JPH09106055A - Silver halide color photosensitive material treatment liquid and treatment method using such treatment liquid - Google Patents

Abstract

PROBLEM TO BE SOLVED: To allow stable treatment, independently of the variation of a treatment amount and prevent the deterioration of photographing performance by containing dextran in treatment liquid. SOLUTION: Dextran is contained in treatment liquid. The average molecule amount of the dextran is preferably 20,000 or less and the content of the dextran is preferably 0.1-100g/l. The treatment can be colored developer which contains p-phenylene diamine based main colored developing chemical with water-soluble groups, bleaching fixer which contains aminopolycarboxylic acid second iron complex salt or stabilizing agent. The dextran is α-1,6 combined D-glucose polymer which is formed by lowering native dextran obtained by the operation of dextran producing bacteria under the existance of sugars to a desired molecule amount with partial decomposition polymerization using acid, alkali and enzyme.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a processing solution for silver halide color photographic light-sensitive materials and a method for processing silver halide color photographic light-sensitive materials using the processing solution.
More specifically, it has excellent processing stability, does not cause undesired stains or crystal precipitation in the process, has less stains on the edges of the photosensitive material, and further improves the stain of the unexposed portion during storage over time. The present invention also relates to a processing solution for a silver halide color photographic light-sensitive material and a method for processing a silver halide color photographic light-sensitive material using the processing solution.

[0002]

2. Description of the Related Art The processing of a color light-sensitive material basically consists of two steps of development and desilvering, and development is a color development step.
Desilvering consists of a combination of bleaching and fixing steps, including a bleach-fixing step. In addition to this, a washing process, a rinsing process, a stabilizing process, a stabilizing process as a substitute for washing, and the like are added.

In color development, exposed silver halide is reduced to silver and at the same time oxidized to aromatic primary silver halide.
Secondary amine developing agents react with the coupler to form a dye. During this process, halogen ions generated by the reduction of silver halide are eluted and accumulated in the developer. Separately, components such as an inhibitor contained in the light-sensitive material are also eluted and accumulated in the color developing solution. In the desilvering step, silver produced by development is bleached with an oxidizing agent, and then all silver salts are removed from the light-sensitive material as soluble silver salts by a fixing agent. A one-bath bleach-fixing method in which the bleaching step and the fixing step are collectively processed simultaneously is also known.

In such a processing step, the problem of environmental protection has been emphasized in recent years, and a large amount of washing water used in the washing step following the processing (fixing or bleach-fixing processing) with a processing solution having fixing ability. It is desired to reduce or reduce water to zero. For this reason, there has been proposed a technique of directly stabilizing the fixing or bleach-fixing process without washing with water.

In recent years, with the rapid increase in small-scale developing laboratories called minilabs, the difference in processing conditions between minilabs has become a problem. In other words, there is a problem that some minilabs have a very small amount of processed light-sensitive material and are not in operation for most of the day, and some minilabs are in full operation during business hours. Furthermore, the number of minilabs, which process a large amount of light-sensitive material at the beginning of the week, but hardly process it on the weekend, has a large fluctuation in the amount of processing, and is increasing.

In such a situation, so-called fluctuations in photographic performance, as represented by the maximum and minimum densities of prints, occur, causing a serious problem in the value of the product. Furthermore, the oxidation of the treatment chemicals is promoted, so that insoluble matters such as tar and sludge are generated, and the treatment machine is soiled, and in some cases, the print, which is a product, is soiled or damaged. This problem has become an extremely serious problem in carrying out so-called low replenishment that can reduce the amount of waste liquid as one of recent environmental protection measures.

Further, in recent years, there is a strong need for rapid processing, and an increasing number of users desire to obtain prints in the shortest possible time after requesting development processing. However,
When such rapid processing is performed, the time it takes for the developing agent, fixing agent, or bleaching agent to diffuse from the light-sensitive material and flow out into the processing solution is shortened. It will remain. Such a residue causes various stains in the unexposed area to lose commercial value when the processed photosensitive material is stored over time, and in the case of a photosensitive material, particularly a photosensitive material using paper as a base, Contamination of the edges will occur and the commercial value will be lost.

