JPS604942A - Processing solution having bleaching power for color photographic sensitive silver halide material - Google Patents

Abstract

PURPOSE:To prevent stain due to a complex salt as an oxidizing agent and to obtain a processing soln. having power of rapidly bleaching silver and superior shelf stability and causing no stain by adding a specified complex salt as the oxidizing agent and specified metallic ions. CONSTITUTION:This processing soln. contains an iron (III) complex salt of diethylenetriaminepentaacetic acid as an oxidizing agent and metallic ions of Ni, Co, Zn, Ce, Ru, Y or Sm. A potassium salt, a sodium salt or an ammonium salt is used as the complex salt, and >=2 kinds of complex salts may be used combinedly. The complex salt is used by an arbitrary amount, preferably >=0.05mol. The metallic ions are fed in the form of any compound such as halide, hydroxide, sulfate, carbonate, phosphate or acetate, and they are used by 0.0001- 2mol/l.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a processing solution having bleaching ability for halogen-arsenic color photographic light-sensitive materials. This invention relates to an effective whitening solution and bleach-fixing solution for halogen F silver color photographic light-sensitive materials.

[Prior art]

Generally, imagewise exposed...Okunr11. In order to obtain a color image by processing a color photographic material, a step is provided after the color development step to treat the produced metallic silver with a processing solution having bleaching ability.

As processing liquids having bleaching ability, bleaching liquids and ryohakusai liquids are known. When an egg white solution is used, a step of fixing the silver arsenic with a fixing agent is usually added after the bleaching step, but with a albumen fixer, bleaching and fixing are performed in one step.

The processing solution with bleaching ability in processing halogen arsenic color photographic photosensitive materials contains inorganic acids such as red blood salts and arsenic salts as acids and arsenals for bleaching image silver. Widely used.

However, some serious drawbacks have been pointed out to the processing liquids containing these inorganic oxidizing agents and having sea bream whitening properties. For example, it is relatively excellent in terms of red blood salt and weight amuta salt image silver bleaching blade, but 1. There is a risk that it will be decomposed by light and produce anion and hexavalent chromium ion that are harmful to the human body, and it has the property that it cannot be lit in order to prevent pollution. In addition, because these acids (arsenic agents) are extremely strong, it is difficult to coexist halogen-arsenic soluble arsenic agents such as thiosulfur R salts in the same processing solution, and It is almost impossible to use these oxidizing agents in fixing baths, which makes it difficult to achieve the goals of rapidity and simplification of processing. has the disadvantage that it is difficult to reuse the waste liquid after treatment without discarding it.

In contrast, metal complexes of organic acids such as aminopolycarboxylic acid metal complex salts have been proposed as those that have fewer pollution problems, can be processed quickly, are easy to use, and can be recycled and reused. Processing solutions that use complex salts as acid agents have come into use. The disadvantage is that the silver (metallic silver) nickel whitening speed (acid rate) is slow.For example, 911 is considered to have the strongest bleaching edge among the aminopolycarboxylic acid gold PAM salts. Ethylenediaminetetraacetic acid iron (Ml complex salt) is used in some practical applications as a bleaching solution and a bleach-fixing solution, but high-sensitivity products based on silver bromide and silver iodobromide emulsions... Materials, especially color paper for photography, color negative film for photography, and color reversal film that contain silver iodide as silver halide, lack bleaching blades and may leave traces of image silver even after long processing times. , the desilvering property becomes poor.

This tendency is particularly noticeable in a bleach-fix solution in which an arsenic, a thiosulfate, and a sulfate coexist because the acid arsenic reduction potential is lowered.

On the other hand, despite great efforts to develop bleaching accelerators to increase the silver source of bleaching solutions or bleach-fixing solutions containing metal complex salts of organic acids, satisfactory results have not yet been obtained. The reality is that it is not.

