JPH05232653A - Color developing solution for silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To ensure stable photographic characteristics for a long period even under rapid processing and low-replenishing processing and to prevent occurrences of fixed deposit to the members of an automatic developing machine and to facilitate operation. CONSTITUTION:The developing solution contains at least one of compounds represented by formula I, and >=0.02mol/l of the color developing agent and aromatic sulfonic acid or its ester in an amount of >=2.5mol per 1mol of the developing agent. In formula I, each of A and B is straight or branched alkylene; each of n and m is an integer of 0-100 but both are not 0 at the same time and when n+m=1, A or B is >=3C straight or branched alkylene. It is preferred that this sulfonic acid or its ester is a benzene or naphthalene ring having at least one sulfonic acid or its ester, and the other substituents, such as H, halogen, or unsaturated alkyl.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color developing solution for a silver halide color photographic light-sensitive material, and more specifically, it does not cause precipitation even if a high concentration of a color developing agent is dissolved in a color developing replenisher. The present invention relates to a color developing solution for a silver halide color photographic light-sensitive material, which enables rapid and stable development processing with a smaller replenishing amount than before and can remarkably improve the maintainability of an automatic developing machine.

[0002]

BACKGROUND OF THE INVENTION The processing of a light-sensitive material basically comprises two steps of color development and desilvering, and desilvering comprises a bleaching and fixing step or a bleach-fixing step. In addition to this, rinsing treatment, stabilizing treatment, and the like are added as additional treatment steps.

In color development, the exposed silver halide is reduced to silver and at the same time oxidized to the aromatic primary silver halide.
The primary amine developing agent reacts 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 silver halide photographic light-sensitive material are also eluted and accumulated in the color developing solution.

Further, in the desilvering step, silver produced by development is bleached with an oxidizing agent, and then all silver salts are converted into soluble silver salts by a fixing agent and removed from the photographic light-sensitive material.
There is also known a one-bath bleach-fix processing method in which the bleaching step and the fixing step are collectively processed at the same time.

In the color developing solution, the development inhibitor is accumulated by developing the photographic material as described above, while the color developing agent and benzyl alcohol are consumed or accumulated in the photographic light-sensitive material and taken out. The component concentration of is decreasing. Therefore, in the development processing method in which a large amount of silver halide photographic light-sensitive material is continuously processed by an automatic developing machine or the like, the components of the color developing solution are kept within a certain concentration range in order to avoid a change in development finish characteristics due to a change in component concentration. Means are needed.

[0006] As such means, a method of replenishing a replenisher for diluting unnecessary increasing components and supplementing deficient components is usually adopted. Since the replenishment of the replenisher inevitably causes a large amount of overflow and is discarded, this method poses a serious economic and pollution problem. Therefore, in recent years, in order to reduce the overflow solution, a method of regenerating a developer by an ion exchange resin method or an electrodialysis method, a concentrated low replenishment method, or a method of adding a regenerant to the overflow solution and using it again as a replenisher. Have been proposed and put to practical use.

Regeneration of the developing solution is carried out by removing bromide which is an unnecessary accumulating component and compensating for the deficient component.
This method (ion exchange resin method and electrodialysis method) has the drawback that the development processing characteristics of the light-sensitive material are impaired unless the developer components are quantified and made constant by chemical analysis, and complicated management is required. However, it is almost impossible to introduce it in a small-scale photo lab or a mini lab without special skills. Furthermore, there is a drawback that the initial cost is extremely high.

Further, the method of adding a regenerant to the overflow solution and reusing it as a replenishing solution does not require any particular skill, but it requires a space such as a stock tank, and has the drawback that it is complicated for a developing station.
This method is also extremely difficult to introduce into minilabs. However, concentrated and low replenishment does not require any new equipment and is easy to manage, so it can be said that it is an extremely suitable method for small-scale laboratories such as minilabs.

However, this method also has some drawbacks. For example, a color-developing agent usually used for developing a color photographic light-sensitive material has a limited solubility in a pH region required for dye formation, and there is a problem that the developing agent is precipitated when a certain concentration or more is added.

The occurrence of such precipitation in the replenishing liquid causes clogging of the strainer of the replenishing pump, which hinders pump operation and eventually causes pump damage. In addition, with the development of the photographic industry in recent years,
The market for small-scale laboratories (minilabs) tends to expand, but the amount of processing in such laboratories is extremely small compared to the conventional large laboratories.

In this minilab, when a processing solution containing a high concentration of a color developing agent is used and the processing is carried out discontinuously for a long period of time, the processing solution evaporates and the solution taken out of the photosensitive material scatters to cause a color development processing tank. Occurrence of deposits on the inner rack and roller part occurs. It has been found that due to this, particularly in the color print material, the white background portion is colored, the color density is lowered, the sensitivity is lowered, etc., and the commercial value is remarkably lowered.

To solve such a problem, there is a method of adding a certain specific water-soluble surfactant to the color developing solution to prevent the rack and roller portions in the color developing tank of the automatic processor from being soiled. JP-A-62-42154 and JP-A-64-2215
However, none of them has a remarkable effect.

Conventionally, with respect to this precipitation, the processing tank portion of the automatic developing machine has been cleaned at the beginning of work, and the dirt has been removed by flowing a cleaning paper, but in any case, daily maintenance is required. However, there were problems such as the installation of managers, which was a major obstacle to the expansion of the minilab market.

