JPH087417B2 - Processing method of silver halide color photographic light-sensitive material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for processing a silver halide color photographic light-sensitive material, more specifically, a developing property using a high silver chloride silver halide photographic light-sensitive material. In particular, the present invention relates to a development processing method which is excellent in the color developability and photographic property variation of a cyan color image and is excellent in desilvering property.

(Prior Art) In recent years, in the photographic processing of a color photographic light-sensitive material, it has been desired that the processing time be shortened as the delivery time for finishing and the labor for laboratories are reduced. As a method for shortening the time of each treatment step, a temperature increase and a replenishment amount increase are general methods, but in addition, many methods of strengthening stirring or adding various accelerators have been proposed.

Among them, for the purpose of accelerating color development and / or reducing the replenishment amount, a color photographic light-sensitive material containing a silver chloride emulsion in place of the silver bromide emulsion or silver iodide emulsion which has been widely used in the past is processed. It is known how to do it. For example, International Publication No. WO87-04534 describes a method of rapidly processing a high silver chloride silver halide color photographic light-sensitive material with a color developing solution containing substantially no sulfite ion and benzyl alcohol.

However, based on the above method, it was found that streak-like fogging occurs when the development processing is performed using an automatic developing machine for paper. It is presumed that this is a so-called liquid pressure sensitizing muscle, in which streaky fog occurs when the photosensitive material comes into contact with a roller or the like in the developing tank of an automatic processor and is pressure sensitized. To be done.

Furthermore, during continuous processing, the photographic characteristics fluctuate significantly (especially the minimum and maximum densities of cyan), and desilvering defects occur,
The fact that the white background was heavily polluted became clear.

As described above, rapid development processing using high silver chloride color photographic light-sensitive materials has serious problems such as pressure-sensitized fog in the liquid, fluctuation in photographic properties, desilvering failure, and other serious problems. It wasn't worth it.

In a rapid processing method using a high silver chloride color photographic light-sensitive material, a method for reducing fluctuations in photographic characteristics (particularly fog (Dmin)) due to continuous processing is disclosed in JP-A-58-95345.
No. 59-232342, it is known to use organic antifoggants. However, the effect of preventing fog is insufficient to prevent the occurrence of pressure sensitizing muscles in the liquid and the increase in Dmin due to continuous processing, and further increase the occurrence of desilvering failure due to continuous processing. It turned out to let me.

In JP-A-61-70552, a high silver chloride silver halide color photographic light-sensitive material is used, and the replenishment amount of the developing solution is made low by adding a replenishing amount that does not cause overflow into the developing bath during the development processing. JP-A-63-106655 discloses a silver halide color photographic light-sensitive material in which the silver halide emulsion layer has a high silver chloride content for the purpose of stabilizing the processing. And a method of developing with a color developing solution containing chloride at a predetermined concentration or higher. However, these methods cannot be put to practical use because the pressure sensitizing lines generated by the above-mentioned processing using the automatic processor, the fluctuations in photographic characteristics during continuous processing and the occurrence of defective desilvering are recognized.

Further, as means for improving the color developability of cyan, for example, JP-A-62-178261, JP-A-62-232649, and JP-A-62-232650.
Nos. 62-242939 and 63-96656 are known. However, when the halogen concentration in the developing solution was within the range of the present invention, it was unexpected that the compounds of the present invention exhibited a specifically high color-forming property and little variation in photographic property, which was completely surprising.

(Problems to be Solved by the Invention) Accordingly, the first object of the present invention is to provide a development processing method using a high silver chloride color photographic light-sensitive material, which is quick and prevents generation of streaky fog. It is to be.

A second object of the present invention is to provide a development processing method using a high silver chloride color photographic light-sensitive material, in which fluctuations in photographic properties (especially maximum density and minimum density of cyan color image) due to continuous processing are significantly suppressed. Is to provide.

A third object of the present invention is to provide a development processing method which uses a high silver chloride color photographic light-sensitive material and has a small amount of residual silver and improved desilvering property.

(Means for Solving the Problem) An object of the present invention is to provide a silver halide color photographic light-sensitive material with a color developing solution containing at least one aromatic primary amine color developing agent in an amount of 80 mol%. It has at least one layer of the above high silver chloride silver halide emulsion consisting of silver chloride, and has a layer containing at least one of the compounds represented by the following general formulas (A) to (G). In addition, a silver halide color photographic light-sensitive material with a total coated silver amount of 0.75 g / m ² or less was added with chlorine ions of 3.
5 × 10 ^{-2 to} 1.5 × 10 ^-1 mol / l and bromide ion 3.
It was achieved by a method for processing a silver halide color photographic light-sensitive material characterized by processing with a color developer containing 0 × 10 ^{-5 to} 1.0 × 10 ^-3 mol / l.

HOOC-R ₃ General formula [B] Y ₄ OR ₄ -O _r R ₅ General formula [C] R ₆ -NHSO ₂ -R ₇ General formula [D] R ₈ CONHCOR ₉ General formula [E] HO-R ₁₀ General formula [G] In the general formula [A], D represents a divalent electron-withdrawing group, R ₁ and R ₂ may be the same or different and each is an alkyl group, an aryl group or an alkoxy group. Represents a group, an aryloxy group, an alkylamino group, an anilino group, or a heterocyclic group. p is an integer of 1 or 2 and q is 0 or 1. U represents a benzene ring or a hetero ring which may be condensed with a phenol ring.

In the general formula [B], R ₃ is an alkyl group, an aryl group,
Represents a heterocyclic group.

In the general formula [C], Y ₄ is an aryl group, an alkyl group,
A heterocyclic group, Represents R ₄ represents an alkylene group, an arylene group or an aralkylene group, and R ₅ represents an alkyl group or an aryl group. However, Y ₄ and R ₅ are not an alkyl group at the same time. R _7a and R _7b are an alkyl group, an aryl group,
It represents an amino group, an alkoxy group or an aryloxy group. r represents an integer of 1 to 5. Here, if Y ₄ and R ₅ are alkyl groups at the same time, the effect of the present invention cannot be sufficiently achieved.

In the general formula [D], R ₆ is an alkyl group, an aryl group,
It represents an alkyl or phenylsulfonyl group and an acyl group. R ₇ represents a substituent having the same meaning as R ₅ . R ₁₅ and R ₁₆ may be closed to form a 5- to 7-membered ring.

In the general formula [E], R ₈ and R ₉ represent a substituent having the same meaning as R ₅ , but may be ring-closed to form a 5-, 6- or 7-membered ring.

In general formula [F] Represents a 5-, 6- or 7-membered heterocycle.

In the general formula [G], R ₁₀ represents an alkyl group and has 12 or more carbon atoms. If it is less than 12, the effect of the present invention cannot be sufficiently exhibited.

Chloride ion is well known as one of the antifoggants, but its effect is small, and even if it is used in a large amount, the increase of fog due to continuous processing and the streak-like pattern that occurs when processed by an automatic processor Fogging was not completely prevented, but the development was delayed and the maximum density was lowered.

Bromide ion is also well known as one of the antifoggants, but when used alone, the amount of addition can prevent fog and streak-like pressure fog associated with continuous processing. Was suppressed, the maximum density and the sensitivity were lowered, and it was not practical.

However, as a result of various studies, the inventors of the present invention include any one of the general formulas (A) to (G) and have a silver chloride content of 80.
Using a high silver chloride color light-sensitive material having a coating amount of 0.75 g / m ² or less and mol% of chlorine ion and bromine ion of 3.5 × 10 ^{-2 to} 1.5 × 10 ^-1 mol / l and 3.0 ×, respectively. 10 ^-5 ~ 1.0 ×
By processing with a color developer containing 10 ^-3 mol / l, the maximum density is high, and streak-like pressure fog occurs in processing with an automatic developer, and photographic fluctuations associated with continuous processing (especially cyan It has been found that the minimum and maximum densities can be prevented and the amount of residual silver can be significantly reduced. These facts were unexpected and quite surprising.

