JPS6031139A - Method for processing silver halide color photosensitive material - Google Patents

Abstract

PURPOSE:To prevent oxidation or decomposition of effective components, especially, a black-and-white developer, to retain effectivity of the developing soln. for a long term, and to prevent tar and sludge for a long term by processing development in the presensce of an aromatic primary amine type color developing agent, the black-and-white developer, and manganese salt and/or a cerium salt. CONSTITUTION:A color developing agent is used generally in an concn. of 0.1- 30g, the black-and-white developer in 0.003-10g, and a manganese salt and a cerium salt in 0.1-20mg in terms of ions, all per liter of the developing soln. The use of only the color developing agent cannot achieve rapid development, and deteriorates storage stability. The use of a combination of said agent and the black-and-white developer can achieve rapid development, but deteriorates storage stability. The use of the agent and the manganese salt or the cerium salt improves storage stability but cannot achieve rapid development.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for processing silver halide color photographic light-sensitive materials, and more specifically, to a method for processing silver halide color photographic materials using a stable color developing solution with improved storage stability. This invention relates to a method for processing photographic materials.

[Conventional Wave #I] In general, silver halide color photographic light-sensitive materials form dye images through 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 undergoes a coupling reaction with the coexisting color coupler to form a dye image with an image pattern, and at the same time, reduced silver is generated. 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 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 processing baths such as backing removal processing baths 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. In addition, dihydroxyacetone, anilinoethanol, hydroxylurea, etc. are known as sulfite and hydroxyl ane kl:fl preservatives.

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 solution to become longer, and the developing solution is increasingly subject to air oxidation. There is.

In addition, as processing becomes faster, a method is known in which black and white developers such as 3-pyrazolidones and hydroquinones are added to the color developing solution to accelerate development due to their super-additivity. In color developers, where large amounts of sulfite cannot be added because of the adverse effect it would have on the color, the black and white developer is extremely unstable.

Furthermore, as another means of speeding up processing, photographic materials are now being processed at high temperatures of 30°C or higher.
Problems such as deterioration of these developing solutions are becoming more and more serious due to oxidation caused by high temperatures.

[Object of the Invention] The object of the present invention relates to these problems, and the first object is to develop a silver halide color photograph using a color developing solution containing a black and white developer that has good long-term storage stability and good processing durability. An object of the present invention is to provide a method for processing photosensitive materials (hereinafter abbreviated as color photosensitive materials).

A second object is to provide a method for processing color photosensitive materials using a color developer containing a black and white developer, which is capable of reducing the generation of tar and sludge due to the oxidation of color developing agents during long-term storage.

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.

[Structure of the Invention] The color photosensitive material processing method of the present invention is characterized in that after the color photosensitive material is imagewise exposed, development processing is carried out in the presence of the following (a), ←) and (c). .

(a) Aromatic primary amine color developing agent compound (b)
Black and white color developing agent (c) Manganese salt and/or cerium salt The aromatic primary amine color developing agent compound according to the present invention is '9-
722Diamine-based color developing agent compounds are preferred, such as 4-anoN, N-diethylaniline, 3
-Methyl-4-Ryominnow N, N-diethylaniline, 4
-Amino-H-Ethyl-N-β-Hydroxyethylaniline, 3-Methyl-4-amino-N-ethyl-β-Hydroxyethylaniline, 3-Methyl Ichiban-Ryominor N
-Ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-in-β-methoxyethylaniline, 3-β-methanesulfonomidoethyl-4-methanesulfonamidoethylaniline, N-diethyl Ryonirin, 3-
methoxy-4-amino-N-ethyl-N-β- and drexyethyl ryoniline, 3-methoxyichiban-amino-N-ethyl-N-β-methoxyethylaniline, 3-acedodate-4-amino-N, N-diethylaniline, 4-amino-N, M-dimethylaniline, N-ethyl-N-β
[β-(diβ-methoxyethoxy5-cy]ethoxy]ethyl-5-methyl-4-aminoaniline or N-ethyl-N-N-β-(β-methoxyethoxy)ethyl-3-methyl-4-aminoaniline and salts thereof, such as sulfates, hydrochlorides, sulfites or 11-)luenesulfonic acid.
．． It is used at a concentration of 1 g to about 3 Q.lit, more preferably about 1 g to about 15 g per developer solution 11.

