JP2522996B2 - Silver halide color-processing method of 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. The present invention relates to a development processing method having excellent desilvering property.

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

Among them, for the purpose of accelerating color development and / or reducing the replenishment amount, a color photographic light-sensitive material containing a silver chloride emulsion in place of the silver bromide emulsion or silver iodide emulsion which has been widely used in the past is processed. It is known how to do it. For example, International Publication WO87 / 04534 describes a method of rapidly processing a high silver chloride silver halide color photographic light-sensitive material with a color developer containing substantially no sulfite ion and benzyl alcohol. However, it has been found that when the developing process is simply performed based on the above method, the minimum density (Dmin) after the process is high and the white background is contaminated.

Further, it has been found that when the high silver chloride color photographic light-sensitive material is rapidly desilvered, defective desilvering occurs.

As described above, in the rapid processing using the high silver chloride color photographic light-sensitive material, the increase of the minimum density (Dmin) accompanying the development processing,
It has become clear that there is a practically serious problem that the white background is significantly contaminated due to the occurrence of so-called stains and the desilvering failure associated with the desilvering process. In a rapid processing method using a high silver chloride color photographic light-sensitive material, JP-A-58-95345 and JP-A-59-232342 have been proposed as a method for suppressing the increase in the minimum density (particularly, fog) generated in the development processing. It is known to use organic antifoggants. However, it has been found that the antifoggant effect is insufficient, and furthermore, the occurrence of defective desilvering associated with the rapid desilvering processing is further increased.

Further, in JP-A-61-70552, a high silver chloride color photographic light-sensitive material is used to add a replenishing amount that does not cause overflow into the developing bath during development to reduce the replenishment of the developing solution. JP-A-63-106655 discloses a silver halide color photographic light-sensitive material in which the silver halide emulsion layer has a high silver chloride content as a hydroxyamine-based compound for the purpose of stabilizing the processing. A method of developing with a color developing solution containing chloride at a predetermined concentration or higher is disclosed.

However, in these methods, the increase in stain and the occurrence of defective desilvering associated with the above-mentioned development processing were recognized, and they were not practically usable.

(Problems to be Solved by the Invention) In the conventional processing of a silver halide color photographic light-sensitive material comprising a high silver chloride emulsion, an increase in the minimum density after processing, that is, an increase in so-called stain is a problem. It is considered that this is due to sensitizing dyes eluted from the light-sensitive material, adhesion of tar components caused by oxidation of dyes and developing agents, and fog. In Japanese Patent Laid-Open No. 63-106655, a specific hydroxyamine compound is used as a preservative in a color developing solution, and the aim is to stabilize the photographic performance even if the replenishment amount is significantly reduced. In terms of preventing stains, it is still unsatisfactory.

On the other hand, if the bleaching of the image silver formed by color development is incomplete due to the formation of silver sulfide, the color of the color photograph (especially noticeable in the yellow part) becomes dark. It has been found that the formation of silver sulfide is remarkable especially in the high silver chloride light-sensitive material. Therefore, the improvement of desilvering property is an important issue, but the method described in JP-A-63-106655 is a process in which a color developing solution containing chloride, which has less inhibitory effect on the stabilized color development, is used for desilvering property. It was not enough in terms of.

Therefore, a first object of the present invention is to use a silver halide color photographic light-sensitive material comprising a high silver chloride emulsion,
Further, it is to provide a processing method in which the maximum density is high and the minimum density is low, and the developability is improved.

A second object of the present invention is to provide a processing method using a high chloride silver halide color photographic light-sensitive material, in which the amount of residual silver is small and the desilvering property is improved.

