JPS60263152A - Solution capable of bleaching for processing silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a bleaching or a bleach-fixing soln. superior in silver bleaching power and not causing processing stains by incorporating diethylenetriaminepentaacetic acid ferric complex salt and a specified compd. in said soln. CONSTITUTION:The processing soln. contains diethylenetriaminepentaacetic acid ferric complex salt as an oxidizing agent and at least one of the following group: Tetramethylurea, phosphoric acid-tris-dimethylamide, epsilon-caprolactam, N- methylpyrrolidone, N-methylmorpholine, tetraethyleneglycol monophenyl ether, glycol monomethyl ether, dimethylsuolfone, and acetonitrile. Said compd. is used, preferably, in an amt. of 1-20g/l of the processing soln., and the soln. is kept, preferably, in a pH of 5.5-8.5, and it is used at a temp. of <=80 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a processing solution 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 silver halide color photographic materials, which have improved various processing performance and solution properties.

[Conventional technology]

In general, when a color image is obtained by processing a silver halide color photographic light-sensitive material that has been exposed one-imagewise, a step is provided after the color development step to treat the generated metal chains with a processing solution having bleaching ability. .

Bleaching solutions and bleach-fixing solutions are known as processing solutions having bleaching 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 salt and dichromate are widely used as oxidizing agents for bleaching autonomous silver in processing solutions with bleaching ability for processing silver halide color photographic materials. .

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 excellent in terms of bleaching blades, but there is a risk that they will decompose when exposed to light and produce cyanide ions and hexavalent chromium ions that are harmful to the human body. , has unfavorable properties in terms of pollution prevention. In addition, these oxidants have extremely strong oxidizing power, so K
.

It is difficult to coexist silver halide solubilizers such as thiosulfates in the same processing solution, and it is almost impossible to use these oxidizing agents in bleach-fixing baths. and make it difficult to achieve the goal of simplification. 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 are used as oxidizing agents as they have few pollution problems, speed up and simplify treatment, and enable recycling of waste liquids. It has become increasingly common for treatment liquids to be used. However, processing solutions using metal complex salts of organic acids have a slow oxidizing power, so the 1Ik formed during the development process
It has the disadvantage that the bleaching rate (oxidation rate) of i-image silver (metallic silver) is slow. For example, ethylenediaminetetraacetic acid iron complex salt, which is considered to have a strong bleaching edge among aminopolycarboxylic acid metal complex salts, has been put into practical use as a bleaching solution and a color fixing solution in some places, but silver bromide , High-sensitivity silver halide materials based on silver iodobromide emulsions 2 - Photographic light-sensitive materials, especially color papers for photography, color negative films for photography, and color reversal films containing silver iocide as silver halide, There is a lack of bleaching blades, and traces of silver remain on the entire image even after long-term processing, resulting in poor desilvering performance.

This tendency is noticeable in % because in a bleach-fix solution in which an oxidizing agent and thiosulfate and sulfite coexist, the fermentation reduction 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 diethylenetriaminepentaacetic acid complex salt as an oxidizing agent that has excellent oxidizing power particularly in the high - range among aminopolycarboxylic acid metal complex salts. Bleach and bleach-fix solutions that use diethylenetriaminepentaacetic acid (iron diethylenetriamine pentaacetate@) complex salt as an oxidizing agent have a - value of 4 or more, especially 6 or more, and have a rapid silver bleaching reaction, less staining when directly bleached, and further bleaching. It has extremely excellent performance in that the fixer has good storage stability. however,
It has been found that when this bleaching solution or bleach-fixing solution is used and the washing time after processing is short, or when stabilizing processing is performed without washing, there is a drawback that processing stains are likely to occur. Particularly when processing with a bleaching solution containing diethylenetriaminepentaacetic acid iron(2) complex salt as a bleaching agent or using a bleach-fixing solution immediately after development using an automatic processor, and when the washing processing time is short as described above. It has been found that this treatment stain is likely to occur during the waterless washing stabilization treatment. Therefore, there is a strong demand for the development of a technology that does not cause staining or the like at all with a processing solution containing diethylenetriaminepentaacetic acid iron(1) complex salt and having bleaching ability.

