JP2811117B2 - Color developer for silver halide color photographic materials - Google Patents

Description

Description: 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, to a color developing method in which deterioration of a white background due to a low replenishment amount of a color developing process is improved. Regarding treatment.

[Background of the Invention]

Processing of a silver halide color photographic light-sensitive material basically includes two steps of color development and desilvering, and desilvering comprises a bleaching and fixing step or a bleach-fixing step. In addition, additional processing steps such as rinsing processing and stabilizing processing are added.

In color development, the exposed silver halide is reduced to silver while the oxidized aromatic 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. In the desilvering step, silver generated by development is bleached by an oxidizing agent, and then all silver salts are removed from the photographic 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 the color developing solution, the development inhibitor accumulates by developing the photographic light-sensitive material as described above, while the color developing agent and benzyl alcohol are consumed, or are accumulated in the photographic light-sensitive material and taken out, and these components are removed. The concentration decreases. In addition, the pH decreases due to hydrogen ions released by the development reaction.

Therefore, in a developing 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 the development finish characteristics due to a change in the component concentration. Means is needed. As such means, a method is usually employed in which a replenisher for replenishing deficient components and diluting unnecessary increased components is replenished. The replenishment of the replenisher inevitably causes a large amount of overflow and is discarded, so that this method is a serious problem in terms of economy and pollution. 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 low concentration replenishment method, and furthermore, a method of adding a regenerant to the overflow solution and using it again as a replenisher solution Have been proposed and put to practical use.

Regeneration of the developer is carried out by removing the eluate from the photosensitive material, which is an unnecessary accumulation component, to compensate for the deficient components. This method (ion exchange resin method and electrodialysis method) is based on chemical analysis. If it is not determined and determined to be constant, there is a disadvantage that the development processing characteristics of the photosensitive material are impaired,
Since it requires complicated management, it is almost impossible to introduce it in small-scale laboratories or mini-labs without special skills. There is also a disadvantage that the initial cost is extremely high.

Furthermore, the method of regenerating the replenisher by adding a regenerant to the overflow solution does not require any special skills, but requires space such as a stock tank, and has the disadvantage that it is complicated for a developing laboratory. It is extremely difficult to introduce them into such as. However, the concentrated low replenishment method does not particularly require a new apparatus and the processing can be easily controlled. Therefore, it can be said that the concentrated low replenishment method is extremely suitable for a small-scale developing laboratory (minilab) having a small processing amount. However, the concentrated low replenishment method also has some problems.

That is, due to the low replenishment processing, the renewal rate of the color developing solution is reduced, the color developing solution is colored by a decomposition product of the contained components by air oxidation or the like, and the photosensitive material treated with such a color developing solution has a white background. There is a problem of contamination, and furthermore, the color developing solution becomes tarred due to air oxidation or the like, and consequently, tar stains are generated on racks and rollers in the processing tank, which causes a failure that contaminates the photosensitive material to be processed. There is a problem to do.

To solve such problems, Japanese Patent Application Laid-Open No. Sho 62-250444 discloses a method using alkanolamines.
JP-A-547 discloses a method using dialkylhydroxylamines, and JP-A-63-48548 discloses a method using a preservative such as a hydrazine derivative. However, none of them are dramatically effective, and if these preservatives are added too much, they deactivate the photographic performance, so that they are difficult to use and have a drawback that the cost is large. .

Another problem associated with the low replenishment process is that if the replenishment amount is small, the rate of evaporation of the color developing solution increases, the color developing solution is concentrated, and fogging is likely to occur.

[Problems to be solved by the invention]

Accordingly, an object of the present invention is to provide a technique that improves the above-mentioned problem associated with low replenishment of color development processing,
Specifically, it is an object of the present invention to provide a technique for preventing coloring and tarring of a color developing solution, preventing contamination of a white background by such a color developing solution, and generation of fog due to concentration of the color developing solution.

[Means for solving the problem]

The above object of the present invention, pka10.5 or more buffer agent,
This is achieved by a color developing solution for silver halide color photographic light-sensitive materials, characterized by containing at least a surfactant and at least 6 × 10 ^-2 mol / chloride.

The pka here, HAH ^{+ +} A ^- acid dissociation constant in the acid dissociation reaction of And a numerical value represented by pka = −log ₁₀ ka. Here, H ⁺ represents an acidic species, and A ⁻ represents a conjugate base.

Preferred embodiments of the present invention include the following, in which the objects of the present invention are more highly achieved.

The surfactant contained in the color developer is an anionic surfactant.

When the chloride content is 8 × 10 ^-2 as chloride ion concentration
2.02.0 × 10 ⁻¹ mol /.

The pka of the buffer agent is 11.0 to 13.0.

