JP2607364B2 - Processing method of silver halide color photographic light-sensitive material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a method for processing a silver halide color photographic light-sensitive material. More specifically, the present invention enables rapid processing and improves processing stability in the rapid processing. And a method for processing a silver halide color photographic light-sensitive material.

[Background of the Invention] In recent years, there has been a demand in the art for a technique that enables rapid processing of a silver halide color photographic light-sensitive material, and that has excellent processing stability and stable photographic characteristics. There is a demand for a method for developing a silver halide color photographic light-sensitive material which can be rapidly processed.

That is, the silver halide color photographic light-sensitive material is subjected to a running process by an automatic developing machine provided in each laboratory. Users are required to return them, and recently, even within a few hours from the reception desk, it is required to develop a technology that can process quickly.

Looking at the prior art for rapid processing of silver halide color photographic light-sensitive materials, [1] technology by improving silver halide color photographic light-sensitive materials, [2] technology by physical means during development processing, [3] development processing The method [1] is mainly based on the improvement of the composition of the processing solution used in the above-mentioned (for example, Japanese Patent Application Laid-Open No. Sho 51-77223). Japanese Unexamined Patent Publication No. Sho 58-183142, Japanese Patent Publication No. Sho 56-18939, a technique for lowering silver bromide of silver halide), and the use of additives (for example, a specific structure described in JP-A-56-64339). Of adding 1-aryl-3-pyrazolidone to a silver halide color photographic light-sensitive material;
No. 44547, No. 58-50534, No. 58-50535 and No. 58-50536, in which 1-arylpyrazolidones are added to silver halide color photographic light-sensitive materials), high-speed reactive couplers (For example, a technique using a high-speed reactive yellow coupler described in JP-B-51-10783, JP-A-50-123342, and JP-A-51-102636), and a technique for thinning a photographic constituent layer (for example, -204992), and the above-mentioned [2] is based on a processing solution stirring technique (eg, a processing solution stirring technique described in Japanese Patent Application No. 61-23334). With regard to the above [3], a technique using a development accelerator, a technique for enriching a color developing agent, a technique for reducing the concentration of halogen ions, particularly bromide ions, and the like are known.

Processing of the photosensitive 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, additional treatment steps such as rinsing treatment, stabilizing treatment, washing with water or alternative washing treatment with water are added. That is, in color development, the exposed silver halide is reduced to silver and simultaneously oxidized aromatic primary
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. In addition, components such as an inhibitor contained in the photosensitive 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 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.

Among the rapid processing techniques of the above [1], techniques using a silver halide photosensitive material containing silver halide grains composed of a high concentration of silver chloride (for example, JP-A-58-95345, JP-A-60-1985)
-19140 and JP-A-58-95736) give particularly excellent speeding-up performance. However,
The use of such a high silver chloride-containing light-sensitive material has a disadvantage that a sulfite usually contained in a color developing solution causes a physical development reaction, which results in an insufficient dye concentration. For this reason, high silver chloride-containing light-sensitive materials are destined to be used in a concentration region in which sulfite is extremely low. However, when a photosensitive material containing high silver chloride is developed using a color developing solution having a low sulfite concentration, sufficient rapidity can be obtained, but if a bleach-fixing process is subsequently performed, the preservative in the color developing solution is used. It has been found that the color base is oxidized due to a low sulfite concentration and so-called bleach fog is likely to occur.

In particular, bleach-fixing solutions tend to have low replenishment or high regeneration rates due to recent demands for low pollution and cost reduction, and the amount of color developing solution accumulated in the bleach-fixing solution has increased.
That is, when the bleach-fixer is reduced in replenishment rate or increased in regenerating rate, the effect of evaporation or regenerating operation, or the difference in the processing amount of photographic light-sensitive material (for example, between the beginning of the week when the order quantity is large and the weekend when the order quantity is decreasing) is reduced. The amount of the color developing solution in the bleach-fix solution increases due to a difference in the amount of processing or a difference in the amount of processing between the high season and the off season. Under such circumstances, the photographic properties are significantly reduced such as bleaching fog is further increased, and conventionally known techniques (for example, JP-A-50-136031, UK Patent No. 1,131,335, US Patent No. 3,293,036) ), Etc., is becoming increasingly incomplete.

As another problem, a high silver chloride-containing photosensitive material, which is a very effective technology for speeding up the process, is difficult when a heavy metal ion (for example, ferric ion or copper ion) is mixed in the color developing solution and the aging occurs. It was found that the occurrence of stain during the bleach-fixing process became more remarkable. In particular, recently, color developing solutions tend to be replenished at low levels due to demands for low pollution and low cost. Along with this, the amount of heavy metal ions accumulated in the color developing solution also tends to increase, and the situation is increasingly severe for high silver chloride-containing photosensitive materials.

[Object of the Invention] Accordingly, a first object of the present invention is to provide a silver halide color photographic light-sensitive material capable of imparting rapid developability using a high chloride silver halide and having improved fog in a bleach-fix solution. In providing a processing method. A second object of the present invention is to provide a method for processing a silver halide color photographic light-sensitive material which causes less fog even when the bleach-fix solution is replenished at a low level. A third object of the present invention is to provide a method for processing a silver halide color photographic material having improved processing stability. A fourth object of the present invention is to provide a method for processing a silver halide color photographic light-sensitive material in which generation of fog in a bleach-fixing solution is improved even when heavy metal ions are mixed in a color developing solution.

[Constitution of the invention] As a result of various studies, the inventors of the present invention have found that the object of the present invention is to form a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer by imagewise exposing it to at least a color developing step. And a method for processing a silver halide color photographic light-sensitive material which performs a process including a bleach-fixing step subsequent to the color development step, wherein the silver halide emulsion layer contains silver halide grains comprising 80 mol% or more of silver chloride. The color developing solution used in the color developing step, which is a silver halide emulsion layer containing at least one compound selected from a compound represented by the following general formula [I] and a compound represented by the following general formula [II] And at least one triazylstilbene-based fluorescent whitening agent represented by the following general formula [XV], and having a sulfite concentration of 4 per color developing solution.
× 10 ⁻³ mol or less, and the bleach-fixing solution used in the bleach-fixing step is achieved by a method for processing a silver halide color photographic light-sensitive material having a pH in the range of 4.5 to 6.8. This is what led to the invention.