(Object of the Invention) The first object of the present invention is to provide an excellent bleaching solution or bleach-fixing solution for silver source white blades that does not cause processing stains, and the second object is to provide a bleaching solution or a bleach-fixing solution that does not cause processing stains. The third objective is to provide a processing solution with bleaching ability for silver halide color photographic light-sensitive materials that does not cause processing stains even when a color developer is mixed in.The third objective is to reduce processing stains even if the washing time is shortened. The fourth object of the present invention is to provide a processing solution for color photographic materials that does not require staining and does not require staining even after stabilization treatment. VC that provides a processing solution with bleaching ability
be.

[Structure of the invention]

As a result of intensive research by the present inventors, the purpose of the book is to contain diethylenetriaminepentaacetic acid iron (1) complex salt as an oxidizing agent, and to contain the following compound (hereinafter referred to as the compound of the present invention) with a ψ of at least 1 m. Mourning to find out what is achieved.

(Compound) Tetramethylurea phosphate-tris-dimethylamide ξ-caglolactam N-methylpyrrolidone N-methylmorpholine Tetraethylene glycol monophenyl ether glycol monomethyl ether dimethylsulfone acetonitrile Generally iron ethylene diamino tetraacetate (bleaching ability using town salt) In a processing solution having J color development m+ by continuous processing,
It was rare that treatment stay/occurrence was observed immediately after treatment, even if it was treated directly after treatment or stabilized without washing with water. However, when diethylenetriaminepentaacetic acid (iron) complex salt is used as a bleaching solution, processing stains tend to occur, and it is often necessary to directly process from color development with a processing solution containing diethylenetriaminepentaacetic acid (1) complex salt that has bleaching ability. In some cases, this treatment stain can occur significantly, and this stain can be further reduced by shortening the washing time after treatment with a treatment solution that has bleaching ability, by lowering the washing temperature, or by extremely reducing the water flow basin. Easy to occur. In particular, this stain occurs significantly when the water washing treatment is omitted and the stabilization treatment is performed.

As a result of various studies, the present inventors have discovered that the compound of the present invention extremely effectively prevents treatment stains associated with treatment solutions having bleaching ability containing these diethylenetriaminepentaacetic acid iron (2) complex salts. Even if the compound of the present invention, which is well known as a water-soluble organic solvent, is known to be added to other general processing solutions, it is not effective for the processing solution having bleaching ability of the present invention. This was a serious discovery, as it was completely unexpected that it would be possible to prevent this, improve the efficiency of the water washing process, and extremely effectively suppress the staining caused by the stabilization process.

The compound of the present invention can be applied to a treatment solution [S
It is used in addition, but the prefectural addition amount is 0.0l-1oo per 1fifi of processing liquid. , preferably in the range of 0.1 to 50 g, more preferably in the range of 0.5.9 to 30.9, preferably in the range of B to 20 g, and l
Any combination of oval or 2s or more can be used.

The compound of the present invention may be added to the processing liquid having bleaching ability KIITh directly, or it may be added to the replenishing liquid and then added to the replenishing liquid. However, it may be added to the prebath and contained by the photosensitive material.

The present invention was completed as a result of extensive research into a method for preventing staining after treatment while maintaining the various disturbed properties of diethylenetriaminepentaacetic acid iron (1) complex salt.

The diethylenetriaminepentaacetic acid 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 a triethanolamine salt. Preferably, potassium salt, sodium salt, and ammonium salt are used. In terms of speed and stability, ammonium salts are preferred.

