JP2829445B2 - 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 and a processing method for a silver halide photographic material, and more particularly, to a photographic processing containing a novel chelating agent for concealing metal ions harmful to photographic processing. Compositions and treatment methods.

[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, and a silver halide color photographic material (hereinafter referred to as a color photographic material). After the exposure, is subjected to processing steps such as color development, desilvering, washing with water, and stabilization. The silver halide color reversal photosensitive material is subjected to processing such as color development, desilvering, washing with water, and stabilization after exposure, black-and-white development and reversal processing.

In the color development step in the processing of a color photosensitive material, the exposed silver halide particles are reduced to silver by a color developing agent, and an oxidized product of the color developing agent is reacted with a coupler to form an image dye. To form
In the subsequent desilvering step, the developed silver produced in the developing step is oxidized to a silver salt by a bleaching agent having an oxidizing action (bleaching), and is further exposed to a photosensitive agent together with unused silver halide by a fixing agent which forms soluble silver. It is removed from the layer (fixation). Details of these processing steps and their compositions are described in James, "The Theory of Photograph Process" (4th edition).
ic Process "4 'thedition) (1977), Research Disclosure No. 17643, pp. 28-29, ibid.
8716, 651 left column to right column, and No. 307105-8
It is described on pages 80 to 881 and the like.

[0004] In addition to the above basic processing steps, various auxiliary steps are added for the purpose of maintaining the photographic and physical quality of the dye image or maintaining the stability of the processing. For example, a washing step, a stabilizing step, a hardening step,
And a stopping step.

The above-mentioned processing steps are generally performed by an automatic developing machine. In recent years, a small automatic developing machine called a minilab 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 water used in preparing the processing solution.
In addition, the iron chelate used in the processing solution having the bleaching ability splashes into the developer in the pre-bath and is mixed with the developer in the pre-bath. Sometimes brought in. The effect of the mixed ions differs depending on the ions and the processing solution.

Calcium and magnesium ions mixed in the developing solution react with carbonates generally used as buffering agents to form precipitates and sludges, which cause clogging of a circulating system filter of an automatic developing machine and contamination of a film during processing. Cause problems. 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 lowered, and problems such as poor bleaching occur. Also in the fixing solution, in a fixing solution using a normal thiosulfate as a fixing agent, the stability is reduced 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 developing machine causes a decrease in the circulating flow rate, causing instability or causing processing contamination on the film.

Such a phenomenon in the fixing solution also occurs in the washing water subsequent to the fixing solution. In particular, when the amount of the washing water is reduced, the liquid exchange rate in the tank is reduced, and decomposition and sulphation of thiosulfate called sulphide. The problem of silver precipitate formation is 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) described in JP-B-48-30496 and JP-B-44-30232, or JP-A-56-97347, JP-B-56-39359 and West German Patent No. 2 And organic phosphonic acids described in JP-A-52-102726 and JP-A-53-102726.
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.

[0011]

Although some of these compounds have been put to practical use, their performance has not been fully satisfactory. For example, ethylenediaminetetraacetic acid has a large masking ability against calcium ions, but when added to a developer, promotes the decomposition of a developing agent and a preservative of the developing agent in the presence of iron ions, resulting in a decrease in image density and an increase in fog. This leads to poor 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 a photographic processing solution has been decreasing in accordance with an increasing social demand for environmental protection, and accordingly, the residence time of the processing solution in a processing machine has become longer. Therefore, the deterioration of the preservability becomes a bigger problem than before. Therefore, there has been a demand for the development of an excellent new chelating agent that effectively masks metal ions accumulated in a processing solution without causing any adverse effects.

Accordingly, it is a first 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. The second purpose is to reduce the effective components in the processing solution by mixing metal ions,
It is an object of the present invention to provide a stable processing composition without the formation of a photographically adverse component. It is a third object of the present invention to provide a processing composition and a processing method using the same, in which a decrease in image storability caused by metal ions in the processing composition remaining on the processed photographic material is improved. .

[0014]

The above object has been achieved by a treatment composition containing at least one of the compounds represented by the following general formulas (I) and (II) and a treatment method using the same. General formula (I)

[0015]

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Formula (II)

[0017]

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The compounds represented by formulas (I) and (II) will be described in detail below. In the general formula (I) or the general formula (II), Ra, Rb and Rc each independently represent a hydrogen atom, an alkyl group, an aryl group, X
Represents -Y-.

The alkyl group represented by Ra, Rb and Rc may be linear, branched or cyclic, may be substituted, and preferably has 1 to 10 carbon atoms.
More preferably, the alkyl group is a methyl group or an ethyl group.

The aryl groups represented by Ra, Rb and Rc may be substituted, preferably have 6 to 10 carbon atoms, more preferably phenyl group.

L ₁ , L ₂ and L ₃ are respectively

[0022]

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Represents the following. Here, X ₁ and X ₂ represent an oxygen atom or a sulfur atom. It preferably represents an oxygen atom.

R ₁ , R ₂ and R ₃ each represent a hydrogen atom, an alkyl group or an aryl group. The alkyl group represented by R ₁ , R ₂ and R ₃ may be linear, branched or cyclic, may be substituted, and has 1 to 1 carbon atoms.
0 is preferred. The aryl groups represented by R ₁ , R ₂ and R ₃ may be substituted and have 6 to 1 carbon atoms.
0 is preferred. R ₁ and R ₂ are linked to form 5
An 8-membered ring may be formed. Examples of the ring formed by linking R ₁ and R ₂ include a morpholine ring, a piperidine ring,
Examples include a pyrrolidine ring and a pyrazine ring.

R ₄ is an alkyl group, an aryl group, —N (R
₅ ) represents R ₆ or —OR ₇ ; These groups may be substituted. R ₅ and R ₆ have the same meanings as R ₁ , respectively. R ₇ represents an alkyl group or an aryl group. The alkyl group or the aryl group represented by R ₇ has the same meaning as the alkyl group or the aryl group represented by R ₁ .

Particularly preferred as R ₁ , R ₂ and R ₃ are a hydrogen atom, an optionally substituted alkyl group having 1 to 4 carbon atoms, and an optionally substituted phenyl group.

Y, Y ₁ and Y ₂ each represent a divalent linking group containing an alkylene group or an arylene group, preferably an alkylene group having 1 to 4 carbon atoms, an arylene group having 6 to 12 carbon atoms, or a carbon atom having 6 to 12 carbon atoms. Represents 7 to 12 aralkyl groups, which may be substituted. More preferably, they are a methylene group or an ethylene group, and Y ₁ and Y ₂ are particularly preferably a methylene group.

Ra, Rb, Rc, R ₁ , R ₂ , R ₃ , R
₄ , an alkyl group or an aryl group represented by R ₅ , R ₆ or R ₇ ,
Examples of the substituent of the alkylene group or the arylene group of Y, Y ₁ and Y ₂ include an alkyl group (eg, methyl and ethyl),
Aralkyl groups (eg, phenylmethyl), alkenyl groups (eg, allyl), alkynyl groups, alkoxy groups (eg, methoxy), aryl groups (eg, phenyl), amino groups (eg, amino, dimethylamino), acylamino groups (eg, acetylamino), Sulfonylamino group (eg, methanesulfonylamino), ureido group, urethane group, aryloxy group (eg, phenoxy), sulfamoyl group (eg, methanesulfamoyl), carbamoyl group (eg, carbamoyl, methanecarbamoyl), alkylthio group (eg, methylthio) , An arylthio group (eg, phenylthio), a sulfonyl group (eg, methanesulfonyl), a sulfinyl group (eg, methanesulfinyl), a hydroxy group, a halogen atom (eg, a chlorine atom, a bromine atom), a cyano group , A sulfo group, a carboxyl group, a phosphono group, an aryloxycarbonyl group (e.g. phenoxycarbonyl), an acyl group (e.g. acetyl,
Benzoyl), an alkoxycarbonyl group (for example, methoxycarbonyl), an acyloxy group (for example, acetoxy), a carbonamide group (for example, methanecarbonamide), a sulfonamide group (for example, methanesulfonamide), and a nitro group. Preferably, they are a carboxy group, a sulfo group, a phosphono group, a hydroxy group, a carbamoyl group, and an alkyl group.

X is preferably -OH, -COOM ¹ ,-
PO ₃ M ² M ³ or SO ₃ M ⁴ (M ¹ , M ² , M ³ and M ⁴ each represent a hydrogen atom or a cation. Examples of the cation include alkali metals (eg, lithium, sodium, potassium), ammonium, pyridinium And the like, and particularly preferably -COOM ¹ .

L ₁ , L ₂ and Ra, Rb, Rc, L ₃ may be linked together to form a ring, if possible.

In the general formula (II), W is an alkylene group,
It represents a linking group having 2 or more carbon atoms including an arylene group. The alkylene group may be a cycloalkylene group.

The linking group represented by W can be preferably represented by the following general formula (W). General formula (W)-(W ¹ -Z) _m -W ^2-

In the formula, W ¹ and W ² may be the same or different and include an alkylene group having 1 to 10 carbon atoms (including a cycloalkylene group having 5 to 10 carbon atoms) and a carbon atom having 6 to 10 carbon atoms.
Represents an arylene group or a divalent heterocyclic group of 10.
As an arylene group, a 1,2-phenylene group is preferable. Z is a mere bond, -O-, -S-, -N (Rw)
-Represents a divalent nitrogen-containing heterocyclic group. Rw is hydrogen atom, a hydrocarbon _{^{group, -L A COOM 5, -L A}} PO 3 M 6
M ^7, _-L A _OH, represents an -L A _SO 3 ^{M 8.} L _A Ali 6-10 alkylene group or a carbon number of 1 to 8 carbon atoms - represents an alkylene ^{group, M 5, M 6, M} 7 and ^{M 8} are each a hydrogen atom, such as a cation (e.g. Na, K Alkali metal, ammonium). m represents an integer of 0 to 3, and when m is 2 or 3, W ¹ -Z may be the same or different. These linking groups represented by W may have a substituent, for example, R
Those mentioned as the substitution of the alkyl group and the aryl group of a are appropriate.

