JPH06266071A - Processing solution for silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide the stable processing solution for the silver halide photographic sensitive material preventing occurrence of precipitation and sludge due to the presence of metal ions. CONSTITUTION:The processing solution for the silver halide photographic sensitive material is characterized by containing a polymer having at least one group of repeating units each having a carboxylic group or its salt and its main polymer chain substantially comprising the form of the condensation product, or the processing solution is characterized by containing a polymer having its main polymer chain comprising ester bonds and/or amido bonds.

Description

Detailed Description of the Invention

[0001]

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, for sequestering harmful metal ions or for use as a bleaching agent,
The present invention relates to a processing solution for a silver halide photographic light-sensitive 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, it is necessary to treat with various processing solutions including a developing solution and a fixing solution. More processing steps are required, especially for obtaining color images. Since the treatment liquid used for these treatments contains a large number of components, if the water used for its preparation contains metal ions such as calcium, magnesium and iron, it reacts with them to cause precipitation. And generate sludge. Then, there are drawbacks such as clogging of a filter attached to the automatic developing processor 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 when preparing the processing solution, metal ions may be eluted from the photographic light-sensitive material during processing, or metal ions may be brought in from the previous processing step. It was extremely difficult to completely prevent the generation of sludge. Furthermore, some of the various components contained in the treatment liquid lose their effectiveness because their oxidation and decomposition are promoted by the action of metal ions, so when treated with this treatment liquid,
There are drawbacks such as generation of fog and deterioration of photosensitivity.

In order to prevent these undesirable effects of metal ions on the processing solution, it has been proposed and put into practice to add a so-called chelating agent for sequestering metal ions to the photographic processing composition. For example, British Patent 520,
Polyphosphates such as sodium hexametaphosphate proposed by US Pat. No. 5,933, alkylidene diphosphonic acids proposed by US Pat. No. 321,445, US Pat. No. 3,201,24
Examples thereof include aminopolymethylenephosphonic acid proposed in No. 6 and aminopolycarboxylic acid represented by ethylenediaminetetraacetic acid. However, even when these chelating agents are blended, there are various drawbacks in practical use and they are not satisfactory. That is, since polyphosphate has a small sequestering power for metal ions and is particularly weak against heavy metal ions, it cannot be put to practical use.

Alkylidene diphosphonic acid has a problem that when calcium ions and sodium ions coexist at a certain concentration or more, solid precipitates are generated and the automatic development processor is hindered. Ordinary aminopolycarboxylic acids represented by ethylenediaminetetraacetic acid and aminopolymethylenephosphonic acids represented by aminotrimethylenephosphonic acid have excellent sequestering power, but a color developer containing hydroxylamine. However, there is a disadvantage that hydroxylamine is decomposed in the coexistence of metal ions and fog occurs when processed with this developing solution, and in a black and white developing solution, oxidation of the developing agent is promoted to deteriorate storage stability and It has the drawback of causing significant fog on the speed film.

As described above, all of the conventionally proposed chelating agents have some drawbacks, and in reality, they are not sufficiently effective when used in a photographic processing composition. Further, due to recent social and environmental requirements such as low pollution and economic requirements such as cost reduction, the replenishment amount of the photographic processing solution tends to be reduced more and more. The accumulation amount of metal ions also tends to increase.

The raw materials used for photographic materials are also
For the purpose of cost reduction, lower grade and cheaper ones tend to be used, and the amount of metal ions accumulated in a photographic processing solution is increasing.

For this reason, in recent years, there is a situation in which conventional techniques cannot control the situation.

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

As means for solving this problem, German Patents DE 3,939,755 and DE 3,939,756 describe nitrilomonopropionic acid diacetic acid (NMPDA), nitrilodipropionic acid monoacetic acid (NDPMA), The technique of using general nitrilotriacetic acid (NTA) as a benign degradation chelate has already been disclosed. However, the NMPDA
And NDPMA are in the easy-degradability test “Modified MITI method” that is approved by the Ministry of International Trade and Industry as a biodegradability evaluation method (if it is certified as good degradation by this method, it means rapid degradation in the natural world). It has been confirmed that it hardly decomposes, and is not a fundamental solution to this problem.