At least one of these iron (ml complex salts) may be used, but 2Il+ or more can also be used in combination.The amount used can be selected arbitrarily, and is selected depending on the silver color and silver halide composition of the photosensitive material to be processed. However, since it generally has a high oxidizing power, it can be used at a lower concentration than other aminopolycarboxylic acid salts (for example, it can be used at a concentration of 10.01 mol or more per IQ of the working solution (preferably) 10.05 mol or more). Ru. In addition, it is desirable to use the replenisher in a highly concentrated form with the highest solubility in order to reduce the Via thickness.

The treatment solution with bleaching ability of the present invention has a must! Various chelate compounds and their iron (1) lead salts can be added depending on the conditions. The appearance of free chelate compounds and complex salts is not specified by JK, but chelate iron cutting (1)
) The complex salt is preferably an equimolar amount or less of the diethylenetriamine complex salt. If the amount exceeds the equimolar amount, the strong oxidizing power of the complex salt will be slightly lost, but
The stain-preventing effect of the compound of the present invention remains unchanged.

Specific chelate compounds that can be added to the treatment solution having bleaching ability of the present invention are dicarboxylic acids, polycarboxylic acids, oxy/carboxylic acids, aminocarboxylic acids, polycarbonate, organic phosphonic acids, aminopolycarboxylic acids, and aminopolyphosphonic acids. Examples include acids, aminophosphonic acids, phosphonocarboxylic acids, iron (■) complex salts thereof, and the aminocarboxylic acids shown below in percentage are effectively used.

Exemplary compounds> (B-1) Dihydroxyethylglycine (+3-2)
Iminoniacetic acid (B-3) Methyliminodiacetic acid (H-4) Ethyliminodiacetic acid ([4-5) Diethylenetriaminepentaacetic acid (B-6)
Impropylenediaminetetraacetic acid (B-7) Butyliminodiacetic acid (B-8) Hydroxyethyliminodiacetic acid (B-9)
Nitrilotriacetic acid (B-10) Nitrilodiacetic acid propionic acid (H-11
) Nitrilotripropionic acid (B-12) Ethylenediaminediacetic acid (B-13) Ethylenediaminedipropionic acid (B-14) Ethylenediaminediorthohydroquinphenylacetic acid (B-15) Hydroxyethylethylenediaminetriacetic acid (B-16) Ethylenediamine Tetraacetic acid (B-17)
Diaminopropanoltetraacetic acid (B-18) Diaminoglopanoltetraacetic acid (B-19)) Cyclohexanediaminetetraacetic acid (B-20) Glycol ether diamine diacetic acid (B
-21) ) Liethylenetetaminehexaacetic acid These chelating agents and their iron ([complex salts include free acids, alkali gold salts such as sodium salts, potassium salts, lithium salts, or ammonium salts, or water-soluble amine salts. For example, it is used as a triethanolamine salt, etc. At least one of these may be used, but two or more may be used in combination.

The amount used is 1g of liquid, 0.0001 mole to 2
Moles are preferred, particularly preferably in the range from 0001 mol to 1 mol.

Preferred chelating agents and their iron complex salts include ethylenediaminetetraacetic acid, hydroxyethylethylenediaminetriacetic acid, inopropylenediaminetetraacetic acid, and iron(iron) complex salts thereof.
Of) It is a complex salt.

It is preferable to add the following metal ions to the treatment 'wLK having bleaching ability containing the diethylenetriaminepentaacetate iron (1) complex salt of the present invention. It can also be added as gold 1!4 salt.

Specific examples of metal ions include zinc, nickel, cobalt, cerium, ruthenium, yttrium, sulfur, magnesium, calcium, bismuth, strontium, manganese, aluminum, tin, barium, indium, thallium, zirconium, etc. . These metal ions may be in any form such as chloride, hydroxide, acetate, carbonate, phosphate, acetate, etc., but water-soluble salts are preferred.

These metal ions may be used alone or in combination of two or more. The amount used is preferably from 0,000 mol to 2 mol, particularly preferably from 0,001 mol to 3 mol.

Preferred metal ions include magnesium, calcium, nickel, zinc, cobalt, cerium, bismuth, aluminum, and strontium, and most preferably magnesium, calcium, nickel, zinc, bismuth, cerium, and aluminum.

