JPH07117720B2 - Color developing solution for silver halide color photographic light-sensitive materials with improved safety and homeostasis - Google Patents

Description

Detailed Description of the Invention

FIELD OF THE INVENTION The present invention relates to a color developing solution for silver halide color photographic light-sensitive materials, and more specifically, a silver halide color using a preservative in place of hydroxylamine, which is harmful and harmful to humans. The present invention relates to a color developing solution for photographic light-sensitive materials. BACKGROUND OF THE INVENTION In color development, exposed silver halide is reduced to silver and simultaneously oxidized primary aromatic amine developing agent reacts with a 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 heavy metal ions contained in other processing solutions such as bleaching solutions and bleach-fixing solutions are also brought into and accumulated in the color developing solution by so-called back contamination. A color developer used for such color development usually contains a sulfite or a water-soluble salt of sulfite and hydroxylamine as a preservative (antioxidant) in order to increase the preservability. Among them, like the former, when the sulfite is used alone, fogging occurs remarkably over time.Therefore, by using the sulfite and the water-soluble salt of hydroxylamine together, the stability of the developer is maintained. Is significantly increased, and the generation of fogging due to aged developer is reduced. However, hydroxylamine has the following drawbacks and disadvantages. First, it was reported that hydroxylamine is harmful to the human body [eg PGStecher, “The Merck
Index An Encyclopedia of Chemical and Drugs "8th.Ed. (195
3 years)]. Secondly, even in the Poisonous and Deleterious Substances Control Law, in order to handle and sell hydroxylamine salt, it is necessary to register a general sales agent for poisonous and deleterious substances and to set up a person in charge of handling, which is extremely inconvenient to handle. Is. Thirdly, hydroxylamine is a kind of black-and-white developer and has silver developability with respect to silver halide. Therefore, the utilization efficiency of silver halide in the silver halide color photographic light-sensitive material is poor, and it is necessary to use more silver halide or coupler in the light-sensitive material in order to obtain a desired dye concentration, which is economical. Is extremely detrimental to. Fourth, hydroxylamine decomposes when heavy metal ions (for example, iron ions or copper ions) are mixed in the color developing solution to produce ammonia, which causes fogging on the color light-sensitive material and also improves photographic performance. It has a drawback that it has a bad effect on From the viewpoint of economical efficiency and pollution, color developers tend to be low in replenishment in recent years, and the grade of raw materials such as potassium carbonate is being reduced for the purpose of cost reduction. The amount of the heavy metal ions accumulated in the developing solution is increasing more and more. For this reason, the fourth problem “occurrence of fogging” due to the decomposition of hydroxylamine is becoming more severe. Therefore, in the future, when performing in-house self-treatment or color copying equipped with a color developing system, it is strongly desired to develop a preservative that replaces hydroxylamine because of pollution problems. As preservatives replacing hydroxylamine, 2-anilinoethanol and dihydroxyalkene have been proposed in US Pat. Nos. 3,823,017 and 3,615,503, respectively. However, in all of these compounds, the compound itself is unstable, and the preservative effect in the color developing solution is extremely weak. On the other hand, in a developer (for black and white photography) containing hydroquinone or N-alkyl-p-aminophenol as a developing agent, sucrose (sucrose) is known as a preservative, but sucrose is an aromatic primary amine. A color developing solution containing as a developing agent has little effect as a preservative. Further, ascorbic acid and its derivatives are known as preservatives for black-and-white photographic developers and color developers, but they have a drawback that they inhibit color formation and cause a remarkable decrease in color density. Inferior to amines. Further, α-hydroxy aromatic alcohols described in JP-A-52-7779, hydroxamic acid compounds described in JP-A-52-27638, α-aminocarbonyl compounds described in JP-A-52-143020, and JP-A-52-102727 are described. Of the above-mentioned monosaccharides and amino acid derivatives described in No. 52-140324 are disclosed. However, when a large amount of monosaccharides and amino acid derivatives are used,
Although it shows a considerable degree of homeostasis at room temperature, it is easily decomposed by heat and has undesirable characteristics in terms of pollution. And D-glucosamine hydrochloride is known as a typical compound of the α-aminocarbonyl compound, but this compound is inferior in preservability to hydroxylamine. Further, the hydroxamic acid compound has the same level of preservative property as hydroxylamine, but has the disadvantage of high cost. Japanese Patent Publication No. 61-48698 discloses a technique in which hydroxylamine or its derivative and a bisulfite adduct of aldehyde are used together as a preservative for a color developing solution.
JP-A No. 1994-242 discloses a technique in which diethanolamine is further used in combination with the above constitution. According to the study by the present inventors, the above configuration is insufficient as the preservation ability. Therefore, it is easily conceivable that a sulfite coexists in order to enhance the preservative ability, but it was revealed that the following problems occur when the sulfite coexists. First, there is a problem that the density of the coloring pigment decreases. It is known that the concentration of the coloring dye decreases when the amount of sulfite added is increased. However, according to the study of the present inventors, a photosensitive material having a higher silver chloride content has a greater coloring dye concentration. It turned out to be easy to fall. Secondly, when used in a color developer for direct positive image formation, for example, a color developer represented by photo-fog development, increasing the amount of sulfite tends to cause yellow stains, resulting in a large loss of image quality. The problem also turned out. Third, in the case of rapid processing development, the presence of sulfite ion concentration and hydroxylamine greatly affects the rapidity, and it is necessary to reduce sulfite ion concentration as much as possible and to use no hydroxylamine. There is a problem that the homeostasis tends to deteriorate. Therefore, it is possible to lower the sulfite ion concentration,
Moreover, according to the study by the present inventors, the homeostasis is not significantly deteriorated even if the sulfurous acid concentration is lowered, and it is rather sufficient to coexist with sulfite to some extent as the homeostasis ability. I understood. However, as a result of further study by the present inventors, it was found that there are the following two problems. First, unexpectedly insufficient preserving ability of the color developing solution when low replenishment processing is performed due to high-temperature rapid processing and pollution control measures. Secondly, when aldehyde bisulfite is used. This means that floating substances are generated on the surface of the treatment liquid, the filter is clogged, the circulation becomes poor, and the treatment characteristics become unstable. OBJECTS OF THE INVENTION Accordingly, an object of the present invention is to solve the above-mentioned drawbacks, to contain a preservative which is harmless to the human body and is easy to handle, and has improved preservative properties as compared with a conventional color developer, and has photographic properties. It is intended to provide a color developing solution which can be rapidly processed without giving much influence to [Constitution of the Invention] The above object of the present invention is to contain a bisulfite addition compound of an aldehyde and to contain sulfite ion at 1.0 × 10 ⁻⁴ per 1