The divalent nitrogen-containing heterocyclic group is preferably a 5- or 6-membered ring in which the hetero atom is nitrogen, and more preferably a group in which adjacent carbon atoms are bonded to W ¹ and W ^2. . As the divalent nitrogen-containing heterocyclic group,

[0035]

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And the like. W is preferably an alkyl group having 2 to 4 carbon atoms or a cyclohexylene group, wherein m = 0 or 1 in the general formula (W), and W ¹ and W ² are preferable. Specific examples of W include, for example, the following.

[0037]

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Among the compounds represented by the general formula (I) or (II), more preferred are the compounds represented by the following general formulas (III) or (IV),
Compounds represented by V) are particularly preferred.

[0039]

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Wherein Y ₃₁ , Y ₃₂ , Y ₃₃ and Y
₄₁ , Y ₄₂ , Y ₄₃ , and Y ₄₄ each independently have the same meaning as Y ₁ , and preferably have 1 carbon atom which may be substituted.
To 4 alkylene groups, more preferably a methylene group or an ethylene group, and particularly preferably a methylene group.
M ⁹ , M ¹⁰ and M ¹¹ each represent a hydrogen atom or a cation (such as an alkali metal or ammonium).
R ³¹ , R ³² , R ³³ , R ³⁴ , R ⁴¹ , R ⁴² , R
⁴³ and R ⁴⁴ have the same meaning as R ₁ in formula (I) or (II).

Specific examples of the compound represented by formula (I) or (II) are shown below, but it should not be construed that the invention is limited thereto.

[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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Next, examples of the synthesis of these compounds are shown below. Synthesis Example 1 Synthesis of Compound 19 100 g of acid anhydride of ethylenediaminetetraacetic acid under ice cooling (for the synthesis method, see French Patent No. 1,548,888).
(0.390 mol) was suspended in 200 ml of water, and 98.0 g (0.811 mol) of 29% aqueous ammonia was added at an internal temperature of 5 to 10 ° C.
Slowly added to keep. 1.5 with ice cooling
After stirring for 8 hours, 86.0 g of 36% hydrochloric acid (0.848 mol
l) was added, followed by 1 liter of ethanol. The precipitated solid was collected by filtration and recrystallized from water / ethanol to give 78.0 g (0.215 g) of the dihydrochloride of the desired product 19.
mol). 55% yield. 145-147 ° C (decomposition)

Synthesis Example 2 Synthesis of Compound 20 Acid anhydride of ethylenediaminetetraacetic acid 100 under ice cooling
g (0.390 mol) was suspended in 200 ml of water, and 163.0 g (0.811 mol) of a 40% aqueous solution of methylamine was added.
1) was added slowly so as to keep the internal temperature at 5 to 10 ° C. After stirring for 1.5 hours while continuing ice-cooling, 36% hydrochloric acid 8
After adding 6.0 g (0.848 mol), the mixture was concentrated under reduced pressure until the content became about 200 ml. One liter of methanol was added to the concentrated solution, and the precipitated solid was collected by filtration and further recrystallized from water / ethanol to obtain the desired product 20-2.
93.0 g (0.238 mol) of the hydrochloride was obtained. Yield 6
1%. 200-202 ° C (decomposition)

Synthesis Example 3 Synthesis of Compound 21 Under ice cooling, 5.1 acid anhydride of ethylenediaminetetraacetic acid
2 g (20.0 mmol) are suspended in 20 ml of water, and 3.61 g (40.01 mm
ol) was added slowly so as to keep the internal temperature at 5 to 10 ° C.
After stirring for 30 minutes while continuing ice-cooling, the mixture was further stirred at room temperature for 2 hours. 4.06 g of 36% hydrochloric acid (40.0 mol
After addition of l), methanol and then acetone were added.
The precipitated solid was collected by filtration and recrystallized twice from water / acetone to give 3.86 g of the dihydrochloride of the desired product 21 (9.
21 mmol). Yield 46%. Melting point 191-192
° C (decomposition)

Synthesis Example 4 11. Synthesis of Compound 41 Acid anhydride of ethylenediaminetetraacetic acid under ice-cooling
8 g (50.0 mmol) are suspended in 40 ml of water, and 10.2 g (110 mmol) of aniline is suspended at an internal temperature of 5 to 10 ° C.
Slowly added to keep. After stirring for 30 minutes while continuing ice-cooling, the mixture was further stirred at room temperature for 1 hour. The precipitated solid was collected by filtration and recrystallized from methanol to obtain 15.9 g (36.0 mmol) of target product 41. Yield 72%. 159-161 ° C (decomposition)

Synthesis Example 5 Synthesis of compound 45 At room temperature, acid anhydride of ethylenediaminetetraacetic acid 5.1
2 g (20.0 mmol) was converted to 6.20 g (8
(2.6 mmol) was suspended in 20 ml of water, stirred for 6 hours, and 8.37 g (82.6 mmol) of 36% hydrochloric acid was added. After stirring for 30 minutes while continuing ice-cooling, the mixture was further stirred at room temperature for 1 hour. After the reaction solution was concentrated under reduced pressure to about 20 ml, 40 ml of acetone was added. The precipitated solid was collected by filtration and recrystallized from water / acetone to give 3.40 g (7.10 mm) of the dihydrochloride of the target compound 45.
ol) obtained. Yield 36%, melting point 204-206 ° C (decomposition)

Synthesis Example 6 Synthesis of Compound 50 3.77 g of N, N-dimethylethylenediamine under ice-cooling
(42.8 mmol) was dissolved in 100 ml of acetonitrile, and 5.27 g (2.06 mmol) of an acid anhydride of ethylenediaminetetraacetic acid while maintaining the internal temperature at 5 to 10 ° C.
Was added. After returning to room temperature and stirring for 30 minutes, the precipitated crystals were collected by filtration. Yield 7.04 g (16.3 mmol)
l). Yield 79%, melting point 170-173 ° C (decomposition)

Synthesis Example 7 Synthesis of Compound 24 2.47 g of a 40% aqueous methylamine solution (318
6.34 g (22.3 mm) of an acid anhydride of 1,4-butanaminetetraacetic acid (for the synthesis method, see French Patent No. 1,548,888) while keeping -8 to + 1 ° C.
ol) and stirring was continued for 2 hours. After evaporating the solvent and methylamine under reduced pressure, 4.46 m of 5N aqueous sodium hydroxide solution
1 was added and the mixture was distilled off under reduced pressure. The pH was adjusted to 7 with concentrated hydrochloric acid, and the solvent was completely distilled off. 20 ml of concentrated hydrochloric acid was added, the salt was filtered off, acetonitrile was added, the mixture was stirred, and the precipitated crystals were collected by filtration to obtain the desired dihydrochloride dihydrate. Yield 7.62 (16.7 mmol) Yield 75
%. 117-120 ° C (decomposition)

Synthesis Example 8 Synthesis of Compound 44 14.77 g of o-anilinesulfonic acid (85.3 mmol)
l) was dissolved in 80 ml of water, and 4.51 g of sodium carbonate was dissolved.
(85.3 mmol) was added. Cool on ice and adjust the internal temperature to -5
While maintaining the temperature at + 4 ° C., 9.93 g (38.8 mmol) of acid anhydride of ethylenediaminetetraacetic acid was added, and the mixture was stirred for 4 hours. After returning to room temperature and concentrating, concentrated hydrochloric acid is gradually added with stirring until the solution becomes cloudy. The stirring was continued for another 30 minutes, and the precipitated crystals were collected by filtration to obtain the desired product 44 dihydrochloride dihydrate. 19.75 g yield
(31.8 mmol) yield 82%. Melting point 215-220
° C (decomposition)

Synthesis Example 9 Synthesis of compound 48 6.38 g of 2-aminoethanesulfonic acid (51.0 mm
ol) in 50 ml of water and sodium carbonate 5.40
g (51.0 mmol) was added. Cool on ice and adjust the internal temperature to 0
While maintaining the temperature at 10 ° C., 5.93 g (23.1 mmol) of acid anhydride of ethylenediaminetetraacetic acid was added, and the mixture was stirred for 4 hours. After concentration, concentrated hydrochloric acid was added, the precipitated salt was separated by filtration, and methanol was added to the filtrate. The precipitated crystals are collected by filtration, and water /
The target compound 48 was recrystallized from methanol to give 4.
90 g (7.86 mmol) were obtained. Yield 34%. Melting point 2
35 to 238 ° C (decomposition)

Synthesis Example 10 Synthesis of Compound 49 At room temperature, 7.13 g of 2-methylthioethylamine (7
8.20 mmol) was dissolved in 300 ml of acetonitrile, and 9.1 g of acid anhydride of ethylenediaminetetraacetic acid was dissolved.
(35.5 mmol) was added and stirred for 1 hour. After standing overnight, the precipitated result was collected by filtration to obtain 12.1 g of the target product 49.
(27.6 mmol) were obtained. Yield 78%, melting point 147-
150 ° C (decomposition)

Synthesis Example 11 Synthesis of Compound 25 Under ice-cooling, 10.0 g of 29% aqueous ammonia (170 mmol)
l) While maintaining the internal temperature of 20 ml of water at -5 ° C to + 2 ° C, acid anhydride of (±) -trans-1,2-diaminocyclohexanetetraacetic acid (synthesis method is French Patent No. 1,548,88).
4.65 g (15.0 mmol) was added and the mixture was stirred for 1 hour. After concentration, 10 ml of concentrated hydrochloric acid was added, and the precipitated crystals were collected by filtration. Yield 3.67 g (8.10 mmol
l), 54% yield. (Obtained as dihydrochloride, dihydrate) Melting point: 147 to 150 ° C (decomposition)

