JP2601686B2 - Processing method of silver halide color photographic light-sensitive material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a method for processing a silver halide color photographic light-sensitive material, and in particular, to a rapid silver halide color photographic light-sensitive material in which the replenishment amount of a color developer is remarkably reduced. And, at the same time, a processing method which is excellent in color developability and has a remarkably small change in photographic characteristics during continuous processing.

(Prior art) The processing of silver halide color photographic light-sensitive material basically consists of two steps of color development (in the case of a color reversal material, the first black-and-white development before it) and desilvering. Consists of a bleaching and fixing step or a single-bath bleach-fixing step used together or alone. If necessary, additional processing steps such as water washing, stop processing, stabilizing processing, and pre-processing for promoting development are added.

In color development, the exposed silver halide is reduced to silver while the oxidized aromatic primary amine developing agent reacts with the coupler to form a dye. In this process, the halogen ions generated by the decomposition of silver halide are eluted and accumulated in the developer. On the other hand, the color developing agent is consumed by the reaction with the coupler described above. Further, other components are carried out by being held in the photographic light-sensitive material, and the concentration of the components in the developer decreases. Therefore, in a development processing method in which a large amount of silver halide photographic light-sensitive material is continuously processed by an automatic processor or the like, the components of the color developing solution are kept within a certain concentration range in order to avoid a change in the development finish characteristics due to a change in the component concentration. We need a way to keep it.

For example, when the effect of concentration of a consumable component such as a developing agent or a preservative is small, the concentration in the replenisher is generally increased. In some cases, the eluate having an effect of suppressing development, such as halogen, is reduced in concentration or not contained in the replenisher. Further, a compound may be contained in the replenisher to remove the influence of the eluate. Also
In some cases, the pH or the concentration of the alkali or chelating agent is adjusted. As such means, a method is usually employed in which a replenisher for replenishing the insufficient component and diluting the increased component is replenished. However, replenishment of the replenisher inevitably generates a large amount of overflow, which is a serious problem in terms of economy and pollution.

In recent years, reduction of the replenishment amount of the developer has been strongly desired for the purpose of speeding up the development processing, saving resources and reducing pollution.
However, when the color developer is simply replenished, the photographic characteristics may be significantly impaired by the leached material of the photosensitive material.
For example, the accumulation of bromine ions reduces the development activity,
Speed is impaired. In addition, photographic characteristics (gradation and minimum density) vary depending on the release and accumulation of the sensitizing dye. In particular, since the latter is decomposed in a processing solution with the passage of time, photographic characteristics fluctuate depending on the amount of processing at the time of continuous processing, which seriously impairs the finished quality. In the case of rapid processing, the latter may remain in the light-sensitive material, which may increase the minimum density and cause so-called stain.

Despite low replenishment, in order to carry out rapid processing,
Conventionally, many technologies have been studied.

For example, as one of them, it is known to increase the speed by increasing the pH of the developer and the processing temperature. However, this method has a serious problem that the fog is high, the stability of the developing solution is deteriorated, and the fluctuation of photographic characteristics is increased during continuous processing. Further, as another accelerating technique, a technique of adding various development accelerators is known, but the accelerating effect is insufficient and is not satisfactory.

Further, for the purpose of reducing the accumulation of bromide ion, which is a strong development inhibitor, and speeding up the development, JP-A-58-95345
No. 59-232342, No. 61-70552, and International Publication (PCT application) WO 87-04534 disclose a method using a silver halide photosensitive material having a high silver chloride content, and develop without deteriorating the speed. It is considered to be an effective means for reducing the amount of liquid replenishment. However, if an attempt is made to reduce the replenishment amount of the developing solution without impairing the speed, the photographic characteristics fluctuate remarkably during continuous processing, and floating substances considered to be eluted from the photosensitive material in the processing solution are generated, It has been found that a new problem arises that causes a failure such as contamination of the rollers of the processing machine, clogging of the filter, and damage and contamination of the photosensitive material, which is not practically feasible.

Currently, replenishing amount of color developer is less even cowpea in the light-sensitive material to development processing different processing photosensitive material 1 m ² per
About 160-1000 ml is generally required. Because, if the replenishment rate is further reduced without impairing the rapidity, as described above, during continuous processing, the photographic characteristics greatly fluctuate, and a very serious problem that floating matters are generated in the developing solution occurs. This is because there is no technology that can fundamentally solve these problems.

(Problems to be Solved by the Invention) Accordingly, a first object of the present invention is to remarkably reduce the replenishment amount of a color developing solution without impairing the processing speed, and to improve the photographic characteristics, especially the minimum An object of the present invention is to provide a development processing method in which variations in density, maximum density and gradation are small.

A second object of the present invention is to provide a developing method which can remarkably reduce the replenishment amount of a color developing solution by using a high silver chloride photosensitive material, and which does not generate floating matter in the developing solution during continuous processing. is there.

(Means for Solving the Problems) The object of the present invention has been achieved by the following methods.
That is, the method of the present invention includes: 1) a method of continuously processing a silver halide color photographic light-sensitive material with a color developer containing at least one aromatic primary amine color developing agent; A silver halide color photographic light-sensitive material having at least one silver halide emulsion containing the sensitizing dye and silver chloride in an amount of at least 0.80 g / m ² , the tank solution, not contained in the replenisher both and the replenishing amount of the silver halide light-sensitive material 1 m ² per 12
A method for processing a silver halide color photographic light-sensitive material, wherein the processing is performed with a color developer of 0 ml or less.

