JPS62169162A - Method for processing silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To reduce the space required to install an automatic developing machine and to also reduce the cost of the developing machine by processing a sensitive material having restricted iodine and bromine contents in <=1min in a processing vessel having bleaching power. CONSTITUTION:A sensitive material having <=0.3mol% iodine content and <=80mol% bromine content is processed in <=1min in a processing vessel having bleaching power. A color developing soln. used contains aromatic primary amine as a color developing agent and aminophenol and p-phenylenediamine derivs. These compounds are generally used in the form of salts such as hydrochlorides or sulfates because the compounds are more stable in the form of salts than in the free state. The preferred concn. of the compounds used is about 0.1-30g, especially about 1-15g per 1l color developing soln.

Description

[Detailed description of the invention] [Industrial application field]

The present invention has two different iodine contents! This invention relates to improvements in the processing method of silver halide color photographic light-sensitive materials.

[Prior art]

Silver halide color photographic light-sensitive materials are developed at a photo lab. Generally, a photographic color photosensitive material is developed to create a photosensitive image, and this image is printed onto a color positive photosensitive material for printing using a printing machine, and the photosensitive material is developed using a different developing device. A blurred image is obtained on the photosensitive material by developing the photosensitive material at the same time. In order to obtain color photographic images in this way, it was necessary to install Wi-Fi equipment for three processes: an automatic developing machine for negative light-sensitive materials, an automatic developing machine for positive light-sensitive materials, and an automatic photographic printing device. 0 These 81 instruments are usually characterized by a predetermined amount of work space around them, especially these 8! There is a space around the automatic developing machine in the device to replace the tank liquid and install a tank for replenishment according to the processing amount, a space to dissolve and adjust the brightening liquid, and a space to store the dissolved replenisher. Space for transferring to lln light tank, space required for refill cock adjustment, etc.
The installation area required for replenishment work occupies a large proportion of the area within the photofinishing laboratory. In addition, in the development process of photosensitive materials, as mentioned above, 2
The process is composed of the above-mentioned processing steps, and since a replenisher is prepared for each step, a large amount of space is required as described above. These replenishment operations require a large amount of time due to the high frequency of 't8 solution adjustment of the replenisher. In addition, when an automatic developing machine for negative photosensitive materials and an automatic developing machine for blurring photosensitive materials are used separately, the temperature W4ffB device and the processing J! l!
A liquid circulation device, a filter device, a replenishment tank, a replenishment device, etc. are each required, which goes against the trend of making automatic processors more compact and reducing costs. As one means for solving such problems, automatic developing machines are known that can process both negative and blurred light-sensitive materials in the same processing bath. For example, after processing a large amount of a color photosensitive material with an iodine content of 3 mol% or more in a processing tank having substantially the same bleaching ability, the iodine content is 0.3 mol%.
When the following color photosensitive materials for black are processed, the iodine ion concentration in the bleach bath or bleach-fix bath increases, resulting in defective desilvering and the formation of iodine ions on the positive color photosensitive materials after anhydrous washing and stabilization treatment. Yellow stain often occurs.

[The problem that Hatsuho is trying to solve]

Therefore, the present invention saves the installation space of an automatic processor,
The purpose of Pt51 is to reduce the cost of automatic processors, and also to eliminate desilvering defects that occur when two types of color photosensitive materials with different iodine contents are processed in a processing tank with the same bleaching capacity. The second purpose is to prevent yellow stain that occurs when stored for a long time after washing stabilization treatment.

[Means to solve the problem]