General formula [I] General formula [II] (Wherein, R ₁ , R ₂ , R ₃ and R ₄ are each a hydrogen atom, a halogen atom, a sulfonic acid group, an alkyl group having 1 to 7 carbon atoms, —OR ₅ , —COOR ₆ , Or, it represents a phenyl group. Also, R ₅ , R ₆ , R ₇ and R ₈
Represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, respectively. However, when R ₂ represents —OH or a hydrogen atom, R ₁ is a halogen atom, a sulfonic acid group, and has 1 to 1 carbon atoms.
An alkyl group of 7, -OR ₅ , -COOR ₆ , Or, it represents a phenyl group. ) General formula [XV] (Wherein X ₁ , X ₂ , Y ₁ and Y ₂ each represent a hydroxyl group, a halogen atom, a morpholino group, an alkoxy group, an aryloxy group, an aryl group, an amino group, an alkylamino group, or an arylamino group. Represents a hydrogen atom, sodium, potassium, ammonium or lithium.) [Specific Constitution of the Invention] The processing method of the silver halide color photographic light-sensitive material of the present invention uses a silver halide emulsion in order to enable rapid development processing. The layer contained silver halide grains of 80 mol% or more of silver chloride.

Then, in the present invention, such high-prone when the silver chloride content light-sensitive material was used, a decrease in dye density due to silver development reaction, color development a sulfite concentration used as a preservative Developer 1 per 4 × 10 ^{- This} was prevented by controlling the amount to ³ mol or less.

Further, in the present invention, one of the problems caused by the use of the photosensitive material containing high silver chloride, namely, the generation of stain during the bleach-fixing process which occurs when heavy metal ions are mixed in the color developing solution and aging occurs. This was prevented by including at least one compound selected from the compounds represented by the above general formulas [I] and [II] in the color developing solution. In addition, in the present invention, bleaching fog, that is, generation of stain in the bleach-fix solution is prevented by adjusting the pH of the bleach-fix solution to a range of 4.5 to 6.8.

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

It is known that the addition of the compound represented by the general formula [I] or [II] according to the present invention to a color developing solution can prevent the decomposition of hydroxylamine by heavy metal ions (see, for example, 56-47038, JP-A-59-1
No. 60141, JP-A-59-160142, U.S. Pat.No. 3,746,544
No. Research Disclosure No. 18,843 (Dec. 1979
Month)).

However, even when a high silver chloride-containing light-sensitive material is processed with a color developing solution having a very low sulfite concentration, the use of the compound represented by the above general formula [I] or [II] makes it possible to obtain a color which is caused by the incorporation of heavy metal ions. It is surprising that destabilization of the developing agent, that is, bleaching fog due to oxidation of the developing agent, can be prevented.

The color developing solution used in the present invention has a sulfite concentration of 4 × 10 ⁻³ mol or less, preferably 2 × 10 ^{−3 to} 0 mol per color developing solution.

In the conventional color developing solution, sulfite was used as one of the preservatives in an amount of usually about 8 × 10 ^-3 to 4 × 10 ^-2 mol per color developing solution. When applied to silver chloride, dissolution of silver chloride causes a decrease in color density.Therefore, the present invention solves the above problem by reducing the sulfite concentration to a specific range, and furthermore, the specific pH described above.
The problem was solved by using a bleach-fixing solution in combination.

Examples of the sulfite used in the present invention include sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, and the like.

The color developing solution used in the present invention contains at least one compound selected from the compound represented by the general formula [I] and the compound represented by the general formula [II] (hereinafter, referred to as the compound of the present invention).

General formula [I] General formula [IV] In the general formulas [I] and [II], R ₁ , R ₂ , R ₃ and R ₄
Represents a hydrogen atom, a halogen atom, a sulfonic acid group,
An alkyl group having a carbon number of 1~7, -OR _5, -COOR _6, Or, it represents a phenyl group. In addition, R ₅ , R ₆ , R ₇ and R ₈
Represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, respectively. However, when R ₂ represents —OH or a hydrogen atom, R ₁ is a halogen atom, a sulfonic acid group, a carbon atom 1
To 7 alkyl groups, —OR ₅ , —COOR ₆ , Or, it represents a phenyl group.

Examples of the alkyl group represented by R ₁ , R ₂ , R ₃ and R ₄ include a methyl group, an ethyl group, an iso-propyl group, and n
-Propyl group, t-butyl group, n-butyl group, hydroxymethyl group, hydroxyethyl group, methylcarboxylic acid group, benzyl group, etc., and R ₅ , R ₆ , R ₇ and R ₈
The alkyl group represented by has the same meaning as described above, and further includes an octyl group.

Examples of the phenyl group represented by R ₁ , R ₂ , R ₃ and R ₄ include a phenyl group, a 2-hydroxyphenyl group and a 4-aminophenyl group.

Representative specific examples of the chelating agent of the present invention are shown below, but are not limited thereto.

(I-1) 4-isopropyl-1,2-dihydroxybenzene (I-2) 1,2-hydroxybenzene-3,5-disulfonic acid (I-3) 1,2,3-trihydroxybenzene-5- Carboxylic acid (I-4) 1,2,3-trihydroxybenzene-5-carboxymethyl ester (I-5) 1,2,3-trihydroxybenzene-5-carboxy-n-butyl ester (I-6) 5-t-butyl-1,2,3-trihydroxybenzene (II-1) 2,3-dihydroxynaphthalene-6-sulfonic acid (II-2) 2,3,8-trihydroxynaphthalene-6
Sulfonic acid (II-3) 2,3-dihydroxynaphthalene-6-carboxylic acid (II-4) 2,3-dihydroxy-8-isopropyl-
Naphthalene (II-5) 2,3-dihydroxy-8-chloro-naphthalene-6-sulfonic acid Among the above-mentioned compounds, the compound particularly preferably used in the present invention includes 1,2-hydroxybenzene-3,5-disulfonic acid And also usable as alkali metal salts such as sodium salt and potassium salt.

