JPH0410059B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a method for processing a silver halide color photographic light-sensitive material, and more particularly to a method for processing a silver halide color photographic light-sensitive material using a stable developer with improved storage stability. [Prior Art] In general, a silver halide color photographic light-sensitive material forms a dye image by a series of photographic processes whose basic steps are a color development step and a desilvering step after image exposure. In the above color development step, the oxidized color developing agent forms a dye image with an image pattern by a coupling reaction with the coexisting color coupler,
At the same time, reduced silver is produced. In the subsequent desilvering step, the silver produced here is oxidized by a bleaching agent, transformed into a soluble silver complex by the action of a fixing agent, and dissolved away by washing with water. In the actual processing process, in addition to the basic steps for color development and desilvering mentioned above, stopping baths, hardening baths, and stabilizing baths are required due to the need to improve the photographic or physical properties of images. , auxiliary treatment baths such as a bagging removal treatment bath are provided. On the other hand, in ordinary color developing solutions, sulfite or a water-soluble salt of sulfite and hydroxylamine is added as a preservative to prevent oxidation of the aromatic primary amine color developing agent. It is already known that adding hydroxylamine as a water-soluble salt can provide effective preservability since adding these sulfites alone to the developer does not necessarily provide sufficient preservability. There is. Additionally, dihydroxyacetone, anilinoethanol, hydroxylurea, etc. are known as preservatives in place of sulfites and hydroxylamine. In recent years, there has been a trend toward low replenishment of developing solutions for economic and pollution reasons, and this has led to a tendency for the residence time of the developing solutions to become longer, and the developing solutions are often subject to air oxidation. It's summery. Furthermore, as processing becomes faster, photosensitive materials
Processing is now being carried out at high temperatures of 30° C. or higher, and problems such as coloring of the developer due to high temperature oxidation are becoming more and more serious. [Object of the Invention] The object of the present invention is to solve these problems, and the first object is to provide a color developing solution for silver halide color photographic light-sensitive materials that has good long-term storage stability and good processing durability. . A second object is to provide a color developing solution for silver halide color photographic light-sensitive materials in which generation of tar or sludge due to oxidation of a color developing agent during long-term storage is improved. A third object of the present invention is to provide a color developing solution for silver halide color photographic light-sensitive materials that does not cause problems in processing due to contamination of the processing tank of an automatic processor due to the tar or sludge and clogging of filters. [Structure of the Invention] The color developing solution for silver halide color photographic light-sensitive materials of the present invention has the following (e), (b), and (c) and/or (d).
It is characterized by containing. (a) Aromatic primary amine color developing agent compound (b) Manganese salt and/or cerium salt as manganese ion and cerium ion per color developer 0.1 to 20 mg (c) Diphosphonic acid sequestering agent and Magnesium salt and/or lithium salt (d) At least one sequestering agent selected from the following general formulas (), (), and () General formula () In the formula, A ₁ represents a carboxylic acid group, a phosphoric acid group, or a salt thereof, and X represents a hydroxyl group or a salt thereof. B represents a halogen atom, a hydroxyl group, an alkyl group, a carboxylic acid group, a phosphoric acid group, or a salt of a hydroxyl group, a carboxylic acid group, or a phosphorus residue. r and l each represent 0, 1 or 2, n represents an integer from 1 to 4, m
represents an integer from 0 to 3. General formula () General formula () In the formula, A ₂ , A ₃ , A ₄ , A ₅ , A ₆ , A ₇ and A ₈ are
Each represents an alkylene group, and Z represents a divalent organic group, preferably an alkylene group, a cycloalkylene group, or an alkylene group containing an oxygen atom or a nitrogen atom, and furthermore, an alkylene group containing the oxygen atom or a nitrogen atom. as,
Those represented by the following general formula () or () are preferred. General formula () In the formula, n represents the same group as defined in the above general formula (), and A ₉ represents a lower aliphatic carboxylic acid. General formula () -L-O-L-O-L- In the formula, L represents an alkylene group, for example, an ethylene group. Moreover, M ₁ to _{M 7} represent a hydrogen atom or an alkali metal atom. Next, typical examples of the compound according to the present invention represented by the above general formula () will be listed, but the invention is not limited thereto. These compounds are synthesized by general synthetic methods such as those described in US Pat. No. 3,632,637 and Journal of the American Chemical Society Vol. 89 (1967), page 837. Next, typical examples of the compound according to the present invention represented by the above general formula () or () will be listed, but the invention is not limited thereto. -1 Trisodium nitrilotriacetate -2 Nitrilotripropionic acid -3 Propionic acid nitrilodiacetate -1 Pentasodium diethylenetriaminepentaacetate -2 Glycol ether diamine tetraacetic acid -3 1,3-diamino-2-propanol tetraacetic acid -4 Cyclohexanediamine tetraacetic acid -5 Disodium ethylenediaminetetraacetate-6 1,2-diaminopropane-N,N,
