JP3200717B2 - Processing solution for silver halide photographic materials - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an improvement in a photographic processing solution for processing an exposed silver halide photographic light-sensitive material. More specifically, to sequester metal ions that have deleterious effects, or to use as a bleach,
The present invention relates to a processing solution for a silver halide photographic material containing a novel chelating agent for photographic use.

[0002]

2. Description of the Related Art Generally, in order to process an exposed silver halide photographic light-sensitive material to obtain an image, processing with various processing solutions including a developing solution and a fixing solution is required. In particular, more processing steps are required to obtain a color image. Since the treatment liquid used in these treatments contains a large number of components, if the water used in the preparation contains metal ions such as calcium, magnesium and iron, they react with these and precipitate. And produce sludge. In addition, there are drawbacks such as clogging of a filter attached to the automatic processing machine or adhesion to the surface of the photographic light-sensitive material being processed to cause contamination. or,
Even if pure water is used to prevent this during preparation of the processing solution, metal ions are eluted from the photographic light-sensitive material during processing, or metal ions are brought in from the previous processing step. It was extremely difficult to completely prevent sludge formation. Further, some of the various components contained in the processing solution, the oxidation and decomposition is promoted by the action of metal ions and loses its efficacy.
There are drawbacks such as the occurrence of fog and a decrease in photosensitivity.

In order to prevent these undesirable effects of metal ions on the processing solution, it has been proposed and put into practice that a so-called chelating agent for blocking metal ions is added to the photographic processing composition. For example, UK Patent 520,
Polyphosphates such as sodium hexametaphosphate proposed by U.S. Pat.No. 593; alkylidene diphosphonic acid proposed by U.S. Pat.No. 321,445; U.S. Pat.
And aminopolycarboxylic acids typified by aminopolymethylenephosphonic acid and ethylenediaminetetraacetic acid proposed in No. 6. However, even in the case where these chelating agents are blended, there are various drawbacks in practice, and it is not satisfactory. In other words, polyphosphate has a small sequestering power and is particularly weak against heavy metal ions, so that it cannot be put to practical use.

The alkylidene diphosphonic acid has a problem that when calcium ions and sodium ions coexist at a certain concentration or more, a solid precipitate is generated, which causes an obstacle to an automatic processor. Normal aminopolycarboxylic acid represented by ethylenediaminetetraacetic acid and aminopolymethylenephosphonic acid represented by aminotrimethylenephosphonic acid have excellent sequestering power and are excellent in color developer containing hydroxylamine. However, there is a disadvantage that hydroxylamine is decomposed in the presence of metal ions and fogging occurs when treated with this developer. In black-and-white developers, the oxidation of the developing agent is promoted and storage stability is deteriorated. There is the disadvantage of causing significant fogging on the speed film.

As described above, the chelating agents proposed so far all have some drawbacks, and in fact, they have not been able to obtain a sufficiently satisfactory effect when used in photographic processing compositions. Furthermore, the replenishment rate of photographic processing solutions tends to be further reduced due to recent social and environmental demands such as low pollution and economic demands such as low cost. The amount of accumulated metal ions also tends to increase.

[0006] Also, the raw materials used for photographic materials are:
For the purpose of cost reduction, inexpensive materials of lower grade tend to be used, and the amount of metal ions accumulated in a photographic processing solution is constantly increasing.

[0007] For this reason, in recent years, the situation has become increasingly uncontrollable with conventional techniques.

In recent years, from the standpoint of protecting the global environment, it has been desired to use a material having good biodegradability. However, it has been known that the above-mentioned ferric ethylenediaminetetraacetic acid complex salt has extremely poor biodegradability. And not preferred. Recently, in Germany, there has been a voluntary regulation to reduce the amount of EDTA used by half in the next five years due to the high EDTA concentration in drinking water.

As means for solving this problem, German Patents DE 3,939,755 and DE 3,939,756 describe nitrilomonopropionate diacetic acid (NMPDA), nitrilopropionate monoacetic acid (NDPMA), A technique using common nitrilotriacetic acid (NTA) as a biodegradable chelate has already been disclosed. However, the NMPDA
And NDPMA are based on the easily degradable test “Modified MITI method” approved by the Ministry of International Trade and Industry as an evaluation method for biodegradability (meaning that if the product is degraded by this method, it will be rapidly degraded in nature). It has been confirmed that it hardly decomposes, and does not provide a fundamental solution to this problem.

[0010] However, the chelating agent of the present invention is extremely excellent in biodegradability, and is also an excellent material in this sense.

[0011]

SUMMARY OF THE INVENTION The present invention has been made to solve these problems, and a first object of the present invention is to provide a stable silver halide photograph free of precipitation and sludge generation due to the presence of metal ions. An object of the present invention is to provide a processing solution for a photosensitive material. A second object of the present invention is to provide a processing solution for a silver halide photographic light-sensitive material capable of performing stable processing over a long period of time when processing is performed by an automatic developing processor and without causing clogging of an attached filter. is there.

A third object is to provide a processing solution for a silver halide photographic light-sensitive material having a good desilvering property and excellent bleaching ability for a silver halide photographic light-sensitive material having excellent liquid storage stability. To provide.

A fourth object is to provide a processing solution for a silver halide photographic light-sensitive material which has excellent biodegradability and is suitable for protecting the global environment.

Further, other objects will become clear from the following specification.

[0015]

The object of the present invention is achieved by the following processing solution for a silver halide photographic material.

1. A halogenated compound comprising a polymer compound having a carboxyl group or a salt thereof in at least one repeating unit, wherein the polymer main chain is substantially in the form of a condensate. Processing solution for silver photographic photosensitive materials.