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. A first object of the present invention is to provide a stable silver halide photograph free from precipitation and sludge generation due to the presence of metal ions. It is to provide a processing solution for a photosensitive material. A second object is to provide a processing solution for a silver halide photographic light-sensitive material, which can be stably processed for a long period of time when processed by an automatic development processor and does not cause 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 an excellent bleaching ability for a silver halide photographic light-sensitive material having excellent storage stability. To provide.

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

Further, other purposes will be apparent from the following specification.

[0015]

The objects of the present invention can be achieved by the following processing solution for silver halide photographic light-sensitive materials.

1. Halogenated polymer compound having a carboxyl group or a salt thereof in at least one repeating unit, the polymer main chain being substantially in the form of a condensate. A processing solution for silver photographic light-sensitive materials.

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

3. The above-mentioned 1 characterized by containing an amino acid or a salt thereof as a monomer component constituting the polymer.
Alternatively, the processing solution for silver halide photographic light-sensitive material as described in 2 above.

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

5. 3. The processing solution for silver halide photographic light-sensitive materials as described in 1 to 3, wherein the polymer compound is a polyamino acid.

6. 6. The processing solution for a silver halide photographic light-sensitive material as described in 1 to 5 above, which contains at least aspartic acid and / or glutamic acid as a monomer component constituting the polymer.

7. 7. The processing solution for 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 silver halide photographic light-sensitive material as described in 1, 2, 3, 4, 6 or 7, wherein the polymer compound is a copolyesteramide composed of aspartic acid and malic acid.

9. The number average molecular weight of the polymer compound is 4
1 to 8 characterized in that it is from 00 to 50,000
The processing liquid for a silver halide photographic light-sensitive material as described above.

10. 10. The processing solution for silver halide photographic light-sensitive materials described in 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 silver halide photographic light-sensitive materials described in 1 to 9, wherein the processing solution is a bleaching solution or a bleach-fixing solution.

12. 10. The processing solution for silver halide photographic light-sensitive materials described in 1 to 9, wherein the processing solution is a fixing solution.

13. 10. The processing solution for a silver halide photographic light-sensitive material as described in 1 to 9, wherein the processing solution is a stabilizing solution.

14. 12. The processing solution for a silver halide photographic light-sensitive material 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.

The present invention will be described in detail below. The processing liquid in the present invention means a developing tank liquid and a replenishing liquid.

Specific preferred examples of the polymer compound are shown below, but the invention is not limited thereto.

[0032]

[Chemical 1]

[0033]

[Chemical 2]

As the method for synthesizing the polymer compound in the present invention, ring-opening polymerization and ring-opening copolymerization can also be preferably used. Further, when an amino acid is included 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 Material” by Yoshiharu Dohi (Industrial Research Association of Japan), Chapter 7 and other generally known methods.

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

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

The photographic processing solution of the present invention can be applied to any processing solution for processing a silver halide photographic light-sensitive material. For example, general black-and-white developing solution, squirrel infectious developing solution, color developing solution, bleaching solution, fixing solution, bleach-fixing solution, stop solution, hardening solution, stabilizing solution, fog solution and toning solution can be mentioned. However, the present invention is not limited to these.
Further, the photographic processing liquid of the present invention should be used for the processing of all silver halide photographic light-sensitive materials such as color films, color photographic papers, black and white films for general use, X-ray films, lith films for printing and micro films. You can

After the bleach-fixing treatment employed in the present invention, it is preferable to employ a stabilizing treatment with a stabilizing solution.

