JPS606949A - Processing solution capable of bleaching silver halide color photosensitive material - Google Patents

Abstract

PURPOSE:To prevent deterioration of silver bleaching power even after long-time continuous operation and leuco conversion of a cyan dye by incorporating diethylenetriamine pentaacetate iron (III) complex salt, specified metal ions, and a chelating agent except this complex salt. CONSTITUTION:A bleaching soln. and a bleach fixing soln. contain a diethylenetriamine pentaacetate iron (III) complex salt, preferably, K, Na, or NH4 salt, and ions of at least one kind of metal selected from a group Ni, Co, Zn, Ce, Ru, Y, and Sm, and a chelating agent except said complex salt. Ones usable effectively for this agent is aminocarboxylic acids, such as dihydroxyethylglycine, ethylenediaminetetraacetate, and triethylenetetraminehexaacetate.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a processing liquid having a whitening ability for use in /%O silver genide color photographic light-sensitive materials. More specifically, the present invention relates to an effective bleaching solution and egg white fixing solution for silver halide color photographic materials, which have improved various processing performance and solution properties.

[Prior art]

Generally, in order to obtain a color image by processing an imagewise-exposed silver agenide color photographic sensitizer 41, after a color development process, the generated metallic silver is treated with a processing solution having 1912 whitening ability. A processing step is provided.

Bleaching solutions and bleach-fixing solutions are known as processing solutions having brightening ability. When a bleaching solution is used, a step of fixing the silver halide with a fixing agent is usually added after the bleaching step, but with a bleach-fixing 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 that have bleaching ability in processing silver halide color photographic light-sensitive materials. .

However, some serious drawbacks have been pointed out to processing solutions containing these inorganic oxidizing agents. Although it is relatively good in this respect, there is a risk that it will decompose when exposed to light and produce heptadan ions and hexavalent chromium ions that are harmful to the human body, which is an unfavorable property in terms of pollution prevention. Because these oxidizing agents have extremely strong oxidizing power, it is difficult to coexist with silver halide solubilizers such as thiosulfate in the same processing solution, and it is difficult to use these oxidizing agents in bleach electrodeposition baths. This makes it difficult to achieve the goal of speeding up and simplifying the process.
It has 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, are used as oxidizing agents, as they have fewer pollution problems and meet the demands of speeding up and simplifying treatment, and enabling the reuse of waste liquids. 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(III) complex salt of ethylenediaminetetraacetate, which is considered to have a strong bleaching edge among the metal complex salts of Ryominopolycarboxylic acid, has been put into practical use as a bleaching solution and a bleach-fixing solution, but High-sensitivity silver halide color photographic materials based on silver and silver iodobromide emulsions, especially...Color paper for photography and color negative film for photography containing silver boroide as silver agenide, Color River length Rufilm lacks a bleaching blade, leaving traces of image silver even after long processing times, resulting in poor desilvering performance.

This tendency is particularly noticeable in a bleach-fix solution in which an oxidizing agent, thiosulfate, and 11fi sulfate coexist because the redox potential decreases.

On the other hand, despite great efforts to develop bleaching accelerators to increase the silver whiteness of whitening solutions or bleach-fixing solutions containing metal complexes of organic acids, satisfactory results have not yet been achieved. The reality is that we are not getting it.

The present inventors have discovered iron diethylenetriaminepentaacetate ([1 complex salt) as an oxidizing agent that has excellent oxidizing power particularly in the high pH region among aminopolycarboxylic acid metal complex salts. Bleach and bleach-fix solutions that use complex salts as oxidizing agents have a rapid silver bleaching reaction when the pH is 4 or higher, especially 7 or higher, produce less staining when directly bleached, and have long been storage stable bleach-fix solutions. However, when this bleach solution is used as a bleach-fix solution and is continuously processed in an automatic processor, it causes deterioration of the silver source white blade and leuco formation. It has become clear that when bleaching or bleach-fixing processing is applied, the color of the N'an dye is not sufficiently developed, which is called defective color recovery. This occurs significantly during continuous processing.