General formula [I] Where Z₁And Z_TwoIs benzene fused to each heterocycle
List the atoms required to form a ring or naphthalene ring.
You. The heterocyclic nucleus formed may be substituted with a substituent.
No. R₁And R_TwoMay be the same or different from each other
Represents an alkyl group, R_ThreeIs a hydrogen atom or an atom having 1 to 3 carbon atoms.
Represents an alkyl group. X₁ Represents an anion, p is 0 or
Represents 1. Y₁And Y_TwoIs oxygen, sulfur, selenium
, A nitrogen atom and a terium atom.

 Hereinafter, the present invention will be described in detail.

Using high silver chloride color photographic material of more than 80 mol% silver chloride content, in the processing method for reducing the replenishment rate of the developing solution, if with a reduced replenishing amount of the developer below the photosensitive material 1 m ² per 120 ml, generally A color photographic material containing a sensitizing dye of the formula (1), that is, the high silver chloride emulsion spectrally sensitized with the sensitizing dye of the general formula (I), is treated with a color developer containing no sulfite ion. Thus, it was completely unexpected from the prior art that the fluctuation of photographic characteristics during continuous processing was remarkably improved and the generation of the above-mentioned suspended matter in the developing solution was significantly prevented.

Sulfite ions usually have a function of dissolving silver halide and reacting with an oxidized developing agent at the same time as a function as a preservative of the developing agent, thereby reducing dye formation efficiency. In particular, it is noteworthy that when a photographic material containing a sensitizing dye represented by the general formula (I) is continuously processed with a processing solution containing no sulfite ion, fluctuations in photographic characteristics and generation of suspended matter are remarkably reduced. Deserve. Because of this effect,
Fluctuations in the sulfite ion concentration during continuous processing are presumed to be one of the causes of the increase in fluctuations in photographic characteristics due to the decrease in the development replenisher. Further, when the high silver chloride photosensitive material having a high silver chloride content is continuously processed by reducing the development replenishment amount, the suspended matter specifically generated is presumed to be silver eluted from the photosensitive material due to the action of sulfite ions. You. However, these details are unknown.

In the present invention, the replenishment amount of the color developing solution
It is impractical in the prior art to reduce the volume to 0 ml or less due to the above-mentioned problems, and it has been made possible for the first time by the present invention. Although the lower limit of the replenishment amount is slightly different depending on the photosensitive material, the replenishment amount of the developer is larger than the replenishment amount of the processing solution brought out by the photosensitive material, and the processing solution is reduced. It is sufficient if the range is not possible. Normally, the replenishment amount of 20 ml per 1 m ² of the photosensitive material is such that the carry-out amount of the processing solution by the photosensitive material and the replenishment amount are substantially equal.

The replenishment amount of the color developing solution of the present invention is preferably from 20 ml to 120 ml, more preferably from 30 ml to 100 ml, per m ² of the photographic material. However, the replenishment amount referred to here indicates a replenishment amount of a so-called color developing replenisher, and the amount of an additive or the like for correcting aging or concentration is out of the replenishment amount of the present invention. . Note that the additive herein refers to, for example, water for diluting concentration, a preservative that is susceptible to deterioration with time, or an alkali agent that increases pH.

In the practice of the present invention, it is necessary to use a color developer which does not substantially contain sulfite ions.
Here, the color developer containing substantially no sulfite ion means a processing solution in which the sulfite ion is 5.0 × 10 ⁻³ mol / l or less. 5.0 × 10 ^-3 mol / l means that a light-sensitive material having a high chloride silver halide emulsion comprising 80 mol% or more of chloride was continuously processed with a replenishment rate of a developing solution of 120 ml or less per m ² of the light-sensitive material. In this case, it indicates the maximum value of the sulfite ion concentration within a range that does not change the photographic characteristics.

More preferably, it does not contain any sulfite ions. However, in the present invention, a very small amount of sulfite ion used for preventing the oxidation of the kit of the processing agent in which the developing agent is concentrated before preparing the working solution is excluded.

It is necessary that the developer used in the present invention does not substantially contain sulfite ions, but it is more preferable that the developer does not substantially contain hydroxylamine. This is because hydroxylamine is a preservative of the developer and has silver developing activity at the same time, and it is considered that the fluctuation in the concentration of hydroxylamine greatly affects photographic characteristics. The term "substantially free of hydroxylamine" as used herein means that the developer contains not more than 5.times.10.sup.- ³ mol / l per developer.

The method of the present invention is highly effective when applied to continuous processing. Here, continuous processing refers to continuous processing while maintaining processability constant using means for adding a replenisher to the fatigue of the processing liquid accompanying the development processing.

The light-sensitive material used in the present invention needs to have at least one high chloride silver halide emulsion composed of 80 mol% or more of silver chloride, and the coated silver amount is 0.80 g / m 2 as silver amount. ^When it is ² or less, it is very preferable in terms of rapidity in the development processing and prevention of the above-mentioned suspended matter generation.

In the present invention, it is necessary that the color developer does not substantially contain sulfite ions. However, in order to suppress the deterioration of the developer, the developer is not used for a long time, and the color developer is floated in order to suppress the influence of air oxidation. Physical means such as using pigs or reducing the degree of opening of the developing tank, chemical means such as suppressing the temperature of the developing solution, and adding an organic preservative 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, organic compounds having a function of preventing oxidation of a color developing agent by air or the like, among which hydroxylamine derivatives (excluding hydroxylamine; the same applies hereinafter), hydroxamic acids, hydrazines, hydrazides, phenols, α-hydroxy ketones, α-amino ketones, sugars, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, fused amines It is a particularly effective organic preservative. These are disclosed in Japanese Patent Application Nos. 61-147823, 61-173595 and 61-173595.
-165621, 61-1888619, 61-197760, 61-
186561, 61-198987, 61-201861, 61-18
Nos. 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.

