JPH087408B2 - 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 silver halide color photographic light-sensitive material having a high silver chloride content. The present invention relates to a development processing method in which a material (hereinafter simply referred to as a high silver chloride color light-sensitive material) is used, development characteristics are improved, and desilvering property is excellent.

(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 color photographic light-sensitive material with a color developer substantially free of 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. This is because when a photosensitive material comes into contact with a roller or the like in a developing tank of an automatic processor, streaky fog occurs due to pressure sensitization. Pressure sensitizer)
Is estimated to be

Further, it became clear that during continuous processing, the photographic properties fluctuate significantly (especially minimum density (Dmin) and maximum density (Dmax)), desilvering failure occurs, and the white background is significantly contaminated.

As described above, the rapid development processing using the high silver chloride color light-sensitive material has serious problems such as pressure sensitizing streaks in the liquid, fluctuation of photographic properties, and desilvering failure. It wasn't something.

In a rapid processing method using a high silver chloride color photographic light-sensitive material, a method for reducing fluctuations in photographic characteristics (especially minimum density (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.

Further, in JP-A-61-70552, a method for lowering the replenishment of a developing solution, in which a high silver chloride color photographic light-sensitive material is used and a replenishing amount is added during development so that overflow does not occur in a developing bath. JP-A-63-106655 discloses a method of developing a high silver chloride color light-sensitive material with a color developing solution containing a hydroxylamine compound and a chloride at a predetermined concentration or more for the purpose of stabilizing the processing. It is disclosed. However, in these methods, the pressure sensitizing line generated in the processing using the above-mentioned automatic processor, the fluctuation of photographic characteristics during continuous processing and the occurrence of defective desilvering were observed, and they were not practical.

Further, the dye formed in the color developing process is not sufficiently oxidized in the bleaching process or the bleach-fixing process, and remains in the state of a leuco dye which is a reaction intermediate, and the dye is not completely formed, so-called defective color restoration occurs, which is a serious problem. It became an obstacle. This phenomenon is particularly remarkable in cyan dyes.

Heretofore, various techniques have been known to improve the color restoration failure. For example, JP-A-49-17732 and JP-A-51-65939.
The method of adding a bromate or a persulfate to the bleaching solution described in the above-mentioned specification is not an appropriate method because it causes bleaching fog. Further, in Japanese Patent Application Laid-Open Nos. 48-43938, 48-45238, 48-46334 and the like, there is proposed a method of treating a leuco body with a red blood salt to a dye after treating with a bleach-fixing solution. However, this method is not preferable because it causes environmental pollution. U.S. Patent No.
No. 3770437 proposes a method of adding a bromate and an iodide or a bromide to a bleach-fixing bath, but the stability of the bleach-fixing solution is deteriorated, and a preferable method is to form a bleaching fog. I can't say. Further, JP-A-48-26139 proposes a method of treating with a treatment solution containing a persulfate before or after the bleach-fixing bath, but the effect of preventing color restoration failure is small, and However, bleaching fog is generated and is not suitable for practical use. Further, Japanese Patent Publication No. 54-38894 proposes a method of combining different kinds of aminopolycarboxylic acid metal complexes, but the stability of the bleach-fixing solution is deteriorated, and it is disadvantageous in terms of cost and is a practical method. I can't say. Also, Japanese Patent Publication Sho 51-2317
No. 9, a method of adding p-phenylenediamines and pyrazolidones to a bleach-fixing solution, and JP-A-57-192953.
The methods of adding alkanolamines and the like described in Japanese Patent Laid-Open Publication No. 1994-242242 are inadequate because of their small effects.

(Problems to be Solved by the Invention) Accordingly, an object of the present invention is to provide a rapid processing method using a high silver chloride color light-sensitive material, which has improved pressure sensitizing lines and shows stable photographic properties even in continuous processing. To provide.

In addition, it is another object of the present invention to provide a development processing method using a high silver chloride color light-sensitive material, having a small amount of residual silver, an improved desilvering property, and a large effect of preventing a color restoration defect.

