JPH01295255A - Method for processing silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To lessen the generation of a fog, and to stabilize the title material for a long period even in case of mixing a heavy metal ion in a color developer by incorporating at least 90mol.% of silver chloride in at least one layer of silver halide emulsion layers, and by subjecting the photosensitive material to a development processing with the color developer at specified conditions. CONSTITUTION:At least 90mol.% of the silver chloride is incorporated in at least one layer of the silver halide emulsion layers contd. in the silver halide color photographic sensitive material, and the color developer contains at least a bromide of >=4X10<-4>mol.% and 0.3-10g of benzyl alcohol per 1l of the color developer, and the processing time of the photosensitive material in a color development processing step is >=90sec. The concrete example of the bromide is exemplified by potassium bromide, sodium bromide and lithium bromide, etc. Thus, the generation of the fog is reduced, even in the case of mixing the heavy metal ion in the color developer, and the stable photographic characteristic of the photosensitive material is obtd. for the long period.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for processing silver halide color photographic materials, and more specifically, to a method for processing silver halide color photographic materials that provides stable processing characteristics over a long period of time. Regarding the method.

[Background of the invention]

Generally, in a method of forming a dye image by processing a silver halide color photographic light-sensitive material, after imagewise exposure, an oxidized p-phinididine diamine color developing agent and a dye image-forming coupler are combined. They are reacted to form a dye image. In this method, a subtractive color reproduction method is usually applied, and cyan, magenta and yellow dye images corresponding to red, green and blue are formed in respective photosensitive layers. In recent years, in forming such dye images, high-temperature development and omission of processing steps have generally been carried out in order to shorten the development processing time. In particular, in order to shorten the development time, it is extremely important to increase the development speed in color development. The development speed in color development is influenced by two directions. One is a silver halide color photographic light-sensitive material, and the other is a color developer.

In the former case, the composition of the grains of the silver halide emulsion used has a great influence on the development speed, and in the latter case, the conditions and composition of the color developing solution have a great influence on the development speed.

Hydroxylamine and sulfites have traditionally been used as preservatives in color developers. Hydroxylamine is particularly effective as a preservative for p-phenylenediamine color developers.

However, hydroxylamine has the disadvantage of being oxidized and decomposed to generate ammonia. This ammonia acts on the silver halide photographic light-sensitive material, causing ammonia fog in the light-sensitive material. In particular, the presence of heavy metal ions (iron ions, copper ions, etc.) in the color developing solution makes hydroxylamine more easily decomposed.

Various chelating agents have been devised and used to complex heavy metal ions and prevent their adverse effects. Specific examples of these chelating agents include aminopolycarboxylic acids, polyphosphoric acids, and organic phosphoric acids. However, although these chelating agents are effective against iron ions, they are not very effective against copper ions.

In addition, there is a recent trend toward low replenishment of color developing solutions due to economic efficiency and reducing the amount of waste liquid, and the concentration of heavy metal ions that accumulate in color developing solutions tends to increase, so it is necessary to eliminate the above drawbacks. is increasingly desired.

On the other hand, silver halide color photographic light-sensitive materials (hereinafter referred to as
It is called a silver chloride color photographic material. ) can be developed more quickly than conventional color photographic materials made of silver halide emulsions containing silver bromide or silver iodide, such as silver chlorobromide, silver chloroiodobromide, or silver iodobromide emulsions. Moreover, bromide ions and iodide ions, which control the development reaction, are not accumulated in the color developing solution, making it extremely useful as a light-sensitive material for rapid processing. The present inventor conducted various studies using a silver chloride color photographic light-sensitive material suitable for rapid processing and found that it had the following drawbacks.

That is, firstly, the hydroxylamine, which is conventionally used as a preservative, acts as a developer for silver chloride, and silver development progresses, resulting in color development of the final dye image. The concentration has decreased.

=3- Also, secondly, sulfite, which is used as another conventional preservative, acts as a dissolving agent for silver chloride, and physical phenomena proceed rapidly, resulting in the silver development reaction and coupling reaction. The balance was disrupted, that is, silver development took too much of an advance and the compulsory reaction was delayed, resulting in a decrease in color density.