With respect to the preferred organic preservatives, general formulas and specific compounds 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 / 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 a hydroxylamine derivative and / or a hydrazine derivative is preferable.

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

General formula (II) 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 are not hydrogen atoms at the same time and may be linked to each other to form a heterocyclic ring together with the nitrogen atom. The ring structure of the hetero ring is a 5- to 6-membered ring and is constituted by a carbon atom, 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 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 hetero ring formed by linking R ¹¹ and R ¹² include a piperidyl group, a pyrrolidyl group, an N-alkylpiperazyl group, a morpholyl group, an indolinyl group, and a benzotriazole 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 example The following are preferred as hydrazines and hydrazides.

General formula (III) 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 is a hydroxy group, a hydroxyamino group, a substituted or unsubstituted group, Represents an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a carbamoyl group, or an amino group. The heterocyclic group is a 5- to 6-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 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 the general formula (III), R ³¹ , R ³² and R ³³ represent a hydrogen atom or C ₁ to
Preferably represents an alkyl group of C _10, in particular R ^31, R ³²
Is most preferably a hydrogen atom.

In the general formula (III), 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. Here, preferable substituents of the alkyl group include a carboxysyl group, a sulfo group, a nitro group, an amino group and a phosphono group. X ³¹ is preferably —CO— or —SO ₂ —, and most preferably —CO—.

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

General formula (IV) 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 preferred. Examples of the substituent include a hydroxyl group, a sulfo group, a carboxyl group, a halogen atom, a nitro group, an amino group, and the like.

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

Here, R ¹ and R ² may be the same or different from each other.

Of the general formula (V), particularly preferred are those of the general formula (V
-A) and (Vb).

In the formula, X ¹ represents N or CH. R ¹ and R ² are defined as in general formula (V), and R ³ is the same group as R ¹ and R ² , or Represents

In the general formula (Va), X ¹ is preferably N. The number of carbon atoms of R ¹ , R ² and R ³ is preferably 6 or less, more preferably 3 or less, and most preferably 2.

R ¹ , R ² and R ³ are preferably an alkylene group or an arylene group, and most preferably an alkylene group.

In the formula, R ¹ and R ² are defined as in the general formula (V).

In the general formula (Vb), it is preferable that R ¹ and R ² have 6 or less carbon atoms. R ¹ and R ² are preferably an alkylene group or an arylene group, and most preferably an alkylene group.

Among the compounds of the general formulas (Va) and (Vb), the compound represented by the general formula (Va) is particularly preferable.

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

Next, the sensitizing dye represented by formula (I) will be described in detail.

In particular, it is noteworthy that the use of the sensitizing dye of the general formula (I) markedly improved the photographic characteristics during continuous processing due to low replenishment, and reduced residual color even in rapid processing. .

The sensitizing dye represented by formula (I) is preferably used for a green-sensitive emulsion layer.

General formula [I] Where Z₁And Z_TwoIs benzene fused to each heterocycle
List the atoms required to form a ring or naphthalene ring.
You. The heterocyclic nucleus formed may be substituted with a substituent.
No. R₁And R_TwoEach represents an alkyl group; R_ThreeIs hydrogen field
And represents an alkyl group having 1 to 3 carbon atoms. X₁ Is shade
Represents on and p represents 0 or 1. Y₁And Y_TwoIs oxygen source
Atom, sulfur atom, selenium atom, nitrogen atom and terium atom
Represents

Preferred substituents among the substituents for the formed heterocyclic nucleus are a halogen atom, an aryl group, an alkenyl group,
An alkyl group and an alkoxy group. More preferred substituents are a halogen atom, a phenyl group and a methoxy group,
The most preferred substituent is a phenyl group.

Preferably, Z ₁ and Z ₂ are both a benzene ring or a thiazole ring fused to an oxazole ring, and at least one of these benzene rings is substituted with a phenyl group at the 5-position, or one of the benzene rings The 5-position is substituted with a phenyl group, and the 5-position of another benzene ring is substituted with a halogen atom. R ₁ and R ₂ are each an alkyl group, preferably each is an alkyl group substituted with a carboxyl group or a sulfo group, most preferably a sulfoalkyl group having 1 to 4 carbon atoms, and most preferably a sulfoethyl group. Group. R ₃ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, preferably a hydrogen atom or an ethyl group.

The sensitizing dye represented by the general formula [1] used in the present invention can be used as a so-called supersensitizing combination in combination with another sensitizing dye. In this case, the respective sensitizing dyes may be dissolved in the same or different solvents, and these solutions may be mixed or separately added to the emulsion prior to addition to the emulsion. When they are added separately, their order and time interval can be arbitrarily determined according to the purpose.

Specific compounds of the sensitizing dye represented by the general formula [I] are shown below, but the sensitizing dye used in the present invention is not limited to these compounds.

