JPS59228251A - Method for processing color photographic sensitive silver halide material - Google Patents

Abstract

PURPOSE:To color-develop a color photographic sensitive silver halide material without forming tar or sludge by developing the material in the presence of an aromatic primary amine compound as a color developing agent, a manganese salt and a specified sequestering agent. CONSTITUTION:An imagewise exposed color photographic sensitive silver halide material is color-developed in the presence of an aromatic primary amine compound (A) as a color developing agent, a manganese salt and/or a cerium salt (B) and diphosphoric acid (C) as a sequestering agent combined with a magnesium salt and/or a lithium salt and/or a sequestering agent (D) represented by formula I , II or III (where A1 is carboxylic acid or phosphoric acid; X is hydroxyl; B is halogen or the like; each of r and l is 0-2; n is 1-4; m is 0-3; each of A2-A8 is alkylene; Z is a bivalent org. group; and each of M1-M7 is H or an alkali metal).

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to the processing of silver halide color photographic materials.
More specifically, the present invention relates to a method for processing a silver halide color photographic material using a stable developer with improved stability.

[Prior Art] In general, silver halide color photographic photosensitive d materials undergo a series of 7 basic steps, after image exposure, including a color development step and a desilvering step.
A dye image is formed by f true processing y1 (.

In the above color development step, the oxidized color developing agent undergoes a coupling reaction with the coexisting color coupler to form a dye image of an image pattern, and at the same time, silver is produced. In the subsequent desilvering process, the silver produced here is oxidized by a bleaching agent, transformed into soluble silver Cjt by the action of a fixing agent, and dissolved by washing with water.

In the actual development process, in addition to the basic steps for color development and desilvering described in 1.7, due to the need to improve the fundamental or physical characteristics of the image, a stop bath, hardening film, etc. Auxiliary treatment baths such as bath, stabilization bath, and backing removal treatment bath are provided.

On the other hand, in ordinary color developing solutions, sulfuric acid or water-soluble salts of sulfite and hydroxylamine are added as preservatives to prevent oxidation of the primary aromatic amine color developer. There is.

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. In addition, dihydroxyacetone, anilinoethanol, hydroxylurea, etc. are known as preservatives that can replace sulfites and hydroxylamine.

In recent years, there has been a trend toward low replenishment of developing solutions due to economical and pollution reasons, and as a result, the residence time of developing solutions has also tended to become longer, and developing solutions are often subject to air oxidation. ing. Furthermore, as processing becomes faster, photographic materials are being processed at high temperatures of 30°C or higher, and problems such as coloring of the developer due to high-temperature oxidation are becoming even more serious. .

[Objective of the Invention] The object of the present invention relates to these problems.The first object is to use a developing solution that has good long-term storage stability and processing durability. The purpose of the present invention is to provide a processing method for the following.

A second object is to provide a method for processing color photosensitive materials using a developer solution in which the generation of tar 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 method for processing color photosensitive materials that does not cause problems in processing due to the tar or sludge staining the processing tank of an automatic processor or clogging of the filter.

[Configuration of the Invention] The color photosensitive material processing method of the present invention includes the following (a), (b), and (c) after subjecting the color-sensitive material to imagewise atomization.
It is characterized by carrying out color development treatment in the presence of J and/or (d).

(a) Aromatic primary amine coloring phenomenon-dominant mulberry thread compound (b)
Manganese salt and/or cerium salt (c) Niphosphonic acid sequestering agent and magnesium salt and/or lithium salt) At least one sequestering agent selected from the following general formulas (I), 1 and (III). (I) A, A.

In the formula, A1 represents a carboxylic acid group, a phosphoric acid group, or a salt thereof, or 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 phosphoric acid group. r and l each represent 0, 1 or 2, n represents an integer from 1 to 4, and m represents an integer from O to 3.

General formula (■) General formula (■ In the formula, A3, A7, and A8 each represent an alkylene group, and 2 represents a divalent organic group, preferably an alkylene group or a cyclo It represents an alkylene group or an alkylene group containing an oxygen atom or a nitrogen atom, and the alkylene group containing an oxygen atom or a nitrogen atom is preferably one represented by the following general formula (1) or (V).

General formula (1V) (-(!H,su.N-(-0uma nayu A.