In the present invention, the compound of the present invention can be used in an amount of 5 mg to 20 g per developer, preferably 10 to 20 g.
Good results are obtained by adding from mg to 10 g, more preferably from 20 mg to 3 g.

The compounds of the present invention may be used alone or in combination. Furthermore, aminopolyphosphonic acids such as aminotri (methylenephosphonic acid) or ethylenediaminetetraphosphoric acid, oxycarboxylic acids such as citric acid or gluconic acid, 2-phosphonobutane-1,2,
Other chelating agents such as phosphonocarboxylic acid such as 4-tricarboxylic acid and polyphosphoric acid such as tripolyphosphoric acid or hexametaphosphoric acid may be used in combination.

As the color developing agent used in the color developing solution used in the present invention, a p-phenylenediamine compound having a water-soluble group is preferable from the viewpoint of the effects of the present invention.

The p-phenylenediamine-based compound having a water-soluble group has less contamination of the photosensitive material and has less skin damage than a para-phenylenediamine-based compound having no water-soluble group such as N, N-diethyl-p-phenylenediamine. Not only has the advantage of being less susceptible to fogging, but in particular, the object of the present invention can be efficiently achieved by combining with the compound represented by the general formula [I] in the present invention.

The water-soluble group are those having at least one is listed on the amino group or benzene nucleus of p- phenylenediamine compound, as a specific water-soluble _{group, - (CH 2) n-} CH 2 OH, - _{(CH 2) m-NHSO 2} - (CH 2) n-CH 3, - (CH 2) mO- (CH 2) n-CH 2, - (CH 2 CH 2 O) nCmH 2m + 1 (m and n Represents an integer greater than or equal to O.), a —COOH group, and a —SO ₃ H group.

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

Illustrative color developing agents 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 (A-
1).

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

The color developing agent having a water-soluble group used in the present invention is usually preferably used in an amount of 1 × 10 ^-2 to 2 × 10 ^-1 mol per color developing solution, but from the viewpoint of rapid processing, the color developing agent is preferably used. The range is more preferably 1.5 × 10 ^-2 to 2 × 10 ^-1 mol per liquid.

In the present invention, when a triazylstilbene-based fluorescent whitening agent represented by the following general formula [XV] is used in the color developing solution according to the present invention, the effects of the present invention are more favorably exhibited.

General formula [XV] In the formula, X ₁ , X ₂ , Y ₁ and Y ₂ are each a hydroxyl group, a halogen atom such as chlorine or bromine, a morpholino group, an alkoxy group (for example, methoxy, ethoxy, methoxyethoxy and the like),
An aryloxy group (eg, phenoxy, p-sulfophenoxy, etc.), an alkyl group (eg, methyl, ethyl, etc.),
An aryl group (eg, phenyl, methoxyphenyl, etc.),
Amino group, alkylamino group (for example, methylamino, ethylamino, propylamino, dimethylamino, cyclohexylamino, β-hydroxyethylamino, di (β
-Hydroxyethyl) amino, β-sulfoethylamino, N- (β-sulfoethyl) -N′-methylamino,
N- (β-hydroxyethyl-N′-methylamino and the like), arylamino groups (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, etc.). M
Represents a hydrogen atom, sodium, potassium, ammonium or lithium.

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

[Exemplary compound] The triazylstilbene-based brightener of the present invention is, for example, “Fluorescent brightener” edited by The Chemical Industry Association of Japan (issued in August 1976).
It can be synthesized by the usual method described on page.

These triazylstilbene-based brighteners are preferably used in the range of 0.2 to 6 g, more preferably 0.4 to 3 g, per color developing solution used in the present invention.

The color developer used in the invention may contain the following developer components in addition to the above components.

As an alkali agent other than the above carbonate, for example, sodium hydroxide, potassium hydroxide, silicate, sodium metaborate, potassium metaborate, trisodium phosphate, tripotassium phosphate, borax or the like alone or in combination, The above-mentioned effects of the present invention, that is, no precipitation occurs, and a pH stabilizing effect can be maintained. Furthermore, various salts such as disodium hydrogen phosphate, dipotassium hydrogen phosphate, sodium bicarbonate, potassium bicarbonate, and borate are used for the purpose of preparation or for the purpose of increasing ionic strength. can do.

If necessary, inorganic and organic antifoggants can be added.

Further, a development accelerator can be used if necessary. As development accelerators, various pyridinium compounds represented by U.S. Pat. Nos. 2,648,604, 3,671,247, and JP-B-44-9503, and other cationic compounds,
Cationic dyes such as phenosafranine, neutral salts such as thallium nitrate, U.S. Pat.Nos. 2,533,990, 2,531,8
No. 32, 2,950,970, 2,577,127, and polyethylene glycol and derivatives thereof described in JP-B-44-9504, nonionic compounds such as polythioethers, organic solvents described in JP-B-44-9509 and Organic amine, ethanolamine, ethylenediamine, diethanolamine, triethanolamine and the like are included. In addition, benzyl alcohol and phenethyl alcohol described in US Pat. No. 2,304,925, and acetylene glycol, methyl ethyl ketone, cyclohexanone, thioethers, pyridine, ammonia, hydrazine, amines and the like can also be mentioned.

In the above, particularly for poorly soluble organic solvents represented by benzyl alcohol, tar is liable to be generated particularly in running processing in a low replenishment method by using the color developing solution for a long time, and the generation of such tar is Adhesion to the processed paper light-sensitive material may even lead to a serious failure that significantly impairs its commercial value.

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

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 labor and cost,
It is preferable to reduce or eliminate the usage as much as possible.