The present inventors have discovered that aminopolycarboxylic acid gold kTpmtlX
Among these, diethylenetriaminepentaacetic acid iron(4) complex salt was discovered as an oxidizing agent having excellent oxidizing power particularly in the high pH region. Iron diethylenetriaminepentaacetate (+!+
) Bleach and bleach-fix solutions that use complex salts as acid and arsenic agents have a rapid silver-whitening reaction, less staining when directly bleached, and are said to have good storage stability. It has extremely excellent performance. However, diethylenetriaminepentaacetic acid iron complex salt is 1! When used as a fixing agent in bleach or bleach-fix solutions, iron I
H! It was found that yellow staining, which was thought to be caused by the coloring of the salt, was likely to occur. Particularly when the water washing sound was insufficient, remarkable yellow staining was observed, which was found to be a serious problem in terms of reproduction and reproduction of eggs. Therefore, in order to use diethylenetriaminepentaacetate iron(2) complex salt in practical use as a concentrated white solution or bleach-fix solution, it is necessary to prevent yellow staining due to diethylenetriaminepentaacetate iron(2) complex salt, and to use diethylenetriaminepentaacetate σ? There is a strong need to develop a technology that does not impair the silver bleaching ability, stain resistance, and liquid storage stability of iron (Qi) complex salts.

[Purpose of the invention]

The purpose of the present invention is to provide a quick silver source white blade, no staining, and to have excellent storage stability of the C (white fixing solution) even when used as a bleach-fixing solution as a processing solution that has bleaching ability. The fourth object of the present invention is to provide a processing liquid having bleaching ability for a halogen-arsenic color photographic p-sensitive material, which does not cause contamination with diethylenetriaminepentaacetic acid iron (It) complex salt.

Other objects of the invention will become apparent from the following description of the invention al.

[Structure of the invention]

As a result of intensive research, the present inventors have found that the above objects have been achieved by a bleaching solution and a bleach-fixing solution containing diethylenetriaminepentachloride salt as an oxidizing agent and containing the following metal ions of the present invention. I found out that it can be done.

〔Metal ions〕

Nickel, cobalt, bent lead, cerium, ruthenium, yttrium, and maricum.

Contamination by ethylenediamine 461:iron (ill) complex salt, which is generally used for some purposes among aminopolycarboxylic acid iron (1) complex salts, is not observed in normal processing, and in the water washing process. Due to the reduced washing time and water washing rate, it becomes easy to remain in the photosensitive material or paper support.
Iron (It takes on the color of iron itself and is contaminated!1
! It is well known that the problem occurs at the edges of color paper. On the other hand, iron diethylenetriaminepentaacetate (
jl) Contamination with complex salts is caused by ethylenediaminetetraacetic acid (1
! It is thought that this is due to the same cause as for complex salt 11, but r
The /r'\ sign has an extremely large degree of L color contamination.

These people's filth! , 1'! Although this can be prevented to some extent by extending the washing time and increasing the water washing side, in the case of diethylene triamine five vinegar steel frame R1 group, yellow contamination cannot be sufficiently prevented even if the above measures 8c are applied. This becomes a big problem when the purpose is rapid treatment or when it is difficult to secure water resources and reduce costs.

The present invention has zero iron diethylenetriaminepentaacetate! l) Water washing t1- while maintaining the second r strength of the lead group.
This was achieved as a result of various studies on ways to prevent yellow staining caused by diethylenetriaminepentavinegar (ε iron part) complex salts without increasing the amount of diethylenetriamine.

The diethylenetriamine iron pentaacetate according to the present invention ([1 complex salt is a free acid (hydrogen salt), an alkali metal salt such as a sodium salt, a potassium salt, a lithium salt, or an ammonium salt, or a water-soluble amine salt is triethanolic. It is used as an amine salt, etc., but potassium salt, sodium salt, and ammonium salt are preferably used.At least one type of these iron(5) complex salts may be used, but two or more types can also be used in combination.Amount used can be selected arbitrarily, and must be selected depending on the amount of silver in the photosensitive material to be processed and the composition of arsenic (arsenic), but generally it has a high oxidation potential, so it is used at lower concentrations than other aminopolycarboxylate salts. For example, it can be used in an amount of 1 mole or more, preferably 0.05 mole or more, per 11 moles of the working solution.

In addition, in the replenishment solution, it is preferable to use concentrated and low replenishment liquids, which have the highest solubility and the highest concentration ratio.