Synthesis Example 12 10. Synthesis of Compound 43 Acidic anhydride of ethylenediaminetetraacetic acid under ice-cooling
5 g (44.9 mmol) of acetonitrile in 100 ml
8.6 g (98.7 mmol) of morpholine and 20 parts of acetotitril 20 while maintaining the internal temperature at 0 to 10 ° C.
ml of solution was added dropwise. After stirring for 2 hours, the precipitated crystals were collected by filtration and recrystallized with methanol to give the desired product 43 as 8.
16 g (19.0 mmol) were obtained. Yield 42%. 200-202 ° C (decomposition)

Synthesis Example 13 Synthesis of Compound 23 Under ice cooling, 17.61 g of 29% aqueous ammonia was added to 20 ml of water.
In addition, while maintaining the internal temperature at −10 to + 5 ° C., 16.63 g of an acid anhydride of 1,3-propanediaminetetraacetic acid (refer to French Patent No. 1,548,888 for the synthesis method).
5 mmol) and stirred for 1 hour. After concentration under reduced pressure, 25 g of concentrated hydrochloric acid was added, and the precipitated crystals were collected by filtration. Yield 17.
7 g (42.9 mmol) yield 70%. Melting point 144-1
47 ° C (decomposition) (obtained as dihydrochloride, dihydrate)

Synthesis Example 14 Synthesis of Compound 51 9.67 g (125 mmol) of 40% methylamine under ice-cooling
l) was added to 10 ml of water, and while keeping the internal temperature at -1 to 5 ° C, 8.29 g (30.6 mmol) of acid anhydride of 1,3-propanediaminetetraacetic acid was added, followed by stirring for 1.5 hours. 11.12 ml of 5N sodium hydroxide aqueous solution
(50.6 mmol) was added and ammonia was distilled off under reduced pressure. After adjusting the pH to 2 with concentrated hydrochloric acid and concentrating under reduced pressure, the salt was filtered off. Concentrated hydrochloric acid was added to the filtrate, and the precipitated crystals were collected by filtration to obtain 5.88 g (17.7 mmol) of the desired product 51. Yield 5
8%. (Obtained as dihydrochloride) Melting point 90-92 ° C (decomposition)

Synthesis Example 16 Synthesis of Compound 52 29% aqueous ammonia 22.98 (391 mmol) under ice-cooling
l) While maintaining the internal temperature of -10 to 0 ° C, 8.53 g of acid anhydride of 1,4-butanediaminetetraacetic acid (30.0 m
mol)) and stirred for 1 hour. After concentration under reduced pressure of ammonia, the mixture was adjusted to pH 6 with concentrated hydrochloric acid and stirred. The precipitated crystals were collected by filtration to obtain 30 g (8.47 mmol) of target product 52. Yield 28%. Mp 158-159 ° C (obtained as dihydrate). Other compounds are synthesized similarly.

The amount of the compound represented by the general formula (I) and / or (II) varies depending on the treatment composition to be added, but is usually from 10 mg to 50 g per liter of the treatment composition.
Used in the range.

More specifically, for example, when it is added to a black-and-white developer or a color developer, the preferred amount is 0.5 to 10 g per liter of the processing solution.
When added to a bleaching solution (for example, composed of hydrogen peroxide, persulfuric acid, bromic acid, etc.), 0.1 to 20 g per liter
When added to a fixing solution or a bleach-fixing solution, 1
It is 1 to 40 g per liter, and 50 mg to 1 g per liter when added to the stabilizing bath. The compounds represented by formulas (I) and / or (II) may be used alone or in combination of two or more.

The compound represented by formula (I) or (II) can be applied to any processing composition for processing a silver halide light-sensitive material. For example, black and white developers for general use, infectious developers for squirrel films, color developers,
Bleaching solution, fixing solution, bleach-fixing solution, adjusting solution, stopping solution, hardening solution, washing water, stabilizing solution, rinsing solution, fogging solution, toning solution, and the like, but are not limited thereto. Absent.

In the color developing solution and the black-and-white developing solution, precipitation can be prevented and the stability of the solution can be improved by adding the compound of the present invention. The color developing solution contains a known aromatic primary amine color developing agent. A preferred active ingredient is a p-phenylenediamine derivative, representative examples of which are shown below, but are not limited thereto. D-1 N, N-diethyl-p-phenylenediamine D-2 2-amino-5-diethylaminotoluene D-3 2-amino-5- (N-ethyl-N-laurylamino) toluene D-4 4- [ N-ethyl-N- (β-hydroxyethyl) amino] aniline D-5 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline D-6 4-amino-3-methyl -N-ethyl-N-
[Β- (methanesulfonamido) ethyl] aniline D-7 N- (2-amino-5-diethylaminophenylethyl) methanesulfonamide D-8 N, N-dimethyl-p-phenylenediamine D-9 4-amino- 3-methyl-N-ethyl-N-methoxyethylaniline D-10 4-amino-3-methyl-N-ethyl-N-β
-Ethoxyethylaniline D-11 4-amino-3-methyl-N-ethyl-N-β
-Butoxyethylaniline D-12 2-methoxy-4- [N-ethyl-N- (β-
(Hydroxyethyl) amino] aniline Among the above p-phenylenediamine derivatives, D-5 and D-
6, D-12 are preferably used. In addition, these p
-The phenylenediamine derivative is preferably used as a salt such as sulfate, hydrochloride, sulfite, p-toluenesulfonate and the like. The amount of the aromatic primary amine color developing agent to be used is preferably about 0.01 to 1 liter of the color developing solution.
0.06 molar concentration.

In the color developing solution, sodium sulfite, potassium sulfite, sodium bisulfite,
Sulfites such as potassium bisulfite, sodium metasulfite, and potassium metasulfite, and carbonyl sulfite adducts can be added as necessary. Also, various hydroxylamines such as those described in JP-A-63-5-5 can be used as compounds which directly (preserving) the aromatic primary amine color developing agent.
Compounds described in JP-A-341-341 and JP-A-63-106655, in particular, compounds having a sulfo group or a carboxy group are preferred. Hydroxamic acids described in JP-A-63-43138, hydrazines and hydrazides described in JP-A-63-146041, 63-44657 and 63-584.
It is preferable to add phenols described in No. 43, α-hydroxyketones and α-aminoketones described in JP-A-63-44656, and / or various sugars described in JP-A-63-36244. Also, in combination with the above compounds, JP-A-63-4235, JP-A-63-24254 and JP-A-63-24
Nos. 1647, 63-146040, 63-278
Monoamines described in No. 41 and No. 63-25654, No. 63-30845, No. 63-14640,
Diamines described in JP-A-63-43139 and the like;
Nos. 21647, 63-26655 and 63-4
No. 4655, polyamines described in JP-A-63-53551, alcohols described in JP-A-63-43140 and JP-A-63-53549, and 63.
Oximes described in JP-A-56654 and JP-A-63-239.
It is preferable to use tertiary amines described in No. 447.

Other preservatives include those described in JP-A-57-441.
Various metals described in JP-A Nos. 48 and 57-53749, salicylic acids described in JP-A-59-180588,
Alkanolamines described in JP-A-54-3582,
If necessary, polyethyleneimines described in JP-A-56-94349, aromatic polyhydroxy compounds described in U.S. Pat. No. 3,746,544, and the like may be contained. Particularly, addition of an aromatic polyhydroxy compound is preferred.

The amount of these preservatives to be added depends on the amount of the color developer 1
0.005 to 0.2 mol, preferably 0.1 to 0.2 mol per liter.
It is from 0.01 mol to 0.05 mol.

The color developer used in the present invention has a pH of 9
To 12, but preferably 9.
5 to 11.5. The color developing solution may further contain a compound of a known developing solution component.

In order to maintain the above pH, it is preferable to use various buffers.

Specific examples of the buffer include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, and borate. Potassium citrate, sodium tetraborate (borax), potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate,
Sodium 5-sulfo-2-hydroxybenzoate (5-
Sodium sulfosalicylate) and potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate). However, the invention is not limited to these compounds.

The amount of the buffer added to the color developer is 0.1
Mol / liter or more, preferably 0.1 mol / liter or more.
It is particularly preferred that the amount is 0.4 mol / liter.

In the present invention, various chelating agents can be used in combination as long as the effects of the compound of the present invention are not impaired. As the chelating agent, an organic acid compound is preferable, and examples thereof include aminopolycarboxylic acids, organic phosphonic acids, and phosphonocarboxylic acids. Specific examples include nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ', N'
-Tetramethylenephosphonic acid, transcyclohexanediaminetetraacetic acid, 1,2-diaminopropanetetraacetic acid, hydroxyethyliminodiacetic acid, glycol ether diaminetetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid Acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N'-bis (2-hydroxybenzyl) ethylenediamine-N, N'-diacetic acid and the like.

These chelating agents can be used in an amount of, for example, 0.0001 mol to 0.05 mol per liter of the processing solution.

An optional development accelerator can be added to the color developer if necessary. Examples of the development accelerator include JP-B-37-16088, JP-B-3-5987, and JP-B-38-87.
Nos. 7826, 44-12380 and 45-9919
Thioether compounds described in U.S. Pat. No. 3,818,247 and JP-A-52-49829.
P-phenylenediamine compounds described in JP-A No. 0-15554, JP-A-50-137726, JP-B-44-30.
No. 074, JP-A-56-156826 and JP-A-52-43.
Quaternary ammonium salts described in US Pat. No. 4,494,903, 3,128,182, 4,230,796, 3,253,919, and JP-B-41. No. 11431, U.S. Pat. No. 2,482,54
No. 6, No. 2,496,926, No. 3,582,3
Amine compounds described in No. 46, etc., JP-B-37-160
No. 88, No. 42-25201, U.S. Pat.
8,183, JP-B-41-11431, 42-2
No. 3,883, U.S. Pat. No. 3,532,501, and the like, and imidazoles such as 2-methylimidazole and imidazole. It is also preferable to add 1-phenyl-3-pyrazolidones as an auxiliary developing agent for rapid development.