It is achieved by a color developer for silver halide color photographic light-sensitive material, which contains a concentration of from 1 mol to 1.5 × 10 ^-2 mol and more, and further contains a hydroxylamine derivative represented by the following general formula [1]. General formula [1] In the formula, R ₁ and R ₂ each represent a hydrogen atom or an optionally substituted alkyl group. However, R ₁ and R ₂ are not hydrogen atoms at the same time. The combined use of an aldehyde bisulfite addition compound with sulfite is described in JP-B-61-48698 and JP-A-61-48699, and from the viewpoint of homeostasis, it is sufficient to use a large amount of the compound. It can be easily presumed that the composition has a homeostatic property, but there is also a problem in that, for example, photographic characteristics cause a decrease in color dye concentration, and the addition amount dependency is large, so that the optimum addition amount is limited. ing. According to the study by the present inventors, a photosensitive material having a higher silver chloride content for rapid processing has a higher dependency on the sulfite ion concentration, and even a high silver bromide-containing photosensitive material can be directly positive photosensitive material depending on the amount of sulfite. It was found that there was a marked difference in the degree of yellow stain. Further, from the viewpoint of homeostasis, it is presumed that the higher the sulfite ion concentration is, the higher the homeostasis ability is as described above. However, according to the study by the present inventors, it is certain that the sulfite concentration is increased to some extent. Although there is an advantage that the number of days of occurrence of tarling is shortened, the deterioration rate of sulfurous acid depends on the residual concentration of sulfurous acid, so that the deterioration rate becomes faster and, as a result, the remarkable homeostatic ability is increased. It turns out that I can't hope for a rise. However, when it is used in combination with an aldehyde bisulfite adduct, even if the sulfite concentration is lowered, the homeostasis does not significantly deteriorate, and rather the presence of a certain amount of sulfite is sufficient as the homeostasis ability. I found out. However, as described above, as a result of the examination by the present inventors, it was found that there are the following two problems. First, unexpectedly insufficient preserving ability of the color developing solution when low replenishment processing is performed due to high-temperature rapid processing and pollution control measures. Secondly, when aldehyde bisulfite is used. This means that floating substances are generated on the surface of the treatment liquid, the filter is clogged, the circulation becomes poor, and the treatment characteristics become unstable. Such a fact has never been known so far and was unexpected for the present inventors. According to the study by the present inventors, the following points are greatly improved by using a bisulfite addition compound of an aldehyde and a derivative of a specific hydroxylamine, further, the sulfite ion concentration in the color developing solution is improved. It was found that the presence thereof at a concentration of 1.5 × 10 ^-2 mol / l or lower improves the efficiency better. Firstly, the stability of the color developing solution is greatly improved, secondly, when the bisulfite addition compound of aldehyde is used, no suspended matter generated over time is generated at all, and further thirdly In the case of rapid processing, for example, when processing a light-sensitive material having an increased silver chloride content, hydroxylamine causes a large decrease in density, whereas a color developer using a hydroxylamine derivative causes almost no decrease in density. It is suitable for rapid processing, and fourthly, by using a hydroxylamine derivative together, stains that are considered to be caused by anti-irradiation dyes are prevented, and further color development is performed in light fog development using direct positive photosensitive material. It was clarified that the filter effect due to the coloring of the liquid was reduced and stable photographic performance was obtained. Therefore, according to the present invention, it is possible to provide a stable color developing solution whose preservability is improved more than that of the color developing solution using hydroxylamine and which does not impair photographic performance. Further, it was possible to provide a color developing solution suitable for rapid processing and light fog development. The aldehyde bisulfite addition compound preferably used in the present invention is a compound represented by the following general formula [2] or [3]. General formula [2] General formula [3] A ₁ , A ₂ , A ₃ and A ₄ each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a formyl group, an acyl group or an alkenyl group, M represents an alkali metal atom, and n represents 0 to 4 Represents an integer. The alkyl group having 1 to 6 carbon atoms includes linear or branched ones, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, an isopentyl group, a hexyl group and an isohexyl group. Or may be substituted, and specifically, formyl group (for example, each group such as formylmethyl and 2-formylethyl), amino group (for example, each group such as aminomethyl and aminoethyl),
Hydroxyl group (eg, each group such as hydroxymethyl, 2-hydroxyethyl, 2-hydroxypropyl), alkoxy group (eg, each group such as methoxy, ethoxy, etc.), halogen atom (eg, chloromethyl, trichloromethyl, dibromomethyl, etc.) Groups) and the like. Examples of the acyl group include an acetyl group, a propionyl group, a butyryl group and a valeryl group. The alkenyl group includes substituted and unsubstituted groups, the unsubstituted group includes groups such as vinyl and 2-propenyl, and the substituted group includes, for example, 1,2-dichloro-2
Groups such as carboxyvinyl and 2-phenylvinyl. The alkali metal atom represented by M is, for example, sodium or potassium. Hereinafter, specific examples of the aldehyde that forms the addition compound represented by the general formula [2] or [3] will be described, but the present invention is not limited thereto. [Exemplified compound] II-1 formaldehyde II-2 acetaldehyde II-3 propionaldehyde II-4 isobutyraldehyde II-5 n-butyraldehyde II-6 n-valeraldehyde II-7 isovaleraldehyde II-8 methylethylacetaldehyde II- 9 Trimethylacetaldehyde II-10 n-Hexaldehyde II-11 Methyl-n-propylacetaldehyde II-12 Isohexaaldehyde II-13 Glyoxal II-14 Malonaldehyde II-15 Succinaldehyde II-16 Glutaraldehyde II-17 Adipaldehyde II-18 Methylglyoxal II-19 Acetoacetaldehyde II-20 Glycolaldehyde II-21 Ethoxyacetaldehyde II-22 Aminoacetaldehyde II-23 Betainealdehyde II-24 Chloral II-25 Chloroacetoal Hyd II-26 Dichloroacetaldehyde II-27 Bromar II-28 Dibromoacetaldehyde II-29 Iodoacetaldehyde II-30 α-Chloropropionacetaldehyde II-31 α-Bromopropionacetaldehyde II-32 Mucochloric acid Sulfite adducts and acetaldehyde bisulfite adducts are preferred because of their large effects. The amount of aldehyde bisulfite adduct added to the color developing solution is suitably 0.1 to 30 g / l, preferably 0.7 to 10 g / l. In the color developer of the present invention, in order to contain sulfite ion at an ion concentration of 1.5 × 10 ^-2 mol or less per color developer, in addition to the addition of the bisulfite adduct of the aldehyde, a water-soluble sulfite, for example, Sodium sulfite, potassium sulfite, etc. may be added. The color developer of the present invention has a sulfite ion concentration of 1.5 × 1.
0 exceeds ² mol / l and the concentration reduction for the high chloride silver photosensitive material is increased, reduction in preservability is problematic and less than 1.0 × 10 ^-4 mol / l. In the general formula [1], as the substituent of the alkyl group represented by R ₁ and R ₂ , a sulfonic acid group, a hydroxyl group,
Examples thereof include an alkoxy group (methoxy group, ethoxy group, propyloxy group, etc.), a carboxyl group, an amino group, and the like. Examples of these include US Pat. Nos. 3,287,125 and 3,2,3.
