JPS59184345A - Method for processing color photographic sensitive silver halide material - Google Patents

Abstract

PURPOSE:To prevent light fading, dark fading, bluing and staining and to eliminate the effect of no washing on the finish of a dye image by processing a color photographic sensitive silver halide material with a stabilizing soln. contg. a specified amount of an ammonium compound. CONSTITUTION:A color photographic sensitive silver halide material is processed with a stabilizing soln. of >=5.0pH contg. an ammonium compound added by 0.001-1.0mol/l in the final stage of color processing. A compound capable of releasing ammonium ion in an aqueous soln. is used as the ammonium compound, and for example, an aqueous ammonia soln., ammonium bromide or ammonium carbonate is used. By using the stabilizing soln. of >=5.0pH contg. the ammonium compound in the final processing stage, dyeing with a fluorescent dye or a sensitizing dye is prevented, and the deterioration of an image during storage can be perfectly prevented.

Description

[Detailed description of the invention]

[Technical Field] The present invention relates to a stability ratio processing method for halogen arsenic color photographic light-sensitive materials, and in particular to a stability ratio processing method for ridged images that can completely prevent bright and dark fading and also prevent the occurrence of bluing and staining. Regarding. [Prior Art] As is well known, in silver halide color photographic materials, colored images can be obtained by forming azomethine dyes and indoaniline dyes using a color development method. It is well known that these pigments fade when exposed to ultraviolet rays or visible light, and these pigments also fade even when stored in the dark. This fading is particularly accelerated under high temperature and high humidity. Fading of these colored images is a major defect in color photography, and there has been a strong desire to improve this defect. Conventionally, various methods have been known for preventing fading of colored images in bright or dark places using silver halide color photographic materials. For example, U.S. Patent No. 2.788,
Treatment with curved lead solution of No. 274, same No. 2,913,33
treatment with calcium, magnesium, and cadmium salts as described in British Patent No. 8; treatment with solutions containing monosancalide, dibuncalide, and hexitol as described in British Patent No. 909.824 and British Patent No. 1,001,446; Methods such as treatment with a solution containing formaldehyde and polycarboxylic acid are known. However, with these methods, the effect obtained was slight, and even though they could improve the fading property in the dark, they actually made the original fading (bright fading) thicker, and in some cases, the stain did not increase. Even if it could be suppressed, the fading of the dye would deteriorate, resulting in problems such as 19. In addition, in recent years, photofinishers, which automatically and continuously develop color photographic materials, have developed environmentally friendly and water-resistant materials. As resource issues have become more important, it has been desired to reduce or eliminate the large amount of washing water used in the washing process following the processing of the fixing solution and bleach-fixing solution. For this reason, a technique has been proposed that directly performs stabilization treatment without washing with water after fixing or bleach-fixing. For example, inthiazoline-3 described in JP-A No. 57-8542
-Technology using derivatives of -one compounds, JP-A-58-14
There is a technique of incorporating a soluble iron salt as described in Japanese Patent Publication No. 834, and a technique of using a chelating agent such as polycarboxylic acid or organic phosphonic acid as described in Japanese Patent Application Laid-open No. 57-132L46 and Japanese Patent Application Publication No. 58-18631. However, these techniques have drawbacks such as deterioration in image storage and poor effectiveness in suppressing the increase in yellow stain in uncolored areas due to long-term storage. As a technique to solve this drawback, Japanese Patent Application Laid-Open No. 58-854
A technique for making a stabilizing solution acidic is known, as described in Publication No. 3. However, when the stabilizer is made acidic, new problems arise, such as so-called bluing, which is thought to be caused by the fluorescent brightener, in which the black color at the highest density part turns blue under sunlight, and the problem that the fluorescent brightener is eluted from the photosensitive material during continuous processing. It has been found that a problem known as so-called staining occurs in which unexposed areas are stained yellow, which is thought to be caused by the dye being easily adsorbed. Furthermore, it was found that the fixing component and soluble silver complex salt increased in the stabilizing solution, and the stability of the cyan dye against light (bright fading) decreased. [Object of the Invention] The object of the present invention is to solve the above-mentioned drawbacks, to prevent light fading and dark fading, and to prevent bluing and staining.
In particular, even if the washing water is reduced 4 or the stable fhi process is performed without washing, the finish of the dye image will not be affected in any way.
An object of the present invention is to provide a method for stable processing of dye images. [Summary of the Invention] The method for processing a silver halide color photographic light-sensitive material according to the present invention comprises adding 0.0 OL to 1.0 mol/7 ammonium compound to the silver halide color photographic light-sensitive material in the final stage of color processing. It is characterized in that it is treated with an added stabilizing solution having a pH of 5.0 or higher. According to a preferred embodiment of the present invention, the stabilization treatment of the present invention is a step subsequent to the bleach-fixing bath or the fixing bath, and substantially no washing treatment is performed. [Structure of the Invention] The present invention will be explained in detail below. The present inventors have found that the reverse adhesion of sensitizing dyes eluted from photographic materials occurs when treated with an acidic stabilizing solution, and by increasing the pH of the stabilizing solution to 5 or higher, fluorescent dyes and sensitizing dyes can be It was also found that reverse dyeing can be prevented. However, although the above-mentioned drawbacks of the prior art are overcome by treatment with a stabilizing solution having a pH higher than neutrality, the disadvantages are that the sample after treatment tends to generate yellow stain when stored, and the color fading of the cyan dye increases. arises. As a result of intensive research on technology that can solve both of these problems at the same time, we found that the pH of the stabilizer was 5.
