JPS60130738A - Bleaching solution for processing silver halide color photosensitive material - Google Patents

Abstract

PURPOSE:To speed up bleaching of silver in a bleaching soln. and a bleach fixing soln., to prevent staining, and to improve storage stability by incorporating iron (III) diethylenetriamine-pentaacetate complex and specified metal ions. CONSTITUTION:Yellow staining can be prevented without lowering superior characteristics of an iron complex salt, by using a bleaching soln. or bleach processing soln. contg. iron (III) diethylenetriamine-pentaacetate complex having high silver bleaching speed, and metallic ions, such as Mg, Ca, Bi, Sr, Mn, Al, Sn, Ba, In, Tl, or Zr. In this case, it is not especially necessary to elongate washing time and increase the amt. of washing water, thus permitting rapid bleach processing, prevention of yellow staining, ensuring of water resorces, and reduction of cost.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to a processing liquid having bleaching ability for silver halide color photographic materials. More specifically, the present invention relates to an effective bleaching solution and bleach-fixing solution for use in silver halide color photographic light-sensitive materials, which have improved processing performance and properties.

[Prior art]

Generally, in order to obtain a color image by processing an imagewise exposed silver halide color photographic light-sensitive material, after the color development step, there is a step of treating the produced metallic silver with a processing solution having bleaching ability. provided.

Bleaching solutions and bleaching solutions are known as processing solutions having bleaching ability. When a bleach solution is used, it is usually
Following the bleaching step, a step of fixing the silver chloride with a fixing agent is added, but with a bleach-fix solution, bleaching and fixing are performed in one step.

Inorganic oxidizing agents such as red blood salts and dichromates are widely used as oxidizing agents for bleaching image silver in processing solutions with bleaching ability in the processing of silver halide color photography. There is.

However, several serious drawbacks have been pointed out to processing solutions containing these inorganic oxidizing agents and having bleaching ability. For example, red blood salt and dichromate are relatively superior to the bleaching blade of image silver, but they may be decomposed by light and produce cyanide ions and hexavalent chromium ions that are harmful to the human body. It has a tag that is undesirable from a pollution prevention standpoint. In addition, because these oxidizing agents have extremely strong oxidizing power, it is difficult to coexist with silver halide solubilizers such as thiosulfates in the same processing solution, and it is difficult to use these oxidizing agents in bleach-fixing baths. This makes it difficult to achieve the goal of speeding up and simplifying the process. Furthermore, processing liquids containing these inorganic oxidizing agents have the disadvantage that it is difficult to reuse the waste liquid after treatment without discarding it.

On the other hand, metal complex salts of organic acids such as aminopolycarboxylic acid metal complex salts have been used as oxidizing agents to meet the requirements of speeding up and simplifying treatment, and enabling reuse of waste liquids, with fewer pollution problems. In recent years, treatment solutions have come to be used. However, treatment solutions using metal complex salts of organic acids are
Because the oxidizing power is slow, the image silver (
It has the disadvantage that the bleaching rate (oxidation rate) of silver (metallic silver) is slow. For example, iron(1)l salt of ethylenediaminetetraacetate, which is thought to have a strong bleaching edge among aminopolycarboxylic acid metal complexes, has been put into practical use as a bleaching solution and a bleach-fixing solution in some places, but it has an odor. High-sensitivity silver halide color photographic materials, especially silver halide emulsions, especially -
・Color vapor for photography, color negative film for photography, and Color River length film that contain silver iodide as silver halogenide do not have enough bleaching blades, and even after long-term processing, only traces of silver remain in the image. Desilvering properties become poor.

This tendency is particularly noticeable in bleach-fix solutions in which oxidizing agents and thiosulfates and sulfites coexist because the redox potential decreases.

