JP2819487B2 - Photographic processing composition and processing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a processing composition for a silver halide photographic material and a processing method using the same.

[0002]

2. Description of the Related Art In general, a silver halide black-and-white photographic light-sensitive material is subjected to processing steps such as black-and-white development, fixing, and washing with water after exposure.
It is called a color photosensitive material. ) Is subjected to processing such as color development, desilvering, washing with water, and stabilization after exposure.
The silver halide color reversal photosensitive material is exposed, black-and-white developed,
After the reversal process, it is processed by processing steps such as color development, desilvering, washing with water, and stabilization. In the color development step in color development, the exposed silver halide particles are reduced to silver by the color developing agent, and the oxidized product of the color developing agent formed reacts with the coupler to form an image dye.

In the subsequent desilvering step, the developed silver produced in the developing step is oxidized (bleached) to a silver salt by a bleaching agent (oxidizing agent) having an oxidizing action, and is further unused by a fixing agent forming soluble silver. Is removed from the photosensitive layer together with the silver halide (fixing). Bleaching and fixing may be performed as independent bleaching steps and fixing steps, respectively, or may be performed simultaneously as bleach-fixing steps. Details of these processing steps and their compositions are described in James, The Theory of Photographic Process (4th Edition).
Edition) (James, “The Theory of Photographic Process
"4'th edition) (1977), Research Disclosure No. 17643, pp. 28-29, ibid.
No. 307105 No. 880 of No. 307105
On page 881. In addition to the above basic processing steps, to maintain the photographic and physical quality of the dye image,
Alternatively, various auxiliary steps are added for the purpose of maintaining the stability of the treatment and the like. For example, a washing step, a stabilizing step, a hardening step, a stopping step and the like can be mentioned.

The above-mentioned processing steps are generally carried out by an automatic developing machine. In recent years, a small automatic developing machine called a mini lab has been installed at a store from a large-scale developing facility having a large automatic developing machine. Photo processing has been performed in various places up to the photo shop, and accordingly, there has been a case where the processing performance is reduced. One of the major causes is that metal ions are mixed into the processing solution. Various metal ions enter the processing solution through various routes. For example, calcium, magnesium, and in some cases, iron ions, and calcium contained in the gelatin of the light-sensitive material, are mixed into the processing solution through the water used in preparing the processing solution. In addition, the iron chelate used in the bleach-fixing solution splashes into the developing solution in the pre-bath and the ions impregnated in the pre-bath are brought in by introducing the solution impregnated into the film. There is also. The effect of the mixed ions differs depending on the ions and the processing solution.
Calcium and magnesium ions mixed into the developer
Reacts with carbonates used as buffering agents, causing precipitation and sludge, clogging of filters in the circulation system of the developing machine,
This causes problems such as film processing stains. In addition, when transition metal salts such as iron ions are mixed into the developing solution, the decomposition of paraphenylenediamine-based color developing agents, black developing agents such as hydroquinone and monol, and preservatives such as hydroxylamine and sulfite are also considered. Through which a marked decrease in photographic properties occurs.

Further, if a transition metal such as iron ion is mixed in a bleaching solution using hydrogen peroxide or persulfate, the stability of the solution is also remarkably reduced, causing problems such as poor bleaching. Also in the fixing solution, in the case of a thiosulfate fixing solution which is usually used, the stability decreases due to the incorporation of a transition metal salt, and turbidity and sludge are generated in the solution. As a result, clogging of the filter of the automatic processing machine causes a decrease in the circulating flow rate, resulting in poor fixing or generation of processing stain on the film. Such a phenomenon in the fixing solution also occurs in the washing water following the fixing solution, and in particular, when the amount of washing water is reduced, the liquid exchange rate in the tank decreases, decomposition of thiosulfate called sulfide, precipitation of silver sulfide, and the like. Generation problems are extremely likely to occur. In such a state, a fatal stain often occurs on the film surface. In a stable liquid prepared using hard water containing a large amount of calcium and magnesium, bacteria are generated using these as a nutrient source, causing turbidity of the liquid and causing film contamination. In addition, when transition metal ions such as iron ions are mixed, these ions remain in the film, thereby deteriorating the storage stability of the processed film. As described above, the incorporation of metal ions into the processing solution causes various adverse effects, and there has been a strong demand for an effective ion masking agent.

As a method for solving the above-mentioned problem, a chelating agent for concealing metal ions has been used. For example,
Aminopolycarboxylic acids (for example, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, etc.) described in JP-B-48-30496 and JP-B-44-30232, or JP-A-56-97347, JP-B-56-39359 and West German Patent Organic phosphonic acids described in 2,227,639 or JP-A Nos. 52-102726 and 53-42.
No. 730, No. 54-112127, No. 55-12262
And phosphonocarboxylic acids described in JP-A-58-195845 and JP-A-55-65556.
Compounds described in JP-A-8-203440 and JP-B-53-40900 can be exemplified. Although some of these compounds have been put to practical use, their performance has not been fully satisfactory. For example, ethylenediaminetetraacetic acid has a high masking ability against calcium ions, but when added to a developer, accelerates the decomposition of the developing agent and the preservative of the developing agent in the presence of iron ions, resulting in a decrease in image density and an increase in fog. Causes deterioration of the photographic properties. Also, for example, alkylidene diphosphonic acid does not cause such an adverse effect even in the presence of iron ions, but generates solids in a processing solution prepared with hard water containing much calcium and causes a failure of a developing machine. Such troubles have occurred. Particularly, in recent years, the amount of replenishment of photographic processing solutions has been decreasing in response to the increasing social demands for environmental protection, and the residence time of the processing solutions in the processing machine has been lengthened accordingly. Even more, the deterioration of the preservability becomes a serious problem.
Accordingly, there has been a demand for the development of a technique for effectively concealing metal ions accumulated in a processing solution without causing any adverse effects. Also,
In recent years, from the viewpoint of environmental conservation, it has been desired to detoxify photographic processing waste liquid generated from photographic processing, and particularly to a processing composition which is easily biodegradable. However, none of the practically used chelating agents sufficiently satisfies biodegradability and performance.

