JPH08254803A - Replenisher for color developer for silver halide color photographic sensitive material and processing method - Google Patents

Abstract

PURPOSE: To provide a replenisher for a color developer for a silver halide photographic sensitive material having good storage property and stable max. density, and to provide its processing method. CONSTITUTION: The replenisher contains a p-phenylenediamine color developing agent and a compd. expressed by formula. In formula, R1 is C1 C2 alkyl group or hydrogen atom, R2 is a substd. or unsubstd. C1-C3 alkyl group, sulfonate group, carboxyl group, hydroxyl group or hydrogen atom, R3 is a hydrogen atom or hydroxyl group, p is an integer 0 to 2, r is an integer 1 to 3, A may be substituted for a hydrogen atom at any position of a benzene ring, s is an integer 0 to 50, t is an integer 0 or 1, and u is an integer 2 to 150.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color developing replenisher for a silver halide color photographic light-sensitive material (hereinafter also simply referred to as a light-sensitive material) and a processing method using the same. More specifically, it relates to a stabilized color developing replenisher and a method of processing a silver halide color photographic light-sensitive material capable of obtaining stable photographic characteristics.

[0002]

2. Description of the Related Art Generally, it is known that a color developer containing an aromatic primary amine developing agent and a color developer are autoxidized when contacted with air.

In particular, recently, due to the spread of minilab machines, the number of in-store processing at general camera stores and DP handling stores is increasing.
On the other hand, from the viewpoint of environmental protection, there is a strong demand for reduction of processing waste liquid.

In order to deal with this, stabilization of the processing solution and low replenishment of the processing solution have been attempted in the processing of photosensitive materials. With the spread of minilab machines, it is difficult from an economical point of view to have a manager with technical knowledge in all processing equipment,
A system that a traveling service person manages the treatment liquid is being adopted. The service personnel often visit once every two to three weeks, and the stabilization of the treatment liquid has been gradually devised so that no trouble occurs during that period. As a measure to reduce the replenishment of the processing solution, for example, for the color developing solution, a method of regenerating the overflowed solution by an ion exchange resin method or an electrodialysis method, a method of replenishing the concentrated replenishing solution with a low replenishment rate, and A method of adding a regenerant to the overflow solution and using it again as a replenisher has been proposed and put to practical use.

The most important factors in reducing the replenishment of the color developing solution are stability of the replenisher with time and stability of the quality of the processed light-sensitive material. The retention time of the replenishing solution in the replenishing tank becomes longer in a replenishing tank having a constant volume as the replenishing rate is lowered, and the time in which the color developing replenishing solution comes into contact with air becomes longer. The replenishment tank is built into the side of the processing tank due to the design of the automatic processing machine, and is often in the shape of a vertically long rectangular parallelepiped. When the color development replenisher is full in the replenishment tank, the air contact area is relatively small, but the volume of the solution gradually decreases as it is replenished, so the relative air contact area per volume of the replenisher gradually increases. Will be done. The lower the replenishment rate, the longer the air contact time and the more accelerated the oxidation of the color developing solution replenisher.

The aromatic primary amine type color developing agent in the color developing replenisher and the color developing solution is a compound which is very easily oxidized, and a compound generally called an antioxidant or a preservative is used together. . As antioxidants for color developing agents, the compounds most often used conventionally are sulfite and hydroxylamine sulfate or hydrochloride.

Recently, an increasing number of minilab stores sell short-time processing called 1 Hour Photo (45 minutes to 1 hour finish) for sale. For this reason, color papers having a high content of silver chloride, which are excellent in developability, have become popular. When a large amount of the above-mentioned sulfite salt or hydroxylamine salt is added to the color developing solution for processing color paper mainly containing silver chloride, a physical development phenomenon of silver halide dissolution occurs, and silver halide grains having latent image nuclei are formed. It has been known that it dissolves and hinders the reaction with the color developing agent, and does not give a sufficient dye concentration.

Therefore, alkanolamines described in, for example, JP-A No. 62-250444 are used as antioxidants for color developing solutions that are less likely to affect the developing characteristics of a light-sensitive material using an emulsion having a high silver chloride content. Using JP-A-63-325
Methods using a dialkylhydroxylamine described in JP-A No. 47, etc., methods using a hydrazine derivative described in JP-A No. 63-48548, etc. have been known. In this situation, it cannot be said that it is a sufficient countermeasure.

Further, recently, there is a tendency that the number of minilabs in which the development processing amount of the light-sensitive material is extremely small is increasing, and when low replenishment is applied to these minilabs, it becomes a particularly big problem.