(Means for Solving the Problems) An object of the present invention is to provide a silver halide color photographic light-sensitive material having a red-sensitive emulsion layer, a green-sensitive emulsion layer and a blue-sensitive emulsion layer with at least one aromatic primary species. In a method of processing with a color developer containing an amine color developing agent, at least one layer has a silver halide emulsion containing 80 mol% or more of silver chloride and the total coated silver amount is 0.80 g / m ² or less. And a silver halide color photographic light-sensitive material containing at least one hardener represented by the following general formula (I) or (II) and having a sulfite ion concentration of 3 × 10 ^-3 mol / l or less. And the chloride ion concentration is 3.5 × 10 ^{-2 to} 1.5 × 10 ^-1 mol / l,
And a processing method of a silver halide color photographic light-sensitive material characterized by processing with a color developer having a bromine ion concentration of 3 × 10 ^-5 to 1 × 10 ^-3 mol / l.

(In the formula, X ₁ is a halogen atom, an N-methylolamino group,
Glycidoxy group, Y ₁ is H, halogen atom, -OH, -OM
(M is an alkali metal ion), an amino group, a substituted amino group (for example, as a substituent, phenyl, sulfonated phenyl, carboxylated phenyl, alkyl, sulfonated alkyl, carboxylated alkyl, hydroxyalkyl), alkyl or phenyl ether group. , An alkyl or phenyl thioether group or a sulfonamide or an alkyl sulfonamide group.

Z ₁ is selected from the same group as Y _1, may be the same or different from Y _1. ) Chloride ion is well known as one of the antifoggants, but its effect is small, and even if used in a large amount, it does not completely prevent the increase of fog, and on the contrary delays the development,
This had the adverse effect of reducing the maximum concentration. It is also known that when a high chloride silver halide light-sensitive material is treated with a developer containing sulfite ions, the color developability is significantly deteriorated due to the action of sulfite ions to dissolve silver halide. There was no fact that fog was suppressed by processing with a non-developing solution. However, when a high silver chloride light-sensitive material using a hardener represented by the general formula (I) or (II) is used, chlorine ions of 3.5 × 10 ^{-2 to} 1.5 × 10 ^-1 mol / l
And the concentration of sulfite ion is 3 × 10 ⁻³ mol / l or less, the minimum concentration is low, and
The fact that the amount of residual silver was small and the developability and desilvering property were significantly improved was unexpected and quite surprising.

Specific examples of the hardeners represented by the general formulas (I) and (II) used in the present invention are listed, but the present invention is not limited thereto.

Specific examples of the compound represented by the general formula (II) used in the present invention are shown below.

Among the compounds represented by the general formula (I) or (II) of the present invention, particularly preferred are compounds in which X ₁ is a chlorine atom.

Although various kinds of Y ₁ can be selected, an alkylamino group or an arylamino group in which a water-soluble group such as -OM (M is an alkali metal ion), a sulfonic acid or a carboxyl group is substituted is preferable.

Particularly preferred compounds are I-1, I-2, I-4, I-
Is 10.

In the present invention, the hardener may be added to the coating solution in advance, or may be mixed with the coating solution immediately before coating.

In the present invention, the hardener may be added to all layers of the photographic layer coated on the support (eg, photosensitive emulsion layer, intermediate layer, surface protective layer, filter layer, etc.), and any layer ( It may be a single layer or plural layers). The amount of hardener added is an amount sufficient to harden gelatin, and 0.5 × 10 ^{−3 to} 100 × 10 per 100 g of gelatin.
^-3 mol, preferably 1.0 x 10 ^-3 to 30 x 10 ^-3 mol is used.

As a result of further earnest research, the present inventors have found that the compound of the general formula (I)
Alternatively, it is unexpected to use a compound having at least two vinylsulfonyl groups in addition to the compound represented by (II), which prevents the occurrence of stain and improves the desilvering property.
It has been found that the strength of the coating film and the hardening speed are preferable.

The compound having at least two vinyl sulfone groups preferably used in the present invention is represented by the following general formula (II
It is a compound represented by I).