The details of the effect of preventing streaky pressure fog in the automatic processor processing are unknown, but it is estimated as follows. It is considered that when excessive pressure is applied to the light-sensitive material in the color developing solution after the exposure, the portion under pressure is assisted to form fog nuclei and fog occurs. However, the developer of the present invention suppresses only the development of fog nuclei by containing an appropriate amount of bromine ions and chlorine ions, does not suppress the development of latent image nuclei, and does not delay development and decrease the maximum density and sensitivity. It is estimated to prevent fogging.

In addition, the effect of preventing photographic fluctuations associated with continuous processing is due to the presence of suitable amounts of bromine and chlorine ions,
It is considered that this is because the performance is stable and the amount of coated silver is 0.75 g / m ² or less against the fluctuation of pH of the preservative of the main agent and the pH of the developing solution.

The remarkable effect of suppressing desilvering is presumed as follows. The cause of defective desilvering is the high silver chloride photosensitive material,
It is presumed that silver sulfide is likely to be formed due to the small amount of bromine ions existing in the vicinity of developed silver, resulting in poor desilvering. The developer contains a suitable amount of bromine and chlorine ions to suppress the formation of silver sulfide and the coated silver amount is 0.75.
It is presumed that the fact that g / m ² or less is advantageous for desilvering is related to the suppression of defective desilvering.

Next, the compounds represented by the general formulas [A] to [G] will be described in detail.

D in the general formula (A) is preferably Represents an electron-withdrawing group.

R _{1 to} R ₁₀ and Y ₄ in the above general formulas (A) to (G),
The alkyl group in R _7a and R _7b is a linear or branched alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, a cycloalkoxy group, a cycloalkenyl group, etc., and an aryl group is phenyl, 4-t-butylphenyl, 2,4- Di-t-amylphenyl, naphthyl and the like, the alkoxy group is methoxy, ethoxy, benzyloxy, heterodecyloxy,
Octadecyloxy, aryloxy groups such as phenoxy, 2-methylphenoxy, naphthoxy, etc., alkylamino groups such as methylamino, butylaminooctylamino, etc., and anilino groups such as phenylamino, 2-chloroanilino, 3-dodecyloxycarbonylanilino, etc. , The alkylene group is methylene ethylene, 1,10 decylene, -CH ₂ CH ₂
OCH ₂ CH _2-, etc., the arylene group is 1,4-phenylene, 1,3
-Phenylene, 1,4-naphthylene, 1,5-naphthylene, etc. are aralkylene groups Etc., hetepyrazolyl, imidazolyl, triazolyl,
It represents pyridyl, quinolyl, piperidyl, triazinyl and the like.

Further, a substituted alkyl group in R _{1 to} R ₉ , a substituted aryl group, a substituted alkoxy group, a substituted aryloxy group, a substituted alkylamino group, a substituted anilino group, a substituted alkylene group,
The substituted arylene group, the substituted aralkylene group, and the substituent in the substituted heterocyclic group include a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an acyloxy group, and a carbamoyloxy group. Group, silyloxy group, sulfonyloxy group, acylamino group, anilino group, ureido group, imide group, sulfamoylamino group, carbamoylamino group,
Alkylthio group, arylthio group, heterocyclic thio group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamide group, carbamoyl group, acyl group, sulfamoyl group, sulfonyl group, sulfinyl group, alkoxycarbonyl group, aryloxycarbonyl group Represent.

In general formula (F) The heterocyclic group represented by is the same as the above-mentioned heterocyclic group, and may have the above-mentioned substituent.

Of the compounds represented by the general formulas (A) to (G), those represented by the general formulas (A), (C) and (D) are preferable, and the compounds represented by the general formulas (A) and (D) are more preferable. Is represented by.

The compounds represented by the general formulas (A) to (G) can be introduced into the photosensitive material by an oil-in-water dispersion method, and the dispersion form thereof can be a single dispersion or a combined dispersion with other photosensitive material constituent components. The combined use with an oil-soluble coupler is preferred. The position of addition to the light-sensitive material may be any layer, but it is preferably a red-sensitive photosensitive layer or a layer adjacent thereto, more preferably a red-sensitive photosensitive layer.

The amount of the compounds represented by the general formulas (A) to (G) added is arbitrary, but is preferably 20 to 300 mol%, more preferably 40 to 150 mol% based on the oil-soluble coupler dispersed in combination. .

Next, specific examples of the compounds represented by the general formulas (A) to (G) are shown, but the present invention is not limited thereto.

(C-5) (C ₄ H ₉ OCH ₂ CH ₂ O) ₃ P = 0 _{(G-1) C 18 H} 37 OH (G-2) C 12 H 25 OH (G-3) C 10 H 21 O (CH 2) 5 O (CH 2) 2 OH The silver halide emulsion of the present invention consists essentially of silver chloride. Here, "substantially" means that the content of silver chloride is at least 80 mol%, preferably at least 95 mol%, more preferably at least 98 mol%, based on the total silver halide amount. Maximum concentration,
From the viewpoints of pressure sensitizing muscle and quickness, the higher the content of silver chloride, the more preferable.

The coating amount of silver halide light-sensitive material of the present invention is 0.75 g / m ²
It must be: Preferably 0.65-0.3g / m
² When the amount of coated silver is more than 0.75 g / m ² , the pressure sensitizing muscle is generated, the photographic property is greatly changed due to continuous processing, and the amount of residual silver is large, which does not achieve the object of the present invention. . This is considered to be due to the effect of reducing the film thickness in addition to the reduction of the silver amount.

In the present invention, chlorine ion is added to the color developer at 3.5.
It is necessary to contain x10 ^{-2 to} 1.5 x 10 ^-1 mol / l.
It is preferably 4 × 10 ^-2 to 1 × 10 ^-1 mol / l. When the chlorine ion concentration is more than 1.5 × 10 ⁻¹ mol / l, there is a drawback that the development is delayed, and the object of the present invention of rapid and high maximum concentration cannot be achieved. Also, if it is less than 3.5 × 10 ^-2 mol / l, it is not possible to prevent streak-like pressure fog, and furthermore, the photographic fluctuations associated with continuous processing (especially the minimum and maximum densities of cyan) Large, with a large amount of residual silver,
It does not achieve the object of the present invention.

In the present invention, a bromine ion of 3.0 is contained in the color developer.
It is necessary to contain x10 ^-5 mol / l to 1.0 x 10 ^-3 mol / l. It is preferably 5.0 × 10 ^{−5 to} 5 × 10 ⁻⁴ mol / l.
When the bromine ion concentration is more than 1 × 10 ^-3 mol / l, the development is delayed, the maximum concentration and sensitivity are lowered, and 3.0 × 10 ^-5 mol / l
If it is less than 1, it is not possible to prevent streaky pressure fog, and further it is not possible to prevent photographic fluctuations (especially minimum density and maximum density) and desilvering defects associated with continuous processing, It does not achieve the object of the present invention.

Here, the chlorine ion and the bromine ion may be directly added to the developing solution or may be eluted from the photosensitive material in the developing solution.

When directly added to a color developer, examples of the chloride ion supply material include sodium chloride, potassium chloride, ammonium chloride, lithium chloride, nickel chloride, magnesium chloride, manganese chloride, calcium chloride, and cadmium chloride, of which the preferred ones Are sodium chloride and potassium chloride.

It may also be supplied from a fluorescent whitening agent added to the developing solution.

As a source of bromide ions, sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide, magnesium bromide, manganese bromide, nickel bromide, cadmium bromide, cerium bromide, thallium bromide Among them, potassium bromide and sodium bromide are preferable.

When it is eluted from the photosensitive material in the developing solution, chlorine ions,
Both bromine ions may be supplied from the emulsion, or may be supplied from other than the emulsion.

In the present invention, it is preferable that the color developing solution contains substantially no sulfite ion from the viewpoint of processing stability during continuous processing and prevention of streaky pressure fog. Do not use the liquid for a long time, use a floating pig to suppress the effect of air oxidation, use physical means such as reducing the opening of the developing tank, suppress the temperature of the developing solution, or use an organic preservative. Chemical means such as addition or the like can be used. Among them, the method using an organic preservative is advantageous from the viewpoint of simplicity.