As a result of repeated studies on the causes of these occurrences, the present inventors found that the diethylenetriaminepentaacetic acid iron ([I) complex salt produced by the silver bleaching reaction was not sufficiently oxidized to the diethylenetriaminepentaacetic acid iron ([I) complex salt] by gas oxidation. , therefore diethylenetriaminepentaacetate iron (II) complex J:! It has been found that the above-mentioned problems arise due to the accumulation of Therefore, in order to put the diethylenetriamine iron pentaacetate (11) complex into practical use as a bleaching solution or a bleach-fixing solution, a technology that significantly accelerates the air oxidation rate of the diethylenetriamine iron pentaacetate (11) complex salt is strongly desired.

[Purpose of the invention]

An object of the present invention is to have a whitening ability for a silver halide color photographic light-sensitive material that is equipped with a rapid Sa white blade and does not cause deterioration of the silver source white blade or A-equalization of cyan dye even when subjected to long-term continuous processing. The objective is to provide a processing solution.

[Structure of the invention]

As a result of intensive research, the present inventors have found that the above object contains diethylenetriaminepentaacetic acid iron (II complex salt) as an oxidizing agent, and at least one of the following metal ions and a chelating agent other than diethylenetriaminepentaacetic acid (hereinafter referred to as the present invention). It has been found that this can be achieved by a !4 white liquor and a bleach-fix solution containing a chelating agent).

<Metal ions> Nickel, cobal), IIL cerium, ruthenium,
Indrium, Pumarium.

In general, the &l white ability of amine polycarboxylic acid iron (lil) complex salt is expressed as aminopolycarboxylic acid iron Gl[)! Oxidizing power of salt, concentration in treatment solution, iron content in treatment solution) complex salts and iron ()
It is known that it is determined by the ratio of complex salts, etc.

On the other hand, it is said that the a-equalization of cyan dyes occurs when the iron (II) complex salt produced by the silver false whitening reaction reduces the dye. As the concentration of (Il[) complex salt increases, iron(Il[)
[It is reoxidized by the complex salt and restores its color to a pigment.

Therefore, in order to increase the silver bleaching ability and prevent cyan dye from becoming a-equal, it is necessary to use silver or a-co color pigment to increase the oxidizing power and iron ([D complex salts are easily exposed to iron ([1 complex salts]). However, diethylenetriaminepentaacetic acid iron(f) complex salt needs to have the property of being easily oxidized by ethylenediaminetetraacetic acid iron(f), which is commonly used as a bleaching agent.
Compared to complex salts, the oxidizing power of silver and the oxidizing power of leuco-formed pigments to pigments are higher, and the corresponding iron (ffl) complex salts have a higher oxidizing power than that of silver and leuco-formed pigments. Despite the fact that the cyan dye is highly a-equalized, when it is continuously processed using an automatic processor, it causes a decrease in the silver deep white edge and a significant failure in color recovery.

As a result of repeated investigations into this cause, we found that diethylenetriaminepentaacetate iron (ff) complex salt has an extremely slow air oxidation rate, and when continuously treated, iron (
II) It has become clear that the accumulation of M salt causes deterioration of the white silver blade and poor color restoration.

In other words, when iron ethylenediaminetetraacetate, which has been partially put into practical use, is processed in an automatic processing machine, the iron complex salt produced by the bleaching reaction is released into the air on the surface of the processing solution tank of the automatic processing machine. Iron θff) &+ is oxidized to a It has been found that the air oxidation rate of the iron pentaacetate ([1] complex salt is extremely slow, approximately 1710 times that of the ethylenediaminetetraacetate iron ([1) complex salt), and therefore cannot be sufficiently oxidized by such a conventional air oxidation method.

The present invention maintains various excellent properties of the diethylenetriaminepentaacetic acid iron (2) complex salt, while maintaining the corresponding iron (I) complex salt.
This method was completed as a result of various studies to promote the 9-gas oxidation of ll complex salt to iron[) complex salt.

The diethylenetriamine pentaacetic iron (1) 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 triethanolamine. It is used as a salt, etc., but potassium salt, sodium salt, and ammonium salt are preferably used. These iron G
[l! At least one type of salt may be used, but two or more types can also be used in combination. The sound used can be selected arbitrarily and must be selected depending on the amount of silver and silver halide composition of the photosensitive material to be processed, but it is generally used at a lower concentration than other aminopolycarphonates because of its high oxidizing power. can. For example, it can be used in an amount of 0.01 mol or more per 11 working liquids, preferably 0.05 mol or more. In addition, in the replenisher, it is desirable to use it in a highly concentrated form with the highest solubility in order to achieve low concentration and low replenishment.