2. 2. The processing solution for a silver halide photographic light-sensitive material according to the above 1, wherein the main chain of the polymer comprises an ester bond and / or an amide bond.

3. The above-mentioned (1), wherein the polymer comprises an amino acid or a salt thereof as a monomer component.
Or the processing solution for silver halide photographic light-sensitive materials according to 2.

4. 4. The processing solution for a silver halide photographic light-sensitive material as described in any one of the above items 1 to 3, which contains at least a hydroxycarboxylic acid compound or a salt thereof as a monomer component constituting the polymer.

[5] 4. The processing solution for a silver halide photographic light-sensitive material according to any one of the above 1 to 3, wherein the polymer compound is a polyamino acid.

6. 6. The processing solution for a silver halide photographic light-sensitive material according to any one of the above items 1 to 5, wherein the processing solution contains at least aspartic acid and / or glutamic acid as a monomer component constituting the polymer.

7. 7. The processing solution for a silver halide photographic light-sensitive material as described in 1, 2, 3, 4 or 6, wherein the hydroxycarboxylic acid compound is malic acid, citric acid or tartaric acid.

8. 8. The processing solution for a silver halide photographic material according to 1, 2, 3, 4, 6 or 7, wherein the polymer compound is a copolyesteramide comprising aspartic acid and malic acid.

9. The number average molecular weight of the polymer compound is 4
The above-mentioned 1-8, wherein the number is from 00 to 50,000.
A processing solution for a silver halide photographic light-sensitive material as described above.

10. 10. The processing solution for a silver halide photographic light-sensitive material according to any one of the above 1 to 9, wherein the processing solution is a black-and-white developing solution or a color developing solution.

11. 10. The processing solution for a silver halide photographic light-sensitive material according to any one of the above 1 to 9, wherein the processing solution is a bleaching solution or a bleach-fixing solution.

12. 10. The processing solution for a silver halide photographic light-sensitive material according to any one of 1 to 9, wherein the processing solution is a fixing solution.

13. 10. The processing solution for a silver halide photographic light-sensitive material according to any one of 1 to 9, wherein the processing solution is a stabilizing solution.

14. 12. The processing solution for a silver halide photographic light-sensitive material as described in 1 to 9 or 11, wherein the processing solution is a bleaching solution or a bleach-fixing solution containing a complex of the polymer compound and ferric ion.

Hereinafter, the present invention will be described in detail. The processing liquid in the present invention refers to a developing tank liquid and a replenisher.

Preferred specific examples of the polymer compound will be shown below, but it should not be construed that the invention is limited thereto.

[0032]

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[0033]

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As a method for synthesizing the polymer compound in the present invention, ring-opening polymerization and ring-opening copolymerization can also be preferably used. When an amino acid is contained as a monomer component, the N-carboxy anhydride (NCA) method is also preferably used. The polymer compound of the present invention can be synthesized by the method described in Chapter 7 of "Biodegradable Polymer Materials" by Yoshiharu Dohi (Industrial Research Institute Co., Ltd.) or other generally known methods.

First, the case where the processing solution of the present invention is other than a bleaching solution or a bleach-fixing solution will be described.

When the processing solution of the present invention is a processing solution other than the bleaching solution or the bleach-fixing solution, good results can be obtained by adding 0.1 to 50 g, preferably 0.5 to 10 g of the polymer compound per liter of these processing solutions. Is obtained. When blending,
Two or more compounds represented by the above general formulas may be used, or they may be used in combination with other chelating agents. The formulation may be added to the treatment solution together with other components when preparing the treatment solution, or may be blended with the other components in a powdery state in a kit or in a concentrated solution kit. Good.

The photographic processing solution of the present invention can be applied to any processing solution for processing a silver halide photographic material. For example, a general black-and-white developer, an infectious developer for squirrel, a color developing solution for color, a bleaching solution, a fixing solution, a bleach-fixing solution, a stop solution, a hardening solution, a stabilizing solution, a fog solution, a toning solution, and the like. However, the present invention is not limited to these.
The photographic processing solution of the present invention may be used for processing all silver halide photographic materials such as color films, color photographic papers, general black and white films, X-ray films, lithographic films for printing, and microfilms. Can be.

After the bleach-fixing process employed in the present invention, a stabilizing process using a stabilizing solution is preferably employed.

It is particularly preferable for the purpose of the present invention that the stabilizer contains a chelating agent having a chelate stability constant for iron ions of 8 or more. Here, the chelate stability constant refers to “Stability” by LGSillen and AEMarttell.
Constants of Metal-ion Complexes ”The Chemical
Society, London (1964), by S. Chaberek, AEMartell
Organic Sequestering Agents "means constants generally known by Wiley (1959) and the like.

The chelate stability constant for iron ions is 8
Examples of the chelating agent include an organic carboxylic acid chelating agent, an organic phosphoric acid chelating agent, an inorganic phosphoric acid chelating agent,
And polyhydroxy compounds. Note that the iron ion means ferric ion (Fe ³⁺ ).

The chelate stability constant with ferric ion is 8
Specific compound examples of the above chelating agent, in addition to the polymer compound of the present invention, include the following compounds,
It is not limited to these. That is, ethylenediamine diorthohydroxyphenylacetic acid, diaminopropanetetraacetic acid, nitrilotriacetic acid, hydroxyethylenediaminetriacetic acid, dihydroxyethylglycine, ethylenediaminediacetic acid, ethylenediaminedipropionic acid, iminodiacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, Diaminopropanoltetraacetic acid, transcyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, ethylenediaminetetrakismethylenephosphonic acid, nitrilotrimethylenephosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, 1,1-diphosphonoethane-2-carboxylic acid , 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxy-1-phosphonopropane-1,2,3-tricarboxylic acid, catechol-3,5-diphosphonic acid, sodium pyrophosphate , Sodium tetrapolyphosphate, sodium hexametaphosphate and the like, particularly preferably diethylenetriaminepentaacetic acid, nitrilotriacetic acid, nitrilotrimethylenephosphonic acid, 1-hydroxyethylidene-1,1
-Diphosphonic acid and the like, and among them, 1-hydroxyethylidene-1,1-diphosphonic acid is most preferably used.