In the formula, n represents the same group as defined in the general formula CI), and A9 represents a lower aliphatic carboxylic acid.

General formula (VJ -L-0-L7-0-L In the formula, L represents an alkylene group, for example, an ethylene group. M1 to M7 represent a hydrogen atom or an alkali metal atom.

Next, typical examples of the compound according to the present invention represented by the general formula (I) will be listed, but the invention is not limited thereto.

-1 0H,0OOH ■-2 0H,0OOHOH,0OOH OH,0OOOHH,0OOOH,C0OH-4 -9 0H1POINal ■-10 0H, (!0ONa OH, COONa These compounds are described in U.S. Patent No. 3,632,637 and Journal of the American Chemical Society Vol. 8
9 (1967), page 837.

Next, typical examples of the compounds according to the present invention represented by the general formula (■) or (IIl) will be listed, but the invention is not limited thereto.

I[-] trisodium lylotriacetate ['-2 nitrilotripropionic acid [-3 nitrilodiacetic propionate 1Ji-1 diethylenetriamine pentaacetic acid pentasodium In-2 glycol ether diamine tetraacetic acid lll
-31,3-diamino-2-probanol tetra Nishiv
6-In-4 cyclohexanediamine triacetic acid lll-5
Ethylenediamine disodium triacetate 11'J-61,2-diaminopropane-N,N,N:
N1-tetraacetic acid In the present invention, the compound represented by the general formula (I) is present at a concentration of 3 to 1 per 17 of the developing solution. Good results can be obtained by adding preferably 7 m2 to 0.5 g, preferably 8 m2 to 0.1 g to 1M. Furthermore, the compounds represented by the general formulas (1■'' and (III)) were added at a rate of 0.1 per 11 of the developer.
g to 5I, preferably 0.g to 5I.
Good results are obtained by adding between 5g and 3g.

The compounds represented by the general formula (I), (■) or (III) may be used alone or in combination. Furthermore, aminopolyphosphonic acids such as methylene phosphonic acid or ethylenediaminetetraphosphoric acid, oxycarboxylic acids such as citric acid or gluconic acid, phosphonocarboxylic acids such as 2-phosphonobutane-1,2,4-)licarboxylic acid, etc. Other chelating agents such as acids, polyphosphoric acids such as tripolyphosphoric acid or hexametaphosphoric acid may be used in combination.

Furthermore, among the compounds represented by the general formulas CH) and (IITJ), diethylenetriaminepentaacetic acid and 1,3-diamino-2-propatoltetraacetic acid are particularly preferably used.

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-diamine, etc. Minnow N, N-diethylaniline, 4-ami-1=N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-
4-amino-N-ethyl-N-β-methanesulfone, midoethyl-niline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline, 3-β-methanesulfone, midoethyl-4-amino- N,N-diethylaniline, 3-methoxy-4-amino-N-ethyl-N
-β-hydroxyethylaniline, 3-methoxy-4-
Minnow N-ethyl-N-β-methoxyethylaniline, 3-acetamido-4-minnow N, N-diethylaniline, 4-minnow N, N-dimethylaniline, N-
Ethyl-N-β[β-(β-methoxyethoxynoethoxy]ethyl-3-methyl-4-aminorin or N-
Ethyl-N-N-β-(β-methoxyethoxyλethyl-3-methyl-4-aminotriline and these places, such as 1 basin of sulfuric acid, hydrochloric acid, speculation r+'fE M salt or p-)
Such as luenesulfonate.

These color developing agents generally have a concentration of about 0 per liter of developer solution.
．． Concentrations of from 1 g to about 30 g, more preferably from about 1 g to about 15.9 g per developer solution 11 are used.

The above color developing agent may be used alone or in combination of two or more, and if desired, a black and white developing agent such as phenidone 4 may be used.
-Hydroxymethyl-4-methyl-1-phenyl-3-
It may be used in combination with pyrazolidone, metol, etc.

