JP2671042B2 - Processing method of silver halide color photographic light-sensitive material - Google Patents

Description

The present invention relates to a method for processing a silver halide color photographic light-sensitive material, and more specifically, to a developing method using a high silver chloride silver halide photographic light-sensitive material. It relates to an excellent development processing method.

(Prior Art) In recent years, in photographic processing of a color photographic light-sensitive material, it has been desired that the processing time be shortened in accordance with the shortening of the final delivery time and the reduction of lab work. As a method for shortening the time of each treatment step, a general method is to raise the temperature or increase the replenishing amount. However, many other methods have been proposed for enhancing the stirring or adding various accelerators.

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 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, it was found that streak-like fog was generated when the development processing was carried out using an automatic processor based on the above method. It is presumed that this is a so-called liquid pressure sensitizer that causes streaky fogging due to scratches and pressure sensitization when the photosensitive material comes into contact with rollers in the developing tank of an automatic processor. It

Further, it has been found that there is a problem that the photographic characteristics fluctuate during continuous processing (particularly the gradation and maximum density of the cyan coloring layer).

As described above, rapid processing using a high silver chloride color photographic light-sensitive material has serious problems of pressure-sensitized fog in the liquid and fluctuation of photographic characteristics, and it has been strongly desired to solve these problems.

Further, 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) due to continuous processing is disclosed in JP-A-58-9534.
5. It is known to use organic antifoggants in JP-A-59-232342. However, its fog-preventing ability does not prevent the occurrence of pressure-sensitizing muscles in the liquid, and when used in a large amount, a decrease in the maximum density and development delay are found, and the above-mentioned problems cannot be solved. There wasn't.

Further, in JP-A-61-70552, a high silver chloride color photographic light-sensitive material is used, and a replenishment amount of an amount that does not cause overflow to the developing bath is added during development to reduce the replenishment of the developing solution. A method is described in JP-A-63-106655, and for the purpose of stabilizing the processing, a silver halide color photographic light-sensitive material having a high silver chloride content in a silver halide emulsion layer is referred to as a hydroxylamine compound. A method of developing with a color developing solution containing chloride at a predetermined concentration or higher is disclosed.

However, in these methods, the pressure sensitizing line generated in the development processing using the above-mentioned automatic developing machine and the fluctuation of the photographic characteristics during the continuous processing (particularly the gradation change and the maximum density change of the cyan color developing layer) are recognized. However, the above problems could not be solved.

(Problems to be Solved by the Invention) Therefore, a first object of the present invention is to provide a rapid development processing method using a high silver chloride light-sensitive material, in which generation of streaky fog is prevented.

A second object of the present invention is to provide excellent photographic characteristics with a high maximum density and a low minimum density in a rapid development process using a high silver chloride color photographic light-sensitive material. It is an object of the present invention to provide a development processing method in which fluctuations (especially gradation and maximum density change of a cyan coloring layer) are significantly suppressed.

(Means for Solving the Problem) An object of the present invention is to develop an exposed silver halide color photographic light-sensitive material using an automatic developing machine to develop a color containing at least one aromatic primary amine color developing agent. The method of liquid treatment comprises a red-sensitive emulsion layer, a green-sensitive emulsion layer and a blue-sensitive emulsion layer containing a high silver chloride silver halide emulsion consisting of 98 mol% or more of silver chloride, and the total coating A silver halide color light-sensitive material having a silver amount of 0.65 g / m ² or less is used, and chloride ion and bromide ion are respectively added to 3.5
Treatment with a color developer containing x10 ^{-2 to} 1.5 x 10 ^-1 mol /, 1.0 x 10 ^{-4 to} 3.0 x 10 ^-4 mol / mol, and a compound represented by the general formula (I). It was achieved by the processing method of the characteristic silver halide color photographic light-sensitive material.

General formula (I) In the formula, R ¹ and R ² 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 ₁ and R ₂ are not hydrogen atoms at the same time, and may be linked to each other to form a heterocycle together with the nitrogen atom. The ring structure of the hetero ring is a 5- to 6-membered ring,
It is composed of a hydrogen atom, a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom and the like, and may be saturated or unsaturated.

Chloride ion is well known as one of antifoggants, but its effect is small, and even if it is used in a large amount, it is necessary to completely prevent streaky fog that occurs when processed by an automatic processor. On the contrary, the development was delayed, and the maximum density was lowered, which had an adverse effect.

Bromide ion is also known as one of the antifoggants, but depending on the addition amount, it is possible to prevent the generation of streak pressure fog, but it suppresses development and lowers the maximum density and sensitivity, making it practically useable. I didn't get it.

The compound represented by the general formula (I) is described in International Publication WO87-04.
534, a preservative of a developing agent described in JP-A-63-106655, etc., having excellent preservability, when the high silver chloride photographic material is processed, the maximum density is high, It is known that color alienation is small. However, the poor stability of the compound itself and the low development activity, which has a developing activity, are one of the major causes of fluctuations in photographic characteristics during continuous processing (especially gradation and maximum density change in the cyan color developing layer). It turned out to be one.

As a result of various studies, the present inventors have confirmed that a high silver chloride color light-sensitive material containing a high silver chloride emulsion having a silver chloride content of 98 mol% or more has a chloride ion concentration and a bromide ion concentration of 3.5, respectively. × 10 ^{-2 to} 1.5 × 10 ^-1 mol /, 1.0 × 10 ^-4 to
It has been found that by processing with a color developing solution of 3.0 × 10 ⁻⁴ mol / m, rapid processing in which the pressure fog is prevented is possible. Further, they have found that the combined use with the compound of the general formula (I) further enhances the effect of preventing pressure fog.

It has also been found that the variation in photographic properties associated with the continuous processing attributed to the compounds of general formula (I) is significantly reduced by the combined use of chloride and bromide ions of the present invention.

As described above, the effect of the combination of a relatively large amount of chloride ion, an extremely small amount of bromide ion, and the compound of the general formula (I) has not been known until now, and the details of the effect are unknown. , Will be clarified by future research.

JP-A-63-106655 discloses a method of processing a silver chloride light-sensitive material of 70 mol% or more with a developer containing 2 × 10 ^-2 mol or more of chloride and a compound represented by the general formula (I). Is listed. However, the concentration of bromide ion in the developing solution is a treatment outside the present invention, further, the specific effect of the combination of bromide ion and chloride ion of the present invention in an appropriate amount is not described at all, and the present invention is The problem to be solved is not described and the present invention is not analogized.

 The present invention will be described in detail below.

The silver halide emulsion of the present invention consists essentially of silver chloride. From the viewpoint of rapidity, the higher the silver chloride content, the better.

The coated silver amount of the silver halide light-sensitive material of the present invention is 0.65 g / m ²
The following is required for promptness, desilvering and prevention of pressure sensitizing muscles. This may be due to the effect of reducing the film thickness in addition to simply reducing the amount of silver. From the viewpoint of image density, etc.
0.3 g / m ² or more is preferable.

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 / mol. It is preferably 5 × 10 ^-2 to 1 × 10 ^-1 mol / mol. If the chlorine ion concentration is more than 1.5 × 10 ^-1 mol / mol, it has the drawback of delaying the development and does not achieve the object of the present invention of rapid and high maximum concentration. Also, 3.5 × 1
0 ^-2 mol / below, can not be prevented streaky pressure fogging, further, preventing the accompanying photographic properties vary in continuous processing (especially the maximum density and gradation change of the cyan coloring layer) Therefore, the object of the present invention is not achieved.

In the present invention, the bromine ion in the color developer is 1.0
It is necessary to contain x10 ^-4 mol / to 3.0 x 10 ^-4 mol /. When the bromine ion concentration is more than 3 × 10 ^-4 mol / development, the development is delayed, the maximum density and the sensitivity are lowered, and 1.0
When the amount is less than × 10 ^-4 mol / mol, streaky pressure fog cannot be prevented, and further, fluctuations in photographic properties (especially maximum density and gradation change of cyan color forming layer) due to continuous processing are prevented. It is not possible to 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 added directly to the color developer, examples of the chlorine ion supplying substance include sodium chloride, potassium chloride, ammonium chloride, nickel chloride, magnesium chloride, chloride magazine, calcium chloride and cadmium chloride. Among them, preferred is sodium chloride. , Potassium chloride.