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 an oxidizing agent and a diethylenetriaminepentaacetic acid iron(1) complex salt that has excellent oxidizing power particularly in a high pH region among aminopolycarboxylic acid metal complex salts. Bleach and bleach-fix solutions that use diethylenetriaminepentaacetic acid complex as an oxidizing agent have a rapid silver bleaching reaction, less staining when directly bleached, and have good storage stability. It has extremely excellent performance. However, it has been found that when diethylenetriaminepentaacetic acid iron(1) complex salt is used as an oxidizing agent in a bleach solution or a bleach-fix solution, yellow staining likely occurs, which is thought to be caused by the coloring of the iron(lI) complex salt. In particular, when the amount of washing with water was insufficient, remarkable yellow staining was observed, which was found to be a serious problem in terms of photographic performance. Therefore, it is necessary to put diethylenetriaminepentaacetate iron (1) M salt into practical use as a bleaching solution or bleach-fix solution. There is a strong desire to develop a technology that does not impair silver bleaching ability, stain rigidity, and liquid storage stability.

[Purpose of the invention]

It is an object of the present invention to provide a rapid silver source white blade, to prevent staining, and to have excellent storage stability even when used as a bleach-fixing solution as a processing solution having bleaching ability. An object of the present invention is to provide a processing solution having bleaching ability for silver halide color photographic light-sensitive materials, which does not cause contamination with iron pentaacetate complex salts.

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

[Structure of the invention]

As a result of intensive research, the present inventors have found that the above objects are achieved by a bleaching solution and a bleach-fixing solution containing diethylenetriaminepentaacetic acid iron(1) complex salt as an oxidizing agent and the following metal ions of the present invention. I discovered that.

〔Metal ions〕

Magnesium, calcium, bismuth, strontium, manganese, aluminum, tin, noricum, indium, thallium, zirconium.

The present invention will be explained in detail below.

Among the aminopolycarboxylic acid iron(1) complex salts, ethylenediaminenishiacetate iron(t) is used in some practical applications.
Contamination by complex salts is not observed in normal processing, and tends to remain in the photosensitive material or paper support when the washing time or amount of washing in the washing process is reduced. color and become contaminated. It is particularly well known that this phenomenon occurs at the edges of color paper.

Furthermore, methods of adding metal ions or soluble complex salts of metal ions and abanopolycarboxylic acid using an aminopolycarboxylic acid iron complex salt as an oxidizing agent are disclosed in Japanese Patent Publication No. 34-180, Japanese Unexamined Patent Publication No. 13418-1983, Japanese Patent Publication No. 53-13418, No. 31134, both methods use ethylenediaminetetraacetic acid iron complex salt as the main oxidizing agent and add metal ions or soluble complex salts of metal ions and abanopolycarboxylic acid, which pose a pollution problem. What's more, it aims to prevent the production of leuco pigments.

Therefore, the present invention uses diethylenetriamine iron pentaacetate [) fiN salt among aminopolycarboxylic acid iron complex salts as an oxidizing agent, and uses the diethylene triamine pentaacetate iron ([) complex salt as an oxidizing agent, especially when yellow staining is extremely large. −
The above-mentioned known example is based on the fact that it was discovered that yellow staining can only be prevented by adding the metal ion of the present invention or a soluble complex salt of a metal ion and an aminopolycarboxylic acid in order to prevent u'-extruded points and yellow staining. The technical philosophy is different from that.

Furthermore, although the yellow stain described above can be prevented from changing by extending the washing time or increasing the amount of water washed, in the case of diethylenetriaminepentaacetic acid complex salt, yellow stain cannot be sufficiently prevented even if the above measures are taken. However, the above-mentioned method poses a big problem when the purpose is rapid treatment or when securing water resources and reducing costs are considered.

The present invention provides a method for extremely preventing yellow staining caused by diethylenetriamineferric pentaacetate complex salt, without increasing the amount of water washing, while maintaining various excellent properties of diethylenetriamineferric pentaacetate ([)R salt. This was achieved after careful consideration.

The diethylene trigone pentaacetic acid (7) complex salt according to the present invention 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 such as triethanol. It is used as amine salt, etc., but potassium salt, sodium salt and ammonium salt are most commonly used. These iron Q [
) At least one type of complex salt may be used, but two or more types can also be used in combination. You can choose which one you want to use,
The choice must be made depending on the amount of silver and silver halide composition of the photosensitive material to be processed, but generally it can be used at lower concentrations than aminopolycarboxylic acid salts, which have a high oxidizing power. For example, the working solution 1 can be used in an amount of 0.01 mol or more, preferably 0.05 mol or more. Note that it is desirable to use the replenisher in a highly concentrated form with the highest solubility in order to achieve high concentration and low replenishment.