In a recent mini-lab, a large amount of light-sensitive material is processed at the beginning of the week, but almost no processing is performed on the weekend. There is a phenomenon that the maximum density of the print decreases or fluctuates, which causes the density of the shadow part of the print to decrease, and for example, the black formal wear part does not look black, and good print quality can be obtained. It is gone, which is a big problem.

Further, when the replenishment is made low in the color developing step, it is necessary to maintain the activity of the color developing treatment solution with a small amount of the replenishing solution, so that the color developing agent in the color developing replenishing solution is maintained. It is necessary to maintain a very high concentration of 9 g / l or more, and in some cases exceeding 11 g / l. However, most of the commonly used color developing agents are para-phenylenediamine type compounds, and these para-phenylenediamine type color developing agents are used in the pH of the color developing replenisher.
It has a drawback that it tends to crystallize and precipitate in the form of a free amine in an extremely alkaline solution having a value of 10 to 12.

In order to compensate for this drawback, for example, Japanese Patent Laid-Open No. 3-5
No. 9654 describes a technique using a naphthalene sulfonic acid derivative. However, these derivatives can improve the solubility of the color developing agent and prevent the precipitation of crystals in the solution immediately after the color developing replenisher is dissolved. It has been found that there is a defect that the oxidation of the color developing replenisher adhering to the tank wall due to the phenomenon is significantly caused. Furthermore, what is oxidized on the wall surface of the tank gradually increases and crystallizes, or turns black and becomes large crystals, which eventually fall into the color development replenisher and become seeds for crystal growth in the tank. ,
There was a drawback that caused the tarring phenomenon.

In order to make up for the above-mentioned drawbacks, for example, in JP-A-3-223757 and JP-A-3-436947, a large amount of a water-soluble surfactant is added to improve the solubility of a color developing agent, and to improve the color developing solution. A technique for improving the precipitation property and preventing oxidation is described. However, when these water-soluble surfactants are added in a large amount, the color developing solution foams, which is extremely difficult to handle. When these compounds are further added, the surfactant agglomerates on the surface of the conveying roller for the photosensitive material of the color developing tank solution, gradually accumulates on the surface of the roller, and finally forms a thin film. It has a drawback that the transport function is deteriorated and the photosensitive material slips.

[0014]

SUMMARY OF THE INVENTION The first object of the present invention is to provide a stabilized silver halide color photograph free from crystal precipitation and tar generation in a color developing replenisher containing a concentrated paraphenylenediamine color developing agent. The present invention provides a color developing replenisher for a light-sensitive material and a method for processing a luminescent material using the replenisher.

Secondly, in the low replenishment process, even if the process amount is not constant, it is processed without impairing the conveying function of the developing machine, and the maximum density of the photosensitive material is very high. It is intended to provide a color development replenisher for a silver halide color photographic light-sensitive material which is stably obtained, and a method for processing a light-sensitive material using the replenisher.

Thirdly, a low replenishing process is made possible, which makes it possible to reduce the amount of waste liquid discharged from the automatic developing machine, and a color developing replenishing liquid for silver halide color photographic light-sensitive materials excellent in environmental suitability and the replenishing process. Another object is to provide a method for processing a silver halide color light-sensitive material using a liquid.

[0017]

As a result of intensive studies for achieving the above object, the present inventors have found that the above object can be achieved by adopting any one of the following configurations.

1) A color developing replenisher for silver halide color photographic light-sensitive materials, which contains a p-phenylenediamine type color developing agent and a compound represented by the following general formula [1].

[0019]

Embedded image

[Wherein R ₁ represents an alkyl group having 1 to 2 carbon atoms or a hydrogen atom, and R ₂ is a substituted or unsubstituted alkyl group having 1 to 3 carbon atoms, a sulfonic acid group,
It represents a carboxyl group, a hydroxyl group and a hydrogen atom, and R ₃ represents a hydrogen atom or a hydroxyl group. P is an integer of 0 to 2 and γ is 1
Represents an integer of 3. A may be replaced by any hydrogen atom on the benzene ring. Further, S represents 0 to 50, t represents an integer of 0 or 1, and u represents a number of 2 to 150. 2) For the silver halide color photographic light-sensitive material according to 1), wherein the content of the compound represented by the general formula [1] is 0.001 to 5.0 g per liter of color developing replenisher. Color development replenisher.

3) The color developing replenisher for silver halide color photographic light-sensitive materials as described in 1) or 2) above, wherein the color developing replenisher contains a compound represented by the following general formula [2].