Further, an optional antifoggant can be added to the color developing solution, if necessary. As an anti-fogging agent,
Alkali metal halides such as sodium chloride, potassium bromide, potassium iodide and organic antifoggants can be used. Examples of the organic antifoggant include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole,
5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2
Nitrogen-containing heterocyclic compounds such as -thiazolylmethyl-benzidazole, indazole, hydroxyazaindolizine, and adenine can be mentioned as typical examples.

Further, the color developing solution may contain a fluorescent whitening agent. As the fluorescent whitening agent, a 4,4'-diamino-2,2'-disulfostilbene compound is preferable.
The addition amount is 0 to 5 g / liter, preferably 0.1 g to 4 g.
g / liter. Further, various surfactants such as alkyl sulfonic acid, aryl sulfonic acid, fatty acid carboxylic acid, and aromatic carboxylic acid may be added as needed.

The processing temperature of the color developing solution in the present invention is 20 to 50 ° C., preferably 33 to 55 ° C. Processing time is 30 seconds to 3 minutes and 20 minutes for color photographic materials.
The time is preferably from 1 minute to 2 minutes and 30 seconds, and in the case of a color printing material, from 10 seconds to 1 minute and 20 seconds, and preferably from 20 seconds to 60 seconds.

Various well-known additives which are usually added to the black-and-white first developer used in the color reversal process in which the compound of the present invention can be used, and the black-and-white developer of the black-and-white silver halide photosensitive material. Can be contained.

Representative additives include 1-phenyl-
Developing agents such as 3-pyrazolidone, methol and hydroquinone; preservatives such as sulfites; accelerators composed of alkalis such as sodium hydroxide, sodium carbonate and potassium carbonate; potassium bromide and 2-methylbenzimidazole; Examples thereof include inorganic or organic inhibitors such as benzthiazole, water softeners such as polyphosphate, and development inhibitors comprising a small amount of iodide or mercapto compound.

The bleaching solution in which the compound of the present invention can be used contains at least an oxidizing agent for oxidizing silver and a rehalogenating agent (or an organic ligand instead). As the bleaching agent, known iron (III) complex salts of polyaminocarboxylic acid, hydrogen peroxide, persulfate, bromate and the like are used, and these may be used in combination. The bleaching agent is used in an amount of 0.05 to 2 mol, preferably 0.1 to 5 mol, per liter of the bleaching solution. As the rehalogenating agent, halides such as chloride, bromide and iodide are generally used, but an organic ligand which forms a sparingly soluble silver salt may be used instead. Their amount is between 0.1 and 2 mol / l, preferably between 0.3 and 1.5 mol / l.

The above-mentioned halides are added as alkali metal salts or ammonium salts, or salts such as guanidine and amine. Specific examples include sodium bromide, ammonium bromide, potassium chloride, guanidine hydrochloride, and the like, with ammonium bromide being preferred.

The addition of the compounds represented by the general formulas (I) and / or (II) to the bleaching solution improves the storage stability of the bleaching solution. Notable when bromate is used.

The bleach-fixing solution to which the compound of the present invention can be added contains, in addition to the bleaching agent, a fixing agent described below, and if necessary, the above-mentioned rehalogenating agent.
The amount of the bleaching agent in the bleach-fix solution is the same as in the case of the bleaching solution. The amount of the rehalogenating agent is from 0 to 2.0 mol /
Liter, preferably 0.01 to 1.0 mol / liter.

By adding the compound of the present invention to a bleach-fix solution, the storage stability of the solution is improved.

The bleaching solution or bleach-fixing solution according to the present invention may further contain a bleaching accelerator, a corrosion inhibitor for preventing corrosion of the processing bath, a buffer for maintaining the pH of the solution, a fluorescent brightening agent, an antifoaming agent, and the like. It is added as needed.

Examples of the bleaching accelerator include, for example, US Pat. No. 3,893,858 and German Patent 1,290,81.
No. 2, U.S. Pat. No. 1,138,842;
No. 95630, Research Disclosure No. 171
No. 29 (1978), compounds having a mercapto group or disulfide group, thiazolidine derivatives described in JP-A-50-140129, U.S. Pat.
Thiourea derivatives described in JP-A-6-561, JP-A-49-4
No. 0943, the imidazole compounds described in German Patent No. 2,748,430, polyethylene oxides, and the polyamine compounds described in JP-B-45-8836 can be used. In particular, U.S. Pat.
138,842 are preferred.

As the corrosion inhibitor, a nitrate is preferably used, and ammonium nitrate, potassium nitrate and the like are used. The addition amount is 0.01 to 2.0 mol / l, preferably 0.05 to 0.5 mol / l.

PH of the bleaching solution or bleach-fixing solution of the present invention
Is 2 to 8, preferably 3 to 7.5. When bleaching or bleach-fixing is performed immediately after color development, the pH of the solution is preferably 6 or less, and preferably 5.5 or less in color photographic materials in order to suppress bleaching fog. In a color printing material, the pH is preferably in the range of 3 to 7 in order to prevent leuco from the cyan dye.

Accordingly, any pH buffering agent can be used as long as it is not easily oxidized by the bleaching agent and has a buffering action in the above pH range.
For example, organic acids such as acetic acid, glycolic acid, lactic acid, propionic acid, butyric acid, malic acid, chloroacetic acid, levulinic acid, ureidopropionic acid, pyridine, dimethylpyrazole, 2-methyl-o-oxazoline, aminoacetonitrile and the like Organic bases and the like. The amount of these buffers used is 0 to 3 mol / l, preferably 0.5 to 2 mol / l.
Mol / l. These buffers may be used in combination of a plurality of substances.

The bleaching or bleach-fixing step is carried out at 30.degree.
It is carried out in a temperature range of 0 ° C., preferably 35 ° C. to 45 ° C.
It is. The time of the bleaching process is in the range of 10 seconds to 5 minutes in the case of a color photographic material, but is preferably 10 seconds to 60 seconds, and in the case of a color print photographic material, it is 5 seconds to 70 seconds. Preferably, it is 5 seconds to 60 seconds. Under these preferred processing conditions, good results were obtained that were rapid and free of stain.

Known fixing agents are used for the fixing solution or the bleach-fixing solution. These are thiosulfates, thiocyanates, thioethers, amines, mercaptos, thiones, thioureas, iodides, and the like, for example, ammonium thiosulfate, sodium thiosulfate, potassium thiosulfate, guanidine thiosulfate, Potassium thiocyanate, dihydroxyethyl-thioether, 3,6-dithia-
1,8-octanediol, imidazole and the like can be mentioned. Of these, thiosulfates, particularly ammonium thiosulfate, are preferred for quick fixing. Furthermore, by using two or more types of fixing agents in combination, it is possible to perform quicker fixing. For example, in addition to ammonium thiosulfate, it is also preferable to use the above ammonium thiocyanate, imidazole, thiourea, thioether and the like in this case.
It is preferable to add in the range of 0 mol%.

The amount of the fixing agent is fixed solution or bleach-fix solution 1
0.1 mol to 3 mol per liter, preferably 0.5 to 3 mol
2 moles. The pH of the fixer depends on the type of fixer,
Generally, it is 3 to 9, and especially when thiosulfate is used, 6.5 to 8 is preferable for obtaining stable fixing performance.

A preservative may be added to the fixing solution and / or the bleach-fixing solution to enhance the stability of the solution over time. In the case of a fixer or bleach-fixer containing thiosulfate,
As a preservative, a sulfite and / or a bisulfite adduct of hydroxylamine, hydrazine or aldehyde (for example, a bisulfite adduct of acetoaldehyde, particularly preferably an aromatic aldehyde described in JP-A-1-298935) Bisulfite addition) is effective. In addition, JP
It is also preferable to use the sulfinic acid compound described in 0-283881.

It is also preferable to add a buffer to the fixing solution and / or the bleach-fixing solution in order to keep the pH of the solution constant. For example, phosphate, or imidazole,
Imidazoles such as 1-methyl-imidazole, 2-methyl-imidazole, 1-ethyl-imidazole, triethanolamine, N-allylmorpholine, N
-Benzoylpiperazine and the like. In the fixing solution according to the present invention, the addition of the compound represented by the general formula (I) and / or (II) not only improves the storage stability of the solution but also masks the iron ions brought in from the bleaching solution. Stability can be improved.

The same effect can be obtained by adding the compound of the present invention to washing water and a stabilizing solution. Various surfactants can be contained in the washing water or the stabilizing solution used in the washing step in order to prevent unevenness of water droplets when the processed photosensitive material is dried. As these surfactants,
Polyethylene glycol type nonionic surfactant, polyhydric alcohol type nonionic surfactant, alkylbenzene sulfonate type anionic surfactant, higher alcohol sulfate ester type anionic surfactant, alkylnaphthalene sulfonate type There are anionic surfactants, quaternary ammonium salt-type cationic surfactants, amine salt-type cationic surfactants, amino acid-type amphoteric surfactants, and betaine-type amphoteric surfactants. It is preferable to use a nonionic surfactant since an insoluble substance may be formed by combining with various ions mixed in with the treatment, and an alkylphenol ethylene oxide adduct is particularly preferable. Octyl, nonyl, dodecyl and dinonylphenol are particularly preferred as alkylphenols, and the number of moles of ethylene oxide added is particularly preferably 8 to 14 mol. It is also preferable to use a silicon surfactant having a high defoaming effect.

The washing water or the stabilizing solution may contain various antibacterial agents and fungicides in order to prevent generation of water rust and mold generated in the photosensitive material after processing. Examples of these antibacterial agents and fungicides include thiazolylbenzimidazole compounds as disclosed in JP-A-57-157244 and JP-A-58-105145, and JP-A-54-27424 and JP-A-54-27424. Kaisho 57
No. 8542, isothiazolone compounds, or chlorophenol compounds represented by trichlorophenol, or bromophenol compounds, or organotin or organozinc compounds, or thiocyanic acid or isothiocyanic acid compounds Compounds, or acid amide compounds, or diazine or triazine compounds, or thiourea compounds, benzotriazole alkylguanidine compounds, or quaternary ammonium salts such as benzalkonium chloride, or penicillin Antibiotics such as those represented by Journal Antibacterial and Antifangus Agent (J. Antibact.A
ntifung.Agents) Voll. No. 5, p.207-223 (1
983) may be used in combination of one or more.