Formula _{(III) CH 2 = CHSO 2} -R 11 -SO 2 CH = CH 2 R 11 represents a divalent linking group, the alkylene group or substituted alkylene group (the substituent, a halogen, a hydroxyl group, a hydroxyalkyl Group, an amino group) and may have an amide linking part, an ether linking part or a thioether linking part between them.

In the present invention, the chlorine ion concentration of the color developer is 3.
5 × 10 ^{-2 to} 1.5 × 10 ^-1 mol / l, preferably 4 × 10 ^-2
˜1.0 × 10 ⁻¹ mol / l. Chloride ion concentration is 1.5 × 10 ^-1
When it is more than mol / l, it has a drawback that the developing speed is delayed, and it does not achieve the object of the present invention such as rapidity and high maximum density. If it is less than 3.5 × 10 ^-2 mol / l, the minimum concentration and the amount of residual silver are high, and the effects of the present invention cannot be sufficiently obtained.

Here, chlorine ions may be added directly to the color developing solution or may be eluted from the photosensitive material in the developing solution. When added directly to the color developer, it can be used as a chloride ion supplying substance such as sodium chloride, potassium chloride, ammonium chloride, nickel chloride, magnesium chloride, manganese chloride,
Calcium chloride and cadmium chloride can be mentioned, of which sodium chloride and potassium chloride are preferred. Further, it may be supplied as a counter ion such as an optical brightener added to the developing solution. When it is eluted from the light-sensitive material in the developing solution, it may be supplied from a silver chloride emulsion or a fluorescent whitening agent.

In the present invention, the sulfite ion concentration of the color developer is 3 × 10 ⁻³ mol / l or less, preferably 0 to 1.5.
It is × 10 ^-3 mol / l, and most preferably contains no sulfite ion at all.

When the amount of sulfite ion is 3 × 10 ⁻³ mol / l or more, the increase of stain, particularly the increase of fog, and the desilvering property are deteriorated, and the object of the present invention is not satisfied.

In the present invention, the color developer is 3 × 10 ⁻⁵ to 1 × 10 ^−3.
It is necessary to contain mol / l of bromide ion in order to improve stain and desilvering property. In the presence of bromine ions at a concentration exceeding 1 × 10 ^-3 mol / l, the object of the present invention cannot be achieved in terms of development progress and reduction in maximum concentration. However, the fact that the presence of a trace amount of bromine ions of 3 × 10 ^-5 to 1 × 10 ^-3 mol / l does not have the above-mentioned drawbacks and further improves the stain and desilvering property is unexpected and surprising. there were.

In the present invention, the bromine ion present in the color developing solution may be added directly or may be eluted from the color photographic light-sensitive material.

In the present invention, the color developer contains 3 sulfite ions.
It is necessary to contain substantially no x10 ^-3 mol / l or less, but the developer is not used for a long time to suppress the deterioration of the developer, and a floating pig is used to suppress the influence of air oxidation. Alternatively, a physical means such as reducing the opening degree of the developing tank may be used, a developing means temperature may be suppressed, an organic preservative may be added, or a chemical means may be used. Among them, the method using an organic preservative is advantageous from the viewpoint of simplicity.

The organic preservative described in the present invention refers to all organic compounds that reduce the deterioration rate of an aromatic primary amine color developing agent by being added to a processing solution of a color photographic light-sensitive material. That is, although it is an organic compound having a function of preventing the oxidation of the color developing agent due to air or the like, among them, a hydroxylamine derivative (excluding hydroxylamine; hereinafter the same), hydroxamic acids, hydrazines, hydrazides, noenols, Particularly, α-hydroxyketones, α-aminoketones, saccharides, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, condensed amines, etc. It is an effective organic preservative. These are Japanese Patent Application No. 61-147823, Japanese Patent Application Laid-Open Nos. 63-30845 and 63-21.
No. 647, No. 63-44655, Japanese Patent Application No. 61-197760, JP-A No. 63-4
No. 3140, Japanese Patent Application No. 61-198987, No. 61-201861, Japanese Patent Laid-Open No. 63
-43138, European Patent Publication 254280, JP-A-63-44657,
63-44656, U.S. Pat.Nos. 3,615,503 and 2,494,903.
And JP-A-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 preferable to add it at a concentration of / l.