The metal ions used in the present invention may be supplied by any method. For example, it can be supplied in any form such as agenide, waterline compound, sulfate, carbonate, phosphate, acetate, etc., but it is particularly effective to supply it with the following compounds ( Hereinafter, the metal compound that supplies these metal ions of the present invention will be referred to as the metal compound of the present invention.)

However, it is not limited to these supply methods;
Other methods such as electrical methods may also be used.

Example 1 Water compounds> (A-1) Zinc chloride (A-2) Zinc bromide (A-3) Zinc sulfate (A-4) Bent lead nitrate (A-5) Disodium chloride (A-6) Nitric acid Nickel (A-7) Nickel sulfate (A-8) Nickel acetate (A-9) Nickel bromide (A-10) Nickel iodide (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) Indium sulfate (A- 20) Indium nitrate (A-21) Yttrium chloride (A-22) Indium fluoride (A-23) Samarium chloride (A-24) Samarium bromide (A-25) Samarium sulfate (A-26) Samarium carbonate (A-27) Samarium nitrate (A-28) Samarium acetate These metal compounds of the present invention may be used alone, or two
More than one species can also be used together. The amount used is 1 liquid
The amount is preferably from 1 mole to 2 moles, particularly preferably from 0.001 mole to 1 mole.

As the chelating agent of the present invention, dicarboxylic acids, polycarboxylic acids, oxycarboxylic acids, aminocarboxylic acids, polyphosphoric acids, organic phosphonic acids, aminophosphonic acids, phosphonocarboxylic acids, etc. can be used, but in particular, the aminocarboxylic acids shown below are used. Acids are used effectively.

<Exemplary compound>(B-'1) Dihydro aquinethylclean (B-2)
Iminoniacetic acid (B-3) Methyliminodiacetic acid (B-4) Ethyliminodiacetic acid (B-5) Butyliminodiacetic acid (B-6) Human axyethyl iminodiacetic acid (B-7)
Nitri-a triacetic acid (B-8) Nitri-a diacetic acid propionic acid (B-9)
Nitri-a-tripropionic acid (B-10) Ethylenediaminediacetic acid (B-1,1)
Ethylenediamine nib apionic acid (B-12) Ethylenediamine diorthohydroxyphenylacetic acid (B-13) Human mixyethylethylenediaminetriacetic acid (B-14) Ethylenediaminetetraacetic acid (B-15)
Diaminobu-a-panoltetraacetic acid (B-16) Diaminobab-a-panoltetraacetic acid (B-17)) Lance-Schiff a-hekipundiaminetetraacetic acid (B-18) Chrycol ether diaminetetraacetic acid (B-18)
-9)) Liethylenetetraminehexaacetic acid These chelating agents of the present invention are free acids, alkali metal salts such as sodium salts, potassium salts, and lithium salts, or ammonium salts, or water-soluble amine salts such as triethanolamine salts, etc. used as. At least these guys are Ifl! I
It is also possible to use two or more types of the first type of f used in combination.

The amount used is preferably 0.0001 mol to 2 mol, particularly preferably 0.001 mol to 1 mol, per 1 working solution.

Note that when diethylenetriaminepentaacetic acid is used in place of the chelating agent of the present invention, the air oxidation of diethylenetriaminepentaacetic acid iron (ff) complex salt to iron (11 complex salt) cannot be promoted. Pentaacetic acid is excluded from the chelating agents of the present invention, but when diethylenetriaminepentaacetic acid and the chelating agent of the present invention are used in combination, the present invention That is, in the present invention, as long as at least one of the chelating agents of the present invention is added, the diethylenetriaminepentaacetic acid may or may not be added.

The metal compound and chelating agent of the present invention can be added separately as described above, or can be added as a metal chelate compound.

The bleaching solution and bleaching 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, preferably 5.0 or more.
．． 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 whitening solution of the present invention contains diethylenetriaminepentaacetic acid iron 1)g salt as a bleaching agent as described above, the metal ion of the present invention, and a chelating agent, and may also contain various additives. As additives, it is particularly desirable to include alcasino 1lide or ammonium halide, such as potassium bromide, sodium bromide, sodium chloride, ammonium bromide, potassium iodide, sodium iodide, ammonium iodide, thiourea, etc. . In addition, pH buffering agents such as borates, oxalates, acetates, carbonates, and phosphates, solubilizing agents such as triethanolamine, alkylamines,
Those known to be added to electrical bleaching solutions, such as polyethylene oxides, can be added as appropriate.