The present inventors have conducted various studies to address the above-mentioned problems, and found that an automatic developing machine consisting of at least a color developing tank, a processing tank with bleaching ability, and a water-washing alternative stabilizing tank has two different iodine contents. In a processing method in which different types of silver halide color photographic light-sensitive materials are processed in processing tanks having substantially the same whitening capacity, the above-mentioned light-sensitive materials have an iodine content of 0.3 mol% or less and a bromine content. is 80 mol%
The following photosensitive materials have bleaching ability J! ! It has been found that the above object can be achieved by a method for processing a silver halide color photographic light-sensitive material, which is characterized in that the processing time in the bath is 1 minute or less. The present invention will be explained in more detail below. In the present invention, [two types of silver halide color photographic materials with different iodine contents] include, for example, a color negative photosensitive material for photography (color negative film) and a color bokeh photosensitive material for printing (color paper). It refers to a combination of different types of halogenated Wi-7X sensitive materials, such as color reversal film and color reversal paper, and color X-ray film and color X-ray film. In particular, a color X-ray film and a color paper, and a color reversal film and a color reversal paper are two different types of preferred silver halide photographic materials according to the present invention. In the present invention, types of color photosensitive materials are distinguished based on a specific amount of iodine content. For example, a light-sensitive material with an iodine content of 3 mol% or more is referred to as a color-bottled light-sensitive material, and a light-sensitive material with an iodine content of 0.3 mol% or less is a color-bottled light-sensitive material. The composition of the silver halide constituting the color photosensitive material as described above will be described later. According to the present invention, two silver halide color photographic light-sensitive materials having different bMi types as described above can be processed in processing tanks having substantially the same bleaching ability. This not only saves space and the space required for replenishment, but also reduces the frequency and time of melting. In particular, small photo labs do not have enough space to store large quantities of various types of dissolved and adjusted replenishers, and small processing agent kits are used to adjust a small amount of replenishment at a time. When the present invention is applied, the effect is particularly high, and since only one treatment tank having bleaching ability is sufficient, the equipment attached to the apparatus can be reduced, and it is possible to achieve downsizing and cost reduction at the same time. As described above, the present invention is preferably applied to a combination of color negative film and color paper. In other words, one print is usually produced from one shot of color tape film, and even if some additional prints are taken into account, the processing area of color negative film and the processing area of color vane (-) are approximately proportional. On the other hand, for example, if an automatic processor is designed so that the replenisher is replenished according to the amount of color negative film processed, and the replenisher prescription is designed, both FI!fit can be used at certain times of the day. Although the balance may be different,
When averaged over the course of a day, there is a balance between the throughputs of the two, and this problem occurs when the balance between the throughputs of two extremely different types of photosensitive materials is disrupted! ! Fluctuations in liquid composition can be avoided. Therefore, in the present invention, even if two processing tanks having bleaching ability for processing silver denide color photographic light-sensitive materials of different types are substantially the same tank, it is more difficult than -77 The treatment liquid in the Fl tank has the bleaching ability of the other treatment tank J!
I! It may also be piped so that it mixes with the liquid. Two more PIs! The equipment may be completely separated, or all circulation equipment such as circulation pumps, replenishment equipment such as replenishment tanks, drain cocks, filters, etc. may be separated from each other.
! ! ! Although these devices and the like may be arranged on one side of the apparatus, in the present invention, it is most preferable that the two processing sections are completely integrated into one processing apparatus. The processing method of the present invention may include any other processing bath in addition to the color developing bath, and typical examples of the processing method include the following steps. (1) Color development → bleach-fix → stable (2) color development → bleach-fix → washing with a small amount of water → stable (3) color development → bleach-fix → first stable → second stable (4) color development →
Washing with water → Bleach-fixing → Stable (5) Color development → Stable → Bleach-fixing → Stable (6) Color development → Stop → Bleach-fixing → Stable (7) Color development → Bleaching - Washing with water and fixing → Stable (8) Color development → Bleaching → Fixing → Stable (9) Color development - Bleaching → Fixing → 1st stable → tj%2 stable (10) Color development → Bleaching → Washing with a small amount of water → Fixing → Washing with a small amount of water →
Stable (11) Color development-m fixing → bleach fixing → first stable → second
Stability (12) Color development → bleaching acceleration → bleaching → fixing → first stabilization →
rjS2 stable (13) color development → washing with a small amount of water → bleaching → washing dish with water → fixing →
Small amount of water washing → stable (I4) color development → stop → bleaching → small amount of water washing → fixing → small amount of water washing → stable (15) black and white development → water washing (or stable) - reversal - color development → bleaching → fixing → before stabilization (1G) Hardening → Neutralization → Black and white development → Stop → Color development → Bleaching → Fixing → Stability The effects of the present invention are more pronounced even in the range of these processing steps, so (1), (3), (5) , (6), (8
), (11), (12) and (16), which do not include water washing, are more preferably used in the present invention. l! The two color photographic materials with different IMs are
These two color photographic light-sensitive materials may be processed in any one of the two processing steps, and the processing steps for these two color photographic materials may be the same processing step or different processing steps. It is preferable that the color light-sensitive material and the black color light-sensitive material are subjected to color development processing in the same color development tank. The color developing solution used in the present invention includes aromatic primary amine color developing agents, including those widely used in various color photographic processes. These color developing agents are Ami/7E/-
and p-7x nylene diamine derivatives. These compounds are generally used in the form of salts, such as hydrochlorides or sulfates, because they are more stable than the free state. In general, the concentration of these compounds in the color developer 11 is preferably about 0.1 g to 30 g, more preferably 1 g.
A concentration of about 13 to about 152 parts per part is used. In the present invention, a compound represented by the following general formula [^] can be preferably used as a color developing agent. In the formula, R7 represents a hydrogen atom, a halogen atom, or an alkyl group, and this alkyl group is a straight chain or branched chain having 1 to 5 carbon atoms.
represents an alkyl group, which may have a substituent. Ls
and (/R+ s is a hydrogen atom, an alkyl group, or 7
Although it represents a aryl group, these groups may have a substituent, and in the case of an alkyl group, an alkyl group substituted with an aryl group is preferable. and at least 1 of R1 and 11+9
One is an alkyl group substituted with a water-soluble group such as a hydroxyl group, a carboxyl group, a sulfonic acid group, an amide group, a sulfonamide group, or ←C112hOniR2. This alkyl group may further have a substituent. Good 1. Incidentally, R2° represents a hydrogen atom or an alkyl group, and the alkyl group represents a linear or branched alkyl group having at to 5 carbon atoms, and q and r represent integers of 1 to 5. Next, typical examples of the compound represented by the general formula [^] will be listed, but the invention is not limited thereto. The following is in the margin ^-5) H2 (^-6) (^-10) (^-15) (8-16) In addition to the above-mentioned aromatic primary amine color developing agent, the color developing solution contains known developing agents. Components can be included. For example, water-soluble salts of hydroxylamine,