 Hereinafter, the present invention will be described in more detail.

As used herein, the term "buffer agent" refers to a substance that is resistant to changes in the concentration of free hydrogen ions in a solution. The buffer capacity of the buffering agent is generally in the range of the acid dissociation constant of the substance, pka ± 1, with the maximum capacity at pH = pka. Among these buffer agents, pka is 10.5
The object of the present invention can be achieved satisfactorily by adding the above-mentioned compounds to the color developing solution, and two or more kinds can be used in combination.

Examples of the buffer agent preferably used in the present invention include the following buffer agents having a pka value of 10.5 or more. The buffer may be used in the form of a salt such as a Na salt or a K salt.

The buffer agent contained in the color developing solution of the present invention has a pka of 10.5 or more as described above, but is preferably p
ka is from 11.0 to 13.0, most preferably phosphoric acid and its salts.

The surfactant referred to in the present invention has two groups in the molecule, which are opposite in solubility in a solvent, a hydrophilic group and a hydrophobic group,
It is a so-called amphoteric substance and refers to a water-soluble substance.

Surfactants are divided into ionic surfactants and nonionic surfactants depending on whether they show ionicity in aqueous solution, and ionic surfactants are further water-soluble, depending on the ionic species of the surface active part, It is divided into anionic surfactants, cationic surfactants, and amphoteric surfactants. Any of these surfactants can be used for achieving the object of the present invention, and two or more surfactants can be used in combination.

Examples of the surfactant preferably used in the present invention include compounds represented by the following general formulas [I] to [XI].

In formula (I) _A-OB m C _n X Formula (I), A is a monovalent organic group, for example, carbon atoms 6 to 50, preferably an alkyl group having 6 to 35 (e.g. hexyl, heptyl, octyl , Nonyl, decyl, undecyl or dodecyl) or an aryl group substituted with an alkyl group having 3 to 35 carbon atoms or an alkenyl group having 2 to 35 carbon atoms.

As a preferable group substituted on the aryl group, an alkyl group having 1 to 18 carbon atoms (eg, an unsubstituted alkyl group such as methyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl), Examples thereof include a substituted alkyl group such as benzyl and phenethyl or an alkenyl group having 2 to 20 carbon atoms (for example, an unsubstituted alkenyl group such as oleyl, cetyl and allyl group, and a substituted alkenyl group such as styryl group).

Examples of the aryl group include phenyl, biphenyl, naphthyl and the like, and a phenyl group is preferable.
The position to be substituted with the aryl group may be any of the ortho and metapara positions, and a plurality of groups can be substituted.

B and C are each an ethyleneoxy group, a propyleneoxy group, a trimethyleneoxy group or (Where n ₁ , m ₁ and l ₁ are each 0, 1, 2 or 3, and p is 0
Or 1. M and n represent an integer of 0 to 100.

x is a hydrogen atom, an alkyl group, an aralkyl group or an aryl group, and examples thereof include the groups described for A.

In the general formula [II], R ¹ represents a hydrogen atom, an aliphatic group or an acyl group, and R ² represents a hydrogen atom or an aliphatic group.

E ¹ is an ethyleneoxy group, E ² is a propyleneoxy group, E ³
Represents an ethyleneoxy group, X represents a carbonyloxy group,
-O- or The stands, R ³ is an aliphatic group, a hydrogen atom or And R ⁴ represents a hydrogen atom or an aliphatic group.

l ₁ , l ₂ , m ₁ , m ₂ , n ₁ or n ₂ each represents an integer of 0 to 100.

In formula (III) R ¹ _{X-L l} COOM general formula [III], R ¹ represents an aliphatic group (e.g., saturated or unsaturated, substituted or unsubstituted, linear or branched alkyl group), X is , (R ² and R ³ each represent a hydrogen atom or a group defined by R ¹ ), 1 is 0 or 1, M is a hydrogen atom or an alkali metal atom (eg, Na, K, etc.), an ammonium ion or Represents an organic ammonium ion. L represents an alkylene group.

In formula [IV] ^{_{R 1 X-L l Y m}} SO 3 M Formula [IV], R ¹ represents an aliphatic group (e.g., saturated or unsaturated, substituted or unsubstituted, linear or branched alkyl group) Where X is Or -COO- (R ² and R ³ are each a hydrogen atom, or R ¹
And l and m are each 0 or 1, L represents an alkylene group, Y represents an oxygen atom, and M represents
Represents an alkali metal atom (for example, Na, K, Li, etc.).