(Means for Solving the Problems) The present invention has been found to be solved by the following processing method. That is, in the method of treating a silver halide color photographic light-sensitive material with a color developing solution containing at least one aromatic primary amine color developing agent, the silver halide color photographic light-sensitive material contains 80 mol% or more. A silver halide emulsion comprising silver chloride, and a total silver halide emulsion containing at least one compound represented by the following general formula (A):
And the total amount of coated silver is 0.75 g / m ² or less, the color developer has chlorine ions of 3.5 × 10 ^{−2 to} 1.5 × 10 ⁻¹ mol / l, and bromine ions of 3.0 × 10 ^{−5 to} 1.0. A method for processing a silver halide color photographic light-sensitive material, characterized by containing ^{x10 -3} mol / l.

General formula [A] In the formula, R represents a hydrogen atom or a hydrolyzable protecting group. R ₁ , R ₂ , R ₃ , R ₄ and R ₅ may be the same or different and each represents a hydrogen atom or a substituent excluding a substituted and unsubstituted benzotriazole group.
However, all of R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are not hydrogen atoms. And by coupling with the developing agent oxidant,
Excludes those that develop color substantially. R and R ₁ or R ₁ , R ₂ ,
Of R ₃ , R ₄ and R ₅ , those in the ortho positions may combine with each other to form a 5-, 6- or 7-membered ring.

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, it causes the increase of fog due to continuous processing and the streaky fog generated when processed by an automatic processor. It was not possible to completely prevent it, but on the contrary, the development was delayed and the maximum density was lowered, which had an adverse effect.

Bromide ion is also well known as one of the antifoggants, but when used alone, the addition amount can prevent fog and streak pressure fog associated with continuous processing, but suppresses development. Decrease the maximum density and sensitivity,
It wasn't practical.

However, as a result of various studies, the inventors of the present invention used a high silver chloride light-sensitive material having a silver chloride content of 80 mol% or more and a coating silver amount of 0.75 g / m ² or less. Ions 3.5 × 10 ^{-2 to} 1.5 × 10 ^-1 mol / l, 3.0 × 10 ^-5
The maximum density is high when processed with a color developer containing ~ 1.0 × 10 ^-2 mol / l, and the streak-like pressure fog that occurs in processing with an automatic processor and photographic fluctuations associated with continuous processing (especially minimum It has been found that the residual silver amount can be remarkably reduced by preventing the concentration and the maximum concentration).

Further, they have found that it is possible to prevent defective color restoration by adding the compound [A] to a layer containing a silver halide emulsion. The effect of preventing color restoration defects is
Especially, chlorine ion and bromine ion in the developer are respectively 3.
5 x 10 ^{-2 to} 1.5 x 10 ^-1 mol / l, 3.0 x 10 ^{-5 to} 1.0 x 10 ^-3 mol
It was found that the effect is remarkably large when the content is / l.

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 presumed as follows.

It is considered that when a temperature pressure is applied to the photosensitive material in the color developing solution after the exposure, the pressured portion 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.

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 ions and chlorine ions to suppress the formation of silver sulfide, and the coated silver amount is 0.
It is presumed that the desilvering treatment at 75 g / m ² or less is advantageous for desilvering treatment and the like, which is related to the suppression of desilvering failure.

In addition, the effect of preventing photographic fluctuations associated with continuous processing is that the presence of suitable amounts of bromine ions and chlorine ions stabilizes the performance against developing agents, preservatives for the main agents, and changes in the pH of the developer, and This is probably because the coated silver amount was 0.75 g / m ² or less.

 The present invention will be described in detail below.

The silver halide emulsion of the present invention has a silver chloride content of 80 mol% or more, preferably 95 mol%, based on the total amount of silver halide.
Or more, more preferably 98 mol% or more. From the viewpoint of rapidity, the higher the silver chloride content, the better.

The coating amount of silver halide light-sensitive material of the present invention is 0.75 g / m ²
It must be: When the amount of coated silver is more than 0.75 g / m ² , the photographic characteristics fluctuate greatly with continuous processing.
Since the amount of residual silver is large, the object of the present invention is not achieved.

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, 3.5 × 10 ^-2 mol /
If it is less than 1, it is impossible to prevent streak-like pressure fog, and further, the photographic property fluctuations (especially minimum density and maximum density) due to continuous processing are large, and the amount of residual silver is large, so that the object of the present invention can be achieved. Not something to do.

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
When it is less than 1, the streak-like pressure fog cannot be prevented, and further, fluctuations in photographic properties (particularly minimum density and maximum density) and desilvering failure due to continuous processing cannot be prevented, and thus the present invention Does not achieve the purpose of.