Further, the aromatic primary amine color developing agent compound which is conveniently added to the Sensitive C material includes a dye precursor. A typical dye precursor is JP-A-58-
65429, 5B-24137, etc. are used, specifically, for example, 21,41-bismethanesulfonamide-4-diethylaminodiphenylamine, 21-methanesulfonamide-41-(・2,4
．． 6-Doliisopropylnobenzenesulfonamide 2
-Methyl-4-IJ -(2-Methanesulfonamide ethylnoethylaminodiphenylamine , 4-N-(2-methanesulfonamidoethylnoethylamino-2-methyl-p,l
, 41-bis(2,4,,,6-)lyisoprobyrfuhenzenesulfonamide diphenylamine, 2.4
1-bismethanesulfonamide-4-N, N-diethylminodiphenylamine, 4-n-hexyloxy-gmethanesulfonamide-41-(2+ 4 + 6-
Doliisopropylbenzenesulfonamide diphenylamine, 4-methoxy-21-methanesulfonamide
4'-(2,'4.6-)Isopropylbenzenesulfonamidiphenylamine, 4-dimethylamino-4'-(214,'6-)Isopropylbenzenesulfonamidiphenylamine, 4-n- hexyloxy-bumethyl-4'-(2,4,6-)lyisopropylbenzenesulfonylamide)diphenylamine, 4-
N,N-dimethylamino-4'-(2,4,6-dolyisobrobylbenzenesulfonamide 2-diphenylamine, 4-N,N-dimethylamino-2-phenylsulfonyl-4'-(2,4 , 6-) lyisobrobylbenzenesulfonamide] diphenylamine, etc.

The amount of the dye precursor added to the light-sensitive material is preferably 0.5 to 22 cm, more preferably 4 to 12 cm, per 100 d of the sensitive C 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 (Ii?i, acid manganese bromide manganese phosphate manganese nitrate manganese permanganate potassium acetate manganese oxalate manganese citrate manganese ethylene diamine tetraacetate manganese sulfate cerium nitrate cerium chloride cerium carbonate cerium phosphate cerium acetate citric acid Cerium Cerium Oxalate These manganese salts and cerium salts can be used in the form of ions (manganese ions and cerium ions) in an amount of 0.1-20 J19 per developer solution, preferably 0.3 m9-20 J19 per developer solution. 8■ To be made to exist.

The niphosphone butyrometal ion sequestering agent used in the present invention is
A mixture of 2 tsubo or more of niphosphonate metal ion sealant may be used. Compounds useful in the present invention for T1s' include compounds represented by the following general formula (Vl) and derivatives thereof. .

General formula (VI) POsH.

R, -0-OH ■ P.O., H.

In the general formula CVI), Ro represents an alkyl group having 1 to 5 carbon atoms.

Other useful compounds include compounds represented by the general formula (■) and derivatives thereof.

General formula (VID P.O., H.

R, -〇-NH.

■ P.O., H.

In the general formula (V[), R2 represents an alkyl group having 1 to 5 carbon atoms.

As for the compounds included in the above general formulas (VD and (W),
(■-lyl-hydroxyethylidene-1゜1-niphosphonic acid, (VI-2 no-hydroxypropylidene-1,
Examples of 1-diphosphonic acid and the latter aminophosphonic acid include (■-1) 1-aminoethane-1,1-niphosphonic acid and (■-2) 1-aminopropane-1,1-niphosphonic acid.

These include alkali metals (such as potassium salts or sodium salts), ammonium salts or water-soluble amine salts (
For example, it can also be used as triethanolammonium salt, trimethylammonium salt, etc.