N',N'-Tetraacetic acid In the present invention, the compound represented by the general formula () can be used in an amount of 3 mg to 1 g per developer, preferably 5 mg to 0.5 g, more preferably 8 mg to 1 g. Good results are obtained by adding 0.1g. Furthermore, the compounds represented by the above general formulas () and () are 0.1 g or more per developer.
Can be used in the range of 5g, preferably 0.5g
Good results are obtained by adding ~3g. The compounds represented by the general formula (), () or () 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, phosphonocarboxylic acids such as 2-phosphonobutane-1,2,4-tricarboxylic acid, Other chelating agents such as polyphosphoric acids such as tripolyphosphoric acid or hexametaphosphoric acid may be used in combination. Among the compounds represented by the general formulas () and (), particularly preferably used are:
They are diethylenetriaminepentaacetic acid and 1,3-diamino-2-propanoltetraacetic acid. The aromatic primary amine color developing agent compound according to the present invention is preferably a p-phenylenediamine color developing agent compound, such as 4-amino-N,N-diethylaniline, 3-methyl-4
-amino-N,N-diethylaniline, 4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N
-β-hydroxyethylaniline, 3-methyl-4
-Amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline, 3-β-methanesulfonamidoethyl-4-
Amino-N,N-diethylaniline, 3-methoxy-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methoxy-4-amino-
N-ethyl-N-β-methoxyethylaniline,
3-acetamido-4-amino-N,N-diethylaniline, 4-amino-N,N-dimethylaniline, N-ethyl-N-β[β-methoxyethoxy)ethoxy]ethyl-3-methyl-4-amino Aniline or N-ethyl-N-N-β-(β-methoxyethoxy)ethyl-3-methyl-4-aminoaniline and salts thereof, such as sulfate, hydrochloride, sulfite or p-toluenesulfonate. It is. These color developing agents are generally used in concentrations of from about 0.1 g to about 30 g per developer solution 1, more preferably from about 1 g to about 15 g per developer solution 1. The above color developing agents may be used alone or in combination of two or more, and if desired, may be used in combination with a black and white developing agent such as phenidone 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone or metol. Good too. Further, examples of the aromatic primary amine color developing agent compounds that are conveniently added to the light-sensitive material include dye breaker. As typical dye breaker, those described in JP-A-58-65429 and JP-A-58-24137 are used, and specifically, for example, 2',
4'-bismethanesulfonamide-4-diethylaminodiphenylamine, 2'-methanesulfonamide-4'-(2,4,6-triisopropyl)benzenesulfonamide-2-methyl-4-N-(2
-methanesulfonamidoethyl)ethylaminodiphenylamine, 2'-methanesulfonamide-
4'-(2,4,6-triisopropyl)benzenesulfonamido-4-(hydroxytrisethoxy)diphenylamine, 4-N-(2-methanesulfonamidoethyl)ethylamino-2-methyl-2',4' -bis(2,4,6-triisopropyl)benzenesulfonamide diphenylamine,
2,4'-bismethanesulfonamide-4-N,N
-diethylaminodiphenylamine, 4-n-hexyloxy-2'-methanesulfonamide-4'-
(2,4,6-triisopropyl)benzenesulfonamide diphenylamine, 4-methoxy-
2'-methanesulfonamide-4'-(2,4,6-
triisopropyl)benzenesulfonamide diphenylamine, 4-dihexylamino-4'-(2,
4,6-triisopropylbenzenesulfonamido) diphenylamine, 4-n-hexyloxy-3'-methyl-4'-(2,4,6-triisopropylbenzenesulfonamido) diphenylamine, 4-N,N-diethylamino- 4'-(2,4,
6-triisopropylbenzenesulfonamide)
Diphenylamine, 4-N,N-dimethylamino-2-phenylsulfonyl-4'-(2,4,6-
Examples include triisopropylbenzenesulfonamide) diphenylamine. The amount of the dye breaker added to the photosensitive material is:
The amount is preferably 0.5 to 22 mg, more preferably 4 to 12 mg per 100 cm ² of the photosensitive material. Manganese salts and cerium salts according to the present invention refer to compounds that release manganese ions or cerium ions when dissolved in a developer, and are preferably used as listed below, but are not limited to these. . Manganese chloride Manganese sulfate Manganese sulfite Manganese bromide Manganese phosphate Manganese nitrate Manganese permanganate Potassium acetate Manganese oxalate Manganese citrate Manganese ethylene diamine Tetraacetic acid Manganese sulfate Cerium nitrate Cerium chloride Cerium carbonate Cerium phosphate Cerium acetate Cerium citrate Cerium oxalate These manganese The salt and cerium salt are each used in the form of ions (manganese ion and cerium ion) in an amount of 0.1 mg to 20 mg per developer, preferably 0.3 mg to 8 mg. The diphosphonic acid sequestering agent used in the present invention may be a mixture of two or more diphosphonic acid sequestering agents. Particularly useful compounds in the present invention include the following general formula () Examples include compounds represented by and derivatives thereof. General formula () In the general formula (), R ₁ has 1 to 1 carbon atoms.
5 shows the alkyl group. Other useful compounds include compounds represented by the general formula () and derivatives thereof. General formula () In the general formula (), R ₂ has 1 to 1 carbon atoms
5 shows the alkyl group. Compounds included in the above general formulas () and () include (-1) 1-hydroxyethyldene-1,1-diphosphonic acid, (-2)-hydroxypropylidene-1,1-diphosphonic acid and For the latter aminophosphonic acid, (-1)1-
Aminoethane-1,1-diphosphonic acid, (-2)
Examples include 1-aminopropane-1,1-diphosphonic acid. These can also be used as alkali metal salts (eg, potassium or sodium salts, etc.), ammonium salts, or water-soluble amine salts (eg, triethanolammonium salts, trimethylammonium salts, etc.). The above diphosphonic acid sequestrant is in the range of 0.01g to 10g, preferably 0.1g to 10g per developer.