Further, the above color developing agents may be used alone or in combination of two or more. Furthermore, the above-mentioned color developing agent may be incorporated into the color light-sensitive material. For example, there are methods such as U.S. Patent No. 3,719,492 in which a color developing agent is made into a metal salt and incorporated therein, and U.S. Patent No. 3,342,559 and Research Disclosure (Re*earoh Di
golosure) A method of incorporating a color developing agent into a Schiff salt as shown in 19'76 A15159, JP-A-58-65429 and JP-A-58-241.
No. 3'7, etc., and a method of incorporating the dye precursor as a dye precursor, as shown in U.S. Pat. No. 3,342.5,
The black and white developer according to the present invention is a developer that reacts with a coupler and does not produce a dye, and is a developer having the following general formula [I ] 3-pyrazolidones or hydroquinones, a-phenols or phenylenediamines, and the like can be mentioned.

General formula [I R.

In the formula, R,, R,, R, and R4 are each a hydrogen atom,
R represents an alkyl group or an aryl group, and R6 represents a hydrogen atom or a cetyl group.

Next, specific exemplary compounds of the black and white developer used in the present invention will be listed, but the compounds are not limited thereto.

Exemplary compound I-1■-4 I-s I-a I-5I-6 1-'y ■-8 9- II-III-1! H 10- II-5II-6 11-7n-8 H ■-I III-2 H [[-3III-4 NHOH,0OOH IV-3IV These black and white developers usually contain sulfates, hydrochlorides, and nitric acid rings. , sulfite or p-)luenesulfonate, but it does not need to be a salt. The black and white developer is generally developer 11.
It is used at a concentration of about 39 to 10 g per developer, more preferably from 9 to 5 g per developer. Furthermore, the above-mentioned black and white developing agents may be used alone or in combination of two or more.

Furthermore, the black and white developer may be incorporated into the color photosensitive material. For example, JP-A No. 58-53532,
No. 58-501536 and British Patent No. 1,032,925
A method of incorporating 3-pyrazolidones as described in U.S. Pat. No. 2,592,3 f321, U.S. Pat.
'i' and British Patent No. 1,177,488, in which catechol and hydroquinone derivatives are dispersed and incorporated into emulsions; No. 3,379,529;
No. 3,246,988 and British Patent No. 1,055,920
No. 11066.991, a method of incorporating the precursor as a precursor is known.

Among these black and white developers, 3-pyrazolidones are particularly preferably used from the viewpoint of superadditivity effects.

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 manganese nitrate 13- Potassium permanganate Manganese 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 Cerium 1.2-cyclohexanediaminetetraacetic acid cerium salt These manganese salts and cerium salts can be used in the form of ions (-rganese ion and cerium ion) in the range of 0.11n9 to 20 Da per developer 11, Preferably it is present in an amount of 0.31119 to 8.

14-Furthermore, the manganese salt may have any valence of divalent, trivalent, tetravalent, hexavalent or heptavalent, but divalent manganese salt is particularly preferably used in the present invention. Further, the cerium salt may be either trivalent or tetravalent, but trivalent cerium salt is particularly preferably used in the present invention.

Furthermore, these manganese salts and cerium salts may be incorporated into color photosensitive materials.

In the present invention, the desired effect of the present invention is achieved when the aromatic primary amine color developing agent compound, black and white developer, and (manganese salt and/or cerium salt) coexist. Particularly favorable effects are achieved when all of the relevant compounds are present in the developer.

The aromatic primary amine color developing agent black-and-white developer and (manganese salt and/or cerium salt) according to the present invention are used when the amount of the black-and-white developer added is 1. Main ingredient]: [Black and white developer]: [Manganese salt and/or
or cerium salt]=(0,01-10000):
1: Used in a ratio of (0,00001 to 7).