Thirdly, research conducted by the present inventors has revealed that fogging is particularly likely to occur when heavy metal ions are mixed. This fog increased overall, but in particular, when used to prevent a decrease in dye image density, the fog in cyan color development was large.

These heavy metal ions pose a particular problem when a large amount of light-sensitive materials are processed continuously.

In addition, in development processing methods in which silver halide photographic light-sensitive materials are continuously processed using an automatic processor, etc., the components of the color developer are kept within a constant concentration range in order to avoid changes in development finish characteristics due to changes in component concentration. means are necessary. As such a method, a method is usually used to replenish the deficient components and dilute the unnecessary increased components.

The replenishment of this replenisher inevitably results in large amounts of overflow, which are discarded, making this method a major economic and pollution problem. Therefore, in recent years, in order to reduce the overflow liquid, the so-called concentrated low replenishment method, in which these replenishers are concentrated and replenished in small amounts, and the electrodialysis method, which effectively replenishes the replenishment liquid in small quantities, and the regeneration of the developer using ion exchange resin have been developed. There is a social need for such a method, and in such a method, heavy metal ions are particularly likely to accumulate, and a solution to the above problem is strongly desired.

Furthermore, it has been found that in such low replenishment processing, the amount of evaporation increases, resulting in concentration of the color developing solution, resulting in other drawbacks such as difficulty in obtaining stable photographic properties (especially maximum yellow density). It's here. In particular, this drawback cannot be ignored when running processing is performed discontinuously over a long period of time, such as in minilabs.

[Object of the present invention]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a method for processing a silver halide color photographic light-sensitive material that causes less fogging even when heavy metal ions are mixed into a color developing solution and provides stable photographic properties over a long period of time.

[Structure of the invention]

The above object of the present invention is to provide a method for processing a silver halide color photographic material in which the silver halide color photographic material is imagewise exposed and then processed using a color developing solution. At least one of the silver halide emulsion layers contains at least 90 mol % of silver chloride, and the color developing solution contains at least 4 x 10-'' moles of bromide and benzyl alcohol from 0.3 g to 0.0 g per color development α. This has been achieved by a method for processing a silver halide color photographic material, which is characterized in that the processing time of the color development processing step is 90 seconds or more.

[Specific structure of the invention]

Specific examples of bromides used in the color developing solution of the present invention include potassium bromide, thorium bromide, and lithium bromide. is essential, preferably 8X]0 mole/a to 1.2X 10-2 mole10. ,
More preferably 1.6X 10-3 mol/Q-1.0X
10-2 mol/L, particularly preferably 3.2X]
, O bow mol/a to 8.4X 10-3 mol/L1, the desired effects of the present invention can be achieved satisfactorily.

Furthermore, benzyl alcohol according to the present invention is a color developer I.
The desired effect of the present invention is achieved when used in a range of 0.3 g to 10 g per Q, and the desired effect cannot be obtained outside this range. Especially 0.5 g/4-5 g/(t
and especially in the range of 0.7 g/l
The range of ~35g/Q is good.

The color development process in the present invention is usually carried out at 20°C to 800°C.
The temperature is preferably 30°C to 50°C.

The pH of the color developing solution used for development is generally 8 or higher, preferably 9.5 or higher.

Development is carried out in the presence of pH buffers, development inhibitors, antifoggants, water softening complexing agents, preservatives, development accelerators, competitive couplers, fogging agents, auxiliary developer compounds and viscosity modifiers. Can be done; Lisa-8 = Ichichie Disclosure (Researchb Dis
Closure) 17544. December 1978, Section XXI, Industrial Opportunities, Inc.
1. td, ), (Homewell Havant.

Hampsbire, published by GrentBritain, and published by Ullmanns Endiklovedei der Techni.
Nocien Hemy (formerly 1mans Enzy)
klpudie der technisehe
nChemie), 4th edition, vol. 18, 1979, especially pages 451-452 and 463-465. A suitable developer composition is found in Grant Haist.
st), Modern Photographic Processing
ssing), John Willey and 5ans, 1
973, Vol. 2 and 2.