[0007]

SUMMARY OF THE INVENTION It is, therefore, a primary object of the present invention to provide a photographic processing composition which does not generate precipitation or sludge even when metal ions are mixed therein, and a processing method using the same. A second object of the present invention is to provide a stable processing composition and a processing method using the same, which do not reduce the effective components in the processing solution or generate a component having a photographic adverse effect even when metal ions are mixed. Is to provide a way.
A third object of the present invention is to provide a processing composition and a processing method using the same, in which a reduction in image storability caused by metal ions in a processing solution component remaining on the processed photographic material is improved. It is in. A fourth object of the present invention is to
An object of the present invention is to provide a treatment composition having no environmental problem of waste liquid and a treatment method using the same.

[0008]

The above object has been attained by the following method. That is, the following general formula (II) or
General formula (III) with a compound represented by or at least treatment composition for silver halide photographic light-sensitive material characterized by containing one and a processing method using the same of its salts. General formula (II)

[0009]

Embedded image ( _Wherein L _2a and L _3a each represent an alkylene group.
I forgot. R _2a and R _3a each represent a carboxyl group,
Represents a suphono group, a sulfo group or a hydroxy group. M _1a
And M _2a each represent a hydrogen atom or a cation.
m _a represents an integer of 0 or 1-5. ) General formula (III)

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(Where L _2b and L _3b are each a general formula
It has the same _{meaning as} L _2a and L _3a in the formula (II) . R
_2b and R _3b are each _{independently} R in general formula (II)
It is synonymous with _2a and R _3a . M _2b has the general formula (II)
Has the same _{meanings as} M _1a and M _2a . m _b is 0 or
Represents an integer of 1 to 3. X _b represents a substituent. k is 0
Or an integer of 1 to 5. ) The above formula (I
I) and the general formula (III) are collectively represented by the following general formula (I)
(The general formula (I) represents the scope of the present invention.
It does not specify the enclosure. ). General formula (I)

Embedded image (.L ₁ represent wherein, R ₁ represents carboxyl group, an aliphatic group or an aromatic group .R ₂ and R ₃ are each a carboxyl group, a phosphono group, a sulfo group or a hydroxy group,
L ₂ , L ₃ and L ₄ each represent an alkylene group.
X represents a hydrogen atom, an aliphatic group or an aromatic group. M represents a hydrogen atom or a cation. m and n each represent 0 or an integer of 1 to 3; )

First, the compound represented by formula (I) will be described in detail below. In the formula, the aromatic group represented by R ₁ and X is a monocyclic or bicyclic aromatic hydrocarbon group which may have a substituent. Preferably, it is a phenyl group or a naphthyl group which may have a substituent, and more preferably, a phenyl group which may have a substituent. As the substituent, an alkyl group (for example, methyl, ethyl, is
o-propyl), aralkyl group (eg, phenylmethyl), alkenyl group (eg, allyl), alkoxy group (eg, methoxy, ethoxy), aryl group (eg, phenyl, p-methylphenyl), acylamino group (eg, acetylamino), sulfonyl Amino group (eg, methanesulfonylamino), ureido group (eg, methylureide), alkoxycarbonylamino group (eg, methoxycarbonylamino), aryloxycarbonylamino group (eg, phenoxycarbonylamino), aryloxy group (eg, phenyloxy) , A sulfamoyl group (eg, methylsulfamoyl), a carbamoyl group (eg, carbamoyl, methylcarbamoyl), a mercapto group, an alkylthio group (eg, methylthio, carboxylmethylthio), Reelthio group (eg, phenylthio), sulfonyl group (eg, methanesulfonyl), sulfinyl group (eg, methanesulfinyl), hydroxy group, halogen atom (eg, chlorine atom, bromine atom, fluorine atom), cyano group, sulfo group, carboxyl group, phosphono Groups, an aryloxycarbonyl group (eg, phenyloxycarbonyl), an acyl group (eg, acetyl, benzoyl), an alkoxycarbonyl group (eg, methoxycarbonyl), an acyloxy group (eg, acetoxy), a nitro group, and a hydroxamic acid group. Preferred substituents are an alkyl group, an alkoxy group, a sulfinyl group, a hydroxy group, a halogen atom, a cyano group,
They are a sulfo group, a carboxyl group, a phosphono group, an acyl group and a nitro group, and an alkoxy group, a hydroxy group and a carboxyl group are particularly preferred.

The aliphatic groups represented by R ₁ and X include:
It may be linear, branched or cyclic, and is preferably linear or branched. Examples of the aliphatic group include an alkyl group, an alkenyl group, and an alkynyl group, and an alkyl group is preferable. The aliphatic group may be substituted, and as the substituent, for example, those exemplified as the substituent which the aromatic group represented by R ₁ and X may have can be applied. Preferred substituents include a hydroxy group,
They are a sulfo group, a carboxyl group, and a phosphono group, and a hydroxy group and a carboxyl group are particularly preferable. R ₁ is preferably a carboxyl group or an aromatic group, and more preferably a carboxyl group. X is preferably an aliphatic group or a hydrogen atom, and more preferably a hydrogen atom. R ₂ and R ₃ each represent a carboxyl group, a phosphono group, a sulfo group or a hydroxy group. Of these, a carboxyl group or a hydroxy group is preferred,
Most preferred are carboxyl groups.