．． It has been discovered that by adding an ammonium compound to a stabilizer with a concentration of 0 or more and using it in the final processing step, it is possible to prevent staining of fluorescent dyes and tower dyes and to completely prevent image deterioration due to storage. . It was also found that a stabilized solution containing an ammonium compound has disadvantages in that when the pH is less than 5.0, it not only tends to cause staining of dyes and pigments, but also causes significant fading of cyan pigments. . The ammonium compound added to the stabilizing solution of the present invention is a compound that has the possibility of emitting ammonium ions 't-m in an aqueous solution, and specifically includes aqueous ammonia, ammonium bromide, ammonium carbonate, Ammonium chloride,
Ammonium chromate, main ammonium chromate, ammonium hypophosphite 1 ammonium phosphate, IIJ ammonium phosphate, ammonium fluoride, ammonium acid phthalate, ammonium fluoroborate, ammonium arsenate, ammonium hydrogen carbonate, ammonium hydrogen relative to feces, ammonium bisulfate, ammonium bisulfite,
Ammonium iodide, ammonium nitrate, ammonium pentaborate, ammonium perchlorate, ammonium beloquilinisulfate, ammonium persulfate, ammonium phosphomolybdate, ammonium phosphotungstate, ammonium silicate, ammonium flufamate, ammonium sulfate, ammonium sulfite, ammonium tetraborate , ammonium salts of inorganic acids such as ammonium tetrafluoroborate, ammonium thiocyanate, ammonium tungstate, ammonium nocunadate, ammonium polyphosphate, ammonium birophosphate, ammonium acetate, ammonium adipate, ammonium aralintricarponate, Ammonium benzoate, ammonium carbamate, ammonium citrate, ammonium diethyldithiocarbamate, ammonium formate, ammonium hydrogen malate, ammonium hydroxide oxalate,
Ammonium hydrogen phthalate, ammonium hydrogen tartrate,
flJ2 ammonium, ammonium malate, ammonium maleate, ammonium oxalate, ammonium phthalate, ammonium picrate, ammonium pyrrolidine dithiocarbamate, ammonium salicylate, ammonium succinate, ammonium sulfanilate, ammonium tartrate, ammonium thioglycolate, 2.4 .6-1-linitrophenol ammonium,
Ammonium iminodiacetate, ammonium hydroxyethyliminodiacetate, ammonium nitrilotriacetate, ammonium ethylenediaminetetraacetate, ammonium diethylenetriaminepentaacetate, ammonium hydroxyethylethylenediaminetriacetate, ammonium trans-cyclohexanediaminetetraacetate, ammonium diaminopropacetate, nitrilotriacetate Ammonium propionate, ammonium nitrilotrismethylenephosphonate, ammonium ethylenediaminetetramethylenephosphonate, ■-Hydroxyethythene-1. Ammonium salts of organic acids such as ammonium l'-2 phosphonate, ammonium 2-phosphobutane-1,2,4-) recarboxylate, ammonium di(2- and droxyethyl) aminomethane sulfonate, ammonium alum, ceric sulfate Ammonium, ammonium manganese sulfate, iron sulfate (2) ammonium (12 water)
, Leinenke salt (hydrate), ammonia-metal complexes such as ammonia copper sulfate, ammonia calcium complex salts, and ammonia magnesium complex salts. In other words, it is a compound that releases ammonia or ammonium ions (including those bound to hydrates) or ammonium hydroxide when ammonium monoxide is added to the stabilizing solution,
It is not limited to the specific example of the compound described above. The ammonium compound used in the present invention can be added to the stabilizing bath in an amount of 0.001 to 1.0 mol, preferably in an amount of 0.002 to 0.2 mol. I can do it. The stabilizing solution (stabilizing bath) according to the present invention has a pH of 5.0 or more, preferably pH -5.0 to 10.0. A particularly desirable pH range is from 6.0 to 9.0. In addition, the desirable pH of the above-mentioned stable bath in a continuous treatment method in which the treatment process consists of multiple stable baths, and is processed in a countercurrent method and replenished from the final tank; j is the pH in the final tank of the stable bath. . If the pH of the stabilizing bath is less than 5.0, the ammonia compound used in the present invention will not have the effect of preventing color fading, and in some cases may actually accelerate the color fading of the dye. Moreover, if the pH is 10 or more, the gelatin film becomes weak, which is not preferable. Various compounds may be added to the stabilizer of the present invention,
For example, pHM buffering agents, fluorescent brighteners, surfactants, fungicides, preservatives, chelating agents, hardening agents, various metal salts, etc.