Further, various germicides described in JP-A-48-83820 can also be used.

It is preferable to use various chelating agents in a range that does not impair the effects of the compound of the present invention.
Preferred compounds of the chelating agent include aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, and ethylenediamine-N, N, N ', N'-.
Examples thereof include organic phosphonic acids such as tetramethylene phosphonic acid, and hydrolysates of a maleic anhydride polymer described in EP 345172 A1.

Further, it is preferable that a preservative which can be contained in the above-mentioned fixing solution or bleach-fixing solution is contained in the washing water.

As the stabilizing solution, for example, an organic acid or a pH 3
A solution having a buffer capacity of -6, a liquid containing aldehyde (eg, formalin or glutaraldehyde), hexamethylenetetramine, hexahydrotriazine, or a solution containing an N-methylol compound (eg, dimethylolurea, N-methylolpyrazole). And, if necessary, an ammonium compound such as ammonium chloride or ammonium sulfite, a metal compound such as Bi or Al, an optical brightener,
Hardening agents, alkanolamines described in US Pat. No. 4,786,583, and the like can be used.

In the washing step and the stabilizing step, a multi-stage countercurrent method is preferable, and the number of stages is preferably two to four. The replenishment amount is 2-30 of the amount brought in from the previous bath per unit area.
Times, preferably 2 to 15 times.

Examples of the water used in the washing step or the stabilizing step include tap water, water deionized to a Ca or Mg concentration of 5 mg / liter or less with an ion exchange resin, halogen, an ultraviolet germicidal lamp, and the like. It is preferred to use more sterile water.

As the water for correcting the evaporation, tap water may be used, but it is preferable to use deionized water or sterilized water which is preferably used in the washing step or the stabilizing step. Is good.

[0110] In each of the processing liquids of the present invention, it is preferable that the stirring of the processing liquid is strengthened as much as possible. Examples of the method of strengthening the stirring include a method described in JP-A-62-183460, in which a jet of a processing solution is caused to collide with the emulsion surface of a photosensitive material, and a stirring effect using a rotating means described in JP-A-62-18346. A method of improving the stirring effect by moving the photosensitive material while bringing the emulsion surface into contact with a wiper blade or a squeeze roller provided in the solution and turbulently flowing the emulsion surface. There is a method of increasing the circulation flow rate.

The processing method of the present invention is preferably carried out using an automatic developing machine. The conveying method in such an automatic developing machine is described in JP-A-60-191257 and JP-A-60-191257.
No. 191258 and No. 60-191259. In addition, in order to perform rapid processing using the processing composition of the present invention, it is preferable to shorten the crossover between processing tanks in an automatic processor. 1 crossover time
For an automatic developing machine set to 0 seconds or less, see JP-A-1-319.
No. 038.

When continuous processing is carried out using an automatic developing machine according to the processing method of the present invention, consumption of processing solution components accompanying processing of a light-sensitive material is compensated for, and undesired components eluted from a light-sensitive material are eliminated. In order to suppress accumulation in the processing solution, it is preferable to add a replenisher in accordance with the amount of the processed photosensitive material.
Further, each processing step may be provided with two or more processing baths, and in that case, it is preferable to adopt a countercurrent system in which the replenisher is poured from the rear bath to the front bath. In particular, a cascade of two to four stages is preferably used in the washing step and the stabilizing step.

It is preferable to reduce the amount of the replenisher as long as the composition change in each processing solution does not affect the photographic performance or inconvenience of contamination of other solutions.

[0114] The amount of color developer replenisher, in the case of a color photographic material, the photosensitive material 1 m ² per 100Ml～1500ml, preferably is 100Ml～1000ml, in the case of a color print material, the photosensitive material 1 m ² per 20ml~ 220 ml, preferably 30 ml to 160 ml.

The amount of the bleaching replenisher is 10 ml to 500 ml, preferably 10 ml to 160 ml, per m ^{2 of} the light-sensitive material in the case of a color photographic material. In the case of a color print material, ²⁰ ml to 300 ml per square meter of the photosensitive material, preferably 5 ml
0 ml to 150 ml.

[0116] The amount of bleach-fixing replenisher in the case of a color photographic material, the photosensitive material 1 m ² per 100Ml～3000ml, preferably is 200ml~1300ml, 20ml~ per photosensitive material 1 m ² in the case of the color print material The volume is 300 ml, preferably 50 ml to 200 ml. The bleach-fix solution may be replenished as one solution, may be separately replenished as a bleaching composition as a fixing composition, or may be replenished as a bleach bath and / or a bleach bath.
Alternatively, a bleach-fix replenisher may be prepared by mixing an overflow solution from a fixing bath.

In the case of a color photographing material, the amount of the fixing replenisher is 300 ml to 3000 ml per 1 m ^{2 of} the photosensitive material.
It is preferably from 300 ml to 1000 ml, and in the case of a color printing material, from ²⁰ ml to 1 m2 of the photosensitive material.
It is 300 ml, preferably 50 ml to 200 ml.

The replenishing amount of the washing water or the stabilizing solution is 1 to 30 times, more preferably 2 to 15 times, the amount brought in from the previous bath per unit area.

To further reduce the amount of the replenisher for environmental protection, it is preferable to use a combination of various regeneration methods. Regeneration may be carried out while circulating the processing solution in the automatic developing machine, or after removing from the processing tank once, applying an appropriate regeneration processing, and returning it to the processing tank again as a replenisher. Is also good.

The regeneration of the developer is performed by removing the accumulated matter by ion exchange treatment with an anion exchange resin, electrodialysis treatment, or the like.
And / or the addition of a chemical called a regenerant. The regeneration rate is preferably 50% or more,
% Or more is more preferable. Although a commercially available anion exchange resin can be used, it is also preferable to use a highly selective ion exchanger described in JP-A-63-11005.

The metal chelate bleach in the bleaching solution and / or the bleach-fixing solution is brought into a reduced state with the bleaching treatment. When the metal chelate in the reduced state accumulates, not only does the bleaching performance decrease, but in some cases, the image dye becomes a leuco dye, causing a reduction in image density. For this reason, it is preferable that the bleaching solution and / or the bleach-fixing solution take a continuous regeneration method in cooperation with the processing. Specifically, it is preferable that air is blown into the bleaching solution and / or the bleach-fixing solution by an air pump to reoxidize the reduced metal chelate with oxygen. In addition, regeneration can be performed by adding an oxidizing agent such as hydrogen peroxide, persulfate, or bromate.

The regeneration of the fixing solution and the bleach-fixing solution is carried out by electrolytic reduction of accumulated silver ions. In addition, it is also preferable to remove the accumulated halogen ions with an anion exchange resin in order to maintain the fixing performance. In order to reduce the amount of washing water used, ion exchange or ultrafiltration is used, and it is particularly preferable to use ultrafiltration.

The photographic light-sensitive materials 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, black-and-white light-sensitive materials for X-rays, 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 (for example, a silver halide emulsion layer having a sensitivity to each of red, green and blue, an undercoat layer, a halation layer, etc.) depending on the purpose of the photographic material. Prevention layer, filter layer,
(Intermediate layer, surface protective layer) and arrangement.

Support for photographic light-sensitive material according to the present invention; Coating method; types of silver halide used for silver halide emulsion layer, surface protective layer, etc. (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, dimensions) Stabilizers, adhesion inhibitors, stabilizers, stain inhibitors, dye image stabilizers, stain inhibitors, chemical sensitizers, spectral sensitizers, sensitivity enhancers, supersensitizers, nucleating agents, couplers (eg , Pivaloylacetanilide type and benzo Le acetanilide type yellow couplers, 5-pyrazolone type and pyrazoloazole type magenta coupler, phenol type and naphthol type cyan couplers, DIR couplers, bleach accelerator-releasing couplers,
Competitive couplers, colored couplers), coupler dispersion method (eg, oil-in-water dispersion method using high boiling point organic solvent), plasticizer, antistatic agent, lubricant, coating aid, surfactant, brightener, formalin Scavenger, light scattering agent,
Matting agent, light absorber, ultraviolet absorber, filter dye,
There are no particular restrictions on irradiation dyes, development improvers, matting agents, preservatives (for example, 2-phenoxyethanol), anti-binders, and the like. For example, Product Licensing, Vol. 92, pp. 107-110 (1971) December) and Research Disclosure (RD) No. 1
7643 (December 1978), RD Magazine No. 18716
(November 1979), RD Magazine No. 307105 (19
November 1989) can be referred to.

The photographic light-sensitive material according to the present invention may contain a developing agent. As a developing agent which can be contained in the light-sensitive material, RD Magazine No. 17643, p.
vel-oping agents ". Particularly, hydroquinone and pyrazolidones are preferably used.

As described above, the photographic light-sensitive material according to the present invention may use a coupler that develops yellow, cyan, and magenta colors, as described in RD Magazine No. 17643, VII-C.
-G, various couplers described in the patents described in RD-No.
What is described in detail in 2-215272 is mentioned.

[0128]

EXAMPLES The present invention will be described below with reference to examples.
The present invention is not limited to these. Example 1 After a corona discharge treatment was applied to the surface of a paper support laminated on both sides with polyethylene, a gelatin undercoating phase containing sodium dodecylbenzenesulfonate was provided, and various photographic constituent layers were further applied to form a layer structure shown below. A multilayer color photographic paper was produced. The coating solution was prepared as follows.