Usually, in order to spectrally sensitize a silver halide emulsion, a method is used in which after a grain is completely formed, a spectral sensitizing dye is adsorbed on the surface of the grain. In contrast, U.S. Pat.No. 2,735,766 discloses a method of adding a merocyanine dye during precipitation of silver halide grains, which describes that non-adsorbed dyes can be reduced. . Japanese Patent Application Laid-Open No. 55-26589 discloses a method in which a silver sensitizing dye is added during the addition of an aqueous solution of a silver salt or an aqueous solution of a halogen salt to form silver halide crystal grains and is adsorbed. Thus, the spectral sensitizing dye may be added during the formation of the silver halide crystal grains, after the formation is completed, or even before the formation is started. Specifically, "before the start of formation" means that a spectral sensitizing dye is introduced into a reaction vessel in advance before the reaction for forming a silver halide crystal is started. The term “after the formation of particles” means that the particles are added and adsorbed after the substantial particle formation process is completed. The silver halide emulsion of the present invention is chemically sensitized after the completion of the grain formation, and the addition of the spectral sensitizing dye after the completion of the grain formation, even before the start of such chemical sensitization, may be carried out during the chemical sensitization. Or after completion of chemical sensitization or when the emulsion is subjected to coating. In the present invention, it is preferable that the above-mentioned addition of the spectral sensitizing dye is added and adsorbed in at least one step of any step after the step in which the formation of silver halide grains is substantially completed. The addition may be carried out over two or more steps or in portions. Further, in one step, the addition may be intensively performed in a short time, or may be continuously performed over a long time. Some of these addition methods may be combined.

The spectral sensitizing dye to be added may be added as it is as a crystal or powder, but it is preferable to add it by dissolving or dispersing it by any method. 1 carbon to dissolve
Or a water-soluble solvent such as alcohol, acetone, pyridine and methyl cellosolve, or a mixed solvent thereof. Also, micelle dispersion or other dispersion can be carried out using a surfactant.

Although the amount of the spectral sensitizing dye to be added depends on the purpose of spectral sensitization and the content of the silver halide emulsion, it is usually from 1 × 10 ^-6 mol to 1 × 10 ⁶ mol per mol of silver halide. ^-2 mol, more preferably 1 × 10 ^-5 to 5 × 10 ^-3 mol is added.

The spectral sensitizing dyes used in the present invention may be used alone or in combination of two or more. Including a dye that has no spectral sensitizing effect by itself with the spectral sensitizing dye, or a supersensitizer that has no substantial absorption in the visible region but enhances the sensitizing effect of the spectral sensitizing dye Is also good.

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, representative examples of which are shown below, but are 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 4-4 4-amino-3-methyl-N-ethyl-N-
(Β-methanesulfonamidoethyl) -aniline Further, these p-phenylenediamine derivatives may be salts such as sulfate, hydrochloride, p-toluenesulfonate and the like. The amount of the aromatic primary amine developing agent used is preferably about 0.1 g to 20 g, more preferably about 0.5 to about 10 g, per developing solution.

The color developer used in the present invention 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 is preferably at least 0.1 mol / l, particularly preferably from 0.1 mol / l to 0.4 mol / l.

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, N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid, 1,3- Diamino-2-propanoltetraacetic acid, transcyclohexanediaminetetraacetic acid, nitrilotripropionic acid, 1,2-
Diaminopropanetetraacetic acid, hydroxyethyliminodiacetic acid, glycol etherdiaminetetraacetic acid, hydroxyethylenediaminetriacetic acid, ethylenediamineorthohydroxyphenylacetic 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-sulfosalicylic acid, 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. For example, 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 by 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 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 as required. As the antifoggant, alkali metal halides such as sodium chloride, potassium bromide and potassium iodide and organic antifoggants can be used. Examples of organic antifoggants include benzotriazole, 6
-Nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2
Nitrogen-containing heterocyclic compounds such as -thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine and adenine can be mentioned as typical examples.

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 / l, preferably 0.1 to 6 g / l.

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

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

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 agent used in the bleach-fixing solution or 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; It is a thioether compound such as bisthioglycolic acid and 3,6-dithia-1,8-octanediol and a water-soluble silver halide dissolving agent such as thioureas. These may be used alone or in combination of two or more. can do. 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 10 are preferable, and 5 to 9 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 / l, more preferably 0.04 to 0.40 mol / l.

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 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. Of these, the relationship between the number of washing tanks and water volume in the multi-stage countercurrent method is described in the Journal of the Society of Motion Picture and Television Engineers (Journal of the Society of Motion Picture and
Terevision Engineers), Vol. 64, pp. 248-253 (May, 1955).

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 antifungal technology of microorganisms" edited by the Sanitary Technology Association, and "Encyclopedia of Antifungal and Antifungal Agents" 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, the application, and the like, but in general, the range is 20 seconds to 10 minutes at 15 to 45 ° C, preferably 30 seconds to 5 minutes at 25 to 40 ° C. Is done.

Further, the light-sensitive material of the present invention can be processed directly with a stabilizing solution instead of the washing with water. In such 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 developing solution 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 4 minutes or less.

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

The silver halide emulsion of the present invention consists essentially of silver chloride. Here, "substantially" means that the content of silver chloride is at least 80 mol%, preferably at least 95 mol%, more preferably at least 98 mol%, based on the total silver halide amount. From the viewpoint of rapidity, the higher the silver chloride content, the better. The high silver chloride of the present invention may contain a small amount of silver bromide or silver iodide. This may increase the amount of light absorption in terms of photosensitivity, enhance the adsorption of spectral sensitizing dyes, or reduce the desensitization due to spectral sensitizing dyes, and there are many useful points. Similarly, the silver composition of the other emulsion layer not containing the sensitizing dye of the formula (I) is also
Molar% or more is preferred.