General formula [2] R ₄ —SO ₃ M [In the formula, R ₄ is an alkyl group having 1 to 8 carbon atoms, a phenyl group, a naphthalene group or an ethylenically unsaturated group, and these repeating units are It may be a polymer having. M
Represents a hydrogen atom, an alkali metal atom or an ammonium group. 4) In a method of continuously treating a silver halide color photographic light-sensitive material coated on a support with a color developing solution containing a p-phenylenediamine type color developing agent, the color developing solution is replenished. The method for processing a silver halide color photographic light-sensitive material, wherein the color developing replenisher used contains at least one compound represented by the general formula [1].

5) The silver halide color photographic according to 4), wherein the color developing replenisher described in 1) to 4) is replenished in an amount of 30 to 150 ml per 1 m ^{2 of the} silver halide color photographic light-sensitive material. Method of processing photosensitive material.

In the present invention, favorable results are obtained when the color developing replenisher is used for a long period of time or when it is used in cold regions in winter. Especially, the throughput is small (about 24 negatives, about 10 pieces / day, 2.5m ^{2 of} paper)
(Amount to be processed / about 1 day), if the replenisher once dispensed is used for more than 3 weeks, the replenishment tank will be full of color development replenisher immediately after the replenishment in the replenisher tank, and the floating lid etc. The relative air contact area of the color developer (opening area (m ² ) / replenisher volume (m ² )) can be reduced to about 0.001 cm ⁻¹ by using the color developer, but the color developer replenisher gradually develops the color. Since it is supplied to the tank according to the processing of the light-sensitive material, the relative air contact area increases and becomes about 0.1 cm ^-1 at the bottom of the replenishing tank.

The color-developing agent in the color-developing replenisher is a material which is susceptible to air oxidation, and when it is kept in contact with air for a long period of time, it may be oxidized and the color-developing function may be lost.

In the present invention, the color developing replenisher contains a compound selected from the general formula [1] so that the function of the color developing agent is not lost for a long period of time even if the relative air contact area is increased. Found. Further preferable results can be obtained by using the compound of the general formula [2] together.

On the other hand, when the automatic processor is used in a cold region, the replenishment tank does not have a temperature control function, so 0 ° C.
There are cases where it falls below. When the color developing replenisher is stored under such conditions, the color developing agent has a low solubility.In particular, the low replenishing type color developing replenisher contains a high concentration of the color developing agent, so the temperature is low. Then, it has the property of precipitating the once dissolved color developing agent.

When the compound selected from the general formula [1] of the present invention is contained, it is possible to provide such a color developing replenisher that the above drawbacks are improved and the color developing function is not lost for a long period of time. Further preferable results can be obtained by incorporating the compound of the general formula [2].

That is, if the color developing replenisher is used for a long period of time under the above-mentioned conditions, the quality of the processed light-sensitive material to be processed is deteriorated by the conventional techniques. There was a drawback that it decreased or changed,
The present invention solves this drawback.

In the present invention, the addition amount of the compound of the general formula [1] is preferably 0.001 to 5 g, and more preferably 0.01 to 3 g, per liter of color developing replenisher.

The compound of the general formula [2] is preferably added in an amount of 0.01 to 60 g per liter of color developing replenisher.
More preferably, it is 0.05 to 50 g.

In particular, by improving the stability of the color developing replenisher having a low sulfite concentration, it is possible to improve the finish quality of a light-sensitive material to be continuously processed (meaning that the processing amount is not constant for a long period of time). It was a discovery of a technology to improve, which was totally unexpected.

Next, the general formula [1] will be described.

In the general formula [1], R ₁ represents an alkyl group having 1 or 2 carbon atoms (eg methyl group, ethyl group) or a hydrogen atom, and R ₂ is a linear or branched substituted or unsubstituted group. An alkyl group having 1 to 3 carbon atoms (for example, methyl group, ethyl group, propyl group, (i) propyl group, hydroxymethyl group, sulfomethyl group, hydroxyethyl group,
Sulfoethyl group, disulfoethyl group, dihydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 1-sulfopropyl group, 2-sulfopropyl group, trihydroxy (i) propyl group, 1,2-disulfopropyl group ), A sulfonic acid group, a carboxyl group, a hydroxy group and a hydrogen atom, and R ₃ represents a hydrogen atom or a hydroxy group.

P is an integer of 0 to 2 and γ is an integer of 1 to 3.