Examples include sulfates, hydrochlorides and phosphates. As alkaline agents, buffers, etc., sodium hydroxide, silicate, sodium carbonate, potassium metaborate, or boric acid may be added alone or in combination. Furthermore, disodium hydrogen phosphate, sodium bicarbonate, boric acid, etc. may be used for reasons of pharmaceutical necessity or for the purpose of increasing ionic strength. In addition, it is also possible to add inorganic or organic antifoggants as necessary, and representative compounds include inorganic halide compounds such as potassium bromide and potassium iodide, as well as U.S. Patent No. 21496 6- described in No. 940
Nitropenzimiguzole, tIS2,497,91
7 and 2,656,271, as well as 0-7z nylenediamine, mercaptobenziimigsol, mercaptobenzoxazole, thiolausi J, and 5-methylbenzoimiguzole. Triacy J or Special Publication Showa 46-41675
Examples include the heterocyclic compounds described in the publication. In addition to these various components, Japanese Patent Publications No. 46-19039 and No. 45-6149, U.S. Pat.
A development inhibitor disclosed in No. 976 and a development accelerator may also be added if necessary. Among these development accelerators are U.S. Pat. No. 2,648,604; U.S. Pat. No. 3,671.
247, various bilinonium compounds typified by Japanese Patent Publication No. 44-9503, other cationic compounds, cationic dyes such as 71nosa7lanine, neutral salts such as thallium nitrate, U.S. Patent No. 2,533 , 990, fi 2,531,832, fi 2,950,9
70, fjS2, 577.127, and 7-ionic compounds such as polyethylene glycol and its derivatives, polythioethers described in Japanese Patent Publication No. 44-9504, and organic solvents and organic compounds described in Japanese Patent Publication No. 44-9509. Includes amines, ethanolamine, ethylenenoamine, jetanolamine, and triethanolamine. In addition, benol alcohol, 7-enethyl alcohol, and others described in U.S. Pat. etc. are also effective development accelerators. , and, if necessary, ethylene glycol, methyl selon, methanol, acetone, dimethylformamide, β-cyclodextrin, and others.
The compounds described in Japanese Patent Nos. 3378 and 44-9509 can be used as organic solvents to increase the solubility of the developing agent. The color developer also contains water softeners and heavy metals i! may contain various chelating agents as sedatives. Such chelate cuttings include phosphates such as polyphosphates,
Nitrilotriacetic acid, 1,3-noaminopropanoltetraacetic acid, noethylenetriaminepentaacetic acid, 7minobolycarboxylic acids such as hydroxyethyliminodiacetic acid, citric acid, oxycarboxylic acid of glucon FilF, 1-hydroxyethylidene-1, Examples include organic phosphonic acids such as 1-nophosphonic acid, 7-minobolyphosphonic acids such as ami/tri(methylenephosphonic acid), and polyhydroquine compounds such as 1,2-cyhydroxybenzene-3,5-nosllephonic acid. Furthermore, auxiliary developers can also be used with the developing agents. These auxiliary developers include, for example, N-methyl-p-7mi/7ethylhexal 7ate (methol).
, phenidone, N,N'-diethyl-11=huminophenol hydrochloride, N,N,N',N'-tetramethyl-p
-Phenylenenoamine hydrochloride and the like are known, and the amount added thereof is usually preferably 0.01 g to 1.0 g/V. In addition, a competitive coupler, a fogging coupler, a colored coupler, a development inhibitor IllM-releasing coupler (so-called DIR coupler), or a development inhibitor-releasing compound can be added as required. The color developing solution can be used at a pH of 8 to 14, more preferably at a pH of 9.5 to 12. The processing temperature is 8
It is used at a temperature of 0°C or lower, preferably 55°C or lower, most preferably 45°C or lower to suppress evaporation. Processing time is within 3 minutes. According to the present invention, the color photosensitive material according to the present invention is processed in a bleaching treatment Fl tank after color development processing, but in the present invention, the processing tank having bleaching ability is a bleach-fixing tank. It is preferable that there be. In the present invention, therefore, in addition to the above-mentioned color developing solution, a whitening or bleach-fixing solution (with bleaching ability as a treatment tank) is used, and these bleaching or bleach-fixing solutions contain ethylenediaminetetra-15r acid as a bleaching agent. Organic acid t52 iron complex salts such as diiron complex salts are used. Particularly preferred specific examples include ferric complex salts of organic acids shown below. (1) Noethylenetriaminepentaacetic acid (2) Noethylenetriaminepentamethylphosphonic acid (3) Cyclohexanoaminetetraacetic acid (4) Ethylenenoaminetetraacetic acid (5) Methylaminodiacetic acid (6) Propyliminoni1lff acid (7) Butylimy/diacetic acid (8) Cyclohexanenoamine tetramethylene phosphonic acid (9) Triethylenetetramine hexaacetic acid (10) ) Lyethylenetetramine hexamethylenephosphonic acid (11) Glyfur ether diamine tetraacetic acid (12) Glyfur ether noamine tetraacetic acid Methylenephosphonic acid (13) 1.2-diaminopropanetetraacetic acid (14) 1.
2-Noaminopropane tetramethylenephosphonic acid (15) 1.3-diaminopropan-2-ol tetraacetic acid (16) 1.3-noaminopropane-2-ol tetramethylenephosphonic acid (17) Ethylenediamine diorthohydroxy 7 Enylacetic acid (18) Ethylenedi7minethiorthohydroxyphenylmethylenephosphonic acid (19) Ethylenediaminetetranotylenephosphonic acid Organic acid ferric salt can be arbitrarily selected from these and used. Moreover, two or more types can be used in combination as necessary. The fjS2 iron complex salt of the organic acid is a 7 Li acid (hydrogen salt)
, alkali metal liquids such as sodium salts, potassium salts, lithium salts, or ammonium salts, or water-soluble amine salts such as triethanolamine salts, preferably potassium salts, sodium salts, and ammonium salts. used. At least one of these ferric complex salts may be used, but 2!91 or more may also be used in combination. The amount used can be arbitrarily selected and needs to be selected depending on the ffi amount and silver halide composition of the photosensitive material to be processed.
"Can be used at 90.01 mol or more, preferably 0.05
~0.6 mol is used. In addition, regarding replenishment fluid,
It is desirable to use it in concentrated form with the highest solubility for low replenishment. Peroxides may also be used as bleaching agents, and hydrogen peroxide, percarbonates, perborates, and persulfates are preferably used as peroxides. In addition, examples of these salts include potassium salts, sodium salts, ammonium salts, etc., and the preferable amount of these used is 0.01 to 6.0 ao.
l/l range, more preferably 0.05 to 3.0 wheels 0
It is in the range of 1/l. The bleaching agent used in the present invention has a molecular weight of 2.
Bleaching agents with a rating of 80 or higher are particularly preferred. The bleach-effect V bleach-fix solution can be used at a pH of 0.2 to 9.5, preferably 1 to 9, more preferably 2.0 to 8.5.
used in The treatment temperature is used at 80° C. or lower, preferably 55° C. or lower, most preferably 45° C. or lower to suppress evaporation. Place 1 with the bleaching agent of the present invention! The processing time for a photosensitive material in which the iodine content is 0.3% or less and the bromine content is 80 mol% or more in tank Ii is within 1 minute, but the processing time for the other photosensitive material is preferably within 8 minutes; More preferably, it is within 6 minutes. The bleach or bleach-fix solution can contain various additives along with the bleaching agent as described above. As additives, it is desirable to include alkali halides or ammonium halides, such as potassium bromide, sodium bromide, sodium chloride, ammonium bromide, potassium iodide, sodium iodide, ammonium iodide, and the like. In addition, pH-adjusting Al additives such as acid salts, acetates, carbonates, and phosphates, solubilizers such as triethanolamine, 7-cetyl-7-cetone, phosphonocarboxylic acids, polyphosphoric acids, organic phosphonic acids, and oxylcarboxylic acids. , polycarboxylic acids, alkylamines,
It is possible to appropriately add substances known to be added to ordinary bleaching solutions, such as polyethylene oxides. This bleach-fixing solution has a composition in which a small amount of a halogen compound such as potassium bromide is added, or conversely, it has a composition in which a large amount of a halogen compound such as potassium bromide or ammonium bromide is added. It is also possible to use bleach-fixing solutions, as well as special bleach-fixing solutions consisting of a combination of the bleaching agent of the present invention and a large amount of a halogen compound such as potassium bromide. In addition to potassium bromide, the halogen compounds include hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide,