Particularly useful color developing agents used in the color developing solution of the present invention are N,N'-dialkyl-p-phenylenediamine compounds, and the alkyl group and phenyl group may be substituted with any substituent. Among them, particularly useful compounds include N,N-diethyl-p-7enylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride,
N,N-dimethyl-p-phenylenecyamine hydrochloride, 2
-Amino-5-(N-ethyl-N-Fde/R-N-dodecylamino)-toluene sulfate, N-ethyl-N-β-
Methanesulfonamide edyl-3-methyl-4-aminoaniline sulfate, N-ethyl-N-β-hydroxyethyl-3-methyl-4-aminoaniline sulfate, 4-amino-3-methyl-N,N '-diethylaniline sulfate,
Examples include 4-amino-N-(2-methoxyethyl)-N-ethyl-3-methylaniline-p-toluenesulfonate.

Other suitable color developers are e.g.
American Chemical Society (J.

Amer, Cbem, Soc, ) 73.310
0 (1951). Additionally, black and white developer materials may also be used.

According to one particularly preferred embodiment, the color developing solution is as follows:
The color developer is usually I x 10 per 1Q of color developer.
It is preferable to use the amount in the range of -2 moles to 2X 10-' moles, but from the viewpoint of rapid processing, the range of 1.5X 10-2 moles to 2X 10-' moles per color developer 112 is more preferable.

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

Furthermore, when the color developing solution of the present invention contains a compound represented by the following formula [■], it is not possible to achieve particularly good effects of the present invention, but also to prevent crystal precipitation on the liquid surface of the color developer tank. Because it becomes good and has different effects,
This is listed as one of the more preferred embodiments of the present invention.

General Formula [I] In the formula, R1 and R2 each represent an alkyl group or a hydrogen atom. However, both R1 and R2 are not hydrogen atoms at the same time. Further, R1 and R2 may form a ring.

In the general formula [I], R1 and R2 each represent an alkyl group or a hydrogen atom that is not a hydrogen atom, or
The alkyl groups represented by R1 and R2 may be the same or different, and each is preferably an alkyl group having 1 to 3 carbon atoms. The alkyl groups of Ro and R2 include those having substituents, and R1 and R2 may be combined to form a ring, for example, a heterocyclic ring such as piperazine, piperazine, or morpholine.

Specific compounds of the hydroquinlamine derivative represented by the general formula [■] are described in U.S. Patent Nos. 3,287,125, 3,293,034, and 3,287,124, However, particularly preferred specific exemplary compounds are shown below.

These compounds are usually free amines, hydrochlorides, sulfates,
p-toluenesulfonate, oxalate, phosphate,
It is used in the form of acetate, etc.

The concentration of the compound represented by the general formula CI) in the color developer is usually 0.2 g/L to 50 g/L, preferably 0.5 g/L.
/Q~30gIQ, more preferably 1g/(1~1
It is 5g#l.

Furthermore, a compound represented by the general formula [■] and a conventionally used hydroxylamine can also be used in combination.

When the color developing solution according to the present invention contains a compound represented by the following general formula [D], it not only exhibits the effects of the present invention better, but also prevents air oxidation of the color developing solution. It is more preferably used because it shows an improvement effect.

General formula [D] In the formula, R2 is a hydroxyalkyl group having 2 to 6 carbon atoms,
R22 and R23 are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group having 2 to 6 carbon atoms, a benzyl group, or an integer of formula 6, X' and Z' are each a hydrogen atom, and each is a hydrogen atom, and
represents an alkyl group or a hydroxyalkyl group having 2 to 6 carbon atoms.

Preferred specific examples of the compound represented by the general formula [D] are as follows.