A method of using a benzenesulfonic acid derivative for dissolving a p-phenylenediamine type color developing agent at a high concentration in an alkaline aqueous solution is described in British Patent 669.
No. 505. However, this method is insufficient as the concentration of the color developing agent necessary for high concentration and low replenishment and rapid processing as one of the objects of the present invention, and also the deposition of the color developing agent in the automatic processor. Has not come to prevent.

Therefore, as a result of various studies on this point, the inventor of the present invention has found that the combination of the present invention can improve the liquid performance even in a long-term storage state in an automatic developing machine such as a minilab which has a very small throughput. It has been found that it is possible to prevent the deposition and sticking to the members of the automatic processor without causing deterioration and to significantly improve the maintainability of the automatic processor, which is unexpected for the present inventors. It was.

[0016]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a color developing solution for a silver halide color photographic light-sensitive material, which has stable photographic performance for a long period of time even if a rapid processing or a low replenishing processing is carried out. Secondly, it is an object of the present invention to provide a color developing solution for silver halide color photographic light-sensitive materials in which the automatic developing machine can be easily managed and the fixing of precipitates and the resulting damage to the members of the automatic developing machine do not occur.

[0017]

In order to achieve the above object, the present inventors have
As a result of intensive studies, the present invention has been achieved. That is, the color developing solution for a silver halide color photographic light-sensitive material of the present invention contains at least one compound represented by the following general formula [1] and contains 0.02 mol / liter or more of a color developing agent. And for 1 mol of color developing agent,
It is characterized by containing 2.5 mol or more of aromatic sulfonic acid or aromatic sulfonic acid ester.

[0018]

[Chemical 4]

[In the formula, A and B each represent a linear or branched alkylene group, and n and m each represent an integer of 0 to 100, provided that both n and m are not 0, When n + m = 1, A or B is a linear or branched alkylene group having 3 or more carbon atoms. ]

In order to achieve the effect of the present invention better,
The aromatic sulfonic acid or aromatic sulfonic acid ester contained in the color developer is represented by the following general formula [2] or general formula [3]
Is a compound represented by.

[0021]

[Chemical 5]

[Wherein A to F are at least 1
Is a sulfonic acid group or a sulfonic acid ester group,
The rest represents a hydrogen atom, a halogen atom, or a saturated or unsaturated alkyl group. ]

[0023]

[Chemical 6]

[Wherein G to N are at least 1
Is a sulfonic acid group or a sulfonic acid ester group,
The rest represents a hydrogen atom, a halogen atom, or a saturated or unsaturated alkyl group. ]

In the present invention, the content of the compound represented by the general formula [1] is preferably 2.0 to 100 g / liter, more preferably 5.0 to 50 g / liter. Is.

The present invention will be described in more detail below. The color developer for silver halide color photographic light-sensitive material of the present invention contains at least one compound represented by the general formula [1].
Seed-containing, 0.02 mol / liter or more of a color developing agent, and 2.5 mol per 1 mol of the color developing agent.
It is characterized by containing a molar amount of aromatic sulfonic acid or aromatic sulfonic acid ester, by which it is possible to prevent the precipitation of the developing agent in the excellent color developing solution, and to perform rapid processing and low replenishment processing. In addition, stable photographic performance can be obtained over a long period of time, and precipitation and sticking to the members of the automatic processor can be prevented, so that the maintainability of the automatic processor can be significantly improved.

Preferred specific examples of the compound represented by the above general formula [1] are as follows.

[0028]

[Chemical 7]

[0029]

[Chemical 8]

[0030]

[Chemical 9]

The compounds preferably used in the general formula [1] are (1-10), (1-17) and (1-26).
The addition amount of the compound represented by the general formula [1] to the color developer is preferably 2.0 to 100 g / liter, more preferably 5.0 to 50 g / liter.

Next, the aromatic sulfonic acid or aromatic sulfonic acid ester used in the present invention refers to a compound in which a sulfonic acid salt or a sulfonic acid ester salt is directly bonded to an unsaturated conjugated ring showing aromaticity. .. The sulfonic acid machine or sulfonic acid ester group may be one or plural. The ring exhibiting aromaticity may contain a hetero atom,
Further, it may have an arbitrary substituent. A single compound may have a plurality of rings exhibiting aromaticity and may be a polymer. Examples of the salt include alkali metal salts such as lithium, sodium and potassium, and ammonium salts.

The aromatic sulfonic acid or sulfonic acid ester preferably used in the present invention includes the compounds represented by the above general formula [2] or [3]. In the general formula [2] or [3], A to F or G to N
The saturated or unsaturated alkyl group represented by has preferably 1 to 10 carbon atoms. The carbon number may be linear or may have a side chain.

Specific examples of the compound represented by the general formula [2] or [3] are shown below, but the invention is not limited thereto. All the exemplified compounds are shown as sodium salts,
Some or all of the sulfonic acid or sulfonic acid ester may be another salt.

[0035]

[Chemical 10]

[0036]

[Chemical 11]

[0037]

[Chemical 12]

The amount of the aromatic sulfonic acid or sulfonic acid ester used in the color developing solution of the present invention is essentially 2.5 mol or more, preferably 3 mol, per 1 mol of the color developing agent. That is all.