Formula (V) _{A-OCH 2 CH 2 O n} SO 3 M in formula (V), M represents an alkali metal atom (e.g. Na, K, Li, etc.), n is an integer of 1 to 100,
A is a monovalent organic group, for example, an alkyl group having 6 to 20, preferably 6 to 12 carbon atoms (for example, each group such as hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl), or a carbon atom having a carbon number of 6 to 20; An aryl group substituted with an alkyl group having 3 to 20 carbon atoms, and the substituent preferably has 3 carbon atoms.
~ 12 alkyl groups (e.g., propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl,
Each group such as undecyl or dodecyl), and the aryl group includes each group such as phenyl, tolyl, xinyl, biphenyl or naphthyl, and is preferably a phenyl group or a tolyl group.

The position where the alkyl group is bonded to the aryl group may be any of the ortho, meta and para positions.

In the general formula [VI], R ₁ , R ₂ and R ₃ are each a substituted or unsubstituted alkyl group, and R ₁ and R ₂ or R ₂ and R ₃ may each form a ring. A is (R ₄ represents a hydrogen atom or an alkyl group, and n is 1, 2 or 3
Represents).

In the general formula [VII], R ₁ is as defined for A in the general formula [I]. R ₂ represents a hydrogen atom or an alkyl group (for example, a methyl group or an ethyl group), m and n are each 0, 1 or 2, and A is an alkyl group or a substituted or unsubstituted aryl group.

X is -COOM or -SO ₃ H, M represents a hydrogen atom or an alkali metal atom.

In the general formula [VIII], R ₁ , R ₂ , R ₃ and R ₄ are each a hydrogen atom, a substituted or unsubstituted alkyl group or a substituted or unsubstituted phenyl group.

 X Is halogen atom, hydroxyl group, sulfate group, carbonate group, nitric acid
Groups, acetic acid groups, anions such as p-toluenesulfonic acid groups
Show.

In the general formula [IX], _one of R ₁ and R ₂ represents a hydrogen atom or an alkyl group, and the other represents a group represented by the formula —SO ₃ M (M represents a hydrogen atom or a monovalent cation). .

A represents an oxygen atom or a group represented by the formula —N (R ₅ ) — (R ₅ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms).

R ₃ and R ₄ each represent an alkyl group having 4 to 30 carbon atoms.
However, the alkyl group represented by R ₃ , R ₄ or R ₅ may be substituted by a fluorine atom or a hydroxyl group, and an oxy group may be present between carbon atom chains of the alkyl group.

In the general formulas (X) and (XI), R ₁ , R ₂ , R ₃ , R ₄ and
R ₅ represents a hydrogen atom or an alkyl group, and M has the same meaning as M in the general formula [III]. n and p are each 0
Represents an integer of up to 4, and is a value satisfying 1 ≦ n + p ≦ 8.

Exemplary compounds of the general formulas [I] to [XI] are shown below, but are not limited thereto.

The content of the surfactant in the color developing solution of the present invention is 0.01 to
It is preferably 5.0 g /, more preferably 0.02 to 2.0 g /. When the content of the surfactant exceeds 20 g /, there is a problem that precipitation or smearing of the solution occurs, which is not practical.

Anionic surfactants are preferably used as the surfactant used in the present invention, and are preferable for achieving the effects of the present invention.

When a cationic surfactant is added to a color developing replenisher, a precipitate may be formed during continuous processing.

In order to further enhance the effect of the surfactant according to the present invention, a substance generally called a builder can be used in combination. Builders include inorganic salts such as carbonates such as sodium carbonate and sodium bicarbonate, silicates such as sodium metasilicate, sodium orthosilicate and sodium sesquisilicate, and phosphates such as sodium pyrophosphate, sodium tripolyphosphate and sodium tetraphosphate. Builder and carboxymethylcellulose, methylcellulose, hydroxyethylcellulose,
There are organic builders typified by carboxymethyl starch and the like, and any builder can be used. However, an organic builder is more preferred as having more effects of the present invention. A solution containing a surfactant is generally known to foam, but in the case of a photographic processing solution, since the foaming phenomenon is often inconvenient, an antifoaming agent can be used if necessary. .

As the chloride contained in the color developing solution of the present invention, an alkali metal chloride, for example, potassium chloride, sodium chloride, lithium chloride and the like can be preferably used.
As described above, the content is 6.0 × 10 ⁻² mol / or more, preferably 8 × 10 ⁻² mol / ≦ [Cl ⁻ ] ≦ 2.0 ×
It is an amount corresponding to the range of 10 ^-1 mol /.

In the color developing solution of the present invention, JP-A-63-146043 is used in place of hydroxylamine conventionally used as a preservative.
Nos. 63-146042, 63-146041, 63-146040
Nos. 63-135938 and 63-118748 and hydroxamic acids, hydrazines, hydrazides, phenols, α-hydroxyketones and α-aminoketones described in JP-A-64-62639. , Saccharides, monoamines, diamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, and condensed amines are preferably used as organic preservatives.