To solve the problem of deterioration of photographic performance caused by low replenishment processing, by containing a specific surfactant and aromatic sulfonic acid in the color developing replenisher, the maximum concentration of the light-sensitive material can be stably obtained. Technology is disclosed in Japanese Patent Laid-Open No. 4-35085.
No. 5. However, it has been found that this method does not have sufficient effect on the fluctuation of the above-mentioned treatment amount, and has no effect on the occurrence of stain during the above-mentioned storage with time, which is particularly problematic in rapid processing. . Furthermore, the effect was low with respect to the generation of stains due to the oxidation of the treatment chemicals.

As a technique for improving the occurrence of stains, edge contamination, etc. during storage with the passage of time, a technique of incorporating a hydroxyalkylated cyclodextrin into a treatment liquid is disclosed in Japanese Patent Laid-Open No. 7-
As disclosed in Japanese Patent No. 64248, when the amount of processing changes as described above, the effect is not sufficient, and there is another problem that the change in photographic performance, in particular, the density of unexposed areas increases. I understand.

[0010]

SUMMARY OF THE INVENTION It is therefore an object of the present invention to provide a processing solution for a silver halide color photographic light-sensitive material having the following characteristics and a processing method using the processing solution.

1 Stable processing is possible regardless of fluctuations in the processing amount, there is no deterioration in photographic performance, 2 Staining of the processor is small, and prints are not stained. 3 When the processed photosensitive material is stored with time. In addition, less stain is generated in the unexposed area. 4 Stain is less generated in the edge portion of the photosensitive material.

[0012]

In order to solve the above problems, the inventors of the present invention have made extensive studies, and as a result, found that the object of the present invention can be achieved by any of the following constitutions (1) to (7). It was

(1) A processing liquid for a silver halide color photographic light-sensitive material, which contains dextran.

(2) The processing solution for a silver halide color photographic light-sensitive material as described in the above item 1, wherein the dextran has an average molecular weight of 20,000 or less.

(3) The dextran content is 0.1 to 1
The processing liquid for silver halide color photographic light-sensitive materials as described in 1 or 2 above, wherein the processing liquid is 00 g / l.

(4) The processing solution is a color developing solution containing a p-phenylenediamine type color developing agent having a water-soluble group, and any one of the above 1 to 3 is characterized.
A processing solution for a silver halide color photographic light-sensitive material as described in the above item.

(5) The silver halide color photographic light-sensitive material as described in any one of the above items 1 to 3, wherein the processing solution is a bleach-fixing solution containing a ferric aminopolycarboxylic acid complex salt. Treatment liquid.

(6) The processing solution for silver halide color photographic light-sensitive material as described in any one of the above items 1 to 3, wherein the processing solution is a stabilizing solution.

(7) Halogenation characterized in that an imagewise exposed silver halide color photographic light-sensitive material is treated with the processing solution for silver halide color photographic light-sensitive material described in any one of 1 to 6 above. Processing method of silver color photographic light-sensitive material.

The dextran used in the present invention is α-
It is a polymer of 1,6-bonded D-glucose, and generally, a native dextran obtained by acting a dextran-producing bacterium (leuconostoc, mesenteroides, etc.) in the presence of a saccharide, for example, sucrose, is treated with an acid, an alkali or an enzyme. It can be obtained by reducing the molecular weight to a desired value depending on the partial decomposition polymerization method used. The average molecular weight of dextran used in the present invention is preferably 20,000 or less, more preferably 10,000 or less. The amount of dextran used in the present invention is 0.
The range of 1 to 100 g is preferable, and 0.5 is more preferable.
~ 50g.

The processing solution of the present invention includes a color developing solution, a bleaching solution, a bleach-fixing solution, a fixing solution, a stabilizing solution, a neutralizing solution, a stopping solution,
Although a fogging bath solution and the like can be mentioned, in the present invention, a color development processing solution, a bleach-fix processing solution and a stabilizing solution are preferably used.

The effect of the present invention is better exhibited when the color developing solution according to the present invention contains the compound represented by the following general formula [I].