The gold parent ion used in the present invention may be supplied by any method. For example, halogen can be supplied in any form such as arsenic, hydroxide, sulfate, carbonate, phosphate, acetate, etc.; (Hereinafter, these gold 81 of the present invention
The metal compound that supplies ions is referred to as the metal f arsenide of the present invention. ). However, the method is not limited to these methods, and other methods such as electrical methods may also be used.

<f11 (F, compound)> (A-1) Salt salt lead (A-2) Odoriferous lead (A-3) Lead sulfate (A-4) Bent lead nitrate (A-5)' Salt: Nickel (A-6) Nickel nitrate (A-7) Nickel sulfate (A-8) Nickel acetate (A-9) Nickel oxide (A-XO) Nickel iodine (A, -11) Nickel phosphate ( A-12) Cobalt chloride (A-13) Cobalt nitrate (A-14) Cobalt sulfate (A-15) Cobalt acetate (A-16) Cerium sulfate (A-17) Ruthenium sulfate (A-18) Ruthenium chloride (A -19) Yttrium sulfate (A-20) Yttrium nitrate (A-21) Hyttrium salt (A-22) Hyttrium salt (A-23) Maricum salt (A-24) Samarium bromide (A- 25) Cerium sulfate (A-26) Samarium carbonate (A-27) Purulium nitrate (A-28) Samarium acetate These metal arsenic compounds of the present invention may be used alone, or
Two or more types can also be used in combination. The amount used is preferably from 0.0001 mol to 2 mol, particularly preferably from 1,001 mol to 1 mol per 11 mol of the solution used.

The whitening solution and whitening solution of the present invention have a pH of 0.2 to 9.
5, preferably 4.0 or more, more preferably 5.0 or more, and the most preferable pH range is 5.0 or more, more preferably 5.0 or more.
．． It is 5 or more and 940 or less. The treatment temperature is preferably 80° C. or lower, but preferably 55° C. or lower to suppress evaporation.

The bleaching solution of the present invention contains diethylenetriaminepentaacetic acid iron complex salt as a bleaching agent as described above and the metal ion of the present invention, and may also contain various additives. Additives include, in particular, alkali halides or ammonium oxides, such as odorous halides, chlorinated chlorides, salts such as chlorinated halides, chlorinated hymonium, potassium iodide, chlorinated sodium iodine, ammonium iodide, thiourea, etc. It is desirable to contain pH buffering agents such as borates, oxalates, acetates, carbonates, slagates, soluble additives such as triethanolamine, alkylamines, polyethylene oxides, etc. Excessive bleaching liquids such as compounds known to be added can be added as appropriate.

The bleach-fixing solution of the present invention may contain diethylenetriamine iron pentaacetate ([1 complex salt] and the metal ion of the present invention as a bleaching agent as described in Section 61J, and contain thiosulfate, thiocyanate, thiourea, thioethers, etc.).・・a-ken [
A solution having a composition containing one arsenic adhesive is applied. Also,
In addition to the bleaching agent of the present invention and the above-mentioned arsenic fixer, a bleach-fixing solution consisting of a small amount of an arsenic compound such as odorous 1-hypotassium or, conversely, Odor: A bleach-fix solution consisting of a large amount of halogen compounds such as hyammonium, and even a large amount of odor 1
A special bleach-fix solution having a composition consisting of a combination with a halogen compound such as hicpotium can also be used.

The above-mentioned halogen compounds include the odor "hypotassium" as well as the salt f arsenic acid, hydrobromide, lithium fluoride, odor "hysodium, ammonium bromide, sodium iodide, potassium iodide, ammonium iodide" etc. can also be used.

(included in the bleach-fix solution)・C-Ken ``A compound that reacts with arsenic to form a water-soluble complex salt, such as potassium thiosulfate 9 Typical examples include thiosulfates such as sodium thiosulfate, ammonium thiosulfate, thiocyanates such as potassium thiocyanate, sodium thiocyanate, and ammonium thiocyanate, thioureas, thioethers, highly convex bromides, and iodides. These fixing agents can be used in an amount of 5 g/4 or more, as long as they can be dissolved.