The organic preservative described in the present invention refers to all organic compounds that reduce the deterioration rate of an aromatic primary amine color developing agent by being added to a processing solution of a color photographic light-sensitive material. That is, although it is an organic compound having a function of preventing the oxidation of the color developing agent by air or the like, among them, a hydroxylamine derivative (excluding hydroxylamine; hereinafter the same), hydroxamic acids, hydrazines, hydrazides, phenols, Particularly, α-hydroxyketones, α-aminoketones, saccharides, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, condensed amines, etc. It is an effective organic preservative. These are disclosed in Japanese Patent Application Nos. 61-147823, 61-173595 and 61-173595.
-165621, 61-188619, 61-197760, 61-
186561, 61-198987, 61-201861, 61-18
6559, 61-170756, 61-188742, 61-1887
No. 41, U.S. Pat.Nos. 3,615,503 and 2,494,903,
52-143020 and JP-B-48-30496.

Regarding the preferable organic preservatives, general formulas and specific compounds thereof are listed below, but the present invention is not limited thereto.

The amount of the following compounds added to the color developer is 0.005
Mol / l to 0.5 mol / l, preferably 0.03 mol / l to 0.1 mol
It is desirable to add so that the concentration becomes / l.

Particularly, addition of hydroxylamine derivative and / or hydrazine derivative is preferable.

The hydroxylamine derivative is preferably represented by the following general formula (I).

General formula (I) In the formula, R ¹¹ and R ¹² represent a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted aryl group, or a heteroaromatic group. R ¹¹ and R ¹² do not become hydrogen atoms at the same time and may be linked to each other to form a heterocycle together with the nitrogen atom. The heterocyclic ring structure is a 5- or 6-membered ring and is composed of carbon atoms, hydrogen atoms, halogen atoms, oxygen atoms, nitrogen atoms, sulfur atoms and the like, and may be saturated or unsaturated.

R ¹¹ and R ¹² are preferably alkyl or alkenyl groups, and preferably have 1 to 10 carbon atoms, and particularly preferably 1 to 5 carbon atoms. Examples of the nitrogen-containing heterocycle formed by connecting R ¹¹ and R ¹² include a piperidyl group, a pyrrolidylyl group, an N-alkylpiperazyl group, a morpholyl group, an indolinyl group, and a benztriazole group.

Preferred substituents of R ¹¹ and R ¹² are hydroxy group, an alkoxy group, an alkyl or arylsulfonyl group, an amido group, a carboxy group, a cyano group, a sulfo group, a nitro group and an amino group.

Compound The following are preferred as hydrazines and hydrazides.

General formula (II) In the formula, R ³¹ , R ³² , and R ³³ represent a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, or a heterocyclic group, and R ³⁴ represents a hydroxy group, a hydroxyamino group, a substituted or unsubstituted, It represents an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a carbamoyl group or an amiki group. The heterocyclic group is a 5- to 5-membered ring,
It is composed of C, H, O, N, S and a halogen atom, and may be saturated or unsaturated. X ³¹ is -CO-, -S
O ₂ −, or Represents a divalent group selected from, and n is 0 or 1. In particular, when n = 0, R ³⁴ represents a group selected from an alkyl group, an aryl group, and a heterocyclic group, and R ³³ and R ³⁴ may form a heterocyclic ring together.

In formula (II), R ³¹ , R ³² , and R ³³ are hydrogen atoms or C ₁ to C.
_It is preferably an alkyl group of ₁₀ , particularly preferably R ³¹ and R ³² are hydrogen atoms.

In the general formula (II), R ³⁴ is preferably an alkyl group, an aryl group, an alkoxy group, a carbamoyl group, or an amino group. Particularly, the case of an alkyl group or a substituted alkyl group is preferable. Preferred substituents of the alkyl group here are carboxysyl group, sulfo group, nitro group, amino group, phosphono group and the like. X ³¹ is preferably —CO— or —SO ₂ —, and most preferably —CO—.

(Compound example) II-2 NH ₂ NHCH _{2 4} SO ₃ H II-3 NH ₂ NHCH _{2 2} OH _{II-6 NH 2 NHCOCH 3 II} -7 NH 2 NHCOOC 2 H 5 II-10 NH ₂ NHCONH ₂ II−12 NH ₂ NHSO ₃ H II-14 NH ₂ NHCOCONHNH ₂ II-15 NH ₂ NHCH ₂ CH ₂ CH ₂ SO ₃ H II-18 NH ₂ NHCH ₂ CH ₂ COOH Use of the compound represented by the general formula (I) or (II) and the amine represented by the following general formula (III) or (IV) in combination improves the stability of the color developer. Is more preferable from the viewpoint of improving the presentation stability of continuous treatment.

General formula (III) In the formula, R ⁷¹ , R ⁷² and R ⁷³ represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group or a heterocyclic group. Where R ⁷¹ and R ⁷² , R ⁷¹ and R ⁷³ or R ⁷² and R
⁷³ may be linked to form a nitrogen-containing heterocyclic ring.

Here, R ⁷¹ , R ⁷² and R ⁷³ may have a substituent. As R ⁷¹ , R ⁷² and R ⁷³ , a hydrogen atom and an alkyl group are particularly preferable. Examples of the substituent include a hydroxyl group, a sulfo group, a carboxyl group, a halogen atom, a nitro group, an amino group, and the like.

(Compound example) III-1 NCH ₂ CH ₂ OH) ₃ III-2 H ₂ NCH ₂ CH ₂ OH III-3 HNCH ₂ CH ₂ OH) ₂ III-10 (HOCH ₂ CH _{2 2} NCH ₂ CH ₂ SO ₂ CH ₃ III-11 NHCH ₂ COOH) ₂ III−13 H ₂ NCH ₂ CH ₂ SO ₂ NH ₂ III-15 H ₂ N-CCH ₂ OH) ₂ General formula (IV) In the formula, X represents a trivalent atomic group necessary for completing the condensed ring, R ⁵¹ and R ⁵² are an alkylene group, an arylene group,
Represents an alkenylene group and an aralkylene group.

Here, R ⁵¹ and R ⁵² may be the same or different from each other.

Of the general formula (IV), the particularly preferred one is the general formula (IV
-A) and compounds represented by (IV-b).

In the formula, X ¹ represents N or CH. R ⁵¹ and R ⁵² are simultaneously defined in the general formula (IV), and R ⁵³ is the same group as R ⁵¹ and R ⁵² , or Represents

In the general formula (IV-a), X ¹ is preferably N. The carbon number of R ⁵¹ , R ⁵² , and R ⁵³ is preferably 6 or less, more preferably 3 or less, and most preferably 2.

R ⁵¹ , R ⁵² , and R ⁵³ are preferably an alkylene group or an arylene group, and most preferably an alkylene group.

In the formula, R ⁵¹ and R ⁵² are defined as in the general formula (IV).

In formula (IV-b), it is preferable that R ⁵¹ and R ^{52 each} have 6 or less carbon atoms. R ⁵¹ and R ⁵² are preferably an alkylene group or an arylene group, and most preferably an alkylene group.

Among the compounds of the general formulas (IV-a) and (IV-b), the compound represented by the general formula (IV-a) is particularly preferable.

The above organic preservatives can be obtained as commercial products, but can also be synthesized by the methods described in Japanese Patent Application Nos. 62-124038 and 62-24374.

Hereinafter, the color developer used in the present invention will be described.

The color developing solution used in the present invention contains a known aromatic primary amine color developing agent. A preferred example is p-phenylenediamine, and representative examples thereof are shown below, but the invention is not limited thereto.

D-1 N, N-diethyl-p-phenylenediamine D-2 4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline D-3 2-methyl-4- [N-ethyl-N -(Β-Hydroxyethyl) amino] aniline D-4 4-amino-3-methyl-N-ethyl-N-
(Β-methanesulfonamidoethyl) -aniline Further, these p-phenylenediamine derivatives may be salts such as sulfate, hydrochloride, p-toluenesulfonate and the like. The amount of the aromatic primary amine developing agent used is preferably about 0.1 g to 20 g, more preferably about 0.5 to about 10 g, per developing solution.