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

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

General formula (IV) 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 (V) 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 Represents a divalent group selected from, and n is 0 or 1. In particular, when n = 0, R ³⁴ represents a group selected from an alkyl group, an aryl group, and a heterocyclic group, and R ³³ and R ³⁴ may form a heterocyclic ring together.

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

In the general formula (V), 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) V-2 NH ₂ NHCH _{2 4} SO ₃ H V-3 NH ₂ NHCH _{2 2} OH _{V-6 NH 2 NHCOCH 3 V} -7 NH 2 NHCOOC 2 H 5 V-10 NH ₂ NHCONH ₂ V-12 NH ₂ NHSO ₃ H V-14 NH ₂ NHCOCONHNH ₂ V-15 NH ₂ NHCH ₂ CH ₂ CH ₂ SO ₃ H V-18 NH ₂ NHCH ₂ CH ₂ COOH The combined use of the compound represented by the general formula (IV) or (V) and the amine represented by the following general formula (VI) or (VII) improves the stability of the color developer. Is more preferable from the viewpoint of improving stability during continuous treatment.

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

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

(Example of compound) VI-1 NCH ₂ CH ₂ OH) ₃ VI-2 H ₂ NCH ₂ CH ₂ OH VI-3 HNCH ₂ CH ₂ OH) ₂ VI-10 (HOCH ₂ CH _{2 2} NCH ₂ CH ₂ SO ₂ CH ₃ VI-11 NHCH ₂ COOH) ₂ VI-13 H ₂ NCH ₂ CH ₂ SO ₂ NH ₂ VI-15 H ₂ N-CCH ₂ OH) ₂ General formula (VII) 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.

Among the general formula (VII), particularly preferred are those represented by the general formula (V
II-a) and (VII-b).

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

In general formula (VII-a), 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 (VII).

In general formula (VII-6), it is preferable that R ¹ and R ^{2 each} 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 (VII-a) and (VII-b), the compound represented by the general formula (VII-a) is particularly preferable.

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

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

The color developing solution used in the present invention contains a known aromatic primary amine color developing agent. A preferred example is p-phenylenediamine, 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 D-4 4-amino-3-methyl-N-ethyl-N-
(Β-methanesulfonamidoethyl) -aniline Further, these p-phenylenediamine derivatives may be salts such as sulfate, hydrochloride, p-toluenesulfonate and the like. The amount of the aromatic primary amine developing agent used is preferably about 0.1 g / 20 g, more preferably about 0.5 to about 10 g per developing solution.

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

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

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

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

Specific examples are shown below, but the present invention is not limited thereto. Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, triethylenetetraminehexaacetic acid, N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid, 1,3- Diamino-2-propanoltetraacetic acid, transcyclohexanediaminetetraacetic acid, nitrilotripropionic acid, 1,2-
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, and these chelating agents may be used in combination of two or more, if necessary.

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

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

As a development accelerator, Japanese Examined Patent Publication Nos. 37-16088 and 37-5987
No. 38-7826, No. 44-12380, No. 45-9019, and thioether compounds represented by U.S. Pat. No. 3,813,247, etc., and p-represented by JP-A Nos. 52-49829 and 50-15554. Phenylenediamine compounds, JP-A-50-137726
No. 4, JP-B-44-30074, JP-A-56-156826 and 52-
43429 and the like, quaternary ammonium salts, p-aminophenols described in U.S. Pat. Nos. 2,610,122 and 4,119,462, U.S. Pat. Nos. 2,494,903 and 3,128,182.
No. 4,230,796, 3,253,919, Japanese Patent Publication No. 41-11431
U.S. Pat.Nos. 2,482,546, 2,596,926 and 3,
582,346 and other amine compounds, JP-B-37-16088
No. 42-25201, U.S. Pat.No. 3,128,183, Japanese Patent Publication No. 41-
11431, 42-23883 and U.S. Pat.No. 3,532,501 and other polyalkylene oxides, other 1-phenyl-3-pyrazolidones, hydrazines, mesoionic compounds, ionic compounds, imidazoles, etc. It can be added accordingly.