The coated silver amount of the silver halide emulsion of the present invention is preferably 0.75 g / m ² or less and 0.3 g / m ² or more in terms of silver amount. Silver coating amount
When it is 0.8 g / m ² or less, it is very preferable in terms of quickness and prevention of the occurrence of stain.

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, a multiphase structure having a bonding structure, or a whole grain. It may consist of a homogeneous phase. 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 silver halide may be fine grains having a grain size of about 0.2 μm or less or large grains having a projected area diameter of about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion.

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

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

Tabular grains having an aspect ratio of about 5 or more can also be used in the present invention. Tabular grains are described in Gatoff, Gutoff, Photographic Science and Engineerin.
g), 14, 248-257 (1970); U.S. Pat.
4,226, 4,414,310, 4,433,048, 4,439,520
And British Patent No. 2,112,157.

The crystal structure may be uniform, the inside and the outside may be composed of different halogen compositions, or may have a layered structure. Further, silver halides having different compositions may be joined by an epitaxial junction, or may be joined to a compound other than silver halide, such as, for example, rhodan silver or lead oxide.

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

As the silver halide emulsion, usually, those subjected to physical ripening, chemical ripening and spectral sensitization are used. The additive used in such a process is Research Disclosure No. 1
7643 and No. 18716, and the relevant portions are summarized in the table below.

Known photographic additives which 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, and specific examples thereof are described in the patents described in the aforementioned Research Disclosure (RD) No. 17643, VII-CG.

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

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

Cyan couplers include phenolic and naphthol couplers, U.S. Pat.Nos. 4,052,212, 4,146,396, 4,228,233, 4,296,200,
No. 2,369,929, No. 2,801,171, No. 2,772,162
No. 2,895,826, No. 3,772,02, No. 3,758,308
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. 3,4
No. 46,622, No. 4,333,999, No. 4,451,559, No. 4,
427,767 and EP 161,626A are preferred.

Colored couplers for correcting unwanted absorption of coloring dyes are described in Research Disclosure No.17643 VII.
Section G, U.S. Pat.No. 4,163,670, JP-B-57-39413,
U.S. Pat.Nos. 4,004,929 and 4,138,258; British Patent No.
Those described in 1,146,368 are preferred.

As a coupler in which the coloring dye has an appropriate diffusivity,
Preferred are 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 (Published) No. 3,234,533.

Typical examples of polymerized dye-forming couplers include U.S. Patent Nos. 3,451,820, 4,080,211 and 4,367,282.
And British Patent No. 2,102,173.

Couplers that release a photographically useful residue upon coupling can also be preferably used in the present invention. DIR couplers that release development inhibitors are described in RD17643, VII-F above.
Patents, JP-A-57-151944 and JP-A-57-1542
Nos. 34, 60-184248 and U.S. Pat. No. 4,248,962 are preferred.

Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include UK Patent Nos. 2,097,140 and 2,1
No. 31,188, JP-A Nos. 59-157638 and 59-170840 are preferred.

In addition, as couplers that can be used in the light-sensitive material of the present invention, competitive couplers described in U.S. Pat.No. 4,130,427, U.S. Pat.Nos. 4,283,472 and 4,338,393,
No. 4,310,618 and the like, multi-equivalent couplers described in
And DIR redox compound releasing couplers described in, for example, JP-A-185950, and couplers that release dyes that recolor after release as described in EP 173,302A.

The coupler used in the present invention can be introduced into a 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 U.S. Pat. No. 4,199,363 and West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.

Suitable supports that can be used in the present invention include, for example, those described above.
From page 28 of RD.No.17643, and from the right column of page 647 of No.18716
It is described in the left column on page 648.

Next, preferred embodiments of the present invention will be described below.

(1) The processing method according to claim 1, wherein the color developer contains substantially no hydroxylamine.

(2) A processing step in which bleach-fixing processing is performed after a color developing step, followed by washing and / or stabilizing processing, wherein the total processing time is 4 minutes 30 seconds or less. 2. The method for processing a silver halide color photographic light-sensitive material according to claim 1.

(Examples) Examples of the present invention will be specifically described below, but the present invention is not limited thereto.

(Effects of the Invention) According to the method of the present invention, the replenishment amount of the color developer can be remarkably reduced without impairing the processing speed, and the photographic characteristics, especially the minimum density, the maximum density, and the gradation change during continuous processing are small. An excellent effect that a developing process can be performed is exhibited. Further, according to the method of the present invention, the replenishment amount of the color developing solution can be remarkably reduced by using a high silver chloride photosensitive material, and the developing process can be performed without generating floating matters in the developing solution during continuous processing.

(Examples) Examples of the present invention will be specifically described below, but the present invention is not limited thereto.

Example 1 A multilayer color photographic paper A having the following layer constitution was produced on a paper support laminated on both sides with polyethylene.

The coating solution is prepared by mixing and dissolving an emulsion, various chemicals, and an emulsified dispersion of a coupler. The respective preparation methods are described below.

Preparation of coupler emulsion 19.1 g of yellow coupler (ExY) and color image stabilizer (Cp
d-1) In 4.4 g, 27.2 cc of ethyl acetate and a solvent (Solv-
1) 7.7 cc was added and dissolved, and this solution was emulsified and dispersed in 185 cc of a 10% aqueous gelatin solution containing 8 cc of 10% sodium dodecylbenzenesulfonate.

Hereinafter, magenta, cyan, and emulsions for the intermediate layer were prepared according to this method.

 The compounds used for each emulsion are shown below.