General formula [I] R ¹ (R ² ) N-OH [In the formula, R ¹ and R ² each represent a substituted or unsubstituted alkyl group, aryl group, R ³ CO- or hydrogen atom.
However, R ¹ and R ² are not hydrogen atoms at the same time.
Also, they may be bonded to each other to form a ring.

R ³ represents a substituted or unsubstituted alkoxy group, alkyl group or aryl group. ] It was achieved by.

The compound represented by the above general formula [I] will be described in detail.

The substituted or unsubstituted alkyl groups represented by R ¹ and R ² in the general formula [I] may be the same or different and each has 1 to 10 carbon atoms or less, preferably 1 to 5 carbon atoms. Although a group is preferable, examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a methoxyethyl group, a hydroxyethyl group, a propenyl group, a t-butyl group, a hexyl group, and a benzyl group. These may be linear, branched, or cyclic, and include those having a substituent. As the substituent, an alkyl group (methyl group, ethyl group etc.), a halogen atom (eg chlorine atom, bromine atom etc.), an aryl group (eg phenyl group etc.), a hydroxyl group, a carboxyl group, a sulfo group, a phosphono group,
Phosphanic acid residue, cyano group, alkoxy group (methoxy group, ethoxy group, etc.) or each alkyl or /
And an amino group, an ammonio group, a carbonamido group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, a sulfonyl group, an oxycarbonyl group, a carbonyloxy group and the like, which may be substituted with an aryl group.

Examples of the substituted or unsubstituted aryl group represented by R ¹ and R ² include phenyl group, o-methoxyphenyl group, m-chlorophenyl group and the like. Further, those having a substituent are also included, and as the substituent, those similar to the above-mentioned alkyl group are preferable.

R ¹ and R ² may combine with each other to form a ring, for example, piperidine, pyridine, triazine,
A heterocycle such as morpholine may be formed.

R ³ represents an alkoxy group, an alkyl group or an aryl group, and more specifically, as an alkyl group among these alkoxy groups, alkyl groups and aryl groups, R ¹ ,
Those having the same meaning as in the case of R ² are preferred.

Specific examples of the hydroxylamine compound represented by the above general formula [I] are shown in US Pat. No. 3,287,12.
No. 5 and No. 3,329,034 and No. 3,287,1
No. 24, etc., but particularly preferred specific exemplified compounds include Japanese Patent Application No. 2-203169, 36 to 38.
(A-1) to (A-39) described in pages and JP-A-3-33.
(1) to (53) described in No. 845, pp. 3 to 6 and JP-A-Hei 3
-63646, pages 1 to 5 (1) to (52) and JP-A-3-184044, pages 4 to 6 (1) to (5).
4), particularly (1) and (7).

The particularly preferred specific exemplified compounds of the general formula [I] are shown below.

(I-1) HO-N <(C ₂ H ₄ SO ₃ Na) ₂ (I-2) HO-N <(C ₂ H ₄ COONa) ₂ (I-3) HO-N <(C ₂ H ₄ OH) ₂ These compounds represented by the general formula [I] are usually used in the form of free amine, hydrochloride, sulfate, p-toluenesulfonate, oxalate, phosphate, acetate and the like. The amount used in the present invention is, for example, 0.5 to 2 per liter of developer.
The range of 0 g is preferable, and more preferably 3 to 10 g / l.
It is.

When the processing agent in the present invention is a color development processing solution, as the color developing agent used, a p-phenylenediamine compound having a water-soluble group exhibits the desired effect of the present invention, and fog It is preferably used because it rarely occurs.

The p-phenylenediamine-based compound having a water-soluble group has less contamination of the light-sensitive material than the para-phenylenediamine-based compound having no water-soluble group such as N, N-diethyl-p-phenylenediamine. As for the skin, not only has the advantage that the skin is less likely to be fogged, but the object of the present invention can be achieved more effectively by combining it with the color developing agent of the present invention.

Examples of the water-soluble group include those having at least one on the amino group of the p-phenylenediamine compound or on the benzene nucleus, and specific water-soluble groups include-
_{(CH 2) nCH 2 OH,} - (CH 2) mNHSO 2 (CH
_{2) nCH 3, - (CH} 2) mO (CH 2) nCH 3, -
(CH ₂ CH ₂ O) nCmH ₂ m ₊₁ (m and n are each 0
Represents the above integer. ), —COOH group, —SO ₃ H group and the like are preferred.