The processing solution (bleach solution and bleach-fix solution) having bleaching ability of the present invention can be used at a pH of 0.2 to 95, preferably 40.
As mentioned above, it is more preferable to use a range of 50 or more, and the most preferable range is 55 or more and 85 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 diethylenetriaminepentaacetic acid iron (1) complex salt as a bleaching agent as described above, and also contains %
It can contain various additives. dl as additive
Especially alkali halides or ammonium halides,
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. In addition, V1 buffers such as borates, oxalates, acetates, carbonates, and phosphates, solubilizers such as triethanolamine, ordinary bleaching solutions such as aminopolycarboxylic acids or their salts, alkylamines, and polyethylene oxides. It is possible to appropriately add substances that are known to be added to.

J 4 Invention 0 Bleach-fixing solution C is a bleach-fixing agent containing diethylenetriaminepentaacetic acid (ferric diethylenetriamine pentaacetate) complex salts as a bleaching agent as described above, as well as thiosulfate, thiocyanate, thiourea, thioethers, etc. A liquid having a composition containing is applied. In addition, a bleach-fix solution consisting of a composition in which a small amount of a halogen compound such as potassium bromide is added in addition to the bleaching agent and the silver halogenide fixer, or conversely, a halogen compound such as potassium bromide or ammonium bromide may be used. Lots of Kl! A bleach-fixing solution consisting of a composition containing 5Σ, and a VC
A special bleach-fixing solution having a composition consisting of a combination of the bleaching agent of the present invention and a large amount of a nitrogen compound such as potassium bromide can also be used.

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.

The above-mentioned halogenated fixing agent to be included in the bleach-fixing solution is a compound that reacts with the halogenated chain to form a water-soluble complex salt, such as thiosulfuric acid, which is used in ordinary fixing processing. Thiosulfates such as potassium, sodium thiosulfate and ammonium thiosulfate, thiocyanates such as potassium, sodium thiocyanate and ammonium thiocyanate, or thioureas, thioethers,
Typical examples include high concentrations of bromide and iodide. These fixing agents can be used in a range where they can dissolve 5 g/f1 or more.

The bleach-fix solution contains KIM acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate,
Acetic acid, acetic acid) A single buffer consisting of various salts such as IJium and ammonium hydroxide is used as a single buffer.1-12? ! 1
A combination of the above may be contained. Sara K also,
It is also possible to contain various fluorescent brighteners, antifoaming agents, or surfactants.

Distilled mA of hydroxylamine, hydrazine, sulfites, isomeric bisulfites, aldehydes and ketone compounds!
Preservatives such as adducts, organic chelating agents such as aminopolycarboxylic acids or stabilizers such as nitroalcohol nitrates, solubilizers such as alkanolamines, stain inhibitors such as organic amines, other additives, methanol, An organic solvent such as dimethylformamide 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 KIJ4 white or bleach fixing immediately after color development, but after performing processing 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 bleach-fixing, the amount of washing water can be reduced and the washing temperature can be lowered, which is preferable for economical reasons. Also, the water washing process time is 273~'
There is also the advantage that the VC can be shortened by /3. The washing can be carried out at a water washing temperature Vi of 3 to 40°C, preferably 5 to 35°C, more preferably 15 to 28°C.

It is also a preferable method to omit the water washing treatment and carry out the stabilization treatment.

The efficient water washing treatment and stabilization treatment used in the present invention, or the water washing alternative stabilization treatment Fi, is the treatment method described in JP-A No. 55-7793, No. 57-8542, No. 57-8543, etc. , Characteristics of treatment liquid Fi JP-A-58-134
No. 636, No. 58-3448, No. 58-132743
No. 57-232146, etc., these treatment solutions contain various compounds for stabilizing the dye 1I. is pH 3-9.