In addition, as in the case of bleaching solution, the bleaching solution contains boric acid, borax,
A pH buffering agent consisting of various salts such as wood vinegar, hysodium hydroxide, hypotassium carbonate, potassium carbonate, sodium bicarbonate, PArR potassium, acetic acid, sodium acetate, hyammonium hydroxide, etc. alone or in combination. A combination of the above may be contained.In addition, various fluorescent brighteners, antifoaming agents, or surfactants may be contained.Furthermore, human aqueous fluamine, hydrazine, sulfites, and isomeric heavy!II Preservatives such as sulfates, aldehydes and debentured sulfuric acid adducts of ketones, stabilizers such as alcohol nitrates, soluble arsenic agents such as alkanolamines, stain inhibitors such as organic amines, etc. Other additives and organic solvents such as methanol, dimethylformamide, and dimethyl sulfoxide may be appropriately included.

In the processing power method using the processing solution of the present invention, the most preferable processing power method is to perform bleaching or dark fixing immediately after color development, but after performing treatments such as washing or rinsing and stopping immediately after color development, bleaching Alternatively, bleach-fixing may be performed, or a prebath containing a bleach accelerator may be used as a processing solution prior to bleaching or bleach-fixing.

After bleaching and fixing (or applying false whites), stabilization treatment may be performed by washing with water, or washing with water may be performed followed by stabilization treatment. In addition to the above steps, known auxiliary steps may be added as necessary, such as hardening, neutralization, black and white development, reversal, and washing with a small amount of water. A typical example f11 of a preferred treatment method includes the following steps.

fl) Color development → bleach fixing → washing with water (2) color development → beard white footwear → small valve washing with water → washing with water (3) color development → bleach fixing Sakaki washing with water → stabilization (4) color development → bleaching and fixing - Stable (5) Color development → washing with water → bleaching footwear → washing with water f61 color development → stop → bleaching footwear → washing with water (7) development ρjQ image → bleaching →
Washing with water → Footwear → Washing with water → Stability (8) Coloring Chi D, image → Bleaching →
Seta → Wash with water → Stabilize (9) Color development → White mark → Wash with a little water → Fix → Wash with a little water → Wash with water → Stable (If)) Color development → Wash with a little water → Wash with a little water → Ugly white → Wash with a small amount of water → Fix → Shokei water washing → water washing → stabilization (11) color development modern → stop → elephant white → small amount of water washing → fixation → shobang water washing → water conditions → stabilization (12) black and white development → water washing → reversal → color development → bleaching → fixed clearing → water 6e → Stable (J3) Pre-hardening → Neutralization → Black and white border image → Stop → Color development → Bleaching → Fixing → Washing with water 5 → Stable Black and white used before processing with a processing solution that exhibits the whitening ability of the method of the present invention The developer is a so-called black-and-white first developer used in the processing of commonly known color photographic photosensitive materials, or a developer used in the processing of black-and-white photographic materials, and is generally added to the black-and-white developer. Various additives can be contained.

Typical additives include 1-phenyl-3-pyrazolidone, developing agents such as metol and nohydroquinone, preservatives such as atomyl sulfates, water 4 parts arsenic, sodium carbonate, carbonate 1 part. Accelerators consisting of alkalis such as potassium and 2-methylbenzimidazole,
Inorganic or organic inhibitors such as methylbenzthiazole, water softeners such as IJ phosphates, surface overdevelopment inhibitors consisting of trace amounts of iodide and mercapto compounds, etc. I can do it.

The aromatic primary amine color developing agent used in the color developer used in mill processing with the processing solution having bleaching ability of the present invention is widely used in various color photocopies. This includes all known methods. These developers include amine phenol and p-phenylene diamine derivatives. Because these compounds are stable in the free state, they are generally used in the form of a free salt, such as a hydrochloride or a sulfate. Generally, these compounds are present in a concentration of about 0.1 g to about 30 g per ton of color developer, more preferably about Ig to about 30 g per ton of color developer.
Use at a concentration of approximately 15g.

Examples of amine phenol developers include 0-amine phenol, p-aminophenol, 5-amino-2-
Included are oxy-toluene, 2-amino-3-oxy-toluene, 2-oxy-3-amino-1,4-dimethyl-benzene, and the like.