The amount of the above-mentioned niphosphonic acid sequestering agent is in the range of 0.01 g to 109 per developer solution, preferably 0.1 g to 1
Good results are obtained when used in the g 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 acetate Magnesium nitrate Magnesium phosphate Magnesium oxalate Magnesium citrate Lithium chloride (pfj) Lithium nitrate Lithium phosphate Lithium acetate These magnesium salts and lithium salts are used in combination with the above-mentioned niphosphonic acid to form niphosphonic acid. It is added for the purpose of preventing acid precipitation. Magnesium salts and lithium salts may be used alone in combination with niphosphonic acid, or magnesium salts and lithium salts may be used simultaneously in combination with niphosphonic acid. In the present invention, the magnesium salt and lithium salt are used in a developer solution in an amount corresponding to 1 to 3 times the mole of the diphosphonic acid according to the present invention. amine color developing main compound], (manganese salt and/or cerium salt) and phosphonic acid sequestering agent and magnesium and/or
or lithium chloride is used in combination, or (
aromatic primary amine color developing agent compound), (manganese salt and/or cerium salt), and (the above general formula (I),
When UD and (at least one sequestering agent selected from IID) are used in combination, the desired effects of the present invention are achieved, and each can be used alone or
If any one of them is missing, various defects will occur, making it impractical. For example, if the group (manganese salt and/or hexasur salt) is missing, the color developing agent will be significantly oxidized during long-term storage, and the diphosphonic acid, general formula (I), C
If the combination of metal ion buttoning agents shown in 11) and (III) is missing, it becomes impractical to decompose due to the presence of manganese salts and cerium salts in the presence of preservatives such as hydroxylamine in the developer. It ends up. For these reasons, in the present invention, it is necessary to use all of the column configuration requirements of the present invention in combination as described above.

Furthermore, instead of the mankan salts and cerium salts according to the invention, other metal salts such as V salts, copper salts, barium salts can be used.
4) does not exhibit the desired effect of the present invention, and furthermore, when another metal ion sequestering agent 1) (for example, polyphosphorus, citric acid, oxalic acid) is used instead of the metal ion sequestering agent of the present invention, Oxycarboxylic acids such as aminopolyphosphoric acid, hydroxyiminodiacetic acid, and phosphonocarboxylic acids do not exhibit the desired effects 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,
It is optional to add and use aminopolyphosphoric acid, hydroxypolycarboxylic acid, phosphonocarboxylic acid, etc.

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 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, surfactants, and organic solvents such as methanol, dimethylformamide or dimethyl sulfoxide can be appropriately contained.

Further, the pH of the developer according to the present invention is usually 7 or more,
Preferably it is about 9-13.

In addition, the color developer used in the present invention requires IJ.
k Depending on the antioxidant, hydroxylamine, ascorbic acid, tetronic acid, tetronimide, 2-anilinoethanol, dihydroxyacetone, aromatic secondary alcohol, hydroxamic acid, hendose or hexose pyrogallol-1°3-dimethyl ether, etc. It may be included.

[Example] Hereinafter, the present invention will be explained in more detail with reference to Examples.
The embodiments of the present invention are not limited to these.

[Example 1] (Actual @l) An experiment was conducted using the following color developing solution for color negatives as a basic formulation.

(Color developing solution composition) 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 thereto. It was stored at room temperature for 1 day. The amount of decomposition of the color developing agent in the developer after storage was determined, and the absorption at 450 nm was measured using a fractionator to determine the degree of tar in the developer.

(Experiment 2) Sakura Cassie Negative Film (Konishi Roku Photo Industry)
Sample of developer solution after being left for 4 days in an experiment after applying white gradation and exposure using a KS-7 type sensor (Kose [1 Daishako 9 Co., Ltd. ili+)] Using each of (A) to (T), color development treatment was performed according to the following steps.

Processing pH process Humidity (℃) Time (minutes) Color development
38 3 minutes 25 seconds bleach 38 6 minutes 5 seconds.

Wash with water 33 Fix for 3 minutes
38 6 minutes 5 seconds washing 33 4 minutes stable 33 2 minutes drying
43-52 The bleaching solution, fixing solution, and stabilizing solution used were all Sakura Chikara Synecative Film Processing Agent Type-4 (0NK-4) (
The product manufactured by Konishi Rokupage Kogyo Co., Ltd. was used.

For those that have undergone the above color development process, PDA-60
The maximum blue density was measured using a photoelectric density monitor (manufactured by Koshiroku Photo Industry Co., Ltd.).

Key No. 1 Table 1 Table 2 *The degree of coloration of the developed γσ is shown by the absorbance C at 450 nm, and the lower the absorbance, the less coloring and the lower the degree of tar.

As the above results show, the developer sample (B) according to the present invention
It can be seen that the decomposition of the color developing agent is small, the tar level of the developer is extremely low, and the decrease in the maximum density measured by sensitometry is also extremely small.