The alkylene groups represented by L ₁ , L ₂ , L ₃ and L ₄ may be linear, branched or cyclic, and are preferably linear alkylene groups. The alkylene group preferably has 1 to 6 carbon atoms. The alkylene group may be substituted, and as the substituent, for example, those mentioned as the substituent which the aromatic group represented by R ₁ and X may have can be applied. The substituent is preferably an alkoxy group, a sulfo group, a hydroxy group, a carboxyl group, or a phosphono group, and more preferably a carboxyl group. L _{1 to} L
Preferred specific examples of ₄ include the following.

[0014]

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Particularly preferably, they are a methylene group or an ethylene group. Examples of the cation in M include alkali metals (for example, lithium, potassium, and sodium), ammonium (for example, ammonium and tetraethylammonium), and pyridinium. Book
In the invention, the compound represented by the general formula (I) or a compound thereof
Of the salts, represented by the general formula (II) or (III)
Or a salt thereof. General formula (II)

[0016]

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[0017] In the formula, L _2a and L _3a are respectively synonymous with L ₂ and L ₃ in the general formula (I). R _2a and R
_3a has the same _{meaning as} R ₂ and R ₃ in formula (I), respectively. M _1a and M _2a have the same _{meaning as} M in the general formula (I), respectively. m _a represents an integer of 0 or 1 to 5,
It preferably represents 0, 1 or 2, more preferably 1 or 2. General formula (III)

[0018]

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In the formula, L _2b and L _3b have the same _{meanings as} L ₂ and L ₃ in formula (I), respectively. R _2b and R _3b have the same _{meanings as} R ₂ and R ₃ in formula (I). M _2b has the same _{meaning as} M in formula (I). m
_b represents 0 or an integer of 1 to 3, preferably 0, 1 or 2, more preferably 0 or 1. X _b
Represents a substituent. As the substituent of _Xb , those exemplified as the substituent which the aromatic group represented by R ₁ and X in the general formula (I) may have can be applied. The substituent is preferably a hydroxy group or an alkoxy group. k represents 0 or an integer of 1 to 5, preferably 0. Particularly preferred in the present invention is formula (II).
Specific examples of the compound represented by formula (II) or (III) are shown below, but the present invention is not limited thereto.

[0020]

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[0021]

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[0022]

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[0023]

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[0024]

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[0025]

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[0026]

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[0027]

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[0028]

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The compound represented by the general formula (II) or (III ) may be an ammonium salt (eg, ammonium salt, tetraethylammonium salt) or an alkali metal salt (eg, lithium salt, potassium salt, sodium salt). There may be. Next, typical synthesis examples of the compound of the present invention are shown below. The compound of the present invention is described in “Bretane of the Chemical Society of Japan” Vol.
835-2840 (1969) (BULLETIN)
OF THE CHEMICAL SOCIETY
OF JAPAN VOL. 42 2835-2840
(1969)), Aspartic-N, N-diatic acid.
acetic acid), Inorganic Chemistry 34
(1974), West German Patent 3739610, JP-A-63
The compound can be synthesized by the synthesis method described in US Pat.

Synthesis Example 1 Synthesis of Compound (1) L-aspartic acid 2 was placed in a 1-liter three-necked flask.
6.0 g (0.195 mol) and 200 ml of water were added, and 35.0 g (0.4%) of sodium hydrogen carbonate was added with good stirring.
17 mol) was added in small portions. Separately, 200ml of water
In this solution, 47.3 g (0.501 mol) of monochloroacetic acid was dissolved and 42.0 g (0.501 mol) of sodium hydrogen carbonate was dissolved.
And neutralized. This aqueous solution was added to the three-necked flask and heated to 70 to 80 ° C. in a hot water bath. 18.0 g (0.450 mol) of sodium hydroxide was dissolved in 50 ml of water and added dropwise to the above aqueous solution. At this time, the pH was kept at 9-11. After completion of the dropwise addition, heating was continued for another hour to complete the reaction. After cooling, the solution was adjusted to pH 2 with concentrated hydrochloric acid, and evaporated under reduced pressure until the volume became half. The precipitated salt was separated by filtration, and the solvent was distilled off under reduced pressure. After the salt was filtered off, a small amount of acetone was added and left in the refrigerator for two weeks. The precipitated white powder was collected by filtration and recrystallized from acetone-water (1: 1).
Yield 11.5 g (4.62 × 10 ^-2 mol) Yield 23.7
% Melting point: 177 ° C-Decomposed gradually.

Elemental analysis value C ₈ H ₁₁ O ₈ N

Synthesis Example 2 Synthesis of Compound (2) 40.0 g of sodium L-glutamate monohydrate
(0.214 mol) and 200 ml of water were placed in a 1-liter three-necked eggplant flask, and 18.0 g (0.214 mol) of sodium hydrogen carbonate was added little by little with good stirring.
52.0 g of monochloroacetic acid in 200 ml of separately prepared water
(0.550 mol) dissolved in sodium hydrogen carbonate 4
6.2 g (0.550 mol) was added for neutralization. This aqueous solution was added to a three-necked flask, and heated to 70 to 80 ° C. in a hot water bath. 21.0 g of sodium hydroxide in 50 ml of water
(0.525 mol) was dissolved and added dropwise to the above aqueous solution.
At this time, the solution was added dropwise so as to maintain the pH at 9 to 11.