Further, it may be supplied in the form of a counterpart salt of the optical brightener added to the developer.

Sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide, magnesium bromide, manganese bromide, nickel bromide, cadmium bromide, cerium bromide, thallium bromide 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 (I) will be described in detail.

General formula (I) In the formula, R ¹ and R ² 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 ₁ and R ₂ are not hydrogen atoms at the same time, and may be linked to each other to form a heterocycle together with the nitrogen atom. The ring structure of the hetero ring is a 5- to 6-membered ring,
It is composed of a hydrogen atom, a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom and the like, and may be saturated or unsaturated.

R ¹ and R ² 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 hetero ring formed by linking R ₁ and R ₂ include a piperidyl group, a pyrrolidyl group, an N-alkylpiperazyl group, a morpholyl group, an indolinyl group, and a benzotriazole group.

Among the compounds represented by the general formula (I), the compounds represented by the following general formula (Ia) are particularly preferable from the viewpoints of preventing photographic fluctuation and preventing the above-mentioned streaking.

General formula (Ia) In the formula, L represents an alkylene group which may be substituted;
Is a carboxy group, a sulfo group, a phosphono group, a phosphinic acid residue, a hydroxy group, an amino group which may be alkyl-substituted, an ammonium group which may be alkyl-substituted, a carbamoyl group which may be alkyl-substituted, or an alkyl-substituted group. R represents a hydrogen atom or an optionally substituted alkyl group;

 The general formula (Ia) will be described in detail below.

In the formula, L represents a linear or branched alkylene group having 1 to 10 carbon atoms which may be substituted, and preferably has 1 to 5 carbon atoms. Specifically, methylene, ethylene, trimethylene,
Propylene is a preferred example. Examples of the substituent include a carboxy group, a sulfo group, a phosphono group, a phosphinic acid residue, a hydroxy group, and an ammonium group which may be alkyl-substituted, and preferred examples thereof include a carboxy group, a sulfo group, a phosphono group, and a hydroxy group. . A is a carboxy group, a sulfo group, a phosphono group, a phosphinic acid residue, a hydroxy group, an amino group which may be alkyl-substituted,
Ammonio group which may be substituted with alkyl (preferably 1 to 5 carbon atoms), carbamoyl group which may be substituted with alkyl (preferably 1 to 5 carbon atoms), and alkyl (preferably 1 to 5 carbon atoms) Represents a good sulfamoyl group,
Carboxy group, sulfo group, hydroxy group, phosphono group,
A preferred example is a carbamoyl group which may be alkyl-substituted. Preferred examples of -LA include a carboxymethyl group, a carboxyethyl group, a carboxypropyl group, a sulfoethyl group, a sulfopropyl group, a sulfobutyl group, a phosphonomethyl group, a phosphonoethyl group, and a hydroxyethyl group. Groups, carboxyethyl groups, sulfoethyl groups, sulfopropyl groups, phosphonomethyl groups, and phosphonoethyl groups can be mentioned as particularly preferred examples. R represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms which may be substituted, and preferably has 1 to 5 carbon atoms. Examples of the substituent include a carboxy group, a sulfo group, a phosphono group, a phosphinic acid residue, a hydroxy group, an amino group which may be alkyl-substituted, an ammonium group which may be alkyl-substituted, a carbamoyl group which may be alkyl-substituted, and an alkyl group. Represents a sulfamoyl group which may be substituted. There may be two or more substituents. R represents a hydrogen atom, a carboxymethyl group,
Carboxyethyl group, carboxypropyl group, sulfoethyl group, sulfopropyl group, sulfobutyl group, phosphonomethyl group, phosphonoethyl group, hydroxyethyl group can be mentioned as preferred examples, hydrogen atom, carboxymethyl group, carboxyethyl group, sulfoethyl group, Particularly preferred examples include a sulfopropyl group, a phosphonomethyl group, and a phosphonoethyl group. L and R may combine to form a ring.

Specific examples of the compound of the general formula (I) in the present invention are shown below, but the present invention is not limited thereto.

The amount of the following compounds added to the color developer is 0.005
Mol / ~ 0.5 mol /, preferably 0.03 mol / ~
It is desirable to add so as to have a concentration of 0.1 mol /.

Compound example I-29 HO-NH-CH 2 CO 2 H I-30 HO-NH-CH 2 CH 2 CO 2 H I-36 HO-NH-CH ₂ CH ₂ SO ₃ H I-38 HO-NH- (CH 2) 3 SO 3 H I-39 HO-NH- (CH 2) 4 SO 3 H I-40 HO-NH-CH 2 PO 3 H 2 I-42 HO-NH-CH ₂ CH ₂ PO ₃ H ₂ I-43 HO-NH-CH ₂ CH ₂ OH I-44 HO-NH- (CH ₂ ) ₃ OH I-45 HO-NH-CH _2- PO ₂ H ₂ I-56 HONHCH ₂ CH (PO ₃ H ₂ ) ₂ The compound represented by the general formula (I) can be synthesized by subjecting commercially available hydroxylamines to an alkylation reaction (nucleophilic substitution reaction, addition reaction, Mannich reaction). West German Patent No. 1159634, "Inorganica Chimica A
cta), 93, (1984) 101-108, etc., but the specific method is described below.

Synthesis Example Synthesis of Exemplified Compound (7) In a 200 ml aqueous solution of hydroxylamine hydrochloride (20 g), sodium hydroxide (11.5 g) and sodium chloroethanesulfonate (9) were added.
Add 6g, keep at 60 ℃ 40m of aqueous solution of 23g of sodium hydroxide
l was added slowly over 1 hour. 3 hours at 60 ° C
, The reaction mixture is concentrated under reduced pressure,
Heated to ° C. Filter the insolubles and add 500 ml of methanol to the filtrate.
Was added to give the desired product (exemplified compound (7)) as monosodium salt crystals. 41 g (yield 53%) Synthesis of Exemplified Compound (21) Formalin 32.6 g was added to a hydrochloric acid aqueous solution of hydroxylamine hydrochloride 7.2 g and phosphorous acid 18.0 g, and the mixture was heated under reflux for 2 hours. The resulting crystals were recrystallized from water and methanol to obtain 9.2 g (42%) of Exemplified Compound (11).

In the present invention, it is preferable that the color developer contains substantially no sulfite ion from the viewpoints of processing stability during continuous processing and preventing streaky pressure fog.

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

D-1 N, N-diethyl-p-phenylenediamine D-2 2-amine-5-diethylaminotoluene D-3 2-amino-5- (N-ethyl-N-laurylamino) toluene D-4 4- [ N-ethyl-N- (β-hydroxyethyl) amino] aniline D-5 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline D-6 4-amino-3-methyl -N-ethyl-N-
[Β- (methanesulfonamido) ethyl] -aniline D-7 N- (2-amino-5-diethylaminophenylethyl) methanesulfonamide D-8 N, N-dimethyl-p-phenylenediamine D-9 4-amino -3-Methyl-N-ethyl-N-methoxyethylaniline D-10 4-Amino-3-methyl-N-ethyl-N-β
-Ethoxyethylaniline D-11 4-amino-3-methyl-N-ethyl-N-β
-Ethoxyethylaniline Among the above p-phenylenediamine derivatives, 4-amino-3-methyl-N-ethyl-N- [β- is particularly preferable.
(Methanesulfonamido) ethyl] -aniline (Exemplified Compound D-6) and 2-methyl-4- [N-ethyl-N
-(Β-hydroxyethyl) amino] aniline (Exemplary compound D-5).

Further, these p-phenylenediamine derivatives may be salts such as sulfate, hydrochloride, sulfite, and p-toluenesulfonate. The amount of the aromatic primary amine developing agent used is preferably about 0.1 to about 20 g, more preferably about 0.5 g to about 15 g per developer.

In the color developer according to the present invention, the compound represented by the following formula [A] is more preferably used from the viewpoint of improving the effect of the present invention.