The amount of the chelating agent used is preferably from 0.01 to 50 g per liter of the stabilizing solution, more preferably from 0.05 to 20 g.
Good results are obtained in the range of g.

Preferred compounds to be added to the stabilizing solution include ammonium compounds. These are supplied by various inorganic and organic ammonium salts. Specifically, for example, ammonium hydroxide, ammonium bromide, ammonium carbonate, ammonium chloride, ammonium hypophosphite, ammonium phosphate, ammonium phosphite, Ammonium fluoride, ammonium acid fluoride, ammonium fluoroborate, ammonium arsenate,
Ammonium hydrogen carbonate, ammonium hydrogen fluoride, ammonium hydrogen sulfate, ammonium sulfate, ammonium iodide, ammonium nitrate, ammonium pentaborate, ammonium acetate, ammonium adipate, ammonium laurate tricarboxylate, ammonium benzoate, ammonium carbamate, ammonium citrate, Ammonium diethyldithiocarbamate, ammonium formate, ammonium hydrogen malate, ammonium hydrogen oxalate, ammonium hydrogen phthalate, ammonium bitartrate, ammonium thiosulfate, ammonium sulfite, ethylenediaminetetraacetate, ferric ammonium ethylenediaminetetraacetate, ammonium lactate, apple Ammonium acrylate, ammonium maleate, ammonium oxalate, phthalate Ammonium, ammonium picrate, pyrrolidine ammonium dithiocarbamate,
Ammonium salicylate, ammonium succinate, ammonium sulfanilate, ammonium tartrate, ammonium thioglycolate, 2,4,6-trinitrophenol ammonium and the like. These may be used alone or in combination of two or more. The amount of the ammonium compound to be added is preferably in the range of 0.001 mol to 1.0 mol, more preferably in the range of 0.002 to 0.8 mol per liter of the stabilizing solution.

Further, it is preferable that the stabilizing solution contains a sulfite. The sulfite may be any organic or inorganic substance, as long as it releases sulfite ions, but is preferably an inorganic salt. Preferred specific compounds include, for example, sodium sulfite, potassium sulfite, ammonium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, sodium metabisulfite, potassium metabisulfite, ammonium metabisulfite and hydrosulfite. Can be The above sulfite is preferably added to the stabilizing solution in an amount of at least 1 × 10 ⁻³ mol / l, more preferably 5 × 10 ⁻³ mol / l to 10 ⁻¹ mol / l. Such an amount is added, which has an effect of preventing stains in particular. As an addition method, it may be added directly to the stabilizing solution, but it is preferably added to the stabilizing replenishing solution.

Other compounds that can be added to the generally known stabilizer include polyvinylpyrrolidone (PVP K-
15, K-30, K-90), organic acid salts (eg, citric acid, acetic acid,
Succinic acid, oxalic acid, benzoic acid, etc.), pH adjusters (eg, phosphates, borates, hydrochloric acid, sulfuric acid, etc.), fungicides (eg, phenol derivatives, catechol derivatives, imidazole derivatives, triazole derivatives, thiabendazole) Derivatives, organic halogen compounds, other fungicides known as slime control agents in the paper-pulp industry) or fluorescent brighteners, surfactants, preservatives, Bi, Mg, Zn,
There are metal salts such as Ni, Al, Sn, Ti, and Zr. One or more of these compounds can be arbitrarily selected and used as long as the effects of the present invention are not impaired.

After the stabilization treatment, no water washing treatment is required, but rinsing, surface washing and the like by a small amount of water washing within an extremely short time can be arbitrarily performed as necessary.

The presence of a soluble iron salt in the stabilizing solution is preferred for achieving the effects of the present invention. The soluble iron salt is preferably used in the stabilizer at a concentration of at least 5 × 10 ⁻³ mol / l, more preferably in the range of 8 × 10 ^{−3 to} 150 × 10 ⁻³ mol / l, and still more preferably. 12 × 10 ^-3
100100 × 10 ⁻³ mol / liter. Further, these soluble iron salts may be added to the stabilizing solution (tank solution) by adding to the stabilizing solution replenishing solution, or may be eluted from the photosensitive material in the stabilizing solution to the stabilizing solution (tank solution). It may be added to the stabilizing solution (tank solution) by attaching it to the photosensitive material to be processed from the pre-bath and bringing it in.

In the present invention, a stable solution in which an ion exchange resin treatment is performed to reduce calcium ions and magnesium ions to 5 ppm or less may be used. You may use the method of making it.

In the present invention, the pH of the stabilizer is 5.5 to 10.
A range of 0 is preferred. PH that can be contained in the stabilizing solution
The modifier may be any of the commonly known alkali or acid agents.

The treatment temperature for the stabilization treatment is 15 ° C. to 70
C is preferred, and more preferably in the range of 20C to 55C. The processing time is preferably 120 seconds or less, more preferably 3 seconds to 90 seconds, and most preferably 6 seconds to 50 seconds.

The replenishing amount of the stabilizing solution is preferably 0.1 to 50 times, more preferably 0.5 to 30 times, the carry-in amount of the prebath (bleach-fixing solution) per unit area of the light-sensitive material from the viewpoint of rapid processing and preservation of the dye image. preferable.