Further, the color developing solution used in the present invention, if necessary, ethylene glycol, methyl cellosolve, methanol, acetone, dimethylformamide, β-cyclodextrin, other JP-B-47-33378, JP 44-9509 The compounds described can be used as organic solvents for increasing the solubility of the developing agents.

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'-tetra Methyl-p-phenylenediamine hydrochloride and the like are known, and the addition amount thereof is usually preferably from 0.01 g to 1.0 g / l. In addition, if necessary, competing couplers, fogging agents, colored couplers, development inhibitor releasing couplers (so-called DIR)
Coupler) or a development inhibitor releasing compound.

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

Each component of the color developing solution can be prepared by sequentially adding to a certain amount of water and stirring. In this case, the component having low solubility in water can be added as a mixture with the organic solvent such as triethanolamine. More generally, a concentrated aqueous solution containing a plurality of components each of which can stably coexist, 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. Obtainable.

In the present invention, the above-mentioned color developing solution can be used in an arbitrary pH range, but is preferably from pH 9.5 to 13.0, more preferably from pH 9.8 to 13.0, from the viewpoint of rapid processing.

In the present invention, the processing temperature of the color development is 30 ° C. or higher and 50 ° C. or lower, and the higher the temperature, the faster the processing can be performed in a shorter time, which is preferable.On the other hand, the higher the image storage stability, the better. Preferably, the treatment is carried out at a temperature of from 33 ° C to 45 ° C.

Conventionally, the color development time is generally about 3 minutes and 30 seconds, but in the present invention, it can be made within 2 minutes, and can be performed in the range of 30 seconds to 1 minute and 30 seconds. It is.

In the method for processing a silver halide color photographic light-sensitive material of the present invention, the color developing solution contains at least one compound selected from the compounds represented by the general formulas [I] and [II] and further has a sulfite concentration. Using a color developing solution having a concentration of 4 × 10 ^-3 mol or less per one bath treatment and other various methods, for example, a spray method of spraying a processing solution, or impregnating with a processing solution. Various processing methods such as a wet method by contact with a carrier or a developing method using a viscous processing solution can be used, but the processing steps are substantially the same as steps of color development, bleach-fixing, washing with water or stabilization processing instead of this. Become.

The bleach-fixing step of the present invention is bleach-fixing in which bleaching and fixing are performed in a single bath, and is performed with the pH of the bleach-fix solution in the range of 4.5 to 6.8. For this reason, in the present invention, it is possible to effectively prevent the generation of stain, which easily occurs in the bleach-fix solution.

Bleaching agents that can be preferably used in the bleach-fixing solution used in the present invention are metal complex salts of organic acids. The complex salt is obtained by coordinating a metal ion such as iron, cobalt and copper with an organic acid such as aminopolycarboxylic acid or oxalic acid or citric acid. The most preferred organic acids used to form such metal complexes of organic acids include polycarboxylic acids. These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts. Specific examples of these are as follows.

[1] Ethylenediaminetetraacetic acid [2] Diethylenetriaminepentaacetic acid [3] Ethylenediamine-N- (β-oxyethyl)
-N, N ', N'-triacetic acid [4] propylenediaminetetraacetic acid [5] nitrilotriacetic acid [6] cyclohexanediaminetetraacetic acid [7] iminodiacetic acid [8] dihydroxyethylglycine citric acid (or tartaric acid) [9] Ethyl ether diamine tetra acetic acid [10] Glycol ether diamine tetra acetic acid [11] Ethylene diamine tetrapropionic acid [12] Phenylenediamine tetra acetic acid [13] Ethylene diamine tetra acetic acid disodium salt [14] Ethylene diamine tetra acetic acid tetra (trimethyl ammonium) salt [15] ] Ethylenediaminetetraacetic acid tetrasodium salt [16] Diethylenetriaminepentaacetic acid pentasodium salt [17] Ethylenediamine-N- (β-oxyethyl)
-N, N ', N'-triacetate sodium salt [18] Propylenediaminetetraacetate sodium salt [19] Nitriloacetate sodium salt [20] Cyclohexanediaminetetraacetate sodium salt These bleaching agents are 5-450 g / l and more. Preferably 20-15
Use at 0g / l. To the bleach-fixing solution, a solution having a composition containing a silver halide fixing agent in addition to the bleaching agent as described above and, if necessary, a sulfite as a preservative is applied. Also,
A bleach-fixing solution having a composition in which a small amount of a halide such as ammonium bromide is added to the above-mentioned silver halide fixing agent, and a halide such as ammonium bromide. It is possible to use a bleach-fixing solution having a composition added in a large amount, or a special bleach-fixing solution having a composition comprising a combination of an iron (III) complex salt of ethylenediaminetetraacetate and a large amount of a halide such as ammonium bromide. it can. As the halide, in addition to ammonium bromide, hydrogen chloride solution, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, and the like may be used. it can.

As the silver halide fixing agent contained in the bleach-fix solution, a compound capable of forming a water-soluble complex salt by reacting with silver halide used in a usual fixing process, for example, potassium thiosulfate, sodium thiosulfate, thiol Representative examples thereof include thiosulfates such as ammonium sulfate, potassium thiocyanate, sodium thiocyanate, thiocyanates such as ammonium thiocyanate, thiourea, and thioether. These fixing agents are used in an amount of 5 g / l or more, which can be dissolved, but generally used in an amount of 30 to 150 g / l.

In addition, boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate,
Various pH buffers such as sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate and ammonium hydroxide can be used alone or in combination of two or more.
Furthermore, various fluorescent whitening agents, antifoaming agents or surfactants can be added. Preservatives such as hydroxylamine, hydrazine and bisulfite adducts of aldehyde compounds; organic chelating agents such as aminopolycarboxylic acids; and stabilizers such as nitro alcohols and nitrates; organic compounds such as methanol, dimethylsulfamide and dimethylsulfoxide. A solvent or the like can be appropriately contained.

The bleach-fixing solution used in the present invention includes JP-A-46-280, JP-A-45-8506, JP-A-46-556, and Belgian Patent No. 770,910.
And various bleaching accelerators described in JP-B-45-8836, JP-B-53-9854, JP-A-54-71634 and JP-A-49-42349.