The metal ions used in the present invention may be supplied by any method. For example, inorganic salts such as halides, hydroxides, acid salts, carbonates, phosphates, acetates, and aminopolycarboxylic acids.

It can be supplied as a soluble complex salt with a chelating agent such as ox7carboxylic acid, polyphosphoric acid, or organic phosphonic acid.

The metal ions of the present invention can be supplied as the following compounds,
The supply method is not limited to these, and other methods such as supplying as a soluble complex salt, electrical method, etc. may also be used.

<Exemplary compound> A-1My(CH5COO)2.4H20A-2MgC
j2・6H20 A-3Mg5(c6H50y)2・14H20A-4M
g(NO3)2・6H20 A-5MgC20II・2H20 A-6Mg5(Pot)2・5H20 A-7Mgso11・7H20 A -8Ca(CH3COO)2・H20A-9CaC
O3 A-10CaCl2・2) I20 A-11Ca(C6H507)2 ・4H20A-12
Ca(OH)z A 13 CaC4H20II A 14 Ca(NO3)2・4H20A-15B1C
45 A-16B1C6H507 A-17Bi(NO3)5II5H20A-188r(
CH3CO0)2・1/2H20A-198rCO3 A-208rC12Φ6H20 A-215r80u A-22Mn(CH3CO0)2・4H2OA-23M
nCO3・nH20 A-24MnCl2#4HzO A-25Mn(NO3)2-nH2゜A-26Mn5Oq ・nH20 A-27AlCl3・6H20 p, -28Az (NO5h・9H20 A-29AjP014 A-3O5nCt2 e2H20 A-318net++ A-32811804 A -338aC12 A-348a(NO3)2 A-35IH2(SoII)5 A-36InC13 A-37TlC1 A-38TtCNO3)2 A-39Zr(S011)2 ・4H20 These metal 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 in the range of +y 5 X 10 mol to 2 mol, particularly preferably in the range of 3 x 10 8 mol to 1 mol per solution 1.

The bleaching solution and bleach-fixing solution of the present invention can be used at a pH of 2 to 9.5, preferably 4.0 or higher, more preferably 5.0 or higher, and the most preferred pH range is 5.0. It is 5 or more and 9.0 or less. The treatment temperature is 80° C. or lower, preferably 55° C. or lower to prevent evaporation.

The bleaching solution of the present invention contains the diethylenetriaminepentaacetate 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 chelating agents such as polycarboxylic acid, aminopolycarboxylic acid, oxycarboxylic acid, aminocarboxylic acid, polyphosphoric acid, organic phosphonic acid, aminophosphonic acid, phosphonocarboxylic acid, alkali halide or ammonium-ride. For example, it is desirable to contain potassium bromide, sodium bromide, sodium chloride, ammonium bromide, potassium iodide, sodium iodide, ammonium iodide, thiourea, and the like. Additionally, T)H buffers such as borates, oxalates, acetates, carbonates, and phosphates, solubilizers such as triethanolamine, alkylamines, polyethylene oxides, etc. can be added to ordinary bleaching solutions. The bleach-fixing solution of the present invention may contain a diethylenetriaminepentaacetate iron button complex salt as a bleaching agent as described above and a metal ion of the present invention, and may contain a thiosulfate, a thiosulfate, A liquid having a composition containing a silver halide fixing agent such as thiocyanate, thiourea, or thioether and the above-mentioned chelating agent is applied. In addition, a bleach-fixing solution consisting of the bleaching agent of the present invention and a small amount of a halogen compound such as potassium bromide in addition to the above-mentioned silver halogenide fixing agent, or conversely, a bleach-fixing solution containing a halogen compound such as potassium bromide or, conversely, potassium bromide or ammonium bromide may be used. It is also possible to use a bleach-fix solution having a composition in which a large amount of a rogene compound such as the following is added, or a special bleach-fixing solution having a composition in combination with a large amount of a rogene compound such as potassium bromide.

In addition to potassium bromide, the halogen compounds include hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide,
Ammonium bromide, sodium iodide, potassium iodide, ammonium iodide, etc. can also be used.