(D-1) Ethanolamine, (D-2) Jetanolamine (D-3) l-jetanolamine, (D-4) Di-isopropanolamine, (D-5) 2
-Methylaminoethanol, (D-6) 2-diethylaminoethanol, (D-7) 2-dimethylaminoethanol, (1)-8) 2-diethylaminoethanol (D-
9) l-diethylamino-2-propatol, (D-1
0) 3-diethylamino-1-propatol, (D-
], ], ) ]]3-dimethylamino-1-propatol D-12) Isopropylaminoethanol, (D
-13) 3-amino-1-propatol, (Di4)2
-amino-2-methyl-1,3-brono(diol), (D-15) ethylenediaminetetraisobronoquinol, (D-16) benzyljetanolamine, (D-1
7) 2-amino-2-(hydroxymethyl)-1,3-
Propanediol.

From the viewpoint of the desired effect of the present invention, these compounds represented by the general formula CD) should be used in a range of 1 g to 1 g per color developer IQ.
Preferably used in the range of 00g, more preferably 2g
It is used in the range of ~30g.

In the processing method of the present invention, the effect of the present invention is especially remarkable when the replenishment amount of the color developer is in the range of 1Qm12 to 300m(2) per 1m2 of the light-sensitive material. Preferably it is in the range of 30m4 to 100mQ.

In the present invention, the processing time of the color development process is 90
It is essential that the time is at least seconds; if it is less than this, the desired effect of the present invention cannot be achieved. A range of 100 seconds to 360 seconds is particularly preferred, a range of 120 seconds to 300 seconds is especially preferred, and most preferably a range of 150 seconds to 24 seconds.
The range is 0 seconds.

In the present invention, from the viewpoint of rapid processing, a bleach-fix solution is preferably used after color development.When a high silver chloride photosensitive material is used as in the present invention and bleach-fix treatment is carried out immediately after color development, a solution called bleach-fixing solution is used. Stains are easy to form. Therefore, after various studies, the I)H of the bleach-fix solution was 4.5 to 6.8.
It has been found that by using the scale within the range of , it is not possible to solve this problem, but it also has the effect of speeding up the silver bleaching rate.

Particularly, this effect is good when the pH of the bleach-fixing solution is 5 to 6.3.

In the process of the present invention, silver may be recovered by known methods from processing solutions containing soluble silver complexes such as washing or washing substitute stabilizing solutions, fixing solutions, bleach-fixing solutions, and the like. For example, electrolysis method (French Painting Patent No. 2,299゜667), precipitation method (
Japanese Patent Application Publication No. 52-73037, German Patent 2゜331.22
0), the ion exchange method (JP-A-51-17114, German Patent No. 2,548.237), and the metal substitution method (British Patent No. 1,353,805) can be effectively used.

In the processing method of the present invention, after color development, bleaching and fixing (or bleach-fixing), stabilizing treatment may be performed without washing with water, or washing with water may be performed followed by stabilizing processing. 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. A typical example of a preferred treatment method includes the following steps.

(1) Color development → Bleach-fix → Water washing (2) Color development - Bleach-fixing One small amount of water washing One water wash (3) Color development - Bleach-fixing - First stabilization (4) Color development → Bleach-fixing - Stability (5) Color development - Bleach-fixing - 1st stability - 2nd stability (6)
Color development - washing with water (or stable) - bleach-fixing - washing with water (or stable) (7) Color development → stop - bleach-fixing → washing with water (or stable) (8) Color development - bleaching, washing with water, constant fixing, washing with water, stabilizing (9) )
Color development → Bleaching constant → Washing - Stable (10) Color development →
Bleaching - Small amount of water washing → Fixing - 1st stability - 2nd stability (11) Color development - Bleach - Small amount of water washing Constant fixing - Small amount of water washing →
Washing with water → Stable (12) Color development → Washing with a small amount of water → Bleaching → Washing with a small amount of water → Fixation →
A small amount of water washing -> Water washing - Stability (13) Color development - Stopping - Bleaching - Small amount of water washing - Constant setting -> Small amount of water washing - Water washing -> Stability Among these steps, especially the steps (4) and 5) are preferably used.

The silver halide grains used in the silver halide emulsion layer of the present invention contain at least 90 mol% of silver chloride, and the remainder may contain bromide and iodide, but it is preferable that they are substantially silver chloride, and bromide , iodide is preferably present in a very small amount.