For the purpose of the present invention, it is particularly preferable that the stabilizing solution contains a chelating agent having a chelate stability constant of 8 or more for iron ions. Here, the chelate stability constant is the value of Stability by LG Sillen, AEMarttell.
Constants of Metal-ion Complexes ”The Chemical
Society, London (1964), S.Chaberek, AEMartell “
Organic Sequestering Agents ”Wiley (1959) etc. mean a constant generally known.

The chelate stability constant for iron ions is 8
As the chelating agent as described above, an organic carboxylic acid chelating agent, an organic phosphoric acid chelating agent, an inorganic phosphoric acid chelating agent,
Examples thereof include polyhydroxy compounds. The iron ion means ferric ion (Fe ³⁺ ).

The chelate stability constant with ferric ion is 8
Specific examples of the chelating agent are the following compounds, in addition to the polymer compound of the present invention,
It is not limited to these. That is, ethylenediaminedioltohydroxyphenylacetic 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, among which 1-hydroxyethylidene-1,1-diphosphonic acid is most preferably used.

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

As a preferable compound added to the stabilizing solution, an ammonium compound can be mentioned. These are supplied by various inorganic and organic ammonium salts, and 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 hydrogen tartrate, ammonium thiosulfate, ammonium sulfite, ammonium ethylenediaminetetraacetate, ferric ammonium ethylenediaminetetraacetate, ammonium lactate, apple Ammonium acid, ammonium maleate, ammonium oxalate, phthalate Ammonium, ammonium picrate, pyrrolidine ammonium dithiocarbamate,
Examples thereof include ammonium salicylate, ammonium succinate, ammonium sulfanilate, ammonium tartrate, ammonium thioglycolate, and 2,4,6-trinitrophenol ammonium. These may be used alone or in combination of two or more. The addition amount of the ammonium compound is preferably 0.001 mol to 1.0 mol, and more preferably 0.002 to 0.8 mol, per liter of the stabilizing solution.

Further, the stabilizing solution preferably contains sulfite. The sulfite may be any organic substance or inorganic substance as long as it releases a sulfite ion, but is preferably an inorganic salt. Examples of preferred specific compounds include sodium sulfite, potassium sulfite, ammonium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, sodium metabisulfite, potassium metabisulfite, ammonium metabisulfite and hydrosulfite. To be The above sulfite is preferably added to the stabilizing solution in an amount of at least 1 × 10 ^-3 mol / liter, more preferably 5 × 10 ^-3 mol / liter to 10 ^-1 mol / liter. Such an amount is added, and it is particularly effective in preventing stains. As an addition method, it may be added directly to the stabilizing solution, but it is preferably added to the stabilizing replenishing solution.

Other commonly known compounds that can be added to the stabilizing solution 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 adjuster (eg phosphate, borate, hydrochloric acid, sulfuric acid, etc.), antifungal agent (eg phenol derivative, catechol derivative, imidazole derivative, triazole derivative, siabendazole) Derivatives, organohalogen compounds, and other paper-antifungal agents known as slime control agents in the pulp industry) or optical brighteners, surfactants, preservatives, Bi, Mg, Zn,
There are metal salts such as Ni, Al, Sn, Ti and Zr. One or two or more of these compounds can be arbitrarily selected and used within a range that does not impair the effects of the present invention.

No washing treatment is required after the stabilizing treatment, but rinsing by a small amount of washing in a very short time, surface washing and the like can be optionally performed.

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 stabilizing solution at a concentration of at least 5 × 10 ⁻³ mol / liter, more preferably 8 × 10 ^{−3 to} 150 × 10 ⁻³ mol / liter, and further preferably 12 x 10 ^-3
It is in the range of up to 100 × 10 ⁻³ mol / liter. These soluble iron salts may be added to the stabilizing solution (tank solution) by adding them to the stabilizing solution replenishing solution, or they can be dissolved in the stabilizing solution (tank solution) from the photosensitive material to form the stabilizing solution (tank solution). It may be added, or may be added to the stabilizing solution (tank solution) by adhering it to the photosensitive material to be processed from the prebath and bringing it in.