Included in the bleach-fixing solution - Silver halogenide fixing agents that are not used in ordinary fixing processes - Compounds that react with silver halogenide to form water-soluble complex salts, such as potassium thiosulfate and sodium thiosulfate. Typical examples include thiosulfates such as ammonium thiosulfate, thiocyanates such as potassium thiocyanate, sodium thiocyanate, ammonium thiocyanate, or thioureas, thioethers, and high concentrations of bromide and iodide. It is. These foot adhesives can be used in an amount of 5 g or more, as long as they can be dissolved.

The bleach-fix solution contains boric acid, borax, and
Sodium hydroxide, potassium hydroxide, sodium carbonate,
pHM agents consisting of various salts such as potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide may be contained alone or in combination of two or more. Furthermore, various fluorescent whitening agents, antifoaming agents, or surfactants can be contained. In addition, preservatives such as hydroxyl aban, hydrazine, myelate, isomeric bisulfite, bisulfite adducts of aldehydes and ketone compounds, stabilizers such as nitroalcohol nitrate, solubilizers such as alkanolamines, organic Anti-stinting agents such as amines, additives such as amines, methanol,
An organic solvent such as dimethylformhumide or dimethyl sulfoxide can be appropriately contained.

In the processing method using the processing solution of the present invention, the most preferable processing method is to perform bleaching or bleach-fixing immediately after color development. Fixing treatment -C may also be used, and a pre-bath containing a bleach accelerator may be used as a processing solution prior to bleaching or bleach-fixing.

After bleaching and fixing (or bleach-fixing), stabilization treatment may be performed without washing with water, or washing with water may be performed and then stabilization treatment may be performed. In addition to the above steps, known auxiliary steps such as hardening, neutralization, black-and-white development, reversal, and washing with a small amount of water may be added as necessary. A typical example of a preferred treatment method includes the following steps.

(1) Color development → bleach-fixing → washing with water (2) color development → bleach-fixing → washing with water → washing with water (3) color development → bleach-fixing → washing with water → stable (4) color development → bleach-fixing → stable (5) Color development → washing with water → bleach-fixing → washing with water (6) color development → stop → bleach-fixing → washing with water ゝ, (7) color development → bleaching →
Washing → Fixing → Washing → Stable (8) Color development → Bleaching → Fixing →
Washing with water → stable (9) Color development → bleaching → washing with a small amount of water → footwear → washing with a small amount of water → washing with water → stable (10) color development → washing with a small amount of water → bleaching → washing with a small amount of water → fixation →
Small amount of water → washing with water → stable (11) color development → stop → bleaching → washing with a small amount of water → footwear → small -
m Water washing → Water washing → Stabilization (12) Black and white development → Water washing → Reversal → Color development → Bleaching → Foot wear → Water washing → Stabilization (13) Prehardening → Neutralization → Black and white development → Stop → Color development → Bleaching → Fixation → Water washing →Stable The black-and-white developer used before processing with the processing solution having egg white ability of the present invention is the so-called black-and-white first developer used in the processing of commonly known color photographic materials, or the black-and-white developer used in the processing of color photographic materials, or the black-and-white developer used in the processing of color photographic materials. It is used for processing materials, and can contain various additives that are generally added to black and white developers.

Typical additives include developing agents such as 1-phenyl-3-pyrazolidone, metol and hydroquinone;
Preservatives such as myelate, accelerators consisting of alkalis such as sodium hydroxide, sodium carbonate, potassium carbonate, inorganic or organic inhibitors such as potassium bromide, 2-methylbenzimidazole, methylbenzthiazole, etc. side,
Examples include water softeners such as polyhydric acid salts, and surface overdevelopment inhibitors comprising trace amounts of iodides and mercapto compounds.

The aromatic primary amine color developing agent used in the color developer used before processing with the processing solution having bleaching ability of the present invention includes known ones that are widely used in various color photographic processes. be done. These developers include aminophenol and p-phenylenediamine derivatives. Since these compounds are more multistable than the free state, they are generally used in the form of salts, such as hydrochlorides or sulfates. Further, these compounds are generally used at a concentration of about 0.1 g to about 30 g per color developer 11, and more preferably at a concentration of about 1 g to about 15 g per color developer 11.

Examples of aminophenol-based developers include 0-aminephenol, p-abanophenol, 5-adano2-
Included are oxy-toluene, 2-amino-3-oxy-toluene, 2-oxy-3-avano-1,4-dimethyl-benzene, and the like.