A may be replaced by a hydrogen atom at any position on the benzene ring. Further, S represents 0 to 50, t represents an integer of 0 or 1, and u represents a number of 2 to 150.

Specific compounds represented by the above general formula [1] will be given below.

[0038]

Embedded image

[0039]

[Chemical 4]

[0040]

Embedded image

Of the above specific compounds, preferably [1] -2, [1] -3, [1] -4, [1] -5,
[1] -6, [1] -13, [1] -17, and more preferably [1] -2, [1] -3, [1] -4,
[1] -5.

Next, the general formula [2] will be described.

In the general formula [2], R ₄ has 1 to 1 carbon atoms.
The alkyl group of 8 is an alkyl group having 1 to 8 carbon atoms (for example, methyl group, carboxymethyl group, phenylmethyl group, ethyl group, hydroxyethyl group, sulfonylethyl group, propyl group, butyl group, heptyl group, octyl group). Etc.) can be mentioned. These may be linear or branched, and also include those having a substituent. As the substituent, a halogen atom (eg, chlorine atom, bromine atom, etc.), an aryl group (eg, phenyl group, etc.), a hydroxyl group, an amino group, a nitro group, a carboxylic acid group (including a salt thereof), a sulfonic acid group (a salt thereof) Including))).

The phenyl group represented by R ₄ also includes those having a substituent, and as the substituent, a halogen atom (eg, chlorine atom, bromine atom, etc.), an alkyl group (preferably having 1 to 4 carbon atoms) Alkyl group) (for example, methyl group, ethyl group, propyl group, butyl group, etc.), hydroxyl group, amino group, nitro group, carboxylic acid group (including its salt), sulfonic acid group (including its salt), etc. The number of the substituents on the phenyl group may be one or 2 to 5, and in the case of 2 to 5, the substituents may be the same or different.

The naphthalene group represented by R ₄ also includes those having a substituent, and the substituent is an alkyl group (preferably an alkyl group having 1 to 4 carbon atoms) (eg, methyl group, ethyl group). Group, propyl group, isopropyl group,
Butyl group, isobutyl group, etc.), hydroxyl group, amino group, nitro group, carboxylic acid group (including its salt), sulfonic acid group (including its salt), and the substituent on the naphthalene group is 1
The number of substituents may be the same as or different from 2 to 7, and in the case of 2 to 7, the substituents may be the same or different.

Further, R ₄ is an ethylenically unsaturated group,
It may be a polymer having these repeating units.

R ₄ is preferably a phenyl group,
Those having a substituent are more preferable, and preferable substituents are an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, a carboxylic acid group (including a salt thereof), a sulfonic acid group (including a salt thereof).
Is.

Specific compounds represented by the above general formula [2] are listed below.

[0049]

[Chemical 6]

[0050]

[Chemical 7]

[0051]

Embedded image

[0052]

[Chemical 9]

[0053]

[Chemical 10]

Of the above specific compounds, 2-
20,2-21,32,32,2-49, and most preferably 2-32,2-49.

The pH of the color developing replenisher according to the present invention is 10.0
It is preferable to set the pH value to -13.0, and it is preferable to set the pH set value higher as the replenishment amount is reduced.

For example, when the replenishing amount is 60 ml / m ² or less, the pH is 10.
It is preferable to set it to 6 or more, and to set pH at 50 ml / m ² or less.
It is preferable to set it to 10.9 or more, and further to set the pH to 11.2 or more when it is 40 ml / m ² or less.
The color developing agent used in the present invention is an aromatic primary amine color developing agent. A preferred example is a p-phenylenediamine derivative, and typical examples thereof are shown below, but the invention is not limited thereto.

1 N, N-diethyl-p-phenylenediamine 2 2-amino-5-diethylaminotoluene 3 2-amino-5- (N-ethyl-N-laurylamino) toluene 4 4- (N-ethyl-N -(β-Hydroxyethyl) amino) aniline 5 2-methyl-4- (N-ethyl-N- (β-hydroxyethyl) amino) aniline 6 4-amino-3-methyl-N-ethyl-N- (β -(Methanesulfonamide) ethyl) aniline 7 N- (2-amino-5-diethylaminophenylethyl) methanesulfonamide 8 N, N-dimethyl-p-phenylenediamine 9 4-amino-3-methyl-N-ethyl- N-methoxyethylaniline 10 4-amino-3-methyl-N-ethyl-N-β-ethoxyethylaniline 11 4-amino-3-methyl-N-ethyl-N-β-ethoxyethylaniline p-phenylenediamine Among the derivatives, the compound particularly preferably used in the present invention is 4-amino-3-methyl-N-ethyl.
-N- (β- (methanesulfonamido) ethyl) -aniline (Exemplified compound 6) and 2-methyl-4- (N-ethyl-N- (β-hydroxyethyl) amino) aniline (Exemplified compound 5) is there.