Specific examples of the color developing agent preferably used in the present invention are (C-1) to (C-1) described in JP-A-4-8671, pages 26 to 31.
6), 4-amino-3-methyl-N- (3-hydroxypropyl) aniline and the like.

In particular, in the present invention, CD-3
(4-amino-3-methyl-N-ethyl-N- [β-
(Methanesulfonamide) ethyl] aniline sulfate)
And CD-4 (4-amino-3-methyl-N-ethyl-
N- [β- (hydroxy) ethyl] aniline sulfate) is preferably used.

The color developing agent is usually used in the form of a salt such as hydrochloride, sulfate, p-toluenesulfonate.

Further, the color development processing solution according to the present invention includes a sulfite salt described in JP-A-4-338953, page 12, line 15; a buffer agent described in page 12, line 18;
Antifoggants such as bromides and chlorides, development accelerators, and triazinyl stilbene-based optical brighteners described in JP-A-4-118649, pages 62 to 67 can be used.

Further, the color development processing solution is described in JP-A-4-11.
No. 8649, page 69 from bottom to lines 9 to 74, chelating agents represented by general formula [K] and exemplified compounds K-1 thereof.
From the viewpoint of effectively achieving the object of the present invention, it is preferable to add K-22.

Among these chelating agents, K-2 and K-
9, K-12, K-13, K-17, and K-19 are preferably used, and particularly when K-2 and K-9 are added to the color developing agent of the present invention, the effect of the present invention is more exerted. To do.

The amount of these chelating agents added is preferably in the range of 0.1 to 20 g per 1000 ml of color developing solution,
It is more preferably 0.2 to 8 g.

The ferric aminopolycarboxylic acid ferric salt in the bleach-fixing solution according to the present invention is preferably a ferric iron complex salt of an organic acid represented by the following general formula [L].

[0044]

Embedded image

In the formula, A _{1 to} A ₄ may be the same or different and each represents --CH ₂ OH, --COOM or --PO ₃ M ₁ M ₂ . M, M ₁ and M ₂ each represent a hydrogen atom, an alkali metal atom or an ammonium group. X is a substituted or unsubstituted alkylene group having 2 to 6 carbon atoms, or

[0046]

Embedded image

Represents

The compound represented by the general formula [L] will be described in detail below.

[0049]

Embedded image

A _{1 to} A ₄ are as defined above, and n is 1 to 8
Represents an integer. B ₁ and B ₂ may be the same or different and each represents a substituted or unsubstituted alkylene group having 2 to 5 carbon atoms (for example, ethylene, propylene, butylene, pentamethylene, etc.). As the substituent, a hydroxyl group, having 1 to 1 carbon atoms
And the lower alkyl group of 3 (methyl group, ethyl group, propyl group) and the like.

[0051]

Embedded image

In the formula, R ₁ represents a hydrogen atom or a hydroxyl group,
n is 1 or 2, x is 2 or 3, y is 0 or 1, and the sum of x and y is always 3. B represents H or -COOH.

[0053]

Embedded image

In the formula, A _{1 to} A ₄ may be the same or different and each represents --CH ₂ OH, --PO ₃ M ₁ M ₂ or --COOM ₃ . M ₁ , M ₂ or M ₃ represents a hydrogen atom, an alkali metal atom (eg, sodium or potassium) or another cation (eg, ammonium, methyl ammonium, trimethyl ammonium, etc.). X has 2 carbon atoms
~ 6 substituted or unsubstituted alkylene group or-(B ₁
O) n-B ₂ - represents a. B ₁ and B ₂ may be the same or different and each represents a substituted or unsubstituted alkylene group having 1 to 5 carbon atoms.

Examples of the alkylene group represented by X include ethylene, trimethylene and tetramethylene.
Examples of the alkylene group represented by B ₁ or B ₂ include methylene, ethylene, trimethylene and the like. X, B
Examples of the substituent of the alkylene group _one or the B ₂ represents a hydroxyl group, an alkyl group (e.g. methyl group, ethyl group, etc.) having 1 to 3 carbon atoms, and the like. n represents an integer of 1 to 8, and preferably 1 to 4. Preferred specific examples of the compound represented by the general formula [P] are shown below, but it should not be construed that the invention is limited thereto.