Particularly useful primary aromatic amine color developers include N, N-
A dialkyl-p-phenylenediamine compound,
Alkyl and phenyl groups may be substituted or unsubstituted. Among these, particularly useful chemical compounds include N,N-diethyl-p-phenylenediamine hydrochloride, N-mef-p-phenylenediamine hydrochloride, and N,N-dimefk-p-phenylenediamine hydrochloride. , 2-amino-5-(N-ethyl-N-dobucilla 1
))-Toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline 51f
, acid salt, N-ethyl-N-β-hydroxyethylaminoaniline, 4-amino-3-methyl-N,N-diethylaniline, 4-amino-N-(2-methoxyethyl)-
N-ethyl-3-methylaniline-p-toluenesulfonate may be mentioned.

The alkaline color developer used before the treatment with the processing solution having bleaching ability of the present invention is usually added to the color developer in addition to the above-mentioned primary aromatic aban color developer. various ingredients such as alkali agents such as sodium hydroxide, sodium hydroxide, potassium carbonate, alkali metal sulfites, alkali metal bisulfites, alkali metal thiocyanates, alkali metal halides, benzyl alcohol, diethylenetriaminepentaacetic acid, Water softeners and thickeners such as 1-hydroxyethylidene-1,1-diphosphonic acid can also be optionally included. The pH value of the color developing solution is usually 7 or higher, most commonly about 10 to about 13.

The silver halide color photographic light-sensitive material to which the processing solution having bleaching ability of the present invention can be applied is an internal development method in which a color former is contained in the light-sensitive material (US Pat. No. 2,376,679, Ibid.!2). 801.171), as well as external development methods in which a color former is contained in the developer (U.S. Pat. No. 2.252.718, U.S. Pat. No. 2.592.243, U.S. Patent No. 2. .590.970, Ministry of Specification). Further, as the coloring agent, any coloring agent generally known in the art can be used. For example, a cyan color former is based on a naphthol or phenol structure and forms a diindoaniline dye through coupling, and a magenta color former has a skeletal structure of a 5-pyrazolone ring with an active methylene group. As a yellow color forming agent, those having a benzoylacedoanilide, pivalyl acetanilide, or acylacedoanilide structure having an active methylene chain, with or without a substituent at the coupling position, may be used. Can be used. In this way, as a coloring agent, it is thick! Both a so-called 2-equivalent type cuffler and a 4-equivalent type cuffler can be applied. The silver halide emulsions that can be used include silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, silver chloroiodobromide, or mixtures thereof. Silver halide may be used. Furthermore, as protective colloids for l.silver halide, natural products such as gelatin, as well as various products obtained by synthesis can be used. Silver halide emulsions include
Conventional photographic additives such as stabilizers, sensitizers, hardeners, sensitizing dyes, and surfactants may also be included.

The bleaching solution and bleach-fixing solution of the present invention are applicable to silver halide color photographic films such as color film, color negative film, color positive film, color reversal film for slides, color reversal film for movies, and color reversal film for TV. Can be applied to 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 thereto.

Example 1 A paper support whose surface was coated with a polyethylene layer containing titanium oxide in anatase form as a white pigment was pretreated by corona discharge, and then the following layers were sequentially applied to produce color photographic paper. Had made.

1st layer: as a yellow coating
A blue-sensitive silver chlorobromide emulsion containing silver chloride in a 5 molar range and containing α-vivalyl-2-chloro-5-r-(2,4-di-t-amylphenoxy)butyramide]acetanilide. layer.

Second layer: gelatin intermediate layer containing UV absorbers.

3rd layer: 1- (2,4,6-
A green-sensitive silver chlorobromide emulsion layer containing dolichlorophenyl 1-3-(2-chloro-5-octadecenylbuccinimidoanilino)-5-pyrazolone and containing 15 molar width of silver chloride.

4th layer: gelatin middle layer same as 2nd layer.

2,4-dichloro-3- as the fifth layer dian coupler
A red-sensitive silver chlorobromide emulsion layer containing methyl-6-(r-(2,4-cyamylphenoxy)butyramide)phenol and containing 15 molar width of silver chloride.

6th layer: gelatin protective layer.