In the present invention, a stabilizing solution containing calcium ion and magnesium ion of 5 ppm or less which has been treated with an ion-exchange resin may be used, and the stabilizer containing the anti-biological agent and the halogen ion-releasing compound. You may use the method.

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

The treatment temperature during the stabilization treatment is 15 ° C. to 70 ° C.
C is preferable, and more preferably in the range of 20 to 55 ° C. The treatment 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, and more preferably 0.5 to 30 times the carrying amount of the pre-bath (bleach-fixing solution) per unit area of the light-sensitive material in view of rapid processing property and storability of dye image. preferable.

The stabilizing tank is preferably composed of a plurality of tanks, preferably 2 to 6 tanks, particularly preferably 2 to 3 tanks, and more preferably 2 tanks. It is preferable to use a system in which the solution is supplied to the post-bath and overflows from the pre-bath.

As the color developing agent used in the color development processing step, there are aminophenol compounds and p-phenenediamine compounds, but in the present invention, p-phenenediamine compounds having a water-soluble group are used. Compounds are preferred. Such water-soluble groups, those having at least one on the amino group or base benzene nucleus of p- phenylenediamine compound, as a specific water-soluble _{group, - (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.

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

[0055]

[Chemical 3]

[In the formula, 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]

[Chemical 4]

[Wherein, R ₁₃ and R ₁₄ are each a carbon number of 1 to
4 represents an alkyl group of 4 and R ₁₅ represents a linear or branched alkylene group having 3 to 4 carbon atoms. ]

[0059]

[Chemical 5]

[Wherein R ₁₆ represents an alkyl group, and R ₁₇
Represents an alkylene group having 2 or more carbon atoms in the main chain. R ₁₈
R ₁₉ 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 invention are shown below.

[0061]

[Chemical 6]

[0062]

[Chemical 7]

Of the above-illustrated color developing agents, preferred for use in the present invention are (A-1), (A-2), and (A-
3), (A-4), (A-6), (A-7) and (A-
15), (A-17) and (A-18), and particularly (A-1) or (A-3).

The above color developing agent is usually used in the form of a salt such as a hydrochloride, a sulfate or a p-toluenesulfonate. The amount of color developing agent added is preferably 0.5 × 10 ^-2 mol or more, more preferably 1.0 × 10 ^{-2 to} 1.0 × 10 ^-1 mol, and most preferably 1.5 per liter of the color developing solution. It is in the range of × 10 ^{-2 to} 7.0 × 10 ^-2 mol.

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

The pH of the color developer is usually 7 or higher, preferably about 9-13.

In the color developing solution, if necessary, as an antioxidant, for example, tetronic acid, tetronimide, 2-anilinoethanol, dihydroxyacetone, secondary aromatic 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 sequestering agents. In addition to polymer compounds, other chelating agents such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid and other aminopolycarboxylic acids, 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
Examples thereof include phosphonocarboxylic acid such as tricarboxylic acid, polyphosphoric acid such as tripolyphosphoric acid or hexametaphosphoric acid, and the like.

The preferable replenishment amount of the color developing solution in the continuous processing is the photosensitive material 1 for the color negative film.
It is preferably 1500 ml or less per m ² , more preferably 250 ml to 9
It is 00 ml, more preferably 300 ml to 700 ml. 20-300 ml, preferably 30-1 for color paper processing
It is 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 polymer compound in the form of ferric complex salt in the bleaching solution or the bleach-fixing solution.

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

In the present invention, the bleaching solution or the bleach-fixing solution may contain, as a bleaching agent, a ferric iron complex salt of the following compound in addition to the iron complex salt of the polymer compound.