The above general formulas [L], [M], [N],
As specific examples of the compound represented by [P], the following compounds are particularly preferably used in the present invention.

[0057]

Embedded image

Among them, those which are particularly preferably used in the present invention are (L-1) and (L-
14), (N-1), (N-3), and (P-1).

The amount of the ferric iron complex salt of an organic acid added is preferably in the range of 0.1 to 2.0 mol, more preferably 0.15 to 1.
It is 5 mol / l.

A bleach-fixing solution is disclosed in JP-A 64-29525.
By containing the imidazole and the derivative described in No. 8 or the compounds represented by the general formulas [I] to [IX] described in the same item and at least one of these exemplified compounds, the effect is rapidly exhibited.

In addition to the above accelerators, JP-A-62-1234
The same applies to the exemplified compounds described in JP-A No. 59, pages 51 to 115, the exemplified compounds described in JP-A No. 63-17445, pages 22 to 25, the compounds described in JP-A Nos. 53-95630 and 53-28426. Can be used for.

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

As the thiosulfate according to the present invention, sodium thiosulfate, ammonium thiosulfate, potassium thiosulfate and the like can be used, and especially, the weight ratio of sodium thiosulfate to ammonium thiosulfate is (1-2).
A mixture having a ratio of 0) :( 80 to 99) more effectively exerts the effect of the present invention.

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

The bleach-fixing solution is described in JP-A 64-29525.
It is preferable to add the compound represented by the general formula [FA] described in No. 8, page 56 and the exemplified compounds thereof, and not only the effect of the present invention is exhibited more, but also a small amount of the light-sensitive material is processed for a long period of time. Another effect is that sludge generated in the processing liquid having fixing ability is extremely small.

In the present invention, the stabilizing solution preferably contains a chelating agent having a chelate stability constant for ferric ions of 8 or more. Here, the chelate stability constant is defined as L.C. G. FIG. Silen A. E. FIG. Martell's “Stability Constants of M”
et al-ion Complexes ", The C
chemical Society, London (19
64), S. Chaberek A. E. FIG. Martel
l "Organic Sequestering A"
gents ", Wiley (1959), etc., and generally known constants.

As a chelating agent having a chelate stability constant of 8 or more with respect to ferric ion, Japanese Patent Application No. 2-23477 can be used.
No. 6, No. 1-324507, etc. are mentioned. The amount of these chelating agents used is 1000 ml of stabilizer.
It is preferably 0.01 to 50 g, more preferably 0.05 to 20 g, and good results are obtained.

Ammonium compounds are mentioned as preferred compounds to be added to the stabilizing solution. These are supplied by ammonium salts of various inorganic compounds. The addition amount of the ammonium compound is preferably in the range of 0.001 to 2.0 mol, more preferably 0.002 to 1.0 mol, per 1000 ml of the stabilizing solution. Further, it is preferable that the stabilizing solution contains sulfite.

Furthermore, it is preferable that the stabilizing solution contains a metal salt in combination with the chelating agent. Examples of such metal salts include Ba, Ca, Ce, Co, In, La, Mn,
Ni, Bi, Pb, Sn, Zn, Ti, Zr, Mg, A
There are metal salts of 1 or Sr, halides, hydroxides,
It can be supplied as an inorganic salt such as a sulfate, a carbonate, a phosphate, an acetate or a water-soluble chelating agent.

The amount used is preferably 1 × 10 ^-4 to 1 × 10 ^-1 mol, more preferably 4 × 10 ^-4 to 2 × 10 ^-2 mol, per 1000 ml of the stabilizing solution.

To the stabilizing solution, organic acid salts (citric acid, acetic acid, succinic acid, oxalic acid, benzoic acid, etc.), pH adjusters (phosphate salts, borate salts, hydrochloride salts, sulfate salts, etc.) are added. be able to.