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 added directly to the color developing solution, examples of the chlorine ion supplying substance include sodium chloride, potassium chloride, ammonium chloride, lithium chloride, nickel chloride, magnesium chloride, manganese chloride, calcium chloride, and cadmium chloride. Are sodium chloride and potassium chloride. Further, it may be supplied from an optical brightener 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 and thallium bromide can be mentioned, and among them, preferred are potassium bromide and sodium bromide.

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.

The compound represented by formula [A] will be described in more detail.

R represents a hydrogen atom or a hydrolyzable protecting group. The hydrolyzable group referred to herein is a silyl group (for example, trimethylsilyl, tert-butyldimethylsilyl, phenyldimethylsilyl), a phosphoric acid ester group (for example, dimethylphosphoric acid, diethylphosphoric acid), an acyl group (for example,
Acetyl, benzoyl, trifluoroacetyl), sulfonyl groups (eg methanesulfonyl, butanesulfonyl,
Benzenesulfonyl), carbamoyl group (eg N, N-
Dimethylcarbamoyl, N, N-diethylcarbamoyl), a sulfamoyl group (eg, N, N-dimethylsulfamoyl, N, N-diethylsulfamoyl), or an oxycarbonyl group (eg, ethoxycarbonyl, phenoxycarbonyl).

R ₁ , R ₂ , R ₃ , R ₄ and R ₅ may be the same or different and represent a hydrogen atom or a substituent, and the substituent is, for example, an alkyl group (for example, methyl, tert-butyl,
tert-hexyl, cyclohexyl), alkenyl groups (eg vinyl, allyl), aryl groups (eg phenyl,
Naphthyl), amino group (eg dimethylamino, dibutylamino), acyl group (eg acetyl, benzoyl,
Tetradecanoyl), sulfonyl group (eg benzenesulfonyl, octanesulfonyl), acylamino group (eg tetradecanoylamino, benzoylamino), sulfonamide group (eg benzenesulfonamide, octanesulfonamide), carbamoyl group (eg N, N −
Dimethylcarbamoyl, N, N-diethylcarbamoyl), sulfamoyl group (eg N, N-dimethylsulfamoyl, N, N-dihexylsulfamoyl), oxycarbonyl group (eg ethoxycarbonyl, 2,4-diter)
t-butylphenoxycarbonyl), a halogen atom, a hydroxy group, a sulfo group, —O—R ₆ and —S—R ₇ . However, all of R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are not hydrogen atoms. In addition, those that are coupled with the oxidized product of the developing agent and substantially develop color are excluded. The term "substantially color-developing" as used herein means a compound having a cyan density of 0.2 or more when subjected to exposure and color development when the compound of the general formula [A] of the present invention is replaced with the coupler of Example 1 described later in an equimolar amount. To tell. R ₆
And R ₇ is an alkyl group (eg methyl, octio), an alkenyl group (eg vinyl, allyl), an aryl group (eg phenyl, naphthyl), an acyl group (eg acetyl, benzoyl), a sulfonyl group (eg methanesulfonyl, benzenesulfonyl). , Sulfamoyl groups (eg N, N-dimethylsulfamoyl, N, N-dioctylsulfamoyl) and carbamoyl groups (eg N, N-dimethylcarbamoyl, N, N-dibutylcarbamoyl). R and R ₁ or R ₁ , R ₂ , R ₃ , R ₄ and R _{5 in} the ortho positions with each other are bound to each other to form 5
A 6-membered, 6-membered or 7-membered ring, which may be a monocyclic ring, a polycyclic ring, an alicyclic ring, an aromatic ring, a heterocyclic ring, or a spiro ring, and is further substituted with a substituent. May be.

In the general formula [A], the preferred range is R ₁
An alkyl group is introduced into R ₃ , R ₄ or R ₃ ,
This is the case where a substituent is introduced into R ₅ .

More preferably, an alkyl group is introduced into R ₁ ,
In addition, the substituent introduced into R ₃ , R ₄ or R ₃ , R ₅ is an alkyl group, an alkenyl group, an aryl group, an oxycarbonyl group and —O—R ₆ .

Particularly preferably, the alkyl group introduced into R ₁ is a tertiary alkyl group, and the substituent introduced into R ₃ , R ₄ or R ₃ , R ₅ is an alkyl group, an alkenyl group or an aryl group. is the case of the oxycarbonyl group and -O-R _6.