Further, these p-phenylenediamine derivatives may be salts such as sulfates, hydrochlorides, sulfites and p-toluenesulfonates.

The color developing agent is used in an amount of 5.0 to 20 g per liter of the color developing solution replenisher of the present invention. It is preferable to design the addition amount of the color developing agent to be higher as the replenishing amount is reduced.

For example, when the amount of replenishment is 60 ml / m ² , it is preferably 9.0 g / l or more, and when it is 50 ml / m ² , it is preferably 10 g / l or more,
In the case of 40 ml / m ² , the preferred embodiment is designed to be 11.5 g / l or more.

In the present invention, other known development replenisher components are added. For example, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, sodium metaborate, potassium metaborate as a buffer to maintain pH.
Examples thereof include sodium salicylate, sodium 5-sulfosalicylate, potassium 5-sulfosalicylate, and the like. The addition amount of these is preferably 10.0 to 50.0 g / l, and more preferably 20.0 to 40.0 g / l.

In addition, various chelating agents are added as a precipitation preventing agent for calcium and magnesium or as a masking agent for other metal ions such as Fe ions and Cu ions.

For example, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, triethylenetetraminehexaacetic acid, nitriloN, N, N-methylenephosphonic acid,
Ethylenediamine N, N, N ', N'-tetramethylenephosphonic acid, 1,3-diamino-1,2-propanoltetraacetic acid, hydroxyethyliminodiacetic acid, ethylenediamineorthohydroxyphenylacetic acid, 2-phosphonobutane 1,2,4 -Tricarboxylic acid, 1-hydroxyethylidene 1,1'-diphosphonic acid,
N, N′-bis (2-hydroxybenzyl) ethylenediamine N,
Examples thereof include N'-dicarboxylic acid and 1,2-dihydroxybenzene-3,5-disulfonic acid. Of these chelating agents, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, triethylenetetraminehexaacetic acid, 1-hydroxyethylidene-1,1′-diphosphonic acid, and 1,2-dihydroxybenzene-3,5-disulfonic acid are preferably used. To be These chelating agents may be used alone or in combination of two or more. The amount of these chelating agents added is preferably 0.05 to 10.0 g per liter of color developing replenisher.

Further, the color developing replenisher of the present invention contains a thioether compound as a development accelerator (Japanese Patent Publication No. 37-16088,
37-5987, 38-7826, 44-12380, 45-9019
And U.S. Pat. No. 3,813,247) and p-
Aminophenols (US Pat. Nos. 2,610,122 and 4,119,4)
62) and polyalkylene oxides (Japanese Patent Publication Nos. 37-16088, 42-25201, and U.S. Pat. No. 3,12).
8,183, Japanese Patent Publications 41-11431, 42-23883, U.S. Patents
No. 3,532,501 etc.) and the like can be added as necessary. If necessary, chlorine ions, bromine ions and optional antifoggants can be added. As the antifoggant, for example, organic antifoggants such as benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-nitrobenzotriazole, and adenine can be added.

Further, the color developing replenisher of the present invention contains a fluorescent whitening agent such as 4,4'-diamino-2,2'-for the purpose of improving whiteness.
Disulfostilbene compounds are advantageously used. The amount added is preferably 0.2 to 10 g per liter of color developing replenisher.
And more preferably 0.5 to 5.0 g.

As the fixing solution, the bleaching solution, the bleach-fixing solution and the stabilizing solution used in the present invention, compositions and composition solutions known in the color photographic industry can be used.

[0067]

EXAMPLES Examples of the present invention will be given below, but the embodiments of the present invention are not limited thereto.

Example 1 A rectangular parallelepiped (length 5 cm × width 3.5 cm ×) in which 200 ml of a color developing replenisher shown below was prepared and can be filled as a replenishing tank
Each polyethylene container having a height of 10 cm was filled with 150 ml and subjected to a storage test at 25 ° C. After filling the replenisher, a floating lid capable of adjusting the air contact area is floated on the surface of the replenisher, and the relative air contact area (opening area (cm ² ) / replenisher volume (cm ³ )) is set to 0.01 cm ⁻¹ . did.