Any compound may be used in any combination as long as it does not affect photographic performance. The preferable stability ratio treatment of the present invention does not include substantially no water washing in the step following the bleach-fixing bath or the fixing bath. Although not generally carried out, it is meant that a short silver recovery bath, rinse, etc. for silver recovery may be provided between the bleach-fix bath or fix bath and the stabilization treatment. However, it is preferable that nothing be provided between the bleach-fix bath or the fix bath and the stabilizing bath. After the stability ratio 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 period of time, surface cleaning, etc. can be optionally performed as necessary, but preferably Preferably, the stabilizing process is followed by a direct drying process. The treatment temperature during stabilization treatment is 103-6
0°C, preferably in the range of 5°C to 40°C. In addition, the processing time is preferably short from the viewpoint of rapid processing, but it is usually 20 seconds to 10 minutes, most preferably 30 seconds to 5 minutes.
It is 8 degrees. Further, the temperature and time of the drying process can be selected arbitrarily, but it is preferable to set the temperature to 50°C or higher. The fixing bath or bleach-fixing bath of the present invention is not particularly limited, and as the fixing agent, for example, thiosulfate, thiocyanate, iodide, bromide, thioether, thiourea, etc. are used, and as the bleaching agent, For example, red blood salt, iron chloride, persulfate, hydrogen peroxide, organic acid ferric complex salt, etc. are used. The method of bringing the stabilizer of the present invention into contact with the entire photosensitive material is preferably to immerse the photosensitive material in the solution in the same way as a general processing solution.
It may be applied to the emulsion surface of the photosensitive material such as a sponge or synthetic fiber cloth, both sides of the conveyor belt, or it may be sprayed onto the conveyor belt. The treatment method of the present invention includes color vapor, inverted crab E+
-Can be used to process paper, colorbond film, colorbond film, color reversal film, color X-ray film, etc. Incidentally, in cases where the stabilizing solution of the present invention contains a soluble silver salt, silver can also be recovered from the collected solution. Silver recovery methods include ion exchange resin method, metal replacement method,
Electrolysis method, silver sulfide precipitation method, etc. can be used. In the present invention, the cyan coupler used in the halogenated color photographic light-sensitive material has the following general formula (I') or 11
-1! , (rl) has the added effect of improving the light stability of the cyan dye produced during color development. It is a group represented by -CONHCOR2 or -CONHsO2R2. Here, R2 is an alkyl group (preferably has 1 to 20 carbon atoms)
Alkyl groups (e.g. methyl, ethyl, butyl, dodecyl, etc.), alkenyl groups (preferably alkenyl groups having 2 to 20 carbon atoms, e.g. acyl, oleyl, etc.), cycloalkyl groups (preferably 5- to 7-membered rings, e.g. cyclohexyl, etc.), aryl groups (phenyl, tolyl, naphthyl, etc.), heterocyclic groups (preferably 5- to 6-membered Hege O-rings containing 1 to 4 nitrogen atoms, oxygen atoms, or sulfur atoms, For example, it represents a furyl group, a chenyl group, a benzothiazolyl group, etc.). R3 is a hydrogen atom or R2
represents a group represented by R2 and R3 may be bonded to each other to form a 5- to 6-membered heterocycle containing a nitrogen atom. Note that any substituent can be introduced into R2 and R3, such as an alkyl group having 1 to 10 carbon atoms (for example, ethyl, i-propyl, i-butyl, t-butyl, t-
octyl, etc.), aryl groups (e.g. phenyl, naphthyl), halogen atoms (e.g. fluorine, chlorine, bromine, etc.), cyano, nitro, sulfonamide groups (e.g. methanesulfonamide, butanesulfonamide, p-)
sulfamoyl group (e.g. methylsulfamoyl, phenylsulfamoyl), sulfonyl group (N, tid methanesulfonyl, p-
) luenesulfonyl-IE), fluorosulfonyl, carbamoyl group (fLt haunmethylcarbamoyl, phenylcarbamoyl, etc.), oxycarbonyl group (e.g. ethoxycarbonyl, phenoxycarbonyl, etc.), acyl group (e.g. acetyl, benzoyl, etc.), petero ring Examples include groups (eg, pyridyl group, pyrazolyl group, etc.), alkoxy groups, aryloxy groups, acyloxy groups, and the like. In the general formulas (1) and ((I), R1 is the general formula (
Represents a ballast group necessary for imparting diffusion resistance to a cyan coupler represented by D and () and a cyan dye formed from the cyan coupler. Preferably, an alkyl group having 4 to 30 carbon atoms, an aryl group, etc. is a heterocyclic group, for example a linear or branched alkyl group (e.g. t