Preferably, the color developer is substantially free of benzyl alcohol. Substantially means per color developer
The amount is 2.0 ml or less, more preferably, it is not contained at all.
When the content is not substantially contained, the fluctuation of photographic characteristics during continuous processing is small, and more preferable results are obtained.

In the present invention, any antifoggant can be added if necessary. 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 and 6
-Nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2
Typical examples are nitrogen-containing heterocyclic compounds such as -thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine and adenine.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced, but due to the increase in the residence time of water in the tank, bacteria propagate, and the suspended matter produced adheres to the photosensitive material, etc. Problem arises. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, the method for reducing calcium and magnesium described in Japanese Patent Application No. 61-131632 can be used very effectively. Further, isothiazolone compounds and siabendazoles described in JP-A-57-8542, chlorine-based bactericides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc., Hiroshi Horiguchi, "Chemistry of Antibacterial and Antifungal Agents" It is also possible to use the fungicides described in "Microbial Sterilization, Sterilization, and Antifungal Technology" edited by the Society for Hygiene Technology, "Dictionary of Antibacterial and Antifungal Agents" edited by Japan Society for Antibacterial and Antifungal Agents.

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

Further, the light-sensitive material of the present invention can be processed directly with a stabilizing solution instead of the washing with water. In such stabilization treatment, JP-A-57-8543, 58-14834,
59-184343, 60-220345, 60-238832, 60-
239784, 60-239749, 61-4054, 61-118749
All the known methods described in the publications and the like can be used. Especially 1-hydroxyethylidene-1,1-diphosphonic acid, 5-chloro-2-methyl-4-isothiazoline-3
A stabilizing bath containing -one, a bismuth compound, an ammonium compound and the like is preferably used.

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

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

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

The silver halide emulsion of the present invention consists essentially of silver chloride. Here, "substantially" means that the content of silver chloride is at least 80 mol%, preferably at least 95 mol%, more preferably at least 98 mol%, based on the total silver halide amount. From the viewpoint of rapidity, the higher the silver chloride content, the better. The high silver chloride of the present invention may contain a small amount of silver bromide or silver iodide. 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.

The coating silver amount of the silver halide emulsion of the present invention is preferably 0.8 g / m ² or less, more preferably 0.75 g / m ² or less 0.3 as a silver amount.
It is 0 g / m ² or more. When the coating silver amount is 0.80 g / m ² or less,
It is very preferable in terms of quickness and prevention of the stain generation.

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. Moreover, they may be mixed.

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

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

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

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

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), Vol. 14, pp. 248-257 (1970); U.S. Pat. No. 4,43.
4,226, 4,414,310, 4,433,048, 4,439,520
It can be easily prepared by the method described in Japanese Patent No. 2,112,157 and the like.

The crystal structure may be uniform, may have different halogen compositions inside and outside, or may have a layered structure. Further, silver halides having different compositions may be joined by 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 having various crystal forms may be used.

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

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

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

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

As the magenta coupler, 5-pyrazolone-based and pyrazoloazole-based compounds are preferable, and US Patent No. 4,310,
Nos. 619, 4,351,897, EP 73,636, U.S. Pat. Nos. 3,061,432 and 3,725,067, Research Disclosure No. 24220 (June 1984), JP-A-60-33552.
No., Research Disclosure No. 24230 (June 1984)
JP-A-60-43659, U.S. Pat. Nos. 4,500,630 and 4,540,654 are particularly preferable.