Each of the above photosensitive emulsion layers has a total silver content of 100 - equivalent #)
It was coated to give a coating thickness of 10 cm. The /S silver halide photographic emulsions used in each light-sensitive emulsion layer were chemically sensitized using sodium thiosulfate, and conventional additives such as stabilizers and sensitizing dyes were added. Further, a hardening agent and a spreading agent were added to the coating solution for all layers.

Print the colored photographic paper made as above (
After 7 cycles), continuous replenishment processing was performed using a roll-type automatic developing machine (hereinafter referred to as self-developing running processing).

Self-development running processing process Processing temperature (to) Processing time (minutes) 1, color development 33±0.3 3.5 2, bleach-fixing 30-34 1.5 3, washing with water 30-34 3.5 4, drying 75 ~85 Among the above processing steps, for color development and bleach-fixing, each sample was treated with a color development replenisher and a bleach-fix replenisher for 12 minutes.
Each was continuously replenished at a rate of 325- after each treatment. The color development replenisher and color development solution used are as follows.

[Color developer replenisher]

Benzyl alcohol 20m Ethylene glycol 20- Fluorescent brightener (4,4'-diaminostilbendisulfonic acid derivative) 20g Hydroxyamine sulfate 4.0g 3-Methyl-4amino-N-ethyl-N-(β-methanesulfonamide) ethyl)aniline sulfate 7.0g Charcoal-dispersed potassium 30g 1-hydroxyethylidene-1,1-diphosphonic acid (6
11- Potassium myelate (50ml solution) 5- Potassium hydroxide 3.0g After finishing the total amount to 1t, add potassium hydroxide as appropriate to adjust pT (10.40) .

Color developer: Add the following color development starter to 8OO- of the above color developer replenisher and add water to make 11.1 ton of color developer with a pH of 10°20 will be obtained. It was created and used as appropriate.

[Color development starter]

Potassium carbonate 2.2 g Potassium hydrogen carbonate 3.4 g Potassium bromide 0.64 g Potassium chloride 0.50 g The bleach-fix solution and bleach-fix replenisher used were as follows.

[Bleach-fix solution and bleach-fix replenisher (1)] Ethylenediaminetetraacetic acid iron Q[) complex salt 70g Ethylenediaminetetraacetic acid 20g Ammonium sulfate (50% solution) 30-ammonium thiosulfate (70% solution) 140me ammonium ammonium solution) 30td aqueous ammonia or p with acetic acid
Finish it so that it becomes H7.0 and the total amount is 1 ton.

[Bleach-fix solution and bleach-fix replenisher (2)] Diethylenetriaminepentaacetate iron (1) Ammonium 80g Diethylenetriaminepentaacetate Cl 24g Ammonium sulfite (
50 solution) 30-Ammonium thiosulfate (701 solution) 140d ammonia water (28 width) solution 30- Adjust the pH to 7.0 with ammonia water or acetic acid,
Also, finish it so that the total amount is 11.

Using the bleach-fix solution and the bleach-fix replenisher (1) and (2), perform a self-development process until the number of months each bleach-fix replenisher is used becomes twice the tank capacity of the bleach-fix bath,
Collect 3 to 5 meters of color photographic paper at the end of the run, cut the edges into 5-inch pieces, then roll tightly into a roll.
The blue reflection density at the edge was measured, and this was taken as the contamination characteristic of the edge.

Also, water θ′1 aquascape is 7t/lr? and 300 m/i. Furthermore, in order to examine the effect of containing metal ions in the present invention, 6.0 g/7 of the metal compounds shown in Table 1 were added to the bleach-fix solution (1) and the bleach-fix replenisher (2), and the above-mentioned It was evaluated using various methods.

Table 1 As is clear from Table 1, the diethylene triamine 7 pentaacetic acid m iron l) R salt has extremely high contamination at the edges compared to the ethylene diavantetraacetic acid iron (II) complex salt, and the amount of water used for washing is extremely large. This tendency becomes even more pronounced as the number decreases. Metal compound (A-2) in the iron (1) complex salt of ethylenediaminetetraacetate
Even when the solution is added, there is no change in the contamination at the edges, whereas the bleach-fix solutions of the present invention (K materials 4 to 13) have less contamination at the edges than the diethylenetriaminepentaacetic acid complex salt (Na 3 ). The contamination of
It can be seen that the inhibitory effect is greater than that of complex salts.