In particular, when a compound represented by the following general formula [A] or [B] is contained, it is preferable to reduce rapid processing and bluing, and also good for tar deposition on the wall surface of the color developing solution tank. Since it also has an effect, it is cited as one of more preferred embodiments of the present invention.

In the general formula (A), R ₁ and R ₂ are not hydrogen atoms at the same time, respectively, an alkyl group, an aryl group, R′—CO—,
Or a hydrogen atom, the alkyl groups represented by R ₁ and R ₂ may be the same or different, and are each preferably an alkyl group having 1 to 3 carbon atoms.

R 'represents an alkoxy group, an alkyl group or an aryl group.

The alkyl group and the aryl group represented by R ₁ , R ₂ and R ′ include those having a substituent, and R ₁ and R ₂ may combine with each other to form a ring, for example, piperidine, pyridine,
A heterocyclic ring such as triazine and morpholine may be formed.

Specific examples of the hydroxylamine compound represented by the general formula [A] are described in U.S. Pat. Nos. 3,287,125 and 3,293,034.
No. 3,287,124, etc., and particularly preferred specific exemplary compounds are shown below.

In the general formula [B], R ₁ , R ₂ and R ₃ are each a hydrogen atom,
Represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, and R ₄ is a hydroxy group, a hydroxyamino group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted group; Represents a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted carbamoyl group or an amino group. The heterocyclic group is a 5- to 6-membered ring,
It is composed of C, H, O, N, S and halogen atoms and may be saturated or unsaturated. R ₅ is -CO -, - SO ₂ - or -C (= NH) -
And n represents 0 or 1. In particular, when n = 0, R ₄ represents a group selected from an alkyl group, an aryl group, and a heterocyclic ring, and R ₃ and R ₄ may form a heterocyclic group together.

In the general formula [B], R ₁ , R ₂ and R ₃ are preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and most preferably R ₁ and R ₂ are a hydrogen atom.

In the general formula [B], R ₄ is preferably an alkyl group, an aryl group, a carbamoyl group or an amino group, particularly preferably an alkyl group or a substituted alkyl group. Here, preferred substituents of the alkyl group are a carboxyl group, a sulfo group, a nitro group, an amino group, a phosphono group and the like.

Hereinafter, specific examples of the compound represented by the general formula [B] are shown.

The compound represented by the general formula [A] or the general formula [B] is usually in the form of free amine, hydrochloride, sulfate, p-toluenesulfonate, oxalate, phosphate, acetate and the like. Used.

The concentration of the compound represented by the general formula [A] or the general formula [B] in the color developing solution is usually 0.2 to 50 g /, preferably 0.5 to 30 g /, more preferably 1 to 15 g /.

It is also possible to use a compound represented by the general formula (A) or the general formula (B) in combination with a conventionally used hydroxylamine and the organic preservative,
Preferably, hydroxylamine is not used from the viewpoint of developability.

When the color developing solution of the present invention contains a compound represented by the following general formula [C], it also has an effect of improving the air oxidation of the color developing solution, and even when mixed in the bleach-fix solution, It is preferably used because it has no adverse effect.

In the general formula [C], R ₁ is a hydroxyalkyl group having 2 to 6 carbon atoms, R ₂ and R ₃ are each a hydrogen atom, and 1 to 6 carbon atoms.
An alkyl group, a hydroxyalkyl group having 2 to 6 carbon atoms,
Benzyl group or In the above formula, n is an integer of 1 to 6, X and Y are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or 2 to 6 carbon atoms.
Represents a hydroxyalkyl group.

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

C-1 ethanolamine C-2 diethanolamine C-3 triethanolamine C-4 di-isopropanolamine C-5 2-methylaminoethanol C-6 2-ethylaminoethanol C-7 2-dimethylaminoethanol C-8 2 -Diethylaminoethanol C-9 1-Diethylamino-2-propanol C-10 3-Diethylamino-1-propanol C-11 3-Dimethylamino-1-propanol C-12 Isopropylaminoethanol C-13 3-Amino-1-propanol C-14 2-amino-2-methyl-1,3-propazinol C-15 ethylenediaminetetraisopropanol C-16 benzyldiethanolamine C-17 2-amino-2- (hydroxymethyl) -1,3
-Propanediol The compound represented by the general formula [C] is preferably used in an amount of 1 to 100 g, more preferably 2 to 50 g per color developing solution from the viewpoint of preventing air oxidation.

The color developing agent used in the color developing replenisher of the present invention is preferably a p-phenylenediamine compound having a water-soluble group, wherein the water-soluble group is located on the amino group of the p-phenylenediamine compound or on the benzene nucleus. At least one
One has intended, as a specific water-soluble _{group, - (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) nCmH 2 m +1 (m and n each represents an integer of 0 or more.), - COOH group, -SO ₃ H group Are preferred.