Heptammonium bromide, potassium iodide, sodium iodide, ammonium iodide, etc. can also be used. The silver halide fixing agent to be included in the bleach-fixing solution is a compound that reacts with silver halide to form a water-soluble complex salt, such as potassium thiosulfate, thiosulfate, etc., which is used in ordinary fixing processes. Typical examples include thiosulfates such as sodium cum sulfate and 7 ammonium thiosulfate, thiocyanates such as potassium thiocyanate, sodium thiocyanate, and ammonium thiocyanate, thioureas, thioethers, and high concentrations of bromides and iodides. It is something. The amount of these fixing agents is preferably 5 g/1 or more, more preferably 50 g/1 or more.
It can be used in an amount that can dissolve y/1 or more, more preferably 70971 or more. Note that this bleach-fix solution contains boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide, as in the case of the above bleaching solution. p II buffer consisting of various salts such as
A combination of two or more types can be contained. And yet again ll'l's whitening? It is also possible to contain a 1'1 foaming agent or antifouling agent. In addition, preservatives such as hydroxylamine, hydranone, sulfites, isomeric m-sulfites, bisulfite adducts of aldehydes and ketone compounds, acetyl 7-setone, phosphonocarboxylic acid, polyphosphoric acid, organic phosphonic acid, oxycarboxylic acid, Carboxylic acids, dicarboxylic acids and ami/polycarboxylic acids! I! ν1 is stable nl of nitroalcohol, nitrate, etc.
A solubilizing agent such as alkaliamine, an anti-staining agent such as an organic amine, an additive thereof, and an organic solvent such as methanol, trimethylformamide, trimethylsulfoxide, etc. can be appropriately contained. Further, in the present invention, it is preferable that at least 1 Wfi of a bleach accelerator represented by the following general formulas (1) to [■] is contained in the processing bath having i-vote whitening and V/or its mixed bath. General formula (1) General formula [11) General formula CI [
[] General formula ([V) General formula (V) General formula (■) General formula [■] [In the above general formula, Q is a heterocycle containing one or more N atoms (
A represents an atomic group necessary to form a 7J B
represents an alkylene group having 1 to 6 carbon atoms, M represents a divalent metal atom, and X and X7/ are =S, =O or =N
R" represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group, an aryl group, a heterocyclic residue (at least one unsaturated ring of 5 to 6 shells is fused to this) number of 1 to 6 alkyl groups, cycloalkyl groups, aryl groups, heterocyclic residues (including those to which at least one unsaturated ring of 5 to 6 shells is fused) or amino represents 7 groups, R2, R co, R', R', R and R
'respectively represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxy group, a carboxy group, an ami7 group, an acyl group having 1 to 3 carbon atoms, an aryl group, or an alkenyl group, provided that R' and R4 are -B-8Z may also be represented, and R and R
', R'' and Rco, R4 and R5 are respectively cyclized with each other to form a heteroagglomerate (at least one unsaturated ring of 5 to 6 shells).
(including those condensed thereto) may also be formed. R9R represents an alkyl group or -(CHz)nsSO
Represents xo with R8 or -(CHz)nes O, IO
, q represents O or 1. ) GO is anion, +1
11, m, and n to R8 are each 1 to 6
, and lll5 represents an integer from 0 to 6. R6 is a hydrogen atom, alkali N. However, Q' has the same meaning as Q above. D represents a simple bond, an alkylene group or vinylene group having 1 to 8 single primes, and q represents an integer of 1 to 10. A plurality of D's may be the same or different, and the ring formed with the sulfur atom may be further fused with 5 to 6 unsaturated rings. Y' is 1000M', -08, -8Os M', -CONH2, -8
○2 NH2, -NH□, -3H, -CN, -Co
2R16, -8○ l (1g, -OR+ 6, -
N Rl 'R17, -SR 6, -3o,
R", -NHCOR Tsuta 6, -NH3O2R",
-0COR'' or -S O2R'', Y' represents or a hydrogen atom, and n each represents an integer from 1 to 10, R11, R12, R14, R'', R'' and R'8 are hydrogen atom, lower alkyl group, acyl group or -
(represents fJ-X', R" represents a lower alkyl group, SR" is -NR
2°R'', +OR?2 or -3[' (represents 22, R
2° and R'' represent a hydrogen atom or a lower alkyl group,
R22 represents an atomic group necessary to connect with R'' to form a ring. R20 or R21 and R11 may be connected to form a ring. M' represents a hydrogen atom or a cation. The compounds represented by the general formulas (1) to (V) include dinolized compounds and salts thereof.] General formula [■] Each represents a lower alkylene group. R23, 1124,
R25 and 1+26 each represent a hydroxy-substituted lower alkyl group. G' represents an anion, X and y each represent an integer of O or 1, and 2 represents an integer of 0.1 or 2. ]
The stabilizing solution used in the stabilizing bath of the Ch bleach-fix solution of the present invention contains pre-bath components (for example, bleach-fix solution composition and constant rI solution components) brought in from the bent bath by adhering to the light-sensitive material, etc. , neutralizing, desalting, and inactivating functions that do not deteriorate the storage stability of dyes, functions as a draining bath to prevent contamination such as uneven washing, and functions that stabilize color images by blocking the active sites of unreacted couplers. , a coloring adjustment function for coloring a color image, and an antistatic function by containing an antistatic agent, and two or more of these functions may be combined. When a contains at least one compound selected from the following group, the generation of silver sulfide in the stabilizing solution is improved for low renewal rate processing, and the staining of unexposed areas of the processed light-sensitive material is improved. [Compounds] (^) Benzoic acid compounds (B) 71-noyl compounds (C) Thiazoline compounds (D) Imigusol compounds (E) Guaninone compounds Compound (F) Carbamate compound (G) Morpholine compound (11) Quaternary phosphonium compound (+) Quaternary ammonium compound (J) Urea compound (K) Inxazole compound (L) Propylamine compound (M) 7mi/acid-based compound (N) Triazine-based compound (0) Specific compounds of the above compounds (^) to (0) contained in the Pirikun-based compound stabilizing solution include the following. Not limited to these: [Exemplary compounds] (1): Sodium orthophenylphenol (2):
2-octyl-4-inthiazoline (3): Benzinthin-7zolin-3-one (4): 2-7thyl-4-isothiazolin-3-one (5): 5-chloro-2-7thyl-
4-isothiazolin-3-one (6): 2-thiomethyl-4-dityl 7mi/-6-(1
,2-methylpropylamino>-9-)ryanone(7
): hexahydro-1,3,5-)lis(2-hydroxyethylton-S-trifunone (8): 4-(2-nitrobutyl) morboline (9):
4-(3-nitrobutyl)morpholine (10):2-(
4-thiazolyl) benraimiguzole (11): dodecylgutunisine hydrochloride (12): t: l' 4-benzobenzoic acid methyl ester (13): t-1/roxybenzoic acid pabil ester (
14): Hydroxybenzoic acid 1-dobutyl ester (15
): p-hydroxybenzoic acid Ha): Benzoic acid methyl ester (17): Orthocyclohexylphenol (18):
1.2-Benzinthiazolin-3-one (19):2
-cutyl-4-isothiazolin-3-one (20):
2-(4-thiazolylpenzimidazole (21):
2.6-methylpyrinone (22): 2.4.6-)methylpyridine (23)
: Sonotumu 2-pyridinethiol-1-oxide (24) Nidiclohexinone (25): Boryhexamethylene big 7 herring hydrochloride (2
6): Methyl-1-(butylcarbamoyl)-2-benzimiguzole carbamate (27): Methyl imiguzole carbamate (28):
) Two n-butyl-tetradecylphosphonium chloride (29): ) Riphenylnitrophenylphosphonium chloride (30) Nidodecyldimethylpencylammonium chloride (31): Didecyldimethylammonium chloride (
32) Nilaurylpyridinium chloride (33):N
-(3,4-nochlorophenyl)-N'-(4-chlorophenyl)urea (34): N-(3-trifluoromethyl°-4-chloro7enyl)-N'-(4-chlorophenyl) Urea (3
5): 3-hydroxy-5-methyl-isoxazole (
36): D, L-2-bennorami/-1-propa/-
(37): 3-diethylamino-1-propanol (
38): 2-dimethylamino-2-methyl-1-propanol (39): 3-7/-1-propanol (40): Isopropanolcyamine (41): Noisopropanolamine (42): N,N-trimethylisopropylamine (
43): N-lauryl-β-aniline Among the above-mentioned antifungal agents, compounds preferably used are thiazoline compounds and a! , aromatic acid compounds, birinone compounds, guanidine compounds, and quaternary ammonium compounds. Furthermore,
Most preferred are thiazoline compounds or benzoic acid compounds. The amount of compounds (^) to (0) added is 0.002g to 50.0g per Lindl of stabilizer. It is preferably used in a range of 0,005 g to 10 g, more preferably in a range of 0,005 g to 10 g. When a specific chelating agent is used in a stabilizing solution, the storage stability of the stabilizing solution is improved. The chelating agent preferably used in the stabilizing solution is iron (III