(Solv-2) Solvent O = PO-C ₈ H ₁₇ ) ₃ (Solv-3) Solvent O = PO-C ₉ H ₁₉ (iso)) ₃ The following dyes were added to the emulsion layer to prevent irradiation.

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

Next, a method of preparing an emulsion used in this example will be described.

Blue-sensitive emulsion (1 liquid) H ₂ O 1000cc NaCl 5.5g gelatin 32 g (2 solution) sulfuric acid (1N) 24 cc (3 solution) the following compound A (1%) 3 cc (4 solution) NaCl 1.7g H ₂ O was added 200 cc (5 solution) AgNO ₃ 5g H ₂ O was added 200 cc (6 _{solution) NaCl 41.3g K 2 IrCl 6 (} 0.001%) 0.5cc H 2 O was added Then, 600 cc (solution 7) of AgNO ₃ 120 g H ₂ O was added, 600 cc (solution 1) was heated to 76 ° C., and (solution 2) and (solution 3) were added.

Thereafter, (liquid 4) and (liquid 5) were added simultaneously for 10 minutes.

After another 10 minutes, (Sixth solution) and (Sixth solution) were simultaneously added for 35 minutes. Five minutes after the addition, the temperature was lowered and desalted. Water and dispersed gelatin were added to adjust the pH to 6.3 to obtain a monodispersed cubic silver chloride emulsion having an average grain size of 1.1 μm and a coefficient of variation (standard deviation divided by average grain size: s / d) of 0.10.

To 1.0 kg of this emulsion was added a spectral sensitizing dye for blue (S-1).
26 cc of a 0.6% solution was added, and a 0.05 μg AgBr ultrafine grain emulsion was added at a ratio of 0.5 mol% to the host AgCl emulsion, followed by mixing and ripening at 58 ° C. for 10 minutes. Thereafter, sodium thiosulfate was added, the chemical sensitization was optimally performed, and a stabilizer (Stb-1) was added at 10 ^-4 mol / mol Ag.

Green-sensitive emulsion (8 fluid) H ₂ O 1000ml NaCl 3.3g gelatin 32 g (9 solution) sulfuric acid (1N) 24 ml (10 Solution) Compound A (1%) 3 ml (11 solution) was added to NaCl 11.00g H ₂ O 200ml (12 solution) AgNO ₃ 32.00g H ₂ O were added 200 ml (13 _{fluid) NaCl 44.00g K 2 IrCl 6 (} 0.001%) 2.3ml H 2 O was added 560 ml (14 fluid) AgNO ₃ 128g H ₂ O In addition, 560 ml (8 solutions) was heated to 52 ° C., and (9 solutions) and (10 solutions) were added. Thereafter, (solution 11) and (solution 12) were added simultaneously for 14 minutes. After another 10 minutes, (solution 13) and (solution 14) were added simultaneously for 15 minutes.

A sensitizing dye (S-2) was added to this emulsion in an amount of 1 mol of silver halide.
4 × 10 ^-4 mol / mol, and then the following (liquid 15) was added over 10 minutes, and 5 minutes after the addition, the temperature was lowered to desalinate.

Add water and disperse gelatin, adjust pH to 6.2, (15 solutions) KBr 5.60 g H ₂ O, 280 ml Add sodium thiosulfate at 58 ° C, perform optimal chemical sensitization, average particle size 0.48 A monodisperse cubic silver chloride emulsion having a μm of 0.10 and a coefficient of variation (standard deviation divided by average grain size; s / d) of 0.10 was obtained.

Further, (Stb-1) was used as a stabilizer in an amount of 1 mol of silver halide.
5 × 10 ^-4 mol / mol.

The red-sensitive emulsion was prepared in exactly the same manner as in the preparation of the green-sensitive emulsion except that the sensitizing dye used was changed to (S-3) and the added amount was 1.5 × 10 ^-4 mol per mol of silver halide. Was prepared.

 Next, the compounds used are shown.

(S-1) Sensitizing dye (S-2) Sensitizing dye (chemical metal I-31) (S-3) Sensitizing dye (Stb-1) Stabilizer (Layer Configuration) The composition of each layer in this sample (multilayer color photographic paper) is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents a coated 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 halide emulsion 0.25 Gelatin 1.86 Yellow coupler (ExY) 0.82 Color image stabilizer (Cpd-1) 0.19 Solvent (Solv-1) 0.35 Second layer (color mixture prevention layer) Gelatin 0.99 Color mixture prevention (Cpd-2) 0.08 Third layer (green sensitive layer) Silver halide emulsion 0.31 Gelatin 1.24 Magenta coupler (ExM) 0.60 Color image stabilizer (Cpd-3) 0.25 Color image stabilizer (Cpd-4) 0.12 Solvent (Solv-2) 0.42 Fourth layer (ultraviolet absorbing layer) Gelatin 1.58 Ultraviolet absorber (UV-1) 0.62 Color mixing inhibitor (Cpd-5) 0.05 Solvent (Solv-3) 0.24 Fifth layer (red-sensitive layer) Silver halide emulsion 0.21 Gelatin 1.34 Cyan coupler (Blend of ExC1 and C2,1: 1) 0.34 Color image stability Agent (Cpd-6) 0.17 Polymer (Cpd-7) 0.40 Solvent (Solv-4) 0.23 6th layer (ultraviolet absorbing layer) Gelatin 0.53 Ultraviolet absorber (UV-1) 0.21 Solvent (Solv-3) 0.08 7th layer (protective layer) Gelatin 1.33 Acrylic modified copolymer of polyvinyl alcohol (degree of modification)
17%) 0.17 Liquid paraffin 0.03 1-oxy-3,5-dichloro-s-triazine sodium salt was used as a hardening agent for each layer.