However, in the comparative samples (J) to 0) and (A), the color developing agent decomposes to a large extent, the developer has a high degree of tar, and the maximum degree of tarness decreases too much, making them impractical. Comparative samples (P) or T) had less coloring in the developer. C<Although the tar content is low, the decomposition of the color developing agent is large, resulting in the highest iQ t! The decrease in r: is also large, which is also not practical.

From these results, 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 current fEQ liquid is highly colored and has a high degree of tar. Furthermore, it can be seen that the color developing agent 5 was decomposed to a large extent, and the developer f9 activity was deteriorated.

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 level of the developer is low, the color developing agent is significantly 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 mankan ions added to the developer (D) used in Example 1 was 0, 0.1, 0.3.0, respectively.
5.1.0.5.0.8.0.20,0.30,0.4
The same experiment as in Example 1 was conducted except that the concentration was changed to 0.0 m9/l. The results are shown in Table 3.

From the above results in Table 3, gold 81εK (manganese) according to the present invention!
When A) is present in the form of ions in an amount of 0.1 to 20 my/l, good results are shown for the decomposition of the 5-image main film for power generation, the tarring of the developer fΦ solution, and the development activity, especially when 0.3
It can be seen that extremely good results are obtained when used in the range of ~Bmt)ll.

[Example 3] Developer solution (G) and (1) used in Experiment 1 of Example 1
Compound examples of the present invention J-1, 0, 1-1, m-1・11
When the same experiment was carried out by adding 3 fJ/11Ffj of each of 1 to 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 developing solution for color negatives used in Example 1 (Real! 5% 1) to the following basic formulation of the color developing solution for color paper. Similar results to Example 1 were obtained.

(Color developing solution for color paper [Example 5] The following experiment was conducted using the basic formulation of the color developing solution for color paper of Example 4 in which hydroxylamine sulfate was removed as the basic formulation.

The developer of the Hanamoto prescription was used as a control sample (U), and the fourth
The compounds shown in the table were added and 1 liter of the developer solution was stored at room temperature for 20 days in a beaker having an opening area of 100 mm. The amount of decomposition of the color developing agent in the developer after storage was quantified, and the tar degree of the developer was measured by measuring absorption at 450 nm using a spectrophotometer. The results are shown in Table 5.

Table 4 Table 5 As shown in the above results, developer sample (W) according to the present invention
It can be seen that the decomposition of the color developing agent and the degree of tarring are extremely good in samples (X) and (X) despite the absence of hydroxylamine.

[Effects of the Invention] When the color photosensitive material processing method of the present invention is used, the following excellent effects can be obtained.

(1) By adding the compound according to the present invention, there is no oxidation or decomposition of the active ingredients in the developer due to air and oxygen dissolved in the developer, and the effectiveness of the developer r'J'iFl is maintained over a long period of time, allowing constant processing. Get results.

(2) Even when stored for a long time, there is no generation of tar or sludge due to the oxides of the color developing agent, there is no dirt in the processing tank like automatic development, there is no clogging of the filter, and there is no problem with the color developing agent being processed. It does not contaminate the original material.

Agent Nozomi Kuwabara

Claims (1)

[Scope of Claims] A silver halide color photographic light-sensitive material is imagewise exposed and then subjected to color development treatment in the presence of (a), (b), and (c) and/or) below. A method for processing silver halide color photographic materials. B) Aromatic primary amine color developing agent thread compound, (B)
mankan salt and/or cerium salt, (c) diphosphonic acid sequestering agent, and magnesium salt and/or lithium salt; and) at least one sequestering metal ion selected from the following general formulas (I), (III), and (III). agent. General formula (IJ AHA1 (in the formula "I AI represents a carboxyl group, a phosphoric acid group, a phosphoric acid group, or a salt thereof, or represents a hydroxyl group or a salt thereof. B is a halogen atom, a hydroxyl group, an alkyl group, a carboxylic acid group, group, phosphate group, or hydroxyl group,
Represents a salt of a carboxylic acid group or a phosphoric acid group. r and l each represent 0.1 or 2, n represents an integer of 1 to 4, and m represents an integer of 0 to 3. ] General formula C11 general formula (IID (wherein, A6, A3, A4, A3, Ao, A, and A
, each represent an alkylene group, and 2 represents a divalent organic group. Moreover, M and ~M represent a hydrogen atom or an alkali metal atom. ]