[A′-1] ethylenediaminetetraacetic acid [A′-2] trans-1,2-cyclohexanediaminetetraacetic acid [A′-3] dihydroxyethylglycinic acid [A′-4] ethylenediaminetetrakismethylenephosphonic acid [A′-4] A'-5] Nitrilotrismethylenephosphonic acid [A'-6] diethylenetriaminepentakismethylenephosphonic acid [A'-7] diethylenetriaminepentaacetic acid [A'-8] ethylenediaminedioltohydroxyphenylacetic acid [A'-9] hydroxy Ethyl ethylenediamine triacetic acid [A'-10] ethylenediamine propionic acid [A'-11] ethylenediamine diacetic acid [A'-12] hydroxyethyliminodiacetic acid [A'-13] nitrilotriacetic acid [A'-14] nitrilotripropion Acid [A'-15] triethylenetetramine hexaacetic acid A'-16] Ethylenediaminetetrapropionic acid The amount of the ferric iron complex salt of an organic acid to be added is preferably in the range of 0.05 to 2.0 mol, and more preferably 0.10 to 1.5 mol / l, per liter of the bleaching solution or the bleach-fixing solution. Is the range.

The bleaching solution and the bleach-fixing solution are described in JP-A 64-295.
Imidazole and its derivative described in Japanese Patent No. 258, or compounds represented by the general formulas [I] to [IX] described in the same publication and at least one of these exemplified compounds are effective for the rapidity of treatment. Can play.

In addition to the above accelerators, the exemplified compounds described on pages 51 to 115 of JP-A-62-123459 and JP-A-6-123459
The exemplified compounds described on pages 22 to 25 of JP-A 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-fixing solution is preferably 5.0 to 9.0, more preferably 6.0 to 8.5.
Is. The pH of the bleaching solution or the bleach-fixing solution is the pH of the processing bath during the processing of the silver halide light-sensitive material, and can be clearly distinguished from the pH of the so-called replenishing solution.

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

The preferable replenishing amount of the bleaching solution or the bleach-fixing solution is 500 ml or less per 1 m ^{2 of the} silver halide color photographic light-sensitive material, preferably 20 ml to 400 ml, most preferably 40 ml to 350 ml, and to a low replenishing amount. The higher the degree, the more remarkable the effect of the present invention becomes.

In the present invention, in order to increase the activity of the bleaching solution or the bleach-fixing solution, air or oxygen may be blown in the processing bath and the tank for storing the replenishing solution, if desired, or suitable oxidation may be carried out. Agents, such as hydrogen peroxide,
Bromate, persulfate and the like may be added as appropriate.

As the 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 thiocyanate is preferably at least 0.1 mol / l or more, more preferably 0.5 mol / l or more, and particularly preferably 1.0 mol / l or more when processing a color negative film. The content of thiosulfate is preferably at least 0.2 mol / l or more, and more preferably 0.5 mol / l or more when processing a color negative film.

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

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

To the bleach-fixing solution, it is preferable to add the compound represented by the following general formula [FA] described on page 56 of JP-A No. 64-295258, and its exemplified compounds. In addition to better performance, another effect is obtained in that, when a small amount of the light-sensitive material is processed for a long time, the amount of sludge generated in the processing solution having fixing ability is extremely small.

[0086]

[Chemical 8]

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

Good results are obtained when the amount of the compound represented by the general formula [FA] added is in the range of 0.1 to 200 g per liter of the treatment liquid.

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

When the ratio of ammonium ion to the total cations in the processing solution for silver halide color photographic light-sensitive material of the present invention is 50 mol% or less, not only the effect of the object of the present invention is better. However, it is one of the preferred embodiments of the present invention because it has little odor. It is particularly preferably 30 mol% or less, particularly preferably 10 mol% or less.

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

[0092]

EXAMPLES 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 A color developing solution having the following composition was prepared as a photographic processing solution.

Potassium carbonate 25.0 g Sodium hydrogen carbonate 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 to pH 10.00 with potassium hydroxide or 20% sulfuric acid.