After treatment with the treatment solution having bleaching ability of the present invention, washing with water may be performed, followed by stabilizing treatment. In addition to the above steps, hardening, neutralization, black and white development, reversal, and washing with a small amount of water are must-haves! Various auxiliary steps may be added depending on the situation. Typical examples of preferred processing methods include the following steps.

(2) Color development → bleach fixing → low water washing (2) color development → bleach fixing → small water washing → stable (3) color development - 4Q white fixing → low temperature water washing → stable (4) color development → bleach fixing → stable ( 5) Color development → water washing - 41!! 4 White fixation → short time water washing (6) Color development → stop → bleach fixing → rinse (7) color development → bleaching → stable (Note 1.) → fixing → stable Note 1. The stabilizing liquid used in this stabilizing treatment may be simply water,
The water may contain various anti-spill agents to prevent water from spoiling, and the treatment liquid having bleaching ability of the present invention may be treated with lI+! One or more of the chelating agents mentioned above may be contained, and the additional VC may be the above-mentioned water washing substitute stabilizing liquid.

(+1)! @ Bleaching before color development → Fixing → Stable - 1 (contains anti-pie agent) → Stable - 2 (contains draining agent) (9) Color development - Bleaching → Sunset washing → Fixing → Washing with a small amount of water → Washing with water → Stable QQ Color development - Wash with a small amount of water → Prefecture white → Wash with a small amount of water → Fix → Wash with a small amount of water - Wash with water → Stable Qρ Color development Sakaki stop → Bleach → Wash with a small amount of water or stabilize (same as Note 1 stable in (7) above J → Fix → Wash with a small amount of water → Wash with water → Stable (2) Black and white development - Stable → Reversal → Color development → Bleaching → Fixed waste →
Stable oJ Prehardening → Neutralization → Black and white development → Stop → Color development → Bleaching → Graduation → Stability The black and white developer used before processing with the processing solution having bleaching ability of the present invention is generally known. Power 2 - What is called the black and white first liquid used in the processing of photographic light-sensitive materials, or what is used in the processing of black and white photographic light-sensitive materials 69
, various kinds of image additives that are generally added to the black and white developer KWiS can be contained.

Typical 6Σ additives include l-phenyl-3-pyrazolidone, modern herbal medicines such as metol and hydroquinone, preservatives such as sulfites, and alkalis such as sodium hydroxide, sodium carbonate, and potassium carbonate. agent,
Surface overdevelopment inhibitors consisting of potassium bromide, inorganic or organic inhibitors such as 2-methylbenzimidazole, methylbenzthiazole, water softeners such as polyphosphates, and trace amounts of iodides and mercapto compounds. etc. can be mentioned.

The aromatic primary amine color developing agent used in the color developing solution used before processing with the processing solution having bleaching ability of the present invention is a known one that is widely used in various photographic processes. is included. These developers include aminophenol and p-phenylenediamine derivatives. These compounds are generally used in the form of a salt, such as a hydrochloride or a sulfate, since they are more stable than in the free state. 1. These compounds generally have a range of about 0.1.9 to about 30.0% for color developer ll1K. I10 concentration is used at a concentration of about 1 g to about 15 g of color developer IIIK.

Examples of amine phenol developers include 0-amine phenol, p-aminophenol, 5-amino-2-
These include oxytoluene, 2-amino-3-ox7-toluene, 2-oxy-3-amino-1,4-dimethyl-benzene, and the like.

Particularly useful primary aromatic amine color developers are N, N'
In the -dialkyl-p-phenylenediamine compound, the acyl group, alkyl group, and phenyl group may be substituted or unsubstituted. Among them, an example of a particularly useful compound is N.

N'-diethyl-p-phenylenediamine! 2m, N-
Methyl-p-phenylenediamine hydrochloride, NrN'-dimethyl-p-7enylenediamine hydrochloride, 2-amino-
5-(N-ethyl-N-dodecylamino)-)luene,
N-ethyl-N-β-methanesulfonamidoethyl-3
-Methyl-4-aminoaniline 411L#i salt, N-ethyl-N-! -Hydroxyethylaminoaniline, 4-
Amino-3-methyl-N,N'-diethylaniline, 4
-amino-N-(2-methoxyethyl)-N-ethyl-
Examples include 3-methylaniline-p-)luenesulfonate.