Particularly useful primary aromatic amine color developers include N, N-
4. Dialkyl-p-phenylenediamine-based compounds, alkyl groups, and phenylenediamines. Even if Fi is replaced,
Alternatively, it may not be replaced. Among them, examples of especially useful arsenic compounds include N,N-diethyl-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride LN,N-dimethyl-p-phenylenediamine hydrochloride, 2- Amino-5-(N-ethyl-N-dodecylami/)-)toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate, N-ethyl-1q-β- Human O-oxyethylaminoaniline, 4-amino-3-methyl-N, N-diethylaniline, 4-amino-N-(2-methoxyethyl)
-N-ethyl-3-methylaniline-p-)luenesulfone)a'.

The alkaline color developing solution used before processing with the pre-bleaching processing solution of the present invention includes, in addition to the above-mentioned primary aromatic amine color developing agent, a coloring parent and a color developing solution that are usually added to the developing solution. Various ingredients such as alkaline agents such as sodium hydroxide, sodium carbonate, and potassium carbonate, alkali metal salts, acid salts, alkali metal monosulfates, alkali metal thiocyanates, alkali metal halogens (arsenic compounds, benzyl alcohol, etc.) , diethylene) IJ 7 Mingo vinegar a
, 1-hydroxyethylidene-1,1-diphosphonic acid, etc. may optionally contain a water-softening arsenic agent and a concentrated arsenic agent. Most commonly from about 10 to about 13.

Haloken “
Hikin color photographic photosensitive materials are manufactured using an internal development method (US Pat. No. 2.37 (i, [
i No. 79, gi2.8 o 1. i No. 71 Mei aI
In addition to the external development method in which the coloring agent is contained in the Tn image solution (US 1i; I/l?n￥F2-2.25
No. 2.718, No. 2,592.243, jWl No. 2
．． 590.970). Further, as the coloring agent, those generally known in the art can be used. 9+1 As a cyan coloring agent, there is naphthol, 1, J + phenol conjugated tX, which forms an indoaniline dye by coupling,
Magenta color formers have a 5-pyrazolone ring with an active methylene group as a skeleton, while yellow color formers have benzoylacedoanilide, bivalylacetanilide, and acylacedoanilide structures having an active methylene chain. Both those having or not having a substituent group at the coupling link position r can be used. In this way, as the coloring agent, it is also possible to use the so-called 2-equivalent type coupler and the cousin of the 4-equivalent type F coupler. The 0g ratio silver emulsions that can be used include silver chloride, silver bromide, silver chloride, silver chloride, silver arsenic, lump method silver, silver arsenic, silver salt (P).
, silver, or a mixture of these.
It is also possible to use arsenic and save money. In addition, various colloids that can be used to capture these halogens include natural products such as gelatin, as well as those obtained by synthesis. hardener,
Common photographic additives such as sensitizing dyes and surfactants may also be included.

The bleaching solution and bleach-fixing solution of the present invention can be used for color vapor, color negative film, color positive film, color reversal film for slides, color reversal film for movies, color reversal film for TV, reversal color vapor, etc. It can be applied to photosensitive materials.

〔Example〕

Hereinafter, the present invention will be explained in detail with reference to examples, but the embodiments of the present invention are not limited to these examples.

Example 1 A paper support whose surface was coated with a polyethylene layer containing acid ratio titanium of the Anacuse type as a white pigment was pretreated by corona discharge, and then the following layers were sequentially applied to produce color photographic paper. made.

1st layer: as a yellow coverr α-[4-(l-benzyl-2-phenyl-3,5-dioxo-1,2,4-
) rearsilicyl)]-]α-bivalyl 2ri ao-5-
Blue-sensitive silver chlorobromide emulsion m containing [:γ-(2,4-di-t-amylphenoxy)butyramide]acetanilide and containing 5 moles of silver chloride.

2nd R4=gelatin intermediate/L containing UV core absorber 3rd layer: magenta cap 2- as 1- (2,4,6-
Contains tric ao phenyl)-3-(2-ri aa-5-ophtatecenyl cinimide ani IJ/)-5-virazolone, and contains 15 moles of silver chloride.

Green-sensitive silver chlorobromide emulsion polish.

4th layer: same gelatin intermediate layer as the 2nd layer, 5th layer 2.4-zik-o as nitrogen coupler.