The above developing solution was used as a sample (A), and the exemplified compound 1 was added thereto at a rate of 2 g / l to prepare a sample (B).
And The same Exemplified Compound 3 (2 g / l) was added to the sample (C), 15 (2 g) was added (D), the same Exemplified Compound 8 (2 g) was added (E), and the same Exemplified Compound 9
(F) with the addition of 2 g of the same, and (G) with the addition of 2 g of the same exemplified compound 11 as sodium hexametaphosphate (HM
P (abbreviated as P) at 2 g / l was added as a sample (H), and 60% solution of 1-hydroxyethylidene-1,1-diphosphonic acid (abbreviated as HEDP) at 3.3 g / l was added as a sample (I). ),
Seven kinds of samples were prepared by adding 2 g / l of ethylenediaminetetraacetic acid (abbreviated as EDTA) to a sample (J) and adding 2 g / l of nitrilotrimethylenephosphonic acid (abbreviated as NTP) to a sample (K). . Since the pH of each sample changed depending on the added substance, potassium hydroxide or dilute sulfuric acid was used to adjust the pH to 10.0, and the following experiments were conducted. The results of each experiment are shown together 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 ion respectively and leaving it to stand at 30 ° C. for 10 days, hydroxylamine was quantitatively analyzed to determine the reduction rate.

Experiment 2 Konica Color XG400 Film (Konica Corporation)
Then, after giving white stepwise exposure using a sensitometer,
Color development processing was performed according to the following steps using the developer samples (A) to (K) after being left for 10 days.

Processing step Processing time Processing temperature Color development 3 minutes 15 seconds 38 ° C Bleach 45 seconds 38 ° C Settling 1 minute 30 seconds 38 ° C Stabilization 50 seconds 38 ° C Drying 1 minute 40 to 70 ° C For the above steps The composition of the treated liquid is as follows.

Bleaching solution 1.3-Propylenediaminetetraacetic acid diiron ammonium 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 with ammonia water or glacial acetic acid. Adjust to.

Fixer (tank solution and replenisher) Ammonium thiosulfate (70% solution) 350 ml Anhydrous sodium bisulfite 10 g Sodium metabisulfite 2.5 g Ethylenediaminetetraacetic acid disodium 0.5 g Stabilizer (tank solution and replenisher) Hexamethylene Tetramine 5g Diethylene glycol 10g

[0101]

[Chemical 9]

The pH was adjusted to 8.0 with KOH, and water was added to 1
Finish to liters.

With respect to the products which have undergone the above color development processing,
The fog density of the unexposed portion blue reflection density 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 sodium ion, and add 7 at 25 ℃
After standing for a day, the occurrence of precipitation was observed.

The results of Experiments 1 to 3 above are summarized in Table 1.

[0106]

[Table 1]

(Note) In Experiment 3, ◯ indicates that no precipitation occurred, and the larger the number x, the more precipitation occurred.

As the results in the above table show, the developer samples (B) to (G) according to the present invention show less decomposition of hydroxylamine, less fog and no precipitation due to the presence of metal ions.

On the other hand, the comparative sample (I) has some effect on the suppression of the decomposition of hydroxylamine and the occurrence of fogging, but has no effect on the occurrence of precipitation due to the presence of metal ions and cannot be used.

Further, the comparative sample (J) has the same effect on the occurrence of precipitation as the chelating agent used in the present invention, but it accelerates the decomposition of hydroxylamine and causes remarkable fog, and cannot be used. Samples (A), (H) and (K) are not suitable for practical use because they decompose hydroxylamine to generate fog and also have a weak ability to prevent precipitation due to the presence of metal ions.

Example 2 As a photographic processing composition, a first developing solution (black and white developing solution) for reversal film having the following composition was prepared.