Immediately after filling each storage container, storage 10
The amount of the color developing agent in the replenisher was quantified after a lapse of days and 20 days after storage, and the degree of fatigue of the solution was checked. At the same time, the deposition of an ascending product of the color developing replenisher solution due to the capillary phenomenon on the inner wall of the storage container and the amount of the oxidized blackened product of the deposition were visually determined.

The results are shown in Table 1.

Color development replenishing solution Water 700 ml Ethylene glycol 15.0 g Potassium sulfite (50 W / V% solution) 1.0 ml Optical brightener (Tinopropanol SFP) 2.8 g Diethylenetriaminepentaacetic acid 3.0 g Diethylhydroxylamine 7.5 g Potassium hydroxide 18.0 g Carbonic acid Potassium 30.0 g Compound of general formula [1] Compound of general formula [2] shown in Table 1 Color developing agent (CD-3) ¹⁾ 11.0 g Water was added to make 1 l and 20% potassium hydroxide or The pH was adjusted to 11.0 with 20% sulfuric acid.

1): CD-3 (trademark of Kodak): 3-methyl-4-amino-N-ethyl-N- (β-methanesulfonamidoethyl) -aniline sulfate

[0073]

[Table 1]

Evaluation XX: A large amount of precipitates are observed and are black. X: Precipitates are recognized and are black. Δ: Precipitates are recognized but not black. ◯: Precipitates are unacceptable.

The CD-3 quantitative value on the same day was 10.8 g ±
It was in the range of 0.2 g / l.

It is understood from Table 1 that the desired amount of residual CD-3 in the replenisher cannot be obtained by storage if the compound represented by the general formula [1] is not present.

Further, the presence of the compound represented by the general formula [2] gives more preferable results, and it is 90% even after storage for 20 days.
It was found that the above CD-3 exists.

Further, the deposition of the rising component of the color developing replenisher on the inner wall of the storage container and the degree of oxidation of the deposited product are almost not oxidized due to the presence of the compound of the general formula [1]. It was found that when the compound of [2] was present, no precipitate was found at all. This means that when such a replenisher is used for a long time, crystals of the replenisher other than the present invention fall from the inner wall of the replenisher tank and float in the replenisher.
They gather at the bottom and are guided to a refilling pipe, etc., which causes clogging of the strainer of the bellows pump. However, it can be seen that the replenisher of the present invention does not cause such trouble.

In addition, the active agent tested for comparison (Experiment No. 2
In No. 4, No. 25), a good result was obtained to some extent in the remaining amount of CD-3, but the generation of precipitates on the inner wall of the container could not be reached, and the desired result was not obtained.

This is a surprising finding. Until now, when CD-3 in the color replenishing solution was present in an amount of 10 g / l or more, the storage stability was extremely poor, and low replenishment was considered difficult. The stability of CD-3 in the replenisher was dramatically improved, low replenishment was achieved, the amount of waste liquid was reduced, and it became easier to adapt to the environment.

Example 2 A 100 ml glass screw bottle was filled up to the neck with the color development replenisher shown below and placed in a -4 ° C. freezer to evaluate the recrystallinity of the replenisher material at low temperature. The evaluation method is as follows. Put a screw bottle filled with color developer into a freezer and confirm that the temperature has reached -4 ° C after 1 day. Then, add 3 to 4 crystal mothers to each screw bottle with a microspatel. Then, the degree of crystal growth was observed after 5 days.

To prepare the crystal mother, add No. 1 replenisher solution to the watch glass 1
0 ml was transferred and stored in a freezer at −10 ° C. for a whole day and night to evaporate the water content and crystallize the color developing solution replenisher material. Further, the hair was completely dried to remove water. Of the obtained crystal matrix, a crystal having a length of about 0.1 to 0.2 mm was used as the crystal matrix.

The results are shown in Table 2.

Color development replenishing solution Water 700 ml Ethylene glycol 15.0 g Potassium sulfite (50 W / V% solution) 3.5 × 10 ⁻³ mol Optical brightener (Tinopropanol SFP) 2.8 g Diethylenetriaminepentaacetic acid 3.0 g Diethylhydroxylamine 7.5 g Hydroxylation Potassium 18.0 g Potassium carbonate 30.0 g Compound of general formula [1] Compound of general formula [2] shown in Table 2 Color developing agent (CD-3) shown in Table 2 Add water to 1 l to make 20% The pH was adjusted to 11.0 with potassium hydroxide or 20% sulfuric acid.