Next, specific examples of the compound represented by the formula [A] will be shown, but the present invention is not necessarily limited to these compounds.

These compounds are disclosed in U.S. Patents 3,432,300 and 3,573,0.
No. 50, No. 3,574,627, No. 3,698,909, No. 3,700,455
Issue, Issue 3,764,337, Issue 3,935,016, Issue 3,982,944,
4,052,216, 4,138,259, 4,430,425, 4,4
52,884, British Patents 2,039,068, 2,043,931, 2,
066,975, European Patents 98,241, 246,766, 265,19
No. 6, JP-B-51-25732, 52-6623, 52-27534
No. 59-21014, No. 60-19308, and JP-A No. 52-35633.
No. 52-72225, No. 52-147434, No. 52-150630
No. 52, No. 52-154632, No. 53-32034, No. 59-108731
No. 60-211455, No. 61-90155, and methods similar thereto.

The compound represented by the general formula [A] of the present application is added in an amount of 1 to 400 mol%, preferably 10 to 200 mol%, based on the coupler. Further, one emulsion layer may contain two or more kinds of compounds represented by the general formula [A], and two or more layers may be added.

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, but in order to suppress deterioration of the developing solution, Do not use the developer for a long time, use a floating pig to suppress the influence of air oxidation, use physical means such as reducing the opening of the developing tank, suppress the temperature of the developer, or use an organic preservative. And other chemical means 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-, -SO 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 and an amine group.

(Compound example) III-1 III-2 NCH ₂ CH ₂ OH) ₃ H ₂ NCH ₂ CH ₂ OH III-10 (HOCH ₂ CH _{2 2} NCH ₂ CH ₂ SO ₂ CH ₃ III-3 N ₂ NCH ₂ CH ₂ SO ₂ NH 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 sulfates, hydrochlorides and p-toluenesulfonates. Use of the aromatic primary amine developing agent The amount is preferably about 01 g to 20 g, and more preferably about 0.5 to 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 developing solution may contain other known developer component compounds.

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 as a precipitation inhibitor of calcium or magnesium in the color developing solution 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, nitrilotripropionic acid, 1,2-
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 Sho 4
1-11431, U.S. Pat. Nos. 2,482,546, 2,596,926 and 3,582,346, etc., amine compounds described in JP-B-3.
Nos. 7-16088, 42-25201, U.S. Pat.No. 3,128,183,
JP-B-41-11431, JP-B-42-23883 and U.S. Pat.
Polyalkylene oxides represented by 532, 501, etc.,
In addition, 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, an optional 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 the organic antifoggant include benzotriazole and 6-
Nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-
Representative examples thereof include nitrogen-containing heterocyclic compounds such as thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine and adenine.

The color developing solution used in the present invention preferably contains a fluorescent whitening agent. 4,4'-
Diamino-2,2'-disulfone tilbene 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 amount of replenishment depends on the light-sensitive material to be processed, but it is generally about 180 to 1000 ml per square meter of light-sensitive 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 with an automatic developer, etc. Inevitably, a large amount of overflow liquid is generated, and it is preferable that the replenishment amount is small in terms of economy and pollution. This preferable amount of replenishment is per 1 m ² of light-sensitive material
20-150 ml. Depending on the photosensitive material,
The replenishment amount of 20 ml per 1 m ^{2 of the} light-sensitive material is an amount at which the amount of the processing solution carried out by the light-sensitive material and the replenishment amount are substantially equal to each other and the overflow is substantially eliminated. 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
-10 are preferable, and 5-9 are especially preferable. When the pH 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 or surfactants, polyvinylpyrrolidone, organic solvents such as methanol and the like.

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, etc. may be added.

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

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 characteristics of the light-sensitive material (for example, depending on the material used such as the coupler), 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. Among these, the relationship between the number of washing tanks and the water volume in the multi-stage countercurrent system is described in the 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 directly processed with a stabilizing solution instead of the above 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 has a silver chloride content of 80 mol% or more, preferably 95 mol% or more, more preferably 98 mol% or more, based on the total amount of silver halide. 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. This increases light absorption in terms of photosensitivity,
In many cases, many useful points can be seen, such as 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 phase different from the inside and the surface layer, may have a multiphase structure having a bonding structure, or may have a uniform whole grain. It may consist of phases. 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 micron or less, or large grains having a projected area diameter of about 10 microns, and may be a polydisperse emulsion or a monodisperse emulsion.