In the present invention, sulfurous acid (salt) is 2.0 ×
The effect of the present invention is remarkable when it is 10 ⁻³ mol / liter or less, preferably 0. When processing a silver chloride-based light-sensitive material, it is preferable that the sulfurous acid concentration be substantially 0 from the viewpoint of developability, but even if added in a small amount for the purpose of preventing oxidation of the color developing agent for the purpose of forming a kit. The color developing solution may be 2.0 × 10 ⁻³ mol / liter or less.

As the color developing agent used in the color development in the present invention, a p-phenylenediamine compound having a hydrophilic group is preferably used because the effect of the object of the present invention is satisfactorily achieved and the fog generation is small. Be done.

The p-phenylenediamine-based compound having a hydrophilic group has less contamination of the photosensitive material than the para-phenylenediamine-based compound having no hydrophilic group such as N, N-diethyl-p-phenylenediamine, and Not only does it have the advantage that the skin does not easily become fogged even when it comes into contact with the skin, but the object of the present invention can be achieved more efficiently by combining it with the color developing agent of the present invention.

Examples of the hydrophilic group include those having at least one on the amino group or benzene ring of the p-phenylenediamine compound, and specific hydrophilic groups include

-(CH ₂ ) _n -CH ₂ OH-(CH ₂ ) _m NHSO _2- (CH ₂ ) _n -CH _3- (CH ₂ ) _m -O- (CH ₂ ) _n -CH _3- (CH _{2 CH 2 O) n C m} H 2m + 1 -. (CH 2) m -CON (C m H 2m + 1) 2 (m and n each represents an integer of 0 or more) -COOH -SO ₃ H, etc. Are preferred.

Specific examples of the color developing agent preferably used in the present invention include Japanese Patent Application No. 2-203169.
Nos. 26-31 (C-1) to (C-1)
6), (1) to (8) described in JP-A No. 61-289350, pages 29 to 31, and JP-A-3-24654.
(1) to (62) described in No. 3, pp. 5 to 9, and particularly preferably, the exemplified compounds (C-1) and (C-3) described in Japanese Patent Application No. 2-203169. , Exemplified compound (2) described in JP-A No. 61-289350, and Exemplified compound (1) described in JP-A No. 3-246543, pages 5 to 9. The color developing agent is usually used in the form of a salt such as hydrochloride, sulfate, nitrate or phosphate.

In order to achieve the object of the present invention, it is essential that the amount of the color developing agent is 2.0 × 10 ^-2 mol or more, preferably 2.2 × 10 ^-2 mol or more. In the color developing solution of the present invention, instead of hydroxylamine which has been conventionally used as a preservative, JP-A-63-146043 is used.
No. 63-146042, No. 63-146041
No. 63-146040 and 63-135938.
Nos. 63-118748 and hydroxamic acids, hydrazines, hydrazides, phenols described in JP-A-64-62639.
α-hydroxyketones, α-aminoketones, sugars,
Monoamines, diamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds and condensed amines are preferably used as the organic preservative.

In particular, when the compound represented by the following general formula [A] or [B] is contained, it is preferable for rapid processing and reduction of bluing, and also good for crystal precipitation on the liquid surface of the color developer tank. In addition, since it has another effect, it is mentioned as one of the more preferable embodiments of the present invention.

[0047]

[Chemical 13]

Detailed description of the compound represented by the formula [A] can be found in Japanese Patent Application No. 2-17833, pages 50 and 54,
It is synonymous with the explanation of the general formula [A] on page 55. Exemplified Compounds of General Formula [A] A-1 to 15 Japanese Patent Application No. 2-178833 No. 51
Page to page 53 same as A-1 to 15 A-16 to 25

Exemplified Compound No. _{R 1 R 2 A-16 -CH} 2 COOH -CH 2 COOH A-17 -C 2 H 4 SO 3 H -C 2 H 4 SO 3 H A-18 -C 2 H 4 PO 3 H 2 -C 2 H _{4 PO 3 H 2 A-19} -CH (C 2 H 5) CO 2 H -CH (C 2 H 5) CO 2 H A-20 -CH (CH 3) CO 2 H -CH (CH 3) CO 2 _{H A-21 -C 3 H 6} SO 3 H -C 3 H 6 SO 3 H A-22 -CH (CH 3) PO 3 H 2 -CH (CH 3) PO 3 H 2 A-23 -H -C ₂ H ₄ CO ₂ H A-24 -H -C ₂ H ₄ SO ₃ H A-25 -CH ₃ -C ₂ H ₄ CO ₂ H

A-26 to 49 Japanese Patent Application No. 2-178833
No. 51 to 53, the same as A-1 to 16 to 39. Next, in the general formula [B], the details of R _{1 to} R ₅ are as follows.
It has the same meaning as R _{11 to} R ₁₅ of the general formula [I ′] described in Japanese Patent Application No. 2-127444, page 15, lines 1 to 16. Specific examples of the compound represented by the general formula [B] are shown below, but the invention is not limited thereto.