Examples thereof include hydroxylamines described in No. 93,034, No. 3,287,124 and the like. The hydroxylamine derivative represented by the general formula [1] is
It is preferable from the viewpoint of improving the homeostasis in comparison with a compound in which R ₁ and R ₂ in the general formula [1] are both hydrogen atoms,
An ethyl group, a methoxyethyl group, in which the C number of R ₁ and R ₂ is 2 or more,
Most preferred are compounds such as ethoxyethyl groups. Preferred specific exemplary compounds represented by the general formula [1] are shown below. _{(1) CH 3 -NH-OH} (2) C 2 H 5 -NH-OH (3) iso-C 3 H 7 -NH-OH (4) C 3 H 7 -NH-OH (5) HO-CH _{2 -NH-OH (6) CH} 3 -O-C 2 H 4 -NH-OH (7) HO-C 2 H 4 -NH-OH (8) HOOC-C 2 H 4 -NH-OH (9) _{HO 3 S-C 2 H 4} -NH-OH (10) N 2 H-C 3 H 6 -NH-OH (11) C 2 H 5 -O-C 2 H 4 -NH-OH (12) HO- _{C 2 H 4 -O-C 2} H 4 -NH-OH These compounds are usually used in the form of salts such as hydrochloride, sulfate, p-toluenesulfonate, oxalate, phosphate and acetate. The concentration of the compound represented by the above general formula [1] in the color developer is usually, for example, preferably 0.1 to 50 g / l, more preferably 0.3 to 30 g / l, particularly preferably 0.5 to 20 g / l. Is. Further, the above compounds may be used in combination of two or more kinds. As the color developing agent used in the color developing solution of the present invention, a p-phenylenediamine compound having a water-soluble group is preferable from the viewpoint of obtaining the effect of the present invention. The p-phenylenediamine compound having a water-soluble group is
Compared with p-phenylenediamine compounds that do not have a water-soluble group such as N, N-diethyl-p-phenylenediamine, they have the advantages that the light-sensitive material is not contaminated and that the skin is less likely to be fogged. 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 3} - (CH 2) n-CH 3, - (CH 2) m-O- (CH 2) n-CH 2, - (CH 2 CH 2 O) nCmH 2m1 (m and n Each represents an integer of 0 or more), —COOH group, —SO ₃ H group and the like. Specific examples of the color developing agent preferably used in the invention are shown below. The above color developing agents are usually used in the form of salts such as hydrochlorides, sulfates and p-toluenesulfonates, and are usually used in the range of 1 × 10 ⁻³ to 2 × 10 ⁻¹ mol per 1 color developing solution. However, from the viewpoint of rapid processing, color developer 1
The range of 1.5 × 10 ^{-3 to} 2 × 10 ^-1 mol is more preferable. The color developing solution of the present invention preferably contains a chelating agent from the viewpoint that the above-mentioned object of the present invention can be achieved to a higher degree.
That is, the deterioration of the color developing solution due to the contamination of heavy metal ions is prevented, and the preservability is improved. Aminopolycarboxylic acid as a preferred chelating agent,
Included are organic phosphonic acids and tyrone derivatives. In particular, the tyrone derivative is preferably used in the sense that it hardly causes precipitation with Ca or Mg in the color developing solution. The aminopolycarboxylic acid is represented by the following general formula [4], and the organic phosphonic acid is represented by the following general formula [5] or [6]. General formula [4] Wherein, E represents an alkylene group, a cycloalkylene group, a phenylene _{group, -B 5 -O-B 5 -} , - B 5 -O-B 5 -O-B 5 - or -B ₅ -Z-B ₅ - the Represent. Z is N-B ₅ -A _5, N-A ₅ 'or Represents B _{1 to} B ₆ each represent an alkylene group.
A ₁ ′ to A ₃ ′ each represent —COOM ′ or PO ₃ (M ′) ₂ , and A ₄ ′ and A ₅ ′ each represent a hydrogen atom, a hydroxyl group,
COOM 'or -PO ₃ (M') represents _2. M'represents a hydrogen atom or an alkali metal atom. General formula [5] In the formula, B ₇ represents an alkyl group, an aryl group or a nitrogen-containing 6-membered ring group. M'represents a hydrogen atom or an alkali metal atom. General formula [6] In the formula, B ₈ , B ₉ and B ₁₀ are each a hydrogen atom, a hydroxyl group,
_{-COOM ', - PO 3 (M} ') represents ₂ or an alkyl group,
L ₁ , L ₂ and L ₃ are a hydrogen atom, a hydroxyl group and -COO, respectively.
_{M ', - PO 3 (M} ') 2 or Represents J represents a hydrogen atom, an alkyl group, -C ₂ H ₄ OH or -PO ₃ (M ') _2. M'represents a hydrogen atom or an alkali metal atom, and n and m are 0 or 1 respectively.
Represents A part of specific examples of the chelating agent represented by the general formula [4], [5] or [6] is shown below. The chelating agent used in the present invention is not limited to the following specific examples. The chelating agent represented by the above general formulas [4] to [6] is preferably used in an amount of 0.01 to 100 g, more preferably 0.05 to 50 g, per 1 color developing solution of the present invention.
Particularly preferably, it is 0.1 to 20 g. The Tyrone derivative is a compound represented by the following general formulas [7] to [10]. General formula [7] General formula [8] In the formula, R ₁₅ , R ₁₆ , R ₁₇ and R ₁₈ are each a hydrogen atom, a halogen atom, a sulfonic acid group, a substituted or unsubstituted alkyl group having 1 to 7 carbon atoms, —OR ₁₉ , —COOR ₂₀ , Alternatively, it represents a substituted or unsubstituted phenyl group. R ₁₉ ,
R ₂₀ , R ₂₁ and R ₂₂ are each a hydrogen atom or a carbon atom number of 1 to 1.