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) ”and the like.

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 bonded by epitaxial bonding, or may be bonded to a compound other than silver halide such as, for example, silver rhodan or lead oxide.

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

As the silver halide emulsion, one which has been physically ripened, chemically thermally sensitized and spectrally sensitized is usually used. 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 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 VII of Research Disclosure No. 17643.
-G item, U.S. Pat. No. 4,163,670, Japanese Patent Publication No. 57-39443,
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 can also be 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 thereof include DIR redox compound releasing couplers described in JP-A-185950 and the like, and couplers which release a dye that recovers 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 and effects of the latex dispersion method, 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.

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, and the resulting dispersion is 420 g of silver chlorobromide emulsion (0.7 mol% silver bromide) containing the following blue completed 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 substances were used as irradiation prevention dyes.

[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-dioxo-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) -4-ylidene) -1
-Pentanyl) -1-pyrazolyl] benzene-4-sulfonato-sodium salt (Layer structure) 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 with polyethylene on both sides First layer (blue sensitive layer) Silver chlorobromide emulsion (AgBr: 0.7 mol%, cubic, average grain size 0.9 µ) 0.27 Gelatin 1.80 Yellow coupler (ExY) 0.60 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) The above-mentioned silver chlorobromide emulsion (AgBr: 0.7 mol%, cubic, average grain size 0.45μ) 0.28 Gelatin 1.40 Magenta coupler (ExM) 0.37 Anti-fading agent (Cpd-3) 0.23 Solvent (Solv-1) 0.20 Solvent (Solv-2) 0.02 Fourth layer (color mixing prevention layer) Gelatin 1.70 Color mixing inhibitor (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 sensitive layer) Silver chlorobromide emulsion (AgBr: 2) Mol%, cubic, average particle size 0.5 μ) 0.19 gelatin 1.80 cyan coupler (ExC-1) 0.26 cyan coupler (ExC-2) 0.12 Cpd-5 0.12 solvent (Solv-1) 0.16 solvent (Solv-2) 0.09 sixth Layer (UV absorbing layer) Gelatin 0.70 UV absorbing agent (UV-1) 0.26 UV absorbing agent (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) butylami] acetanilide (ExM) Magenta coupler 1- (2,4,6- Trichlorophenyl) -3 [2-chloro-5 (3-octadecenylsuccinimide) 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-
tert-amylphenoxy) butylamide] phenol (Cpd-3) anti-fading agent 1.4-di-tert-amyl-2,5-dioctyloxybezene (Cpd-5) p- (p-dodecylphenylsulfonamide) toluene (Solv -3) Solvent Di- (i-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 produced as described above was designated as Sample 101.

Similar to Sample 101 except that the halogen compositions of the silver halide emulsions of the first layer, the third layer, and the fifth layer were added as shown in Table 1 and the compound [A] was added as shown in Table 1. Samples 102 to 127 were prepared by the method described above.

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

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.

Furthermore, 2,5-di-t-butylhydroquinone (A-54) 2 dissolved and dispersed in dibutyl phthalate (DBP)
00 mg / m ² and a yellow coupler having the following structure were contained in an amount of 2 × 10 ^-1 mol per mol of silver halide, and the coating amount 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.

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

As an antioxidant, a compound having the following structure was contained in an amount of 0.3 mol 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 is a red-infected 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 A gelatin layer was coated such that the amount of gelatin was 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 128.

The following experiments were conducted to examine the photographic characteristics of these samples 101-128.

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

The exposed sample was processed using an automatic processor with the following processing steps and processing solution compositions. However, processing was carried out by changing the silver halide concentrations of chlorine and bromine as shown in Table 2 in the composition of the color developing solution.

Treatment process Temperature Time Color development 38 ℃ 45 seconds Bleach fixing 30-36 ℃ 45 seconds Rinse 30-37 ℃ 30 seconds Rinse 30-37 ℃ 30 seconds Rinse 30-37 ℃ 30 seconds Dry 70-80 ℃ 60 seconds Each processing solution The composition of is as follows.