The bleach-fix solution of the present invention contains iron diethylenetriaminepentaacetate (11 complex salt) as a bleaching agent, the metal ion of the present invention, and a chelating agent, and also contains thiosulfate, thiocyanate, thiourea, thioethers, etc. /%
A solution having a composition containing a silver oxide bonding agent is applied. In addition, a bleach-fixing solution containing a small amount of a halogen compound such as potassium bromide in addition to the whitening agent of the present invention and the silver halide fixing agent described above, or conversely, a halogen compound such as potassium bromide or ammonium bromide may be used. It is also possible to use a bleach-fixing solution consisting of a composition in which a large amount of a compound is added, or a special bleach-fixing treatment consisting of a composition consisting of a combination with a large amount of a halogen compound such as embodied potassium.

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

The SO silver genide fixing agent (included in the bleach-fix solution) is a compound that reacts with silver chloride used in normal fixing processing to form a water-soluble complex salt, such as potassium thiosulfate and sodium thiosulfate. Typical examples include thiosulfates such as ammonium thiocyanate, potassium thiocyanate, sodium thiocyanate, thiocyanates such as ammonium thiocyanate, thioureas, thioethers, and high concentrations of bromides and iodides.

These fixing agents can be used in an amount of 5 g/or more, as long as they can be dissolved.

As with the concentrated white solution, the bleach-fix solution contains boric acid, borax,
Sodium hydroxide, potassium hydroxide, sodium carbonate,
pH buffering 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. In addition, various types of fluorescent whitening agents, antifoaming agents, or surfactants can be contained in the coating. Also, droxylamine, dorazine, isostatic acid salts, isomeric monovalent sulfates, aldehyde and ketone compounds.
Preservatives such as sulfuric acid adducts, stabilizers such as alcohol nitrates, solubilizers such as γ-lkanolamine,
Anti-stinting agents such as organic amines, other additives, and organic solvents such as methanol, dimethylformamide, and dimethyl sulfoxide may be appropriately contained.

In the processing method using the processing solution of the present invention, it is preferable to perform bleaching or bleach-fixing immediately after color development. Bleach-fixing may be performed, or a pre-bath containing a bleach accelerator may be used as a processing solution prior to bleaching or bleach-fixing.

After the whitening and fixing (the father is fixing with egg white), stabilization treatment may be performed by washing with water, or washing with water and then stabilization treatment may be performed. In addition to the above-mentioned steps, known auxiliary steps such as hardening, neutralization, black-and-white development, reversal, and washing with water may be added as required. A specific example of a preferred treatment method includes the following steps.

fl) Color f#, image → bleach-fix → water wash (2) color development → bleach-fix → small water wash → water wash (3) color development → bleach-fix → water wash → stable (4) color development → white fix → stable ( 5) Color development → washing with water → bleaching and fixing → washing with water (6) color development → stop → white fixing → washing with water (power color development → bleaching → washing with water →
Fixing → Washing → Stabilization (8) Color development → Bleaching → Fixing → Washing →
Stable (9) Fading development → bleaching → washing with a small amount of water → fixing・→passive・
Washing with water → Washing with water → Stable (10) Color development image → Washing with Sakura water → Bleaching → Washing with a small amount of water → Fixation →
Wash with a little water → Wash with water → Stabilize (11) Color development → Stop → Bleach → Wash with a small amount of water → Fix - → Wash with small lid → Wash with water → Stabilize (12) Black and white development → Wash with water → Reversal → Color development → Clear white → Fix → Wash with water → Stable (13) Predural mater → Neutralization → Black and white dust image → Stop → Color development → Bleaching → Fixation → Water 6. → Stability Black and white developer Fi used before processing with the processing solution having brightening ability of the present invention. This liquid is called a retaining liquid or is used for processing black-and-white military photosensitive materials, and can contain various additives that are generally added to black-and-white developing solutions.

Typical additives include image agents such as 1-phenyl-3-pyrazolidone, metol and hydroquinone;
preservatives such as 0 sulfates, accelerators consisting of alkalis such as sodium hydroxide, sodium carbonate, and potassium carbonate, and inorganic or organic accelerators such as potassium bromide, 2-methylbenzimidazole, and methylbenzthiazole. Inhibitors, water softeners such as polyphosphates, surface overdevelopment inhibitors consisting of characteristic iodides and mercapto compounds, etc. may be mentioned.