Good results are obtained when used in the 1g range. In addition, preferred magnesium salts and lithium salts for use in the present invention are listed below, but are not limited thereto. Magnesium chloride Magnesium sulfate Magnesium acetate Magnesium nitrate Magnesium phosphate Magnesium oxalate Magnesium citrate Lithium chloride Lithium sulfate Lithium phosphate Lithium acetate These magnesium and lithium salts are used in combination with the diphosphonic acid, Added to prevent precipitation. The magnesium salt and the lithium salt may be used alone in combination with a diphosphonic acid, or the magnesium salt and the lithium salt may be used in combination with a diphosphonic acid. The magnesium salt and lithium salt are used in a developer solution in an amount corresponding to 1/2 to 3 times the mole of the diphosphonic acid according to the present invention. In the present invention, (aromatic primary amine color developing agent compound), (manganese salt and/or cerium salt), and (diphosphonic acid sequestering agent and magnesium and/or lithium salt) are used in combination. or (aromatic primary amine color developing agent compound), (manganese salt and/or cerium salt), and (at least one sequestering agent selected from the general formulas (), (), and ()) The desired effects of the present invention are achieved when these are used in combination, but when used alone or when one is missing, various drawbacks occur and are not practical. For example (manganese salt and/or
or cerium salt), the oxidation of the color developing agent will be significant during long-term storage, and the above-mentioned diphosphonic acid and the sequestering agent group represented by the general formulas (), (), and () may be missing. If it is missing,
Preservatives such as hydroxylamine in the developer cause decomposition due to the presence of manganese salts and cerium salts, making them impractical. For these reasons, in the present invention, it is necessary to use all of the constituent elements of the present invention in combination as described above. Furthermore, instead of the manganese and cerium salts according to the invention, other metal salts such as iron salts, copper salts,
If a barium salt, etc.) is used, the desired effect of the present invention is not exhibited, and furthermore, another metal ion sequestering agent (e.g.,
Oxycarboxylic acids such as polyphosphoric acid, citric acid, oxalic acid, aminopolyphosphoric acid, hydroxyiminodiacetic acid, phosphonocarboxylic acids, etc.) do not exhibit the desired effect of the present invention. However, in addition to the metal ion sequestering agent according to the present invention, other metal ion sequestering agents (polyphosphoric acid, oxycarboxylic acid, aminopolyphosphoric acid, hydroxypolycarboxylic acid, phosphonocarboxylic acid, etc.) are added and used. Optional. The color developing solution used in processing in the presence of the organic or inorganic compound according to the present invention may be an alkaline agent commonly used in developing solutions, such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate. , sodium sulfate, sodium metaborate or borax, etc., and may further contain various additives such as benzyl alcohol, alkali metal halides such as potassium bromide or potassium chloride, or development regulators such as citradinic acid, etc. It may contain hydroxylamine or sulfite as a constant agent. Furthermore, various antifoaming agents and surfactants, as well as organic solvents such as methanol, dimethyl formamide, and dimethyl sulfoxide, etc. can be appropriately contained. Further, the pH of the developer according to the present invention is usually 7 or more, preferably about 9 to 13. In addition, the color developer used in the present invention may optionally contain antioxidants such as hydroxylamine, ascorbic acid, tetronic acid, tetronimide, 2-anilinoethanol, dihydroxyacetone, aromatic secondary alcohol, and hydroxamic acid. ,
Pentose or hexose pyrogallol-1,
3-dimethyl ether and the like may also be contained. [Examples] Hereinafter, the present invention will be explained in more detail with reference to Examples, but the embodiments of the present invention are not limited thereto. [Example 1] (Experiment 1) An experiment was conducted using the following color developing solution for color negatives as a basic formulation. (Color developer composition) Potassium carbonate 30g Sodium hydrogen carbonate 2.5g Potassium sulfite 5g Sodium bromide 1.3g Potassium iodide 2mg Hydroxylamine sulfate 2.5g Sodium chloride 0.6g N-ethyl-N-(β-hydroxyethyl)-3
Methyl-p-phenylenediamine sulfate (color developing agent) 4.8g Potassium hydroxide 1.2g Add water to make 1, potassium hydroxide or 20%
The pH was adjusted to 10.06 using sulfuric acid. The above developer was used as a control sample (A), and the metal salts and metal ion sequestering agents shown in Table 1 were added to it.
The developer solution was stored in a beaker with an opening area of 100 cm ² at room temperature for 20 days. The amount of decomposed color developing agent in the developer solution after storage was quantified, and the tar degree of the developer solution was measured by measuring absorption at 450 nm with a spectrophotometer. (Experiment 2) Sakura color negative film (manufactured by Konishiroku Photo Industry Co., Ltd.) was subjected to white stepwise exposure using a KS-7 sensitometer (manufactured by Konishiroku Photo Industry Co., Ltd.). After being left for one day, developer samples (A) to (T) were used to perform color development according to the following steps. Processing process Temperature (°C) Time (min) Color development 38 3 minutes 25 seconds bleaching 38 6 minutes 5 seconds washing 33 3 minutes fixing 38 6 minutes 5 seconds washing 33 4 minutes stabilization 33 2 minutes drying 43~ 52 The bleaching solution, fixing solution, and stabilizing solution used were all Sakura Color negative film processing agent type-4.
(CNK-4) (manufactured by Konishiroku Photo Industry Co., Ltd.) was used. For those that have undergone the above color development treatment,
PDA-60 type photodensitometer (manufactured by Koshiroku Photo Industry Co., Ltd.)
The maximum blue density was measured using The above results are summarized in Table 2.