-3-Methyl-6-[γ-(2,4-cyamylphenoxy)butyramide] A red-sensitive silver chlorobromide emulsion layer containing a 15 molar salt of arsenic.

6th layer: gelatin retention layer.

Each of the above photosensitive emulsion layers has a total silver content of 100 d/1
It was applied so that it was 0q. In addition, the Haloken silver photographic emulsion used in each light-sensitive emulsion layer was chemically sensitized with sodium thiosulfate, and conventional additives such as stabilizers and sensitizing dyes were added. A hardener and a spreading agent were added to the solution.

Print the colored photographic paper made as above (
Thereafter, the film was continuously replenished using an A-R type automatic developing machine (hereinafter referred to as self-developing running process).

Self-development running processing process Processing temperature ('C) Processing time (minutes) 1 Color development 33±0.3 3.5 2 Bleach-fixing 30-34 1.5 3 Washing 30-34 3.5 4 Drying 75-85 Above Among the processing steps, color development replenisher and bleach-fix replenisher f: trial is 1 for color development and bleach-fixing, respectively.
They were continuously replenished at a rate of 325 - each after each treatment. The color development replenisher and color development solution used were as follows.

[Color developer replenisher]

Benzyl alcohol 20tne Ethylene glycol 20% Whitening agent (4,4'-diaminostilbendisulfonic acid derivative) '2.0g Human ax7amine@acid acid 4.0g 3-methyl-4amino-? 1-ethyl-he-(β-methanesulfonamidoedyl) aniline sulfate 7.0 g Dispersed potassium 30 g
1.1 d Calicum sulfate (50% solution) 5 Calicum hydroxide 3.0 g After finishing the total amount to lt, adjust the pH to 10.40 by adding potassium hydroxide as appropriate. .

Color developer: Color developer replenisher 800me
By adding the following color development starter and adding water to make 1 ton, a color development solution 17 having a pH of 10.20 was prepared, and the amount necessary for processing was appropriately prepared and used.

[Color development starter]

Potassium carbonate 2.2 g Potassium bicarbonate 3.4 g Odor: Hypotassium 0.64 ft Salt [Hypotassium 0.5 t) g The bleach-fix solution and bleach-fix replenisher used were as follows.

[Bleach solution and bleach-fixing replenisher (1)] Iron ethylenediaminetetraacetate (lilJ complex salt 70g ethylenediaminetetraacetic acid 2()g) Ammonium sulfate A (50 cycles solution) 30mA'Ammonium thiosulfate (70% solution) 140mA aqueous ammonia (
28% solution) 30m! ! Finish with aqueous ammonia or acetic acid to a pH of 7.

[Weimyo white stain solution and bleaching foot wash solution (2)] Iron diethylenetriaminepentaacetate (ammonium III 80g
Diethylenetriaminepentaacetic acid 24g Bait: Ammonium (50% solution) 30'd Naohakuni 6i ammonium (70% solution) 140ml Aqueous ammonia [28%] solution 30m Adjust pH to 7.0 with aqueous ammonia or acetic acid. ,
I will finish it so that the total loss will be ltK.

M! 77 each using Hakujo A liquid and Gabe Hakujo Jukusoe liquid (1) and (2)! ”, iThe amount of white fixer replenisher used is r(
The color photographic paper at the end of the run is treated with violet, which has twice the capacity of the white fixing bath, and the color photographic paper is
After cutting the edge part into 5 mm and 1 liter, it was rolled tightly into a roll and the degree of evening color repulsion of the edge part was measured, and the force was taken as the contamination characteristic of the edge part.

Also, is the washing water L1 5 t/tr? and 2oOi/-
Processed with. In order to see the effect of the gold nine ion content of the present invention, 5 g of the metal f-hybrid compound shown in Table 1 was added to the bleaching electrodeposition solution IL+ and the bleach-fixing replenisher (2). Evaluation was performed using the method described above.

Table 1 As is clear from Table 1, the diethylenetriamine iron pentaacetate (2) complex salt is extremely contaminated at the edges compared to the ethylenediamine tetraacetate iron (2) complex salt, and the washing water f
As -t decreases, this tendency becomes even more pronounced. In addition, a metal f arsenic compound (A-5) is added to the iron I complex salt of ethylenediaminetetraacetate.
Even when t-'1 ljs was applied, there was no contamination at the edge, whereas the nickel silver curing solution of the present invention (sample 4 to
10), compared to iron diethylenetriaminepentaacetate (lffl complex salt (NI13)), contamination of the edge area was largely prevented regardless of the amount of washing water; Recognize.