After the completion of the dropwise addition, heating was further continued for 1 hour to complete the reaction. After cooling, the solution was adjusted to pH 2 with concentrated hydrochloric acid, and evaporated under reduced pressure until the volume became half. The precipitated salt is filtered off,
Further, the solvent was distilled off under reduced pressure. After the salt was filtered off, a small amount of acetone was added and left in a refrigerator for one month. The precipitated white powder was collected by filtration and recrystallized from acetone-water (1: 1). Yield 15.3 g (5.81 × 10 ^-2 mol) Yield 2
7.2%

Elemental analysis value C ₉ H ₁₃ O ₈ N ¹ H NMR (D ₂ O + NaOD) δ ppm δ 1.78 (m 2H) δ 2.14 (t 2H) δ 3.15 (t 1H) δ 3.20 (q 4H)

Synthesis Example 3 Synthesis of Compound (21) 25.3 g (0.167 mol) of L-phenylglycine,
6.68 g (0.167 mol) of sodium hydroxide in 30 ml of water
After 15 ml of an aqueous solution of l) was added and dissolved, 58.4 g (0.501 mol) of sodium chloroacetate and 200 ml of water were added. 40 ml of an aqueous solution of 20.0 g (0.500 mol) of sodium hydroxide while heating to 50-55 ° C and stirring.
Was slowly added dropwise so as to maintain pH 9 to 10. After completion of the dropwise addition, the mixture was further heated and stirred for 2 hours and then returned to room temperature. 67.6 g (0.667 mol) of concentrated hydrochloric acid was added, and the precipitated solid was collected by filtration and recrystallized from water to give the desired compound (2).
3) g (0.113 mol) of 1) was obtained. Yield 68% Melting point: 219-221 ° C (decomposition)

Elemental analysis value C ₁₂ H ₁₃ NO ₆ ¹ H NMR (D ₂ O + NaOD) δ ppm δ 3.01 (d 2H) δ 3.13 (d 2H) δ 4.50 (s 1H) δ 7.40 (s 5H)

Synthesis Example 4 Synthesis of compound (22) 25.4 g (0.154 mol) of L-phenylalanine,
6.16 g (0.154 mol) of sodium hydroxide in 30 ml of water
After 15 ml of an aqueous solution of l) was added and dissolved, 43.0 g (0.369 mol) of sodium chloroacetate and 200 ml of water were added. 40 ml of an aqueous solution of 14.8 g (0.370 mol) of sodium hydroxide while heating to 50 to 55 ° C and stirring.
Was slowly added dropwise so as to maintain pH 9 to 10. After completion of the dropwise addition, the mixture was further heated and stirred for 2 hours and then returned to room temperature. 53.0 g (0.523 mol) of concentrated hydrochloric acid was added, and the precipitated solid was collected by filtration and recrystallized from water to give the desired compound (2).
29.2 g (0.101 mol) of the hemihydrate of 2) was obtained. Yield 65% Melting point: 139-141 ° C (decomposition)

[0038] Elemental analysis _{C 13 H 15 NO 6 · 1/2} H 2 O ¹ H NMR (D ₂ O + NaOD) δ ppm δ 2.77 to 3.02 (m 2H) δ 3.12 (d 2H) δ 3.26 (d 2H) δ 3.47 (dd 1H) δ 7.19 to 7.50 (m 5H)

Synthesis Example 5 Synthesis of compound (30) 25.3 g (0.167 mol) of D-phenylglycine,
6.68 g (0.167 mol) of sodium hydroxide in 30 ml of water
After 15 ml of an aqueous solution of l) was added and dissolved, 58.4 g (0.501 mol) of sodium chloroacetate and 200 ml of water were added. 40 ml of an aqueous solution of 20.0 g (0.500 mol) of sodium hydroxide while heating to 50-55 ° C and stirring.
Was slowly added dropwise so as to maintain pH 9 to 10. After completion of the dropwise addition, the mixture was further heated and stirred for 2 hours and then returned to room temperature. 67.6 g (0.667 mol) of concentrated hydrochloric acid was added, and the precipitated solid was collected by filtration and recrystallized from water to give the desired compound (3).
0) was obtained in an amount of 33.9 g (0.127 mol). Yield 76% Melting point: 219-221 ° C (decomposition)

Elemental analysis value C ₁₂ H ₁₃ NO ₆ ¹ H NMR (D ₂ O + NaOD) δ ppm δ 3.09 (d 2H) δ 3.30 (d 2H) δ 4.57 (s 1H) δ 7.50 (s 5H)

[0041]

Elemental analysis value C ₁₂ H ₁₃ NO ₆ ¹ H NMR (D ₂ O + NaOD) δ ppm δ 1.60 (d 3H) δ 4.09 (d 2H) δ 4.18 (d 2H) δ 4.34 (q 1H) Other compounds can be synthesized in the same manner.

The compound of the present invention can be applied to any processing composition for processing a silver halide black-and-white light-sensitive material or a silver halide color light-sensitive material. For example, as a processing composition for a black and white photosensitive material, a general black and white developer,
Processing compositions for color light-sensitive materials, such as infectious developing solutions for squirrel films, fixing solutions, and washing water, include color developing solutions, bleaching solutions, fixing solutions, bleach-fixing solutions, adjusting solutions, stopping solutions, hardening solutions, and washing with water. Examples include water, a stabilizing solution, a rinsing solution, a fogging solution, a toning solution, and the like, but are not limited thereto. The addition amount of the compound of the present invention varies depending on the treatment composition to be added, but is used in the range of 10 mg to 50 g per liter of the treatment composition. More specifically, for example, when it is added to a black-and-white developer or a color developer, the preferable amount is 0.5 to 10 g, particularly preferably 0.5 to 5 g per liter of the processing solution. When added to the bleaching solution, the amount is 0.1 to 20 g, preferably 0.1 to 5 g, per liter of the bleaching solution. When added to a fixing solution or a bleach-fixing solution, the amount is from 1 to 40 g, preferably from 1 to 20 g, per liter of the processing solution. When added to a stabilizing solution, the amount is 50 mg to 1 g per liter of the stabilizing solution, particularly preferably 50 to 300 mg.