Further, various chelating agents can be used in combination as metal ion sequestering agents in the developer according to the present invention. For example, as the chelating agent, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, 1
-organic phosphonic acids such as hydroxyethylidene-1,1-diphosphonic acid, polyphosphonic acids such as methylenephosphonic acid 2 or ethylenediaminetetraphosphoric acid, oxycarboxylic acids such as citric acid or gluconic acid, 2-phosphonobutane- 1,2,4-) Phosphonocarboxylic acids such as recarboxylic acid, polyphosphoric acids such as tripolyphosphoric acid or hexametaphosphoric acid, etc., which are particularly preferably used (7) C. The following general formula C
V), (VD, (■) and CVM) General Formula (V) Mul A1 In the formula, AI 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 phosphoric acid group. r and! each represents 0.1 or 2, n represents an integer of 1 to 4, and m represents an integer of 0 to 3.

General formula (VD General formula (V[) 17 In the formula, A3, A4, A6, 0, A, and A each represent an alkylene group, and M1 to M.

represents a hydrogen atom or an alkali metal atom. 2 represents a divalent organic group, preferably an alkylene group, a cycloalkylene group, or an alkylene group containing an oxygen atom or a nitrogen atom; furthermore, the alkylene group containing an oxygen atom or a nitrogen atom is represented by the following general formula ( a) or (
Those represented by b) are preferred.

General formula (1) In the formula, n has the same meaning as defined in the above general formula (I), and A represents a lower aliphatic carboxylic acid.

In the general formula (b) -L-0-L-0-L, L represents an alkylene group, for example, an ethylene group.

18- General formula (vI) P.O., H.

Rmer0-OH Thunder P.O., H.

In the general formula (I), R1 represents an optionally substituted alkyl group having 1 to 5 carbon atoms.

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

Exemplary Compound Ni-1 0H,0OOH -2 -5 OH,0OOOHH,0OOH OH,Cool OH,0OOH 0H@PO,Nb2 These compounds are described in U.S. Patent No. 3,632,637 and Journal of the American It is synthesized by a general synthesis method as described in Chemical Society Volume 1.89 (1967), page 837.

Next, typical specific examples of compounds preferably used in the present invention represented by the general formula (VT) or (■) are listed.
− Includes, but is not limited to.

VI-1 Sodium nitrilotriacetate VI-2 Nitrilotripionic acid VT-3 Propionic acid nitrilodiacetate ■-1 Pentasodium diethylenetriamine pentaacetate ■-2 Glycol ether diamine tetraacetic acid ■-31
, 3-cyano-2-ppanoltetraacetic acid ■-4 Schiff tetrahexanediaminetetraacetic acid ■-6 ethylenediaminetetraacetic acid disodium ■-61,2-diryodennobu tetrapan-N, y, N'.

N'-tetraacetic acid Next, typical examples of compounds preferably used in the present invention represented by the general formula (vID) will be listed, but the compounds are not limited thereto.

■-11-hydroxyethylidene-1,1-diphosphonic acid ■-21-hydroxypropylidene-1,1-22-diphosphonic acid ■-31,2-dihydroxyethane-1,1-diphosphonic acid In the present invention, the general The compound represented by formula (V) can be used in an amount of 3TR9 to 1 g per developer solution, preferably 5 to 0.5 fl, and more preferably 8 to 0.1 g to obtain good results. is obtained. Further, the compounds represented by the general formulas (VD and (■)) can be used in an amount of 0.1 to 5 g per 1! of the developer, and good results can be obtained by preferably adding 0.5 to 3 g. .

Furthermore, the amount of the compound represented by the general formula (■) is in the range of 0.01 g to 10 g per developer solution 11, preferably 0.01 g to 10 g per developer.
．． Good results are obtained when used in the range of 1 g to 1 g.

The general formula (V), (VI), (VID or C (%lN)
The mark compounds shown in TE are those listed in (a) and (b) above according to the present invention.
When used in combination with and (c), they may be used alone or in combination.

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

However, in addition to the metal ion sequestering agent preferably used in the present invention, other metal ion sequestering agents (polyphosphoric acid, oxycarboxylic acid, aminopolyphosphoric acid, hydroxypolycarboxylic acid, phosphonocarboxylic acid, etc.) may be added. Use is optional.