8 represents an alkyl group. n represents an integer of 1 to 3. R ₁₅ may be the same or different. R ₁₅ is preferably a sulfonic acid group. General formula

[9] In the formula, R ₂₃ and R ₂₄ represent a hydrogen atom, a halogen atom or a sulfo group. General formula (10) In the formula, R ₂₉ and R ₃₀ each represent a hydrogen atom, a phosphoric acid group, a carboxylic acid group, —CH ₂ COOH, —CH ₂ PO ₃ H ₂ or a salt thereof, and X
₃ represents a hydroxyl group or a salt thereof, W ₁ , Z ₁ and Y ₁ are each a hydrogen atom, a halogen atom, a hydroxyl group, a cyano group, a carboxylic acid group, a phosphoric acid group, a sulfonic acid group or a salt thereof,
Represents an alkoxy group or an alkyl group. The m ₃ is 0 or 1, n ₃ is an integer from 1 to 4, 1 ₁ 1 or 2, p ₂ is an integer of from 0 to 3, q ₁ is an integer of 0 to 2. Specific examples of the chelating agent represented by the general formulas [7] to [10] are as follows. Among the chelating agents represented by the general formulas [7] to [10],
It is more effective to use the chelating agent represented by [7] or [10], and it is more preferable to use the chelating agent represented by the general formula [10]. It is particularly preferable to use the chelating agent represented by the exemplified chelating agent (45), (49) or (54). 2 of these chelating agents
It is also possible to use a combination of two or more species. The chelating agent represented by any of the above general formulas [7] to [10] used in the present invention is 1 × 10 ⁻⁴ per 1 color developing solution.
It is preferably added in the range of 1 mol to 1 mol, more preferably in the range of 2 × 10 ⁻⁴ to 1 × 10 ⁻¹ mol, and further preferably 5 × 10 ^{−4 to} 5 × 10 ^−. It can be added in the range of ² mol. The color developer of the present invention may contain the following developer components in addition to the above components. As the alkaline agent, for example, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, silicate, sodium metaborate, potassium metaborate, trisodium phosphate, tripotassium phosphate, boric acid, etc., alone or in combination. Can be used. Further, various salts such as disodium hydrogen phosphate, dipotassium hydrogen phosphate, sodium bicarbonate, potassium bicarbonate, borate are used for the necessity of preparation or for the purpose of increasing ionic strength. be able to. Inorganic and organic antifoggants can be added as required. Furthermore, if necessary, a development accelerator can be used. As the development accelerator, various pyridinium compounds represented by U.S. Pat.Nos. 2,648,604, 3,671,247, and Japanese Patent Publication No. 44-9503, other cationic compounds, cationic dyes such as phenosafuran, nitric acid. Neutral salts such as thallium, U.S. Patent Nos. 2,533,990 and 2,53
1,832, No. 2,950,970, No. 2,577,127 and polyethylene glycol and its derivatives described in JP-B-44-9504, nonionic compounds such as polythioethers, organic solvent described in JP-B-44-9509, etc. included. In addition, benzyl alcohol, phenethyl alcohol, and acetylene glycol, methyl ethyl ketone, cyclohexanone, thioethers, pyridine, ammonia, hydrazine, amines and the like described in US Pat. No. 2,304,925 can be mentioned. However, since the color developing solution of the present invention can impart good developing performance without benzyl alcohol harmful to the human body, it is preferable not to contain benzyl alcohol. Furthermore, in the color developer of the present invention, if necessary, ethylene glycol, methyl cellosolve, methanol, acetone, dimethylformamide, β-cyclodextrin, and other Japanese Patent Publication Nos. 47-33378 and 44-9509 are described. An organic solvent for increasing the solubility of the developing agent can be used. Further, an auxiliary developing agent can be used together with the developing agent. Examples of these auxiliary developers include N-methyl-p-aminophenol hexalphate (methol), phenidone, N, N'-diethyl-p-aminophenol hydrochloride, N, N, N ', N'-tetrahydrochloride. Methyl-p-phenylenediamine hydrochloride and the like are known, and the addition amount thereof is usually preferably 0.01 to 10 g / l. In addition to these, competing couplers, fogging agents, colored couplers, development inhibitor-releasing couplers (so-called DIR couplers), development inhibitor-releasing compounds and the like can be added as required. Furthermore, various additives such as other stain preventing agents, sludge preventing agents, and multi-layer effect accelerators can be used. Each component of the color developing solution can be prepared by sequentially adding and stirring to constant water. In this case, a component having low solubility in water can be added by mixing with the above-mentioned organic solvent such as triethanolamine. More generally, it can be obtained by adding a plurality of components, which can coexist stably, in a concentrated aqueous solution or in a solid state prepared in advance in a small container into water and stirring the mixture. The color developing solution of the present invention can be used in any pH range, but from the viewpoint of rapid processing, it is preferably pH 9.5 to 13.0, more preferably pH 9.8 to 12.0. The processing temperature for color development using the color developing solution of the present invention is 30
The temperature is not lower than 50 ° C. and not higher than 50 ° C., and the higher the value, the quicker the treatment can be performed in a short time, which is preferable. However, on the contrary, there is also a problem that the preservability is easily deteriorated. After color development processing using the color developing solution of the present invention, processing is performed with a processing solution having fixing ability. When the processing solution having fixing ability is a fixing solution, bleaching processing is performed before that. As the bleaching agent used in the bleaching solution or the bleach-fixing solution used in the bleaching step, a metal complex salt of an organic acid is preferably used, and the metal complex salt oxidizes metal silver produced by development to convert it to silver halide. At the same time, it has a function of coloring the uncolored portion of the color-developing agent, and its structure is such that an organic acid such as aminopolycarboxylic acid or oxalic acid or citric acid is coordinated with a metal ion such as iron, cobalt or copper. The most preferable organic acid used for forming such a metal complex salt of an organic acid includes a polycarboxylic acid or an aminopolycarboxylic acid. These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts. The bleaching solution used contains the above-mentioned metal complex salt of an organic acid as a bleaching agent and can also contain various additives. As the additive, it is particularly preferable to contain an alkali halide or an ammonium halide, for example, a rehalogenating agent such as potassium bromide, sodium bromide, sodium chloride, ammonium bromide, a metal salt or a chelating agent. In addition, borate, oxalate, carbonate, phosphate and other pH buffers, alkylamines, polyethylene oxides and the like, which are known to be added to ordinary bleaching solutions, can be appropriately added. Further, the fixer and the bleach-fixer are ammonium sulfite,
Sulfites such as potassium sulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite, sodium metabisulfite, boric acid, borax, sodium hydroxide,
A pH buffering agent comprising various salts such as potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide can be used alone or in combination of two or more kinds. When processing is performed while replenishing the bleach-fixing solution (bath) with a bleach-fixing replenisher, the bleach-fixing solution (bath) may contain thiosulfate, thiocyanate, sulfite or the like. The replenisher may contain these salts and may be replenished to the treatment bath. In order to increase the activity of the bleaching solution and the bleach-fixing solution, air may be blown thereinto or oxygen may be blown in the bleaching-fixing bath and the storage tank of the bleach-fixing replenisher, or a suitable oxidizing agent such as, for example, Hydrogen peroxide, bromate, persulfate and the like may be added appropriately. The pH of the bleach-fixing solution is preferably 3.0 to 9.0, more preferably