The compounds of the present invention can be used alone or
A combination of more than one species may be used. In addition, various chelating agents can be used in combination as long as the effects of the compound of the present invention are not impaired. Preferred compounds of the chelating agent that can be used in combination include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, transcyclohexanediaminetetraacetic acid, 1,2-diaminopropanetetraacetic acid, 1,3-diaminopropanetetraacetic acid,
Glycol ether diaminetetraacetic acid, imino-di acetic acid, main <br/> Chiruimino di acetic acid, carbamoylmethyl imino di acetic acid,
Hydroxyethyliminodiacetic acid, ethylenediamine-N
Aminopolycarboxylic acids such as-(β-hydroxyethyl) -N, N ′, N′-triacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, Ethylenediamine-N, N,
Organic phosphonic acids such as N ′, N′-tetramethylene phosphonic acid, and a hydrolyzate of a maleic anhydride polymer described in EP 345172 A1 can be mentioned.

In the black-and-white developer, hydroquinone-based developing agents such as hydroquinone, bromohydroquinone, methylhydroquinone and 2,5-dichlorohydroquinone are preferred as developing agents. Also, as an auxiliary developing agent, N
It is preferable to use a p-aminophenol-based developing agent such as -methyl-p-aminophenol or a 3-pyrazolidone-based developing agent such as 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone in combination. It is preferable to use a sulfite compound such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium metabisulfite, or formaldehyde sodium bisulfite as a preservative.

The pH of the black-and-white developer is preferably in the range of 9 to 13, and examples of the alkaline agent used for setting the pH include sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate. In addition, a pH buffer such as boric acid, borax, silicate, tribasic sodium phosphate and tribasic potassium phosphate can be used in the developer. Also, development inhibitors such as potassium bromide and potassium iodide, organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve, hexylene glycol, ethanol and methanol, indazole compounds, and benzimidazole Antifoggants such as benzotriazole compounds and benzotriazole compounds.
Vol. 176, No. 17643, Section XXI (December Issue, 1978). US Patent 4,
No. 269,929, JP-A-61-267759 and Japanese Patent Application No. 1-29418. Further, a color tone agent, a surfactant, a hardener and the like may be contained as necessary. In the developing solution, a silver stain inhibitor, for example, a compound described in JP-A-56-24347 can be used. In addition, European Patent Publication 1
No. 36582, British Patent No. 958678, U.S. Pat. No. 3,232,761 and Development of an alkanolamine and other amino compounds described in JP-A-56-106244.
It can be used for the purpose of increasing the contrast.

The fixing solution for black and white is an aqueous solution having a pH of 4.2 to 7.0 containing a thiosulfate as a fixing agent. Examples of the thiosulfate include sodium thiosulfate and ammonium thiosulfate. In addition to thiosulfate, JP-A-57-15084
It is also preferable to use the mesoionic compound described in No. 2 together. Fixers include hardeners (eg, water-soluble aluminum salts); tartaric acid, citric acid, gluconic acid or derivatives thereof; preservatives (eg, sulfites, bisulfites);
An H buffer (eg, acetic acid, boric acid) and a pH adjuster (eg, sulfuric acid) can be included.

The color developing solution is an alkaline aqueous solution having a pH of 9 to 12 and containing an aromatic primary amine color developing agent as a main component. Aminophenol compounds are also useful as the color developing agent, but p-phenylenediamine compounds are preferably used. Representative examples thereof include 3-methyl-4-amino-N, N-diethylaniline and 3 -Methyl-4-
Amino-N-ethyl-N-β-hydroxyethylaniline,
4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl- β-methoxyethylaniline and sulfates, hydrochlorides or p-toluenesulfonates thereof. The color developing solution is a pH buffer such as an alkali metal carbonate (eg, potassium carbonate), borate or phosphate; a chloride salt (eg, potassium chloride), a bromide salt (eg, potassium bromide). And a development inhibitor such as an iodide salt (eg, potassium iodide), a benzimidazole, a benzotriazole, a benzothiazole or a mercapto compound, or an antifoggant. If necessary, various preservatives such as hydroxylamines such as hydroxylamine, diethylhydroxylamine and bis (sulfonatoethyl) hydroxylamine, and sulfites such as sodium sulfite and sodium bisulfite; ethylene glycol and diethylene glycol; Organic solvents; development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, and amines; dye-forming couplers; competitive couplers; auxiliary developing agents such as 1-phenyl-3-pyrazolidone; sodium boron hydride and hydrazine Nucleating agent such as a series compound; viscosity-imparting agent; 4,4'-diamino-2,2'-
A fluorescent whitening agent such as a disulfostilbene compound; various surfactants such as an alkylsulfonic acid, an arylsulfonic acid, an aliphatic carboxylic acid, and an aromatic carboxylic acid can be added.

Examples of the bleaching agent used in the bleaching solution or the bleach-fixing solution include compounds of a polyvalent metal such as iron (III); peracids; quinones; and iron salts. Representative bleaches include iron chloride; ferricyanide; dichromate;
Organic complex salts of iron (III) (for example, metal complex salts of aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, and 1,3-diaminopropanetetraacetic acid); and persulfates. A bleaching solution or a bleach-fixing solution using an aminopolycarboxylic acid iron (III) complex salt is used at a pH of 3.5 to 8. Known bleaching solutions and bleach-fixing solutions include rehalogenating agents such as ammonium bromide, sodium bromide, potassium bromide and ammonium chloride; pH buffering agents such as ammonium nitrate; and metal corrosion inhibitors such as ammonium sulfate. Can be added. The bleaching solution and the bleach-fixing solution preferably contain an organic acid in order to prevent bleaching stain in addition to the above compounds. Particularly preferred organic acids are compounds having an acid dissociation constant (pKa) of 2 to 5.5, specifically acetic acid,
Glycolic acid, propionic acid and the like are preferred. Examples of a fixing agent used in a fixing solution or a bleach-fixing solution for a color light-sensitive material include thiosulfates, thiocyanates, thioether compounds, thioureas, mesoionic compounds, and a large amount of iodide salts. In general, thiosulfate is used, and ammonium thiosulfate can be most widely used. It is also preferable to use a combination of a thiosulfate and a thiocyanate, a thioether-based compound, thiourea, or the like. Preservatives such as sulfites, bisulfites, carbonyl bisulfite adducts or sulfinic acid compounds described in EP 294,769A; various fluorescent whitening agents; antifoaming agents; Surfactants; polyvinylpyrrolidone; methanol; buffers such as imidazole; US Pat. No. 3,893,85
Bleaching accelerators such as compounds having a mercapto group or a disulfide group described in No. 8, West German Patent No. 1,290,812, and JP-A-53-95,630.