General formula [A] (Wherein, R ₁₁ is a hydroxyalkyl group having 2 to 6 carbon atoms;
₁₂ and R ₂₃ are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group having 2 to 6 carbon atoms, a benzyl group or a formula n is an integer of 1 to 6, X and X'represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group having 2 to 6 carbon atoms. Preferred specific examples of the compound represented by the general formula [A] are as follows.

(A-1) ethanolamine, (A-2) diethanolamine, (A-3) triethanolamine, (A-4) di-isopropanolamine, (A-5) 2-methylaminoethanol, (A-6). 2-ethylaminoethanol, (A-7) 2-dimethylaminoethanol, (A-8) 2-diethylaminoethanol, (A-9) 1-diethylamino-2-propanol, (A-10) 3-diethylamino-1. -Propanol, (A-11) 3-dimethylamino-1-propanol, (A-12) isopropylaminoethanol, (A-13) 3-amino-1-propanol, (A-14) 2-amino-2- Methyl-1,3-propanediol, (A-15) ethylenediaminetetraisopropanol, (A-16) benzyldiethanolamine, (A-17 2-amino-2- (hydroxymethyl) -1,
3-propanediol.

(A-18) 1,3-diaminopropanol (A-19) 1,3-bis (2-hydroxyethylmethylamino) -propanol These compounds represented by the above general formula [A] are the objects of the present invention. From the viewpoint of effect, it is preferably used in the range of 3 g to 100 g, and more preferably 6 g to 50 g, per color developing solution.

In the color developer according to the present invention, the effects of the present invention are better exhibited, and therefore, the following general formulas [BI] and [B] are used.
-II] is more preferably used.

Wherein R ₁₄ , R ₁₅ , R ₁₆ and R ₁₇ are each a hydrogen atom,
Halogen atom, a sulfonic acid group, an alkyl group having a carbon number of 1 to 7, -OR _18, -COOR _19, Represents a phenyl group. R ₁₈ , R ₁₉ , R ₂₀ and R ₂₁ each represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. However, when R ₁₅ represents —OH or a hydrogen atom, R ₁₄
Is a halogen atom, a sulfonic acid group, an alkyl group having 1 to 7 carbon atoms, -OR ₁₈ , -COOR ₁₉ , Represents a phenyl group.

The alkyl group represented by R ₁₄ , R ₁₅ , R ₁₆ and R ₁₇ includes those having a substituent, for example, a methyl group, an ethyl group, is
o-propyl group, n-propyl group, t-butyl group, n-
Butyl group, hydroxymethyl group, hydroxyethyl group,
Methyl carboxylic acid group, benzyl group, etc.
_18, the alkyl group R _19, R ₂₀ and R ₂₁ represent the same meaning as defined above, can be further octyl group and the like exemplified.

Examples of the phenyl group represented by R ₁₄ , R ₁₅ , R ₁₆ and R ₁₇ include a phenyl group, a 2-hydroxyphenyl group and a 4-aminophenyl group.

Typical examples of the chelating agent of the present invention are shown below, but the chelating agent is not limited to these.

(BI-1) 4-isopropyl-1,2-dihydroxybenzene (BI-2) 1,2-dihydroxybenzene-3,5-disulfonic acid (BI-3) 1,2,3- Trihydroxybenzene-5-carboxylic acid (BI-4) 1,2,3-trihydroxybenzene-5-carboxymethyl ester (BI-5) 1,2,3-trihydroxybenzene-5-carboxy -N
-Butyl ester (BI-6) 5-t-butyl-1,2,3 trihydroxybenzene (BI-7) 1,2-dihydroxybenzene-3,4,6-trisulfonic acid (B- II-1) 2,3-dihydroxynaphthalene-6-sulfonic acid (B-II-2) 2,3,8-trihydroxynaphthalene-6-sulfonic acid (B-II-3) 2,3-dihydroxynaphthalene- 6-carboxylic acid (B-II-4) 2,3-dihydroxy-8-isopropyl-naphthalene (B-II-5) 2,3-dihydroxy-8-chloro-naphthalene-6-sulfonic acid As the compound particularly preferably used in the invention, 1,2-dihydroxybenzene-3,5-
Examples thereof include disulfonic acid, which can be used as an alkali metal salt such as a sodium salt and a potassium salt. ((B-I-2) of Specific Exemplified Compound) In the present invention, the above-mentioned general formulas [BI] and [BI]
The compound represented by the formula I] is 5 mg to 15 g per 1 color developer.
Can be used in the range, preferably 15mg ~ 10g,
More preferably, it is desirable to use in the range of 25 mg to 7 g.

The color developer used in the present invention is preferably pH 9
To 12, more preferably 9 to 11.0, and the color developer may further contain a compound of a known developer component.

In order to maintain the above pH, it is preferable to use various buffers. Buffers include 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 developer was 0.1 mol / mol.
It is preferably at least 0.1 mol / -0.4 mol / m.

In addition, various chelating agents can be used in the color developer as a precipitation inhibitor for calcium or magnesium, or for improving the stability of the color developer.

Specific examples are shown below, but the present invention is not limited thereto. Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, triethylenetetraminehexaacetic acid, nitriloN, N, N-tris (methylenephosphonic acid),
Ethylenediamine-N, N, N ', N'-tetrakis (methylenephosphonic acid), 1,3-diamino-2-propanoltetraacetic acid, transcyclohexanediaminetetraacetic acid, nitrilotriapropionic acid, 1,2-diaminopropanetetraacetic acid , Hydroxyethyliminodiacetic acid, glycol ether diamine tetraacetic acid, hydroxyethylenediamine triacetic acid, ethylenediamine orthohydroxyphenylacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic 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-sulfo Salicylic acid.

Among these chelating agents, ethylenediaminetetraacetic acid, ethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, 1,3-diaminopropanoltetraacetic acid, ethylenediamine-N, N, N ', N'-tetrakis (methylenephosphonic acid) are preferable. ) And hydroxyethyliminodiacetic acid are good.

These chelating agents may be used in combination of two or more as necessary.

These chelating agents may be added in an amount sufficient to block metal ions in the color developer. Eg 1
It is about 0.1g to 10g per unit.

An optional development accelerator can be added to the color developer as needed.

As development accelerators, JP-B-37-16088 and JP-B-37-598
No. 7, No. 38-7826, No. 44-12380, No. 45-9919, and thioether compounds represented in U.S. Pat.No. 3,813,247, and p-type compounds described in JP-A Nos. 52-49829 and 50-15554. Phenylenediamine compounds, JP-A-50-13
Nos. 7726, JP-B-44-30074, quaternary ammonium salts described in JP-A-56-156826 and JP-A-52-43429, p-aminophenols described in U.S. Pat.Nos. 2,610,122 and 4,119,462, U.S. Pat. Patent No. 2,494,903, same
3,128,182, 4,230,796, 3,253,919, Shoko 4
1-111431, U.S. Pat.Nos. 2,482,546, 2,596,926 and 3,582,346, etc.
Nos. 7-16088, 42-25201, U.S. Pat.No. 3,128,183,
JP-B-41-11431, JP-B-42-23883 and U.S. Pat.
532,501 polyalkylene oxide represented, etc.
In addition, 1-phenyl-3-pyrazolidones, hydrazines, mesoionic compounds, ionic compounds, imidazoles, and the like can be added as necessary.

Preferably, the color developer is substantially free of benzyl alcohol. Substantially means per color developer
2.0 ml or less, more preferably not containing at all.
When it is not substantially contained, the increase in stain is small when the photographic characteristics change during continuous processing, and more preferable results are obtained.

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

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

If necessary, various surfactants such as alkylsulfonic acid, arylphosphonic acid, aliphatic carboxylic acid, and aromatic carboxylic acid may be added.

The effect of the present invention is remarkable when the processing time of the color developing solution of the present invention is 10 seconds to 120 seconds, preferably 20 seconds to 60 seconds. The effect of the present invention is particularly remarkable at a treatment temperature of 33 to 45 ° C, preferably 36 to 40 ° C.

The replenishment amount of the color developing solution during continuous processing is 20 to 220 ml, preferably 25 to 160 ml, and particularly preferably 25 to 160 ml per 1 m ² of the light-sensitive material.
30 ml to 110 ml is preferable in that the effects of the present invention can be effectively exhibited.