The processing temperature is 80 ° C. or less and the temperature is 3 ° C. or more, preferably 5 ° C. or more lower than the temperature of the processing solution in the color developing tank.

The halide grains used in the silver halide color photographic light-sensitive material applied to the present invention contain silver chloride of at least 80.
The silver halide grains contain at least 90 mol%, more preferably at least 90 mol%, and still more preferably at least 95 mol%.

The silver halide emulsion containing silver halide grains composed of 80 mol% or more of silver chloride can contain silver bromide and / or silver iodide as a silver halide composition in addition to silver chloride.
In this case, silver bromide is not more than 20 mol%, preferably 10 mol%.
Or less, more preferably 5 mol% or less, and when silver iodide is present, 1 mol% or less, preferably 0.5 mol%.
It is as follows. Such silver halide grains substantially consisting of silver chloride according to the present invention contain at least 80% by weight of all silver halide grains in the silver halide emulsion layer containing the silver halide grains. Preferably, it is 100%.

The crystals of the silver halide grains used in the present invention may be normal crystals, twin crystals or other crystals, and any ratio of {100} plane to {111} plane can be used. Further, the crystal structure of these silver halide grains may be uniform from the inside to the outside, or may be a layered structure (core-shell type) in which the inside and the outside are different. 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-58-113934, Japanese Patent Application No.
0070) can also be used.

The silver halide grains used in the present invention may be obtained by any of the preparation methods such as an acid method, a neutral method, and an ammonia method.

Alternatively, for example, a method may be used in which seed particles are formed by an acidic method and further grown by an ammonia method having a high growth rate to grow to a predetermined size. When growing silver halide grains, controlling the pH, pAg, etc. in the reaction vessel, for example, silver ions in an amount commensurate with the growth rate of silver halide grains as described in Japanese Patent Application No. 54-48521. And halide ions are preferably sequentially and simultaneously injected and mixed.

The preparation of the silver halide grains according to the present invention is preferably carried out as described above. The composition containing the silver halide grains is referred to herein as a silver halide emulsion.

These silver halide emulsions include active gelatin; sulfur sensitizers such as allyl thiocarbamide, thiourea, and cystine; selenium sensitizers; reduction sensitizers such as stannous salts and thiodioxide. Urea, polyamines and the like; noble metal sensitizers such as gold sensitizers, specifically, potassium aurithiocyanate, potassium chloroaurate, 2-aurothio-3-methylbenzothiazolium chloride and the like, or ruthenium, palladium, platinum, Sensitizers of water-soluble salts such as rhodium and iridium, specifically, ammonium chloroparadate, potassium chloroplatinate and sodium chloroparadate (some of these may be sensitizers or fog suppression depending on the amount thereof). Acting alone or in combination as appropriate (for example, a gold sensitizer and a sulfur sensitizer). Combination of agents, together like a gold sensitizer and a selenium sensitizer) may be chemically sensitized with.

The silver halide emulsion according to the present invention is subjected to chemical ripening by adding a sulfur-containing compound, and before, during or after the chemical ripening, a nitrogen-containing heteroatom having at least one hydroxytetrazaindene and a mercapto group. At least one kind of a ring compound may be contained.

The silver halide used in the present invention may contain an appropriate sensitizing dye in an amount of from 5 × 10 ^{−3 to} 3 × 10 ⁻³ per mole of silver halide in order to impart photosensitivity to a desired photosensitive wavelength range. Optical sensitization may be performed by adding a mole. Various sensitizing dyes may be used, and one or two sensitizing dyes may be used.
It can be used in combination of more than one species. Examples of the sensitizing dye advantageously used in the present invention include the following.

That is, examples of sensitizing dyes used in blue-sensitive silver halide emulsions include, for example, West German Patent 929,080 and U.S. Pat.
No. 58, No. 2,493,748, No. 2,503,776, No. 2,519,001
Nos. 2,912,329, 3,656,959, 3,672,897,
Nos. 3,694,217, 4,025,349, 4,046,572, British Patent 1,242,588, JP-B-44-14030, and JP-A-52-24844 can be mentioned. As sensitizing dyes used in green-sensitive silver halide emulsions, for example, U.S. Pat.Nos. 1,939,201, 2,072,908, and 2,739,149
No. 2,945,763, and British Patent No. 505,979, representative of which are cyanine dyes, merocyanine dyes and complex cyanine dyes. Further, as sensitizing dyes used in red-sensitive silver halide emulsions, for example, U.S. Patent Nos. 2,269,234 and 2,270,3
No. 78, No. 2,442,710, No. 2,454,629, No. 2,776,280 and the like can be cited as typical examples of cyanine dyes, merocyanine dyes and composite cyanine dyes. Furthermore, U.S. Pat.No.2,213,995,
Cyanine dyes, merocyanine dyes or complex cyanine dyes as described in 2,493,748, 2,519,001, West German Patent 929,080 and the like can be advantageously used in a green-sensitive silver halide emulsion or a red-sensitive silver halide emulsion.

These sensitizing dyes may be used alone or in combination.

The photographic light-sensitive material of the present invention may be optically sensitized to a desired wavelength region by a spectral sensitization method using a cyanine or merocyanine dye alone or in combination, if necessary.

Representative examples of particularly preferred spectral sensitization methods include, for example, Japanese Patent Publication No. 43-4936 (JP-B-43-4936) relating to a combination of benzimidazolocarbocyanine and benzoxazolocarbocyanine.
Nos. 43-22884, 45-18433, 47-37443, 48-2
No. 8293, No. 49-6209, No. 53-12375, JP-A-52-23931
Nos. 52-51932, 54-80118, 58-153926, 59-
And the methods described in JP-A-116646 and JP-A-59-116647.