The stabilization tank is preferably composed of a plurality of tanks, preferably 2 to 6 tanks, particularly preferably 2 to 3 tanks, more preferably 2 tanks, and a counter current system ( It is preferable to supply to the post-bath and overflow from the pre-bath).

As the color developing agent used in the color developing step, there are an aminophenol compound and a p-pheninylene diamine compound. In the present invention, a p-pheninylene diamine compound having a water-soluble group is used. Compounds are preferred. Such a water-soluble group has at least one on the amino group of the p-phenylenediamine compound or on the benzene nucleus, and specific water-soluble groups include-(CH ₂ ) n -CH ₂ O
_{H, - (CH 2) m} -NHSO 2 - (CH 2) n-CH 3, - (CH 2) mO- (CH 2) n-CH
_{3, - (CH 2 CH 2} O) n-CmH 2 m + 1 (m and n each represents an integer of 0 or more.), - COOH group, and as -SO ₃ H group and the like.

In particular, compounds represented by the following formulas [D], [E] and [F] and exemplified compounds described in Japanese Patent Application No. 4-209834 can be preferably used.

[0055]

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[Wherein, R ₁₀ and R ₁₂ may be the same or different and each represents a methyl group, an ethyl group, a propyl group or a hydroxyethyl group. R ₁₁ represents a hydroxyethyl group, a methoxyethyl group, a sulfoalkyl group or a β-methanesulfonamidoethyl group. ]

[0057]

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[Wherein R ₁₃ and R ₁₄ each have 1 to 1 carbon atoms.
And R ₁₅ represents a linear or branched alkylene group having 3 to 4 carbon atoms. ]

[0059]

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[0060] wherein, R ₁₆ represents an alkyl group, R ₁₇
Represents an alkylene group having 2 or more carbon atoms in the main chain. R ₁₈
And R ₁₉ may be the same or different and each represents a hydrogen atom or an alkyl group having 4 or less carbon atoms. R ₂₀ represents a substituent. n represents an integer of 0 to 4, and when n is 2 or more, R ₂₀ may be the same or different. Specific examples of the color developing agent preferably used in the present invention are shown below.

[0061]

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[0062]

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Among the color developing agents exemplified above, those preferably used in the present invention are (A-1), (Α-2) and (A-
3), (A-4), (A-6), (A-7) and (A-
15), compounds represented by (A-17) and (A-18), particularly (A-1) or (A-3).

The above color developing agents are usually used in the form of salts such as hydrochloride, sulfate and p-toluenesulfonate. The addition amount of the color developing agent is preferably 0.5 × 10 ^-2 mol or more per liter of the color developing solution, more preferably from 1.0 × 10 ^{-2 to} 1.0 × 10 ^-1 mol, most preferably 1.5 × 10 ^{-2 to} 1.0 × 10 ^-1 mol. X 10 ^{-2 to} 7.0 x 10 ^-2 mol.

The color developing solution used in the color developing step is an alkali agent usually used in the developing solution, for example, sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, sodium sulfate, sodium metaborate or Borax or the like can be included. Furthermore, various additives such as benzyl alcohol, alkali halides such as potassium bromide or potassium chloride, or as a development regulator such as citrazic acid, and as preservatives hydroxylamine, hydroxylamine derivatives (eg, diethylhydroxyl) Amines, disulfoethylhydroxylamine, dicarboxyethylhydroxylamine, etc.), hydrazine derivatives (eg, hydrazinodiacetic acid) or sulfites. Furthermore,
Various antifoaming agents and surfactants, and organic solvents such as methanol, dimethylformamide and dimethylsulfoxide can be appropriately contained.

The pH of the color developing solution is usually 7 or more, preferably about 9 to 13.

In the color developing solution, if necessary, as an antioxidant, for example, tetronic acid, tetronimide, 2-anilinoethanol, dihydroxyacetone, aromatic secondary alcohol, hydroxamic acid, pentose or hexose;
Pyrogallol-1,3-dimethyl ether and the like may be combined.

In the color developing solution, various chelating agents can be used in combination as a sequestering agent. Polymer compounds as well as other chelating agents such as ethylenediaminetetraacetic acid, aminopolycarboxylic acids such as diethylenetriaminepentaacetic acid, 1-hydroxyethylidene-
Organic phosphonic acids such as 1,1-diphosphonic acid, aminopolyphosphonic acids such as aminotri (methylenephosphonic acid) or ethylenediaminetetraphosphoric acid, oxycarboxylic acids such as citric acid or gluconic acid, 2-phosphonobutane-1,2,4
-Phosphonocarboxylic acids such as tricarboxylic acids, and polyphosphoric acids such as tripolyphosphoric acid and hexametaphosphoric acid.

The preferable replenishment amount of the color developing solution in the continuous processing is as follows in the case of a color negative film.
The following are preferred m ² per 1500 ml, more preferably 250ml~9
00 ml, more preferably 300-700 ml. 20-300ml for color paper processing, preferably 30-1
60 ml.

Next, the case where the processing solution of the present invention is a processing solution having a bleaching ability, that is, a bleaching solution or a bleach-fixing solution will be described.

In the present invention, it is particularly preferable to use the above-mentioned polymer compound in the form of a ferric complex salt in the bleaching solution or the bleach-fixing solution.

The amount of these compounds to be added to the processing solution having bleaching ability is preferably in the range of 1 to 30 g, more preferably 10 to 15 g, per liter.

In the present invention, in the bleaching solution or the bleach-fixing solution, besides the iron complex salt of the above-mentioned polymer compound, a ferric complex salt of the following compound can be used as a bleaching agent.