[0051]

[Chemical 14]

[0052]

[Chemical 15]

The compounds represented by the general formula [A] or the general formula [B] are usually free amines, hydrochlorides, sulfates,
It is used in the form of oxalate, phosphate, acetate, etc. The concentration of the compound represented by [A] and the general formula [B] in the color developer is usually 0.2 g / liter to 50 g / liter, preferably 0.5 g / liter to 30 g / liter, and more preferably 1 g / liter. It is from liter to 15 g / liter.

The compound represented by the general formula [A] or the general formula [B] may be used in combination with the conventionally used hydroxylamine and organic preservative, but hydroxylamine is preferably used. It is preferable not to use it because of its developability. The color developer used in the present invention may contain the following developer components in addition to the above components.

As the alkaline agent, for example, sodium hydroxide, potassium hydroxide, silicate, sodium metaborate,
Potassium metaborate, trisodium phosphate, tripotassium phosphate, borax, etc. may be used alone or in combination as long as the pH stabilizing effect is maintained without precipitation. Further, various salts such as disodium hydrogen phosphate, dipotassium hydrogen phosphate, sodium bicarbonate, potassium bicarbonate, and borate salts are used for the necessity of preparation or for the purpose of increasing ionic strength. You can

As the surfactant, the following general formula [SI],
A compound represented by [SII] can be added. Formula [SI] _{A-O- (B) m -} (C) n -X Formula [SII] _{A-O- (CH 2 CH 2} O) n -SO 3 M

In the general formula [SI], A is a monovalent organic group such as an alkyl group having 6 to 50 carbon atoms, preferably 6 to 35 carbon atoms (eg, hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl etc. Various) or an alkyl group having 3 to 35 carbon atoms or 2 to 3 carbon atoms
5 is an aryl group substituted with an alkenyl group of 5. The preferred group that is substituted on the aryl group has 1 to 1 carbon atoms.
8 alkyl groups (for example, unsubstituted alkyl groups such as methyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl), substituted alkyl groups such as benzyl and phenethyl, or those having 2 to 20 prime atoms. Examples thereof include an alkenyl group (for example, an unsubstituted alkenyl group such as oleyl, cetyl and allyl groups).

Examples of the aryl group include phenyl, biphenyl and naphthyl groups, and the phenyl group is preferable. The aryl group may be substituted at any of the ortho, meta and para positions, and a plurality of groups can be substituted. B and C are respectively

[0059]

And may be the same or different (provided that a, b and c are 0, 1, 2 or 3 respectively, d is 0 or 1 and Y is a hydrogen atom or a hydroxyl group). ). m and n represent the integer of 1-100. X is a hydrogen atom, an alkyl group, an aralkyl group or an aryl group, and examples thereof include the groups described in A.

In the general formula [SII], M represents an alkali metal (eg, Na, K, Li, etc.) hydrogen atom, ammonium salt or alkanolamine salt, and n is 1 to 1
Is an integer of 00, A is a monovalent organic group, for example, an alkyl group having a prime number of 6 to 20, preferably 6 to 12 (for example, each group such as hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl). , Or 3 to 2 carbon atoms
It is an aryl group substituted with an alkyl group of 0, and the substituent preferably has an alkyl group having a prime number of 3 to 12 (eg, propyl, butyl, pentyl, hexyl, heptyl,
Each group such as octyl, nonyl, decyl, undecyl or dodecyl).

Examples of the aryl group include phenyl, tolyl, xynyl, biphenyl, and naphthyl groups, with a phenyl group or a tolyl group being preferred. The position at which the alkyl group is bonded to the aryl group is ortho,
Either meta or para may be used.

Examples of the compounds represented by the general formulas [SI] and [SII] are shown below, but the invention is not limited thereto.

[0064]

[Chemical 17]

[0065]

[Chemical 18]

[0066]

[Chemical 19]

Among the above exemplified compounds, SI is preferable.
-23, SI-28, SI-31, SI-32, SI-
33, SI-34, SI-36, SI-37, SI-4
7, SII-8 and SII-9. General formula [SI],
The addition amount of the compound represented by [SII] is 0.01 g /
The range of liter to 2.0 g / liter is preferable.

The color developer of the present invention preferably contains a fluorescent whitening agent. The fluorescent whitening agent not only resolves the white background performance of the unexposed area of the light-sensitive material, but also is added to the color developer of the present invention to give good results in preventing crystal precipitation. As the fluorescent whitening agent, a triazinyl stilbene-based one is preferable, and a compound represented by the following general formula [F] is particularly preferable.

[0069]

[Chemical 20]

The detailed description of the compound represented by the general formula [F] is the same as that of the general formula [E] described on pages 73 to 75 of the specification of Japanese Patent Application No. 2-178833. Exemplified Compounds of General Formula [F] F-1 to 45 Japanese Patent Application No. 2-178833 No. 76
Page to page 82 Same as E-1 to 45. The triazinyl stilbene-based whitening agent can be synthesized by the usual method described in, for example, “Fluorescent Whitening Agent” edited by Chemical Industry Association, page 8 (issued in August 1976).

Among the exemplified compounds, F-4, F-24, F-34, F-35 and F-3 are particularly preferably used.
6, F-37 and F-41. The triazinyl stilbene whitening agent is 0.2 to 10 per liter of color developing solution.
It is preferably in the range of g, more preferably 0.4
Is in the range of up to 5 g.