Examples of the combination of a carbocyanine having a benzimidazole nucleus with another cyanine or merocyanine include, for example, JP-B-45-25831, JP-B-47-11114, and JP-B-47-11114.
47-25379, 48-38406, 48-38407, 54-34535
No. 55-1569, JP-A-50-33220, JP-A-50-38526, 51-
107127, 51-115820, 51-135528, 52-10491
No. 6, No. 52-104917 and the like.

Further, as for the combination of benzoxazolocarbocyanine (oxacarbocyanine) with other carbocyanines, see, for example, JP-B-44-32753 and JP-B-46-11627.
Nos., JP-A-57-1483, and those relating to merocyanine include, for example, JP-B-48-38408, JP-B-48-41204, and JP-B-50-406.
No. 62, JP-A-56-25728, JP-A-58-10753, 58-91445,
Nos. 59-116645 and 50-33828.

As for the combination of thiacarbocyanine with other carbocyanines, see, for example, JP-B-43-4932 and JP-B-43-4932.
3-4933, 45-26470, 46-18107, 47-8741,
JP-A-59-114533 and the like, and the method described in JP-B-49-6207 using zero-methine or dimethine merocyanine, monomethine or trimethine cyanine and styryl dye can be advantageously used.

In order to add these sensitizing dyes to the silver halide emulsion according to the present invention, a dye solution such as methyl alcohol, ethyl alcohol, acetone, dimethylformamide, or a fluorinated alcohol described in JP-B-50-40659 is used in advance. Used by dissolving in a hydrophilic organic solvent.

The timing of addition may be at any time at the start of chemical ripening of the silver halide emulsion, during ripening, or at the end of ripening. In some cases, it may be added to the step immediately before the emulsion coating.

To the photographic constituent layers of the silver halide color photographic light-sensitive material of the present invention, a dye (AI dye) capable of decolorizing with a water-soluble or color developing solution can be added. Examples of the AI dye include an oxonol dye and a hemioxonol. Dyes, merocyanine dyes and azo dyes are included. Among them, oxonol dyes,
Hemioxonol dyes and merocyanine dyes are useful. Examples of AI dyes that can be used include UK Patent 584,609
No. 1,277,429, JP-A-48-85130, 49-99620
Nos. 49-114420, 49-129537, 52-108115, 5
9-25845, 59-111640, 59-111641, U.S. Patent 2,2
74,782, 2,533,472, 2,956,079, 3,125,44
No. 8, No. 3,148,187, No. 3,177,078, No. 3,247,127,
3,260,601, 3,540,887, 3,575,704, 3,6
No. 53,905, No. 3,718,472, No. 4,071,312, No. 4,070,35
No. 2 can be mentioned.

These AI dyes are generally used in two moles per mole of silver in the emulsion layer.
It is preferable to use from 10 ^{-3 to} 5 x 10 ^-1 mol, more preferably from 1 x 10 ^-2 to 1 x 10 ^-1 mol.

The photographic coupler used in the present invention is preferably a phenol-based compound or a naphthol-based compound as a cyan coupler, for example, U.S. Patent Nos. 2,369,929 and 2,43.
4,272, 2,474,293, 2,895,826, 3,253,924
Nos. 3,034,892, 3,311,476, 3,386,301,
3,419,390, 3,458,315, 3,476,563, 3,5
Nos. 91,383 and the like, and methods for synthesizing those compounds are also described in the publication.

Examples of magenta couplers for photography include pyrazolone-based, pyrazolotriazole-based, pyrazolino-benzimidazole-based and indazolone-based compounds. Pyrazolone-based magenta couplers include U.S. Pat.
Nos. 3,062,653, 3,127,269, 3,311,476,
3,419,391, 3,519,429, 3,558,318, 3,6
No. 84,514, No. 3,888,680, JP-A-49-29639, No. 49-11
No. 1631, No. 49-129538, No. 50-13041, Special Publication No. 53-47167
Nos. 54-10491 and 55-30615; pyrazolotriazole-based magenta couplers include couplers described in U.S. Pat. No. 1,247,493 and Belgian Patent 792,525; As the magenta coupler, a compound in which an arylazo is substituted at the coupling position of a colorless magenta coupler is used, for example, U.S. Pat.Nos. 2,801,171 and 2,983,608,
3,005,712, 3,684,514, UK Patent 937,621,
Compounds described in JP-A-49-123625 and JP-A-49-31448 are exemplified.

Further, a colored magenta coupler of the type described in U.S. Pat. No. 3,419,391 in which a dye flows out into a processing solution by reaction with an oxidized form of a developing agent can also be used.

As a photographic yellow coupler, an open-chain ketomethylene compound has been conventionally used, and a benzoylacetanilide-type yellow coupler generally used widely,
Bivaloylacetanilide type yellow couplers can be used. Further, 2-equivalent yellow couplers in which the carbon atom at the coupling position is substituted with a substituent capable of leaving during the coupling reaction are also advantageously used. Examples of these are U.S. Pat.Nos. 2,875,057 and 3,265,506.
No. 3,664,841, No. 3,408,194, No. 3,277,155,
3,447,928, 3,415,652, JP-B-49-13576, JP-A-48-29432, JP-A-48-68834, 49-10736, and 49-122
No. 335, 50-28834 and 50-132926 are described together with the synthesis method.

The amount of the diffusion-resistant coupler used in the present invention is generally 0.05 to 0.05 mol per mol of silver in the photosensitive silver halide emulsion layer.
~ 2.0 mol.

In the present invention, a DIR compound is preferably used in addition to the above-mentioned diffusion-resistant coupler.

Further, in addition to the DIR compound, compounds that release a development inhibitor upon development are also included in the present invention.
3,297,445, 3,379,529, West German Patent Application (OLS) 2,4
No. 17,914, JP-A-52-15271, JP-A-53-9116, 59-123838
And No. 59-127038.

The DIR compound used in the present invention is a compound capable of reacting with an oxidized form of a color developing agent to release a development inhibitor.

A typical example of such a DIR compound is a DIR coupler in which a group capable of forming a compound having a development inhibiting action when released from the active site is introduced into the active site of the coupler, for example, British Patent 935,454. U.S. Patent 3,22
Nos. 7,554, 4,095,984 and 4,149,886.