The washing solution and the stabilizing solution include a chlorine-based disinfectant such as inorganic phosphoric acid, isothiazolone compounds, thiabendazoles, chlorinated sodium isocyanurate, etc .;
Metal salts such as Al salts and Bi salts; surfactants; hardeners and the like can be contained. Further, the washing water and / or the stabilizing solution may contain various antibacterial agents and fungicides for preventing generation of water rust and molds generated in the processed photosensitive material. Examples of these antibacterial agents and fungicides include thiazolylbenzimidazole compounds as disclosed in JP-A-57-157244 and JP-A-58-105145, or JP-A-54-27.
No. 424 and JP-A-57-8542, isothiazolone compounds, chlorophenol compounds represented by trichlorophenol, or bromophenol compounds, or organotin or organozinc compounds, or Thiocyanic acid or isothiocyanic acid compound, or acid amide compound, diazine or triazine compound, thiourea compound, benzotriazole alkylguanidine compound, or quaternary such as benzalkonium chloride Ammonium salts, antibiotics represented by penicillin, etc., are described in Journal Antibacterial and Antifungus Agents (A. Antibact. Antifung. Agents) Vol.
207-223 (1983) may be used in combination of one or more. Also, JP-A-48-83820
Various fungicides described in (1) can also be used.

As a dye stabilizer that can be used in the stabilizing solution, formaldehyde is generally used.
From the viewpoint of working environment safety, N-methylolazole, hexamethylenetetramine, formaldehyde bisulfite adduct, dimethylolurea, and azolylmethylamine derivative are preferred. These are disclosed in JP-A-2-1533.
No. 48 and Japanese Patent Application No. 4-270344.
In particular, azoles such as 1,2,4-triazole;
A combination use of an azolylmethylamine derivative such as 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine (described in Japanese Patent Application No. 3-159918) provides high image stability and formaldehyde vapor. Low pressure is preferable. In addition, the stabilizing solution may further contain a pH adjusting buffer such as boric acid and sodium hydroxide; a sulfurizing inhibitor such as alkanolamine; an optical brightener; and the like.

Examples of the photographic light-sensitive material that can be processed with the processing composition of the present invention include ordinary black-and-white silver halide photographic light-sensitive materials (for example, black-and-white light-sensitive materials for photography, X-ray black-and-white light-sensitive materials, and black-and-white light-sensitive materials for printing) Materials), ordinary multilayer silver halide color photographic light-sensitive materials (for example, color negative film, color reversal film, color positive film,
Color negative film for movies, color photographic paper, reversal color photographic paper, direct positive color photographic paper), infrared light sensitive material for laser scanner, diffusion transfer photosensitive material (for example, silver diffusion transfer photosensitive material, color diffusion transfer photosensitive material) And the like. The photographic light-sensitive material according to the present invention has various layer constitutions on one side or both sides (for example, a silver halide emulsion layer having a sensitivity to each of red, green and blue, an undercoat layer, an antihalation layer, (Filter layer, intermediate layer, surface protection layer) and arrangement.

The support of the photographic light-sensitive material according to the present invention; the coating method; the type of silver halide used for the silver halide emulsion layer, the surface protective layer and the like (for example, silver iodobromide, silver iodochlorobromide, odor Silver chloride, silver chlorobromide, silver chloride), its grain shape (eg, cubic, flat, spherical), its grain size, its variability, its crystal structure (eg, core / shell structure, multiphase structure, homogeneous phase) Structure), its production method (for example, single jet method, double jet method), binder (for example, gelatin), hardener, antifoggant, metal doping agent, silver halide solvent, thickener, emulsion sedimentation agent, size Degree stabilizer, adhesion inhibitor, stabilizer, stain inhibitor, dye image stabilizer, stain inhibitor, chemical sensitizer, spectral sensitizer, sensitivity enhancer, supersensitizer, nucleating agent, coupler ( For example, pivaloylacetanilide type or ben Illacetoanilide type yellow coupler, 5-pyrazolone type or pyrazoloazole type magenta coupler, phenol type or naphthol type cyan coupler, DIR coupler, bleach accelerator releasing type coupler, competitive coupler, colored coupler), coupler dispersion method ( For example, an oil-in-water dispersion method using a high boiling point solvent),
Plasticizer, antistatic agent, lubricant, coating aid, surfactant,
Brighteners, formalin scavengers, light scattering agents, matting agents, light absorbers, ultraviolet absorbers, filter dyes, irradiation dyes, development improvers, matting agents, preservatives (for example, 2-phenoxyethanol), anti-blur There are no particular restrictions on the agents and the like. For example, Product Licensing, Vol. 92, pp. 107-110 (19)
December 1971) and Research Disclosure (hereinafter referred to as RD) No. 176.
43 (December 1978), RD Magazine No. 18716 (1
November 997), RD Magazine No. 307105 (1989)
November, 1999, JP-A-4-34548, page 15, lower left column 1
Line 20 to page 20, lower right column, line 3, 4-184432, page 7, right column, line 32 to page 9, right column, line 26, 4-274.
No. 237, page 6, right column, line 30 to page 9, right column, line 49 can be referred to.