The color developer used in the present invention preferably has a pH of 9
-12, more preferably 9-11.0, and the color developer may contain compounds of other known developer components.

In order to maintain the above pH, it is preferable to use various buffers. As the buffer, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate,
Sodium tetraborate (borax), potassium tetraborate, o
-Sodium hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, 5-sulfo-
Examples thereof include sodium 2-hydroxybenzoate (sodium 5-sulfosalicylate) and potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate).

The amount of the buffer added to the color developing solution is preferably 0.1 mol / l or more, and particularly preferably 0.1 mol / l to 0.4 mol / l.

In addition, various chelating agents can be used in the color developing solution as a precipitation preventing agent for calcium and magnesium, or for improving the stability of the color developing solution.

Specific examples are shown below, but the present invention is not limited thereto. Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, triethylenetetraminehexaacetic acid, N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid, 1,3- Diamino-2-propanoltetraacetic acid, transcyclohexanediaminetetraacetic acid, nitrilotriapropionic acid, 1,3-
Diaminopropane tetraacetic acid, hydroxyethyliminodiacetic acid, glycol ether diamine tetraacetic acid, hydroxyethylenediamine triacetic acid, ethylenediamine orthohydroxyphenylacetic acid, nobutane-1,2,4-tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphone acid,
N, N -'- bis (2-hydroxybenzyl) ethylenediamine-N, N'-diacetic acid, catechol-3,4,6-trisulfonic acid, catechol-3,5-disulfonic acid, 5-sulfosalicylic acid, 4 -Sulfosalicylic acid, and these chelating agents may be used in combination of two or more if necessary.

The amount of these chelating agents added may be an amount sufficient to block the metal ions in the color developing solution. Eg 1
It is about 0.1g to 10g.

If necessary, any development accelerator can be added to the color developing solution.

As a development accelerator, Japanese Patent Publication Nos. 37-16088 and 37-598.
No. 7, No. 38-7826, No. 44-12380, No. 45-9019 and thioether compounds represented by U.S. Pat. -Phenylenediamine compounds, JP-A-50-13
7726, JP-B-44-30074, JP-A-56-156826 and JP-A-52-43429, quaternary ammonium salts, p-aminophenols described in U.S. Pat. Patent No. 2,494,903, same
3,128,182, 4,230,796, 3,253,919, Japanese Patent Publication No. 41-11431, U.S. Pat. No. 2,482,546, 2,596,926.
Nos. 3,582,346 and the like, amine compounds, JP-B-37-16088, JP-B-25-25201, and U.S. Pat.
No. 3, Japanese Patent Publication Nos. 41-11431, 42-23883 and U.S. Pat. No. 3,532,501 and other polyalkylene oxides, 1-phenyl-3-pyrazolidones, hydrazines, mesoionic compounds, ionic compounds, Imidazoles and the like can be added as necessary.

The color developer preferably contains substantially no benzyl alcohol. Substantially per color developer
The amount is 2.0 ml or less, more preferably, it is not contained at all.
When the content is not substantially contained, the fluctuation of photographic characteristics during continuous processing is small, and more preferable results are obtained.

In the present invention, any antifoggant can be added in addition to chlorine ion and bromine ion, if necessary. As the antifoggant, an alkali metal halide such as potassium iodide and an organic antifoggant can be used. Examples of organic antifoggants include benzotriazole and 6
-Nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2
Typical examples are nitrogen-containing heterocyclic compounds such as -thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine and adenine.

The color developer used in the present invention preferably contains a fluorescent whitening agent. As a fluorescent brightening agent, 4,4'-
Diamino-2,2'-disulfostilbene compounds are preferred. The addition amount is 0 to 10 g / l, preferably 0.1 to 6 g / l.

If necessary, various surfactants such as alkyl sulfonic acid, aryl phosphonic acid, aliphatic carboxylic acid, aromatic carboxylic acid may be added.

The processing temperature of the color developing solution of the present invention is 20 to 50 ° C, preferably 30 to 40 ° C. The processing time is 20 seconds to 5 minutes, preferably 30 seconds to 2 minutes.

Usually, in color development, the developer is replenished. The replenishment amount depends on the photosensitive material to be processed, but is generally about 180 to 1000 ml per square meter of the photosensitive material. Replenishment is a means for keeping the components of the color developing solution constant in order to avoid a change in development finish characteristics due to a change in component concentration in a development processing method in which a large amount of a light-sensitive material is continuously processed by an automatic developing solution, For replenishment, a large amount of overflow liquid is inevitably generated, and it is preferable that the replenishment amount is small in terms of economy and pollution. This preferable replenishment amount is 1 m ^{2 of} light-sensitive material.
It is about 20 to 150 ml. The replenishment amount of 20 ml per 1 m ² of the light-sensitive material is an amount at which the carry-out amount of the processing liquid by the light-sensitive material and the replenishment amount are substantially equal to each other, though the overflow is substantially eliminated, although the amount of replenishment varies depending on the light-sensitive material. The present invention is effective even in such a treatment with low replenishment.

In the present invention, desilvering processing is performed after color development.
The desilvering step generally consists of a bleaching step and a fixing step, but it is particularly preferred that they are performed simultaneously.

The bleaching solution or bleach-fixing solution used in the present invention includes bromide (eg, potassium bromide, sodium bromide, ammonium bromide), or chloride (eg, potassium chloride,
Rehalogenating agents such as sodium chloride, ammonium chloride) or iodides (eg ammonium iodide) can be included. Boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, if necessary.
Has a pH buffering capacity for sodium citrate, tartaric acid, etc. 1
It is possible to add more than one kind of inorganic acid, organic acid and their alkali metal or ammonium salts, or corrosion inhibitors such as ammonium nitrate and guanidine.

The bleach-fixing solution or the fixing agent used in the fixing solution according to the present invention includes known fixing agents, that is, thiosulfates such as sodium thiosulfate and ammonium thiosulfate; thiocyanates such as sodium thiocyanate and ammonium thiocyanate; ethylene. Bisthioglycolic acid, thioether compounds such as 3,6-dithia-1,8-octanediol, and water-soluble silver halide solubilizers such as thioureas. These are used alone or in admixture of two or more. can do. Further, a special bleach-fixing solution containing a combination of a fixing agent described in JP-A-55-155354 and a large amount of a halide such as potassium iodide can be used. In the present invention, the use of thiosulfates, particularly ammonium thiosulfates, is preferred. The amount of the fixing agent per 1 is preferably 0.3 to 2 mol, more preferably 0.5.
The range is up to 1.0 mol.

The pH range of the bleach-fixing solution or the fixing solution in the present invention is
3 to 10 are preferable, and 5 to 9 are particularly preferable. pH
If it is lower than this, desilvering property is improved, but deterioration of the liquid and leuco conversion of the cyan dye are promoted. On the other hand, if the pH is higher than this, desilvering is delayed and stain is likely to occur.

To adjust the pH, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, bicarbonate, ammonia, caustic potash, caustic soda, sodium carbonate, potassium carbonate and the like can be added as necessary.

Further, the bleach-fixing solution may contain various other fluorescent whitening agents, defoaming agents, surfactants, polyvinylpyrrolidone, organic solvents such as methanol.

The bleach-fixing solution and the fixing solution in the present invention, as a preservative, sulfite (for example, sodium sulfite, potassium sulfite, ammonium sulfite, etc.), bisulfite (for example, ammonium bisulfite, sodium bisulfite, potassium bisulfite, Etc.), metabisulfite (eg, potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.) and the like, and a sulfite ion-releasing compound is contained. These compounds are converted to sulfite ion
The content is preferably 0.02 to 0.50 mol / l, more preferably 0.04 to 0.40 mol / l.

As a preservative, it is common to add sulfite,
In addition, ascorbic acid, carbonyl bisulfite adduct, sulfinic acid, carbonyl compound, sulfinic acid and the like may be added.