[A'-1] ethylenediaminetetraacetic acid [A'-2] trans-1,2-cyclohexanediaminetetraacetic acid [A'-3] dihydroxyethylglycinic acid [A'-4] ethylenediaminetetrakismethylenephosphonic acid [ A'-5] Nitrilotrismethylene phosphonic acid [A'-6] Diethylenetriamine pentakismethylenephosphonic acid [A'-7] Diethylenetriaminepentaacetic acid [A'-8] Ethylenediamine diorthohydroxyphenylacetic acid [A'-9] Hydroxy Ethyl ethylene diamine triacetic acid [A'-10] Ethylene diamine propionic acid [A'-11] Ethylene diamine diacetic acid [A'-12] Hydroxyethyl iminodiacetic acid [A'-13] Nitrilotriacetic acid [A'-14] Nitrilo tripropion Acid [A'-15] triethylenetetramine hexaacetic acid A'-16] Ethylenediaminetetrapropionic acid The addition amount of the above-mentioned ferric organic acid complex salt is preferably 0.05 to 2.0 mol, more preferably 0.10 to 1.5 mol / l, per liter of the bleaching solution or the bleach-fixing solution. Range.

The bleaching solution and the bleach-fixing solution are described in JP-A-64-295.
No. 258 discloses imidazole and derivatives thereof or compounds represented by general formulas [I] to [IX] described in the publication and at least one of these exemplified compounds. Can play.

In addition to the above-mentioned accelerators, exemplified compounds described on page 51 to page 115 of JP-A-62-123459 and JP-A-62-123459.
The exemplified compounds described on pages 22 to 25 of JP-A No. 3-17445, the compounds described in JP-A-53-95630, JP-A-53-28426, and the like can also be used in the same manner.

The temperature of the bleaching solution and the bleach-fixing solution is 20 ° C. to 50 ° C.
It is preferably used at 25 ° C to 45 ° C.

The pH of the bleaching solution is preferably 6.0 or less, more preferably 1.0 or more and 5.5 or less. The pH of the bleach-fix solution is preferably 5.0 to 9.0, more preferably 6.0 to 8.5.
It is. The pH of the bleaching solution or the bleach-fixing solution is the pH of the processing tank when processing the silver halide light-sensitive material, and can be clearly distinguished from the pH of a so-called replenisher.

In addition to the above, the bleaching solution or the bleach-fixing solution may contain a halide such as ammonium bromide, potassium bromide or sodium bromide, various fluorescent whitening agents, defoaming agents or surfactants. it can.

A preferable replenishing amount of the bleaching solution or the bleach-fixing solution is 500 ml or less, preferably 20 ml to 400 ml, most preferably 40 ml to 350 ml per m ^{2 of the} silver halide color photographic light-sensitive material. The effect of the present invention becomes more remarkable as it becomes.

In the present invention, in order to increase the activity of the bleaching solution or bleach-fixing solution, air or oxygen may be blown in the processing bath and in the processing replenisher storage tank as required, or a suitable oxidation may be carried out. Agents such as hydrogen peroxide,
Bromates, persulfates and the like may be appropriately added.

As a fixing agent used in the bleach-fixing solution or the fixing solution according to the present invention, thiocyanates and thiosulfates are preferably used. The content of the thiocyanate is preferably at least 0.1 mol / l or more, and more preferably 0.5 mol / l or more, and particularly preferably 1.0 mol / l or more when a color negative film is processed. The thiosulfate content is preferably at least 0.2 mol / l or more, and more preferably 0.5 mol / l or more when a color negative film is processed.

The bleach-fixing solution or the fixing solution according to the present invention may contain one or two or more pH buffers consisting of various salts in addition to these fixing agents. Further, it is desirable to contain a large amount of a rehalogenating agent such as an alkali halide or an ammonium halide, for example, potassium bromide, sodium bromide, sodium chloride or ammonium bromide. In addition, compounds known to be added to a normal bleach-fix solution, such as alkylamines and polyethylene oxides, can be appropriately added.

Incidentally, silver may be recovered from the bleach-fix solution according to the present invention by a known method.

It is preferable to add to the bleach-fixing solution a compound represented by the following general formula [FA] described on page 56 of JP-A-64-295258 and its exemplified compounds. In addition to better performance, another effect is obtained in that a small amount of sludge is generated in a processing solution having a fixing ability when a small amount of photosensitive material is processed for a long time.

[0086]

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The compound represented by the general formula [FA] in the same specification is disclosed in US Pat. No. 3,335,161 and US Pat. No. 3,260,718.
It can be synthesized by a general method as described in the specification. These compounds represented by the general formula [FA] may be used alone or in combination of two or more.

Good results can be obtained when the amount of the compound represented by the general formula [FA] is in the range of 0.1 to 200 g per liter of the processing solution.

The processing time with the bleaching solution and the bleach-fixing solution is optional, but is preferably 3 minutes and 30 seconds or less, respectively.
More preferably 10 seconds to 2 minutes 20 seconds, particularly preferably 20 seconds to
The range is 1 minute and 20 seconds. The processing time with the bleach-fixing solution is preferably 4 minutes or less, more preferably from 10 seconds to 2 minutes and 20 seconds.

When the ratio of ammonium ion to all cations in the processing solution for a silver halide color photographic light-sensitive material according to the present invention is 50 mol% or less, not only the effect of the present invention is improved, but also the effect is improved. This is one of the preferred embodiments of the present invention because of its low odor. Particularly, it is preferably at most 30 mol%, particularly preferably at most 10 mol%.

The bleaching solution and the bleach-fixing solution according to the present invention include:
It can contain a compound represented by the general formula [II] described in Japanese Patent Application No. 4-64897 and hydroxyacetic acid.