Preparation of Coating Solution for Fifth Layer 32.0 g of cyan coupler (ExC), color image stabilizer (C
pd-2) 3.0 g, color image stabilizer (Cpd-4) 2.0
g, color image stabilizer (Cpd-6) 18.0 g, color image stabilizer (Cpd-7) 40.0 g and color image stabilizer (Cpd-
8) To 5.0 g, 50.0 cc of ethyl acetate and solvent (S
olv-6) was added and dissolved, and this solution was added to 500 cc of a 20% aqueous gelatin solution containing 8 cc of sodium dodecylbenzenesulfonate, and then emulsified and dispersed with an ultrasonic homogenizer to prepare an emulsified dispersion. on the other hand,
Silver chlorobromide emulsion (cubic, 1: 4 of large size emulsion having an average grain size of 0.58 μm and small size emulsion of 0.45 μm)
Mixture (Ag mole ratio). The coefficient of variation of the grain size distribution was 0.09 and 0.11, respectively, and AgBr was used for each size emulsion.
0.6 mol% was locally contained in a part of the particle surface). This emulsion contained the following red-sensitive sensitizing dye E per mol of silver at a concentration of 0.9 × 10 ⁻⁴ per mol of silver emulsion.
Moles, and 1.1 × 10 ^-4 moles for small size emulsions. The emulsion was chemically ripened by adding a sulfur sensitizer and a gold sensitizer. The above-mentioned emulsified dispersion and this red-sensitive silver chlorobromide emulsion were mixed and dissolved to prepare a coating solution for the fifth layer having the following composition.

Coating solutions for the first to fourth, sixth, and seventh layers were prepared in the same manner as the coating solution for the fifth layer. As a gelatin hardener for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used. The total amount of Cpd-10 and Cpd-11 was 2 in each layer.
It was added to a 5.0 mg / m ² and 50.0 mg / m ^2.
The following spectral sensitizing dyes were used for the silver chlorobromide emulsion of each photosensitive emulsion layer.

[Blue-sensitive emulsion layer] Sensitizing dye A

[0132]

Embedded image

And sensitizing dye B

[0134]

Embedded image

(Per mol of silver halide, 2.0 × 10 ⁻⁴ mol for large-size emulsion and 2.5 × 10 ⁻⁴ mol for small-size emulsion, respectively) [Green-sensitive emulsion Layer] Sensitizing dye C

[0136]

Embedded image

(4.0 × 10 ⁻⁴ mol for a large-sized emulsion and 5.6 × 10 ⁻⁴ mol for a small-sized emulsion per mol of silver halide) and sensitization Dye D

[0138]

Embedded image

(Per mol of silver halide: 7.0 × 10 ⁻⁵ mol for large-size emulsion and 1.0 × 10 ⁻⁵ mol for small-size emulsion, respectively) [Red-sensitive emulsion Layer] Sensitizing Dye E

[0140]

Embedded image

(Each mole of silver halide is 0.9 × 10 ^-4 mol for a large-size emulsion, and each is 1.1 × 10 ^-4 mol for a small-size emulsion.) Was added in an amount of 2.6 × 10 ^-3 mol per mol of silver halide.

[0142]

Embedded image

Also, 1- (5-methylureidophenyl) -5-mercaptotetrazole was added to the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer at 8.5 × 10 ⁻ per mole of silver halide. ⁵ mol, 7.7 × 10 ^-4
Mol, 2.5 × 10 ^-4 mol. Further, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer in an amount of 1 × 10 ^-4 mol and 2 × 10 ^-4 mol, respectively, per mol of silver halide. × 10 ^-4
Mole was added. The following dyes were added to the emulsion layer to prevent irradiation (the number in parentheses indicates the coating amount).

[0144]

Embedded image

(Layer Structure) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents a coating amount in terms of silver.

Support Polyethylene laminated paper [polyethylene on the first layer side contains white pigment (TiO ₂ ) and bluish dye (ultramarine)]

First Layer (Blue-Sensitive Emulsion Layer) A silver chlorobromide emulsion (cubic, 3: 7 mixture of a large-size emulsion having an average grain size of 0.88 μm and a small-size emulsion having an average grain size of 0.70 μm (silver molar ratio)). The variation coefficients of the grain size distribution are 0.80 and 0.10, respectively, and 0.3 mol% of silver bromide is locally contained in a part of the grain surface in each emulsion.) 0.30 Gelatin 1.22 Yellow coupler (ExY) 0.82 Color image stabilizer (Cpd-1) 0.19 Solvent (Solv-3) 0.18 Solvent (Solv-7) 0.18 Color image stabilizer (Cpd-7) 0.06

Second layer (color mixture inhibitor) Gelatin 0.64 Color mixture inhibitor (Cpd-5) 0.10 Solvent (Solv-1) 0.16 Solvent (Solv-4) 0.08

Third Layer (Green-Sensitive Emulsion Layer) Silver chlorobromide emulsion (cubic, 1: 3 mixture of large size emulsion having an average grain size of 0.55 μm and small size emulsion of 0.39 μm (Ag molar ratio)). The variation coefficients of the grain size distribution were 0.10 and 0.08, respectively, and 0.8 mol% of AgBr was locally contained in a part of the grain surface in each emulsion.) 0.12 Gelatin 1.28 Magenta coupler (ExM) 0.23 Color image stabilizer (Cpd-2) 0.03 Color image stabilizer (Cpd-3) 0.16 Color image stabilizer (Cpd-4) 0.02 Color image stabilizer (Cpd-9) 02 Solvent (Solv-2) 0.40

Fourth layer (ultraviolet absorbing layer) Gelatin 1.41 Ultraviolet absorbing agent (UV-1) 0.47 Color mixture inhibitor (Cpd-5) 0.05 Solvent (Solv-5) 0.24

Fifth Layer (Red-Sensitive Emulsion Layer) A 1: 4 mixture (Ag molar ratio) of a silver chlorobromide emulsion and a (cubic, large-sized emulsion having an average grain size of 0.58 μm and a small-sized emulsion having a size of 5 μm). The coefficient of variation of the grain size distribution was 0.09 and 0.11, and each emulsion contained 0.6 mol% of AgBr locally on a part of the grain surface.) 0.23 Gelatin 1.04 Cyan coupler (ExC) 0.32 Color image stabilizer (Cpd-2) 0.03 Color image stabilizer (Cpd-4) 0.02 Color image stabilizer (Cpd-6) 0.18 Color image stabilizer (Cpd-7) 40 Color image stabilizer (Cpd-8) 0.05 Solvent (Solv-6) 0.14

Sixth layer (ultraviolet absorbing layer) Gelatin 0.48 Ultraviolet absorbing agent (UV-1) 0.16 Color mixing inhibitor (Cpd-5) 0.02 Solvent (Solv-5) 0.08

Seventh layer (protective layer) Gelatin 1.10 Acrylic-modified copolymer of polyvinyl alcohol (degree of modification 17%) 0.17 Sulfurized paraffin 0.03

[0154]

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[0155]

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[0156]

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[0157]

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[0158]

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[0160]

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[0161]

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Next, the following processing solutions were prepared. The composition is as follows.

[Color developer] water 700 ml 1,2-dihydroxybenzene-4,6-disulfonic acid disodium salt 4.0 g triethanolamine 12.0 g potassium chloride 1.5 g potassium bromide 0.01 g potassium carbonate 27. 0 g Optical brightener (WHITEX 4B manufactured by Sumitomo Chemical) 1.0 g Sodium sulfite 0.1 g Disodium-N, N-bis (sulfonatoethyl) hydroxylamine 10.0 g N-ethyl-N- (β-methanesulfonamide) Ethyl) -3-methyl-4-aminoaniline sulfate 5.0 g Water was added and 1000 ml pH (25 ° C.) 10.05

The above color developer was used as Sample 101, and the compounds of the present invention and comparative compounds were added in the amounts shown in Table 1 to obtain Samples 102 to 112.

[Bleach-fixing solution] Water 600 ml Ammonium thiosulfate (700 g / liter) 100 ml Ammonium sulfite 40 g Ammonium iron (III) ethylenediaminetetraacetate 55 g 5 g ethylenediaminetetraacetic acid 5 g Ammonium bromide 40 g Nitric acid (67%) 30 g Water is added 1000 ml pH (25 ° C) (with acetic acid and ammonia water) 5.8 [Rinse solution] ion-exchanged water (calcium and magnesium are each 3 ppm or less)

[0167] In a beaker was set to an opening ratio 0.10 cm ^-1 ferric ion 5ppm calcium ions 150ppm added to each of the color developing solution, 2 at 38 ° C.
Aged 0 days.

Using a photometer (FWH type, manufactured by Fuji Photo Film Co., Ltd.), the color photographic material was subjected to gradation exposure of a three-color separation filter for sensitometry. The exposure was performed such that the exposure amount was 250 CMS with an exposure time of 0.1 second.

After the 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 method Process Temperature Time Replenishment amount ^* Tank capacity Color development 35 ° C 45 seconds 161 ml 17 liter Bleach-fix 35 ° C 45 seconds 215ml 17 liter Rinse 35 ° C 20 seconds −10 liter Rinse 35 ° C 20 seconds −10 liter Rinse 35 ° C. 20 seconds 360 ml 10 liters drying 80 ° C. 60 seconds (* replenishment rate per photosensitive material 1 m ²⁾ (was 3 tank countercurrent system to rinse →)

Color development over time with respect to the minimum density (Dmin) of yellow when processed with a fresh color developing solution (fresh solution) and the sensitivity of magenta (logarithmic log E of exposure amount giving a density of 0.5) The increase in the minimum yellow density Dmin (ΔDmin) and the change in magenta sensitivity (ΔS) when treated with the liquid (temporary liquid) were calculated. Further, the remaining amount of the developing agent in the aged solution was quantified by high performance liquid chromatography. Further, the presence or absence of generation of a precipitate of the color developer after the lapse of time was observed. The results are summarized in Table 1.