) The chelate stability constant with ions is 8 or more. In the present invention, the chelate stability constant indicates the stability of a complex formed by a metal ion and a chelate in a solution, and means a constant defined as the reciprocal of the M and I constants of the complex. siren, engineering, i, marcil (L, G, 5illen,
^, E, MarLe11) @, “Stability Constance Metalion Complex (Stability
Con5tanLs of MeLai. The Chemical Society London
ety London) (1964),! Chaberek (S, Chaberek, ), Ni, ElMartell (＾. ElMartell), "Organic Sequest-"
ering Agents)”Wiley
(1959) etc., and iron ([11
) As the chelating agent having a chelate stability constant of 8 or more with ions, polyphosphates, 7-minoboricarboxylate salts, oxycarboxylate salts, polyhydroxy compounds, organic phosphates, condensed phosphates, etc. are used. However, particularly good results can be obtained when amide/polycarboxylic acid salts and organic phosphates are used. Specifically, as a chelating agent,
Examples include, but are not limited to, the following: (1) CI+. 1+203P-C-PO311□ (3). 13 ++00cmC-PO,H2 One or more chelating agents may be used in combination, and the amount added can range from 0.05y to 40g per 11 stabilizers, preferably from 0.1 to 20g. range. Among the chelating agents, quethylenetri7minepentaacetic acid and 1-hydroxyethylidene-1,1-diphosphonic acid are particularly preferably used. The pH of the stabilizer is not particularly limited, but is preferably 1]■
In the range of 0.5 to 12.0, more preferably pH 5
,0 to 9.0, particularly preferably pl(6,
It ranges from 0 to 9.0. As the pH 1m adjuster that can be contained in the stabilizing solution, any commonly known alkaline agent or acid agent can be used, but a small amount is preferable. In addition to the above, various stabilizer additives may be added to the stabilizer, and these additives include, for example, optical brighteners, surfactants, organic sulfur compounds, onium salts, and formalin. The treatment temperature during the stabilization treatment is preferably in the range of 15°C to 60°C, preferably 20°C to 45°C. In addition, from the viewpoint of rapid processing, the shorter the treatment time, the better, but it is usually 20 seconds to 10 minutes, most preferably 1 minute to 5 minutes, and in the case of multiple tank stabilization treatment, the first stage tank should be used in a shorter time. It is preferable that the treatment time in the subsequent tank is long. In particular, it is desirable to perform the treatment sequentially with a treatment time that is 20% to 50% longer than that of the previous tank. Although the temperature of the drying step can be arbitrarily selected, it is preferably 50°C or higher, more preferably 70°C or higher. The silver halide color photographic light-sensitive material according to the present invention can be used in addition to an internal development method (see U.S. Pat. Nos. 2,376.679 and 2,801.171) in which a color forming agent is contained in the light-sensitive material. External development method in which a coloring agent is contained in the developer (U.S. Pat. No. 2,252.718, U.S. Pat. No. 2,592,2
No. 43, No. 2゜590.970). Further, as the coloring agent, any coloring agent generally known to those skilled in the art can be used. For example, a cyan coloring agent is one based on a naphthol or 7-el structure and forms an indoaniline dye by coupling, and a magenta coloring agent is one having a 5-pyrazolone ring with an active methylene group as a skeleton structure. As the yellow coloring agent, those having an acylacedoanilide structure such as benzoylacedoanilide and bivalylacetanilide having an active methylene chain, and those having or not having a substituent at the coupling position can be used. can. As described above, as the coloring agent, both the so-called 2-equivalent type coupler and the 4-equivalent type coupler can be used. (a) Silver lodenide emulsions that can be used include silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, silver chloroiodobromide or mixtures thereof. It may also be one using silver halide. Among the silver halides having the above compositions, the silver halides useful for forming the color photosensitive material according to the present invention include silver halides having an iodine content of 3 mol% or more and silver halides having an iodine content of 0.3 mol%. or less and the bromide content is 80 mol%
The following silver halide. In the present invention, the above iodine content is 0°3
Gelatin is usually used for the wood-philic paint used to coat silver halide in silver halide color photographic light-sensitive materials with a bromine content of 80 mol% or less and a bromine content of 80 mol% or less. In some cases, the membrane swelling rate T is preferably smaller than 30 seconds. The swelling rate T% of bangu can be measured according to any method known in the art, for example, as described by Green et al.
Science and Engineering (Pbot, S
ci, Eng,) e19 volume. No. 2, 124-129 A serometer of the type described in Makoto (
By using a swelling membrane)! , Ty2 is a saturated film thickness of 90% of the maximum swelling film thickness reached when treated with a color developing solution at 30° C. for 3 minutes and 15 seconds, and is defined as the time required to reach this film thickness. The membrane swelling rate T can be adjusted by adding a hardening agent to the gelatin used as bangu. Hardening agents include aldehyde-based, 7-norizine-based (for example, PB Report 19,921, U.S. Patent 2,950,1
No. 97, No. 2.964,404, No. 2,983.61
No. 1, No. 3,271,175, Special Publication No. 46-4089
No. 8, JP-A-50-91315, etc.), inoxacillium series (for example, U.S. Pat. No. 3,321.3)
No. 23), epoxy systems (such as those described in U.S. Pat.
゜047,394, West German Patent No. 1,085,663,
British Patent No. 1,033゜518, Special Publication No. 48-3549
No. 5 etc.), vinyl sulfone type (e.g.
PB Rev-) 19,920, West German patent 1,100,9
No. 42, No. 2,337.412, No. 2,545.72
No. 2, No. 2.635,518, No. 2,742,308
No. 2,749,260, British Patent No. 1,251,0
No. 91, British Patent No. 3,539. ．． No. 644, 3,49
0°911, etc.), acryloyl-based (e.g., those described in U.S. Pat. No. 3,640,720), carbodiimide-based (e.g., U.S. Pat. No. 2,938,892)
No. 4,043,818, No. 4.061,499, Japanese Patent Publication No. 46-38715, etc.), triazine type (for example, West German Patent No. 2,410,973, No. 2)
, 553,915, U.S. Pat. No. 3,325,287,
JP-A No. 52-12722, etc.), polymer type (e.g., British Patent No. 822,061, U.S. Patent No. 3,6
No. 23,878, No. 3,396゜029, No. 3,22
No. 6,234, Special Publication No. 47-18578, No. 1857
9, No. 47-48896, etc., maleimide-based, acetylene-based, methanesulfonic acid ester M, and N-methylol-based hardening agents can be used alone or in combination. Useful combination techniques include, for example, West German Patent No. 2,447,587, West German Patent No. 2,505.746, West German Patent No. 2,514.245, and US Patent No. 4,047,95.
No. 7, No. 3,832.181, No. 3.840,417
No. 0 ASrMi No. 48-43319, No. 50-630
No. 82, No. 52-127329, Special Publication No. 48-323
(The combination described in No. 34 etc. is mentioned.) As mentioned above, the film swelling rate T of the binder in the photographic composition tank used in the color photographic material of the present invention is preferably 330 seconds or less, the smaller the better, but the lower limit If it is too small, damage such as scratches may occur without hardening, so it is preferably 1 second or more.More preferably 2 seconds or more25
seconds or less, particularly preferably 20 seconds or less, most preferably 1
51 or less. If it is longer than 30 seconds, the desilvering property, that is, the bleach-fixing performance deteriorates, and the concentration used is particularly high even when a low molecular weight organic acid t52 iron complex salt is used or a high molecular weight organic acid ferric complex salt is used. Sometimes the deterioration is 7 degrees. As these silver halide protective colloids, in addition to natural products such as gelatin, various synthetically obtained colloids can be used. Silver halide emulsions include stabilizers, hardeners,
Conventional photographic treatments such as sensitizing dyes, surfactants, etc. may be included. The silver halide photographic material according to the present invention preferably has a colloidal silver dispersion layer. The colloidal silver dispersion layer may be a filter layer or an antihalation layer,
Furthermore, it may be dispersed in emulsion M. As for how to make these colloidal silver dispersions,
No. 7740, No. 49-43201, No. 45-1489
No. 0, Japanese Patent Application Publication No. 51-89722 and British Patent No. 1,03
It is synthesized and coated by the general method described in No. 2,871 and the like.