-butyl, n-octyl, t-octyl, n-dodecyl, etc.), alkenyl group, cycloalkyl group, 5-membered to 6J
Examples include j-ring, het-a-ring, and the like. In the general formulas ([) and ([1)], 2 represents a water ice atom or a group capable of leaving during the camping reaction with the acid product of the color developing agent. For example, a halogen atom (t
ll is an aryloxy group, a carbamoyloxy group, a carbamoylmethoxy group, an acyloxy group, a sulfonamide group in which an acid atom or a nitrogen atom is directly bonded to the coupling position (chlorine, odorant, fluorine, etc.) , succinimide group, etc., and specific examples include U.S. Pat. No. 3,741,563 and JP-A-47-37
No. 425, Japanese Patent Publication No. 48-36894, Japanese Patent Publication No. 1977-1
No. 0135, No. 50-117422, No. 5O-130
44L, 5l-LO884L@, 5O-L203
No. 34, No. 52-18315, No. 53-t05226
No. 54-14736, No. 54-48237, No. 55-32071, No. 55-65957, No. 56-
No. 1938, No. 56-12643, No. 56-2714
Examples include those described in each publication No. 7. In the present invention, cyan couplers represented by the following general formula (1), general formula (1'hl spanning general formula (2)) are more preferable. , RaFi is a substituted or unsubstituted aryl group (especially preferably a phenyl group). When the aryl group has a substituent, the substituent is -8O2R
6, /・Rogen atom (for example, each atom of fluorine, bromine, chlorine, etc.), -CF3, -No2, -CN. At least one substituent is included. Here, R6 is an alkyl group (preferably 1 carbon number E ~ 20
(e.g., methyl, ethyl, t-butyl, dodecyl, etc.), alkenyl groups (preferably 2 carbon atoms)
~20 alkenyl groups, such as acyl groups, oleyl groups, etc.), cycloargyl groups (preferably 5- to 7-membered rings, such as cyclohexyl groups), aryl groups (phenyl groups,
tolyl group, naphthyl group, etc.), and R7 is a hydrogen atom or a group represented by R6 above. Preferred f-compounds of the phenolic cyankabu 2- represented by the general formula (2) include R11 being a substituted or unsubstituted phenyl group, and the substituent to the phenyl group being cyano,
These are compounds such as nitro, -8O2R6 (R6 is an alkyl group), halogen atom, and trifluoromethyl. In the general formulas GV) and (Foundation), R5 [alkyl group (preferably alkyl group having ~20 carbon atoms, such as methyl, ethyl, t-butyl, dodecyl, etc.), alkenyl group (preferably 2 to 2 carbon atoms), alkenyl groups, such as acyl, oleyl, etc.), cycloalkyl groups (preferably 5
A membered to 7-membered ring, such as cyclohexyl, etc.), an aryl group (phenyl group, tolyl group, naphthyl group, etc.), a heterocyclic group (5- to 6-membered ring containing 1 to 4 nitrogen atoms, oxygen atoms, or sulfur atoms) A heterocyclic ring is preferred; for example, a furyl group, a chenyl group, a benzothiazolyl group, etc.). Any substituents can be further introduced into R6, R7 of the general formula (M) and R5 of the general formula qW and M,
Specifically, in general formulas (1) and (ff), R2
Alternatively, it is a substituent that can be introduced into R3. As a substituent, a halogen atom (for example, a chlorine atom, a fluorine atom, etc.) is particularly preferable. In the general formulas (JID, (IV) and V), 2 and R1 have the same meanings as in the general formulas (T) and (T), respectively. Preferred examples of the ballast group represented by R1 are as follows: It is a group represented by the general formula 〇.General formula αD In the formula, Ji enemy atom, sulfur atom, or sulfonyl group t1 is an integer from ( ) to 4, t is 0 or 1, and when k is 2 or more Two or more RBs may be the same or different, R7 is a straight chain or branched chain having L to 20 carbon atoms,
and a substituted alkylene group such as an aryl group, RB represents a monovalent group, such as a hydrogen atom, a halogen atom (preferably chlorine or bromine), an alkyl group [preferably a linear or branched alkyl group having 1 to 20 carbon atoms] groups (e.g. methyl, t-
butyl, t-pentyl, t-octyl, dodecyl, pentadecyl, benzyl, phenethyl)], aryl groups (e.g. phenyl), heterocyclic groups (preferably nitrogen-containing heterocyclic groups), alkoxy groups (preferably linear or branched alkoxy groups having 1 to 20 carbon atoms (e.g. methoxy, ethoxy, t-butyloxy, octyloxy, decyloxy,
dodecyloxy), aryloxy groups (e.g. phenoxy), hydroxy, acyloxy groups (preferably alkylcarbonyloxy groups, arylcarbonyloxy groups (
For example, acetoxy, benzoyloxy)), carboxy, alkyloxycarbonyl group (preferably carbon number ~
2o linear or branched alkyloxycarbonyl group)
, aryloxysulfonyl group (preferably phenoxycarbonyl), alkylthio group (preferably 1 to 1 carbon atoms)
2°), acyl group (preferably a linear or branched alkylcarbonyl group having 1 to 2 carbon atoms), acylamino group (