Further, a buffering agent, a fluorescent whitening agent, a chelating agent, an antifungal agent and the like may be added if necessary.

The silver halide color photographic light-sensitive material of the present invention is generally subjected to desilvering treatment such as fixing or bleach-fixing, and then washing with water and / or a stabilizing step.

The amount of rinsing water in the rinsing step depends on the nature of the light-sensitive material (for example, depending on the materials used such as couplers), the application, and the rinsing water temperature.
It can be set in a wide range depending on the number of washing tanks (the number of stages), a replenishment system such as countercurrent and forward flow, and various other conditions. Of these, the relationship between the number of washing tanks and water volume in the multi-stage countercurrent method is described in the Journal of the Society of Motion Picture and Television Engineers (Journal of the Society of Motion Picture and
Terevision Engineers) Volume 64, p.248-253 (May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced, but due to the increase in the residence time of water in the tank, bacteria propagate, and the suspended matter produced adheres to the photosensitive material, etc. Problem arises. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, the method of reducing calcium and magnesium described in Japanese Patent Application No. 61-131632 can be used very effectively. Also, isothiazolone compounds and thiabendazoles described in JP-A-57-8542, chlorine-based disinfectants such as chlorinated sodium isocyanurate, and other benzotriazoles, etc. It is also possible to use the disinfectant described in "Sterilization, disinfection, and fungicide technology of microorganisms" edited by the Sanitary Technology Society, and "Encyclopedia of Antifungal and Fungicide" edited by the Japan Society of Antifungals and Fungi.

The pH of the washing water in the processing of the light-sensitive material of the present invention is 4-9.
And preferably 5-8. The washing temperature and washing time can also be variously set depending on the characteristics of the photosensitive material, the application, and the like, but in general, the range is 20 seconds to 10 minutes at 15 to 45 ° C, preferably 30 seconds to 5 minutes at 25 to 40 ° C. Is done.

Further, the light-sensitive material of the present invention can be processed directly with a stabilizing solution instead of the washing with water. In such stabilizing treatment, JP-A-57-8543 and JP-A-58-14834 are used.
No. 59, No. 184343, No. 60-220345, No. 60-238832
No. 60, No. 60-239784, No. 60-239749, No. 61-4054,
All known methods described in JP-A-61-118749 and the like can be used. Especially 1-hydroxyethylidene-1,1-
A stabilizing bath containing diphosphonic acid, 5-chloro-2-methyl-4-isothiazolin-3-one, a bismuth compound, an ammonium compound and the like is preferably used.

Further, there is a case where further stabilization treatment is carried out after the water washing treatment, and an example thereof is a stabilizing bath containing formalin and a surfactant, which is used as a final bath of a color light-sensitive material for photographing. .

The processing time of the present invention is defined as the time from the time when the photosensitive material comes into contact with the color developer to the time when it leaves the final bath (usually a washing or stabilizing bath). The effect of the present invention can be remarkably exhibited in a rapid processing step of 30 seconds or less, preferably 4 minutes or less.

Next, the silver halide color photographic light-sensitive material used in the present invention will be described in detail.

The silver halide emulsion of the present invention consists essentially of silver chloride. Here, "substantially" means that the content of silver chloride is at least 80 mol%, preferably at least 95 mol%, more preferably at least 98 mol%, based on the total silver halide amount. From the viewpoint of rapidity, the higher the silver chloride content, the better. The high silver chloride of the present invention may contain a small amount of silver bromide or silver iodide. There are many useful points in terms of photosensitivity, such as increasing the light absorption amount, enhancing the adsorption of the spectral sensitizing dye, or weakening the desensitization by the spectral sensitizing dye.

The silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention may have a different phase between the inside and the surface layer, may have a multi-phase structure having a junction structure, or may have a whole grain structure. It may consist of a homogeneous phase. Moreover, they may be mixed.

Silver halide grains in photographic emulsions are cubic, octahedral,
Those having a regular crystal form such as tetradecahedron, spherical,
It may be a material having an irregular crystal such as a plate, a material having a crystal defect such as a twin plane, or a compound thereof.

The grain size of silver halide may be fine grains of about 0.2 μm or less, or large grains having a projected area diameter of up to about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion. A monodisperse emulsion having a coefficient of variation of 0.15 or less is preferred.

The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (RD), No. 17643 (1978).
Dec.), pp. 22-23, "I. Emulsion prepara
and types can be prepared using the methods described in "

Monodisperse emulsions described in US Pat. Nos. 3,574,628 and 3,655,394 and British Patent 1,413,748 are also preferable.

Further, tabular grains having an aspect ratio of about 5 or more can be used in the present invention. Tabular grains are described in Gutoff, Photographic Science and Engineerin.
g), Vol. 14, pp. 248-257 (1970); U.S. Pat. No. 4,43.
4,226, 4,414,310, 4,433,048, 4,439,520
It can be easily prepared by the method described in Japanese Patent No. 2,112,157 and the like.

The crystal structure may be uniform, may have different halogen compositions inside and outside, or may have a layered structure. Further, silver halides having different compositions may be joined by epitaxial joining, or may be joined with compounds other than silver halides such as silver rhodanide and lead oxide.

 Also, a mixture of particles having various crystal forms may be used.

The silver halide emulsion is usually one which has been physically ripened, chemically ripened and spectrally sensitized. Additives used in such processes are Research Disclosure No. 1
7643 and No. 18716, the relevant parts are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and the relevant portions are shown in the following table.

Various color couplers can be used in the present invention, specific examples of which are described in the patents described in Research Disclosure (RD) No. 17643, VII-CG.

As the yellow coupler, for example, U.S. Pat.
No. 501, No. 4,022,620, No. 4,326,024, No. 4,40
1,752, Japanese Patent Publication No. 58-10739, British Patent No. 1,425,020
No. 1,476,760 and the like are preferred.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and US Pat. No. 4,310,
619, 4,351,897, European Patent 73,636, U.S. Patents 3,061,432, 3,725,067, Research Disclosure No. 24220 (June 1984), JP-A-60-3355.
2, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, US Pat. No. 4,500,630,
No. 4,540,654, No. 4,556,630, WO (PCT) 88/0479
Those described in No. 5 and the like are particularly preferable.

Cyan couplers include phenol and naphthol couplers, U.S. Pat.Nos. 4,052,212, 4,146,396, 4,228,233 and 4,296,200,
No. 2,369,929, No. 2,801,171, No. 2,772,162
No. 2, No. 2,895,826, No. 3,772,002, No. 3,758,30
No. 8, No. 4,334,011, No. 4,327,173, West German Patent Publication No. 3,329,729, European Patent No. 121,365A, U.S. Patent No.
3,446,622, 4,333,999, 4,451,559, 4,427,767, 4,690,889, 4,254,212,
4,296,199, European Patent 161,626A, JP 61-42658
Those described in No. etc. are preferable.

Colored couplers to correct unwanted absorption of colored dyes are Research Disclosure No. 17643 VII.
-G, U.S. Pat. No. 4,163,670, Japanese Examined Patent Publication No. 57-39413,
U.S. Patent Nos. 4,004,929, 4,138,258, British Patent No.
Those described in No. 1,146,368 are preferable.

As a coupler in which the coloring dye has an appropriate diffusibility,
Those described in U.S. Pat. No. 4,366,237, British Patent No. 2,125,570, European Patent No. 96,570 and West German Patent (Publication) No. 3,234,533 are preferable.

Typical examples of polymerized dye-forming couplers are U.S. Pat.Nos. 3,451,820, 4,080,211 and 4,367,282.
No. 2,102,173 and the like.

Couplers that release a photographically useful residue upon coupling are also preferably used in the present invention. The DIR coupler releasing the development inhibitor is the above-mentioned RD17643, VII-F.
Patents described in paragraphs, JP-A-57-151944 and JP-A-57-1542
The compounds described in U.S. Pat. No. 34,60-184248 and U.S. Pat. No. 4,248,962 are preferable.

Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent Nos. 2,097,140 and 2,1.
Those described in 31,188, JP-A-59-157638 and JP-A-59-170840 are preferable.

Other couplers that can be used in the light-sensitive material of the present invention include competitive couplers described in U.S. Pat.No. 4,130,427, U.S. Pat.Nos. 4,283,472, and 4,338,393,
Multi-equivalent couplers described in U.S. Pat.
Examples of the coupler include a DIR redox compound releasing coupler described in JP-A-185950, and a coupler that releases a dye that restores color after separation described in EP 173,302A.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods.

Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027.

The steps of the latex dispersion method, effects, and specific examples of the latex for impregnation are described in US Pat. No. 4,199,363, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.

Suitable supports that can be used in the present invention are, for example, those mentioned above.
RD.No. 17643, page 28, and RD.No. 18716, page 647 From the right column
See page 648, left column.

The light-sensitive material to which the present invention is applied is, for example, a color photographic light-sensitive material such as a color negative film, a color reversal film (inner type and outer type), a color paper, a color positive film, a color reversal paper, a color diffusion transfer process, and a direct positive color light-sensitive material. However, it is particularly preferably applied to a color negative film, a color reversal film and a color reversal paper.

(Examples) Examples of the present invention will be specifically shown below.
It is not limited to these.

Example 1 A multilayer color photographic paper having the following layer structure was prepared on a paper support laminated on both sides with polyethylene. The coating liquid was prepared as follows.

Preparation of 1st layer coating solution 60.0g of yellow coupler (ExY) and anti-fading agent (Cp
d-1) 28.0 g of ethyl acetate 150 cc and solvent (Solv-
3) Add 1.0 cc and 3.0 cc of solvent (Solv-4) and dissolve, then add 10 cc of this solution containing sodium dodecylbenzene sulfonate.
% Gelatin aqueous solution (450 cc) and then dispersed with an ultrasonic homogenizer. The resulting dispersion is 420 g of silver chlorobromide emulsion (0.7 mol% of silver bromide) containing the following blue-sensitive sensitizing dye.
To prepare a coating solution for the first layer. The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. 1,2-Bis (vinylsulfonyl) ethane was used as a gelatin hardener for each layer.

The following were used as the spectral sensitizing dye in each layer.

Blue-sensitive emulsion layer; anhydro-5-5'-dichloro-3,
3'-disulfoethylthiacyanine hydroxide green sensitive emulsion layer; anhydro-9-ethyl-5,5'-diphenyl-3,3'-disulfoethyloxacarbocyanine hydroxide red sensitive emulsion layer; 3,3 ' -Diethyl-5-methoxy-9,9 '
-(2,2'-Dimethyl-1,3-propano) thiacarbocyanine iodide The following substances were used as stabilizers for each emulsion layer.

The following dyes were used as the anti-irradiation dye.

[3-carboxy-5-hydroxy-4- (3- (3
-Carboxy-5-oxo-1- (2,5-disulfonatophenyl) -2-pyrazolin-4-ylidene) -1-propenyl) -1-pyrazolyl] benzene-2,5-disulfonate-disodium salt N , N '-(4,8-dihydroxy-9,10-dioxy-3,7
-Disulfonatoanthracene-1,5-diyl) bis (aminomethanesulfonate) -tetrasodium salt [3-cyano-5-hydroxy-4- (3- (3-cyano-5-oxo-1- ( 4-sulfonatophenyl)-
2-pyrazolin-4-ylidene) -1-pentanyl)-
1-Pyrazolyl] benzene-4-sulfometho-sodium salt (Layer constitution) The composition of each layer is shown below. Numbers represent coating weight (g / m ² ). The silver halide emulsion represents the coating amount in terms of silver.

Support Paper support laminated on both sides with polyethylene 1st layer (blue sensitive layer) Silver chlorobromide emulsion (AgBr: 0.7 mol%, cubic, grain size 0.9μ) 0.2 Gelatin 1.80 Yellow coupler (ExY) 0.60 Anti-fading Agent (Cpd-1) 0.28 Solvent (Solv-3) 0.01 Solvent (Solv-4) 0.03 Second layer (color mixing prevention layer) Gelatin 0.80 Color mixing inhibitor (Cpd-2) 0.055 Solvent (Solv-1) 0.03 Solvent (Solv -2) 0.015 Third layer (green-sensitive layer) Silver chlorobromide emulsion (AgBr: 0.7 mol%, cubic, grain size 0.
45μ) 0.28 Gelatin 1.40 Magenta coupler (ExM) 0.67 Anti-fading agent (Cpd-3) 0.23 Anti-fading agent (Cpd-4) 0.11 Solvent (Solv-1) 0.20 Solvent (Solv-2) 0.02 Fourth layer (anti-color mixing layer) ) Gelatin 1.70 Anti-color mixing agent (Cpd-2) 0.065 UV absorber (UV-1) 0.45 UV absorber (UV-2) 0.23 Solvent (Solv-1) 0.05 Solvent (Solv-2) 0.05 Fifth layer (red sensation) Layer) Silver chlorobromide emulsion (AgBr: 4 mol%, cube, grain size 0.5)
μ) 0.19 Gelatin 1.80 Cyan coupler (ExC-1) 0.26 Cyan coupler (ExC-2) 0.12 Anti-fading agent (Cpd-1) 0.20 Solvent (Solv-1) 0.16 Solvent (Solv-2) 0.09 Sixth layer (UV absorption) Layer) Gelatin 0.70 UV absorber (UV-1) 0.26 UV absorber (UV-2) 0.07 Solvent (Solv-1) 0.30 Solvent (Solv-2) 0.09 Seventh layer (protective layer) Gelatin 1.07 (ExY) Yellow coupler α-pivalyl-α- (3-benzyl-1-hydantoinyl) -2-chloro-5 [β- (dodecylsulfonyl) butyramide] acetanilide (ExM) magenta coupler 1- (2,4,6-trichlorophenyl)- 3 [2-chloro-5 (3-octenylsuccinimide) anilino] -5
-Pyrazolone (ExC-1) cyan coupler 2-pentafluorobenzamide-4-chloro-5 [2
-(2,4-di-tert-amylphenoxy) -3-methylbutyramidephenol (ExC-2) cyan coupler 2,4-dichloro-3-methyl-6- [α- (2,4-di-te
rt-Amylphenoxy) butylamide] phenol (Cpd-1) anti-fading agent 2,5-di-tert-amylphenyl-3,5-di-tert-butylhydroxybenzoate (Cpd-2) anti-fading agent 2,5-di- tert-octylhydroquinone (Cpd-3) anti-fading agent 1,4-di-tert-amyl-2,5-dioctyloxybenzene (Cpd-4) anti-fading agent 2,2'-methylenebis (4-methyl-6-) (tert-butylphenol) (Solv-3) solvent di (nonyl) phthalate (Solv-4) solvent N, N-diethylcarbonamide-methoxy-2,4-di-t
-Amylbenzene (UV-1) UV absorber 2- (2-hydroxy-3,5-di-tert-amylphenyl) benzotriazole (UV-2) UV absorber 2- (2-hydroxy-3,5-di) -Tert butylphenyl) benzotriazole (Solv-1) solvent di (2-ethylhexyl) phthalate (Solv-2) solvent dibutylphthalate The sample prepared as described above is referred to as sample number 01.

Next, samples 02 to 05 were prepared in the same manner as sample 01, except that the halogen composition of the first, third and fifth layers of the silver halide emulsion was changed as shown in Table 1.

Then, Samples 06 to 10 were prepared in exactly the same manner as Samples 01 to 05 except that the exemplified compound D-5 was introduced by co-dispersion with a cyan coupler in the fifth layer so that the coating amount was 0.12 g / m ^2. It was made.

Further, as another sample, a silver halide color photographic light-sensitive material was prepared by sequentially coating the following layers on a paper support laminated on both sides with polyethylene from the support side.

The first layer is a blue-sensitive silver halide emulsion layer using a silver chlorobromide emulsion consisting of 96 mol% of silver chloride, to which 2.5 × 10 ^-4 mol of a sensitizing dye having the following structure is added per mol of silver halide. (solvent:
Sensitized with (isopropyl alcohol). Further, 350 g of gelatin is contained per mol of silver halide.