Further, an auxiliary developing agent may be used together with the developing agent. Examples of these auxiliary developers include N-methyl-p-aminophenol hexaulfate (methol), phenidone, and N, N'-diethyl-p-.
Aminophenol hydrochloride and N, N, N ', N',-tetramethyl-p-phenylenediamine hydrochloride are known, and the addition amount thereof is usually preferably 0.01 to 1.0 g / liter.

Further, other various additives such as stain inhibitors, sludge inhibitors, baking soda effect accelerators, etc. can be used. Further, it is preferable to add a chelating agent represented by the following general formula [K] to the color developing solution of the present invention from the viewpoint of effectively achieving the object of the present invention.

[0074]

[Chemical 21]

For a detailed description of the compound represented by formula [K], see Japanese Patent Application No. 2-178833, pages 84-85.
It is synonymous with the explanation of the general formula [K] on page. Exemplified compounds of general formula [K] K-1 to 22 Japanese Patent Application No. 178833/85
~ 89 Same as K-1 to 22.

In the present invention, the color developing solution can be used in any pH range, but from the viewpoint of rapid processing, the pH of the color developing solution is 9.
It is preferably 5-13.0, more preferably p
Used in H9.8-12.0. The treatment temperature is generally 30 ° C. or higher, preferably 33 ° C. or higher, particularly preferably 3 ° C.
The treatment time is 5 ° C to 65 ° C, and the treatment time is preferably 90 seconds or less, more preferably 3 seconds or more and 60 seconds or less, and particularly preferably 3 seconds or more and 45 seconds or less.

In the present invention, the replenishing amount of the color developing solution is preferably 120 ml / m ² , and more preferably 110 ml / m ² or less, since the effect of the present invention is excellently exhibited when the replenishment is low. And particularly preferably 100 ml / m ² or less. A known processing method can be adopted for the color developing solution of the present invention.

The light-sensitive material to which the color developing solution of the present invention is applied is not particularly limited, and as long as it is a light-sensitive material processed by a so-called internal development method containing a coupler in the light-sensitive material, color paper, color negative film, Color positive film,
The application to any photosensitive material such as a color reversal film for slides, a color reversal film for movies, a color reversal film for TVs, and a reversal color paper is most preferably applied to a color paper mainly containing silver chloride.

[0079]

EXAMPLES The present invention will now be described in more detail with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1 A color developer having the following composition was prepared.

[Color Developer (1)] Additive (described in Table 1) 15 g N, N-diethylhydroxyamine 4.0 g Diethylenetriaminepentaacetic acid 3.0 g Potassium sulfite 1.0 × 10 ⁻³ mol Potassium carbonate 30 g Covitex MST (Ciba Gay Key Co., Ltd.) 1.8 g Chinopearl SFP (Ciba Gay Key Co., Ltd.) 1.2 g Aromatic sulfonic acid or aromatic sulfonate ester Table 1 Color developing agent (C-1) Table 1 potassium chloride 4.0 Water was added. The total amount was adjusted to 1 liter, and the pH was adjusted to 10.10 with potassium hydroxide or sulfuric acid. The following experiment was conducted using the above color developing solution.

(Experiment 1) Polyethylene was laminated on one side of a paper support and polyethylene having titanium oxide was laminated on one side of the other side of the paper support, and each layer having the following constitution was coated on the support. A color light-sensitive material was produced. The coating liquid was prepared as follows.

First layer coating liquid: 26.7 g of yellow coupler (Y-1), 10.0 g of dye image stabilizer (ST-1), (ST-2) 6.67.
g, 0.67 g of the additive (HQ-1) is added to the high boiling point solvent (DN
P) 60 ml of ethyl acetate was added to 6.67 g and dissolved, and this solution was emulsified and dispersed in 220 ml of 10% gelatin aqueous solution containing 7 ml of 20% surfactant (SU-1) using an ultrasonic homogenizer. A yellow coupler dispersion was prepared.

This dispersion was mixed with a blue-sensitive silver halide emulsion (containing 10 g of silver) prepared under the following conditions to prepare a coating solution for the first layer. The second to seventh layer coating solutions were also prepared in the same manner as the one layer coating solution. Further, as a hardening agent, (H-1) was added to the second and fourth layers, and (H-2) was added to the seventh layer. As the coating aid, surfactants (SU-2), (SU-3)
Was added to adjust the surface tension.

Seventh Layer (Protective Layer) Gelatin 1.0 g / m ²

Sixth layer (UV absorber) Gelatin 0.40 g / m ² UV absorber (UV-1) 0.10 g / m ² UV absorber (UV-2) 0.04 g / m ² UV absorber ( UV-3) 0.16 g / m ² additive (HQ-1) 0.01 g / m ² DNP 0.2 g / m ² PVP 0.03 g / m ² anti-irradiation dye (AI-2) 0.02 g / m ²

Fifth Layer (Red Sensitive Layer) Gelatin 1.30 g / m ² Red photosensitive silver chlorobromide emulsion (EmC) (converted to silver) 0.21 g / m ² Cyan coupler (C-1) 0 .17g / m ² cyan coupler (C-2) 0.25g / m 2 dye image stabilizer (ST-1) 0.20g / m 2 additive (HQ-1) 0.01g / m 2 HBS-1 0 .20 g / m ² DOP 0.20 g / m ²