Specific examples of the color developing agent preferably used in the invention are shown below.

Among the color developing agents exemplified above, those preferably used in the present invention are exemplified by Nos. (A-1), (A-2) and (A-
3), (A-4), (A-6), (A-7) and (A-
15), particularly preferably No. (A-
1).

The above color developing agents are usually used in the form of salts such as hydrochloride, sulfate, p-toluenesulfonate and the like.

In the present invention, the p-phenylenediamine compound having a water-soluble group preferably used is a color developer 1
It is necessary to be at least 4.5 × 10 ⁻³ mol per mol, preferably in the range of 6.5 × 10 ^{−3 to} 3.4 × 10 ⁻² mol.

The color developing replenisher used in the present invention may contain the following developing components in addition to the above components.

If necessary, inorganic and organic antifoggants can be added. Further, if necessary, a development accelerator can be used.

As development accelerators, U.S. Patent Nos. 2,648,604 and 3,6
No. 71,247, various pyridinium compounds represented by JP-B-44-9503, other cationic compounds, cationic dyes such as phenosafranine, neutral salts such as thallium nitrate, U.S. Pat. No.
2,950,970, 2,577,127 and JP-B-44-9504, nonionic compounds such as polyethylene glycol and derivatives thereof, polythioethers, and U.S. Pat.
And acetylene glycol, methyl ethyl ketone, cyclohexanone, thioethers, pyridine, ammonia, hydrazine, amines and the like.

Benzyl alcohol is not preferably used in the present invention, and it is preferable not to use a poorly soluble organic solvent represented by the above-mentioned phenethyl alcohol in order to efficiently achieve the object of the present invention.

When benzyl alcohol is used, tar is liable to be generated due to long-term use of the color developing replenisher, particularly in running processing in a low replenishment method, and such tar generation is caused by adhesion to the processed paper photosensitive material.
It can even lead to serious failures that significantly impair its commercial value.

In addition, poorly soluble organic solvents have poor solubility in water, which not only complicates the necessity of, for example, requiring a stirrer for preparing the color developing solution itself, but also increases the dissolution rate by using such a stirrer. Due to the poor quality, there is a limit to the development promoting effect.

Furthermore, poorly soluble organic solvents have large pollution load values such as biochemical oxygen demand (BOD) and cannot be disposed of in sewers or rivers. Because it has problems such as requiring cost,
It is preferable to reduce or eliminate the use amount of not only benzyl alcohol but also other poorly soluble organic solvents as much as possible.

The replenisher for color development of the present invention preferably contains a triazinylstilbene-based fluorescent whitening agent.

As the triazinylstilbene-based fluorescent whitening agent, those represented by the following general formula [E] are preferable.

In the general formula [E], X ₁ , X ₂ , Y ₁ and Y ₂ each represent a hydroxyl group, a halogen atom such as chlorine or bromine, an alkyl group (eg, methyl, ethyl and the like), and an aryl group (eg, phenyl,
Methoxyphenyl etc.), Or an -OR _25.

Wherein R ₂₁ and R ₂₂ are each a hydrogen atom, an optionally substituted alkyl group, or an aryl group which may have a substituent, R ₂₃ and R ₂₄ each have a substituent R ₂₅ represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent;
Is a cation (eg, sodium, potassium, lithium,
Ammonium). The alkyl group represented by R ₂₁ , R ₂₂ and R ₂₅ preferably has 1 to 6 carbon atoms, and the alkylene group represented by R ₂₃ and R ₂₄ preferably has 1 to 6 carbon atoms.
2.

As the substituents of the alkyl group and aryl group represented by R ₂₁ , R ₂₂ and R ₂₅ and the alkylene group represented by R ₂₃ and R ₂₄ , a hydroxy group, a sulfo group, a sulfoamino group and a carboxyamino group are preferable. .

Examples of the amino group include an amino group, an alkylamino group (for example, methylamino, ethylamino, propylamino, dimethylamino, cyclohexylamino, β-hydroxyethylamino, di (β-hydroxyethyl) amino, β-sulfoethylamino, -(Β-sulfoethyl) -N-methylamino, N- (β-hydroxyethyl-N-methylamino and the like), or an arylamino group (for example, anilino, o
-, M-, p-sulfoanilino, o-, m-, p-chloroanilino, o-, m-, p-toluidino, o-, m-, p-carboxyanilino, o, m, p-hydroxyanilino , Sulfonaphthylamino, o-, m-, p-aminoanilino, o-, m-, p-
Anidino). Specific examples of include a morpholino group, and specific examples of —OR ₂₅ include an alkoxy group (eg, methoxy, ethoxy, methoxyethoxy, etc.) and an aryloxy group (eg, phenoxy, p-sulfophenoxy, etc.).