The general formula (V), (VD, (VID) and (2)
The metal ion sequestering agent shown in the formula has the effect of preventing the decomposition of preservatives such as sulfite and hydroxylamine in the developer by the existing manganese ions and cerium ions, and giving stable photographic properties. .

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, dimethylformide, dimethylsulfoxy F, etc. can be appropriately contained.

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

The color developer used in the present invention may optionally contain antioxidants such as hydroxylamine, tetronic acid, tetronimide, 2-anilinoethanol, dihydroxyacetone, aromatic secondary alcohol, hydroxamic acid, pentose, or Hexose Spirga p-Rue 1.3-
Dimethyl ether and the like may also be contained.

The processing method of the present invention can be applied to any processing of general silver halide color photographic materials such as color negative film, color paper, color positive film, color reversal film, and color reversal paper.

[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] (Experiment 1) An experiment was conducted using the following color developing solution for color paper as a basic formulation.

(Color developing solution composition 26 - 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 in a beaker at room temperature for 20 days.The amount of decomposition of the black and white developing agent in the developer after storage was quantified, and the degree of coloration of the developer was measured by measuring the absorption at 450 mm with a spectrophotometer.

(Experiment 2) Sakura Color PO Paper Type 811 (manufactured by Konishiroku Photo Industries) was used with a KS-7 sensitometer (manufactured by Konishiroku Photo Industries).
After white stepwise exposure was applied using the developer sample, developer samples (A) to (T) after being left for 20 days in Experiment 1 were used to perform color development according to the following steps.

Processing process Temperature C℃) Time (minutes) Color development 33℃ 2 minutes bleach-fixing 33℃ 1 minute 30 seconds Washing 25-35℃ 1 minute Drying 75-80℃ 1 minute The bleach-fix solution used was -Benoku-processing agent, 0PK-15 (manufactured by Konishiroku Photo Industry ■).

For those that have undergone the above color development process, PDA-60
The maximum density of blue was measured using a type densitometer (manufactured by Konishiroku Photo Industry ■).

The above results are summarized in Table 2.

Table 1 29-Table 2 Note 1) The degree of coloration of the developer is shown by the absorbance at 460 mm, and the lower the absorbance, the less coloring and the lower the degree of tar.

30- As the above results show, developer sample (B) according to the present invention
It can be seen that in case of H), the decomposition of the black and white developing agent is small, the degree of coloring of the developer is extremely low, and the decrease in the maximum density measured by sensitometry is also extremely small.

On the other hand, in Comparative Samples (1) to N) and (A), the black and white developing agent decomposes to a large extent, the degree of coloring of the developer is large, and the maximum density is greatly reduced, making them impractical.

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 developer is highly colored and has a high degree of tar. Furthermore, it can be seen that the decomposition of the black and white developer is large and the development activity is deteriorated.

Although the desired effects of the present invention can be obtained without using a sequestering agent, general formulas (V), (V
D, (VID and U (Vl)) It can be seen that even more excellent effects can be achieved when using the gold-14 ion sequestering agent indicated by "1:".

[Example 2] The amounts of manganese ions added to the developer (G) used in Example 1 were O, O, :L, 0.3.0.
5.1.0~50.8.0.20.0.30.0%
The same experiment as in Example 1 was carried out by firing at 40.0 ■/l. The results are shown in Table 3.

From the above results in Table 3, when the metal salt (manganese salt) according to the present invention is present in the form of an ion at 0.1-20 m9/73, the decomposition of the black and white developer, the tarring of the developer, and the development activity are It can be seen that good results are obtained, particularly when used in the range of 0.3 to BH9/l.

[Example 3] (Experiment 3) An experiment similar to that described above (Experiment 1) was conducted by changing the color developer for color paper used in Example 1 (Experiment 1) to the following color developer for color reversal paper (Experiment 1). .

Color developer composition 33- (Experiment 4) The color photosensitive material used in Example 1 (Experiment 2) was replaced with the following color reversal paper (an experiment similar to the experiment was conducted).