Further, 200 mg / m ^{2 of} 2,5-di-t-butylhydroquinone dissolved and dispersed in dibutyl phthalate (DBP) and a yellow coupler having the following structure were contained in an amount of 2 × 10 ^-1 mol per mol of silver halide. The amount of application was 300 mg / m ² .

Second layer Di-t-octylhydroquinone 300mg dissolved in DBP
/ m ² , a mixture of the following 4 as an ultraviolet absorber 200mg / m ²
It is a gelatin layer containing and is applied so as to be 1900 mg / m ² of gelatin.

Third layer A green-sensitive silver halide emulsion layer using a silver chlorobromide emulsion consisting of 96 mol% of silver chloride, the emulsion containing 450 g of gelatin per mol of silver halide and having the following structure per mol of silver halide. Sensitization was carried out by adding 2.5 × 10 ^-2 mol of sensitizing dye.

A magenta coupler having the following structure, which was dissolved in a solvent in which DBP and tricresyl phosphate (TCP) were mixed in a ratio of 2: 1 and contained 1.5 × 10 ^-1 mol per mol of silver halide, contained 280 mg / m of silver. ^It was applied so as to be ² .

As the antioxidant, 0.3 mol of the compound having the following structure was contained per mol of the coupler.

Fourth layer Di-t-octylhydroquinone 30 mg / m ² dissolved and dispersed in dioctyl phthalate (DOP) and a mixture of the compounds (a), (b), (c) and (d) as an ultraviolet absorber. (2: 2: 1.5: 1.5) gelatin weight gelatin layer containing 500 mg / m ² was coated so as to 1900 mg / m ^2.

Fifth layer A red-sensitive silver halide emulsion layer using a silver chlorobromide emulsion consisting of 96 mol% of silver chloride, the emulsion containing 500 g of gelatin per mol of silver halide and having the following structure per mol of silver halide. Sensitization was carried out by adding 2.5 × 10 ⁻⁵ mol of a sensitizing dye.

Further, 150 mg / m ^{2 of} 2,5-di-t-butylhydroquinone dissolved and dispersed in DBP and a cyan coupler having the following structure (mixture in a molar ratio of 1: 1) were added at 3.5 mol per mol of silver halide.
It was applied at a content of × 10 ^-1 mol and a silver amount of 280 mg / m ² .

Sixth layer The gelatin layer was coated so that the gelatin layer would be 900 mg / m ² .

The silver halide emulsions used in the first, third and fifth light-sensitive emulsion layers were prepared by the method described in JP-B-46-7772, and chemically sensitized with sodium thiosulfate pentahydrate. 4-hydroxy-6-methyl- as a stabilizer
1,3,3a, 7-Tetrazaindene was used, bis (vinylsulfonylmethyl) ether as hardener and saponin as coating aid.

The sample manufactured by the above method is referred to as sample 11. Also sample
Sample 12 was prepared in exactly the same manner as Sample 11 except that Exemplified Compound D-5 of the present invention was added to the fifth layer 11 at 0.15 g / m ² .

The following experiments were conducted in order to investigate the photographic characteristics of these samples 01 to 12.

First, each sample was subjected to three-color separation gradation exposure for sensitometry using a sensitometer (FWH type manufactured by Fuji Photo Film Co., Ltd., color temperature of light source: 3200 ° K).
The exposure at this time was performed so that the exposure amount was 250 CMS with the exposure time of 0.1 seconds.

The density of the cyan image obtained after the treatment was measured, and the maximum density (Dmax) was examined. The results are shown in Table-2.

Further, the above samples 01 to 12 were separately subjected to gray uniform exposure using the above-mentioned sensitometer, and subjected to the same treatment as in the above sensitometry to evaluate the pressure sensitizing muscles. The results are shown together in Table 2. However, the evaluation criteria at this time were evaluated by setting the following four stages.

The exposed sample was processed in the following processing steps and processing solution compositions using an automatic processor. However, in the composition of the color developing solution, the halogen ion concentrations of chlorine and bromine were changed as shown in Table 2 to perform the treatment. Step Temperature Time Color developing 38 ° C. 45 seconds blix 30 to 36 ° C. 45 sec Rinse 30 to 37 ° C. 30 sec Rinse 30 to 37 ° C. 30 sec Rinse 30 to 37 ° C. 30 seconds Drying 70 to 80 ° C. 60 seconds each processing solution The composition of is as follows.

Color developer Water 800 ml Ethylenediamine-N, N, N, N-tetramethylenephosphonic acid 3.0 g Organic preservative (I-1) 0.03 mol Sodium chloride See table 2 Potassium bromide See table 2 Potassium carbonate 25 g N-ethyl- N- (β-methanesulfonamidoethyl)
-3-Methyl-4-aminoaniline sulfate 5.0g Triethanolamine 10.1g Fluorescent brightener (4,4'-diaminostilbene type, WHITEX-
4. Sumitomo Chemical Co., Ltd.) 2.0g Add water 1000ml pH (25 ℃) 10.05 Bleach-fix solution Water 400ml Ammonium thiosulfate (70%) 100ml Sodium sulfite 17g Ethylenediaminetetraacetic acid iron (III) ammonium 55g Ethylenediaminetetraacetate disodium 5g Ammonium bromide 40g Glacial acetic acid 9g Water added 1000ml pH (25 ℃) 5.00 Rinse solution Ion-exchanged water (calcium and magnesium 3ppm or less) As is clear from Table 2, when a photosensitive material containing 80 mol% or more of silver chloride and containing the compound of the present invention was treated with a developing solution having a halogen ion concentration within the range of the present invention,
It can be seen that the maximum density of the cyan image is remarkably high and the pressure-sensitized muscle fog is remarkably suppressed.

Example 2 Samples 21 to 28 were prepared in exactly the same manner as in Sample 06, except that the compound of the present invention used in the fifth layer of Sample 06 used in Example 1 was changed as shown in Table 3. The compound was added in equimolar substitution.

Then, samples 06, 21 to 28 and 01 are imagewise exposed and continuously processed using a paper processor with the following processing steps and processing solution compositions until the tank is filled with twice the tank capacity of the color developing solution. (Running test) was performed.

Then, Samples 06, 21 to 28, 01 were exposed under the exposure conditions described in Example 1, and the cyan densities at the start and end of running were measured using the above-mentioned running solution corresponding thereto, and the photographic property by running was measured. I examined the fluctuations.

 The results are shown in Table-4.

The chlorine ion concentration and the bromine ion concentration in the color developer of the running solution are 7.4 to 7.6 × 10 ^-2 mol / l and 1.8 to 1.9 × 10 ^{-4 in} each running solution.
It was in the range of mol / l.

The composition of each treatment liquid is as follows.

Stabilizer (same as tank and replenisher) Formalin (37%) 0.1g Formalin-sulfite adduct 0.7g 5-Chloro-2-methyl-4-isothiazolin-3-one 0.02g 2-Methyl-4-isothiazolin- 3-on 0.01g Copper sulfate 0.005g Ammonia water (28%) 2.0ml Add water 1000ml pH (25 ℃) 4.0 As is clear from Table 4, samples containing the compound of the present invention
It can be seen that 06 and 21 to 28 show sufficient color developability and that the photographic properties hardly change due to running. But,
Among the compounds of the general formulas (A) to (G), the compounds of the general formulas (A) and (D) of the present invention are excellent in terms of prevention of pressure sensitizing muscle generation, reduction of residual silver amount, and maximum concentration. It can be seen that the compound of the general formula (A) is particularly excellent.

Example 3 A multilayer color photographic printing paper 31 having the following layer structure was prepared on a paper support laminated on both sides with polyethylene. The coating liquid was prepared as follows.