It is in the range of 4.0 to 8.0. After bleaching and fixing (or bleach-fixing) after the color development processing using the color developing solution of the present invention, it is possible to carry out stable processing without washing with water, or to carry out stabilizing processing after washing with water. In addition to the above steps, known auxiliary steps such as hardening, neutralization, black-and-white development, reversal, and washing with a small amount of water may be added as necessary. Representative examples of preferred treatment methods include the following steps. (1) Color development → bleach-fixing → washing with water (2) Color developing → bleach-fixing → washing with a small amount of water → water washing (3) Color developing → bleach-fixing → washing → stable (4) Color developing → bleach-fixing → stable (5) Color developing → Bleach-fixing → 1st stability → 2nd stability (6) Color development → Washing (or stable) → Bleach-fixing → Washing (or stable) (7) Color-developing → Stop → Bleach-fixing → Washing (or stable) (8) Color development → Bleaching → Washing → Fixing → Washing → Stable (9) Color developing → Bleaching → Fixing → Washing → Stable (10) Color developing → Bleaching → Washing with a small amount of water → Fixing → 1st stable → 2nd stable (11) Color developing → Bleach → Wash with a small amount of water → Fixing → Wash with a small amount of water → Rinse with water → Stable (12) Color development → Bleach → Fix → Stable (13) Color development → Stop → Bleach → Rinse with small amount of water → Fix → Rinse with small amount of water → Stable → Color development of the present invention Developers are color paper, color film, color positive film, color Di paper, color reversal film, a color reversal film for movie slide,
It can be applied to color photographic light-sensitive materials such as color reversal film for TV and reversal color paper. There is no particular limitation on the light-sensitive material processed by the color developing solution of the present invention. For example, the silver halide composition may be any of those used for ordinary silver halide such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, silver chloroiodobromide, silver chloride and the like. In addition, in the silver halide composition, the silver chloride content is 85
The color developer of the present invention is particularly advantageous in terms of preservability, developability and rapid processability for mol% or more, particularly 90 mol% or more of the emulsion layer. The crystal of the silver halide grain may be normal crystal, twin crystal or other crystal, 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 have a layered structure (core / shell type) in which the inside and the outside are different. Further, these silver halides may be of a type that forms a latent image mainly on the surface or may be of a type that is formed inside the grain. Further, tabular silver halide grains (see JP-A-58-113934 and JP-A-59-170070) may be used. The silver halide grains are preferably substantially monodisperse grains, which may be obtained by any preparation method such as an acidic method, a neutral method or an ammonia method. Since the particle size distribution of the monodisperse emulsion is almost normal, the standard deviation can be easily obtained. The relational expression If the breadth of distribution (%) is defined by
Those having a monodispersity of 20% or less are preferable, and more preferably 10% or less. In the case of spherical silver halide grains, the grain size is the diameter thereof, and in the case of other than spheres, the grain size is calculated as spheres having the same area. The above silver halide may be one in which seed grains 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, control the pH, pAg, etc. in the reaction kettle,
For example, it is preferable to successively inject and mix silver ions and halide ions in an amount corresponding to the growth rate of silver halide grains, as described in JP-A-54-48521. These silver halide emulsions include active gelatin; sulfur sensitizers such as allylthiocarbamide, thiourea, and cystine; sulfur sensitizers; selenium sensitizers; reduction sensitizers such as stannous salt and thiourea dioxide. Noble metal sensitizers such as gold sensitizers, specifically potassium aurithiocyanate, potassium chloroaurate, and 2-orothio-3-.
Sensitizers of methylbenzothiazolium chloride and the like or water-soluble salts such as ruthenium, palladium, platinum, rhodium and iridium, specifically ammonium chloroparadate, potassium chloroplatinate and sodium chloroparadate (these or Some of them act as sensitizers or antifoggants depending on the amount.) Etc. alone or in combination as appropriate (eg combination of gold sensitizer and sulfur sensitizer, gold sensitizer and selenium sensitizer). It may be chemically sensitized by the combined use with a sensitizer). The silver halide emulsion is chemically ripened by adding a sulfur-containing compound, and before, during, or after the chemical ripening, at least one hydroxytetrazaindene and at least one nitrogen-containing heterocyclic compound having a mercapto group are contained. You may make it contain 1 type. The silver halide may be optically sensitized by adding a sensitizing dye in an amount of 5 × 10 ^{−8 to} 3 × 10 ⁻³ mol per mol of the silver halide in order to impart photosensitivity to a desired wavelength range. Good. Various sensitizing dyes can be used,
Further, each sensitizing dye may be used alone or in combination of two or more. The light-sensitive material to which the present invention can be applied is a coupler in the red-sensitive silver halide emulsion layer, the blue-sensitive silver halide emulsion layer, and the green-sensitive silver halide emulsion layer, that is, a dye opposite to the oxidation product of the color developing agent. Those containing a compound capable of forming are preferred. Examples of yellow couplers that can be used include closed ketomethylene compounds, active-point-o-aryl-substituted couplers, active-point-o-acyl-substituted couplers, active-point hydantoin compound-substituted couplers, and active-point urazole compound-substituted so-called 2-equivalent type couplers. Couplers and active-point succinimide compound-substituted couplers, active-point fluorine-substituted couplers. Active point chlorine or bromine substituted couplers, active point-o-sulfonyl substituted couplers and the like can be used as effective yellow couplers. Specific examples of yellow couplers that can be used include U.S. Pat.Nos. 2,875,057, 3,265,506, 3,408,194, and 3,551,155.
No. 3,582,322, No. 3,725,072, No. 3,891,445
No., West German Patent No. 1,547,868, West German Application Publication No. 2,219,917
No. 2,261,361, No. 2,414,006, British Patent No. 1,
No. 425,020, Japanese Patent Publication No. 51-10783, JP-A No. 47-26133,
48-73147, 51-102636, 50-6341, 50
-123342, 50-130442, 51-21827, 50-8
7650, 52-82424, 52-115219, 58-95346
And the like. As magenta couplers that can be used, pyrazolone type,
Examples thereof include pyrazolotriazole compounds, pyrazolinobenzimidazole compounds, and indazolone compounds.
These magenta couplers are the same as the yellow couplers 4
Not only the equivalent type coupler but also a two equivalent type coupler may be used. Specific examples of magenta couplers that can be used include U.S. Pat.Nos. 2,600,788, 2,983,608, and 3,062,
No. 653, No. 3,127,269, No. 3,311,476, No. 3,41
No. 9,391, No. 3,519,429, No. 3,558,319, No. 3,5
82,322, 3,615,506, 3,834,908, 3,
891,445, West German patent 1,810,464, West German patent application (OL
S) No. 2,408,665, No. 2,417,945, No. 2,418,959
No. 2,424,467, Japanese Patent Publication No. 40-6031, and Japanese Patent Laid-Open No. 51-2.
0826, 52-58922, 49-129538, 49-74027
No. 50-159336, No. 52-42121, No. 49-74028.