Further, the color developing solution of the present invention has a liquid opening ratio (air contact area (m ² ) / liquid volume (cm ³ )) which is relatively superior to the combinations other than the present invention under any condition. ,
From the viewpoint of the stability of the color developer, the liquid aperture ratio is 0 to 0.
1 cm ^-1 is preferred. In continuous processing, practically 0.0
Preferably in the range of 01cm ^-1 ~0.05cm ^-1, more preferably 0.
It is 002 cm ^{-1 to} 0.03 cm ^-1 .

In general, when hydroxylamine or the like is used as a preservative, it is widely known that decomposition by heat or trace metals occurs even when the liquid aperture ratio of the color developer is reduced. However, in the color developing solution of the present invention, these decompositions are very small, and the color developing solution can be stored for a long period of time or can be sufficiently put to practical use even when it is used for a long period of time. Therefore, in such a case, the liquid aperture ratio is preferably small, and most preferably ⁰ to 0.002 cm ^-1 .

On the contrary, after treating a certain amount of treatment, there is a case of treating with a wide opening ratio under the condition of discarding, but even in such a treating method, excellent performance can be exhibited according to the configuration of the present invention. it can.

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

The bleaching solution or bleach-fixing solution used in the present invention includes bromide (for example, potassium bromide, sodium bromide, ammonium bromide) or chloride (for example, potassium chloride,
A rehalogenating agent such as sodium chloride, ammonium chloride) or iodide (eg, ammonium iodide) can be included. If necessary, boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid,
1 with pH buffering capacity such as sodium citrate, tartaric acid
More than one kind of inorganic acids, organic acids and alkali metal or ammonium salts thereof, or corrosion inhibitors such as ammonium nitrate and guanidine can be added.

The fixing agents used in the bleach-fixing solution or the fixing solution according to the present invention are known fixing agents, that is, thiosulfates such as sodium thiosulfate and ammonium thiosulfate; thiocyanates such as sodium thiocyanate and ammonium thiocyanate; Ethylenebisthioglycolic acid, thioether compounds such as 3,6-dithia-1,8-octanediol, and water-soluble silver halide solubilizers such as thioureas, which may be used alone or in admixture of two or more. Can be used. Also, a special bleach-fixing solution comprising 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 one is preferably 0.3 to 2 mol, more preferably 0.5 to 2 mol.
In the range of ~ 1.0 mole.

In the present invention, the pH range of the bleach-fixing solution or the fixing solution is as follows:
3 to 8 are preferable, and 4 to 7 are particularly preferable. pH
If the content is lower than this, the desilvering property is improved, but the deterioration of the solution and the leuco formation of the cyan dye are promoted. Conversely, if the pH is higher than this, desilvering is delayed and stains are easily generated.

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 other various types of fluorescent whitening agents, antifoaming agents, surfactants, and organic solvents such as polyvinylpyrrolidone and methanol.

In the present invention, the bleach-fixing solution or the fixing solution may be a sulfite (for example, sodium sulfite, potassium sulfite, ammonium sulfite, etc.), a bisulfite (for example, ammonium bisulfite, sodium bisulfite, potassium bisulfite) as a preservative. ) And metabisulfites (eg, potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.). These compounds are approximately
The content is preferably 0.02 to 0.50 mol / mol, more preferably 0.04 to 0.40 mol / mol. Particularly, addition of ammonium sulfite is preferable.

As a preservative, sulfite is generally added,
In addition, ascorbic acid, carbonyl bisulfite adducts, sulfinic acids, carbonyl compounds, sulfinic acids, and the like may be added.

Further, a buffer, an optical brightener, a chelating agent, a fungicide, and the like may be added as necessary.

The processing time of the bleach-fix solution of the present invention is 10 seconds to 120 seconds, preferably 20 seconds to 60 seconds. Further, the replenishing amount is 30m per photosensitive material 1 m ²
It is 1 to 250 ml, preferably 40 to 150 ml. With the reduction in the replenishment amount, in general, stains and desilvering defects are likely to occur, but according to the present invention, it is necessary to reduce the replenishment amount of the bleach-fix solution without causing such a problem. Can be.

The silver halide color photographic light-sensitive material of the present invention generally undergoes a washing and / or stabilizing step after desilvering processing such as fixing or bleach-fixing.

The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, depending on the material used such as a coupler), the use, the rinsing water temperature,
It can be set in a wide range depending on the number of washing tanks (number of stages), a replenishment method such as countercurrent flow, forward flow, and other various 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 T
elevision Engineers) Volume 64, pp.248-253 (5 May 1955)
Monthly issue) can be obtained.

According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced.However, due to an increase in the residence time of water in the tank, bacteria are propagated, and the generated suspended matter adheres to the photosensitive material. 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. 131632/1986 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 to 9
And preferably 5 to 8. The washing temperature and washing time can also be variously set depending on the characteristics of the photosensitive material, application, etc., but are generally in the range of 15 to 45 ° C for 20 seconds to 2 minutes, preferably in the range of 25 to 40 ° C for 30 seconds to 1 minute 30 seconds. Is selected.

According to the present invention, even in such a short-time water washing,
Good photographic characteristics can be obtained without an increase in stain.

Further, the light-sensitive material of the present invention can be processed directly with a stabilizing solution instead of the above-mentioned water washing. In such a stabilizing treatment, JP-A-57-8543 and JP-A-58-14834.
No. 59-184343, No. 60-220345, No. 60-238832
No. 60-239784, No. 60-239749, No. 61-4054,
The known methods described in JP-A-61-118749 and the like can all be used. In particular, 1-hydroxyethylidene-1,1-
A stable 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, after the water washing treatment, a stabilization treatment may be further performed, and examples thereof include a stabilizing bath containing formalin and a surfactant used as a final bath of a color light-sensitive material for photography. .

The processing time of the present invention is defined as the time from when the photosensitive material comes into contact with the color developer until it leaves the final bath (generally, 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 3 minutes or less.

The color photographic light-sensitive material of the present invention can be constituted by coating at least one blue-sensitive silver halide emulsion layer, one green-sensitive silver halide emulsion layer and one red-sensitive silver halide emulsion layer on a support. In general, color printing paper is usually coated on a support in the order described above, but may be in a different order. Further, an infrared-sensitive silver halide emulsion layer can be used in place of at least one of the above-mentioned emulsion layers. In these light-sensitive emulsion layers, a silver halide emulsion having a sensitivity in each wavelength region and a dye having a complementary color with the light to be exposed, that is, yellow for blue, magenta for green, and cyan for red are formed. By incorporating a so-called color coupler, the color reproduction by the subtractive color method can be performed. However, the photosensitive layer and the color hue of the coupler may not have the above correspondence.

The halogen composition of the emulsion may be different or the same between grains. However, when an emulsion having the same halogen composition between grains is used, it is easy to make the properties of each grain uniform. Regarding the halogen composition distribution inside the silver halide emulsion grains, grains having a so-called uniform structure having the same composition in any part of the silver halide grains, a core inside the silver halide grains and a shell surrounding the core are used. (Shell) [Layer or plural layers] and a so-called laminated type particle having a different halogen composition, or a structure having a non-layered portion having a different halogen composition inside or on the surface of the particle (when the particle is on the particle surface, the edge of the particle, Particles having a structure in which portions having different compositions are joined on corners or surfaces) can be appropriately selected and used. In order to obtain high sensitivity, it is advantageous to use one of the latter two particles rather than particles having a uniform structure, and this is also preferable from the viewpoint of pressure resistance. In the case where the silver halide grains have the above-described structure, even if the boundary between different portions in the halogen composition is a clear boundary, it is an unclear boundary by forming a mixed crystal due to a composition difference. It is also possible to employ a structure in which a continuous structural change is positively provided.

The high silver chloride emulsion preferably has a structure having a localized layer of silver bromide in the inside and / or on the surface of the silver halide grain in the form of layer or non-layer as described above. The halogen composition of the localized phase has at least a silver bromide content.
Those having 10 mol% are preferable, and those having more than 20 mol% are more preferable. These localized layers can be on the inside of the grain, on the edge, corner, or plane of the grain surface. One preferred example is a layer grown epitaxially on the corner of the grain.