In the present invention, a known antifungal agent may be used alone or in combination in the stabilizing solution as long as the effects of the present invention are not impaired.

Next, a color photographic material to which the photographic processing agent of the present invention is preferably applied will be described.

As the silver halide grains in the light-sensitive material,
Silver halide grains mainly containing silver chloride containing at least 80 mol% of silver chloride are used, preferably 90 mol%
Above, particularly preferably 95 mol% or more, most preferably 99 mol% or more is used.

The silver halide emulsion mainly containing silver chloride can contain silver bromide and / or silver iodide as a silver halide composition in addition to silver chloride. In this case, the silver bromide content is 20 mol%.
The following is preferable, more preferably 10 mol% or less, still more preferably 3 mol% or less, and when silver iodide is present, 1 mol% or less is preferable, and more preferably 0.5 mol% or less.
It is less than or equal to mol%, most preferably zero. The silver halide grains mainly composed of silver chloride containing 50 mol% or more of silver chloride may be applied to at least one silver halide emulsion layer, but preferably to all light-sensitive silver halide emulsion layers. It is applied.

The crystal of the silver halide grain may be a normal crystal, a twin crystal or another crystal, and has a [1.0.0] plane and a [1.
Any ratio can be used for the [1.1] plane. Furthermore, even if the crystal structure of these silver halide grains is uniform from the inside to the outside, layers (phases) with different inside and outside
It may be in the shape of a core (core / shell type).
These silver halides may be of a type in which a latent image is mainly formed on the surface or of a type in which a latent image is formed inside a grain. Further, tabular silver halide grains (JP-A-58-11)
3934, Japanese Patent Application No. 59-170070). In addition, JP-A 64-26837 and 6
The silver halides described in 4-26838 and 64-77047 can be used.

The silver halide grains may be obtained by any preparation method such as an acidic method, a neutral method or an ammonia method. Also, for example, seed particles are made by an acid method,
A method of growing by an ammonia method having a high growth rate and growing to a predetermined size may be used. When the silver halide grains are grown, the pH, pAg, etc. in the reaction vessel are controlled, and the amount of silver corresponding to the growth rate of the silver halide grains as described in JP-A-54-48521 is used. Ions and halide ions are preferably sequentially and simultaneously injected and mixed.

[0078]

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

Example 1 Operation A Konica Color QA Paper Type 6 (manufactured by Konica Corporation) was imagewise exposed, and then colored by the following processing steps and processing liquid compositions by a modified machine of Konica Nice Print System NPS-808. A running test was carried out until twice the developing tank capacity was replaced with the replenisher, and the color paper treated at that time was used as an evaluation sample.

Treatment Step Treatment Time Treatment Temperature Replenishment Amount Color Development 25 seconds 38.5 ° C. 120 ml / m ² Bleach-fix 25 seconds 37.5 ° C. 200 ml / m ² Stable-1 25 seconds 35 ° C Stable-2 25 seconds 35 ° C Stable -3 25 seconds 35 ° C. 200 ml / m ² dry 50 seconds 55 ° C. Stable is a countercurrent system from stable -3 to stable -1, and the entire overflow liquid of stable -1 was flowed into the bleach-fixing tank.

The composition of the processing liquid is shown below.

(Color developer) Potassium bromide 0.02 g Potassium chloride 3.6 g Potassium carbonate 30 g Potassium sulfite 0.2 g Diethylhydroxylamine 5 g Diethylenetriamine sodium pentaacetate 2 g Diethylene glycol 10 g Tinopearl SFP (fluorescent brightener manufactured by Ciba Geigy) 2 g Sodium paratoluene sulfonate 35 g 4-Amino-3-methyl-N-ethyl-N- (β- (methanesulfonamido) ethyl) aniline sulfate (CD-3) 7 g Water is added to bring the total volume to 1 liter. At the same time, the pH was adjusted to 10.10 using potassium hydroxide and sulfuric acid.