Effects of the Invention As described above, in the present invention, two types of silver halide color photographic materials having different iodine contents can be processed in processing tanks that naturally have the same bleaching ability. +1 space for installing liquid tanks and dissolving replenishment liquid! ! This makes it possible to save the space for cleaning, the space for transferring the dissolved replenisher to the replenishment tank, and the installation area required for such replenishment work. Since, for example, a temperature adjustment device, a treatment liquid circulation device, etc. are not required redundantly, it is also possible to reduce costs. Further, in the color photosensitive material according to the present invention, the iodine content of the silver halide having a low iodine content is 0.3 mol% or less,
In addition, since the bromine content is 80 mol % or less, the treatment time in a processing tank having bleaching ability can be set to 1 minute or less, and desilvering failure does not occur. It was also possible to prevent the problem of yellow stain in positive color photosensitive materials that occurs when stored for a long period of time after anhydrous washing stabilization treatment. The present invention will be described in more detail below with reference to Examples. Example 11 (Experiment 1) Color film and color paper were produced in the following r' order. An antihalation layer and a gelatin layer are provided on a triacetate film base, and on top of this, a red-sensitive silver halide emulsion layer 7't', a green-sensitive silver halide emulsion layer, a filter layer containing yellow colloidal silver, and a blue-sensitive halogen layer. silver oxide g
The L agent layer was applied so that the total amount of silver was 70 zg per 100 cz2. The above emulsion layer has a mole percent of iodized nails of about 4
．． 59 (,), and in this case, the blue-sensitive silver halide emulsion layer contains α-[4-nitro7] as a yellow coupler.
(2,4-di-
Using t-7mi/phenoxy)butyramide]-2-chloroacetanilide, in the green-sensitive silver halide emulsion layer,
1-(2,4,6-dolichlorophenyl)-3i ((!-(2,4-not-amylphenoxy)-7cetamido]benzamide)-3-pyrazolone and 1-(2,4 ,6-)dichlorophenyl)
-3-([α-(2,4-not-t-amylphenoxy)
-7cetamido] ben -t-Amylphenoxy)butyl)-2-su7tamide was used, and additives such as a sensitizing dye, a hardening agent and a V spreading agent were added to each emulsion layer. A colorne FF film sample was prepared in this way and cut into 24 sheets (373 cm). Also, 2-(1-bentrue 2.4-)oxyimigree was placed as a coupler on a paper support with a resin foot. lysin-3-yl)-2-pivalyl-2'-chloro-
5'-(4-(2,4-cy-1pentyl7ethyl7oxy)
Butane 7-mide] acetanilide was dissolved in butyl 7-talate, dispersed in a gelatin aqueous solution for protection, and then mixed with chlorbromide milk powder and applied. The amount of coated coupler and silver per 100 cz" used at this time was 2412
, ff10,8511g. On top of this, a gelatin intermediate layer containing nooctylhydroquine was provided, and on top of this a gelatin intermediate layer containing 3-12-chloro-5-(1(octadecyl)succinimide)anilinol-1-(2,4
, 6-)lichloro7el)-5-pyrazolone was dissolved in dibutyl 7grate, protected and dispersed in an aqueous gelatin solution, mixed with a green photosensitive silver chlorobromide emulsion, and then coated and dried. The amount of coupler used at this time was 100e
Per I', 49111% silver was 0.87 IIfI. A gelatin solution of dioctylhydroquinone is coated on this layer as a color turbidity prevention layer, and 2-(2-(2,4-not-pentylphenoxy)butanamide)-4, 6-dichloro-5
-Methyl 7 ether/- was dissolved in dibutyl 7 talate, protected and dispersed in an aqueous gelatin solution, mixed with a red-sensitive silver chlorobromide emulsion, and then coated and dried. The amount of coating per 100cz' of the coupler used at this time was 30111? The amount of money was 0.75 g. In addition, as a hardening agent, 2,4-dichloro-6-hydroxy-5-) ryanone sodium was added in layers 2, 4 and 6.
They were added in amounts of O and OZg per 12 gelatin, respectively, and after drying, the swelling rate T of the gelatin film was measured at 30° C. using the following color developer and found to be about 7 seconds. The measurement was carried out using the Lebenzin type swelling index. The silver halide compositions of the emulsion layers described above are as shown in Table 1 below, from 9-1 to p-10. Color paper sample No. created as described above. P-1 to p-10 were cut to a width of 8.25 cm. For processing, an automatic developing machine with a common bleach-fixing tank for color paper and color paper was used, and the processing was carried out according to the processing steps shown below. (Color treatment process Processing temperature (°C) Processing time 1, color development (t (1 tank) 38.0 3 minutes 15 seconds 2, bleach-fixing (1 tree) 38.0 4 minutes 4, 2
Stable (1 tank) 32. O1 minute (color paper processing) Processing process Processing temperature ('C) Processing time j111
1. Color development (1 tank) 38.0 3 minutes 15
2 seconds, bleach-fix (1 tank) 38.0 1 minute The composition of the processing solution used is as follows. [Color development for color negatives [1] [Color development replenisher]