Cyan couplers include phenol and naphthol couplers, U.S. Pat.Nos. 4,052,212, 4,146,396, 4,228,233 and 4,296,200,
No. 2,369,929, No. 2,801,171, No. 2,772,162
No. 2, No. 2,895,826, No. 3,772,002, No. 3,758,30
No. 8, No. 4,334,011, No. 4,327,173, West German Patent Publication No. 3,329,729, European Patent No. 121,365A, U.S. Patent No.
Preferred are those described in 3,446,622, 4,333,999, 4,451,559, 4,427,767, EP 161,626A and the like.

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

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

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

Couplers that release a photographically useful residue upon coupling are also preferably used in the present invention. The DIR coupler releasing the development inhibitor is the above-mentioned RD17643, VII-F.
Patents described in paragraphs, JP-A-57-151944 and 57-154234
And Nos. 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 British Patent Nos. 2,097,140 and 2,1.
Those described in 31,188, JP-A-59-157638 and JP-A-59-170840 are preferable.

Other couplers that can be used in the light-sensitive material of the present invention include competitive couplers described in U.S. Pat.No. 4,130,427, U.S. Pat.Nos. 4,283,472, and 4,338,393,
Multi-equivalent couplers described in JP-A No. 4,310,618 and the like, JP-A-60-
Examples thereof include DIR redox compound releasing couplers described in 185950 and the like, couplers releasing a dye that restores color after separation described in EP 173,302A, and the like.

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

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

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

In the present invention, it is preferable to use the following compounds together with the above-mentioned coupler. In particular, it is preferably used in combination with a pyrazoloazole coupler.

That is, the compound (F) that chemically bonds with the aromatic amine-based developing agent remaining after the color development processing to form a chemically inactive and substantially colorless compound and / or the fragrance remaining after the color development processing. 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 in order to prevent stains and other side effects due to the formation of a coloring dye due to the reaction of the coupler with the color developing agent remaining in the film or its oxidant.

The preferred compound (F) has a second-order reaction rate constant k2 with p-anisidine (in trioctyl phosphate at 80 ° C.) of 1.0 l / mol · sec to 1 × 10 ⁻⁵ l / mol · sec. It is a compound that reacts with. The second-order reaction rate constant can be measured by the method described in JP-A-63-158545.

If k2 is larger than this range, the compound itself becomes unstable, and may react with gelatin or water and decompose. On the other hand, if k2 is smaller than this range, the reaction with the residual aromatic amine-based developing agent is slow, and as a result, the side effect of the residual aromatic amine-based developing agent, which is the object of the present invention, may not be prevented.

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

General formula (FI) R1- (A) n-X General formula (FII) In the formula, R1 and R2 each represent an aliphatic group, an aromatic group, or a heterocyclic group. n represents 1 or 0. A represents a group which reacts with an aromatic amine type developing agent to form a chemical bond, and X represents a group which reacts with an aromatic amine type developing agent and leaves. B represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group or a sulfonyl group, and Y accelerates the addition of the aromatic amine developing agent to the compound of the general formula (FII). Represents the group Here, R1 and X, Y and R2 or B may be bonded to each other to form a cyclic structure.

Among the methods of chemically bonding with the residual aromatic amine-based developing agent, representative ones are substitution reaction and addition reaction.

Specific examples of the compounds represented by formulas (FI) and (FII) are described in JP-A-63-158545, JP-A-62-283338, and Japanese Patent Application No.
Those described in the specifications such as 62-158342 and Japanese Patent Application No. 63-18439 are preferable.

On the other hand, a more preferred compound (G) that chemically bonds with the oxidation product of the aromatic amine-based developing agent remaining after color development processing to form a chemically inactive and colorless compound is represented by the following general formula (GI ).

General formula (GI) RZ In 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 (RGPearson,
A group in which et al., J. Am. Chem. Soc., 90 , 319 (1968) is 5 or more, or a group derived therefrom is preferable.