The sample obtained as described above was designated as A. Next, the sensitizing dye (S-2, I) used for the green sensitive layer used for Sample A was used.
Sample B, except that -31) was changed as follows.
C, D, E, and F were created.

Sample B I-4 Sample C I-6 Sample D I-19 The following experiments were performed to examine the photographic characteristics of these coated samples.

First, the coated sample was subjected to sensitometric gradation exposure 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 /
The exposure was performed so that the exposure amount was 250 CMS with an exposure time of 10 seconds.

After the imagewise exposure of the above photosensitive material, continuous processing (running test) was performed in the following processing step and the following processing composition until the tank capacity of the color developing solution was replenished twice. However, the composition of the color developer was changed as shown in Table 1 and a running test was performed for each of them.

The sensitometry is performed at the start and end of the running test, and the minimum density (Dmin) and maximum density (Dmax) of blue (B) and the gradation (from the point of density 0.5)
The change in the ogE due to continuous processing (density difference up to the 0.3 density point on the high exposure side) was measured using a Macbeth densitometer, and the results are shown in Table 1.

At the same time, the presence of suspended matter in the color developing solution at the end of running was visually checked. The results are shown in Table 1.

The composition of each processing solution is as follows.

Bleach-fix solution (same as tank solution and replenisher) Water 400ml Ammonium thiosulfate (70%) 100ml Sodium sulfite 17g Ammonium iron (III) ethylenediaminetetraacetate 55g Disodium ethylenediaminetetraacetate 5g Ammonium bromide 40g Glacial acetic acid 9g Add water 1000ml pH (25 ℃) 5.40 Rinse solution (tank solution and replenisher are the same) Deionized water (calcium and magnesium are 3ppm or less each) According to Table 1, Sample A using the sensitizing dye of the present invention,
In B, C, and D, the use of the processing of the present invention significantly reduces the change in photographic characteristics during continuous processing, and enables stable photographic performance to be obtained. Low generation of suspended matter.

In particular, the effect is remarkable in the treatment using the organic preservative of the present invention.

(Example 2) In Example 1, the organic preservative II-1 was replaced with II- in the treatment.
Sample A was processed in the same manner as in Example 1 except that II, III-5, III-15, III-16, and III-21 were used. was gotten.

(Example-3) Silver halide emulsion of blue-sensitive silver halide emulsion layer (1)
Was prepared as follows.

(2 liquids) Sulfuric acid (1N) 20cc (3 liquids) The following compound (1%) 3cc (Liquid 1) was heated to 60 ° C, and (Liquid 2) and (Liquid 3) were added. Thereafter, (liquid 4) and (liquid 5) were added simultaneously for 60 minutes. 10 minutes after the addition of (liquid 4) and (liquid 5),
(Sixth solution) and (Sixth solution) were simultaneously added over 25 minutes. Five minutes after the addition, the temperature was lowered and desalted. Water and dispersed gelatin were added, the pH was adjusted to 6.0, and the average particle size variation coefficient was 1.0 μm (standard deviation divided by average particle size; s /) 0.1
1. A monodispersed cubic silver chlorobromide emulsion containing 1 mol% of silver bromide was obtained. Triethylthiourea was added to this emulsion to perform optimum chemical sensitization. Thereafter, the following spectral sensitizing dye (Se
n-1) was added in an amount of ^{7.times.10.sup.-4} mol per mol of the silver halide emulsion.

Silver halide emulsion of green-sensitive silver halide emulsion layer (2)
The silver halide emulsion (3) of the red-sensitive silver halide emulsion layer was prepared in the same manner as described above, except that the amount of the chemical, the temperature and the addition time were changed.

For the silver halide emulsion (2), a spectral sensitizing dye (Sen
-2, modified as shown in Table 2) was added in an amount of 5 × 10 ^-4 mol per mol of the emulsion. For the silver halide emulsion (3), the spectral sensitizing dye (Sen-3) was added to the emulsion 1. 0.9 × per mole
10 ^-4 mol was added.

The shapes, average grain sizes, halogen compositions and variation coefficients of the silver halide emulsions (1) to (3) are as shown below.

(Sen-2) See Table 2 Using the prepared silver halide emulsions (1) to (3),
A multilayer color photographic light-sensitive material having the following layer structure was prepared. The coating solution was prepared as follows.

First Layer Coating Solution Preparation Solution 27.2 cc of ethyl acetate and 3.8 cc of a solvent (Solv-1) were added to 19.1 g of Yellow Coupler (ExY) and dissolved.
10% containing 8cc of 0% sodium dodecylbenzenesulfonate
It was emulsified and dispersed in 185 cc of an aqueous solution of gelatin at 185%. On the other hand, a blue-sensitive sensitizing dye (Sen-1) was added to silver halide emulsion (1).
A solution prepared by adding 5.0 × 10 ⁻⁴ mol per mol was prepared. The emulsified dispersion and the 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 a gelatin hardener for each layer, 1-oxy-3,5-
Dichloro-s-triazine sodium salt was used.

The following compounds were added to the red-sensitive emulsion layer in an amount of 1.9 × 10 ⁻³ mol per mol of silver halide.

Further, to the blue-sensitive emulsion layer, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added in an amount of 1.0 × 10 ^-2 mol per mol of silver halide.