[0088] The fourth layer (ultraviolet absorbing layer) Gelatin 0.94 g / m ² UV absorbent (UV-1) 0.28g / m 2 UV absorbent (UV-2) 0.09g / m 2 UV absorber ( UV-3) 0.38 g / m ² additive (HQ-1) 0.03 g / m ² DNP 0.40 g / m ²

Third Layer (Green Sensitive Layer) Gelatin 1.40 g / m ² Green photosensitive silver chlorobromide emulsion (EmB) (converted to silver) 0.17 g / m ² Magenta coupler (M-1) 0 .35 g / m ² dye image stabilizer (ST-3) 0.15 g / m ² dye image stabilizer (ST-4) 0.15 g / m ² dye image stabilizer (ST-5) 0.15 g / m ² DNP 0.20 g / m ² Anti-irradiation dye (AI-1) 0.01 g / m ²

Second layer (intermediate layer) Gelatin 1.20 g / m ² Additive (HQ-2) 0.12 g / m ² DIDP 0.15 g / m ²

First Layer (Blue Sensitive Layer) Gelatin 1.20 g / m ² Blue-sensitive silver chlorobromide emulsion (EmA) (converted to silver) 0.26 g / m ² Yellow coupler (Y-1) 0 80 g / m ² dye image stabilizer (ST-1) 0.30 g / m ² dye image stabilizer (ST-2) 0.20 g / m ² additive (HQ-1) 0.02 g / m ² Irager Anti-dye (AI-3) 0.01 g / m ² DNP 0.20 g / m ²

Support Polyethylene Laminated Paper

[0093]

[Chemical formula 22]

[0094]

[Chemical formula 23]

[0095]

[Chemical formula 24]

[0096]

[Chemical 25]

[0097]

[Chemical formula 26]

[Preparation Method of Blue-Sensitive Silver Halide Emulsion] 4
In 1000 ml of a 2% gelatin aqueous solution kept at 0 ° C., the following (solution A) and (solution B) were pAg = 6.5, p
Simultaneously added over 30 minutes while controlling H = 3.0, and further the following (C liquid) and (D liquid) pAg = 7.3, pA =
Simultaneous addition was carried out over 180 minutes while controlling at 5.5. At this time, pAg was controlled by the method described in JP-A-59-45437, and pH was controlled by using an aqueous solution of sulfuric acid or sodium hydroxide.

(Solution A) Sodium chloride 3.42 g Sodium bromide 0.03 g Water was added to 200 ml.

(Solution B) Silver nitrate 10 g Water was added to 200 ml.

(Solution C) Sodium chloride 102.7 g Sodium bromide 1.0 g Water was added to 600 ml.

(Solution D) 300 g of silver nitrate 600 g of water was added.

After the addition is completed, Demol N manufactured by Kao Atlas Co., Ltd.
Of 5% aqueous solution of magnesium sulfate and 20% aqueous solution of magnesium sulfate, and then mixed with an aqueous solution of gelatin to have an average particle size of 0.85 μm, coefficient of variation (σ / r) = 0.07, and silver chloride content. A 99.5 mol% monodisperse cubic emulsion EMP-1 was obtained. The following compounds were used in the above emulsion EMP-1 5
Chemical ripening was performed at 0 ° C. for 90 minutes to obtain a blue-sensitive silver halide emulsion (Em-B).

Sodium thiosulfate 0.8 mg / mol AgX chloroauric acid 0.5 mg / mol AgX stabilizer (STAB-1) 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye (BS-1) 4 × 10 ⁻⁴ Mol / mol AgX sensitizing dye (BS-2) 1 × 10 ⁻⁴ mol / mol AgX

[Preparation Method of Green-Sensitive Silver Halide Emulsion]
(A solution) and (B solution) addition time and (C solution) and (D solution)
In the same manner as EMP-1 except that the addition time of
Average particle size 0.43 μm, coefficient of variation (σ / r) = 0.0
8. Monodisperse cubic emulsion E having a silver chloride content of 99.5 mol%
MP-2 was obtained. EMP-2 was chemically ripened at 55 ° C. for 120 minutes using the following compound to obtain a green-sensitive silver halide emulsion (Em-G).

Sodium thiosulfate 1.5 mg / mol AgX chloroauric acid 1.0 mg / mol AgX stabilizer (STAB-1) 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye (GS-1) 4 × 10 ⁻⁴ Mol / mol AgX

[Method for Preparing Red-Sensitive Silver Halide Emulsion]
(A solution) and (B solution) addition time and (C solution) and (D solution)
In the same manner as EMP-1 except that the addition time of
Average particle size 0.50 μm, coefficient of variation (σ / r) = 0.0
8. Monodisperse cubic emulsion E having a silver chloride content of 99.5 mol%
MP-3 was obtained. EMP-3 was chemically ripened at 60 ° C. for 90 minutes using the following compound to obtain a red-sensitive silver halide emulsion (Em-R).

Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX stabilizer (STAB-1) 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye (RS-1) 4 × 10 ⁻⁴ Mol / mol AgX

[0109]

[Chemical 27]

This sample was exposed by a conventional method and then processed using the following processing steps and processing solutions. Treatment process Treatment temperature Treatment time Replenishment amount * (1) Color development 38 ° C. 45 seconds 80 ml / m ² (2) Bleaching development 35 ° C. 45 seconds 100 ml / m ² (3) Stability (3 tank cascade) 30-35 90 ° C. 90 seconds 200 ml / m ² (4) Drying 60 to 80 ° C. 30 seconds * Replenishment amount per 1 m ^{2 of} light-sensitive material The opening area ratio of each tank was 0.01 cm ⁻¹ .

[Color development tank liquid] Additive (described in Table 1) 15 g N, N-diethylhydroxylamine 4.0 g Diethylenetriaminepentaacetic acid 2.0 g Potassium chloride 3.0 g Potassium sulfite 1.0 × 10 ⁻³ mol Potassium carbonate 23 g Ubitex MST (manufactured by Ciba Geigy) 1.2 g Tinopearl SFP (manufactured by Ciba Geigy) 1.0 g Aromatic sulfonic acid or its ester (described in Table 1) 20 g Surfactant (SI-37) 0.1 g Color developing agent ( C-1) 1.5 × 10 ^-2 mol Water was added to make the total amount 1 liter, and the pH was adjusted to 10.10 with potassium hydroxide or sulfuric acid.

[Color developer replenisher] The color developer (1) described above is used. [Bleaching fixer and replenisher] Ethylenediaminetetraacetic acid ferric ammonium salt 53 g Ethylenediaminetetraacetic acid 3.0 g Ammonium thiosulfate (70% solution) 123 g Ammonium sulfite (40% solution) 51 g Ammonium bromide 40 g Ammonia water or glacial acetic acid pH 6 Adjust to 0.5 and add water to make 1 liter.

[0113] [stabilization tanks and Replenisher] orthophenylphenol 0.1g Uvitex (Ciba _{Geigy) 1.0g ZnSO 4 · 7H 2 O} 0.1g Ammonium sulfite (40% solution) 5.0 ml 1-hydroxyethylidene- -1,1-diphosphonic acid (60% solution) 3.0 g Ethylenediaminetetraacetic acid 1.5 g pH was adjusted to 7.8 with aqueous ammonia or sulfuric acid, and water was added to make the total volume 1 liter.

A running process was performed using the color paper and the processing solution prepared as described above. In the running process, the automatic developing machine was filled with the above-mentioned color developing tank solution, the bleach-fixing tank solution and the stabilizing tank solution were filled, and the above-mentioned color developing auxiliary solution was added every 3 minutes while processing the color paper sample. The bleach-fix replenisher and the stable replenisher were replenished through a metering pump. The running process was carried out at 0.0 per day until the amount of the color developing solution replenished in the color developing tank solution became three times the volume of the color developing tank solution.
3R continuous treatment was performed.

Incidentally, 1R means that the color developing replenishing solution for the capacity of the color developing tank is replenished. After continuous treatment, the change in color development and fog was evaluated. Regarding the color forming property, the maximum yellow color developing density (Y-Dmax) was measured. Regarding the fog, the yellow reflection density (Y-Dmin) of the unexposed area was measured. Further, the depositability on the gear portion and the rack in the color developing tank was evaluated according to the following criteria.

∘: None at all Δ: Slightly present on the wall surface ×: Many lump-like deposits are observed in the rack portion XX: Many lump-like deposits in the rack portion and the gear portion Is recognized

(Experiment 2) The color developer (1) was placed in the replenishing tank of the automatic processor and stored under the condition of 0 ° C. for 2 months. At that time, the replenishment pump was operated discontinuously for 10 minutes a day, and 1% of the whole replenisher was discharged. Two months later, the residual rate of the color developing agent in the replenisher remaining at the bottom of the tank and the depositability in the replenishing pump were evaluated according to the following criteria.

∘: None at all Δ: Slight floating material present ×: Small amount of black precipitate XX: Large amount of black lumpy precipitates The results are shown in Table 2. Show.

[0119]

[Table 1]

[0120]

[Table 2]

As is clear from Table 2, the combination of the present invention ensures that stable color development is maintained even after low replenishment treatment and that the whiteness is excellent, and that it is used both in the tank and in the replenisher pump. The effect of excellent precipitation was confirmed.

Example 2 Color developer No. 1 of Example 1 was used. 17, the same experiment was conducted by changing the addition amount of I-17 as shown in Table 3.

Table 3 Addition amount Y-Dmax Y-Dmin Precipitation color developing agent Precipitation residual rate 0 2.20 0.09 × × 80% × × 1.0 2.26 0.05 ○ 90% △ 2. 0 2.30 0.04 ○ 92% ◎ 5.0 2.34 0.04 ◎ 94% ◎ 15 2.36 0.02 ◎ 97% ◎ 30 2.35 0.02 ◎ 96% ◎ 50 2.35 0.02 ◎ 95% ◎ 75 2.30 0.02 ◎ 95% ◎ 100 2.25 0.02 ◎ 96% ◎ 125 2.19 0.02 ○ 93% ◎

From Table 3, the additive amount of the additive (1) is 2.0 to
100 g / liter is preferable, and 5.0 is more preferable.
It can be seen that it is ~ 50 g / liter.