The aromatic primary amine color-forming crude drug used in the color developing solution used before the processing with the processing solution having whitening ability of the present invention is a known herbal medicine that is widely used in various color photographic processes. Includes: These developers include aminophenol and p-phenylenediamine derivatives. These compounds are more multistable than in the free state and are therefore generally used in the form of salts, reportedly hydrochlorides or sulfates. The compound of Kakita, et.
Use at a concentration of

As a γ-minophenol thread developer, f! For example, 〇-aminophenol, p-aminephenol, 5-amino-2-oxy-toluene, 2-amino-3-oxo-
toluene, 2-oxy-3-amino-1,4-dimethyl-benzene, etc. Particularly useful primary aromatic amino yarn color developers include N,N-dialkyl-p-phenylenediamine compounds. and the alkyl group and phenyl group may be substituted or unsubstituted. Among them, examples of particularly useful compounds include N,
N-diethyl-p-phenylenediamine hydrochloride, N-#
f-syl--phenylenediamine hydrochloride, N,N-dimethyl-p-phenylenediamine hydrochloride, 2-amino-5-
(N-ethyl-N-dodecylamino)-)luene, N-
Ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline m< acid salt, N-ethyl-N
-β-hydroxyethylaminoaniline, 4-amino-
Mention may be made of 3-methyA, -N,N-diethylaniline, 4-amino-N-(2-methoxyethyl)-N-ethyl-3-methylaniline-p-)luenesulfonate fxE'c.

The alkaline color developer used before the treatment with the processing solution having bleaching ridges of the present invention is usually added to the color developer in addition to the above-mentioned primary aromatic amine color developer. Various ingredients, such as alkaline agents such as sodium hydroxide, sodium carbonate, potassium carbonate, alkali metal bent sulfates, alkali metal bent sulfates, alkali metal thionanates, alkali metal a-genides, benzyl alcohol, It may optionally contain a water softener and thickener such as diethylenetriaminepentaacetic acid, ``-hydroxyethylidene-1,1-diphosphonic acid, etc.The pH value of this color developing solution is usually 7 or higher. , most commonly about 10 to about 13.

The halogenated &lJ color photographic light-sensitive material to which the processing liquid having bleaching ability of the present invention is applied is produced by an internal development method (U.S. Pat.
No. 9, see No. 2.801, 171), as well as
External development method in which a color former is contained in the developer (U.S. Pat. No. 2.252.718, U.S. Pat. No. 2.592.24)
No. 3, see specification number 2.590.970). Further, as the coloring agent, any coloring agent generally known in the art can be used. For example, cyan color formers are based on a naphthol or H phenol structure and form an indoor yellow color complex by camplinking, magenta color formers have a skeletal structure of a 5-bigron ring having an active methylene group, As the yellow color forming agent, those having a benzoylacedoanilide, bivalylacetanilide, or acylacedoanilide structure having an active methylene chain, with or without a substituent at the camp link position, can be used. Thus, as the coloring agent, both the so-called 2-equivalent type coupler and the 4-equivalent type coupler can be applied. Silver emulsions that can be used include silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, silver chloroiodobromide, or mixtures thereof. It is also possible to use a silver halide such as silver halide. Furthermore, as protective colloids for the halogen arsenic such as and fl, natural products such as gelatin, as well as various products obtained by synthesis can be used. The silver agenide emulsion may contain electrically conductive photographic additives such as stabilizers, sensitizers, hardeners, sensitizing dyes, and surfactants.

The crystal whitening solution and whitening fixing solution of the present invention can be used for color paper, color negative film, color positive film, color reversal film for slides, color reversal film for movies, color reversal film for TV, color reversal paper, etc.
Silver germide can be applied to color photosensitive materials.

[Example 1] The present invention will be described in detail below by way of example, but the embodiments of the present invention are not limited thereto.

Example 1 An egg white constant solution was prepared as follows.

[? Self-sufficiency layer solution (1 noko [dense white fixer (2)] Furthermore, adjust white fixer (3) ~ 061, which is made by adding Yuzu Kire-1-shape and metal compounds to Senpaku Teifu solution (2). did.