Also, the blue-sensitive emulsion layer and the green-sensitive emulsion layer are
(5-methylureidophenyl) -5-mercaptotetrazole was added in an amount of 1.0 × 10 5 per mol of silver halide.
^-3 mol and 1.5 × 10 ^-3 mol were added.

To the red-sensitive emulsion layer, 2.5.times.10.sup.- ⁴ mol of 2-amino-5-mercapto-1,3,4-thiadiazole was added per mol of silver halide.

 The composition of each layer is shown below.

(Layer composition) Support A paper support laminated on both sides with polyethylene [The first layer of polyethylene contains a white pigment: TiO ₂ (2.7 g / m ² ) and a bluish dye (ultramarine)] Layer) Silver halide emulsion (1) 0.26 Gelatin 1.13 Yellow coupler (ExY) 0.66 Solvent (Solv-1) 0.28 Second layer (Color mixture prevention layer) Gelatin 0.89 Color mixture inhibitor (Cpd-1) 0.08 Solvent (Solv-1) 0.20 Solvent (Solv-2) 0.20 Dye (T-1) 0.005 Third layer (green sensitive layer) Silver halide emulsion (2) See Table 2 Gelatin 0.99 Magenta coupler (ExM-1) 0.25 Color image stabilizer (Cpd) -2) 0.10 Color image stabilizer (Cpd-3) 0.05 Color image stabilizer (Cpd-4) 0.07 Color image stabilizer (Cpd-5) 0.01 Solvent (Solv-2) 0.19 Solvent (Solv-3) 0.15 Fourth Layer (UV absorption layer) Gelatin 1.42 UV absorber (UV-1) 0.52 Color mixture inhibitor (Cpd-1) 0.06 Solvent (Solv) 4) 0.26 Dye (T-2) 0.015 Fifth layer (red-sensitive layer) Silver halide emulsion (3) 0.22 Gelatin 1.06 Cyan coupler (ExC-1) 0.16〃 (ExC-2) 0.13 Color image stabilizer (Cpd- 6) 0.32 Color image stabilizer (Cpd-7) 0.18 Solvent (Solv-4) 0.10 Solvent (Solv-5) 0.10 Solvent (Solv-6) 0.11 Sixth layer (ultraviolet absorbing layer) Gelatin 0.48 Ultraviolet absorbing layer (UV- 1) 0.18 Solvent (Solv-4) 0.08 Dye (T-2) 0.005 7th layer (protective layer) Gelatin 1.33 Acrylic modified copolymer of polyvinyl alcohol (degree of modification 17%) 0.05 Liquid paraffin 0.03 The structure of the compound used is as follows.

(Solv-4) Solvent O = PO-C ₉ H ₁₉ -iso) ₃ Samples 201, 202, 203, 204 and 205 were prepared by changing the amounts of the sensitizing dye and the coated silver in the green sensitive layer as shown in the following table.

After imagewise exposure of Samples 201 to 205, continuous processing (running test) was performed using a paper processing machine until the replenishment was twice as large as the color development tank capacity in the following processing steps.

The composition of each processing solution is as follows.

Bleach-fix solution (same as tank solution and replenisher) Water 400ml Ammonium thiosulfate (70%) 100ml Sodium sulfite 17g Ammonium iron (III) ethylenediaminetetraacetate 55g Disodium ethylenediaminetetraacetate 5g Glacial acetic acid 9g Add water 1000ml pH (25 ℃) 5.40 Stabilizer (Tank solution and replenisher are the same) Formalin (37%) 0.1 g Formalin-sulfite adduct 0.7 g 5-Chloro-2-methyl-4-isothiazolin-3-one 0.02 g 2-methyl-4 -Isothiazolin-3-one 0.01 g Copper sulfate 0.005 g Ammonia water (28%) 2.0 ml Add water 1000 ml pH (25 ° C) 4.0 In the same manner as in Example 1, change in Dmin due to running treatment is shown in Table 3. It was shown to.

According to the present invention, the effect of Dmin (increase in stain) due to running is small, and the effect is remarkable particularly in Samples 204 and 205 in which the coated silver amount is 0.8 g / m ² or less.

(Example 4) A running test was performed in the same manner as in Example 3 except that diethylhydroxylamine in the color developer in Example 3 was changed to equimolar compound III-19, and a sample was obtained.
In 204 and 205, the increase in Dmin was remarkably small, and excellent results were obtained.

Claims (1)

(57) [Claims] Claims: 1. A silver halide color photographic light-sensitive material is
Contains at least one aromatic primary amine color developing agent
In the method of continuous processing with a color developing solution,
80 mol% or less of the sensitizing dye represented by the general formula (I) and silver chloride
Having at least one silver halide emulsion contained therein,
0.80g / m silver coating^TwoSilver halide color photo which is
The photosensitive material contains sulfite ions in both tank solution and replenisher solution.
No, and the replenishment amount is 1m^TwoThis
Processing with a color developer that is 120 ml or less.
A method for processing a silver halide color photographic light-sensitive material. General formula [I]Where Z₁And Z_TwoIs a benzene ring fused to each heterocycle
Alternatively, it represents an atomic group necessary for forming a naphthalene ring.
The heterocyclic nucleus formed may be substituted with a substituent. R₁
And R_TwoEach represents an alkyl group; R_ThreeIs a hydrogen atom or
Represents an alkyl group having 1 to 3 carbon atoms. X₁ Is an anion
And p represents 0 or 1. Y₁And Y_TwoIs oxygen atom, sulfur
Atom, selenium atom, nitrogen atom and terium atom
You.