Color developer Water 800ml Ethylenediamine-N, N, N-tetramethylenephosphonic acid 3.0g Organic preservative (I-1) 0.03mol Sodium chloride See Table 1 Potassium bromide See Table 1 Potassium carbonate 25g N-Ethyl- N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 5.0g Triethanolamine 10.0g Optical 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 5 g Ammonium bromide 40 g Glacial acetic acid 9 g Water was added to 1000 ml pH (25 ° C) 5.40 Rinse solution Ion-exchanged water (calcium and magnesium 3 ppm or less each) were treated, and the resulting yellow and color image densities were measured.
The maximum concentration (Dmax) was obtained. The results are shown in Table 1.

Further, the above samples 101 to 128 were separately subjected to the uniform exposure of gray using the above sensitometer, and the same treatment as the above-mentioned sensitometry was performed to evaluate the pressure sensitizer.

The pressure-sensitized muscles were evaluated by visually observing the area of 10 cm x 10 cm at any three points in the processed sample (10
The presence or absence of the pressure sensitizer was examined by observing with a double magnifying glass). The evaluation of the color restoration defect was performed as follows.

First, the above sensitometer was used to subject the above sample to wedge exposure with white light to adjust the pH of the bleach-fix solution to 5.0 (25
The same process as the previous treatment step was performed except that the temperature was changed to 0 ° C). After these treatments, it was dried and the concentration was measured immediately. (The maximum density of the cyan image at this time is Dmax
(R) ′) Next, these samples were immersed in a 20% EDTA.Fe (III) .NH ₄ solution (pH = 7.00) at 40 ° C. for 5 minutes and then 40 ° C.
The sample was washed with running water for 2 minutes, dried and the concentration was measured. (The maximum density of the cyan image at this time is defined as Dmax (R).) The difference in the maximum density of the cyan image before and after the immersion in the 20% EDTA / Fe (III) / NH ₄ solution, that is, ΔD = Dmax ( R) ′-Dmax (R) was used to evaluate the color restoration failure.

 The results are summarized in Table 1.

As is clear from Table 1, when Cl ⁻ and Br ⁻ in the developing solution are small, pressure-sensitized streaks are generated, and conversely, when they are large, the maximum density is decreased.

Further, it is understood that the addition of the compound [A] can improve the color restoration failure without affecting the pressure-sensitized streak and the maximum density. In particular, at the Cl ⁻ and Br ⁻ concentrations of the present invention, the compound [A] has a great effect of preventing the color restoration defect.

Example 2 After the image 127 of the sample prepared in Example 1 was imagewise exposed, a continuous processing (running test) was performed using a paper processor in the following processing steps until the tank capacity of the color developer was doubled. went.

After the above running test was completed, the concentration of Cl ⁻ and Br ^{− in} the color developing solution in the processing step was measured, and among the samples prepared in Example 1, the samples shown in Table 2 were used for the development processing in the processing step. Other than that, the same test as in Example 1 was performed.

As a result, the Cl concentration in the color developer was 7.61 × 10 ^-2 mol /
l, Br ^- concentration was 1.9 × 10 ^-4 mol / l.

The results of maximum density (D _B ), pressure sensitizer and defective color restoration are shown in Table 2.
Are shown together.

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-isothiazoline-3-
On 0.02g 2-Methyl-4-isothiazolin-3-one 0.01g Copper sulfate 0.005g Ammonia water (28%) 2.0ml Add water to 1000ml pH (25 ℃) 4.0 Example 3 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 Yellow coupler (ExY) 19.1g and color image stabilizer (Cp
d-7) 0.7 g of ethyl acetate 27.2 cc and solvent (Solv-
3) Add 8.2 g of the solution and dissolve, and add this solution to 10% sodium dodecylbenzenesulfonate 8cc 10% gelatin aqueous solution 1
It was emulsified and dispersed in 85 cc. 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. The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. The gelatin hardening agent for each layer is 1-oxy-3,5-dichloro-
The s-triazine sodium salt was used.