[0054]

The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the invention thereto. Example 1 The following treatment liquid was prepared. (Color developing solution) Unit (g) Diethylenetriaminepentaacetic acid 1.0 Chelate compound (described in Table 1) 0.01 mol Sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide 1.4 Potassium iodide 1.5 mg Hydroxyl Amine sulfate 2.4 4- (N-ethyl-N-β-hydroxyethylamino) -2-methylaniline sulfate 4.5 Water was added to 1000 ml, pH 10.05.

Samples 101 to 112 were obtained by adding 5 ppm of ferric chloride as ferric ion and 150 ppm of calcium nitrate as calcium ion to the above color developing solution. 5 liters of each of these samples is 10 cm long and 25 cm wide.
cm, 30 cm deep, filled in a rigid vinyl chloride container, and while the liquid in the container is continuously circulated at a rate of 3 liters per minute with a pump, the temperature is adjusted to 38 ° C., and a aging test for 30 days is performed. Was. In addition, the vessel providing a floating lid for covering the liquid surface of 200 cm ^2, the liquid surface area which is open to the air was 50 cm ^2. Next, JP-A-4-274236
No. 35 of the multilayer color photosensitive material sample 101 described in Example 1
The sheet was cut to a width of 4 mm, and a wedge exposure of 5CMS was given at a color temperature of 4800K. Using this as a color developing solution, sample 101
The liquids immediately after the preparation (new solution) and after the aging test of No. 112 were used and were treated by the following treatment steps. [Processing Step] Step Processing time Processing temperature Color development 3 minutes 15 seconds 37.8 ° C Bleaching 50 seconds 38.0 ° C Fixing 1 minute 40 seconds 38.0 ° C Rinse with water (1) 30 seconds 38.0 ° C Rinse with water (2 ) 20 seconds 38.0 ° C Stable 20 seconds 38.0 ° C

(Bleaching solution) Unit (g) 1,3-propanediaminetetraacetic acid iron (III) ammonium 0.55 mol Ammonium bromide 85 Ammonium nitrate 20 Glycolic acid 55 Water was added to the mixture, and 1000 ml pH 4.0 (fixing solution) Unit (g) Ethylenediaminetetraacetic acid diammonium salt 1.7 Ammonium sulfite 14.0 Ammonium thiosulfate aqueous solution (700 g / liter) 260.0 ml Water is added to the mixture, and 1000 ml pH 7.0

(Washing water) Tap water is converted to H-type strongly acidic cation exchange resin (Amberlite IR- manufactured by Rohm and Haas Company).
120B) and a mixed bed column filled with an OH type strongly basic anion exchange resin (Amberlite IRA-400) to reduce the calcium and magnesium ion concentrations to 3
mg / L or less, followed by 20 mg / L of sodium diisocyanurate and 15 mg of sodium sulfate.
0 mg / liter was added. The pH of this solution is 6.5-
It was in the range of 7.5.

(Stabilizing solution) Unit (g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization: 10) 0.2 Disodium ethylenediaminetetraacetate 0.05 1, 2,4-triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 Water was added and 1000 ml pH 8.5

At an exposure amount at which the B concentration measured with blue light (B light) becomes 2.5 when treated with the new solution, the B concentration obtained with the solution after the aging test is compared with the X-Rite 310 photographic densities. measured at Tometer to obtain the difference △ D _B with fresh solution. The residual ratios of the developing agent and hydroxylamine after aging were determined by analysis. Further, the color developing solution after aging was visually inspected for the occurrence of precipitation. Table 1 shows the above results.

[0060]

[Table 1]

As is clear from Table 1, when the conventional chelating agent is added, the prevention of precipitation and the securing of the liquid stability are at an insufficient level, but the addition of the compound of the present invention has a large effect. It can be seen that is obtained.

Example 2 Compound 1 of the present invention was added to the fixing solution of Example 1
7, 13, 21, 22, or 30 was added at 3 g / L, and further, ferric ions corresponding to carry-in from the bleaching solution in the pre-bath were added to obtain Samples 201 to 209 . These samples were aged at 38 degrees at an aperture ratio of 0.1 cm ^-1 for 30 days, and the turbidity of the liquid was observed. In the case where no compound was added, remarkable turbidity occurred after the lapse of time, but it was shown that the fixer to which the compound of the present invention was added maintained a transparent state in all cases and did not generate precipitates.

Example 3 The stabilizer of Example 1 was used as it was as a comparative sample 301.
7, 13, 21, 22, or 30 at 100 mg /
Samples 302 to 310 were prepared by adding at a ratio of 1 liter. The multilayer color photosensitive material sample 101 was processed by the method described in Example 1 using these stabilizing solutions and using a fresh liquid such as the color developing solution of the sample 101 of Example 1 in addition to the stabilizing solution. . 4 samples of the processed multilayer color photosensitive material 101
Aged for one week under the moist heat condition of 5 ° C. and 70% RH, and an increase in magenta stain (ΔDmin) before and after the aging was determined.
Table 2 shows the obtained results.

[0064]

[Table 2]

It can be seen that the use of the stabilizer according to the present invention to which the compound of the present invention is added suppresses an increase in stain and improves image storability.