When the above DIR coupler is subjected to a coupling reaction with an oxidized form of a color developing agent, the coupler nucleus forms a dye,
On the other hand, it has the property of releasing a development inhibitor. In the present invention, U.S. Patent Nos. 3,652,345, 3,928,041, 3,958,99
No. 3, 3,961,959, 4,052,213, JP-A-53-110529
Nos. 54-13333, 55-161237, etc. include a compound that releases a development inhibitor when subjected to a coupling reaction with an oxidized form of a color developing agent but does not form a dye. .

Further, when reacted with an oxidized form of a color developing agent as described in JP-A-54-145135, JP-A-56-114946 and JP-A-57-154234, the mother nucleus forms a dye or a colorless compound. On the other hand, a so-called timing DIR compound in which the released timing group releases a development inhibitor by an intramolecular nucleophilic substitution reaction or elimination reaction is also included in the present invention.

JP-A-58-160954 and JP-A-58-162949, the timing group as described above is present in a coupler nucleus which generates a completely diffusible dye when reacted with an oxidized form of a color developing agent. It also includes the bound timing DIR compound.

The amount of the DIR compound contained in the light-sensitive material is preferably in the range of 1 × 10 ^-4 mol to 10 × 10 ^-1 mol per mol of silver.

The silver halide color photographic light-sensitive material used in the present invention may further contain various photographic additives. For example, antifoggants, stabilizers, ultraviolet absorbers described in Research Disclosure Magazine No. 17643,
Color stain inhibitors, fluorescent brighteners, color image fading inhibitors, antistatic agents, hardeners, surfactants, plasticizers, wetting agents and the like can be used.

In the silver halide color photographic light-sensitive material used in the present invention, hydrophilic colloids used for preparing emulsions include gelatin, derivative gelatin, graft polymers of gelatin and other polymers, proteins such as albumin and casein. , Hydroxyethyl cellulose derivatives, cellulose derivatives such as carboxymethyl cellulose, starch derivatives, polyvinyl alcohol, polyvinyl imidazole,
An arbitrary one such as a single or copolymer synthetic hydrophilic polymer such as polyacrylamide is included.

Examples of the support of the silver halide color photographic light-sensitive material used in the present invention include, for example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, a transparent support having a reflective layer, or a reflective plate, such as a glass plate, Examples include a polyester film such as cellulose acetate, cellulose nitrate or polyethylene terephthalate, a polyamide film, a polycarbonate film, a polystyrene film, and the like, and may be other ordinary transparent supports. These supports are appropriately selected according to the purpose of use of the light-sensitive material.

Various coating methods such as dipping coating, air doctor coating, curtain coating, and hopper coating can be used for coating the silver halide emulsion layer and other photographic constituent layers used in the present invention. U.S. Patent 2,761,79
A simultaneous coating method of two or more layers according to the method described in JP-A Nos. 1 and 2,941,898 can also be used.

In the present invention, the coating position of each emulsion layer can be arbitrarily determined. For example, in the case of a full-color photographic paper light-sensitive material, an arrangement of a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer in this order from the support side is preferred. . Each of these photosensitive silver halide emulsion layers may be composed of two or more layers.

In the light-sensitive material of the present invention, it is optional to provide an intermediate layer having an appropriate thickness according to the purpose. Further, various layers such as a filter layer, an anti-curl layer, a protective layer, and an antihalation layer may be appropriately used as constituent layers. It can be used in combination. In these constituent layers, hydrophilic colloids which can be used in the above-mentioned emulsion layers as binders can be used in the same manner, and the layers can be contained in the above-mentioned emulsion layers. Various photographic additives can be included.

In the method for processing a silver halide color photographic light-sensitive material of the present invention,
Color paper, color negative film, color positive film, color reversal film for slide, color reversal film for movies, color reversal film for TV, as long as the photosensitive material contains a coupler in the photosensitive material and is processed by the so-called internal development method And any silver halide color photographic light-sensitive material such as reversal color paper.

[Specific Effects of the Invention] As described in detail above, in the processing method of a silver halide color photographic light-sensitive material of the present invention, a silver halide grain comprising 80 mol% or more of silver chloride is contained in a silver halide emulsion layer. Since it was contained, rapid development processing became possible.

Further, in the processing method of the present invention, since the concentration of the sulfite as a preservative was set at 4 × 10 ⁻³ mol or less per color developing solution, no decrease in the dye concentration due to the silver development reaction occurred.

Further, in the present invention, since the pH of the bleach-fixing solution used in the bleach-fixing step was in the range of 4.5 to 6.8, generation of bleaching fog, that is, stain in the bleach-fixing solution, was prevented.

In addition, in the present invention, the compound represented by the general formula [I] and / or [II] is contained in the color developing solution, thereby preventing bleaching fog, that is, generation of stain in the bleach-fixing solution.

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

Example 1 The following layers were sequentially coated on a polyethylene-laminated paper support from the support side to prepare a photosensitive material sample.

Layer 1: dissolved in 1.1 g / m ² gelatin, 0.40 g / m ² (silver equivalent, the same applies hereinafter) blue-sensitive silver chlorobromide emulsion (95 mol% as AgCl) and 0.50 g / m ² dioctyl phthalate A layer containing 1.10 × 10 ⁻³ mol g / m ² of the following yellow coupler (Y-1).

Layer 2: an intermediate layer made of 0.6 g / m ² of gelatin.

Layer 3 ...... 1.20g / m ² of gelatin, green (98 mol% as AgCl) sensitive silver chlorobromide emulsion and 0.27 g / m ² of 0.95 × 10 ^-3 mol, dissolved in dioctyl phthalate 0.25 g / m ² A layer containing g / m ² of the following magenta coupler (M-1).

Layer 4: an intermediate layer made of 1.4 g / m ² gelatin.