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 amine color developer. Various ingredients such as sodium hydroxide, sodium carbonate, potassium carbonate J c4. f) A, ka, 3j, a,
□□□, alkali metal bisulfite, alkali metal thiocyanate, alkali metal halide, benzyl alcohol, diethylenetriaminepentaacetic acid, l-hydroxyethylidene-1,l-diphosphonic acidic water softener and #thickening It is also possible to optionally contain agents and the like. The color developer usually has a value of 7 or more, 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 (U.S. Pat. No. 2,376,679) in which a color former is contained in the light-sensitive material.
No. 2. In addition to the external development method in which a coloring agent is contained in the developer (see U.S. Pat.
43, 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 naphthol or phenol structures and form indoaniline dyes through coupling;
The magenta coloring agent has a 5-bidizolone ring having an active methylene group as its skeleton structure, and the yellow coloring agent has a benzoylacedoanilide, pivalylacetanilide, or acylacedoanilide structure having an active methylene chain. Coupling position lit'VC with things etc.
Both those with and without substituents can be used. Thus, as the coloring agent, both so-called 2-equivalent type couplers and 4-equivalent type couplers can be applied. Silver halide emulsions that can be used include chloride steel, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, silver chloroiodobromide, and mixtures of these. Any silver halide may be used. In addition, as these silver halide eye-preserving colloids, natural products such as gelatin, as well as various products obtained by synthesis can be used. Conventional photographic additives such as silver halide emulsion Ki, stabilizers, sensitizers, thickeners, sensitizing dyes, and surfactants may be included.

The bleaching processing 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, and
It can be applied to silver halide color photographic materials such as color reversal films and color reversal vapors.

〔Example〕

Examples of the present invention will be described below, but the present invention is not limited thereto.

Example 1 Silver iodobromide containing 3 mol% silver iodide coated silver fi53■/l
The emulsion was adjusted to give Kl! 00cnl on polyethylene-coated baryta paper using yellow, magenta and cyan couplers. The cloth was dried and colored paper was made by the usual method. This sample was exposed to light to prepare a sample for development, and treated with bleach-fix solutions (1) and (2) K in the following steps, respectively.

Processing step 1, color development 33°C 3 minutes 30 seconds 2 bleach-fixing 33°C 1 minute 30 seconds 3, stabilization 25°-30°C 3 minutes 4 drying 7
5°-80°C for about 2 minutes Processing solution composition (color developing solution) The bleach-fix solution (υ and (2)) that was continuously processed until the silver thiosulfate ions in it became around ``#/fl'' was divided into Iv
The compounds shown in Table IK were added to the mixture, and Vl was adjusted to 7.4KllIIl with ammonium hydroxide and sulfuric acid.

A pre-exposed color paper was pre-exposed so that a white exposed area and an unexposed area could be seen at the same time, and the yellow staining degree (blue light density) was measured by performing the above-mentioned process and the following process. Further, this sample was stored at 60° C., 5osn, +−+ for 2 weeks, and the yellow stain was measured at that time. The stain concentration was measured using a Sakura optical densitometer PDA-65. Further, regarding the white exposure i, observation was performed in a dark place using Noctovigine using infrared rays, and the presence or absence of residual unbleached silver was observed.

As is clear from the results in Table 1, the bleach-fix solution (1 ton of iron ethylenediaminetetraacetate) complex salt bleaching agent is
A whitening fixing formulation 1'Th in which no compound is added and a water VC solution having properties similar to the compounds of the present invention is added, and the organic solvents dimethylformamide and dimethyl sulfoxide are added.
1-N113 and the bleach-fix formulations N114 to Nci12 to which the compounds of the present invention were added, the process stain was low in all cases and therefore there was no effect of the compounds of the present invention. However, poor desilvering due to infrared ray exposure was observed in all of Nn1 to Nn12, and it was found that sufficient silver source white blades were not obtained in Nn7.