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

Blue-sensitive emulsion layer (2.0 × 10 ^-4 moles per mole of silver halide) Green-sensitive emulsion layer (4.0 × 10 ^-4 mol each per mol of silver halide) and (7.0 × 10 ^-5 moles per mole of silver halide) Red-sensitive emulsion layer (0.9 × 10 ⁻⁴ mol per mol of silver halide) To the red-sensitive emulsion layer, 2.6 × 10 ⁻³ mol of the following compound was added 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 Solvent (Solv-3) 0.35 Dye stabilizer (Cpd-7) 0.06 Second layer (Color mixing inhibitor) 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 (1: 3 mixture (Ag mol) ratio of cubic average grain size 0.55μ and 0.39μ). Coefficients of variation of particle size distribution 0.10, 0.08, and AgBr 0.8 mol% were contained locally 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 particle size 0.58) A 1: 4 mixture of μ, 0.23 and 0.45μ (Ag mole ratio) Coefficients of variation of particle size distribution 0.09, 0.11 and AgBr 0.6mol% were 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-7) 0.40 Solvent (Solv-6) 0.15 Sixth layer (UV absorbing layer) Gelatin 0.53 UV absorber ( UV-1) 0.16 Anti-color mixing agent (Cpd-5) 0.02 Solvent (Solv-5) 0.08 Seventh layer (protective layer) Gelatin 1.33 Polyvinyl acetate Acrylic modified copolymer of the call (modification degree 17%) 0.17 Liquid paraffin 0.03 2: 4: 4 mixture by weight of each 2: 4: mixture (weight ratio) 4: 2: 4 mixture (weight ratio) The sample thus obtained was designated as 301.

Then, in the same manner as in Sample 301, the coating silver amount of each emulsion layer was changed as shown in Table 3, and the compound [A] was added as shown in Table 3 to give Samples 302 to 312. It was made.

After image-wise exposing the sample 302, a paper processor was used to perform the following processing steps to reduce the tank capacity of the color developer to 2
Continuous processing (running test) was performed until double replenishment.

After completion of the above running test, samples 301 to 312 were evaluated for pressure sensitizer, residual silver amount, color restoration failure, and the concentration of Cl ⁻ and Br ⁻ in the color developer at the end of running was measured.

The evaluation of the pressure-sensitized streak and the color restoration defect was performed in the same manner as in Example 1, except that the treatment steps were performed using those of this example. The residual silver amount was evaluated by uniformly exposing the coated silver amount of each sample so that 90% of the developed silver was obtained, and then developed by the above-mentioned treatment. It was measured. The results are summarized in Table 3.

The composition of each treatment liquid is as follows.

Rinse liquid Ion exchange water (3 ppm or less for calcium and magnesium each) As is clear from the results of Examples 1 to 3 above, the halogen composition of the emulsion of the light-sensitive material and the coating silver amount are within the scope of the present invention, and the compound represented by the general formula [A] is contained. and Cl in the color developing solution ^- ions, Br ^- only when the ion concentration is within the scope of the present invention show a sufficient color image density in a short time of development, without causing pressure sensitization streaks Also, it can be seen that desilvering can be carried out in a short time, and color restoration failure hardly occurs.

Continuation of the front page (56) Reference JP-A-63-36245 (JP, A) JP-A-63-63044 (JP, A) JP-A-60-60647 (JP, A) JP-A-54-145530 (JP , A)

Claims (1)

[Claims] 1. A method for treating a silver halide color photographic light-sensitive material with a color developer containing at least one aromatic primary primary amine color developing agent, wherein the silver halide color photographic light-sensitive material is red. A high chlorinated emulsion having a sensitive emulsion layer, a green sensitive emulsion layer and a blue sensitive emulsion layer, and the emulsions of these layers are all high chloride chloride emulsions containing 80 mol% or more of silver chloride, at least one of which is It contains at least one compound represented by the general formula (A) and has a total coating silver amount of 0.3 to 0.75 g / m ² , and the color developer has chlorine ions of 3.5 × 10 ^-2 to A method for processing a silver halide color photographic light-sensitive material, which comprises 1.5 × 10 ^-1 mol / 1 and bromine ions in an amount of 3.0 × 10 ^{-5 to} 1.0 × 10 ^-3 mol / l. General formula [A] In the formula, R represents a hydrogen atom or a hydrolyzable protecting group. R ₁ , R ₂ , R ₃ , R ₄ and R ₅ may be the same or different and each represents a hydrogen atom or a substituent excluding a substituted and unsubstituted benzotriazole group. However, all of R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are not hydrogen atoms. In addition, those that are coupled with the oxidized product of the developing agent and substantially develop color are excluded. R and R ₁ or R ₁ , R ₂ ,
Of R ₃ , R ₄ and R ₅ , those in the ortho positions may combine with each other to form a 5-, 6- or 7-membered ring.