(Color Development Replenisher) Potassium bromide 0.01 g Potassium carbonate 30 g Potassium sulfite 0.4 g Diethylhydroxylamine 7.5 g Diethylenetriamine sodium pentaacetate 2 g Diethylene glycol 15 g Tinopearl SFP (fluorescent brightener manufactured by Ciba-Geigy) 2 g Para Sodium toluene sulfonate 50 g 4-Amino-3-methyl-N-ethyl-N- (β- (methanesulfonamido) ethyl) aniline sulfate (CD-3) 11 g Water was added to make the total volume 1 liter, The pH was adjusted to 10.8 with potassium hydroxide and sulfuric acid.

(Bleach-fixing solution) Diethylenetriamine pentaacetate ferric ammonium 70 g Diethylenetriamine pentaacetic acid 2 g Ammonium thiosulfate 75 g Ammonium sulfite 45 g Sulfinic acid 5 g Ammonium bromide 10 g Acetic acid 20 g Water was added to make the total amount 1 liter and acetic acid and ammonia. The pH was adjusted to 7.0 with water.

[0085] Water was added to bring the total amount to 1 liter, and the pH was adjusted to 7.0 using acetic acid and aqueous ammonia.

[0086] Water was added to bring the total amount to 1 liter, and the pH was adjusted to 8.0 with sulfuric acid and aqueous ammonia.

Experiment 1 In the same manner as in Procedure A, except that the compounds shown in Table 1 below were added to the color developing solution and the color developing replenisher so that the concentration in the color developing solution was the value shown in Table 1. Development processing was performed and the yellow reflection density of the highest density part (Dmax) was measured. In addition, the obtained color paper is treated at 70 ° C. and 75
It was stored at% RH for 3 weeks, and the increase in yellow stain density in the unexposed area was measured.

[0088]

[Table 1]

From Table 1 above, it can be seen that by using the dextran of the present invention in the color developing solution, deterioration of photographic performance can be sufficiently suppressed and the increase in stain during storage with time is small.

Experiment 2 In the same manner as in Procedure A, except that the compounds shown in Table 2 below were added to the bleach-fixing solution and the bleach-fixing replenisher so that the concentration in the bleach-fixing solution was the value shown in Table 2. Development processing was performed, and the yellow reflection density of the unexposed area (Dmin) was measured. In addition, stains on the edge portion of the obtained color paper were observed.

There is no ◎ mark on the edge stains, ○
Means that there is almost no, Δ means that there is some, × means that there is clearly, and xx means that the stain is severe.

[0092]

[Table 2]

From Table 2 above, it can be seen that by using the dextran of the present invention in the bleach-fixing solution, deterioration of photographic performance can be sufficiently suppressed and stains on the edge portion are small.

Experiment 3 Procedure A was repeated except that the compounds shown in Table 3 below were added to the stabilizer so that the concentration in the stabilizer was the value shown in Table 3.
The development processing was carried out in the same manner as in, and the yellow reflection density of the unexposed area (Dmin) was measured. The obtained color paper was stored at 70 ° C. and 75% RH for 3 weeks, and the increase in yellow stain density in the unexposed area was measured.

[0095]

[Table 3]

From Table 3 above, it can be seen that by using the dextran of the present invention in the stabilizing solution, the deterioration of photographic performance can be sufficiently suppressed and the increase in stain upon storage with time is small.

Example 2 Operation B In the running test, assuming that the actual processing amount varies, the color developer is 10% on Monday, 5% on Tuesday, 2.5% on Wednesday, 1.25 on Thursday and Friday. % The same test as in Example 1 was carried out except that the test was performed at a renewed pace. The processed prints were sampled every day and used as evaluation samples.

Experiment 4 The same developing treatment as in Procedure B was conducted except that the compounds shown in Table 4 below were added to the color developing solution and the color developing replenisher so that the concentration in the color developing solution was the value shown in Table 4. Then, the yellow reflection density of the highest density portion (Dmax) was measured.
Table 4 shows the maximum fluctuation range of the yellow reflection density of the highest density part (Dmax) between the measured samples.

Further, at the end of the running test, stains on the machine wall of the color developer tank were observed. In Table 4,
Indicates that there is almost no dirt on the machine wall, and that there is some △,
X means there is clearly.

[0100]

[Table 4]

From Table 4 above, by using the dextran of the present invention in the color developing solution, fluctuations in photographic performance can be sufficiently suppressed even when the processing amount changes, and stains on the processor can be effectively suppressed. I understand.