[0092]

Next, the present invention will be described in more detail with reference to examples of the present invention, but the present invention is not limited to these examples.

Example 1 As a photographic processing solution, a color developing solution having the following composition was prepared.

Potassium carbonate 25.0 g Sodium bicarbonate 2.5 g Potassium sulfite 2.0 g Sodium bromide 1.3 g Potassium iodide 1.2 mg Hydroxylamine sulfate 2.8 g Sodium chloride 0.6 g 4-Amino-3-methyl-N-ethyl-N- (β-hydroxylethyl) aniline sulfate 4.4 g Diethylenetriaminepentaacetic acid 3.0 g Potassium hydroxide 1.2 g Add water to make 1 liter, and adjust the pH to 10.00 using potassium hydroxide or 20% sulfuric acid.

The above developer was used as sample (A), and the above-mentioned exemplary compound 1 was added at a ratio of 2 g / l to sample (B).
And Sample (C) to which 2 g / l of the same exemplary compound 3 was added, (D) to which 2 g of the same exemplary compound 8 was added, and (E) to which 2 g of the same exemplary compound 8 was added.
(F), 2 g of the same exemplified compound 11 (G), sodium hexametaphosphate (HM)
(H) and a sample (I) to which 3.3 g / l of a 60% solution of 1-hydroxyethylidene-1,1-diphosphonic acid (abbreviated as HEDP) was added. ),
Sample (J) was prepared by adding 2 g / l of ethylenediaminetetraacetic acid (abbreviated to EDTA), and sample (K) was prepared by adding 2 g / l of nitrilotrimethylenephosphonic acid (abbreviated to NTP) to prepare seven kinds of samples. . Since the pH of each sample varied depending on the substance added, the pH was adjusted to 10.0 using potassium hydroxide or dilute sulfuric acid, and the following experiments were performed. The results of each experiment are summarized at the end.

Experiment 1 The above developer samples (A) to (K) were added with ferric ion of 1.5 p
After adding pm and 0.7 ppm of copper ions, respectively, and allowing the mixture to stand at 30 ° C. for 10 days, hydroxylamine was quantitatively analyzed to determine its reduction rate.

Experiment 2 Konica Color XG400 film (manufactured by Konica Corporation)
Was given a white step exposure using a sensitometer,
Using each of the developer samples (A) to (K) that had been allowed to stand for 10 days, color development was performed according to the following steps.

Processing step Processing time Processing temperature Color development 3 minutes 15 seconds 38 ° C. Bleaching 45 seconds 38 ° C. Fixing 1 minute 30 seconds 38 ° C. Stabilization 50 seconds 38 ° C. Drying 1 minute 40-70 ° C. The composition of the treated solution was as follows.

Bleaching solution 1.3-ammonium diiron propylenediaminetetraacetate 0.32 mol Ethylenediaminetetraacetic acid disodium 10 g ammonium bromide 100 g glacial acetic acid 40 g ammonium nitrate 40 g Water was added to make 1 liter, and the pH was adjusted to 4.4 using ammonia water or glacial acetic acid. Adjust to

Fixing solution (tank solution and replenisher) Ammonium thiosulfate (70% solution) 350 ml Sodium bisulfite anhydrous 10 g Sodium metabisulfite 2.5 g Disodium ethylenediaminetetraacetate 0.5 g Stabilizing solution (tank solution and replenisher) Hexamethylene Tetramine 5g Diethylene glycol 10g

[0101]

Embedded image

Adjust the pH to 8.0 with KOH, add water and add 1
Finish to liter.

[0103] After the above color development processing,
The fog density of the blue reflection density of the unexposed area was measured using a PDA65 type photoelectric densitometer (manufactured by Konica Corporation).

Experiment 3 Calcium ion was added to each of the developer samples (A) to (K).
Add 200ppm and 3000ppm of sodium ion and add 7ppm at 25 ℃
The mixture was allowed to stand for a few days, and the occurrence of precipitation was observed.

Table 1 summarizes the results of Experiments 1 to 3 described above.

[0106]

[Table 1]

(Note) In Experiment 3, ○ indicates that no precipitation occurred, and the larger the number of ×, the more precipitation occurred.

As can be seen from the results in the above table, the developer samples (B) to (G) according to the present invention have a low decomposition of hydroxylamine, a low fog, and no precipitation due to the presence of metal ions.

On the other hand, the comparative sample (I) has some effects on the inhibition of hydroxylamine decomposition and the generation of fog, but has no effect on the generation of precipitates due to the presence of metal ions, and cannot be used.

Furthermore, the comparative sample (J) has the same effect on the occurrence of precipitation as the chelating agent used in the present invention, but accelerates the decomposition of hydroxylamine, generates remarkable fog, and is not usable. Samples (A), (H) and (K) also degrade hydroxylamine to cause fogging and have a weak ability to prevent precipitation due to the presence of metal ions, making them unsuitable for practical use.

Example 2 A first reversal film developer (black and white developer) having the following composition was prepared as a photographic processing composition.

Potassium sulfite (50% solution) 35.0 ml Sodium bromide 2.0 g Sodium thiocyanate 1.1 g Potassium iodide 3.0 mg Diethylene glycol 20.0 ml 1-Phenyl-3-pyrazolidone 0.58 g Hydroquinone 6.5 g Potassium carbonate 25.0 g Potassium hydroxide 2.8 g Make up to 1 liter with water.