On the other hand, in order to minimize the decrease in sensitivity when the photosensitive material is subjected to pressure, even in a high silver chloride emulsion having a silver chloride content of 90 mol% or more, grains having a uniform distribution of the halogen composition in the grains are used. It is also preferably used.

It is also effective to further increase the silver chloride content of the silver halide emulsion in order to reduce the replenishment amount of the developing solution. In such a case, the silver chloride content is 98 mol% to 10 mol%.
Emulsions of substantially pure silver chloride, such as 0 mol%, are also preferably used.

The average grain size of the silver halide grains contained in the silver halide emulsion used in the present invention (the grain size is defined by the diameter of a circle equivalent to the projected area of the grain and the number average thereof is taken) is 0.1 μm to 2 μm. preferable.

In addition, their particle size distribution has a coefficient of variation (standard deviation of particle size distribution divided by average particle size) of 20%
In the following, a so-called monodispersed one of desirably 15% or less is preferable. At this time, for the purpose of obtaining a wide latitude, it is also preferable to use the above monodispersed emulsion by blending it in the same layer, or to perform multi-layer coating.

The silver halide grains contained in photographic emulsions have a regular (regular, cubic, tetradecahedral or octahedral) shape.
r) Those having a crystal form, those having an irregular crystal form such as a sphere or a plate, or those having a complex form thereof can be used. Also,
It may be composed of a mixture having various crystal forms. In the present invention, among these, the particles having the above-mentioned regular crystal form should be contained in 50% or more, preferably 70% or more, and more preferably 90% or more.

In addition, emulsions in which tabular grains having an average aspect ratio (diameter / circle diameter in circle) of 5 or more, preferably 8 or more, as projected area exceeds 50% of all grains can be preferably used.

The silver chlorobromide emulsion used in the present invention is described in Chimi by P. Glafkides.
e et Phisique Photographique (published by Paul Montel, 196
7 years), Photo-graphic Emulsion Chemist by GFDuffin
ry (Focal Press, 1966), VLZelikman et al
By Making and Coating Photographic Emuldion (Focal
Press, 1964) and the like. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and as a method of reacting a soluble silver salt and a soluble halide, any method such as a one-side mixing method, a simultaneous mixing method, and a combination thereof may be used. May be used. A method of forming particles in an atmosphere containing excess silver ions (a so-called reverse mixing method) can also be used. As one type of the double jet method, a method of maintaining a constant pAg in a liquid phase in which silver halide is formed, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a nearly uniform grain size can be obtained.

In the silver halide emulsion used in the present invention, various polyvalent metal ion impurities can be introduced during the process of forming emulsion grains or physical ripening. Examples of the compound to be used include salts of cadmium, zinc, lead, copper, thallium and the like, or salts or complex salts of Group VIII element iron, ruthenium, rhodium, palladium, osmium, iridium and platinum. it can. Especially above VI
Group II elements can be preferably used. The addition amount of these compounds varies widely depending on the purpose, but is preferably from 10 ^-9 to 10 ^-2 mol based on silver halide.

The silver halide emulsion used in the present invention is usually subjected to chemical sensitization and spectral sensitization.

As the chemical sensitization method, sulfur sensitization represented by addition of an unstable sulfur compound, noble metal sensitization represented by gold sensitization, reduction sensitization, or the like can be used alone or in combination. As the compounds used for chemical sensitization, those described in JP-A-62-215272, page 18, lower right column to page 22, upper right column are preferably used.

Spectral sensitization is performed for the purpose of imparting spectral sensitivity to a desired light wavelength range to the emulsion of each layer in the light-sensitive material of the present invention. In the present invention, it is preferable to add a dye that absorbs light in a wavelength range corresponding to the intended spectral sensitivity—a spectral sensitizing dye. Examples of spectral sensitizing dyes used at this time include, for example, Heterocyclic compo by FM Harmer.
unds-Cyanine dyes and related compounds (John Wil
ey & Sons [New York, London], 1964). As specific examples of the compounds and the spectral sensitization method, those described in the above-mentioned JP-A-62-215272, from page 22, upper right column to page 38, are preferably used.

To the silver halide emulsion used in the present invention, various compounds or their precursors are added for the purpose of preventing fogging during the production process, storage or photographic processing of the light-sensitive material, or stabilizing photographic performance. be able to. As specific examples of these compounds, those described on page 39 to page 72 of JP-A-62-215272 described above are preferably used.

The emulsion used in the present invention is any of a so-called surface latent image type emulsion in which a latent image is mainly formed on the grain surface and a so-called internal latent image type emulsion in which a latent image is mainly formed inside the grain. Is also good.

When the present invention is applied to a color light-sensitive material, the color light-sensitive material is coupled with an oxidized form of an aromatic amine-based color developing agent to form a yellow coupler, a magenta coupler, and a cyan coupler which respectively form yellow, magenta, and cyan. Is usually used.

 In the present invention, a cyan coupler and a magenta coupler
And as a yellow coupler, the following general formula (C-
I), (C-II), (M-I), (M-II) and
The mechanism of action is unknown when the one shown in (Y) is used.
However, as mentioned above, a certain amount of Br , Cl Contains
To the compound of the general formula (I) (preferably the general formula (Ia))
Color development with a color developer containing
It is possible to further reduce fluctuations in photographic characteristics.

In the general formulas (CI) and (C-II), R ₁ , R ₂
And R ₄ represents a substituted or unsubstituted aliphatic, aromatic or heterocyclic group; R ₃ , R ₅ and R ₆ represent a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group or an acylamino group; ₃ may represent a non-metallic atomic group forming a 5- or 6-membered nitrogen-containing ring together with R ₂ . Y ₁ and Y _{2 each} represent a hydrogen atom or a group capable of leaving during a coupling reaction with an oxidized form of a developing agent. n represents 0 or 1.

R ₅ in the general formula (C-II) is preferably an aliphatic group, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentadecyl group, a tert-butyl group, a cyclohexyl group, a cyclohexylmethyl group, Examples include a phenylthiomethyl group, a dodecyloxyphenylthiomethyl group, a butanamidomethyl group, a methoxymethyl group, and the like.

Preferred examples of the cyan coupler represented by the general formula (CI) or (C-II) are as follows.

In the general formula (CI), preferred R ₁ is an aryl group,
A heterocyclic group, a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an acylamino group, an acyl group,
More preferably, they are aryl groups substituted by a carbamoyl group, a sulfonamide group, a sulfamoyl group, a sulfonyl group, a sulfamide group, an oxycarbonyl group, or a cyano group.

When R ₃ and R ₂ do not form a ring in formula (CI), R ₂ is preferably a substituted or unsubstituted alkyl group,
It is an aryl group, particularly preferably a substituted aryloxy-substituted alkyl group, and R ₃ is preferably a hydrogen atom.

In formula (C-II), R ₄ is preferably a substituted or unsubstituted alkyl group or aryl group, and particularly preferably a substituted aryloxy-substituted alkyl group.

In the general formula (C-II), preferred R ₅ has 2 to 15 carbon atoms.
And a methyl group having a substituent having 1 or more carbon atoms, and the substituent is preferably an arylthio group, an alkylthio group, an acylamino group, an aryloxy group, or an alkyloxy group.

In the general formula (C-II), R ₅ is more preferably an alkyl group having 2 to 15 carbon atoms, particularly preferably an alkyl group having 2 to 4 carbon atoms.

Preferred R ₆ in formula (C-II) is a hydrogen atom or a halogen atom, and a chlorine atom and a fluorine atom are particularly preferred. Preferred Y ₁ and Y ₂ in the general formulas (CI) and (C-II) are a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, and a sulfonamide group, respectively.

In the general formula (MI), R ₇ and R ₉ represent an aryl group, R ₈ represents a hydrogen atom, an aliphatic or aromatic acyl group, an aliphatic or aromatic sulfonyl group, and Y ₃ represents hydrogen. Represents an atom or a leaving group. The permissible substituents for the aryl group (preferably phenyl group) for R ₇ and R ₉ are the same as the permissible substituents for the substituent R ₁ , and even when there are two or more substituents, they may be the same. It may be different. R ₈ is preferably a hydrogen atom, an aliphatic acyl group or a sulfonyl group, particularly preferably a hydrogen atom. preferable
Y ₃ is of a type capable of leaving with a sulfur, oxygen or nitrogen atom, and a sulfur atom leaving type as described in, for example, US Pat. No. 4,351,897 and International Publication WO88 / 04795 is particularly preferable.