In particular, when silver chloride is 95 mol% or more, the desired effects of the present invention are well exhibited, and more preferably 98 mol% or more.
That's all. In a special case, one preferred embodiment is that the blue-sensitive layer is silver halide containing 30 mol% of bromide, and the other two layers, for example, the green-sensitive layer and the red-sensitive layer, are about 99% chloride. It is.

The silver halide is preferably a core-shell particle and has a double layer structure.

At least 90 mol% of the silver chloride used in the present invention
The /S silver halide emulsion layer containing silver halide grains having a color coupler. These color couplers react with color developer oxidation products to form non-diffusible dyes. Color couplers are advantageously incorporated in non-diffusive form in or closely adjacent to the photosensitive layer.

Thus, the red-sensitive layer can contain, for example, a non-diffusive color coupler, generally a phenolic or alpha-naphthol coupler, which produces a cyan partial color image. The green-light-sensitive layer contains at least one non-diffusive color coupler, usually 5 to produce a magenta partial color image, for example.
- Can include pyrazolone color couplers and pyrazolotriazoles. The blue-sensitive layer may contain, for example, at least one non-diffusive color coupler which produces a yellow color image, generally a color coupler having open chain ketomethylene groups. For example, the color coupler is 6
-14- or 2-equivalent couplers.

In the present invention, 2-equivalent couplers are particularly preferred.

Suitable couplers are disclosed, for example, in the following publications:
Agfa research report (Mitteilunglnaus)
den Forschungslaboratory
der Agfa), Leverkusen/Munchen (Leverkusen/Munchen),
Vol. III, p. 111 (1961) "Color coupler J" by W. Pe1z; K. Venkataraman, r. J(The
Chemistry of 5ynthetic Dy
es), Vol, 4.341-387, Academic
Academic Press, (1971
), T.H. James (7,1, James
), “The Theory of the Photographic
Process J
Photographic Process), 4th edition,
pp. 353-362; and Research Disclosure No. 1
7643, Section ■.

In the present invention, in particular, Japanese Patent Application Laid-Open No. 63-106655
General formula (M-■) as described in the specification, page 26
(Specific examples of magenta couplers include No. 1-No. 77 described in JP-A-63-106655, pages 29-34.) General formula [C
-I) or (c-n) (Specific examples of cyan couplers include the same specification, 37-42
(C'-1) to (C'-82) described on page.

(C)-1, It is preferable to use Y'-1) to (Y''39) in combination with the light-sensitive material of the present invention from the viewpoint of the desired effects of the present invention.

In the present invention, when a nitrogen-containing heterocyclic mercapto compound is used in combination with the high silver chloride light-sensitive material of the present invention, not only the desired effects of the present invention can be favorably achieved, but also a bleach-fixing solution can be added to the color developer. This can be cited as a more preferred embodiment of the present invention because it has the additional effect of minimizing the influence on photographic performance that occurs when it is mixed in.

Specific examples of these nitrogen-containing heterocyclic mercapto compounds include (I'-1,) to (I'-87) described in JP-A-63-106655, pages 42 to 45.

The silver halide emulsions of the present invention having a silver chloride content of 90 mol % or more can be prepared by conventional methods (eg, single flow or double flow with constant or accelerated feed of material). p
Particularly preferred is the preparation method using the double inflow method with controlled Ag; Research Disclosure No. 17643
, see sections ■ and ■.

Emulsions can be chemically sensitized. Particularly preferred are sulfur-containing compounds such as allyl isothiocyanate, allylthiourea or thiosulfate. Reducing agents can also be used as chemical sensitizers, and they are described for example in Belgian Patents Nos. 493,464 and 568,687.
and for example Belgian Patent No. 54.
Polyamines such as diethylenetriamine or aminomethylsulfinic acid derivatives according to No. 7,323. Noble metals and precious metal compounds such as gold, platinum, palladium, iridium, ruthenium or rhodium are also suitable sensitizers. This chemical sensitization method is used in the Zeitschrift Ver Bissenschaftliche Photography (Z,
Wiss, Photo, ) 46.65-72 (195
1) R, Kosiovsk
y): See also Research Disclosure No. 17643, Section 2 above.