On the other hand, diethylenetriamine 501 city railway according to the present invention (
In) In the egg white fixer (2) using a complex salt, the yellow stain was high in both Nci13 to Nci15 to which the compound of the present invention was not added and to which dimethylformamide and dimethylsulfoxide were added.

J In contrast, when the compound of the present invention was added to tooth 10 to tooth 24, yellow stain was observed extensively. Furthermore, it can be seen that the generation of yellow stain is effectively suppressed even when the sample is stored under high temperature and high humidity conditions.

Further, as a result of noctovisine observation, no unbleached steel was observed in any of the areas No. 16 to No. 24.

In addition to this example, a sample of color paper with a coated amount of silver chlorobromide of 13 .mu./100 was treated in the same manner, and substantially the same effect was obtained.

Example 2 After photographing 1000 m of commercially available 35 ni'l+photographic film using a Konica FS-1 (manufactured by Konishiroku Photography FF1TL), continuous replenishment processing was carried out in an automatic mode 11r according to the following process 1 column (hereinafter). Self-presentation run: This process is called ``running process''.

Note that the photosensitive layer of the above color film contains silver iodobromide fi
8 rvC/dm2, and the mole percent of iodide was about 42 mole percent.

The automatic developing machine used was a modified automatic film developing machine type H4-22+IW-2 manufactured by Noriso Koki Co., Ltd.

, Process 1 (38°C) Number of tanks Processing time The composition of the processing solution used is as follows.

[Color developer, replenisher]

[Color developing replenisher] [Bleach-fixing solution and bleach-fixing replenisher (1)] [Bleach-fixing solution and bleach-fixing replenisher (2)] L solution] 1. Stable replenisher] Color developing replenisher is , 4 per 100 color negative films
5nII! The color development bath is replenished, and the bleach-fix replenisher is
A 99 mQ bleach-fix bath was replenished with 100 a+ of the 2-negative film, and an additional 11 stabilizing bath was replenished with stability replenisher per 100 of the color negative film. In addition, the water washing bath was filled with stored water and was not replenished.

Using bleach-fixing and bleach-fixing replenisher solutions (1) and 2), each film was subjected to continuous replenishment treatment for 1000 m.

After each self-development running process was completed, the bleach-fix tank solution was taken out and divided into exactly the same manner as in Example 1, and the sample exposed to white light and the unexposed sample were processed. Yellow stain (fog density) and unbleached silver remained was observed using Noctovisidae.

As a result, qualitatively the same results as in Example 1 were obtained, but
A bleach-fix solution containing iron ethylenediaminetetraacetate complex salt as a bleaching agent did not cause step-out at all and had a large amount of residual silver, making it impossible to measure stain.

Desilvering was completed in all bleach-fix solutions using diethylenetriaminepentaacetate iron (1) complex salt as a bleaching agent, but when the compound of the present invention was not added, the minimum blue density was high;
It was found that stain remained, and the compound of the present invention (
It was found that when the same compound as Examples I Locus 16 to NIIL 24) was added, staining did not occur and there was almost no problem.

There were 8 preferred compounds with a low stain in %: tetramethylurea, phosphoric acid-tris-dimethylamide, ε-cuff rolactam, and N-methylpyrrolidone, but there was little difference from other compounds of the present invention. It was.

In addition to this example, similar effects were obtained when the stabilizing liquid of Example 1 was used in place of the standing water.

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

Claims (1)

[Scope of Claims] A processing solution having bleaching ability for silver halide color photographic materials, which contains diethylenetriaminepentaacetic acid iron (1) complex salt and at least one of the following compounds. [Compound notetramethylurea phosphate-tris-dimethylamide ε-caprolactam N-methylpyrrolidone N-methylmorpholine tetraethylene glycol monophenyl ether glycol monomethyl ether dimethylsulfone acetonitrile