[Color development for color paper 811 (Note 1) Cinobal MSP (Ciba Geigy-yl) was used as a fluorescent whitening agent. [Color developer replenisher for color paper]

[Bleach-fix solution] [j miro fixer replenisher]

[First stable solution and first stable replenisher] (PIS2 stabilizer and second stable replenisher) Color developer, bleach-fix solution, first stabilizer and second stabilizer are placed in the processing tank of the automatic developer.
After filling with the stabilizing solution, color paper for checking sample No. p-1-p-10, which had been exposed to white light using a round tube, was processed. (Actual! 92) Next, the color negative film sample described in Experiment 1 was photographed, and after processing while replenishing the replenisher for 15 rolls of 24 shots, an average of 25 E plates were taken per color negative film (2). 15 pieces of printed sample No. p-IQ color paper were processed while replenishing the replenisher. If the replenisher is a color development replenisher, use 15z1 per 100cj2 of colorne FF film and 100cI of color paper.
The bleach-fix replenisher was added to the white fixing bath at 1.01 IW per 100 cz of color paper; 1 stable 1111 liquid is 10a1ft<1 stable bath per 100cz2 of color negative film? The third tank of the first stabilizing bath is replenished with 2ml per 100ez" of color paper, and the second stable replenisher is replenished with 10xft per 100cm of color paper: A2 stabilizing bath.
After repeating the above process five times and further processing 15 color negative films, the check color paper of sample No. p-1 was processed. Sample No. p-2 to p-1
The same process was repeated for 0. (Experiment 3) After the above Experiment 2 was completed, 24 shots of the color negative film had been taken and 30 shots were processed in the same manner as in Experiment 2, and each color negative film was printed with an average of 25 E plates. Thirty pieces of color paper No. p-1 were treated in the same manner as in Experiment 2. Repeat the above process three times,
After further processing 30 rolls of color negative film, sample N
o, p-1 color paper for ticks was processed. The same process was repeated for samples Nos. p-2 to p-10. (Actual!! 4) After the above experiment 3 was completed, 24 shots of the photographed force 2-ne gamma film were processed in the same way as the actual g42, and 60 pieces were taken.
Sixty pieces of color paper of Sample No. p-1 were processed in the same manner as in Experiment 2, with an average of 25 sheets of E plate printed on each color negative film. Repeat the above process twice,
After processing 60 color negative films, a check color paper of sample No. p-1 was processed. The same process was repeated for samples Nos. p-2 to p-10. The residual percentage of residual silver in the highest density part of the color papers for ticks obtained in Experiments 1 to 4 was determined as fil, and is shown in Table ff11 below. Table 1 From the results in the above table, it is clear that the color paper according to the present invention, which has an iodine content of 0.3 mol% or less and a bromine content of 80 mol% or less, can be produced after bleaching and fixing a large amount of color net. It was found that no defective desilvering occurred even when bleach-fixing was carried out for 1711 minutes in the same bleach-fixing tank.