【table】

【table】

【table】

[Table] The lower the absorbance, the less coloring and the lower the degree of tar.
As shown by the above results, the developer samples (B) to (I) according to the present invention show little decomposition of the color developing agent, very low tar content of the developer, and also extremely low sensitometry maximum concentration. It turns out that there are few. However, comparative samples (J) to (O), and
In (A), the color developing agent often decomposes, the tar level of the developer is large, and the maximum density is greatly reduced, making it impractical. Comparative samples (P) to (T) have less coloring of the developer and a lower degree of tar, but the decomposition of the color developing agent is large and the maximum density is greatly reduced, which is also not practical. From these, when the metal salts (manganese salt and cerium salt) according to the present invention are not used, or when another metal salt is used, the developer is highly colored and has a high degree of tar. Furthermore, it can be seen that the color developing agent decomposes to a large extent and the development activity deteriorates. Further, even when the metal salt according to the present invention is used, if the metal ion sequestering agent according to the present invention is not used, although the tar degree of the developer is low, the color developing agent is largely decomposed and the development activity is deteriorated. However, it has been found that when the metal salt of the present invention and the sequestering agent of the present invention are used in combination, the desired effects of the present invention can be effectively achieved. [Example 2] The amount of manganese ions added to the developer (D) used in Example 1 was 0, 0.1, 0.3, and
The same experiment as in Example 1 was conducted except that the concentrations were changed to 0.5, 1.0, 5.0, 8.0, 20.0, 30.0, and 40.0 mg/l. The results are shown in Table 3.