[0085]

[Table 2]

Evaluation XX: Large amount of crystal precipitation is observed. X: Crystal precipitation is clearly observed. Δ: Precipitates are found but not crystallized. ◯: No precipitates are found.

From Table 2, the compound [1] of the present invention is CD-
When the addition amount of 3 is 8.0 g / l or more, the effect of adding the compound of the general formula [1] of the present invention is exhibited. It was also found that by adding the compound of the general formula [2], no precipitate was observed even if the amount of CD-3 added was 11.0 g / l or more.

Example 3 Konica QA Paper Type A6 was used as a replenisher in the following processing step (Table 3) and composition of the processing solution while imagewise exposure was performed using a printer processor. A running test was conducted until it was updated.

[0089]

[Table 3]

The composition of the processing liquid is as follows.

Color developing tank solution Water 700 ml Diethylene glycol 9.0 g Triethanolamine 9.0 g Potassium sulfite (50% solution) 2.1 × 10 ^-3 mol Optical brightener (Tinopropanol SFP) 2.0 g Diethylenetriamine pentaacetic acid 2.5 g Diethylhydroxylamine 5.0 g Potassium hydroxide 10.0 g Potassium carbonate 25.0 g Potassium bicarbonate 5.0 g Compound of general formula [1] Compound of general formula [2] shown in Table 4 Color developing agent (CD-3) 4.5 g Potassium chloride 6.0 g Water was added to make the volume 1.0 l, and the pH was adjusted to 10.0 with 20% potassium hydroxide or 20% sulfuric acid.

Color development replenishing solution Water 700 ml Diethylene glycol 10 g Triethanolamine 10 g Potassium sulfite (50% solution) 3.5 × 10 ^-3 mol Optical brightener (Tinopropanol SFP) 2.8 g Diethylenetriaminepentaacetic acid 3.0 g Diethylhydroxylamine 7.5 g Hydroxylation Potassium 18.0 g Potassium carbonate 30.0 g Compound of general formula [1] Compound of general formula [2] shown in Table 4 Color developing agent (CD-3) 11.0 g Water-added to 1.0 liter, 20% water The pH was adjusted to 11.5 with potassium oxide and 20% sulfuric acid.

Bleach-fixing solution The bleach-fixing replenisher is diluted 2 times,
The pH was adjusted to 7.0 with 25% aqueous ammonia.

Bleach-fixing replenisher water 500 ml Ethylenediaminetetraacetic acid ferric ammonium salt 120 g Ethylenediaminetetraacetic acid 2 g Ammonium thiosulfate (73 W / V%) 230 ml Ammonium sulfite (40 W / V%) 80 ml Sodium metabisulfite 12 g Water was added 1.0 The pH was adjusted to pH 5.50 with 90% acetic acid or 25% aqueous ammonia.

[0095] stabilizing solution and stabilizing replenisher water 900ml ortho-phenylphenol 0.15g ZnSO ₄ · 7H ₂ O 0.20g of sodium sulfite 1.0g fluorescent brightener (Tinopal SFP) 2.0 g 1-hydroxyethylidene-1,1-diphosphonic acid ( 60% solution) 3.0 g Water was added to make 1 liter, and the pH was adjusted to 7.8 with 25% aqueous ammonia or 20% sulfuric acid.

The running test was conducted at a rate that the color developing tank solution was 10% on Monday, 5% on Tuesday, 2.5% on Wednesday, 1.25% on Thursday and Friday, while maintaining TOP, 0.5.
Round (when the color developing tank solution was renewed 1/2 with color developing replenisher) 1.0 round, 2.0 round The wedge exposed check pieces were processed and the photographic processing performance was observed. Table 4 shows the maximum density values among the obtained photographic performances in which the effects of the present invention are particularly significant.

The addition amounts of the compounds of the general formulas [1] and [2] shown in the table are the amounts added to the color developing replenisher solution, and the amount of the compound added to the replenishing solution is the color developing tank replenisher solution.
60% was added.

Also, during the running test, the carrying function was checked, and the result of the test whether the paper to be processed slips or smoothly passes through the carrying roller at the outlet of the color developing tank and the outlet of the color developing tank Similarly, Table 4 shows the results of observing the generation of precipitates on the squeeze roller.

[0099]

[Table 4]

From Table 4, in the case of running tests 2 to 4 using the color developing replenisher of the present invention, a stable dye image was obtained without changing the maximum density value of the light-sensitive material to be processed, and color developing was performed. It can be seen that there is no slip on the transport roller at the tank outlet and no deposit on the squeeze roller.