Specific examples of the compound represented by the general formula (GI) are described in European Patent Publication No. 255722, JP-A Nos. 62-143048 and 62-22.
No. 9145, Japanese Patent Application No. 63-18439, No. 63-136724, No. 62-2146
Nos. 81 and 62-158342 are preferred.

Further, details of the combination with the compound (G) and the compound (F) are described in Japanese Patent Application No. 63-18439.

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

(Effect of the Invention) According to the photographic processing method of the present invention, the maximum density is high and the occurrence of stains is prevented even when the silver halide color photographic light-sensitive material comprising a high silver chloride emulsion is used and the development processing is carried out rapidly. It has the excellent effect of

Further, according to the processing method of the present invention, even when rapid processing is performed using a silver halide color photographic material comprising a high silver chloride emulsion, the amount of residual silver is low, the occurrence of defective desilvering is prevented, and desilvering is prevented. It is possible to significantly improve the sex.

According to the processing method of the present invention, a silver halide color photographic light-sensitive material can be developed extremely rapidly (usually 60 seconds or less, and further 45 seconds or less).

(Examples) Examples of the present invention are specifically shown below, but the present invention is not limited thereto.

Reference 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) 4.4 g of ethyl acetate 27.2 cc and 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 for preparing the emulsion used in this reference example will be described.

Blue-sensitive emulsion (Liquid 1) was heated to 76 ° C., and (Liquid 2) and (Liquid 3) were added.

Then, (4 solution) and (5 solution) were added simultaneously spending 10 minutes.

After another 10 minutes, (6 solution) and (7 solution) were added simultaneously spending 35 minutes. Five minutes after the addition, the temperature was lowered and the mixture was desalted. Water and dispersed gelatin were added to adjust the pH to 6.3 to obtain a monodisperse cubic silver chloride emulsion having an average grain size of 1.1 μm and a coefficient of variation (standard deviation divided by the average grain size: s / d) of 0.10.

To 1.0 kg of this emulsion, the blue spectral sensitizing dye (S-1) was added.
26 cc of 0.6% solution was added, and 0.05 μg of AgBr ultrafine grain emulsion was added at a ratio of 0.5 mol% with respect to the host AgCl emulsion, and mixed and aged 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. After that, (11 solution) and (12 solution) were spent for 14 minutes and added simultaneously. 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 per unit was added, and the following (15th solution) was added later for 10 minutes, and 5 minutes after the addition, the temperature was lowered to desalt.

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 coefficient of variation (standard deviation divided by average grain size; s / d) of 0.10 was obtained.

In addition, (Stb-1) was used as a stabilizer in 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.

 The compounds used are shown below.

(Layer Configuration) The composition of each layer in this sample (multilayer color photographic paper) is shown below. Numbers represent coating weight (g / m ² ). The silver halide emulsion represents the coating amount in terms of silver.

Support Polyethylene laminated paper (Polyethylene on the first layer side contains white pigment (TiO ₂ ) and bluish dye (marine 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 mixing prevention layer) Gelatin 0.99 Color mixing 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 (UV absorbing layer) Gelatin 1.58 UV absorber (UV-1 ) 0.62 Anti-color mixing agent (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 Sixth layer (UV absorption layer) Gelatin 0.53 UV absorber (UV-1) 0.21 Solvent (Solv-3) 0.08 Seventh layer (protective layer) Gelatin 1.33 Acrylic modified copolymer of polyvinyl alcohol (Degree of modification 17%) 0.17 Fluid paraffin 0.03 Hardener (I-1) 0.09 The sample obtained as described above was designated as A. Next, Samples B, C, D and E were prepared in the same manner except that the hardener (I-1) used in Sample A was changed as follows.

Sample B I-2 Sample C I-4 Sample D Formaldehyde Sample E Dimethylolurea Samples A, B, C, D and E were stored in an atmosphere of 40 ° C. and 70% RH for 16 hours immediately after coating. The amount of the hardener added to Samples B, C, D and E was adjusted so that the swollen film thickness at that time was almost the same as that of Sample A.