[0172]

[Table 1]

As is clear from Table 1, according to the structure of the present invention, the values of ΔDmin and ΔS are small, and the fluctuation of photographic properties is suppressed. In addition, it can be seen that the residual amount of the main drug is still sufficient to obtain sufficient performance by using the compound of the present invention. Further, it can be seen that the generation of precipitation is greatly improved as compared with the comparative example. In particular, in the case of the conventional compounds, those having a large effect of preventing precipitation were poor in preservation of the developing agent, and those having little decomposition of other developing agents were insufficient in preventing the formation of precipitate. On the other hand, it can be seen that the compound of the present invention provides a stable color developer without forming a precipitate.

Example 2 On an undercoated cellulose triacetate film support,
A multilayer color light-sensitive material comprising each layer having the following composition was prepared.

(Composition of photosensitive layer) The coating amount is the amount of silver expressed in g / m ² for silver halide and colloidal silver, and g for couplers, additives and gelatin.
/ M ² , and the sensitizing dye was represented by the number of moles per mole of silver halide in the same layer.

First layer (antihalation layer) Black colloidal silver Silver coating amount 0.20 Gelatin 2.20 UV-1 0.11 UV-2 0.20 Cpd-1 4.0 × 10 ^-2 Cpd-21 0.9 × 10 ^-2 Solv-1 0.30 Solv-2 1.2 × 10 ^-2

Second Layer (Intermediate Layer) Fine grain silver iodobromide (AgI 1.0 mol%, equivalent sphere diameter 0.07 μm) Silver coating amount 0.15 Gelatin 1.00 ExC-4 6.0 × 10 ⁻² Cpd-3 2.0 × 10 ^-2

Third Layer (First Red-Sensitive Emulsion Layer) Silver iodobromide emulsion (AgI: 5.0 mol%, surface height: AgI type, equivalent sphere diameter: 0.9 μm, coefficient of variation of equivalent sphere diameter: 21%, tabular shape) Grain, diameter / thickness ratio 7.5) Silver coating amount 0.42 Silver iodobromide emulsion (AgI 4.0 mol%, internal high AgI type, equivalent spherical diameter 0.4 μm, coefficient of variation of equivalent spherical diameter 18%) , Tetradecahedral particles) Silver coating amount 0.40 Gelatin 1.90 ExS-1 4.5 × 10 ^-4 mol ExS-2 1.5 × 10 ^-4 mol ExS-3 4.0 × 10 ^-5 mol ExC-1 0.65 ExC-3 1.0 × 10 ^-2 mol ExC-4 2.3 × 10 ^-2 mol Solv-1 0.32

Fourth Layer (Second Red-Sensitive Emulsion Layer) Silver iodobromide emulsion (AgI 8.5 mol%, internal high AgI type, equivalent sphere diameter 1.0 μm, coefficient of variation of equivalent sphere diameter 25%, plate shape Particles, diameter / thickness ratio 3.0) Silver coating amount 0.85 Gelatin 0.91 ExS-1 3.0 × 10 ^-4 mol ExS-2 1.0 × 10 ^-4 mol ExS-3 3.0 × 10 ^-5 mol ExC-1 0.13 ExC-2 6.2 × 10 ^-2 mol ExC-4 4.0 × 10 ^-2 mol Solv-1 0.10

Fifth Layer (Third Red Sensitive Emulsion Layer) Silver iodobromide emulsion (AgI 11.3 mol%, internal high AgI type, sphere equivalent diameter 1.4 μm, sphere equivalent diameter variation coefficient 28%, plate shape Particles, diameter / thickness ratio 3.0) Silver coating amount 1.50 Gelatin 1.20 ExS-1 2.0 × 10 ⁻⁴ mol ExS-2 6.0 × 10 ⁻⁵ mol ExS-3 2.0 × 10 ⁻⁵ mol ExC-2 8.5 × 10 ⁻² ExC-5 7.3 × 10 ⁻² ExC-6 1.0 × 10 ⁻² Solv-1 0.12 Solv-1 0.12

Sixth Layer (Intermediate Layer) Gelatin 1.00 Cpd-4 8.0 × 10 ⁻² Solv-1 8.0 × 10 ⁻²

Seventh Layer (First Green Sensitive Emulsion Layer) Silver iodobromide emulsion (AgI 5.0 mol%, surface high AgI type, equivalent sphere diameter 0.9 μm, coefficient of variation of equivalent sphere diameter 21%, tabular Grain, diameter / thickness ratio 7.0) Silver coating amount 0.28 Silver iodobromide emulsion (AgI 4.0 mol%, internal high AgI type, equivalent spherical diameter 0.4 μm, coefficient of variation of equivalent spherical diameter 18%) , Tetradecahedral particles) Silver coating amount 0.16 Gelatin 1.20 ExS-4 5.5 × 10 ^-4 mol ExS-5 2.0 × 10 ^-4 mol ExS-6 1.0 × 10 ^-4 mol ExM-1 0.50 ExM-2 0.10 ExM-5 3.5 × 10 ^-2 Solv-1 0.20 Solv-3 3.0 × 10 ^-2

Eighth Layer (Second Green-Sensitive Emulsion Layer) Silver iodobromide emulsion (AgI 8.5 mol%, internal high AgI type, equivalent sphere diameter 1.0 μm, coefficient of variation of equivalent sphere diameter 25%, plate shape Particles, diameter / thickness ratio 3.0) Silver coating amount 0.57 Gelatin 0.45 ExS-4 3.5 × 10 ^-4 mol ExS-5 1.4 × 10 ^-4 mol ExS-6 7.0 × 10 ^-4 mol ExM-1 0.12 ExM-2 7.1 × 10 ⁻³ ExM-3 3.5 × 10 ⁻² Solv-1 0.15 Solv-3 1.0 × 10 ⁻²

Ninth Layer (Intermediate Layer) Gelatin 0.50 Solv-1 2.0 × 10 ⁻²

Tenth Layer (Third Green Sensitive Emulsion Layer) Silver iodobromide emulsion (AgI 11.3 mol%, internal high AgI type, sphere equivalent diameter 1.4 μm, sphere equivalent diameter variation coefficient 28%, plate shape Particles, diameter / thickness ratio 6.0) Silver coating amount 1.30 Gelatin 1.20 ExS-4 2.0 × 10 ⁻⁴ mol ExS-5 8.0 × 10 ⁻⁵ mol ExS-6 8.0 × 10 ⁻⁵ mol ExM-4 5.8 × 10 ⁻² ExM-6 5.0 × 10 ⁻³ ExC-2 4.5 × 10 ⁻³ Cpd-5 1.0 × 10 ⁻² Solv-1 0.25

11th layer (yellow filter layer) Gelatin 0.50 Cpd-6 5.2 × 10 ^-2 Splv-1 0.12 12th layer (intermediate layer) Gelatin 0.45 Cpd-3 0.10

Thirteenth Layer (First Blue-Sensitive Emulsion Layer) Silver iodobromide emulsion (AgI 2 mol%, uniform AgI type, equivalent sphere diameter 0.55 μm, coefficient of variation of equivalent sphere diameter 25%, tabular grains, Diameter / thickness ratio 7.0) Silver coating amount 0.20 Gelatin 1.00 ExS-7 3.0 × 10 ^-4 mol ExY-1 0.60 ExY-2 2.3 × 10 ^-2 Solv-1 Fifteen

Fourteenth Layer (Second Blue Sensitive Emulsion Layer) Silver iodobromide emulsion (AgI 19.0 mol%, internal high AgI type, sphere equivalent diameter 1.0 μm, sphere equivalent diameter variation coefficient 16%, octahedron Particles) Silver coating amount 0.19 Gelatin 0.35 ExS-7 2.0 × 10 ⁻⁴ mol ExY-1 0.22 Solv-1 7.0 × 10 ⁻²

Fifteenth Layer (Intermediate Layer) Fine-grain silver iodobromide (AgI 2 mol%, uniform AgI type, equivalent sphere diameter 0.13 μm) Silver coating amount 0.20 Gelatin 0.36

Sixteenth Layer (Third Blue-Sensitive Emulsion Layer) Silver iodobromide emulsion (AgI 14.0 mol%, internal high AgI type, sphere equivalent diameter 1.7 μm, sphere equivalent diameter variation coefficient 28%, plate shape Particles, diameter / thickness ratio 5.0) Silver coating amount 1.55 Gelatin 1.00 ExS-8 1.5 × 10 ^-4 mol ExY-1 0.21 Solv-1 7.0 × 10 ⁻²

17th layer (first protective layer) Gelatin 1.80 UV-1 0.13 UV-2 0.21 Solv-1 1.0 × 10 ^-2 Solv-2 1.0 × 10 ^-2

Eighteenth Layer (Second Protective Layer) Fine Particle Silver Chloride (Equivalent Sphere Diameter 0.07 μm) Coating Silver Amount 0.36 Gelatin 0.70 B-1 (1.5 μm Diameter) 2.0 × 10 ⁻² B -2 (1.5 μm in diameter) 0.15 B-3 3.0 × 10 ^-2 W-1 2.0 × 10 ^-2 H-1 0.35 Cpd-7 1.00

[0193] In addition to the above,
1,2-Benzisothiazolin-3-one (average 200 ppm based on gelatin), n-butyl-p-hydroxybenzoate (about 1,000 ppm), and 2-phenoxyethanol (about 10,000 ppm) were added. . Further, B-4, B-5, W-2, W-3, F-1, F-
2, F-3, F-4, F-5, F-6, F-7, F-
8, F-9, F-10, F-11, F-12, F-13
And iron salts, lead salts, gold salts, platinum salts, iridium salts, and rhodium salts. Next, the chemical structural formulas or chemical names of the compounds used above are shown below.