In the general formula (M-II), R ₁₀ represents a hydrogen atom or a substituent. Y ₄ represents a hydrogen atom or a leaving group, particularly preferably a halogen atom or an arylthio group. Za, Zb and
Zc represents methine, substituted methine, = N- or -NH-,
One of the -Zb bond and the Zb-Zc bond is a double bond, and the other is a single bond. The case where the Zb-Zc bond is a carbon-carbon double bond includes the case where it is a part of an aromatic ring. When R ₁₀ or Y ₄ forms a dimer or more multimer, Za,
When Zb or Zc is a substituted methine, the case where the substituted methine forms a dimer or more multimer is included.

Among the pyrazoloazole couplers represented by the general formula (M-II), the imidazo [1,2-b] pyrazole described in U.S. Pat. No. 4,500,630 is advantageous in terms of low yellow side absorption and light fastness of a coloring dye. Are preferred, US Pat.
The pyrazolo [1,5-b] [1,2,4] triazole described in 4,540,654 is particularly preferred.

In addition, a branched alkyl group as described in JP-A-61-65245 is directly linked to the 2-, 3- or 6-position of the pyrazolotriazole ring to form a pyrazolotriazole coupler.
Pyrazoloazole couplers containing a sulfonamide group in the molecule as described in 65246, JP-A-61-147254
Pyrazoloazole couplers having an alkoxyphenylsulfonamide ballast group as described in JP-A No. 226,849 and pyrazoloazole couplers having an alkoxy group or aryloxy group at the 6-position as described in EP-A-226,849 and EP 294,785. The use of zorotriazole couplers is preferred.

In the general formula (Y), R ₁₁ represents a halogen atom, an alkoxy group, a trifluoromethyl group or an aryl group, and R ₁₂ represents a hydrogen atom, a halogen atom or an alkoxy group. A is _{-NHCOR 13, -NHSO 2 -R 13,} -SO 2 NHR 13,
−COOR ₁₃ , Represents Here, R ₁₃ and R ₁₄ each represent an alkyl group, an aryl group or an acyl group. Y ₅ represents a leaving group. R ₁₂
And the substituents of R ₁₃ and R ₁₄ are the same as the substituents permitted for R ₁ and the leaving group Y ₅ is preferably of a type capable of leaving at either an oxygen atom or a nitrogen atom. And a nitrogen atom-elimination type is particularly preferable.

Formulas (C-I), (C-II), (M-I), and (M-
Specific examples of the couplers represented by II) and (Y) are listed below.

The couplers represented by the above general formulas (C-I) to (Y) are usually added in the silver halide emulsion layer constituting the photosensitive layer in an amount of 0.1 to 1.0 mol, preferably 0.1 to 1.0 mol per mol of silver halide.
0.50.5 mol.

In the present invention, various known techniques can be applied to add the coupler to the photosensitive layer. Usually, it can be added by an oil-in-water dispersion method known as an oil protection method, and after being dissolved in a solvent, it is emulsified and dispersed in a gelatin aqueous solution containing a surfactant. Alternatively, water or an aqueous gelatin solution may be added to a coupler solution containing a surfactant to form an oil-in-water dispersion with phase inversion. The alkali-soluble coupler can also be dispersed by a so-called Fisher dispersion method. After removing the low boiling point organic solvent from the coupler dispersion by a method such as distillation, washing with noodles or ultrafiltration, the photographic emulsion may be mixed.

Dielectric constant (25 ° C) as a dispersion medium for such couplers
It is preferable to use a high-boiling organic solvent having a refractive index of 2 to 20 and a refractive index (25 ° C.) of 1.5 to 1.7 and / or a water-insoluble polymer compound.

As the high boiling point organic solvent, preferably, the following general formula (A)
The high-boiling organic solvent represented by (E) is used. In particular, the aforementioned general formulas (C-I), (C-II), (M-
Particularly preferred are couplers represented by I), (M-II) and (Y).

General formula (B) W ₁ -COO-W ₂ Formula (E) W ₁ —O—W ₂ (wherein W ₁ , W ₂ and W ₃ each represent a substituted or unsubstituted alkyl group, cycloalkyl group, alkenyl group, aryl group or heterocyclic group; W ₄ is W ₁ , OW ₁ or SW
_And n is an integer of 1 to 5, and when n is 2 or more, W ₄ may be the same or different. In the general formula (E), W ₁ and W ₂ represent a condensed ring. May be formed).

The high-boiling organic solvent that can be used in the present invention is a compound that is not miscible with water having a melting point of 100 ° C. or less and a boiling point of 140 ° C. or more other than the general formulas (A) to (E). Can be used. The high boiling point organic solvent preferably has a melting point of 80 ° C. or lower. The boiling point of the high boiling organic solvent is preferably 160 ° C.
And more preferably 170 ° C. or higher.

Details of these high-boiling organic solvents are described in
No. 215272, page 137, lower right column to page 144, upper right column.

These couplers may be impregnated with a loadable latex polymer (for example, U.S. Pat.No. 4,203,716) in the presence or absence of the high-boiling organic solvent or dissolved in a water-insoluble and organic solvent-soluble polymer. The emulsion can be dispersed in a hydrophilic colloid aqueous solution.

Preferably, pages 12 to 30 of WO 88/00723
The homopolymers or copolymers described on the page are used, and the use of an acrylamide polymer is particularly preferred for stabilizing a color image.

The light-sensitive material prepared by using the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, and the like as a color fogging inhibitor.

Various anti-fading agents can be used in the light-sensitive material of the present invention. That is, hydroquinones as organic anti-fading agents for cyan, magenta and / or yellow images,
6-hydroxychromans, 5-hydroxycoumarins, spirochromans, p-alkoxyphenols,
Representative examples include hindered phenols, mainly bisphenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines, and ether or ester derivatives obtained by silylating or alkylating the phenolic hydroxyl group of each of these compounds. No. Further, metal complexes represented by (bissalicylaldoximato) nickel complex and (bis-N, N-dialkyldithiocarbamato) nickel complex can also be used.

Specific examples of the organic anti-fading agent are described in the specifications of the following patents.

Hydroquinones are disclosed in U.S. Pat.Nos. 2,360,290 and 2,4
No. 18,613, No. 2,700,453, No. 2,701,197, No. 2,
No. 728,659, No. 2,732,300, No. 2,735,765, No.
No. 3,982,944, No. 4,430,425, UK Patent No. 1,363,921
No., U.S. Pat.Nos. 2,710,801 and 2,816,028,
6-Hydroxychromans, 5-hydroxycoumarins, and spirochromans are described in U.S. Pat.
No. 3,573,050, No. 3,574,627, No. 3,698,909, No. 3,764,337, JP-A-52-152225, Spiroindanes in U.S. Pat.No. 4,360,589, p-Alkoxyphenols in U.S. Pat. UK Patent 2,0
66,975, JP-A-59-10539, JP-A-57-19765, etc., hindered phenols are described in U.S. Pat.
No., JP-A-52-72224, U.S. Pat.
No. 52-6623, gallic acid derivatives, methylenedioxybenzenes and aminophenols are described in U.S. Pat.
No. 3,457,079, No. 4,332,886, Japanese Patent Publication No. 56-21144, etc., hindered amine acid is U.S. Pat.
No. 4,268,593, British Patent No. 1,326,889, No. 1,354,
No. 313, No. 1,410,846, JP-B-51-1420, JP-A-58
Nos. 1-114036, 59-53846 and 59-78344, metal complexes are disclosed in U.S. Pat.Nos. 4,050,938 and 4,241,155.
And British Patent No. 2,027,731 (A). These compounds can achieve the object by adding usually 5 to 100% by weight of the corresponding color coupler to the photosensitive layer after co-emulsification with the coupler. In order to prevent the deterioration of the cyan dye image due to heat and particularly to light, it is more effective to introduce an ultraviolet absorber into the cyan coloring layer and the layers on both sides adjacent thereto.