Example 4 The following color developing solution was prepared. [Color developing solution] Water 600 ml Potassium bromide 0.015 g Potassium chloride 3.1 g Triethanolamine 10.0 g Potassium carbonate 27 g Fluorescent brightener (WHITEX / 4B, manufactured by Sumitomo Chemical) 1.0 g Preservative (disodium) -N, N-bis (sulfonatoethyl) hydroxylamine) 45 mmol N-Ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 5.0 g (25 ° C) 10.05

The color developing solution was used as a sample 401, and the compounds of the present invention and comparative compounds were added in the amounts shown in Table 3 to obtain samples 402 to 408. To each of these color developing solutions, 5 ppm of ferric ion and 150 ppm of calcium ion were added, and the mixture was aged at 38 ° C. for 20 days in a beaker so that the opening ratio was 0.10 cm ⁻¹ . JP-A-4-1
A sample 103 described in No. 45433 was subjected to gradation exposure of a three-color separation filter for sensitometry using a sensitometer (FWH type manufactured by Fuji Photo Film Co., Ltd.). Exposure is 0.
The exposure was performed so that the exposure amount was 250 CMS with an exposure time of 1 second. After exposure, each was processed according to the following steps using the above-prepared fresh solution (fresh solution) and the aged color developing solution (aging solution). [Processing step] Processing time Temperature Color development 38 ° C 45 seconds Bleaching and fixing 35 ° C 25 seconds Rinse 35 ° C 20 seconds Rinse 35 ° C 20 seconds Rinse 35 ° C 20 seconds Drying 80 ° C 60 seconds

[Bleach-fixing solution] Water 400 ml Ammonium thiosulfate (700 g / l) 100 ml sodium sulfite 17 g ammonium ethylenediaminetetraacetate (III) ammonium 55 g disodium ethylenediaminetetraacetate 5 g ammonium bromide 40 g 6.8 [Rinse solution] Ion-exchanged water (calcium and magnesium are each 3 ppm or less)

The minimum density (Dmin) of yellow when processed with a fresh liquid and the sensitivity of magenta (the logarithm of the exposure amount giving a density of 0.5 log E) of yellow have the minimum density Dmin of yellow when processed with an aged liquid. The amount of increase (minDmin) and the amount of change in magenta sensitivity (△ S) were calculated. Further, the remaining amount of the main drug in the temporal solution was quantified by high performance liquid chromatography. In addition, the presence or absence of the formation of a precipitate in the temporal solution was observed.

[0070]

[Table 3]

As is clear from Table 3, the compounds of the present invention have small values of ΔDmin and ΔS, and the fluctuation of photographic properties is suppressed. Furthermore, the occurrence of precipitation is greatly improved as compared with the comparative compound. In particular, compounds having a large effect of preventing precipitation were poor in preservative properties of the main drug, while compounds having little decomposition of the main drug were insufficient in preventing precipitation. On the other hand, it can be seen that the compound of the present invention provides a stable developer without forming a precipitate.

Example 5 The sample No. of the example in JP-A-3-174148 was used. B
Using -6, a developer (B) was prepared in which disodium ethylenediaminetetraacetate in the following developer (A) was replaced with the same molar amount of Exemplified Compound 3, and each developer was heated to 40 ° C.
After a lapse of 4 days, a running treatment was performed. Further, when the remaining amount of hydroquinone and potassium sulfite and the pH of the developer after the lapse of time were measured, the decrease due to air oxidation of hydroquinone and potassium sulfite was minimized, and the increase in pH due to this was also suppressed. ,understood.

Developer (A) Hydroquinone 45.0 g N-methyl-p-aminophenol 1/2 sulfate 0.8 g Sodium hydroxide 18.0 g Potassium hydroxide 55.0 g 5- Sulfosalicylic acid 45.0 g Boric acid 25. 0 g Potassium sulfite 110.0 g Disodium ethylenediaminetetraacetate 1.0 g Potassium bromide 6.0 g 5-methylbenzotriazole 0.6 g n-butyl-diethanolamine 15.0 g Add water to make 1 liter (pH = 11.6) And

Example 6 Modified S defined in the OECD Chemical Test Guidelines
Table 4 shows the results of the biodegradability test performed based on the CAS method.

[0075]

[Table 4]

From the above results, it was confirmed that the compound of the present invention was excellent in biodegradability.

[0077]

According to the treatment liquid containing the compound of the present invention, oxidation or decomposition of the components of the treatment liquid due to the action of metal ions is suppressed, the performance of the treatment liquid is maintained for a long period of time, There is no precipitation in the solution even by accumulation, so there is no trouble such as soiling of the film and clogging of the filter of the automatic processor. Further, the compound of the present invention is a compound having biodegradability and contributes to environmental conservation.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁶ , DB name) G03C 5/305 G03C 5/38 G03C 7/407 G03C 7/42

Claims (2)

(57) [Claims] 1. A compound represented by the following general formula (II) or (II)
A photographic processing composition comprising at least one of the compounds represented by I) or salts thereof. General formula (II ) ( _Wherein L _2a and L _3a each represent an alkylene group.
I forgot. R _2a and R _3a each represent a carboxyl group,
Represents a suphono group, a sulfo group or a hydroxy group. M _1a
And M _2a each represent a hydrogen atom or a cation.
m _a is Wath an integer of 0 or 1-5. ) General formula (III) ( _Wherein L _2b and L _3b are each represented by the general formula (II)
Has the same meaning as L _2a and L _3a in the description. R _2b and R
_3b represents R _2a and R in the general formula (II), respectively.
Synonymous with _3a . M _2b represents M in the general formula (II)
It is synonymous with _1a and M _2a . m _b is an integer of 0 or 1 to 3
Represents a number. X _b represents a substituent. k is 0 or 1 to 5
Represents an integer. ) 2. A silver halide photographic light-sensitive material which has been imagewise exposed to the general formula (II) or the general formula (II) according to claim 1.
A method for processing a silver halide photographic light-sensitive material, characterized by processing with a processing solution containing at least one compound represented by I) or a salt thereof.