Example 3 Color developer No. 3 of Example 1 was used. In 17, the additive 1-
Replace 17 with 2-2, 2-4, 2-25, 2-29,
When an experiment was conducted in the same manner as in Example 2 while changing the addition amount, a reduction of several% was observed in the residual ratio of the main drug, but the effect of the present invention was confirmed.

Example 4 Example 1 was modified by changing the processing steps performed in Experiment 1 as follows.
When the same experiment was performed, the same result was obtained.

Treatment Step Treatment Temperature Treatment Time Replenishment Amount (1) Color development 38 ° C. 25 seconds 100 ml / m ² (2) Bleach fixing 38 ° C. 25 seconds 200 ml / m ² (3) Stability (3 tank cascading) 30-35 ℃ 75 seconds 200 ml / m ² (4) Dry 60-80 ℃ 30 seconds * Replenishment amount per 1 m ^{2 of} light-sensitive material

Color developer No. 1 of Example 1 In Example 17, both Uvitex MST and Tinopearl SFP were removed, and instead, exemplary compounds F-36 and F-36 of the fluorescent whitening agent represented by the general formula [F] were added, respectively, and Experiment 1 of Example 1 was performed. Experiment 2 with 0.02R per day
The same experiment was conducted with the storage period of 3 months. The results are shown in Table 4.

[0129]

[Chemical 28]

[0130]

[Table 4]

As is clear from Table 4, the addition of the triazinyl stilbene type optical brightener brings about more preferable results in the present invention.

Example 5 Color developer No. 1 of Example 1 was used. In 17, the N, N-diethylhydroxylamine was replaced with the preservative shown in Table 5, and continuous treatment of 0.02R per day was carried out in Experiment 1 of Example 1 and the preservation period was 3 months in Experiment 2. A similar experiment was conducted. The results are shown in Table 5.

[0133]

[Table 5]

As is clear from Table 5, it can be seen that when the compound represented by the general formula [A] or [B] of the present invention is used as the preservative, the present invention brings more preferable results.

Example 6 Color developer No. 1 of Example 1 was used. 17, the amount of potassium sulfite was changed as shown in Table 6, and the experiment 1 of Example 1 was performed.
A continuous treatment of 0.02 R per day was performed in the same manner, and the same experiment was performed in Experiment 2 with a storage period of 3 months. The results are shown in Table 6.

[Table 6] Potassium Sulfite Amount Experiment 1 Experiment 2 Y-Dmax Y-Dmin Precipitable Main Agent Residual Precipitation Positivity 0 2.35 0.04 ◎ 95 ◎ 5.0 × 10 ^-4 2.30 0. 04 ◎ 90 ◎ 1.0 × 10 ^-3 2.30 0.04 ◎ 90 ◎ 2.0 × 10 ^-3 2.29 0.04 ◎ 90 ◎ 3.0 × 10 ^-3 2.20 0.04 ○ 90 △ 5.0 × 10 ^-3 2.15 0.05 ○ 88 △ 1.0 × 10 ^-2 2.00 0.06 ○ 88 △ 5.0 × 10 ^-2 1.90 0.08 × 89 ×

As is clear from Table 6, the sulfurous acid concentration of 2.0 × 10 ^-3 mol or less per liter of the color developing solution brings about preferable results in the present invention.

[0138]

INDUSTRIAL APPLICABILITY The present invention allows a color developing solution to contain a compound represented by the general formula [1] and an aromatic sulfonic acid or an ester thereof, even if the color developing solution is stored for a long period of time. No precipitation of the main agent occurs, and therefore, rapid and stable development processing can be performed with a smaller replenishing amount than before, and deterioration of liquid performance does not occur in an automatic developing machine with a very small processing amount during long-term storage. Further, even when the automatic developing machine is used, it is possible to prevent deposition and sticking to various parts, and it is possible to remarkably improve the maintainability of the automatic developing machine. Further, when the aromatic sulfonic acid or its ester is a compound represented by the general formula [2] or [3], the above effect is further promoted.

Claims (3)

[Claims] 1. A compound containing at least one compound represented by the general formula [1], containing 0.02 mol / liter or more of a color developing agent, and 1 mol of the color developing agent. A color developing solution for a silver halide color photographic light-sensitive material, which contains 5 mol or more of an aromatic sulfonic acid or an aromatic sulfonic acid ester. [In the formula, A and B each represent a linear or branched alkylene group, and n and m each represent an integer of 0 to 100,
Both n and m are never 0, and n + m = 1
In the case, A or B is a linear or branched alkylene group having 3 or more carbon atoms. ] 2. The silver halide color photograph according to claim 1, wherein the aromatic sulfonic acid or aromatic sulfonic acid ester is a compound represented by the following general formula [2] or general formula [3]. Color developer for photosensitive materials. [In the formula, at least one of A to F is a sulfonic acid group or a sulfonic acid ester group, and the rest represent any of a hydrogen atom, a halogen atom, and a saturated or unsaturated alkyl group. ] [In the formula, at least one of G to N represents a sulfonic acid group or a sulfonic acid ester group, and the rest represent a hydrogen atom, a halogen atom, or a saturated or unsaturated alkyl group. ] 3. The coloring for a silver halide color photographic light-sensitive material according to claim 1, wherein the content of the compound represented by the general formula [1] is 2.0 to 100 g / liter. Developer.