Layer 5: 1.5 × 10 ⁻³ dissolved in 1.4 g / m ² gelatin, 0.37 g / m ² red-sensitive silver chlorobromide emulsion (98 mol% as silver chloride) and 0.23 g / m ² dibutyl phthalate Layer containing mol g / m ² of the following comparative cyan coupler (C-1).

Layer 6: Layer containing 1.0 g / m ² of gelatin and 0.25 g / m ² of Tinuvin 328 (an ultraviolet absorber manufactured by Ciba Geigy) dissolved in 0.250 g / m ² of dioctyl phthalate.

Layer 7: Layer containing 0.48 g / m ² of gelatin.

As a hardening agent, sodium 2.4-dichloro-6-hydroxy-s-triazine was added to Layers 2, 4 and 7 so that each layer contained 0.015 g per 1 g of gelatin.

Next, these samples were subjected to wedge-shaped exposure by a conventional method, and then subjected to the following development processing.

Processing step Processing temperature Processing time [1] Color development 35 ° C 45 seconds [2] Bleaching and fixing 35 ° C 45 seconds [3] Washing 30 ° C 90 seconds [4] Drying 60 to 80 ° C 60 seconds Color developing solution used and bleach-fixing The liquid used had the following composition.

(Color developing solution)-Potassium chloride 2.0 g-Potassium sulfite (described in Table 1)-Sodium polyphosphate 2.0 g-Color developing agent (Exemplified compound A-1) 5.6 g-Potassium carbonate 30 g-Chelating agent (described in Table 1) (Compound of the present invention) 1 g-Optical brightener (described in Table 1) 2 g Add water to make 1 and adjust the pH with potassium hydroxide and 50% sulfuric acid.
Adjust to 10.15.

[Bleach-fixing solution] Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60.0 g Ethylenediaminetetraacetic acid 3.0 g Ammonium thiosulfate (70% solution) 100.0 ml Ammonium sulfite (40% solution) 27.5 ml Adjust the pH with potassium or glacial acetic acid as described in Table 1.

However, Fe ³⁺ (3 ppm) and Cu ²⁺ (1
ppm), 250 ml of the color developing solution was added to the bleach-fixing solution, and the mixture was stored at 45 ° C. for 3 days, and then subjected to a developing treatment.

Using a sample after development processing, a Sakura photoelectric densitometer PDA-65 (manufactured by Konishi Roku Kogyo Co., Ltd.) is used. The coupling speed is fast, and the magenta density in the unexposed area where fogging is a problem and the development speed are slow, and the color density is low. The yellow density of the highest density part where no blemishes appeared was measured.

 The results are summarized in Table 1.

As apparent from Table 1, the sulfite concentration in the color developing solution is in the range of 4 × 10 ⁻³ mol / l or less, and the sulfonate represented by the general formula [I] or [II] according to the present invention is used. It contains the compound (chelating agent) of the present invention, and furthermore, the pH of the bleach-fixing solution is
In the range of 4.5 to 6.8, and when a specific optical brightener is contained, a sufficient yellow dye density is obtained despite the extremely short color development time of 45 seconds, and the unexposed portion It can be seen that the occurrence of magenta stain is small.
However, the sulfite concentration in the color developing solution or the presence or absence of the compound represented by the general formula [I] or [II] according to the present invention, or the pH of the bleach-fixing solution is outside the range of the present invention or when the fluorescent brightening is performed. Depending on the presence or absence of the agent, a problem such as an insufficient yellow dye concentration or a large amount of magenta stain occurs, which lowers the commercial value. When the unexposed area magenta density is 0.01, the white background is almost pure white but 0.03
The degree is slightly pinkish, and the commercial value is reduced.

When the color developer after storage was observed, tar was generated when the compound of the present invention was not added.

Example 2 The color developing agent (A-) in the color developing solution used in Example 1 was used.
When the same experiment was performed by changing 1) to the following (B-1) or (B-2), the magenta stain in the unexposed portions was deteriorated by 0.02 in all cases. Similarly, the color developing agent (A-1) of Example 1 was replaced with the exemplified compound (A-2),
When the same experiment as in Example 1 was performed by changing to (A-4) and (A-15), almost the same results were obtained.

 ──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-63-502222 (JP, A) JP-A-59-111147 (JP, A) JP-A-58-144071 (JP, A) JP-A-59-104 49537 (JP, A)

Claims (1)

(57) [Claims] An imagewise exposure of a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer, followed by a processing including a bleach-fixing step, followed by a processing step including at least a color developing step. In the method for processing a silver halide color photographic light-sensitive material, the silver halide emulsion layer is a silver halide emulsion layer containing silver halide grains of 80 mol% or more of silver chloride, and is used in the color development step. The color developing solution used is represented by the following general formula [I]
And at least one compound selected from the compounds represented by the general formula [II] and the general formula [X
V], at least one of a triazylstilbene-based fluorescent brightener represented by formula (I) and a sulfite concentration of 4 × 10 ⁻³ mol or less per color developing solution, and further used in the bleach-fixing step. A method for processing a silver halide color photographic light-sensitive material, wherein the bleach-fix solution obtained has a pH in the range of 4.5 to 6.8. General formula [I] General formula [II] (Wherein R ₁ , R ₂ , R ₃ and R ₄ are each a hydrogen atom, a halogen atom, a sulfonic acid group, an alkyl group having 1 to 7 carbon atoms, —OR ₅ , —COOR ₆ , Or, it represents a phenyl group. R ₅ , R ₆ , R ₇ and R ₈ each represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. However, when R ₂ represents -OH or a hydrogen atom, R ₁
Halogen atom, a sulfonic acid group, an alkyl group having a carbon number of 1 to 7, -OR _5, -COOR ₆ is Or, it represents a phenyl group. ) General formula [XV] (In the formula, X ₁ , X ₂ , Y ₁ and Y ₂ each represent a hydroxyl group, a halogen atom, a morpholino group, an alkoxy group, an aryloxy group, an aryl group, an amino group, an alkylamino group, or an arylamino group. Represents a hydrogen atom, sodium, potassium, ammonium or lithium.)