Examples of the ultraviolet absorber include benzotriazole compounds substituted with an aryl group (for example, those described in U.S. Pat. No. 3,533,794), 4-thiazolidone compounds (for example, those described in U.S. Pat. Nos. 3,314,794 and 3,352,681),
Benzophenone compounds (for example, those described in JP-A-46-2784) and cinnamate compounds (for example, US Pat.
3,705,805 and 3,707,395), butadiene compounds (described in U.S. Pat. No. 4,045,229),
Alternatively, benzooxide compounds (for example, US Pat.
Nos. 3,406,070 and 3,677,672 and 4,271,307) can be used. UV-absorbing couplers (eg, α-naphthol-based cyan dye-forming couplers)
Alternatively, an ultraviolet absorbing polymer or the like may be used. These ultraviolet absorbers may be mordanted to a specific layer.

Above all, a benzotriazole compound substituted with the above-mentioned aryl group is preferable.

It is particularly preferable to use the following compounds together with the above-mentioned coupler. In particular, combination use with a pyrazoloazole coupler is preferred.

That is, the compound (F) which forms a chemically inert and substantially colorless compound by chemically bonding with the aromatic amine-based developing agent remaining after the color developing process and / or the aromatic compound remaining after the color developing process. The use of the compound (G), which forms a chemically inactive and substantially colorless compound by chemically bonding with an oxidant of a group amine color developing agent, simultaneously or solely, for example, in storage after processing. It is preferable for preventing the occurrence of stains and other side effects due to the formation of color dyes by the reaction of the coupler with the color developing agent remaining in the film or its oxidant.

Preferred compound (F) is a compound having a second-order reaction rate constant K ₂ (in trioctyl phosphate at 80 ° C.) of 1.0 / mol · sec to 1 × 10 ⁻⁵ / mol · sec with p-anisidine. Compound. The secondary reaction rate constant can be measured by the method described in JP-A-63-158545.

If K ₂ is greater than this range, the compound itself becomes unstable, resulting in decomposition reacts with gelatin or water. On the other hand, if K ₂ is smaller than this range, the reaction with the remaining aromatic amine-based developing agent is slow, and as a result, side effects of the remaining aromatic amine-based developing agent may not be prevented.

More preferable compound (F) can be represented by the following general formula (FI) or (F II).

General formula (FI) R _1- (A) _n -X In the formula, R ₁ and R ₂ each represent an aliphatic group, an aromatic group, or a heterocyclic group. n represents 1 or 0. A represents a group which forms a chemical bond by reacting with an aromatic amine-based developer, and X represents a group which is eliminated by reacting with an aromatic amine-based developer. B represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, or a sulfonyl group, and Y represents that an aromatic amine-based developing agent is added to the compound of the general formula (F II). Represents a promoting group. Here, R ₁ and X, Y and R ₂ or B may be bonded to each other to form a cyclic structure.

Representative methods of chemically bonding with the residual aromatic amine-based developing agent are a substitution reaction and an addition reaction.

Specific examples of the compounds represented by formulas (FI) and (F II) are described in JP-A-63-158545, JP-A-62-283338,
Those described in specifications such as European Patent Publication Nos. 298321 and 277589 are preferable.

On the other hand, the compound (G) which forms a chemically inactive and colorless compound by chemically bonding to an oxidized form of an aromatic amine-based developing agent remaining after the color development treatment is more preferably represented by the following general formula (GI) ).

Formula (GI) RZ In the formula, R represents an aliphatic group, an aromatic group, or a heterocyclic group. Z represents a nucleophilic group or a group which decomposes in the light-sensitive material to release a nucleophilic group. In the compound represented by the general formula (GI), Z is a nucleophilic ⁿ CH ₃ I value of Pearson (RGPearso
n, et al., J. Am. Chem. Soc., 90 , 319 (1968)) or a group derived therefrom is preferred.

Specific examples of the compound represented by the general formula (GI) are described in EP-A-255722, JP-A-62-143048 and JP-A-62-143048.
-229145, Japanese Patent Application Nos. 63-136724 and 62-214681, and European Patent Publications 298321 and 277589 are preferred.

The details of the combination of the compound (G) and the compound (F) are described in EP-A-277589.

The light-sensitive material prepared according to the present invention contains a hydrophilic dye or a dye which becomes water-soluble by photographic processing as a filter dye in a hydrophilic colloid layer, or for various purposes such as prevention of irradiation or halation. May be. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Of these, oxonol dyes, hexoxonol fuels and merocyanine dyes are useful.

As the binder or protective colloid that can be used in the emulsion layer of the light-sensitive material of the present invention, gelatin is advantageously used, but other hydrophilic colloids can be used alone or together with gelatin.

In the present invention, gelatin may be quartz treated,
Either one treated with an acid may be used. The details of the method for producing gelatin are described in Arthur Weiss, The Macromolecular Chemistry of Gelatin (Academic Press, 1964).

As the support used in the present invention, a transparent film such as a cellulose nitrate film or polyethylene terephthalate, which is used in a photographic light-sensitive material, or a reflective support can be used. For the purposes of the present invention, the use of a reflective support is more preferred.

The term "reflective support" used in the present invention refers to a material which enhances reflectivity and sharpens a dye image formed in a silver halide emulsion layer. Examples include those coated with a hydrophobic resin dispersedly containing a light reflecting substance such as titanium oxide, zinc oxide, calcium carbonate, and calcium sulfate, and those using a hydrophobic resin dispersedly containing a light reflecting substance as a support. For example, baryta paper, polyethylene-coated paper, polypropylene-based synthetic paper, a transparent support provided with a reflective layer or combined with a reflective substance, for example, a glass plate, polyethylene terephthalate, a polyester film such as cellulose triacetate or cellulose nitrate, There are polyamide film, polycarbonate film, polystyrene film, vinyl chloride resin and the like.

Other reflective supports include specular or secondary
A support having a seed diffuse reflective metal surface can be used. The metal surface has a spectral reflectance of 0.5 in the visible wavelength range.
The above materials are preferred, and the metal surface is preferably roughened or diffusely reflective using metal powder. As the metal, aluminum, tin, silver, magnesium or an alloy thereof is used, and the surface may be the surface of a metal plate, a metal foil, or a metal thin layer obtained by rolling, vapor deposition, plating, or the like.
Above all, it is preferable to obtain a metal by vapor deposition on another substrate. It is preferable to provide a water-resistant resin, especially a thermoplastic resin layer, on the metal surface. An antistatic layer is preferably provided on the side of the support of the present invention opposite to the side having the metal surface. For details of such a support, see, for example, JP-A-61-210346.
Nos. 63-24247, 63-24251 and 63-24255.

 These supports can be appropriately selected depending on the purpose of use.

As the light-reflective substance, it is preferable to sufficiently knead a white pigment in the presence of a surfactant.
It is preferable to use those treated with a to tetravalent alcohol.

The occupied area ratio (%) per defined unit area of the white pigment fine particles is most typically obtained by dividing the observed area into adjacent 6 μm × 6 μm unit areas and projecting the unit area. It can be determined by measuring the occupied area ratio (%) (Ri) of the fine particles. The coefficient of variation of the occupied area ratio (%) is the ratio s / of the standard deviation s of Ri to the average value of Ri
Can be obtained by The number (n) of the target unit areas is preferably 6 or more. Therefore the coefficient of variation s / Can be obtained by

In the present invention, the occupied area ratio of the pigment fine particles (%)
Is preferably 0.15 or less, particularly preferably 0.12 or less. 0.08
In the following cases, it can be said that the dispersibility of the particles is substantially “uniform”.

(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 constitution was produced on a paper support laminated on both sides with polyethylene. The coating solution was prepared as follows.

Preparation of first layer coating solution 19.1 g of yellow coupler (ExY) and color image stabilizer (Cp
d-1) To 4.4 g of the color image stabilizer (Cpd-7) and 0.7 g of the color image stabilizer (Cpd-7), 27.2 cc of ethyl acetate and 8.2 g of the solvent (Solv-3) were added and dissolved.
It was emulsified and dispersed in 185 cc of a 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 first layer coating solution having the following composition. Coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. As the gelatin hardener for each layer, 1
-Oxy-3,5-dichloro-s-triazine sodium salt was used.

