by weight of anatase titanium oxide was added to a mixture of 20 parts by weight of polyethylene with a density of 0.80, and the mixture was coated onto a high-quality paper with a weight of 170g/rrf to a thickness of 0.035m using an extrusion coating method.
A coating layer of gz was formed, and a coating layer with a thickness of 0.040 mm made only of polyethylene was provided on the back side. The polyethylene-coated surface of this support was pretreated by corona discharge, and then the following layers were sequentially applied. First layer: A blue-sensitive silver halide emulsion layer consisting of a silver chlorobromide emulsion containing 1.0 mol % of silver bromide, the emulsion containing 350 g of gelatin per mol of silver halide, and the following per mol of silver halide The structure of the sensitizing dye [I] was sensitized using 2.5X 10-' mol (using isopropyl alcohol as solvent) and dissolved and dispersed in dibutyl phthalate 2,
5-di-t-butylhydroquinone 200mg/rn'
And as a yellow coupler, it contains [Y-1] with the following structure at 2.0 x 10-' mol per mol of silver halide, and is coated to give a silver amount of 300 B/m. 300 mg/m'' of di-t-octylhydroquinone dissolved and dispersed in 2-(2'-hydroxy-3',5'-di-t-butylphenyl)benzotriazole as a UV absorber. 2-(2'-hydroxy-5'-t-butylphenyl)
Benzotriazole, 2-(2'-hydroxy-3'-
t-Butyl-5'-methylphenyl)-5-chloro-benzotriazole and 2-(2'-hydroxy-3'
, 5'-di-t-butylphenyl)-5-chloro-benzotriazole mixture (1:l:1:1)
A gelatin layer containing 200 mg/rn' was coated to give a gelatin content of 1900 g/ln'. Third layer: A green-sensitive silver halide emulsion layer consisting of a silver chlorobromide emulsion containing 1 mol% of silver bromide. The emulsion contains 450 g of gelatin per mol of silver halide, and has the following structure per mol of silver halide Sensitizing dye [1] 2,5-di-t-butylhydroquinone and magenta coupler sensitized using 2.5 x 10-' moles and dissolved in a solvent consisting of dibutyl phthalate and tricresyl phosphate 2:1 as follows: Structure [M-11 per mole of silver halide 1,5X 1
G-"moles, silver content 230I1g/tn", A
I dye was applied at a rate of 506/in'. In addition, 2,2,4-trimethyl-6 is used as an antioxidant.
-Lauryloxy-7-t-octylchroman was added at 0.30 mol per mol of coupler. Di-t-octylhydroquinone 30+ag/m'' dissolved and dispersed in Nidioctyl phthalate and 2-(2'-hydroxy-3',S'-di-t
-butylphenyl)benzotriazole, 2-(2”
-hydroxy-s'-t-butylphenyl)benzotriazole, 2-(2'-hydroxy-3'-t-butyl-5'-methylphenyl)-5'-chloro-benzotriazole and 2-(2'- Hydroxy-3', 5'
-di-t-butylphenyl)-5-chloro-benzotriazole mixture (2: 1.5: 1.5: 2
) 500+sg/m'' and coated to give a gelatin content of 1900 mg/m''. Fifth layer: A red-sensitive silver halide emulsion layer consisting of a silver chlorobromide emulsion containing 1.0 mol % of silver bromide, the emulsion containing 500 g of gelatin per mol of halide #1, and containing 500 g of gelatin per mol of silver halide. 150 mg of 2,5-di-t-butylhydroquinone sensitized using 2.5 x 10-' moles of a sensitizing dye having the following structure and dissolved and dispersed in dibutyl phthalate.
/rn' and the cyan coupler [CN'' with the following structure.
-1] per mol of silver halide and 10 mol of Sx per mol of silver halide, and was coated to give a silver amount of 280 g/rn'. Sixth layer: This is a gelatin layer, and gelatin is coated at 900B/rn'. The silver halide emulsions used in each photosensitive emulsion layer (layers 1, 3, and 5) were prepared by the method described in Japanese Patent Publication No. 7772/1982, and sodium thiosulfate pentahydrate was used in each case. 4-hydroxy-6- as a stabilizer.
Methyl-1,3,3a,7-tetrazaindene (2.5 g per mole of silver halide), bis(vinylsulfonylmethyl)ether (1 g per 1 g of gelatin) as a hardening agent.
0+ag) and saponin as a coating aid. Sensitizing dye [I] Sensitizing dye [■] Sensitizing dye [m] [Y-1] O [M-1] n Q [CN”-11 After exposing the color vapor produced by the above method, the following Processing was carried out using the processing process and processing solution.Processing process (1) Color development 70°C 5 seconds (2
) Bleach-fixing 70°C for 5 seconds (3) *Water washing The treatment temperature was varied as shown in Table 5 for 5 seconds. (4) Drying 100°C for 30 seconds *Also called stabilization treatment as an alternative to washing. [Color developer] Benzyl alcohol 5g Ethylene glycol 10g 1.2-Dihydroxybenzene-3,5,6-trisulfonic acid 0.3g
Potassium bromide O.01g Potassium chloride 2.3g Potassium sulfite (SOX solution) 0.5m Color developing agent (3-methyl-4-amino-N-ethyl-N-(β
-methanesulfonamidoethyl)-aniline sulfate
20.0g diethylhydroxylamine (85%)5.