Preferably a linear or branched alkylcarboxamide having 1 to 2 o carbon atoms, benzenecarpoamide), a sulfonamide group (preferably a linear or branched alkylsulfonamide group having 1 to 20 carbon atoms, benzenesulfonamide) basis)
, carbamoyl group (preferably a linear or branched alkylaminocarbonyl group or phenylaminocarbonyl group having t-ta prime number of 1 to 20), sulfamoyl group (preferably Schiff is a linear or branched alkylaminosulfonyl group having 1 to 20 carbon atoms) , phenylaminosulfonyl group), etc. Hereinafter, specific examples of cyan couplers used in the present invention will be shown. [Exemplary Compounds] (1) 0■ H CIIH9t Cl2H25 (7) H 2H5 H3 (10) H5 0CH2CONHcH2CH20CHs (14) OH 8O2NHC1lH9 (L5) OH 0C2H5 (17) OH (18). H (19) 5H1lt (20) OH (2L) OH (22) OH3 (25) C21(5 (26) (27) (28) OH (29) (30) OH 12H25 2H5 CI6H330C 1 (34) OH (35 ) OH OH (38) .□ 6°°) . □ (41) C11)19 (42) 343) OH (44) 2H5 C5H11t (46) OH (48) NH8O2CH3 (49) OH C,2H5 OH (51) OH (52) OH (53) C11H9SO2NH Ruled (C, F(2)20C2H5 (,:IIHg (58) OH (59) OH (60) OH (6'') (62) OH (63) OH (64) .8 12H25 (65) o■CIIH9
SO2NH (66) 0■ OH3 IIH9t (69) NHCOCH3 Photographic light-sensitive materials that can be applied to the present invention are developed using an internal development method (U.S. patent No. 2.376,679, No. 2.801,
No. 171 specification), as well as external type 'f#' in which a color former is contained in the developer, and image type (US Pat. No. 2,252,
No. 718, No. 2.592,243, No. 2.590
, No. 970). In addition to the cyan coupler mentioned above, any color forming agent generally known in the drawing industry can be used. The active methylene group is used as a magenta coloring agent! Do 5-
Those with a bilazo O ring as a backbone structure, yellow color formers with active methylene chains such as benzoylacedoanilide, bivalylacetanilide, and acylacedoanilide structures containing a substituent at the camping position. You can use either one with or without. Thus, as the coloring agent, both the so-called 2-equivalent coupler and the 4-equivalent coupler can be used. Silver halide emulsions that can be used include silver halide, silver bromide,
Any silver halide such as silver iodide, silver chlorobromide, silver chlorobromide (#:, &li, silver iodobromide, silver chloroiodobromide) may be used. 1k, these) 1a As the storage colloid for silver genide, various types of colloids obtained by synthesis as well as natural products such as gelatin can be used. The silver halide emulsion may contain conventional photographic additives such as stabilizers, sensitizers, hardeners, sensitizing dyes, and surfactants. The support may be of any material such as polyethylene coated paper, triacetate film, polyethylene terephthalate film, white polyethylene terephthalate film, etc. The black-and-white developer used in the processing of the present invention is a commonly known black-and-white first developer used in processing color photographic materials, or a developer used in processing black-and-white photographic materials. It can contain various color additives that are generally added to black and white developers. Typical additives include developing agents such as ttt-phenyl-3-virazolidone and hydroquinone, preservatives such as sulfites, accelerators consisting of alkalis such as sodium hydroxide, sodium carbonate, potassium carbonate, etc.
Potassium bromide, inorganic or organic inhibitors such as 2-methylbenzoimigusol, methylbenzthiazole, water softeners such as polyphosphates, and microscopic iodine
All examples include surface overdevelopment inhibitors consisting of mercapto compounds and mercapto compounds. The aromatic primary amine color-forming dust imaging agent used in the color developer used in some parts of the present invention is a variety of color photographic printers.
It includes well-known ones that are widely used in the industrial sector. These developers are aminophenolic and p
- Contains phenylenediamine thread derivatives. These f
Since the compound is more stable than the free state, it is generally used in the form of a salt, such as a hydrochloride or a sulfate. These compounds are generally used in color developing solutions [approximately 0.1 g to
The color developer is preferably used at a concentration of about 1 g to about 15 g for t. Examples of the amine phenol developer include 0-aminophenol, p-aminophenol, 5-amino-2-
These include oxytoluene, 2-amino-3-oxy-toluene, 2-oxy-3-amino-1,4-dimethyl-benzene, and the like. Particularly useful aromatic amine color developers include N, N-
A dialkyl-p-phenylenediamine compound,
Alkyl and phenyl groups may be substituted or unsubstituted. Among them, particularly useful chemical compounds include N,N-dikotyl-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, N,N-dimethyl-p-phenylenediamine m+In, 2 -Amino-5-(N-ethyl-N-dodecylamino)~toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-amino=!