Examples thereof include those described in Nos. 50-60233, 51-26541, 53-55122, and Japanese Patent Application No. 55-110943. Examples of cyan couplers that can be used include phenol-based and naphthol-based couplers. And these cyan couplers may be not only 4-equivalent type couplers but also 2-equivalent type couplers like the yellow couplers. Specific examples of cyan couplers that can be used are U.S. Pat.Nos. 2,369,929, 2,434,272, and 2,474,
No. 293, No. 2,521,908, No. 2,895,826, No. 3,03
4,892, 3,311,476, 3,458,315, 3,4
76,563, 3,583,971, 3,591,383, 3,
No. 767,411, No. 3,772,002, No. 3,933,494, No. 3
4,004,929, West German Patent Application (OLS) Nos. 2,414,830, 2,454,329, JP-A-48-5983, 51-26034, and
48-5055, 51-146827, 52-69624, 52-9
Examples thereof include those described in No. 0932, No. 58-95346, and Japanese Patent Publication No. 49-11572. Couplers such as colored magenta or colored cyan couplers and polymer couplers may be used in combination in the silver halide emulsion layer and other photographic constituent layers. For the colored magenta or colored cyan coupler, the description of Japanese Patent Application No. 59-193611 by the present applicant can be referred to, and for the polymer coupler, the description of Japanese Patent Application No. 59-172151 by the present applicant can be referred to. The amount of the coupler added is not limited, but is preferably 1 × 10 ^{−3 to} 5 mol, and more preferably 1 × 10 ⁻² , per mol of silver.
˜5 × 10 ⁻¹ mol. The photographic material to which the present invention can be applied may contain various photographic additives. For example, antifoggants, stabilizers, UV absorbers, color stain inhibitors, fluorescent whitening agents, color image fading inhibitors, antistatic agents, hardeners described in Research Disclosure magazine 17643. Agents, surfactants, plasticizers, wetting agents and the like can be used. In the light-sensitive material to which the present invention is applied, hydrophilic colloids used for preparing an emulsion include gelatin, a derivative gelatin, a graft polymer of gelatin and another polymer, albumin, a protein such as casein, a hydroxyethyl cellulose derivative, Any one of cellulose derivatives such as carboxymethyl cellulose, starch derivatives, single or copolymer synthetic hydrophilic polymers such as polyvinyl alcohol, polyvinyl imidazole, and polyacrylamide is included. Examples of the support of the light-sensitive material to which the present invention is applied include reflective supports such as baryta paper and polyethylene-coated paper, and transparent supports, and these supports are appropriately selected according to the purpose of use of the light-sensitive material. In the light-sensitive material to which the present invention can be applied, it is optional to provide an intermediate layer having an appropriate thickness according to the purpose, and further various layers such as a filter layer, an anti-curl layer, a protective layer and an antihalation layer are constituent layers. Can be used in appropriate combination. A hydrophilic colloid which can be used in the emulsion layer as described above can be similarly used as a binder in these constituent layers, and various hydrophilic colloids can be contained in the emulsion layer as described above. The above photographic additives can be incorporated. The light-sensitive material may contain a DIR compound, and further D
In addition to the IR compound, it is also possible to include a compound that releases a development inhibitor upon development, for example, U.S. Pat.
No. 297,445, No. 3,379,529, West German patent application (OLS)
2,417,914, JP-A Nos. 52-15271, 53-9116, and 59.
-123838, 59-127038, etc. are mentioned. The DIR compound is a compound capable of reacting with an oxidized product of a color developing agent to release a development inhibitor or a development inhibitor precursor, and may be a non-diffusible DIR compound or a diffusible DIR compound. Good. A typical example of such a DIR compound is a DIR coupler in which a group capable of forming a compound having a development inhibitory action when released from the active site is introduced into the active site of the coupler, for example, British Patent No. 935,454. No. 3, U.S. Pat.
27,554, 4,095,954, 4,149,886, etc. The above-mentioned DIR coupler has a property that, when it undergoes a coupling reaction with an oxidized product of a color developing agent, the coupler nucleus forms a dye, while releasing a development inhibitor. In the present invention, U.S. Pat.Nos. 3,652,345, 3,928,041, and 3,95
8,993, 3,961,959, 4,052,213, JP-A-5
Compounds that release a development inhibitor but do not form a dye when subjected to a coupling reaction with an oxidant of a color developing agent as described in 3-1-110529, 54-13333, 55-161237, etc. Is also included. Furthermore, the mother nucleus forms a dye or a colorless compound when reacted with an oxidant of a color developing agent as described in JP-A-54-145135, JP-A-56-114946 and JP-A-57-154234. On the other hand, a so-called timing DIR compound in which the released timing group is a compound which releases the development inhibitor by an intramolecular nucleophilic substitution reaction or an elimination reaction may be used. Further, the timing group as described above is present in the coupler mother nucleus which forms a completely diffusible dye when it reacts with the oxidized product of the color developing agent described in JP-A-58-160954 and JP-A-58-162949. It may be a timing DIR compound attached. These DIR compounds are generally used in an amount of 2 per mol of silver in the emulsion layer.
X10 ^{-5 to} 5x10 ^-1 mol is preferable, and 1x is more preferable.
It is to use 10 ⁻⁴ to 1 × 10 ⁻¹ mol. [Effects of the Invention] The following effects (a) to (e) can be obtained by the present invention. (A) Sufficient stability can be obtained without using hydroxylamine, which has the disadvantage that it is a poisonous substance as the stability of the color developer. (B) As described above, in the color developing solution, if a means for improving one of the preservability, the color density and the rapid processability is taken, it is inevitable that the other is deteriorated, but according to the present invention, Such a relationship between the preservability, the color density and the rapid processing property (particularly for a light-sensitive material having an emulsion layer having a high silver chloride content) is improved as compared with the conventional case. That is, for example, the preservability of the color developing solution can be improved while maintaining the conventional good level in color density and rapid processability. Further, even in the case of low replenishment treatment, sufficiently good preservability can be imparted. (C) Staining which is supposed to be caused by the anti-irradiation dye is prevented. Due to the improvement of the preservative described in (d) and (c), when a silver halide color photographic light-sensitive material having an internal latent image type emulsion is fog-developed, the filter effect due to the coloring of the color developing solution is reduced, Stable photographic characteristics can be obtained. (E) As a preservative, there is no generation of floating substances on the surface of the color developing solution, which is a drawback when using an aldehyde bisulfite addition compound. Specific Examples of the Invention Hereinafter, the present invention will be specifically described with reference to Examples, but the embodiments of the present invention are not limited to these. Example 1 A color developer having the following composition was prepared. (Color-developing solution) Potassium sulfite Amount to obtain sulfite ion concentration in Table 1 Sodium chloride 0.3g Potassium carbonate 25.0g Preservative (described in Table 1) Chelating agent [Exemplified compound (43)] 0.6g Color-developing agent [Exemplified compound 1)] 5.0 g The following optical brightener 2.0 g was added by adding potassium hydroxide and water. The pH is 10.1.