(Color reversal paper) A color reversal paper was prepared by sequentially applying the following layers onto a resin-coated paper support from the support side.

Layer 1...Cyan-forming red-sensitive silver halide emulsion layer JP-A-Sho! An internal latent image type silver halide emulsion was prepared according to the method described in US$5-11'7549.

That is, in zaOml of a 1 molar aqueous solution of potassium chloride containing gelatin 10II, 2 ml of a 1 molar aqueous solution of silver nitrate was added at 60°C.
oo 11114 was added immediately. 3 for 10 minutes
4- After physical ripening, a 1 molar aqueous solution of potassium bromide 20
A mixed solution of 0.0d and 5 owtl of a 0.1 molar aqueous solution of potassium iodide was added. In order to coat the obtained conversion type silver chloroiodobromide grains with a silver chloride shell, 150 uJ of a 1 molar aqueous solution of silver nitrate was added for 5 minutes, and after physical ripening for 20 minutes, the grains were washed with water.

Cyan coupler 2,4-dichloroa-3-methyl-6-
[α-(2,4-di, tart-arylphenoxy)butylamitocophenol 70g, 2゜5-dite
A mixture of 29 g of rt-octylhydroquinone, 50 g of dibutyl phthalate, and 140 g of ethyl acetate was mixed and dissolved, and added to a gelatin solution containing sodium isopropylnaphthalene sulfonate for emulsification and dispersion.

The dispersion was then added to the emulsion which had been spectrally sensitized with the following dyes, and 1 g of 4-hydroxy-6-methyl-1,3,3m, 'F-tetrazaindene, and 2,5-dihydroxy-4 were added. Potassium octadecylbenzenesulfonate II was added, and bis(vinylsulfoylmethylnoether) was added as a hardening agent, and coating was carried out so that the amount of silver was 400 .mu./zi and the amount of coupler was 460 .mu./ze.

Layer 2: Intermediate layer 100 d of a 25% gelatin solution containing gray colloidal silver 5II and dibutyl 7-thalet dispersed 2,5-di-tert-octylhydride p-quinone 10Ii was mixed with colloidal silver 40011% F/m" It was applied so that

N3...Magenta-forming green-sensitive silver halide emulsion layer magenta coupler 1-(2,4,6-)lichlorophenyl J-3-(2-chloro-5-octadecylsuccinimideanilino)-5- Vilazoone 40g, 2,5-
1 g of di-tert-octylhydroquinone and 30 g of dioctyl 7-thaletate qrsgz ethyl acetate were mixed and dissolved, and added to a gelatin solution containing sodium isopropylnaphthalene sulfonate for emulsification and dispersion. The dispersion was then added to the above emulsion which had been spectrally sensitized with the following dyes and 4-hyFOxy-6-methyl-1,B,3m,? - Added 1 g of tetrazaindene, 19 potassium 2,5-dihydroxy-4-octadecylbenzenesulfonate, added 37-thyl bis(vinylsulfonylmethylmethyl) as a hardener, silver amount 4 ooy/m'', coupler. It was applied in an amount of 400 In9/rI?

Layer 4...Yellow filter layer 2 dispersed in 5 g of colloidal silver and dibutyl phthalate,
2 containing 5g of 5-di-tert-octylhydroquinone
．． A 5% gelatin solution was applied so that colloidal silver was 2 oomgz/m.

Layer 5... Yellow-forming blue-sensitive silver halide emulsion layer α-[4-(1-benzyl-) as a yellow coupler
2-phenyl-3,5-dioxo-1゜2.4-)-aziridinyl)]-]α-pivalyl-2-chloro5-[
r -(2T 4-di-tert-amylphenoxybutyramide] acetanilide BO9,2,5-di-tert-octyl #/% 1 g of di-tetraquinone, 80 g of dibutyl 7 thale), i [mix and dissolve 200 g of ethyl, isopropyl It was added to gelatin solution containing sodium naphthalene sulfonate and emulsified and dispersed. The dispersion was then added to the emulsion and 4-hydroxy-6-methyl-1,3°
38- Add 1 g of 3a,7-chitrazaindene, 1 g of potassium 2.5-dihydroxy-4-sec-octadecylbenzenesulfonate, add bis(vinylsulfonyl methyl ether as a hardening agent, silver amount 400q/yy1'',
Coating was carried out so that the amount of coupler was 53oTn9/m7.