 The following were used as the spectral sensitizing dyes 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 per mol of silver halide) and (7.0 × 10 ^-5 mol per mol of silver halide) Red-sensitive emulsion layer (0.9 × 10 ⁻⁴ mol per mol of silver halide) The following compounds were added to the red-sensitive emulsion layer at 2.6 × 10 ⁻³ mol per mol of silver halide.

Also, 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 mole 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.

and (Layer Configuration) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents a coating amount in terms of silver.

Support Polyethylene laminated paper [The first layer of polyethylene contains white pigment (TiO ₂ ) and blue dye (ultra blue)] 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 mixture prevention layer) Gelatin 0.99 Color mixture 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 mean grain size 0.58 with μ,
A 1: 4 mixture of 0.45μ (Ag molar ratio).

Coefficient of variation of particle size distribution 0.09 and 0.11 respectively.

0.6 mol% of AgBr was locally contained in a part of the particle surface. 0.2
3 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 Sixth layer ( UV absorber 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 Acrylic modified copolymer of polyvinyl alcohol (modified) Every time
17%) 0.17 Liquid paraffin 0.03 The sample obtained as described above was designated as H. Next, in the same manner as in Sample H, except that the coating silver amount of each emulsion layer was changed to the fourth
Modifications were made as shown in the table to prepare Samples HL.

After imagewise exposure of the samples H to L, a continuous processing (running test) was carried out by using a paper processor (automatic developing machine) in the following processing steps until the tank capacity of the color developing solution was doubled. . Treatment process temperature Time Replenishment amount ^* Tank capacity Color development 38 ℃ 45 seconds See Table 5 4 Bleach fixing 30-36 ℃ 45 seconds 61ml 4 Water wash 30-37 ℃ 30 seconds-2 Water wash 30-37 ℃ 30 seconds-2 Washing with water 30-37 ℃ 30 seconds 364ml 2 Drying 70-85 ℃ 60 seconds * Replenishment amount per 1m ^{2 of} photosensitive material The composition of each processing solution is as follows.

Color developer [Tank solution] Water 800 ml Ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid 3.0 g Triethanolamine 8.0 g Sodium chloride See Table 5 Potassium bromide See Table 5 Potassium carbonate 25 g N -Ethyl-N- (β-methanesulfonamidoethyl)
-3-Methyl-4-aminoaniline sulfate 5.0 g Organic preservative A (I-1) 0.03 mol Fluorescent whitening agent (WHITEX-4 manufactured by Sumitomo Chemical) 1.0 g Add water and 1000 ml pH (25 ° C) 10.05 Bleach-fixing solution [tank solution] Water 400ml Ammonium thiosulfate (70%) 100ml Ammonium sulfite 38g Ethylenediaminetetraacetic acid iron (III) ammonium 55g Ethylenediaminetetraacetic acid disodium 5g Glacial acetic acid 9g Water is added 1000ml pH (25 ℃) 5.40 [Replenishment] Liquid] 2.5 times concentrated liquid of tank liquid Washing liquid (same as tank liquid and replenisher) Ion-exchanged water (3ppm each for calcium and magnesium)
Hereinafter, distilled water was added to the color developing solution, the bleach-fixing solution, and the washing solution in an amount of distilled water, and continuous processing was performed while correcting the evaporation and concentration.

A gradation exposure for sensitometry was applied to the coated sample using a sensitometer (FWH type manufactured by Fuji Photo Film Co., Ltd., color temperature of light source: 3200K). The exposure at this time is 1/10
The exposure amount was 250 CMS with the exposure time of 2 seconds.

At the start and the end of the running test, the sensitometry is processed, and the maximum density change (ΔDmax) and gradation (red E of 0.3 at the point of density E of 1.5 at the high exposure side of red (RL) at the start of the running) The amount of change in the density difference up to the density point) was measured using a Macbeth densitometer, and the results are shown in Table 5.

Furthermore, at the end of running, the above-mentioned coated sample was used, and a sensitometer (Fuji Photo Film Co., Ltd.
H type, light source color temperature of 3200K) was used to provide uniform exposure of gray, and the same treatment as in the above sensitometry was performed to evaluate the sensitizing muscle. The evaluation standard has four levels and is shown below.

Evaluation of sensitizing muscles Number of sensitizing muscles in 100 cm ² (10 cm × 10 cm) of sample ○ 0 △ △ 1 to 2 × 3 to 5 × × 6 or more Evaluation results are shown in Table 5.

According to Table 5, in the treatment step, the maximum density of the cyan color developing layer (RL) is high, the maximum density and gradation change due to running are small, and further, the sensitizing muscle generation preventing effect is high and good. The results were obtained. It can be seen that the treatment step has a lower concentration of chloride ion and bromide ion than the present invention, and the generation of sensitizing muscle is remarkable as compared with the treatment step of the present invention, and does not achieve the object of the present invention. . The treatment step has a higher concentration of chloride ion and bromide ion than the present invention, and the treatment step of the present invention has a lower maximum concentration of the cyan color-forming layer (RL) and a maximum concentration associated with running and It can be seen that the gradation changes remarkably and the object of the present invention is not achieved.

Further, according to the treatment step, among the present invention,
The chloride ion concentration and the bromide ion concentration in the developer are 4 × 10 ⁻² to 1 × 10 ⁻¹ mol / l × 10 ^{−4 to} 3 ×, respectively.
In the case of 10 ^-4 mol / mol, more preferable results were obtained in terms of maximum density and gradation change associated with running.

Also, according to the treatment process, the amount of coated silver is 0.65 g / m ²
It can be seen that excellent results are obtained in the case of.

Example 2 Same as Example 1, except that in the treatment step:
Instead of I-1 of organic preservative A, I-2, I-3, I-
When 12, I-17, I-36 and I-53 were used, similar good results were obtained.

Example 3 A running test was conducted in the same manner as in Example 1, except that the developer was changed as follows in the processing step.

Table 6 shows the results. Processing temperature Time Replenishment amount ^* Tank capacity Color development 39 ℃ 45 seconds 35ml 4 Bleaching fixing 30-36 ℃ 45 seconds 215ml 4 Stable 30-37 ℃ 20 seconds-2 Stable 30-37 ℃ 20 seconds-2 Stable 30-37 ℃ 20 seconds 364 ml 2 Dry 70 to 85 ° C 60 seconds * Replenishment amount per 1 m ^{2 of} light-sensitive material (3 tank countercurrent system from stable to) The composition of each processing solution is as follows.

The tank solution and the replenisher for the bleach-fixing solution and the washing solution are the same as in Example 1.

According to Table 6, when treated with the developing solution of the present invention, the maximum density of the cyan color-forming layer (RL) is high, the maximum density and gradation change due to running are small, and further, the sensitization line is generated. The preventive effect was high and good results were obtained.

In the present invention, when the preservative is a compound represented by the general formula (Ia) (processing step-), the photographic property change due to running is particularly small, which is more preferable.

Example 4 Similar results as in Example 3 except that I-13, I-21, I-30, I-41, I-54 were used instead of I-12. was gotten.

Claims (1)

(57) [Claims] 1. When the exposed silver halide color photographic light-sensitive material is processed with a color developing solution containing at least one aromatic primary amine color developing agent using an automatic processor, 98 mol% It has a red-sensitive emulsion layer, a green-sensitive emulsion layer and a blue-sensitive emulsion layer containing the above high silver chloride silver halide emulsion consisting of silver chloride, and the total coated silver amount is 0.65 g /
A silver halide color light-sensitive material having a size of m ² or less is added with chloride ions and bromide ions, respectively, at 3.5 × 10 ^{-2 to} 1.5 × 10 5.
^-1 mol /, 1.0 × 10 ^{−4 to} 3.0 × 10 ⁻⁴ mol / containing silver halide color photograph characterized by being processed with a color developer containing the compound represented by formula (I) Method of processing photosensitive material. General formula (I) (Wherein, R ^1, R ² are, .R ¹ represents a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted aryl group or 5- to 6-membered heteroaromatic group, And R ² are never hydrogen atoms at the same time,
They may be linked to each other to form a hetero ring together with the nitrogen atom. )