Experiment 5 In the same manner as in Procedure B, except that the compounds shown in Table 5 below were added to the bleach-fixing solution and the bleach-fixing replenisher so that the concentration in the bleach-fixing solution was the value shown in Table 5. After development, the amount of residual silver in the color paper was measured.

Further, at the end of the running test, the bleach-fixing → stable transition was observed and the roller stains were observed. In Table 5, ∘ means that the roller is hardly soiled, Δ means that it is slightly present, and x means that it is clearly present.

[0104]

[Table 5]

From Table 5 above, by using the dextran of the present invention in the bleach-fixing solution, it is possible to sufficiently suppress desilvering defects even when the processing amount varies, and to effectively suppress roller stains. Recognize.

Experiment 6 Procedure B was repeated except that the compounds shown in Table 6 below were added to the stabilizer so that the concentration in the stabilizer was the value shown in Table 6.
Perform the development process in the same manner as in 7.
It was stored at 0 ° C. and 75% RH for 3 weeks, and the increase in yellow stain density in the unexposed area was measured.

Table 6 shows the print values with the largest increase in the yellow stain density. Furthermore, at the end of the running test, the state of crystal precipitation on the stabilizing tank rack and the roller portion was observed. In Table 6, ◯ means almost no crystal precipitation, Δ means a little, and x means clearly.

[0108]

[Table 6]

From Table 6 above, by using the dextran of the present invention in the stabilizing solution, the increase in stain during storage with time is small even if the processing amount varies, and crystals having various adverse effects on development processing and printing are obtained. It can be seen that there is little precipitation.

Example 3 The same process as in Example 1 was carried out except that the replenishment amount for color development was changed to the value shown in Table 7 in the operation A of Example 1. In addition, the processing of adding dextran having an average molecular weight of 40,000 according to the present invention to a 10 g / l developer was also carried out.

The highest density part of the obtained paper (Dma
x) the yellow reflection density and the increase in the yellow stain density of the unexposed area after the obtained paper was stored at 70 ° C. and 75% RH for 3 weeks, and the value was calculated (value when dextran was not added-dextran addition). Hour value), D
Table 7 shows the differences in the max yellow reflection density and the yellow stain (increase). These values mean that the larger the numerical value, the greater the effect of the present invention.

[0112]

[Table 7]

From Table 7 above, it can be seen that the effects of the present invention are better exhibited in the low replenishment process.

[0114]

According to the present invention, it is possible to provide a processing solution for a silver halide color photographic light-sensitive material having the following characteristics and a method for processing a silver halide color photographic light-sensitive material using the processing solution.

1 Stable processing is possible irrespective of fluctuations in processing amount, no deterioration in photographic performance 2 Little stains on the processor and no stains on prints 3 When the processed photosensitive material is stored with time In addition, less stain is generated in the unexposed area. 4 Stain is less generated in the edge portion of the photosensitive material.

Claims (7)

[Claims] 1. A processing solution for a silver halide color photographic light-sensitive material, which contains dextran. 2. The processing liquid for a silver halide color photographic light-sensitive material according to claim 1, wherein the dextran has an average molecular weight of 20,000 or less. 3. The dextran content is 0.1 to 100 g.
3. The processing liquid for silver halide color photographic light-sensitive materials according to claim 1, wherein the processing liquid is 1 / l. 4. The halogenated product according to claim 1, wherein the processing solution is a color developing solution containing a p-phenylenediamine color developing agent having a water-soluble group. Processing solution for silver color photographic light-sensitive materials. 5. The silver halide color photographic light-sensitive material according to claim 1, wherein the processing solution is a bleach-fixing solution containing an aminopolycarboxylic acid ferric complex salt. Treatment liquid. 6. The processing solution for a silver halide color photographic light-sensitive material according to claim 1, wherein the processing solution is a stabilizing solution. 7. A silver halide color photographic light-sensitive material which has been imagewise exposed is treated with the processing liquid for a silver halide color photographic light-sensitive material according to any one of claims 1 to 6. Processing method of silver color photographic light-sensitive material.