Preferred compounds among the fluorescent whitening agent represented by the general formula X _1, X _2, Y ₁ and Y ₂ are all Or a compound that is -OR ₂₅ , and the most preferred compound is
One of X ₂ and Y ₁ is -OR ₂₅ , and the other is And when one of X ₂ and Y ₂ is -OR ₂₅ , the other is Is a compound.

Specific examples include, but are not limited to, the following compounds.

Triazinyl stilbene-based brighteners preferably used in the present invention include, for example, "Fluorescent Brightener" (edited by the Chemical Industry Association of Japan) (Showa
It can be synthesized by the usual method described on page 8).

Particularly preferred among the exemplified compounds is E-
4, E-24, E-34, E-35, E-36, E-37, E-41
It is.

These triazinylstilbene-based brighteners are preferably in the range of 0.2 to 10 g, more preferably in the range of 0.4 to 5 g per color developing solution.

Further, the color developing solution used in the present invention, if necessary, methylcellosolve, methanol, acetone, dimethylformamide, β-cyclodextrin, and other JP-B-47-33378, JP 44-9509 described The compound can be used as an organic solvent for increasing the solubility of the developing agent.

Further, an auxiliary developer can be used together with the developing agent. These auxiliary developers include, for example, N-methyl-p-aminophenol hexalfate (methol), phenidone, N, N-diethyl-p-aminophenol hydrochloride, N, N, N ', N'-tetramethyl -P-Phenylenediamine hydrochloride and the like are known, and the addition amount thereof is usually preferably from 0.01 to 1.0 g /.

Further, various additives such as a stain inhibitor, an anti-sludge agent, and a layering effect promoter can be used.

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.

In the general formula [K], E is a substituted or unsubstituted alkylene group, cycloalkylene group, phenylene group, -R ₅ OR ₅
—, —R ₅ OR ₅ OR ₅ — or —R ₅ ZR ₅ —, wherein Z is> N—R ₅
Represents -A _{5 or> N-A 5, R 1} ~R 5 represent each a substituted or unsubstituted alkylene group, A ₁ to A ₅ is s hydrogen atom, -OH, -C
It represents OOM or -PO ₃ (M) _2, M represents a hydrogen atom or an alkali metal atom.

Each component of the color developing solution is added to a certain amount of water sequentially,
It can be prepared by stirring. In this case, the component having low solubility in water can be added by mixing with the above-mentioned organic solvent such as triethanolamine.

More generally, a concentrated aqueous solution of a plurality of components that can coexist stably, or a solution prepared in advance in a small container in a solid state is added to water and prepared by stirring to prepare a color developing solution of the present invention. Can be used.

The pH of the color developing replenisher of the present invention is preferably from 9.2 to 13.0, and more preferably from 9.8 to 12.0.

In the present invention, the replenishment amount of the color developing replenisher is 12
It is preferably 0 ml / m ² or less, more preferably 20 to 100 ml / m ² , and particularly preferably 25 to 70 ml / m ² .

As the photosensitive material using the color developing solution of the present invention, color paper, color negative film, color bodice film, color reversal for slide can be used as long as the photosensitive material is processed by a so-called internal developing method containing a coupler in the photosensitive material. It can be applied to any photosensitive material such as a film, a color reversal film for movies, a color reversal film for TV, and a reversal color paper, but is most preferably applied to a silver chloride-based color paper.

〔Example〕

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

Example 1 A color developing solution (1) having the following composition was prepared.

Color developing solution (1) Triethanolamine (C-3) 10 g N, N-diethylhydroxylamine (A-1) 6.0 g Surfactant (described in Table 2) 0.5 g Diethyltriaminepentaacetic acid (K-2) 5.0 g Potassium sulfite 2.5 × 10 ^-3 mol Color developing agent (3-methyl-4-amino-N-ethyl-N- (β-methanesulfonamidoethyl) -aniline sulfate) 6.5 g Buffer agent (described in Table 2) 0.2 mol Potassium bromide 1.6 × 10 ^-4 mol Potassium chloride Table 2 Add water to make the total amount as shown in Table 2, and adjust the pH to 10.10 with potassium hydroxide or sulfuric acid.

 The following experiment was performed using the above color developing solution.

Experiment 1 A multi-layer silver halide color photograph was prepared by coating each layer of the following composition on a support obtained by laminating polyethylene on one side of a paper support and polyethylene containing titanium oxide on the first layer side of the other side. A photosensitive material was prepared.

 The coating solution was prepared as described below.