Layer 6...Protective layer It was applied so that the amount of gelatin was 200+19/m.

Note that layers 11, 2, N3, 4, 5, and 6 contained saponin as a coating aid.

The above sample was subjected to wedge exposure using an MS-7 type sensitizer (manufactured by Konishiroku Photo Industry ■), and then developed according to the following steps.

Processing process (38℃) Processing time Color development 1 minute 30 seconds (For light fog exposure, after immersing the sample in the developer for 10 seconds, place it horizontally in the developer at a height of 13 mm from the liquid level, and expose it to light or vertically. The exposure conditions for fogging were as follows: a daylight color fluorescent lamp was used as the light source, the illuminance was set to 1 on the photosensitive surface, and a neutral density filter was used. I made it look like a lutx.

The bleach-fix solution used was as follows.

Bleach-fix solution (adjusted to pH 7.0 with sodium hydroxide or glacial acetic acid) After the above color development process, use a PDA-60 type photoelectric density needle (manufactured by Konishi Roku Photo Industry ■) to obtain the highest blue color. The concentration was measured.

As a result of conducting the above (Experiment 3) and (Experiment 4), the same results as [Example 1] were obtained.

[Example 4] The color developer used in [Example 1] (Experiment 1) from which the black and white developer (exemplified compound (■-3)) was removed was used as a control sample (0), and the developer ( 0) to which 1 ppm of 0eO1° was added as cerium was used as a developer (N), and the color developing solutions (A) and (D) used in [Example 1] (Experiment 1) were used for development processing. The time required for the maximum blue density to reach 2.40 was measured.

Furthermore, a storage experiment similar to Example 1 (Experiment 1) was conducted. The above results are summarized in Table 4.Table 4 41- In the above table, (-) indicates that the developer was not colored, and x indicates that the developer was heavily colored and some tar was generated.

Table 4 shows that when using only a color developing agent, rapid processing cannot be achieved and storage stability is poor. Furthermore, when a color developing agent and a black and white developer are used in combination, rapid processing is achieved, but storage stability is poor; furthermore, when a color developing agent and a cerium salt are used in combination, storage stability is good. However, rapid processing is not achieved. □However, it can be seen that when the developer (D) of the present invention is used, the storage stability is good and rapid processing can be achieved.

[Example 5] [Example 1] Exemplary compounds in the developer (D) used in (Experiment 1) (■-31 (I-1), Cl-13), (II
-17, ([r-4), (■-3), (IV-4)
and one without additives, and were developed in the same processing steps as in (Experiment 2), and the blue sensitivity obtained with each developer was evaluated.

-4 and -, Table 5 (Note 2) In the table, the sensitivity indicates the relative sensitivity when the sensitivity of the sample without the addition of black and white developer is set as 100.

This shows that when a black and white developer is used in combination, the sensitivity increases significantly despite the addition of a small amount.

It is also found that among black and white developers, when 3-pyrazolidones are used, the effect of this superadditivity is large.

[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, especially the black and white developer, due to air and oxygen dissolved in the developer, and the effectiveness of the developer can be maintained over a long period of time and always maintained at a constant level. Processing results are obtained.

(2) Even after long-term storage, there is no generation of tar or sludge due to the oxides of the color developing agent and black and white developer, there is no staining of the processing tank of the automatic processor, there is no clogging of the filter, and there is no problem with the processing material. It does not contaminate certain color photosensitive materials.

Agent Yoshimi Kuwahara

Claims (1)

[Scope of Claims] Silver halide color photographic light-sensitive material is imagewise exposed and then developed in the presence of the following (a), (b) and (c). How materials are processed. (a) Aromatic primary amine color developing agent compound (b)
Black and white developer (c) Manganese salt and/or cerium salt