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 developing solution was used as a sample (L), and ethylenediaminetetraacetic acid (abbreviated as EDTA) was added thereto at a rate of 2 g / l to obtain a sample (M). Similarly, Exemplified Compound 1
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) to prepare four types of samples. Each sample used potassium hydroxide or 20% sulfuric acid and had a pH of 10.
It was 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 measure the reduction rate of phenidone and the occurrence of precipitation. I observed the situation.

The results obtained are shown in Table 2.

[0116]

[Table 2]

(Note) In the table, ○ indicates that no precipitation occurred,
The larger the number x, the more precipitation is generated.

As the above results show, the comparative sample (M)
Effectively prevents the occurrence of precipitation due to the presence of metal ions, but accelerates the decomposition of phenidone as 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 the prevention 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 suppresses the decomposition of phenidone well.

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 due to metal ions were tested for both solutions.

Fixing solution Ammonium thiosulfate 180 g Ammonium sulfite 20 g Potassium metabisulfite 5 g Water to make 1 liter.

Bleach-fixing solution Ammonium ethylenediaminetetraacetate (III) 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 are used as they are for comparison, and some of Exemplified Compounds 1, 2 and
Each of 3, 8, 9 and 12 was added at a rate of 5 g / l to make 8 kinds of samples. These solutions were adjusted to pH 6.8 for the fixer and pH 7.1 for the bleach-fixer 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 one, to which nothing was added, caused remarkable precipitation in both the fixing solution and the bleach-fixing solution, but Exemplified Compounds 1, 2, 3, 8, 9 and 12 were added. No precipitation occurred.

Example 4 As a photographic processing composition, a stabilizing solution having the following composition (also referred to as a water-washing alternative stabilizing solution) was prepared, 10% of the bleach-fixing solution used in Example 1 was added, and floating by sulfurization was carried out. The effect of preventing the generation of objects was tested.

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

The above stabilizers were used as they were for comparison, and some of the exemplified compounds 1, 3, 5, 7, 9, and 10 were added in an amount of 3.0 g / l, and 6 kinds of each were prepared. I made a sample.

These stabilizing solutions were adjusted to pH 8.2 with KOH or 20% sulfuric acid, and 80 ppm of calcium ions were added to each solution and allowed to stand. As a result, in the comparative sample to which nothing was added, precipitation occurred and a floating substance was generated on the surface in 2 days, but the exemplified compounds 1, 3, 5, 7, 9, and 10
No abnormality was observed in the samples to which was added even after 10 days. Furthermore, the effect was recognized also with respect to the occurrence of odor.

Example 5 Konica Color QA Paper Type A3 (manufactured by Konica Corporation) was exposed by 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) Bleach fixing 35.0 ± 0.5 ° C. 45 seconds (3) Stabilization 30 to 34 ° C. 90 seconds (4) Drying 60 to 80 ℃ 30 seconds Color developer Triethanolamine 10g Diethylene glycol 6g N, N-Diethylhydroxylamine 3.6g 2,2'-hydroxyimino-bis-ethanesulfonic acid disodium salt 5.0g Potassium bromide 20mg Potassium chloride 3g Diethylenetriaminepentaacetic acid 5g 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 Is added to bring the total volume to 1 liter, and the pH is adjusted to 10.10 with potassium hydroxide or sulfuric acid.

Bleach-fixing solution Water 600 ml Ferric nitrate 0.10 mol Polymeric compound of the present invention (chelating agent) described in 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 pH to 6.5 with ammonia water and acetic acid, and add 1 to the total amount.
Finish to liters.

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 pH to 7.8 with aqueous ammonia or sulfuric acid, and make up to 1 l with water.

After processing the above-mentioned light-sensitive material, the amount of residual silver in the exposure-exposed portion was measured by fluorescent X-ray. The results are shown in Table 3.

[0134]

[Table 3]

As the results in Table 3 show, by using the polymer compound of the present invention in combination with ferric ion,
It is found that it has a bleaching performance similar to that of EDTA.