Soft white fixer ti) ~ 06) is whitened and whitened in a nitrogen stream 1
After adding 5 g of silver powder to this and converting a part of the iron (IiIIIjl salt) into iron (11) complex salt, the supernatant liquid bath 507 was transferred to 201
) By placing the mixture in a nrl beaker and standing at 33°C, the ethylenediaminetetraacetic acid iron(2) complex salt and the diethylenetriaminepentaacetic acid h'noiron(lII) complex salt were quantified, and the air content of the corresponding iron(11) complex salt was determined. The initial rate of oxidation was measured.

The results are shown in Table 1 below.

1 margin As is clear from Table 1 above, the air oxidation rate of diethylenetriamine iron pentaacetate (ff) complex salt is usually extremely slow compared to that of ethylenediamine tetraacetate iron (ffl complex salt). It can be seen that the bleach-fix solution has an air oxidation initial rate constant higher than that of the ethylenediaminetetraacetic acid iron (ff) complex salt.

Next, bleach-fix solutions (1) to (11r in 1e + starch solution 11 in which 140 g/7 of ammonium bromide was added in place of ammonium sulfate and ammonium thiosulfate and the pH was adjusted to 6.5) to ae were prepared. The initial rate constant of air oxidation was measured using the same procedure as above, and almost the same results were obtained.

Example 2 Bukura Color ■ Film [manufactured by Konishiroku Photo Industry ■] 10
00 n? After photographing using a Konica FS-1 [manufactured by Konishiroku Photo Industry Co., Ltd.], continuous replenishment processing (hereinafter referred to as self-processing running processing) is performed using an automatic tax imager according to the following processing steps.

) The automatic WJ imager used was a modified hanging type automatic film processor type H4-220W-2 manufactured by Norlin Koki.

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

[Color development liquid]

[Color development replenisher] [Bleach-fix solution and bleach-fix replenisher (1)] [Bleach foot fixing solution and bleach-fix replenisher (2)] [Bleach fixer and film white foot fixer replenisher (3)] [Bleach-fix solution and bleach-fix replenisher (4)
[Slow whitening fixer and whitening fixer replenisher (5)] [Stabilizer] [Stable replenisher] The color development replenisher is a color negative film 100-1
5-The color developing bath is replenished, and the bleach-fixing replenisher is used for color negative film]0〇-This,! l) The 9 d bleach-fix bath is replenished and the stable replenisher is added to the color negative film 1.
11 per 00 cJ was replenished into the stabilizing bath. In addition, in the washing bath, water is filled with 100 color negative films and 1 comb.
50 go flowed.

Using bleach-fixing and bleach-fixing replenisher fil~(5),
Each film was continuously replenished for 1000 m. After each run was completed, the bleach-fix tank solution was stored in a tightly closed refrigerator. After all self-development running processes are completed, the pH of the bleach-fixing tank solution fil~(5) is adjusted to the value shown in Table 81!2, and processing is performed using a piece processing device (hereinafter referred to as manual processing). The desilvering completion time, ie, the clear link time, was measured, and the maximum red density (cyan dye density) of the film obtained by further 30 minutes of self-sufficiency treatment was measured, and the results are shown in Table 2.

The processing conditions were the same as those for the self-dumping process, except for the bleach-fixing process time, and the processing solution used had the same composition as the self-cleaning process, except for the white fixing solution. did. The processed sample was the same film used for the self-development run process, cut into pieces, and subjected to 11# pattern exposure according to a conventional method.

For comparison, a sample treated with Jyukura Color Negative Process 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 margin Kf below and the results in Table 2, the clear link time is short in the bleach constant 'M solutions (3) to (5) of the present invention, and the red crystal concentration is almost the same as 263 in the standard treatment. It can be seen that they match and there is virtually no problem. On the other hand, with bleach-fixing IFj (II and (2)) other than those of the present invention, both the clear link time and the red color randomness cannot be satisfied.

In addition, in the automatic pickling liquids (3) and (5) of the present invention,
When treated in the same manner with the only difference that diethylenetriaminepentaacetic acid (5 g! to 15 g) was used in place of the chelating agent of the present invention, the result was substantially the same as the self-sufficient pickling solution (2) outside the present invention.

Example 3 White Mill 1 A paper support whose surface was coated with a polyethylene layer containing anatase-type titanium oxide was treated with corona/7-electrode, and then the following layers were sequentially applied. I set it up and made color photographic paper.