[0194]

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[0201]

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[0205]

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[0206]

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[0207]

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[0208]

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Next, the following processing solutions were prepared. (Color developer) Mother liquor (g) Replenisher (g) Diethylenetriaminepentaacetic acid 1.0 1.0 Compound of Table 2 0.01 mol (same as mother liquor) Sodium sulfite 4.0 4.9 Potassium carbonate 30. 0 30.0 Potassium bromide 1.4-Potassium iodide 1.5 mg-Hydroxylamine sulfate 2.4 3.6 4- (N-ethyl-N-β-hydroxyethylamino) -2-methylaniline sulfate Salt 4.5 6.4 Add water 1000 ml 1000 ml pH 10.05 10.10

(Bleaching solution) Mother liquor Replenisher 1,3-propanediaminetetraironiron (III) ammonium acetate 0.55 mol 0.83 mol ammonium bromide 85 g 125 g ammonium nitrate 20 g 30 g glycolic acid 55 g 83 g Water was added to 1000 ml 1000 ml pH 4.0 3.8

(Fixing solution) Common to mother liquor and replenisher (g) Ethylenediaminetetraacetic acid diammonium salt 1.7 Ammonium sulfite 14.0 Aqueous ammonium thiosulfate (700 g / liter)

(Washing water) Common tap water was used as the H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas Co.) and the OH type strongly basic anion exchange resin (Amberlite IRA- 4
00) to reduce the concentration of calcium and magnesium ions to 3 mg / l or less, followed by 20 mg / l of sodium diisocyanurate dichloride.
Liters and 150 mg / liter of sodium sulfate were added. The pH of this solution was in the range of 6.5 to 7.5.

(Stabilizing solution) Common to mother liquor and replenisher (unit: g) Formalin (37%) 1.2 ml Surfactant 0.4 [C ₁₀ H ₂₁ -O- (CH ₂ CH ₂ O) ₁₀ -H] ethylene Glycol 1.0 Add water to 1000 ml pH 5.0-7.0

5 ppm of ferric ion was added to the above color developing solution.
150 ppm of calcium ions were added, and samples 201 to 20 were added.
7 as a circulating liquid aging tester with an aperture ratio of 0.11 cm ^-1
The temperature was raised to 8 ° C. and aged for 30 days. The multilayer color light-sensitive material produced as described above was cut and processed into a width of 35 mm, and was subjected to white light (color temperature of light source: 4800 ° K) wedge exposure. After exposure, samples 201 to 201 prepared as described above were prepared.
Using the color developing solution immediately after the preparation and the aged developing solution, processing was carried out according to the following steps.

Processing step Step Processing time Processing temperature Color development 3 minutes 15 seconds 37.8 ° C Bleaching 50 seconds 38.0 ° C Rinse 1 minute 40 seconds 38.0 ° C Rinse (1) 30 seconds 38.0 ° C Rinse (2) 20 seconds 38.0 ° C Stable 20 seconds 38.0 ℃

[0216]

[0219]

[Table 2]

As is clear from Table 2, when no chelating compound was added and when a conventional chelating agent was added, the prevention of precipitation and the securing of liquid stability were at insufficient levels. It can be seen that a great effect can be obtained only by adding the compound represented by the general formula (I) and / or (II) of the invention.

Example 3 To the fixing solution of Example 2, 3 g / l of the compounds 1, 19, 20 and 25 of the present invention were added, and further, ferric ion corresponding to the carry-in from the bleaching solution in the prebath was added. Thus, sample liquids 301 to 304 were obtained. These sample solutions were used with an aperture ratio of 0.
The solution was aged at 38 ° C. for 30 days at 1 cm ⁻¹ , and the turbidity of the solution was observed. When no compound was added, remarkable turbidity occurred after the elapse of time, but it was shown that the fixer to which the compound of the present invention was added maintained a transparent state and did not generate any precipitate.

Example 4 The stabilizer of Example 2 was used as it was for comparison, and to this, Exemplified Compounds 16, 25, 31, and 36 were added at a ratio of 100 mg / L, respectively.
405 were prepared. Using these stable liquids, in addition to the stable liquids, processing was performed by the method described in Example 2 using a fresh liquid such as the color developing solution of the sample 201 of Example 2. The film after the treatment was aged for 1 week under the condition of wet heat of 45 ° C. and 70%, and the increase in magenta stain (ΔDmin) before and after the aging was determined. Table 3 shows the obtained results.

[0221]

[Table 3]

It can be seen that the stabilizing solution according to the present invention to which the exemplified compounds are added suppresses an increase in stain and improves image storability.

Example 5 The following bleaching solution was prepared. Hydrogen peroxide (30%) 50 ml KBr 28 g Potassium hydrogen phosphate 10 g 1 liter pH 3.5 with water

For comparison, a sample 50 to which a comparative compound and compounds 19, 25 and 48 of the present invention were added was added.
1-505 were prepared. In order to examine the bleaching performance, the same multilayer color photosensitive material as in Example 2 was used, and the color developing solution was the sample 201 of Example 2, and the fixing solution, stabilizing solution, and washing water were also used in Example 2.
The same one was used.

With respect to Samples 501 to 505, the following treatment was performed on the solution immediately after the preparation and the solution aged at 40 ° C. for 3 days, and the amount of residual silver in the highest density part was analyzed by X-ray fluorescence. At the same time, the residual amount of hydrogen peroxide was analyzed. Table 4 shows the results.

Process Processing time Processing temperature Color development 3 minutes 15 seconds 38 ° C. Bleaching 50 minutes 40 ° C. Fix 1 minute 40 seconds 38 ° C. Rinse (1) 30 seconds 38 ° C. Rinse (2) 20 seconds 38 ° C. Stable 20 seconds 38 ℃

[0227]

[Table 4]

Thus, it can be seen that the use of the compound of the present invention improves the stability of a bleaching solution using hydrogen peroxide as an oxidizing agent.

Example 6 A sample 201 similar to that of Example 2 was prepared using the sample 201 of Example 2 of JP-A-2-90151 and the photosensitive material 9 of Example 3 and the photosensitive material of Example 1 of JP-A-2-93641. When the evaluation was performed, the same effect was obtained.

Example 7 A developer (B) was prepared by using Sample-1 of Example 1 of JP-A-2-58041 and replacing disodium ethylenediaminetetraacetate in the developer (A) with the same amount of compound 25. )
Was prepared, and each developer was aged at 40 ° C. for 4 days, and then subjected to a running treatment. As a result, the precipitation property was improved.

Example 8 [Adjustment of Developer] A developer having the following composition was prepared. Potassium sulfite 65.0 g Hydroquinone 30.0 g 4-Methyl-4-hydroxymethyl-1-phenyl-3-pyrazolidone 1.0 g Chelating agent (shown in Table 5) 10 mmol Potassium hydroxide 11.0 g Sodium carbonate (1 water Salt) 11.0 g Potassium bromide 3.0 g 5-Methylbenztriazole 0.1 g 2-mercaptobenzimidazole-5-sulfonic acid 0.1 g Diethylene glycol 25.0 g Add water to make 1 liter pH = 10.70 I do.

[Evaluation of Air Oxidizing Property of Developer] Developer 5
00 ml was placed in a 500 ml beaker, the beaker was covered with Saran wrap, and a 2 mm hole was made directly in the cover, and the cover was allowed to stand at room temperature for 14 days. Thereafter, the remaining amount of hydroquinone and potassium sulfite and the value of pH were measured. Table 5 shows the results.

[0233]

[Table 5]

[0234]

[Table 5]

Example 9 [Running Experiment] Xenon with a light emission time of 10 ⁻⁶ seconds was applied to a scanner film (FT-87) manufactured by Fuji Photo Film Co., Ltd. for LD light source through an interference filter having a peak at 780 nm and a continuous wedge. Exposure with flash light. Using this exposed sample, a running experiment was performed under the following conditions using the developer of Example 8 and GF-1 manufactured by Fuji Photo Film Co., Ltd. That is, the above-mentioned developer and fixing solution were filled in an automatic developing machine FG-680A manufactured by Fuji Photo Film Co., Ltd., and operated under the following conditions.

[0236]

The apparatus was operated in the standby state for 9 hours per day and continuously operated for 3 weeks. 4 half-exposed daily
Twenty cut-size film samples were processed, and then the exposed samples described above were developed. At this time, the replenishment amount of the developing solution was set to the amount shown in Table 6, and the replenishment amount of the fixing solution was set to 300 ml / m ² .

[Evaluation of photographic performance] The photographic performance was evaluated by using the reciprocal of the exposure amount giving a density of 4.0 as sensitivity, and the relative sensitivity is shown in Table 6. Table 6 also shows the gradient of a straight line connecting the points of density 0.1 and 3.0 in the characteristic curve as gradation.

[Evaluation of Stability of Developer Composition] A fixed amount of the developer was sampled every seven days, and the pH value, the concentration of hydroquinone and potassium sulfite were measured.

[0240]

[Table 6]

As can be seen from Table 6, under the condition where the replenishment amount of the developing solution is large, there is no problem. However, under the condition where the replenishing amount is small, in the developing solution not using the compound of the present invention, the hydroquinone concentration is greatly reduced by running. The pH value is also much higher than at the beginning. The photographic properties fluctuate greatly and are not very practical. According to the present invention, high sensitivity and gradation can be maintained for a long period of time even under running conditions in which the replenishment amount of the developer is 200 ml / m ² or less.

[0242]

The treatment composition according to the present invention has the following excellent effects. (1) Oxidation or decomposition of the processing solution composition due to the action of metal ions is suppressed, and the performance of the processing solution is maintained for a long time. (2) No precipitation occurs in the solution even by accumulation of metal ions. Therefore, there is no trouble such as contamination of the film and clogging of the filter of the automatic processor. (3) The image storability of the processed photosensitive material is improved.

Claims (2)

(57) [Claims] 1. A photographic processing composition comprising at least one compound represented by the following general formula (I) or (II). General formula (I) General formula (II) 2. A silver halide, wherein the silver halide photographic material which has been imagewise exposed is treated with a processing solution containing at least one compound represented by the following general formula (I) or (II). Processing method of photographic photosensitive material. General formula (I) General formula (II)