[Example 21゜Sample No. P-1 in Experiment 4 described in Example 1
After the experiment using color paper (silver chlorobromide emulsion with a bromine content of 75 mol%) was completed, a color paper of the same check sample No. l'-10 as used in Example 1 was used. Bleach-fixing treatments were carried out by varying the bleach-fixing time as shown in the PAZ table below, and the residual percentage of residual silver in the sample of the processing solution was measured. In addition, the blue density of the lowest density part of this sample was measured using a Sakura charge densitometer PO^-65 (Konishi Roku Photo Industry Co., Ltd.). It was stored for a week and measured using the method described above to examine the increase in the concentration of iodine.The obtained results are shown in Table 2. Color paper with a bromine content of 0.3 mol% or less and a bromine content of 80 mol% or less is processed by bleaching and fixing a large amount of iodine in the same bleach-fixing tank of an automatic processor. It was found that an increase in yellow stain due to long-term storage could be prevented by bleach-fixing within 1 minute.Furthermore, it was also found that defective desilvering did not occur even when the bleach-fixing time was shortened to 20 seconds. [Example 3] Using the Colorne 7y film and color paper sample No. PiO used in Example 1, 24 shots of the already photographed Colorne FF film were taken and 60 shots were processed in the same manner as in Experiment 2 of Example 1. After that, 60 pieces of color paper printed with an average of 25 E plates per color negative film were processed in the same manner as in Experiment 2 of Example 1. The above process was repeated twice, and 6 more pieces of color negative film were printed.
After processing 0 sheets, color paper for checking was processed. However, in this case, the bleach-fix solution and the V bleach-fix replenisher had the following compositions. [Bleach-fixing 81 Organic acid iron (I[l) complex salt (listed in Table 3) 0.3
5 mole 7 ammonium sulfite 11.0° ammonium thiosulfate 150. Oy7 ammonia water (28% solution) 10ml bleach accelerator (
2.0° Add water to bring the solution to 11, and adjust the pH to 7.0 with acetic acid and aqueous ammonia. E Bleach-fix replenisher l Organic acid iron (III) complex salt (listed in Table 3) 0.4 mol Ammonium sulfite 10.0 g Ammonium thiosulfate iso, o. 7mm water (28% solution) 10ml Bleach accelerator (listed in Table 3) Add 2.0° water to make 11, and make 4% pl+7.0ml with acetic acid and aqueous ammonia. Table 3 shows the percentage of residual silver in the check color paper samples and the increase in stain density after storage at high temperature and high humidity. The bleach accelerators (1) and (IF) in Table 3 are shown below. Bleach accelerator (1) Bleach accelerator (II) In Table 3, EDT^-Fe (III) is ethylenenoaminetetraacetic acid iron ([1) ammonium salt, DTP^-Fe (
III) represents noethylenetriaminepentaaic acid iron(1)7-sonium salt. The results in Table 3 also apply when color paper with a halogen composition other than the present invention in Example 1 is used (11-1, 1'-2,
1'-5, r'-6), the stain density is considerably smaller. In fact, by using diethylenetriaminepentaacetate iron(1) ammonium salt as the bleaching agent or by combining it with a bleaching accelerator, staining was unexpectedly lowered and the residual rate of residual silver was also lowered.

Claims (1)

[Claims] Two types of silver halide color photographic light-sensitive materials with different iodine contents can be processed with substantially the same bleaching ability using an automatic developing machine consisting of at least a color developing tank, a processing tank with bleaching ability, and a water-washing alternative stabilizing tank. In the processing method of processing in a processing tank having bleaching ability, the above-mentioned photosensitive material has an iodine content of 0.3 mol% or less and a bromine content of 80 mol% or less. A method for processing a silver halide color photographic material, characterized in that the processing time is 1 minute or less.