The emulsions can be sensitized by optically known methods, for example using common polymethine dyes such as neutrocyanines, basic or acidic carbocyanines, rhodacyanines, hemicyanines, styryl dyes, oxonols and the like:・M Hamer (F, M, Hame
r) “Cyanine Dyes and Related Compounder J”
and related compounds) (196
4) Ullmanns Enzy
klpadie dertechniscben Ch
emie) 4th edition, volume 18, page 431 and the following, and the above Research Disclosure No.

17643, see Section ■.

Conventional antifogging agents and stabilizers can be used in the emulsions. Azaindenes are particularly suitable stabilizers, with tetra- and penta-azaindenes being preferred, especially those substituted with hydroxyl or amine groups. Compounds of this type can be found, for example, in the paper by Birr, Zeitschrift Ver Hinsenschaft.
Nhe Photography (Z, Wiss, Pboto
, ) 47.1952, p. 2-58, and the above-mentioned Research Disclosure No. 17643, Section 2.

The components of the photosensitive material can be incorporated by conventional known methods; for example, U.S. Pat. No. 2,322,027;
See Nos. 2,533,514, 3,689,271, 3,764°336 and 3,765,897. Components of the photosensitive material, such as couplers and UV absorbers, can also be contained in the form of charged latexes; see German Patent Application No. 2.541.274 and European Patent Application No. 14,921. The components can also be immobilized in photosensitive materials as polymers: for example German Patent Application No. 2,044,992, U.S. Pat.
, 370,952 and 4.080,211.

As a support for the light-sensitive material, customary supports can be used, such as, for example, supports of cellulose esters, such as cellulose acetate, and supports of polyester.

Paper supports are also suitable and these can be coated, for example, with polyolefins, in particular polyethylene or polypropylene; in this regard see Research Disclosure No. 17643, Section X■, supra.

Conventional hydrophilic film-forming agents can be used as protective colloids or binders for the layers of the light-sensitive material, such as proteins, especially gelatin, alginic acid or its derivatives such as esters, amides or salts, carboxymethylcellulose and cellulose sulfate. such as cellulose derivatives, starch or its derivatives, or hydrophilic synthetic binders; see also the binders set out in Research Disclosure 17643, supra, Section 2.

The layer of photographic material provided on the support can be hardened by conventional methods, for example using epoxide, heterocyclic ethyleneimine or acryloyl type hardeners. Furthermore, the layer can be cured by a method according to German Patent Application No. 2 218.009 to produce a color photographic material suitable for high temperature operation. The above layer can also be cured with diazine, triazine or 1,2-dihydroquinoline type hardeners or vinylsulfone type hardeners. Other suitable curing agents include German Patent Application No. 2, 4
39゜551, No. 2,225,230 and No. 2,3
No. 17,672 and Research Disclosure No. 17643, supra, Section 2.

[Specific embodiments of the invention]

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the embodiments of the present invention are not limited thereto.

Example 1 An experiment was conducted using the following color paper, processing liquid, and processing steps below.

A photosensitive material was prepared by sequentially coating the following layers on a color paper polyethylene coated paper support from the support side.

Note that polyethylene coated paper has an average molecular weight of 10
0000, 200 parts by weight of polyethylene with a density of 0.95 and polyethylene 20 with an average molecular weight of 2000 and a density of 0.80.
7 parts by weight of anatase titanium oxide
．． A 0.035 mm thick coating layer was formed on the surface of a high-quality paper weighing 165 g/m2 using an extrusion coating method, and a 0.04 mm thick coating layer was formed using only polyethylene on the back side. .

The polyethylene-coated surface of this support was pretreated by corona discharge, and then the following layers were sequentially applied.

First layer: A blue-sensitive silver halide emulsion layer consisting of a silver halide emulsion having the silver halide composition shown in Table 1, where the emulsion is silver halide 1
Containing 340 g of gelatin per mole, it was sensitized using 2.5X 10-' moles of sensitizing dye of the following structure per mole of silver halide (using isopropyl alcohol as the solvent) and dissolved and dispersed in dibutyl phthalate. 2,
5-G Shiichibutylno＼ ・Idoquinone 200mg
/m2 and yellow coupler Y as a yellow horn platy, containing 2X10-' mol per 1 mol of silver saponide, and coated in a silver amount of 290 mg/m2.