J 7'filJRm, N-ethyl-N-β-hydroxyethylaminoaniline, 4-amino-3-methyl-N
, N-diethylaniline, 4-amino-N-(2-methoxyethyl)-N-ethyl-3-methylaniline-P-
) luenesulfonate, etc. In addition to the above-mentioned tertiary aromatic amine color developer, the alkaline color dust imager used in the process of the present invention contains various components normally added to color developers, such as sodium hydroxide. , alkaline agents such as sodium carbonate and potassium carbonate, alkali metal bent sulfates, alkali metal bisulfites, alkali metal thiocyanates, alkali metal halides, benzyl alcohol, water softeners and thickening agents, etc., all optionally included. You can also do that. The pH value of this color developing solution is usually 7 or higher, most commonly about 0 to about 13. The gold M complex salt of an organic acid as a bleaching agent used in the bleaching solution or bleach-fixing solution used in the bleaching process converts all the metallic silver produced during development into silver halide and at the same time removes the remaining color former. It has the effect of coloring the coloring part, and its structure is one in which metal ions such as iron, cobalt, copper, etc. are coordinated with aminopolycarboxylic acid or organic acids such as oxalic acid and citric acid. The most preferred organic acids used to form such metal lead salts of organic acids include:
Examples include polycarboxylic acids and amyl polycarboxylic acids. These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts. Specific representative examples of these include the following. [11 Ethylenediaminetetraacetic acid [2] Diethylenetriaminepentaacetic acid [3] Ethylenediamine-N-(β-oxyethyl)-N,N'
, N'-) diacetic acid [4] Propylenediaminetetraacetic acid [5] Nitrilotriacetic acid [6] Cyclohexanediaminetetraacetic acid [7]/Iminodiacetic acid [8] Hydroxyethylglycine citric acid ('! or tartaric acid)

[9] Ethyl ether diamine tetraacetic acid cto]
Glycol ethernamine detraacetic acid t-tt] Ethylenediaminetetrap-a-pionic acid [12] Phenyleneaminetetraacetic acid [13] Ethylenediaminetetraacetic acid disodium salt [14] Ethylenediaminetetraacetic acid tetra(trimethylammonium) salt [■5 ] Ethylenediaminetetraacetic acid tetrasodium salt [16] Diethylenetriaminepentaacetic acid pentasodium salt [171 Ethylenediamine-N-(β-oxyethyl)
-N,N',N'-Sodium triacetate [18] Sodium propylene diamine tetraacetate [19] Sodium nitrilotriacetate [201 Sodium C hexaneamine tetraacetate The bleaching solution used is as described above. In addition to containing a metal complex salt of scapular acid as one ingredient, it can also contain various additives. As additives, it is desirable to include rehalogenation agents such as alkali halides or ammonium halides, such as odorous chloride, sodium bromide, sodium chloride, and ammonium bromide. pH binding agents such as Ushita salt, I6 salt, acetate, carbonate, phosphate, etc.
Those known to be commonly added to bleaching solutions, such as alkylamines and polyethylene oxides, can be added as appropriate. When the bleaching process is carried out using a strong fixer, the bleach-fixer must have fixing ability in addition to bleaching ability, and in addition to the bleaching agent, the same fixing agent used in the fixing agent must be used. A liquid containing a composition is applied. The fixing solution and bleach-fixing solution used include, in addition to the above-mentioned whitening agent, rll which reacts with silver halide to form a water-soluble complex salt, metals such as thiosulfate, sodium thiosulfate, ammonium thiosulfate, etc. Sulfates, thiocyanates such as potassium thiocyanate, sodium thiocyanate, ammonium thiocyanate, as well as thioureas, thioethers, etc. are eliminated. Rainbow, fixer and lagoon: White fixer contains ammonium sulfite, potassium chloride, ammonium bisulfite, potassium bisulfite, sodium bisulfite, sodium metabicarbonate,
Potassium metabisulfite, metabisulfite) Sulfites such as IJum, boric acid, borax, sodium hydroxide, hypopotassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, water It may contain one or more pH moderating agents consisting of various salts such as hyammonium acid. When separately replenishing a bleach-fixing replenisher to a bleach-fixing solution (bath), the constituent solution of the present invention may contain thiosulfate, thiocyanate, sulfite, etc., but it is separated and supplemented. is preferable. In the present invention, in order to fully increase the activity of the bleach-fix solution, it is possible to blow in air or oxygen as desired in the Taihaku Fixing N bath and the bleach-fixing brightening solution storage tank, or as appropriate. oxidizing agents such as hydrogen peroxide, bromate,]
! A sulfate or the like may be added as appropriate. In the processing of the present invention, silver may be recovered by a known method from a processing solution containing a soluble silver complex salt, such as a fixing solution, a bleach-fixing solution, as well as a stabilizing solution. For example, electrolysis method (described in French Painting Patent No. 2,299,667), precipitation method (described in Japanese Patent Application Laid-Open No. 52-73037, German Patent No. 2,331,2)
No. 20 Akira Midoriya), ion exchange method (% open aB5L-1
7114, German Patent No. 2,548,237) and metal substitution method (British Patent No. 1,353,80)
5) can be effectively used. EXAMPLES Next, the present invention will be explained in detail with reference to Examples, but the present invention is not limited by the Examples. Example - A paper support whose surface is coated with a polyethylene layer containing titanium oxide in anatase form as a white pigment is pretreated by corona discharge, and then the following layers are sequentially applied to produce color photographic paper. made. 1st layer: Salt odor f Arsenic photographic emulsion k containing 5 molar width of silver chloride