In addition, the pa of the tank liquid used (sample NQI ~ 10) was varied from 5.0 to 9.0 and processed using a piece processing device (hereinafter referred to as manual processing), desilvering completion time and red color. The maximum bypass density (cyan dye density) and the minimum green reflectance density (magenta tin) were measured using the bleach-fix solution of the present invention (with a metal arsenate added to diethyl 1/ferric triamine pentaacetate) ( 4 to 10) gave the same results as the bleach-fix solution (3) to which no metal (hypolysate) was added.

Example 2 Sakura color a film [manufactured by Konishiroku Photo Industry ■] 200
After photographing 0nl using a Konica FS-11 (manufactured by Konishiroku Photo Industry ■), it was subjected to a self-development running process according to the following processing steps.

The automatic developing machine used was a modified hanging type automatic film developing machine type H4-220W-2' made by Norlin Koki.

Treatment process (38℃) Number of tanks Treatment time The composition of the treatment liquid used is as follows.

[Color developer]

[Color development replenisher] [Concentrated fixer and bleach-fixer replenisher (1)] [Bleach-fixer and bleach-fixer replenisher (2)] [Bleach-fixer and bleach-fixer replenisher (3)] [Stabilizing solution ] [Stable replenisher] The developer replenisher from the company is used for color negative film 100c, r.
15 ml of color developing bath is refilled, ♂, white fixing replenisher, color negative film 100 ml, 9-bleaching bath is refilled with 11 ml, and stable replenisher is added to 1 me stabilizing bath per 100 c4 of color negative film. replenishment ζi
It was. In the washing bath, the water is filled with color negative film.
I) 0 (150 rainbow streaks were washed away.

g+), self-sufficiency 7i' and 71 blasphemy flood replenisher +Il~
(3) was used to continuously replenish each film for 2000 m. After each running process was completed, the tank solution was stored in a tightly closed refrigerator. After all the self-development running processes are completed, the pH of the white fixing tank liquid fil~(3) is 2.
Adjust to the values in the table, perform manual processing, and obtain the brown color bypass concentration (pollution level) and desilvering completion time ['? The clear link time was measured, and the film was bleached for 35 minutes. The results of only the lotus degree and clearing time are shown in Table 2.

However, the blue transmission density was measured after complete desilvering to distinguish it from an increase in evening color intensity due to poor desilvering.

The processing conditions were the same as those for the self-development running process except for the processing time for egg white fixation, and the processing solution used had the same composition as the self-development run process except for the bleach-fix solution. After 1 treatment, the sample was treated with Sakura Color.
Cut the film [manufactured by Konishi Rokusha Kogyo ■] into pieces,
1 according to the usual method! ′! A type exposure was used.

For comparison, a sample treated with the standard treatment Jukura Color Negative Process CNK-4 was subjected to the same VC measurement. Ishi de-drunkenness 1st place fl+! The time was 6 minutes and 30 seconds for Hamashiro treatment, 7ii:'i treatment (5930 seconds).

As is clear from the r1st floor in Table 2, the metal compound (A
-5) i-weighted wisdom of the present invention; self-sufficiency liquid (3) is metal
Compared to the M self-sufficient solution (2) without the addition of H compound k (lr
1]. Also, good results were obtained with respect to clear link time, with no effect at all due to the addition of the metal compound 155 of the present invention.

The maximum red color (cyan dye density), the minimum green color (magenta tin), and the number of days until the formation of arsenic were also observed in the film obtained by bleaching the film for 35 minutes. However, there was no negative effect at all due to the addition of the metal compound.

Claims (1)

[Scope of Claims] Bleaching for silver halide color photographic light-sensitive materials, characterized in that it contains diethylenetriamine iron pentaacetate (1) complex salt and at least one metal decay ion selected from the group of gold ions below. processing liquid with the ability to [Total bending ions] Nickel, cobal), 1lIi lead, cerium, ruthenium, yttrium, and maricum.