2nd layer 300 mg/m2 of di-1-octylnohydroquinone dissolved and dispersed in nidibutyl phthalate, 2-(2'-hydroxy-3',5'-di-t-butylphenyl)penztriazole as a UV absorber; 2-(2'-hydroxy-57, -t-butylphenyl)benzotriazole, 2-(2'-hydroxy-3'-t~dibutyl5
Gelatin layer containing 200 mg/m2 of a mixture of 2-(2-hydroxy-3', 5'-di-t-butylphenyl)-5-chlorobenzotriazole The gelatin content is 1800mg/m''.

Third layer: A green-sensitive silver halide emulsion layer consisting of a silver halide emulsion having the silver halide composition shown in Table 1, the emulsion containing 420 g of gelatin per mole of silver halide, and containing 1 mole of silver halide.
The following magenta coupler M was sensitized using 2.6 x 10-' moles of a sensitizing dye having the following structure per mole, and dissolved and dispersed in a solvent containing a 2:1 mixture of dibutyl phthalate and tricresyl phosphate. Contains 1.6X 10-' mole per mole of silver halide,
It is coated with a silver content of 270 mg/m2. In addition, as an antioxidant, 2,2.4-1-rifthyl-6-
Lauryloxy-7-t-ocdylchroman was contained in an amount of 0.3 mol-31 per mol of coupler.

Fourth layer: 31 mg/m2 of di-L-octyl-hy-l-quinone dissolved and dispersed in di-dioctyl phthalate and 2-(2'-hydroxy-3',5'-di-t-
butylphenyl)benzotriazole, 2-(2'-hydroxy-5'-t-butylphenyl)penztriazole, 2-(2'-hydroxy-3'-thi-phthyl-5
'-methylphenyl)-5'-chlorobenzotriazole and 2-(2'-hydroquine-3/, 5/
A mixture of t-butylphenyl)-5-chlorobenzotriazole (2: 1.5+ 1.s+2)
The amount of gelatin in the gelatin layer containing g/m2 is 2000 m
g/m2.

5th layer: A red-sensitive silver halide emulsion layer consisting of a silver halide emulsion having the silver halide composition shown in Table 1, the emulsion containing 490 g of gelatin per mole of silver halide, 2. 4X
150 mg/m2 of 2,5-di-butylhydroquinone dissolved and dispersed in dibutyl phthalate and the following cyan couplers C(1) and C(2X1: l) ) in an amount of 3.5×10-' mol per mol of silver halide, and the coating was applied to give a silver amount of 290 mg/m 2 .

6th layer: Gelatin layer coated with a gelatin amount of 1000 mg/m2.

The silver halide emulsions used in each light-sensitive emulsion layer (layers 1, 3, and 5) were prepared by the method described in Japanese Patent Publication No. 7772/1983, and sodium thiosulfate pentahydrate was added to each emulsion. Chemically sensitized using 4-hydroxy-6 as a stabilizer
-Methyl-1,3,3a,7-titrazaindene, bis(vinylsulfonylmethyl)ether as a hardening agent and saponin as a coating aid.

・Yellow coupler Y (1) O ・Yellow coupler Y (2) Vθ ・Magenta coupler M (1) O Cyan coupler C (1) Cyan coupler C (2) Stepwise exposure of the above photosensitive material (silver halide composition changed) was given and treated with the following processing steps and processing solution, and the maximum concentration of yellow dye of the obtained sample was measured. At the same time, the magenta dye density of the unexposed area was measured, and the results are summarized in Table 1 below.