Preparation of 1st layer coating solution Yellow coupler (ExY) 19.1g and color image stabilizer (Cp
d-1) 4.4 g and color image stabilizer (Cpd-7) 0.7 g were dissolved by adding ethyl acetate 27.2 cc and solvent (Solv-3) 8.2 g, and the solution was dissolved in 10% sodium dodecylbenzenesulfonate 8c.
It was emulsified and dispersed in 185 cc of 10% gelatin aqueous solution containing c. On the other hand, a silver chlorobromide emulsion (cubic average grain size 0.88μ, grain size distribution coefficient of variation 0.08, silver bromide containing 0.2 mol% on the grain surface) was mixed with the following blue-sensitive sensitizing dyes at 2.0 × / mol silver. After addition of 10 ^-4 mol, sulfur-sensitized one was prepared. The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a coating liquid for the first layer having the composition shown below. After the coating for the second layer to the seventh layer, the same method as that for the coating liquid for the first layer was prepared. 1 as a gelatin hardening agent for each layer
-Oxy-3,5-dichloro-s-triazine sodium salt was used.

 The following were used as the spectral sensitizing dye in each layer.

The following compounds were added to the red-sensitive emulsion layer in an amount of 2.6 × 10 ^-3 mol per mol of silver halide.

Further, 1- (5-methylureidophenyl) -5-mercaptotetrazole was added to each of the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer per mol of silver halide.
8.5 × 10 ^-5 mol, 7.7 × 10 ^-4 mol and 2.5 × 10 ^-4 mol were added.

The following dyes were added to the emulsion layer to prevent irradiation.

(Layer constitution) The composition of each layer is shown below. Numbers represent coating weight (g / m ² ). The silver halide emulsion represents the coating amount in terms of silver.

Support Polyethylene laminated paper [Polyethylene on the first layer side contains white pigment (TiO ₂ ) and bluish dye (ultraviolet)] First layer (blue sensitive layer) Silver chlorobromide emulsion 0.30 Gelatin 1.86 Yellow coupler (ExY) 0.82 Color image stabilizer (Cpd-1) 0.19 Solvent (Solv-3) 0.35 Color image stabilizer (Cpd-7) 0.06 Second layer (color mixing prevention layer) Gelatin 0.99 Color mixing inhibitor (Cpd-5) 0.08 Solvent (Solv -1) 0.16 solvent (Solv-4) 0.08 third layer (green-sensitive layer) silver chlorobromide emulsion (having a cubic average grain size of 0.55 µ,
(1: 3 mixture (Ag mol) ratio of 0.39μ). Coefficient of variation of particle size distribution 0.10 and 0.08 respectively. 0.8 mol% of AgBr was locally contained on the particle surface.

0.12 Gelatin 1.24 Magenta coupler (ExM) 0.27 Color image stabilizer (Cpd-3) 0.15 Color image stabilizer (Cpd-8) 0.02 Color image stabilizer (Cpd-9) 0.03 Solvent (Solv-2) 0.54 Fourth layer ( UV absorbing layer) Gelatin 1.58 UV absorbing agent (UV-1) 0.47 Color mixing inhibitor (Cpd-5) 0.05 Solvent (Solv-5) 0.24 Fifth layer (red sensitive layer) Silver chlorobromide emulsion (cubic, average grain size) A 1: 4 mixture of 0.58μ and 0.45μ (Ag molar ratio) Coefficients of variation of particle size distribution 0.09 and 0.11, respectively. AgBr 0.6mol% was locally contained in a part of the particle surface.

0.23 Gelatin 1.34 Cyan coupler (ExC) 0.32 Color image stabilizer (Cpd-6) 0.17 Color image stabilizer (Cpd-10) 0.04 Color image stabilizer (Cpd-7) 0.40 Solvent (Solv-6) 0.15 Exemplified compound (Cpd -2) 0.10 Sixth layer (UV absorption layer) Gelatin 0.53 UV absorber (UV-1) 0.16 Color mixing inhibitor (Cpd-5) 0.02 Solvent (Solv-5) 0.08 Seventh layer (protection layer) Gelatin 1.33 Polyvinyl alcohol Acrylic modified copolymer (degree of modification
17%) 0.17 Liquid paraffin 0.03 Next, in the same manner as in Sample 31, except that the coating silver amounts of the first, third and fifth layers of Sample 31 were changed as shown in Table 5,
35 created. Further, except that the compound D-5 used in the fifth layer of Samples 31 to 35 was changed to A-1 (equimolar substitution), Sample 31
Samples 36 to 40 were prepared in exactly the same manner as ~ 35.

After subjecting the above Samples 31 to 40 to imagewise exposure, continuous processing was carried out in the following processing steps using a paper processor until replenishment of twice the tank capacity of the color developing solution.

The chlorine ion and bromine ion concentrations in the color developer at the end of running are 4.8 to 5.0 × 10 ^-2 mol / l and 8.
It was 0 to 8.2 × 10 ⁻⁵ mol / l.

The composition of each treatment liquid is as follows.

Rinse solution (tank solution and replenisher are the same) Ion-exchanged water (calcium and magnesium are each 3 ppm or less) At the start and end of running, the samples 31 to 40 subjected to the gradation exposure described in Example 1 are respectively corresponded. Dm of the cyan image obtained by treating with liquid
Photographic properties of ax and Dmin were evaluated. The results are shown in Table-6.

Subsequently, the samples 31 to 40 were uniformly exposed so as to obtain 90% of developed silver with respect to the coated silver amount, and these were treated with the above running liquid to determine the residual silver amount by fluorescent X-ray. It was measured at. The results are shown in Table 6.

Further, the samples 31 to 40 were subjected to uniform exposure using the sensitometer described in Example 1 so that a gray density of reflection density of 0.5 was obtained, and the samples were processed with the running liquid to increase the pressure. Evaluation of sensitive fog was performed. The evaluation criteria were performed according to the method described in Example 1 above. The results are shown together in Table 6.

As is clear from Table 6, in Samples 31 to 33 and 36 to 38 of the present invention in which the total coated silver amount was 0.75 g / m ² or less, the photographic property fluctuation due to running, desilvering property and pressure sensitized muscle fog were observed. It can be seen that all of the above are good.

(Effects of the Invention) By carrying out the present invention, development processing satisfying both changes in photographic characteristics and defoaming properties of in-liquid pressure sensitized muscle fog can be carried out.

 ─────────────────────────────────────────────────── ─── Continuation of front page (56) References JP-A-63-36245 (JP, A) JP-A-63-223645 (JP, A) JP-A-62-143048 (JP, A) JP-A-63- 226637 (JP, A) JP 63-100454 (JP, A) JP 62-247367 (JP, A) JP 63-163454 (JP, A) JP 59-197037 (JP, A) JP-A-51-27922 (JP, A) JP-A-55-126238 (JP, A)

Claims (1)

[Claims] 1. A method of processing a silver halide color photographic light-sensitive material with a color developing solution containing at least one aromatic primary amine color developing agent, wherein a high chloride content of 80 mol% or more of silver chloride is used. It has a silver halide emulsion in at least one layer and a layer containing at least one of the compounds represented by the following general formulas (A) and (D), and the coated silver amount is 0.75 g. The silver halide color photographic light-sensitive material of less than / m ² is treated with chloride ions at 3.5 × 10 ^-2
~ 1.5 × 10 ^-1 mol / l, and 3.0 × 10 ^-5 bromine ions
A method for processing a silver halide color photographic light-sensitive material, which comprises processing with a color developing solution containing a concentration of about 1.0 × 10 ⁻³ mol / l. R ₆ —NHSO ₂ —R ₇ General formula [D] In the general formula [A], D represents a divalent electron-withdrawing group, and R ₁ and R ₂ are each independently an alkyl group, an aryl group or an alkoxy group. , An aryloxy group, an alkylamino group, an anilino group, or a heterocyclic group, p is an integer of 1 or 2, q is 0 or 1, and U is a benzene ring which may be condensed with a phenol ring or Represents a heterocycle. In the general formula [D], R ₆ is an alkyl group, an aryl group,
It represents an alkylsulfonyl group, a phenylsulfonyl group, or an acyl group, and R ₇ represents an alkyl group or an aryl group.