, anhydro-5-methyl-5'-nodoxy-3,3
'-) Optically sensitized with (3-sulfopropyl) selenacyanine hydroxide, which was combined with 2,5-di-t-butylhydroquinone and yellow curler α-[
4-(L-benzyl-2-phenyl-3,5-dioquine-1,2,4-1-riazoline)]-]α-biparyl-2-chloro5-γ-(2,
4-1-t-amylphenoxy)butylamitocoacetanilide protective dispersion added Gold/Silver 0.35
g/m'. Second layer Ni-t-octerhydroquine and 2-(2'-human ax-3(5'-so-t-butylphenyl)benztriazole, 2-(
2'-hydroxy-5'-t-butylphenyl)benztriazole, 2-(2'-hydroxy-31-t-butyl-51-methylphenyl)-5-carbentriazole and 2-(2-hydroxy -3,'s' -9
A gelatin solution to which a protect dispersion containing a mixture of -t-lylphenyl)-5-chlorobenztriazole was added was applied as an intermediate layer. Third layer: silver chlorobromide photographic emulsion containing 15 molar width of silver chloride, anhydro-9-ethyl-5,5'-nphenyl-3
,3'-(3-sulfopropyl)oxacarbocyanine hydroxide, and 2.5-
Di-t-butylhydroquinone, 2.2.4-trimethyl-6-lauryloxy-7-t-octylchroman and 1-(2,4,6-trica as magenta color)
a. Fourth layer: The same liquid as the second layer was applied as an intermediate layer. 51'ij a Silver chlorobromide copy XflJFe containing 15 molar width of silver chloride, anhydro-2-(3-ethyl-5-
(1-Ethyl-4(LH)-quinolilidene)ethylidene-4-okinothiazolidin-2-ylidene]notero-3-(3-sulfopropyl)benzoxaturium and do-a-oxide were used to optically sensitize the product. 2.5-di-t
-butylhydroquinone and cyan coupler 2,
A protective dispersion of 4-dichloro-3-methyl-6-[γ-(2,4-amylphe/xy)butyramide]phenol was added to the coating so that the silver content was 0.27 g/i. Sixth layer: A gelatin solution was applied as a retention layer. The silver halide photographic emulsions used in each of the above-mentioned photosensitive layers were prepared by the method described in Japanese Patent Publication No. 46-7772, and chemically sensitized with thiosulfuric acid (IJ) as a stabilizer. 4-hydroxy-6-methyl-L3+3'a
s7-chitrazaindene was added. In addition, saponin was added as a coating aid, and bis(vinylsulfonylmethyl) ether was added as a hardening agent to the coating solution for all layers. The color photographic paper produced as described above was subjected to stepwise exposure using a KS-7 sensitometer (manufactured by Konishi Roku Photo Industry Co., Ltd.), followed by color development, bleach-fixing, and washing with water. The solution shown in Table 1 below (1) to (30℃)
After immersing the sample for 1 minute, the sample was dried and used as a test sample. This sample was measured using an optical densitometer (PDA-65, manufactured by Konishiroku Photo Industry Co., Ltd.)
Measure the reflection density of blue, green, and red using
After storing it in a constant temperature and humidity chamber at 75mmRH for 40 days, the concentration was measured again.
The yellow stain density (measured in blue color) of the unexposed area was determined. The results are shown in Table-2. Table 2 From Table 2, compared to the formulation order (1) and (2) where one or two organic acids are simply added and no ammonia is added, the ammonia water solution as in the present invention is It can be seen that formulations (4) to (7) in which the stabilizer is added within the scope of the present invention and subjected to stabilization treatment are extremely effective, with no increase in yellow stain and little fading of red reflection density. In addition, Formulation 1@(
It can be seen that in No. 33, although the yellow stain was very good, the fading rate of the red color was very large, which was undesirable. Example-2 Using the same experimental method as Example-1, the Na shown in Table-3 below was
Experiments were conducted on formulations f8) to α2. The results are shown in Table 4. Margin Table 4 As is clear from Table 4, the formula (8) that does not contain any ammonium salt and the stabilizer solution that contains ammonium have a
In the formulation (9) in which H is lower than the range of the present invention, the color fading due to preservation of the red reflection density is undesirable. On the other hand, in the case of NIQQ)-(13) in which an ammonium salt is present and the desired value is within the range of the present invention, it can be seen that the stain and red reflection density are at desirable values and that fading due to storage is prevented. .However, if the pH is 1
Ugly α treated with a stabilizer of 1.5 is undesirable because the emulsion film swells to a large extent and becomes softened, causing scratches, scratches, and malfunctions. Example 3 After soft printing, the color paper produced in Example 2 was subjected to continuous light supplement processing (referred to as running processing) using an automatic developing machine. The treatment steps and composition of the treatment liquid at this time are as follows. Standard treatment process [1] Color development 33°C 3 minutes 30 seconds [2] Bleached feet 33°C 1 minute 30 seconds [3] Stabilization treatment 25-30°C 3 minutes [4] Drying 75-80