In addition, the OpH of the tank liquid used (sample Nα1 to 13) was varied from 5.0 to 9.0, and a piece treatment device was used to
The desilvering completion time, the maximum red transmission density (cyan dye density), and the minimum green reflection density (Mazenkstein) were measured. The bleach-fix solution of the present invention (Na4-13) to which the metal compound was added gave similar results to the bleach-fix solution (Na3) to which no metal compound was added.

Example 2 1- Ri-2 Kaniy-II film [manufactured by Konishiroku Photo Industry ■] 1500rt? After photographing using a Konica FS-T (manufactured by Konishiroku Photo Industry Co., Ltd.), 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 film automatic developing machine type H4-220W-2 manufactured by Noriso Koki Co., Ltd. with 41 machines.

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

[Color developer]

[Color development replenisher] [Bleach-fix solution and bleach-fix replenisher (1)] Iron ethylenediaminetetraacetate (1) ammonium dihydrate 20 g - [Bleach-fix solution and bleach-fix replenisher (2)] [Bleach-fix solution and bleach-fixing replenisher c3)] [Stable solution] [Stable replenisher] The color developing replenisher is replenished into a 15 ml color developing bath per 100 cd of color negative film, and the bleach-fixing replenisher is replenished into a 15 ml color developing bath per 100 cd of color negative film. A stable replenisher is added to the bleach-fix bath, and a stable replenisher is added to the color negative film.
11 - The stability bath was replenished. Further, 30 times of color negative film was poured into the washing bath.

Bleach-fixing and bleach-fixing replenisher (using 11 to (3),
Each film was continuously replenished for 1500 m. After each running process was completed, the bleach-fix tank solution was stored in a tightly closed refrigerator. After all self-development and running processes are completed, adjust the p)I of bleach-fix tank solutions (1) to (3) to the values shown in Table 2, perform manual processing, and complete blue transmission density (contamination degree) and desilvering. The time, that is, the clearing time, was measured, and the maximum red density (cyan dye density) and minimum green density (magentastin) of the film obtained by bleach-fixing for 35 minutes were measured. Table 2 shows the results for time only. However, the blue transmission density was measured after complete desilvering to distinguish it from an increase in blue density due to poor desilvering.

The processing conditions were the same as those for the self-development running process except for the bleach-fixing processing time, and the processing solution used had the same composition as the self-development running process except for the bleach-fix solution. The treated samples used were those cut into pieces from Teklacolor film (manufactured by Konishiroku Photo Industrial Co., Ltd.) and subjected to model exposure according to a conventional method.

For comparison, a sample treated with Sukura Color Negabusses CNK-4, which is a standard treatment, was similarly measured. However, the desilvering treatment time was 6 minutes 30 seconds for bleaching and 6 minutes 30 seconds for fixing.

As is clear from the results in Table 2, metal compounds (A-t
The bleach-fix solution (3) of the present invention to which a soluble complex salt of 5) and ethylenediaminetetraacetic acid is added has a minimum blue density of 0 in the standard treatment compared to the bleach-fix solution (2) to which no metal compound is added.
．． 67, indicating that contamination by diethylenetriaminepentaacetic acid complex salts is largely prevented. or,
Regarding the clearing time, good results were obtained as there was no influence at all due to the addition of the complex salt of the metal compound of the present invention and the chelating agent.

Furthermore, the maximum red density (cyan dye density) and minimum green density (magenta tin) of the film obtained after bleach-fixing for 35 minutes, and the number of days until silver sulfide formation were observed.
There were no adverse effects due to the addition of metal compounds.

Patent applicant Konishiroku Photo Industry Co., Ltd. Representative Patent Attorney Nobuaki Sakaguchi (1 other person)

Claims (1)

[Scope of Claims] Bleaching for silver halide color photographic light-sensitive materials, characterized by containing a diethylenetriamine iron pentaacetate complex salt and at least one metal ion selected from the following metal ion group: processing liquid with the ability to [Metal ions] Magnesium, calcium, bismuth, strontium, manganese, aluminum, tin, barium, indium, thallium, zirconium.