First layer coating solution 26.7 g of yellow coupler (Y-1), 10.0 g of dye image stabilizer (ST-1), 6.67 g of (ST-2), additive (HQ-
1) 0.67 g of ethyl acetate 6 in 6.67 g of high boiling organic solvent (DNP)
0 ml was added and dissolved, and this solution was added to a 20% surfactant (SU-
1) A yellow coupler dispersion was prepared by emulsifying and dispersing in 220 ml of a 10% aqueous gelatin solution containing 7 ml using an ultrasonic homogenizer.

This dispersion was mixed with a blue-sensitive silver halide emulsion (containing 10 g of silver) prepared under the following conditions to prepare a first layer coating solution.

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer.

In addition, the following H-1 was used as a hardener.

[Preparation Method of Blue-Sensitive Silver Halide Emulsion] The following (solution A) and (solution B) were adjusted to pAg = 6.5 and pH = 3.0 in 1000 ml of a 2% aqueous gelatin solution kept at 40 ° C.
Simultaneous addition over 30 minutes, and the following (Solution C) and (Solution D)
Was added simultaneously over 180 minutes while controlling pAg = 7.3 and pH = 5.5.

At this time, pAg was controlled by the method described in JP-A-59-45437, and pH was controlled using an aqueous solution of sulfuric acid or sodium hydroxide.

(Solution A) Sodium chloride 3.42 g Potassium bromide 0.03 g Add water 200 ml (Solution B) Add 10 g of silver nitrate water and 200 ml (Solution C) Sodium chloride 102.7 g Potassium bromide 1.0 g Add water and 600 ml (Solution D) After adding 300 g of silver nitrate and adding 600 ml of water, desalting was performed using a 5% aqueous solution of Demol N and 20% aqueous solution of magnesium sulfate manufactured by Kao Atlas Co., Ltd., and then mixed with an aqueous gelatin solution to obtain an average particle size of 0.85 μm. Thus, a monodisperse cubic emulsion EMP-1 having a coefficient of variation (σ / r) = 0.07 and a silver chloride content of 99.5 mol% was obtained.

Emulsion EMP-1 was chemically ripened at 50 ° C. for 90 minutes using the following compound to obtain a blue-sensitive silver halide emulsion (Em-1).
A) obtained.

Sodium thiosulfate 0.8 mg / mol AgX Chloroauric acid 0.5 mg / mol AgX Stabilizer SB-5 6.0 × 10 ^-4 mol / mol AgX sensitizing dye D-1 4.3 × 10 ^-4 mol / mol AgX sensitizing dye D- 4 0.7 × 10 ^-4 mol / mol AgX [Preparation method of green-sensitive silver halide emulsion] Addition time of (Solution A) and (Solution B) and (Solution C) and (D
EMP-2), except that the addition time of the liquid was changed, a monodisperse cubic emulsion EMP-2 having an average particle size of 0.43 μm, a coefficient of variation (σ / r) = 0.08, and a silver chloride content of 99.5 mol% was prepared. Obtained.

EMP-2 was chemically ripened at 55 ° C. for 120 minutes using the following compound to obtain a green-sensitive silver halide emulsion (EmB).

Sodium thiosulfate 1.5 mg / mol AgX Chloroauric acid 1.0 mg / mol AgX Stabilizer SB-5 6 × 10 ^-4 mol / mol AgX Sensitizing dye D-2 4 × 10 ^-4 mol / mol AgX [Red-sensitive halogenation Preparation method of silver emulsion] (solution A) and (solution B) addition time and (solution C) and (D
EMP-3 in the same manner as in EMP-1 except that the addition time of the solution was changed. A monodispersed cubic emulsion EMP-3 having an average particle size of 0.50 μm, a coefficient of variation (σ / r) = 0.08, and a silver chloride content of 99.5 mol% was obtained. Obtained.

EMP-3 was chemically ripened at 60 ° C. for 90 minutes using the following compounds to obtain a red-sensitive silver halide emulsion (EmC).

Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX Stabilizer SB-5 6 × 10 ^-4 mol / mol AgX Sensitizing dye D-3 1 × 10 ^-4 mol / mol AgX The sample was processed without exposure using the following processing conditions and processing solution.

The composition of each processing solution is as follows.

Color developing solution The above color developing solution (1) is used.

Bleaching / fixing solution Ferric ammonium salt of ethylenediaminetetraacetic acid 53.0 g Ethylenediaminetetraacetic acid 3.0 g Ammonium thiosulfate (70% solution) 123.0 g Ammonium sulfite (40% solution) 51.0 g Adjust pH to 5.4 with aqueous ammonia or glacial acetic acid Add water to bring the total volume to 1.