°C approx. 2 minutes Processing solution composition Color development + Sλ Image tank liquid> Color development auxiliary liquid><Bleach-fixing tank liquid> Fill the tank with the above color developing tank solution, nickel silver fixing tank solution and the following stabilizing solution, and add the above color developing auxiliary solution and bleach fixing auxiliary solution A and B every 3 minutes while processing the color paper. A running test was carried out after applying the light supplement to a quantitative test. For supplementary light, 324-1 was added as the amount of supplementary light to the color development tank for each color base / 1-1, and 25 d each of hard white constant and light supplementing solutions A and B were added to the bleach-fixing tank, and 25 d each of the hard white constant and supplementary solutions A and B were added to the stabilization tank. The following stabilizing solution '1150m was supplemented as the amount of supplementary light. The stabilization processing baths of the automatic processor are the first to third stabilization baths in the direction of the flow of the photosensitive material, supplementary light is provided from the final bath, and overflow from the final bath flows into the previous tank. A multi-tank simultaneous flow system was adopted in which this overflow liquid was allowed to flow into one previous tank. Continuous processing was carried out until the total amount of bleach-fixing supplementary light Hh and B used was three times the tank capacity of the bleach-fixing solution. After continuous treatment with a stabilizing solution, the self-made paper of Example 1 was subjected to stepwise exposure and used as a sample. The pH of each of the stabilizing baths 1 to 3 was changed as shown in Table 5.The pH was adjusted using potassium hydroxide and sulfuric acid.Next, the samples were treated with each stabilizing solution. After processing, the stabilizing solution was discarded and replaced with tap water, another sample was processed, and the image preservation strength deterioration test was conducted on each sample in the same manner as in Example-[.The results are shown in Table-5.1. The total reflectance of the stain in the unexposed area immediately after processing the sample was measured at 445 nm, and the black area (D max ) was visually observed under bluing gold sunlight.The results are shown in Table 5.Table 5 As is clear from the above, in the comparative example r@a4, which was washed with water, there was no problem with staining or blue ink on the same day, but the occurrence of yellow staining and the rate of red color fading during storage were extremely high. Formula NIQ51 that contains ammonium salt during stabilization treatment but has a low pH of the stabilizing solution.
In this case, the stain on the same day is large and the blueing by visual observation is also extremely large, and although the yellow stain caused by storage is not a problem, the fading rate of the red color density is large and is not favorable. On the other hand, the formulation m(ltp~
In the case of α barrels, there is no yellow stain caused by the adhesion of sensitizing dyes on the same day, no bluing due to the adhesion of fluorescent brighteners, and no yellow stain occurs during storage.
Furthermore, it can be seen that the fading of the red color density is also extremely small and has a preferable value. Example-4 6g of coupler, 3g of high-boiling solvent dibutyl phthalate
1 and 18 g of ethyl acetate, and if necessary, the required amount of methylformamide was heated to 60°C to dissolve it, and then this was mixed with a 5-part aqueous solution of Alkanol B (alkylnaphthalene sulfonate, manufactured by DuPont) 10
The mixture was mixed with 100 g of a 5% aqueous gelatin solution containing d'e, and emulsified and dispersed using an ultrasonic disperser to obtain a dispersion. Next, a dispersion of the cyan coupler shown in Table 1 was added to a silver chlorobromide emulsion (containing 10 moles of silver chloride) so that the IQ molar ratio to silver was used as a hardening agent. 2-His (
Hinylsulfonyl)ethane was added at a rate of 12 cm/g of gelatin and coated onto a polyethylene coated paper support at a coating rate of 5 cm/l 00 cdvc. The color paper sample obtained by applying force was sieved by a conventional method (a 16 nm interference filter was installed, wedge exposure was performed, and then 1 to 3 tanks of the stabilizer treated with Example 3, pH 3-5) were applied. The pH was adjusted to 7.5 using potassium hydroxide and sulfuric acid, and the sample was treated with the treatment steps and treatment solution shown in Example 3.The red reflection density of the sample was approximately 1.
．． After measuring the 0 part, leave it in sunlight for 250 hours,
The previously measured area was measured again, and the fading rate of the cyan dye was determined, which is shown in Table 6. The following couplers were used for comparison. Comparative coupler) Comparative coupler (a) Comparative coupler (b) I Comparative coupler (e) Table 6 From Table 6 above, Higa coupler prevents photofading due to the stabilizer formulation of the present invention. In contrast, the couplers of the present invention (force, (11), (22),
In (45) and (53), when the stabilizer formulation of the present invention was used, photobleaching was significantly reduced, indicating that the stabilizer of the present invention is extremely effective for the cyan coupler of the present invention. Recognize. [Effects of the Invention] As is clear from the above examples, according to the present invention, light fading and dark fading can be prevented, as well as bluing and staining. Patent applicant: Roku Konishi Photo Industry Co., Ltd., patent attorney, which is characterized by the effect that the finish of the dye image is not affected in any way by stable f-processing that is not carried out.
Nobuaki Sakaguchi (and 1 other person)

Claims (1)

[Scope of Claims] (1) Halogen F silver color photographic light-sensitive material in the final stage of color processing at a concentration of 0.001 to 1.0 mol/l.
1. A method for processing a silver halogenide color photographic light-sensitive material, which is characterized in that it is processed with a stabilizer having a pH of 5.0 or more to which an ammonium arsenic compound is added. (2) Stable silver halide color photographic light-sensitive material according to claim 1, characterized in that the treatment is a step subsequent to a bleach-fixing bath or a fixing bath, and substantially no washing treatment is performed. processing method.