The above developer was used as a sample (L), and ethylenediaminetetraacetic acid (abbreviated to EDTA) was added thereto at a ratio of 2 g / l to obtain a sample (M). Similarly, Exemplified Compound 1 is replaced with 2
A sample (N) was added at a rate of g / l, and a sample (O) was added at 2 g / l of ethylenediaminetetramethylenephosphonic acid (abbreviated as EDTP), thereby preparing four kinds of samples. Each sample was prepared using potassium hydroxide or 20% sulfuric acid and had a pH of 10.
Adjusted to be 0.

To each of the above samples, 2.5 ppm of ferric ion and 220 ppm of calcium ion were added, and after storing at 40 ° C. for 5 days, quantitative analysis was performed to determine the phenidone reduction rate, and to determine the occurrence of precipitation. The situation was observed.

Table 2 shows the obtained results.

[0116]

[Table 2]

(Note) In the table, ○ indicates that no precipitation occurred,
The larger the value of ×, the more precipitation occurred.

As shown by the above results, the comparative sample (M)
Although effectively prevents precipitation due to the presence of metal ions, it promotes the decomposition of phenidone, a developing agent.

On the other hand, the comparative samples (L) and (O) have little or no effect on the decomposition of phenidone, and have little effect on preventing the occurrence of precipitation. On the contrary, it can be seen that the sample (N) containing the chelating agent used in the present invention effectively prevents the occurrence of precipitation and also favorably suppresses the decomposition of phenidone.

Example 3 As a photographic processing composition, a fixing solution and a bleach-fixing solution having the following compositions were prepared, and the effects of the exemplified compounds on the occurrence of precipitation by metal ions were tested for both solutions.

Fixing solution Ammonium thiosulfate 180 g Ammonium sulfite 20 g Potassium metabisulfite 5 g Make up to 1 liter with water.

Bleaching / fixing solution Ammonium iron (III) ethylenediaminetetraacetate 70 g Ammonium sulfite (40% solution) 25 ml Ammonium thiosulfate (70% solution) 180 ml Ammonia water (28% solution) 30 ml Make up to 1 liter with water.

The above fixing solution and bleach-fixing solution were used for comparison as they were, and some of the exemplified compounds 1, 2 and
3, 8, 9 and 12 were each added at a rate of 5 g / l to make eight samples each. These solutions were adjusted to pH 6.8 for the fixing solution and pH 7.1 for the bleach-fixing solution using ammonium water or acetic acid, and 200 ppm of calcium ion (added as CaCl ₂ ) was added to each solution. .

When this was left to stand, the comparative sample to which nothing was added caused severe precipitation in both the fixer and the bleach-fixer, but Exemplified Compounds 1, 2, 3, 8, 9 and 12 were added. No precipitate was generated.

Example 4 As a photographic processing composition, a stabilizer having the following composition (also referred to as a washing substitute stabilizer) was prepared, 10% of the bleach-fixer used in Example 1 was added, and the suspension was formed by sulfidation. The effect of preventing the generation of a substance was tested.

Stabilizing solution 5-chloro-2-methyl-4-isothiazolin-3-one 0.03 g 2-methyl-4-isothiazolin-3-one 0.02 g ethylene glycol 2.0 g 2-octyl-4-isoazolin-3-one 0.01 g Benzotriazole 1.2 g Ammonia water (28%) 3.0 ml Make up to 1 liter with water and add potassium hydroxide and 20% sulfuric acid to p.
Adjusted to H8.2.

The above-mentioned stabilizing solution was used as it was for comparison. To one part, Exemplified Compounds 1, 3, 5, 7, 9, and 10 were respectively added at a rate of 3.0 g / l, and each of the six types was added. A sample was made.

These stable liquids were adjusted to pH 8.2 with KOH or 20% sulfuric acid, and 80 ppm of calcium ion was added to each liquid and allowed to stand. As a result, in the case of the comparative sample to which nothing was added, precipitation occurred in 2 days, and a suspended matter was generated on the surface.
No abnormalities were observed even after 10 days. In addition, the effect was also recognized for the occurrence of hue.

Example 5 Konica Color QA Paper Type A3 (manufactured by Konica Corporation) was exposed according to a conventional method, and then developed using the following processing steps and processing solutions.

Processing Step Processing Temperature Processing Time (1) Color Development 35.0 ± 0.3 ° C. 45 seconds (2) Bleaching and Fixing 35.0 ± 0.5 ° C. 45 seconds (3) Stabilization 30-34 ° C. 90 seconds (4) Drying 60-80 Color developing solution Triethanolamine 10 g Diethylene glycol 6 g N, N-diethylhydroxylamine 3.6 g 2,2'-hydroxyimino-bis-ethanesulfonic acid disodium salt 5.0 g Potassium bromide 20 mg Potassium chloride 3 g Diethylenetriaminepentaacetic acid 5 g Potassium sulfite 5.0 × 10 ^-4 mol Color developing agent (3-methyl-4-amino-N-ethyl-N- (β-methanesulfonamidoethyl) -aniline sulfate) 5.5 g Potassium carbonate 25.0 g Potassium hydrogen carbonate 5 g Water To make the total volume 1 liter, and adjust the pH to 10.10 with potassium hydroxide or sulfuric acid.

Bleaching / fixing solution Water 600 ml Ferric nitrate 0.10 mol Polymer compound of the present invention (chelating agent) Table 3 Ammonium thiosulfate 180 g Ammonium sulfite (70% solution) 20 ml Silver chloride 6.5 g 1,3-propanediaminetetraacetic acid 2.0 g Adjust the pH to 6.5 using aqueous ammonia and acetic acid as appropriate,
Finish to liter.