8i! II@: α-[4-(l
-benzyl-2-phenyl-3,5-dioxo-1,2
,4-triacylysyl)]-]α-vivalyl-2-chloro-5-r-(2,4-di-t-amylphenoxy)butyramide]acetani')tf: contains 5 moles of silver chloride. Sensitive silver chlorobromide emulsion L 2nd layer: Gelatin intermediate layer containing an ultraviolet absorber.

3rd layer: Contains 1-(2,4,6-tricao phenyl)-3-(2-chloro(+-5-octadecenyl pucunniimidoanilino)-5-vilazo a) as a magenta coupler. and a green-sensitive silver chlorobromide emulsion layer containing 15 molar silver chloride.

4th XJ: 2nd layer and rolled gelatin middle layer.

2°4-jikuo as the 5th layer nitrogen coupler.

-3-Methyl-6-[γ-(2,4-cyamylphenoxy)butyramide]phenol-containing '44' L, 15
Red-sensitive salt Jj containing silver chloride of moles! : (Arsenal emulsion layer.

6th Layer: Gelatin Retaining Layer Each of the photosensitive emulsion layers described above was prepared so that the total silver filling was 10 mg/100 crl. The 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.

The color photographic paper (roll form) produced as described above was photoprinted and then subjected to a self-explanatory running process using an automatic roll developing machine. [Standard processing process] The composition of the processing solution is as follows.

[Color developer]

[Color development replenisher] [Bleach solution and bleach replenisher (1)] [Bleach solution and bleach replenisher (2)] [Bleach solution and bleach replenisher (3)] [Sinking solution and bleach replenisher ( 4)] [Concentrated white solution and bleach replenisher (5)] [Fixer] [Fixer replenisher] Color developer replenisher and bleach replenisher are used for color photographic paper],
3.2-h per 00 ca is replenished into the color developing bath, and the fixing replenisher is added to the color photographic paper I L) Oad per 0
, 7 m7! The washing bath was refilled with 100 combs of 100 aA color photographic paper. In addition, C (adjust the squeeze before and after self-cleaning and foot bathing, and use color photographic paper.

100 - Bringing in and taking out l of liquid per unit (J, 5
It was dark.

Using the bleaching solution and the bleaching replenisher (5), a self-running process was carried out until the amount of each bleaching replenisher was four times the volume of each tank of the bleaching bath. After each individual run process was completed, the bleach tank solution was stored in a tightly closed refrigerator. After completing all the processes, bleach tank liquid +11~ (
5) Adjust the pH to the value shown in Table 3 and treat with beetles.
Measure the desilvering completion time, that is, clearing time, and record 2
The maximum red transmission density (cyan dye density) of the color photographic paper obtained by the minute bleaching process was measured, and the results are shown in Table 3.

The processing conditions were the same as those for the automatic running process, except for the bleaching time, and the processing liquid used had the same composition as the automatic running process, except for the bleaching solution. The processed sample used was one in which the color photographic paper used in the self-development running process was cut into pieces and exposed to model light according to a conventional method.

As is clear from the results in Table 3 below, the bleaching solution of the present invention (3
It can be seen that 1, (41 and (5)) have extremely good performance with short clearing time and extremely high red crystalline transmission density.On the other hand, whitening liquids fil and (
With 2), both the clearing time and the red color gradient transmission density cannot be satisfied.

In addition, in the whitening solutions (3) and (5) of the present invention, diethylenetriaminepentaacetic acid (
When treated in the same manner with the only difference being that 8g or ]Og) was used, the results were substantially the same as bleaching solution (2) outside the present invention.

Abuse applicant: Konishi Rokushapei Kogyo Co., Ltd. Agent Patent Attorney Haku An Sakaguchi (1 person)

Claims (2)

[Claims] (1) A silver halide containing a diethylenetriaminepentaacetic acid iron(II) complex salt, at least one metal ion selected from the following metal ion group, and a chelating agent other than diethylenetriaminepentaacetic acid. Processing liquid with bleaching ability for color photographic materials. [Metal ions] Nickel, cobalt, curved lead, cerium, ruthenium, indolium, samarium. (2) A processing liquid having bleaching ability for a silver halide color photographic light-sensitive material according to claim 1, wherein the chelating agent other than diethylenetriaminepentaacetic acid is an aminocarboxylic acid.