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

The processing steps are shown below. Color developer Potassium carbonate 28.0g Sodium hydrogen carbonate 2.0g Potassium sulfite 3.0g Sodium bromide 1.2g Potassium iodide 0.9mg Hydroxylamine sulfate 2.7g Sodium chloride 0.6g 4-Amino-3-methyl-N-ethyl-N- (β-hydroxylethyl) aniline sulfate 4.5 g Diethylenetriaminepentaacetic acid 3.0 g Potassium hydroxide 1.2 g Add water to make 1 liter, and adjust to pH 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 Ammonia water, pH adjusted to 4.5 with acetic acid, water In addition, finish to 1 liter.

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

[0140]

[Chemical 10]

The pH was adjusted to 8.0 with KOH, and water was added to 1
Finish to liters.

The residual silver amount in the exposed portion of the developed film sample was measured by the fluorescent X-ray method. The results are shown in Table 4.

[0143]

[Table 4]

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

Example 7 For the chelating agent commonly known for use in photography, ethylenediaminetetraacetic acid (EDTA), Exemplified Compounds 1 and 3, 30 of the OECD Chemicals Test Guideline.
Biodegradability was determined according to the 1C modified MITI test (I) (adopted May 12, 1981).

The results are shown in Table 5.

[0147]

[Table 5]

From Table 5 above, the chelating agent of the present invention has extremely good biodegradability, whereas EDTA hardly decomposes, and the chelating agent of the present invention is extremely preferable from the viewpoint of global environment protection. I know there is.

[0149]

The silver halide photographic processing liquid of the present invention comprises:
It has a good desilvering property, there is no stain on the edges, and it has excellent liquid storage safety, and there is no precipitation or sludge due to the presence of metal ions, and a stable processing liquid can be obtained. It has excellent biodegradability of treatment liquid and is suitable for protecting the global environment.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI technical display location G03C 11/00 501

Claims (14)

[Claims] 1. 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. A featured processing solution for silver halide photographic light-sensitive materials. 2. The main chain of the polymer is an ester bond and / or
Alternatively, the processing liquid for silver halide photographic light-sensitive material according to claim 1, which is composed of an amide bond. 3. The amino acid or a salt thereof is contained as a monomer component constituting the polymer.
Alternatively, the processing solution for silver halide photographic light-sensitive material as described in 2 above. 4. The processing solution for silver halide photographic light-sensitive materials according to claim 1, which contains at least a hydroxycarboxylic acid compound or a salt thereof as a monomer component constituting the polymer. 5. The processing solution for silver halide photographic light-sensitive materials according to claim 1, wherein the polymer compound is a polyamino acid. 6. The processing solution for a silver halide photographic light-sensitive material according to claim 1, which contains at least aspartic acid and / or glutamic acid as a monomer component constituting the polymer. 7. The processing solution for silver halide photographic light-sensitive material according to claim 1, 2, 3, 4, or 6, wherein the hydroxycarboxylic acid compound is malic acid, citric acid, or tartaric acid. 8. The processing for silver halide photographic light-sensitive materials according to claim 1, wherein the polymer compound is a copolyesteramide composed of aspartic acid and malic acid. liquid. 9. The number average molecular weight of the polymer compound is 40.
It is 0 to 50000, It is characterized by the above-mentioned.
The processing liquid 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 the processing solution is a black-and-white developing solution or a color developing solution. 11. The processing solution for silver halide photographic light-sensitive materials according to claim 1, wherein the 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 the processing solution is a fixing solution. 13. The processing solution for a silver halide photographic light-sensitive material according to claim 1, wherein the processing solution is a stabilizing solution. 14. The treatment liquid comprises a second polymer compound and a second polymer compound.
2. A complex containing iron ions is contained.
~ 9 or 11 processing solution for silver halide photographic light-sensitive material.