It was set to 0. Optical brightener Ferric ion 4ppm each color developer, copper ions 2ppm and calcium ions 100 ppm (each by dissolving _{FeCl 3, CuSO 4 · 6H 2} O and CaCl ₂ added) was added, the opening ratio 30c at 50 ° C.
It was stored in a glass container of m ² / l (30 cm ^{2 of} air contact area for 1 developer). The appearance (coloring degree) of the color developing solution after 10 days was observed. However, the appearance of the liquid was divided into the following four stages. The results are shown in Table 1. Separately, the following layers were sequentially coated on a polyethylene-coated paper support from the side of the support to prepare a light-sensitive material. In addition,
Polyethylene coated paper has an average molecular weight of 100,000,
200 parts by weight of polyethylene having a density of 0.95 and an average molecular weight of 2000,
6.8% by weight of anatase type titanium oxide was added to a mixture of 20 parts by weight of polyethylene having a density of 0.80, and the thickness was 0.0 g on the surface of the fine paper of 170 g / m ² by extrusion coating.
A coating layer having a thickness of 35 mm was formed, and a coating layer having a thickness of 0.040 mm was provided on the back surface only with polyethylene. After pretreatment by corona discharge on the polyethylene-coated surface of this support, the following layers were sequentially applied. First layer: a blue-sensitive silver halide emulsion layer comprising a silver chlorobromide emulsion containing 4 mol% of silver bromide, said emulsion containing 350 g of gelatin per mol of silver halide and having the following structure per mol of silver halide. Sensitizing dye (I) 2,5-di-t-butylhydroquinone 200 mg / m ² sensitized with 2.5 × 10 ⁻⁴ mol (using isopropyl alcohol as a solvent) and dissolved and dispersed in dibutyl phthalate Further, as a yellow coupler, [Y-1] having the following structure is contained in an amount of 2.0 × 10 ^-1 mol per mol of silver halide, and the amount of silver is 300 mg / m ² . Second layer: di-t-octylhydroquinone 300 mg / m ² dissolved and dispersed in dibutyl phthalate, 2-
(2'-hydroxy-3 ', 5'-di-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-
5'-t-butylphenyl) benzotriazole, 2-
(2'-Hydroxy-3'-t-butyl-5'methylphenyl) -5-chloro-benzotriazole, 2-
Mixture of (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chloro-benzotriazole (1: 1:
1: 1) gelatin layer containing 200 mg / m ² gelatin 1900 mg /
It is applied so that it will be m ² . Third layer: a green-sensitive silver halide emulsion layer comprising a silver chlorobromide emulsion containing 2 mol% of silver bromide, said emulsion containing 450 g of gelatin per mol of silver halide and having the following structure per mol of silver halide. Sensitizing dye (II) was sensitized with 2.5 × 10 ⁻⁴ mol of 2,5-di-t-butylhydroquinone dissolved in a solvent consisting of dibutyl phthalate and tricresyl phosphate 2: 1 and a magenta coupler as shown below. Containing [M-1] of the structure of 1.5 × 10 ^-1 mol per mol of silver halide, and the amount of silver is 230 mg / m 2.
^2. AI dye is applied at 500mg / m ² . In addition, 0.30 mol of 2,2,4-trimethyl-6-lauryloxy-7-t-octylchroman was added as an antioxidant per mol of the coupler. Fourth layer: di-t-octylhydroquinone 30 mg / m ² dissolved and dispersed in dioctyl phthalate and 2 as an ultraviolet absorber
-(2'-hydroxy-3 ', 5'-di-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-
5'-t-butylphenyl) benzotriazole, 2-
(2'-Hydroxy-3'-t-butyl-5'-methylphenyl) -5-chloro-benzotriazole, 2-
Mixture of (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chloro-benzotriazole (2: 1.
5: 1.5: 2) a gelatin layer containing 500 mg / m ^2, is coated so as to gelatin 1900 mg / m ^2. Fifth layer: a red-sensitive silver halide emulsion layer consisting of a silver chlorobromide emulsion containing 3 mol% of silver bromide, said emulsion containing 500 g of gelatin per mol of silver halide and having the following structure per mol of silver halide: Sensitizing dye (III) was sensitized with 2.5 × 10 ⁻⁵ mol of 2,5-di-t-butylhydroquinone 150 mg / m ² dissolved and dispersed in dibutyl phthalate and a cyan coupler of the following structure [C -1] is 3.5 × 10 ^-1 per mol of silver halide
It is coated so that the amount of silver is 280 mg / m ² and the amount of AI dye is 40 mg / m ² . Sixth layer: It is a gelatin layer and is coated with gelatin at 900 mg / m ² . The silver halide emulsion used in each of the light-sensitive emulsion layers (first, third and fifth layers) was prepared by the method described in JP-B-46-7772, and sodium thiosulfate pentahydrate was used for each. Chemically sensitized, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (2.5 g per mol of silver halide) as a stabilizer, and bis (vinylsulfonylmethyl) ether ( 10 mg per 1 g of gelatin) and saponin as a coating aid. After the color paper produced by the above method was exposed, it was treated using the following treatment steps and treatment liquids. Composition of processing solution [Color developing tank solution] Color developing solution [bleach-fixing tank 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 to 5.50 with aqueous ammonia or glacial acetic acid and add water to make the total volume 1. [Stable tank substitute for washing] Orthophenylphenol 0.2g 1-Hydroxyethylidene-1,1-diphosphonic acid (60%
Solution) 2.0 g Ammonia water 3.0 g Water to 1 and ammonia water and sulfuric acid to pH 7.8. The above-mentioned color developing tank solution, bleach-fixing tank solution and stabilizing tank solution were filled in an automatic processor, and the color paper sample was processed to measure the maximum density of yellow. The results are shown in Table 1. However, the above-mentioned maximum density is shown as a relative value with the density when the developing solution No. 9 is used as 100. From Table 1, the color developer contains the bisulfite adduct of aldehyde and the hydroxylamine derivative represented by the general formula [1] and the sulfite ion concentration is 1.5 × 10 ^-2.
By setting the amount to be less than 1 mol / l, particularly 1.0 × 10 ⁻⁴ or more and 1.0 × 10 ⁻² or less, as compared with the conventional color developing solution, the color developing solution retains good preservability while maintaining the good preservability. It can be seen that the decrease in density when a photosensitive material having a high silver chloride content is rapidly processed, which is a bad side effect on the photographic characteristics, is reduced. Example 2 Example in which the color developing agent was changed from 1) to 3) and the exemplified compound of the general formula [1] was changed from (17) to (13), (18), (20) and (24). The same experiment as in Example 1 was conducted.