Processing steps (1) Color development at 34°C as shown in Table 1 (2) Bleach fixing at 35°C for 1 minute and 30 seconds (3) Washing with water
25°C to 35°C for 1 minute (4) Drying at 75°C
~100°C for about 2 minutes Processing liquid composition Color developing tank liquid Ethylene glycol 15 mff Potassium sulfite 1. Og Sodium chloride 1.5g Potassium carbonate 30.0g 3-Methyl-
4-Amino-N-ethyl-N-(β-methanesulfonamidoethyl)-aniline sulfate 5.5g Fluorescent brightener (diaminostilbene type) 1.0g Hydroxylamine sulfate 1.5g Hydroxyethyliminodiacetic acid 5. 0g benzyl alcohol Table 1i: Listed potassium bromide
1.2-dihydroxybenzene listed in Table 1
3,5-disulfonic acid-distrium salt
Add 0.2g water to bring the total amount to 1a, and
OH and H2SO, Tep H1020.

Bleach-fix tank liquid Nethylene diamine tetraacetate ferric ammonium dihydrate 60 g
Endylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% solution) 100 mf
27.5 m of ammonium sulfite (40% solution) (adjust to pH 7.1 with potassium dicarbonate or glacial acetic acid and add water to make the total volume IQ).

However, the color developer contains 2 ppm of ferric ions (added in the form of ferric ammonium ethylenediaminetetraacetate).
Added 1 ppm of
! (The opening area is 20 cm2, and the color developing solution of IQ is stored. As is clear from Table 1 above, the silver halide composition, the bromide concentration and benzyl alcohol concentration in the color developing solution, and the processing time of the color developing process It can be seen that when the coloring matter is within the scope of the present invention, sufficient yellow dye density can be obtained even when heavy metals are mixed in, and there is little magenta fog even in unexposed areas, which is good.

Example 2 The magenta coupler M(1) in the color paper sample used in Experiment No. 1-8 of Example 1 was
Pyrazolotriazole type magenta couplers (M'-1) and (M'-
2), (M'-4), (M'-21), (M''3
7), (M'-61), and (M'-63) and conducted similar experiments, the maximum yellow density was almost the same as in Experiment No. 1-8 of Example 1. However, the magenta dye density in the unexposed area was 0.01, which was extremely good.

Example 3 Hydroxylamine sulfate in the color developer used in Experiment No. 1-8 of Example 1 was replaced with the same number of moles of hydroxylamine derivative (compound represented by formula [1]) A- 1, A-13, A-18°A, -2LA-7
When the same experiment as in Example 1 was carried out except for the following changes, the maximum yellow density increased by approximately 0.1, and the magenta dye density in the unexposed area decreased by 0.02 to 0.01. Furthermore, the tar property generated in the color developing solution has also been improved.

Example 4 In the color developer used in Experiment No. 1-8 of Example 1,
Exemplary compound 1) of alkanolamine derivatives (compounds represented by the formula CD) -2, D-3, and D-13 were added at 5 gIQ each. When the same experiment as in Example 1 was conducted, yellow The maximum of 0.15 increased, and the magenta dye density in the unexposed area decreased to 0.15. The O1 drop was 0.02. Furthermore, the generation of tar and crystals generated in the color developer tank was also improved.

Example 5 JP-A-63-1.06655 =
Exemplary compound of the heterocyclic mercapto compound described in 41-1 (1'-2
4), (I'-41), (I'-60), (1'-66
), (I"79), and (I'-84) are each 0.12
An experiment was conducted in the same manner as in Example 1 except that mg/m2 was added, and the maximum yellow density did not change, but the magenta fog density in the unexposed area decreased by 0.02 to 0.0.
It became 1.

〔Effect of the invention〕

According to the present invention, even when heavy metal ions are mixed into a color developing solution, fogging is less likely to occur, and stable photographic properties can be provided over a long period of time.

Claims (1)

[Claims] In a method for processing a silver halide color photographic light-sensitive material, the silver halide color photographic light-sensitive material is subjected to imagewise exposure and then processed using a color developing solution, wherein at least one of the silver halide emulsion layers of the silver halide color photographic light-sensitive material is one layer contains at least 90 mol% silver chloride, and the color developer contains 4×10^-^4 moles or more of bromide and 0.3 to 10 g of benzyl alcohol per liter of color developer,
Furthermore, a method for processing a silver halide color photographic material, characterized in that the processing time of the color development processing step is 90 seconds or more.