On the other hand, it can be seen that when a surfactant other than the present invention is used, there is no problem with the dye image, but slip accidents at the transport roller occur.

Therefore, by using the compound of the present invention, a stable dye image can be obtained, and the processing without transport trouble and generation of precipitates is possible for a long time.

Example 4 A running test was conducted by changing the replenishment amount for color development (described in Table 5) in the same processing steps as in Example 3.

The color developing replenisher composition was the same as the replenisher composition used in Example 3 except that the color developing agent, diethylhydroxylamine, the compound of the general formula [1] and the general formula [2], and p were used.
Same as Example 3 except that H was changed as shown in Table 5.

The results are shown in Table 6.

[0106]

[Table 5]

[0107]

[Table 6]

From the results shown in Table 6, when the running test was carried out with a replenishing amount of 30 ml / m ² or less, the maximum dye concentration was lowered overall with running, and there was a tendency that a slightly soft print was obtained. I understand. It has been found that in the replenishment amount range of 30 ml / m ² or more, which is a preferred embodiment of the present invention, there is almost no fluctuation in the maximum dye density and stable quality prints can be obtained.

[0109]

According to the present invention, firstly, stabilized color development for a silver halide color photographic light-sensitive material without crystal precipitation of a color development replenisher replenisher containing a concentrated para-phenylenediamine color developing agent and generation of tar. It is possible to provide a replenisher and a method for processing a light-sensitive material using the replenisher.

Secondly, in the low replenishing process, even if the process amount is not constant, the process is continuously performed for a long period of time without impairing the transport function of the developing machine, and the maximum density of the photosensitive material is very stable. It is possible to provide a color developing replenisher for a silver halide color photographic light-sensitive material obtained in this manner and a method for processing a light-sensitive material using the replenisher.

Thirdly, a low replenishing process is made possible, which makes it possible to reduce the amount of waste liquid discharged from an automatic developing machine, and a color developing replenishing liquid for silver halide color photographic light-sensitive materials excellent in environmental suitability and the replenishing process. A method of processing a silver halide color light-sensitive material using a liquid can be provided.

Claims (7)

[Claims] 1. A color developing replenisher for silver halide color photographic light-sensitive materials, which contains a p-phenylenediamine type color developing agent and a compound represented by the following general formula [1]. Embedded image [In the formula, R ₁ represents an alkyl group having 1 to 2 carbon atoms or a hydrogen atom, and R ₂ represents a substituted or unsubstituted alkyl group having 1 to 3 carbon atoms, a sulfonic acid group, a carboxyl group, a hydroxyl group and It represents a hydrogen atom, and R ₃ represents a hydrogen atom or a hydroxyl group. P represents an integer of 0 to 2 and γ represents an integer of 1 to 3. A may be replaced by a hydrogen atom at any position on the benzene ring. Further, S represents 0 to 50, t represents an integer of 0 or 1, and u represents a number of 2 to 150. ] 2. The content of the compound represented by the general formula [1] is 0.001 to 5.0 g per liter of color developing replenisher.
The color developing replenisher for a silver halide color photographic light-sensitive material according to claim 1, wherein 3. The color developing replenisher is represented by the following general formula [2]:
A compound represented by the formula:
Alternatively, the color developing replenisher for a silver halide color photographic light-sensitive material as described in 2 above. General formula [2] R ₄ —SO ₃ M [wherein R ₄ is an alkyl group having 1 to 8 carbon atoms, a phenyl group, a naphthalene group, an ethylenically unsaturated group, and is a polymer having a repeating unit of these. It may be. M
Represents a hydrogen atom, an alkali metal atom or an ammonium group. ] 4. A method for processing a silver halide color photographic light-sensitive material, which comprises continuously processing a silver halide color photographic light-sensitive material coated on a support with a color developer to replenish the color developer. The method for processing a silver halide color photographic light-sensitive material, wherein the color developing replenisher contains a p-phenylenediamine type color developing agent and a compound represented by the general formula [1]. 5. The content of the compound represented by the general formula [1] is 0.001 to 5.0 g per liter of color developing replenisher.
5. The method for processing a silver halide color photographic light-sensitive material according to claim 4, wherein 6. The color developing replenisher is of the general formula [2].
A compound represented by:
Or the processing method of the silver halide color photographic light-sensitive material as described in 5 above. 7. The silver halide according to claim 4, wherein the color development replenisher is replenished with 30 to 150 ml of the silver halide color photographic light-sensitive material per m ^2. Color photographic light-sensitive material processing method.