0g triethanolamine IO, 0g
Potassium carbonate 30g Ethylenediaminetetraacetic acid sodium salt 2.0g Optical brightener (8
PK-Conc) 2-Add OK water 1
The pH was adjusted to 12.0 with potassium hydroxide or sulfuric acid. [Bleach-fix solution] Propylene diamine tetraacetate ferric ammonium dihydrate Listed in Table 5 Ammonium thiosulfate (70% solution) 150.0 mi Ammonium sulfite (40% solution) 10. Add hJl water to bring the total volume to 11, and adjust the pH with ammonia water or glacial acetic acid.
Adjust the values as shown in Table 5. [Water wash solution] (Water wash substitute stabilizer) Ortho-phenylphenol 1.0g 5-chloro-2-methyl-4-isothiazolin-3-one
0.02g 2-methyl-4-isothiazolin-3-one 0.02g ethylene glycol
1. Og2-octyl-4-isothiazolin-3-one 0.
01g] -Hydroxyethylidene-1,1-diphosphonic acid (60% aqueous solution) 3. OgB
iCJL 3 (45% aqueous solution) 0.65gMg5O<・
7h0 0.2gpvp (
Polyvinylpyrrolidone) 1.0g ammonia water (ammonium hydroxide 25% aqueous solution) 2.5g nitrilotriacetic acid trisodium salt 1.5g with water!
Adjust the pH to 7.0 with aqueous ammonia and sulfuric acid. In the running process, the wedge-exposed check sample was passed through an automatic processor, and the cyan stain density (
Reflection density) and cyan maximum density recovery rate were determined. The results are shown in Table 5. Table 5 From Table 5, in the processing of color vapor photosensitive materials,
In order to suppress the occurrence of cyan stain in unexposed areas and maintain good color recovery properties, when the bleach-fix solution contains 0.25 mol/l or more of iron (III) ions and is processed at 45°C or higher. It turns out that a pH within the range of 4 to 6.5 is extremely preferable. Example 4 The same evaluation as in Example 1 was conducted except that the cyan coupler in the photosensitive material used in Example 1 was changed as shown in Table 6. However, the bleach-fix solution used had an iron (III) ion concentration of 0.5 mol/l. The results are shown in Table 6. *The types of couplers used are as follows. Comparative coupler (1) I2 Comparative coupler (2) Same as the cyan coupler CN-101, but the coupler of the present invention used is as follows. Further, when the above-mentioned Examples were applied to all the couplers of the present invention shown in the above table, the effects of the present invention were obtained. From Table 6, in particular, when using the cyan coupler of the present invention, iron(III) ions are added to the bleach-fix solution at 0.000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000-000000000000000000000000000000000000000000sulan-ion who suppresses the occurrence of cyanstein in unexposed areas and maintains good recoloring property when using the cyan coupler of the present invention? When containing 25 mol/2 or more and processing at 45° C. or higher, it is found that pH 4 to 6.5 is extremely preferable. Example 5 The only difference from Example 3 was that the color development conditions and prescription were changed as described below. That is, color developing prescription A: the amount of color developing agent was 0.015 mol/l, 35°C, 4
The processing time is 5 seconds. Color developing prescription B: The amount of color developing agent was 0.03 mol/again, 35°C, 20
Processed in seconds. Color developing prescription C: The amount of color developing agent was 0.015 mol/fL, and the temperature was 45°C. It is assumed to be a 20 second process. Color developing formulation The amount of color developing agent was 0.0:1 mol/l, 45°C, 1
The processing time is 5 seconds. Color developing prescription E: The amount of color developing agent was 0.015 mol/1, and the temperature was 60°C. The processing time is 11 seconds. Color developing prescription F The amount of color developing agent was 0.03 mol/l, and the process was carried out at 60° C. for 8 seconds. The iron(III) ion concentration of the bleach-fix solution is 0.5 mol/l.
Table 7 shows the results of the cyanstein concentration when the water washing alternative stabilization treatment was performed at 50°C. Table 7 From Table 7, it can be seen that stable photographic performance can be obtained according to the present invention despite changes in the concentration of the color developing agent. Patent applicant Nobuaki Sakaguchi, agent of Konica Co., Ltd., patent attorney

Claims (1)

[Claims] In a method for processing a silver halide color photographic light-sensitive material, which comprises processing with a processing liquid having bleaching ability after color development, the processing with the processing liquid having bleaching ability contains iron (III) ions of 0.25 mol/l or more. Processing of a silver halide color photographic light-sensitive material, characterized in that the processing is carried out at a processing temperature of 45° C. or higher using a bleaching solution or a bleach-fixing solution, and the pH of the bleaching solution or bleach-fixing solution is 4 to 6.5. Method.