Stable liquid ortho-phenyl phenol 0.1g Uvitex CK _{(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 Adjusted to pH 7.9 with aqueous ammonia or sulfuric acid and added with water.
And

Thus, unexposed color paper Po was prepared.

Next, a color developing solution (I) was added to a 1000 ml beaker 500 ml.
Each placed, after the samples were stored for two weeks at 25 ° C., performs processing in the same manner, was created unexposed processed color paper P _2. The Po, each measured reflection absorbance at 550nm for P ₁ Ao, and A _1, and evaluated the difference as white dyeable.

The white dyeability = A ₁ Ao results shown in Table 2.

Experiment 2 100 ml of the color developing solution (1) was placed in a 300 ml glass beaker, and a plastic plate (made of vinyl chloride) was further inserted. This sample was stored at 25 ° C. for 2 weeks, and at that time, the liquid colorability, the residual ratio of the main drug, and the state of generation of tar-like substances on the plastic plate were examined. For the colorability of the solution, the difference in absorbance of the solution before and after storage was measured at λ = 440 nm, and the residual ratio of the main drug was calculated assuming that the amount of the main drug before storage was 100%.

In addition, the occurrence of tar-like substances was evaluated according to the following criteria.

 し な い Not adhered at all ○ Only slightly adhered △ Adhered matter also precipitated on the interface × × Adhered matter was considerably deposited on the interface The results are shown in Table 2.

Experiment 3 The color paper prepared in Experiment 1 was exposed according to a conventional method, and the color developing solution (1) was processed under the same conditions as in Experiment 1 using the bleach-fixing solution and stabilizing solution described in Experiment 1 with a finishing amount of 700 ml. Color development and fog were evaluated. For the color development, the maximum yellow density (Y-Dmax) was measured, and for fog, the color development density (Y-Dmin) of the unexposed yellow portion was measured and used as an index. Table 2 shows the results.

Table 1 shows the buffer agents used. When two buffer agents were used in combination, the amount was 0.1 mol each.

Buffer agent used Table 2 shows that the combination of the present invention can provide, for the first time, a color developing solution free from liquid deterioration and dyeing on a white background due to tar formation of the color developing agent and free from fogging due to concentration of the color developing solution.

The anionic surfactant was most effective.

Example 2 In the color developer of processing solution No. 1-8 of Example 1, diethylenetriaminepentaacetic acid (K-2) was changed to that shown in Table 3 below, and the addition amount was made to be equimolar. Experiment 1
The experiment was performed in the same manner as in Experiments 1 and 2 of Example 1, except that the storage period of the color developer was changed to 4 weeks, and the storage period of the color developer in Experiment 2 was changed to 4 weeks. . Table 3 shows the results.

As is clear from Table 3, the present invention can be made more effective by including the chelating agent represented by the general formula [K].

Example 3 The same experiment as in Example 2 was carried out except that a color developing solution in which 2.0 g / fluorescent brightener shown in Table 4 was added to the processing solution No. 1-8 of Example 1 was used as the color developing solution. An evaluation was performed.
Table 4 shows the results.

As is clear from Table 4, the effect of the present invention can be further enhanced by adding a triazinyl stilber-based brightener.

Example 4 In the color developer of processing solution No. 1-8 of Example 1, N, N-diethylhydroxylamine (A-
1) was subjected to the same experiment and evaluation as in Example 2 for those described in Table 5 below. Table 5 shows the results.

As is clear from Table 5, the present invention becomes more effective by adding the organic preservative represented by the general formula [A] or [B].

Example 5 In the color developer of processing solution No. 1-8 of Example 1, triethanolamine (C-3) was changed to the additives shown in Table 6 below, and the amount of addition was equimolar. The same experiment and evaluation as in Example 2 were carried out. Table 6 shows the results.

As is clear from Table 6, the effect of the present invention is further improved by using the alkanolamine compound represented by the general formula [C] or the glycol compound represented by the general formula [D] in combination. You can see that you can do it.

〔The invention's effect〕

According to the present invention, the color developing solution is colored and tarred, which is a problem associated with low replenishment in the color developing process of a silver halide color photographic light-sensitive material, and contamination of a white background by such a color developing solution, and a color developing solution And a color developing solution in which the generation of fogging due to concentration of the toner is improved.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-62-42154 (JP, A) JP-A-2-5048 (JP, A) JP-A-62-56961 (JP, A) (58) Survey Field (Int.Cl. ⁶ , DB name) G03C 7/407

Claims (2)

(57) [Claims] 1. A color developing solution for a silver halide color photographic light-sensitive material, which comprises at least a buffer agent, a surfactant of pka 10.5 or more and a chloride of 6 × 10 ^-2 mol / or more. 2. A color developing solution for a silver halide color photographic light-sensitive material according to claim 1, wherein said surfactant is an anionic surfactant.