Stabilizer Orthophenylphenol 0.1 g Ubitex MST (manufactured by Ciba Geigy) 1.0 g ZnSO ₄ , 7H ₂ O 0.1 g ammonium sulfite (40% solution) 5.0 ml 1-hydroxyethylidene-1,1-diphosphonic acid (60 % Solution) 3.0 g Ethylenediaminetetraacetic acid 1.5 g Adjust the pH to 7.8 with aqueous ammonia or sulfuric acid and make up to 1 l with water.

After processing the light-sensitive material, the amount of residual silver in the exposed portions was measured by X-ray fluorescence. Table 3 shows the results.

[0134]

[Table 3]

As shown in the results in Table 3, when the polymer compound of the present invention was used in combination with ferric ion,
It turns out that it has the performance as a bleach like EDTA.

Example 6 A Konica Color XG400 film (manufactured by Konica Corporation) was exposed to wedges according to a conventional method, and then developed according to the following processing steps.

The processing steps are described below. Color developing solution Potassium carbonate 28.0 g Sodium hydrogen carbonate 2.0 g Potassium sulfite 3.0 g Sodium bromide 1.2 g Potassium iodide 0.9 mg Hydroxylamine sulfate 2.7 g Sodium chloride 0.6 g 4-Amino-3-methyl-N-ethyl-N- (β-Hydroxyethyl) aniline sulfate 4.5 g Diethylenetriaminepentaacetic acid 3.0 g Potassium hydroxide 1.2 g Water was added to 1 liter, and the pH was adjusted to 10.00 with potassium hydroxide or 20% sulfuric acid.

Bleaching solution Ferric nitrate 0.3 mol Polymer compound of the present invention (chelating agent) described in Table 4 Ethylenediaminetetraacetic acid 10 g Ammonium bromide 1.2 mol Glacial acetic acid 40 ml The pH was adjusted to 4.5 with ammonia water and acetic acid, and water was added. Add to 1 liter.

Fixing solution Ammonium thiosulfate (70% solution) 350 ml Anhydrous sodium bisulfite 10 g Sodium metabisulfite 2.5 g Disodium ethylenediaminetetraacetate 0.5 g Stabilizing solution Hexamethylenetetramine 5 g Diethylene glycol 10 g

[0140]

Embedded image

Adjust the pH to 8.0 with KOH, add water and add 1
Finish to liter.

The amount of residual silver in the exposed portions of the developed film sample was measured by a fluorescent X-ray method. Table 4 shows the results.

[0143]

[Table 4]

As is evident from Table 4, the polymer compound of the present invention has a bleaching performance similar to that of EDTA when used in combination with ferric ion.

Example 7 The chelating agent, ethylenediaminetetraacetic acid (EDTA), which is known to be commonly used for photography, and Exemplified Compounds 1 and 3 are described in OECD Chemical Test Guideline 30.
The biodegradability was determined in accordance with the 1C modified MITI test (I) (adopted on May 12, 1981).

Table 5 shows the results.

[0147]

[Table 5]

From the above Table 5, it can be seen that the chelating agent of the present invention has very good biodegradability, whereas EDTA hardly decomposes, and the chelating agent of the present invention is very preferable from the viewpoint of protecting the global environment. It turns out there is.

[0149]

The processing solution for silver halide photography of the present invention comprises:
Stable processing solution with good desilvering property, no stain on edges, excellent storage stability, no precipitation or sludge due to the presence of metal ions, and photo It is excellent in biodegradability of treatment liquids and is suitable for protecting the global environment.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI G03C 7/42 G03C 7/42 11/00 501 11/00 501

Claims (14)

(57) [Claims] 1. A polymer compound having a carboxyl group or a salt thereof in at least one repeating unit, wherein the polymer has a main chain substantially in the form of a condensate. Characteristic processing solution for silver halide photographic materials. 2. The polymer according to claim 1, wherein the main chain of the polymer has an ester bond and / or
2. The processing solution for a silver halide photographic light-sensitive material according to claim 1, which comprises an amide bond. 3. The method according to claim 1, wherein the monomer component of the polymer comprises an amino acid or a salt thereof.
Or the processing solution for silver halide photographic light-sensitive materials according to 2. 4. The processing solution for a silver halide photographic light-sensitive material according to claim 1, wherein the processing solution contains at least a hydroxycarboxylic acid compound or a salt thereof as a monomer component constituting the polymer. 5. The processing solution for a silver halide photographic light-sensitive material according to claim 1, wherein said polymer compound is a polyamino acid. 6. A processing solution for a silver halide photographic light-sensitive material according to claim 1, wherein at least aspartic acid and / or glutamic acid are contained as monomer components constituting said polymer. 7. A processing solution for a silver halide photographic light-sensitive material according to claim 1, wherein said hydroxycarboxylic acid compound is malic acid, citric acid or tartaric acid. 8. A process for a silver halide photographic light-sensitive material according to claim 1, wherein said polymer compound is a copolyesteramide comprising aspartic acid and malic acid. liquid. 9. The polymer compound having a number average molecular weight of 40
9. The method according to claim 1, wherein the number is from 0 to 50,000.
A processing solution for a silver halide photographic light-sensitive material as described above. 10. The processing solution for a silver halide photographic light-sensitive material according to claim 1, wherein said processing solution is a black-and-white developing solution or a color developing solution. 11. A processing solution for a silver halide photographic material according to claim 1, wherein said processing solution is a bleaching solution or a bleach-fixing solution. 12. The processing solution for a silver halide photographic light-sensitive material according to claim 1, wherein said processing solution is a fixing solution. 13. The processing solution for a silver halide photographic light-sensitive material according to claim 1, wherein said processing solution is a stabilizing solution. 14. The treatment liquid comprising the polymer compound and the second
2. A complex containing an iron ion.
12. The processing solution for a silver halide photographic light-sensitive material according to items 9 to 11.