As a result, although the above (13) was slightly inferior to the above (17) in the preservability, almost the same results as in Example 1 were obtained. Example 3 An internal latent image type light-sensitive material was prepared by sequentially coating the following layers on a polyethylene-laminated paper support from the support side. First layer: cyan-forming red-sensitive silver halide emulsion layer 2,4-dichloro-3-methyl-6 as a cyan coupler
-[Α- (2,4-di-tert-amylphenoquine) butyramide] phenol 90 g, 2,5-di-tert-octylhydroquinone 2 g, tricresyl phosphate 50 g, paraffin 200 g and ethyl acetate 50 g are mixed and dissolved. , Add a gelatin solution containing sodium dodecylbenzene sulfonate,
The particles were dispersed so that the average particle size was 0.6 μm (US Pat.
Internal latent image type silver halide emulsion (prepared by the conversion method according to Example 1 described in No. 92,250) (AgBr: A).
gCl = 70: 30), silver amount 400mg / m ² , AI dye 20mg /
It was applied so that the amount of m ² and the amount of the coupler was 360 mg / m ² . Second layer: intermediate layer containing 5 g of gray colloidal silver and 10 g of 2,5-di-tert-octylhydroquinone dispersed in dibutyl phthalate 2.
100 ml of 5% gelatin solution was applied so that the amount of colloidal silver was 400 mg / m ² . Third layer: magenta-forming green-sensitive silver halide emulsion layer 1- (2,4,6-trichlorophenyl) -3- (2-chloro-5-octadecylsuccinimidoanilino) -5-pyrazolone as a magenta coupler 100 g, 2 , 5--ter
t-octyl hydroquinone 5 g, Sumilizer MDP (Sumitomo Chemical Co., Ltd.) 50 g, paraffin 200 g, dibutyl phthalate 100 g and ethyl acetate 50 g were mixed and dissolved, and a gelatin solution containing sodium dodecylbenzenesulfonate was added,
An internal latent image type silver halide emulsion (AgBr: A) prepared in the same manner as the first layer, dispersed so that the average grain size is 0.6 μm.
gCl = 60: 40), silver amount 400 mg / m ² , AI dye 20 mg /
m ^2, and was applied so that the coupler volume 400 mg / m ^2. Fourth layer: yellow filter layer A 2.5% gelatin solution containing 5 g of yellow colloidal silver and 5 g of 2,5-di-tert-octylhydroquinone dispersed in dibutyl phthalate was applied so that the colloidal silver was 200 mg / m ² . . Fifth layer: yellow-forming blue-sensitive silver halide emulsion layer α- [4- (1-benzyl-2-phenyl-3,5-dioxo-1,2,4-triazolidinyl)]-as a yellow coupler
α-Bivalyl-2-chloro-5- [γ- (2,4-di-ter
t-amylphenoxy) butyramide] acetanilide 1
20 g, 2,5-di-tert-octylhydroquinone 3.5 g, paraffin 200 g, Tinuvin (manufactured by Ciba Geigy) 100 g, dibutyl phthalate 100 g and ethyl acetate 70 ml were mixed and dissolved, and a gelatin solution containing sodium dodecylbenzenesulfonate was added, An internal latent image type silver halide emulsion (AgBr: AgCl = 80: 20) prepared in the same way as the first layer, dispersed so that the average grain size is 0.9 μm, was added, and the silver amount was 400 mg / m ^2. ,
The amount of coupler was 400 mg / m ² . Sixth layer: protective layer It was coated so that the amount of gelatin was 200 mg / m ² . It should be noted that all of the above layers contained saponin as a coating aid. As a hardener, sodium 2,4-dichloro-6-hydroxy-s-triazine was added to layers 2, 4 and 6,
Each of them was added to 0.02 g per 1 g of gelatin. The internal latent image type photosensitive material sample was exposed through an optical wedge and then processed in the next step. Treatment process (38 ℃) Immersion (color developer) 8 seconds Color development 120 seconds (first 10 seconds, uniform exposure of 1 lux light) Bleach fixing 60 seconds Water wash 60 seconds Dry 60-80 ℃ 120 The composition of each processing solution is as follows. (Color developer) Benzyl alcohol 15 ml Ethylene glycol 10 ml Potassium sulphite Amount to obtain sulfite ion concentration in Table 2 Potassium bromide 1.0 g Sodium chloride 0.3 g Potassium carbonate 25.0 g Preservative (listed in Table 2) Chelating agent (Exemplified compound ( 43)) 0.6 g Color developing agent (Exemplified compound (1) / (3) = molar ratio 1 /
1) 7.5 g Optical brightener (same as in Example 1) 2.0 g Potassium hydroxide and water were added to make 1. The pH is 10.2
It was set to 0. (Bleach-fixing solution) Pure water 550 ml Ethylenediaminetetraacetic acid iron (III) ammonium salt 65 g Ammonium thiosulfate (70% aqueous solution) 85 g Sodium bisulfite 10 g Sodium metabisulfite 2 g Ethylenediaminetetraacetic acid-2 sodium 20 g Pure water was added to 1 and PH with aqueous ammonia or diluted sulfuric acid
Adjust to 7.0. The light-sensitive material was subjected to stepwise exposure by a conventional method and processed by the method described above, and the minimum reflection density (blue density) was measured. The colorability of the color developing solution was evaluated in the same manner as in Example 1. The results are shown in Table 2. It can be seen from Table 2 that the color developing solution according to the present invention has a relationship between the internal latent image type light-sensitive material and the increase in blue Dmin, that is, yellow stain, which is an undesired influence on the photographic characteristics of the homeostasis and the homeostasis. It is presumed that the improvement and the improvement of the homeostasis reduce the filter effect due to the coloring of the color developing solution in the light fog development, and obtain the effect of stabilizing the photographic characteristics. Further, it is found that the above effect is particularly large in the range of sulfite ion concentration of 1.0 × 10 ^{−4 to} 1.5 × 10 ⁻² mol / l. Example 4 A compound represented by the general formula [2] or [3] was converted from (1) to (2), (3), (4), (5), (14), (15) and (16). Other than that, the same experiment as in Example 3 was performed, and almost the same result as in Example 3 was obtained.

Continuation of the front page (56) Reference JP 57-185434 (JP, A) JP 58-17439 (JP, A) JP 56-94349 (JP, A) JP 60-57586 (JP , B2)

Claims (1)

[Claims] 1. A bisulfite addition compound of an aldehyde, a sulfite ion having a concentration of 1.0 × 10 ⁻⁴ mol or more and 1.5 × 10 ⁻² mol or less per color developer, and a hydroxyl group represented by the following general formula [1]. A color developing solution for a silver halide color photographic light-sensitive material, which contains an amine derivative. General formula [1] [In the formula, each of R ₁ and R ₂ represents a hydrogen atom or an optionally substituted alkyl group. However, R ₁ and R ₂ are not hydrogen atoms at the same time. ]