[Table] From the above results, when the metal salt (manganese salt) according to the present invention is present in the form of ions at 0.1 to 20 mg/l, good results are obtained for decomposition of the color developing agent, tar formation of the developer, and development activity. , especially 0.3
It can be seen that significantly better results are shown when used in the range of ~8 mg/l. [Example 3] Compounds -10, -1, - of the present invention were added to the developer (G) and (I) used in Experiment 1 of Example 1.
When the same experiment was carried out by adding 3 g/l of each of 1 and -3, the same results as in Example 1 were obtained. [Example 4] The same experiment was carried out by changing the basic formulation of the color developer for color negatives used in Example 1 (Experiment 1) to the following basic formulation of the color developer for color paper. Obtained similar results. (Color developer for color paper) Benzyl alcohol 15ml Ethylene glycol 15ml Potassium sulfite 2g Potassium bromide 0.7g Sodium chloride 0.2g Potassium carbonate 30g Hydroxylamine sulfate 3g 3-Methyl-4-amino-N-ethyl-N-
(β-Methanesulfonamidoethyl) aniline sulfate 5.5g Fluorescent brightener (4,4-diaminostilbendisulfonic acid derivative 1.0g Potassium hydroxide 2g Add water to make 1, potassium hydroxide or 20%
The pH was adjusted to 10.2 using sulfuric acid. [Example 5] The following experiment was conducted using the basic formulation of the color developer for color paper in Example 4 in which hydroxylamine sulfate was removed as the basic formulation. The developer of the basic formulation was used as a control sample (U), and the compounds shown in Table 4 were added to it to create the developer of No. 1.
It was stored at room temperature for 20 days in a beaker with an opening area of 100 cm ² . The amount of decomposed color developing agent in the developer solution after storage was quantified, and the tar degree of the developer solution was measured by measuring absorption at 450 nm with a spectrophotometer. The results are shown in Table 5.

【table】

[Table] As shown by the above results, developer samples (W) and (X) according to the present invention are found to have extremely good decomposition of color developing agent and tar degree despite the absence of hydroxylamine. [Example 6] Similarly to Example 2, the amount of cerium ions added to the developer (C) used in Example 1 was 0, 0.1, 0.3, 0.5, 1.0, 5.0, 8.0, 20.0, respectively. 30.0,
The same experiment as in Example 1 was conducted except that the amount was changed to 40.0 mg/. The results are shown in Table 6.

[Table] From the above results, when the metal salt (cerium salt) according to the present invention is present in the form of ions in an amount of 0.1 to 20 mg, good results are obtained for the decomposition of the color developing agent, the taring of the developer, and the development activity. shown, especially 0.3
It can be seen that significantly better results are obtained when used in the range of ~8 mg/. [Effects of the Invention] When the color developing solution for silver halide color photographic light-sensitive materials of the present invention is used, the following excellent effects can be obtained. (1) By adding the compound according to the present invention, the active ingredients in the developer will not be oxidized or decomposed by air or oxygen dissolved in the developer, and the effectiveness of the developer can be maintained over a long period of time to ensure constant processing results. can get. (2) Even after long-term storage, there is no generation of tar or sludge due to oxides of color developing agents, there is no dirt in the processing tank of automatic processors, there is no clogging of filters, and the color photosensitive material to be processed is not affected. will not contaminate.

Claims (1)

[Scope of Claims] 1. A color developer for silver halide color photographic materials, characterized by containing the following (a), (b), and (c) and/or (d). (b) Aromatic primary amine color developing agent compound, (b) Manganese salt and/or cerium salt as manganese ion and cerium ion per color developer, 0.1 to 20 mg, (c) Diphosphonic acid sequestering metal ion. and magnesium salt and/or lithium salt; (d) at least one sequestering agent selected from the following general formulas (), () and (). General formula () (In the formula, A ₁ represents a carboxylic acid group, a phosphoric acid group, or a salt thereof, and X represents a hydroxyl group or a salt thereof. B represents a halogen atom, a hydroxyl group, an alkyl group, a carboxylic acid group, a phosphoric acid group, or represents a salt of a hydroxyl group, a carboxylic acid group or a phosphoric acid group. r and l are 0 and 1, respectively.
or 2, n represents an integer from 1 to 4,
m represents an integer from 0 to 3. ) General formula () General formula () (where A ₂ , A ₃ , A ₄ , A ₅ , A ₆ , A ₇ and A ₈
each represents an alkylene group, and Z represents a divalent organic group. Moreover, M ₁ to _{M 7} represent a hydrogen atom or an alkali metal atom. )