The hardener used was added directly to the coating solution kept at 40 ° C 30 minutes before coating.

The following experiments were conducted 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.

The above sample was processed by the following processing steps and processing compositions. However, the composition of the color developer was changed as shown in Table 1. Processing steps Temperature Time Color developing 38 ° C. 45 seconds blix 30 to 36 ° C. 45 sec Rinse 30 to 37 ° C. 30 sec Rinse 30 to 37 ° C. 30 sec Rinse 30 to 37 ° C. 30 sec Drying 70 to 80 ° C. 60 seconds each processing solution The composition is as follows.

Color developer Water 800ml Ethylenediamine-N, N, N, N-tetramethylenephosphonic acid 3.0g Organic preservative A (IV-1) 0.03mol Sodium chloride See Table 1 Potassium carbonate 25g N-Ethyl-N- (β -Methanesulfonamide
Cyl) -3-methyl-4-aminoaniline sulfate 5.0 g Triethanolamine 10.0 g Optical brightener (4,4'-diaminostilbene type) 2.0 g Sodium sulfite See Table 1 1000 ml pH with water 10.05 Bleach-fixing solution Water 400ml Ammonium thiosulfate (70%) 100ml Sodium sulfite 17g Ethylenediaminetetraacetic acid iron (III) ammonium 55g Ethylenediaminetetraacetic acid disodium 5g Ammonium bromide 40g Glacial acetic acid 9g Water added 1000ml pH (25 ℃ ) 5.40 Rinse solution (tank solution and replenisher are the same) Ion-exchanged water (calcium and magnesium are each 3ppm or less) Blue (B), green (G),
The minimum density (Dmin) of red (R) and the maximum density (Dmax) of blue (B) were measured using a Macbeth densitometer, and the results are shown in Table 1.

At the same time, the photosensitive material was uniformly exposed so as to obtain 90% of developed silver with respect to the coated silver amount, and then this was processed,
The developed silver amount and the residual silver amount were measured by fluorescent X-ray, and the results are shown in Table 1.

According to Table 1, Sample A using the hardener of the present invention,
As can be seen from Experiment Nos. 1 to 6, in B and C, the maximum density is high and the minimum density is very low, and the residual silver amount is small.

Especially, the effect is that the sulfite ion concentration in the developer is 3.0 × 10 ^-2 mol / l or less and the chloride ion concentration is 4 × 10 4.
^It can be seen that it is remarkable in the case of ⁻² to 1 × 10 ⁻¹ mol / l.

Reference Example 2 As in Sample A of Reference Example 1, except that the hardener I-
3 was changed to I-6, I-8, II-1, and II-3, and the developing solution of Experiment No. 1 of the same reference example was used. Few good results were obtained.

Example 1 Using Samples A and D of Reference Example 1, the developability and desilvering property were tested in the same manner as in Reference Example 1.

The composition treatment process of each treatment liquid is as follows. However, the chlorine ion concentration and the bromine ion concentration in the color developing solution were changed as shown in Table 2. Step Temperature Time Color developing 38 ° C. 45 seconds blix 30 to 36 ° C. 45 sec Rinse 30 to 37 ° C. 30 sec Rinse 30 to 37 ° C. 30 sec Rinse 30 to 37 ° C. 30 sec Drying 70 to 80 ° C. 60 seconds Color developer Water 800ml Ethylenediamine-N, N, N, N-tetramethylenephosphonic acid 3.0g Organic preservative A (IV-1) 0.03mol Sodium chloride See Table 2 Potassium bromide See Table 2 Potassium carbonate 25g N-Ethyl-N -(Β-Methanesulfonamide
Cyl) -3-methyl-4-aminoaniline sulfate 5.0 g Triethanolamine 10.0 g Optical brightener (4,4'-diaminostilbene type) 2.0 g Water was added to 1000 ml pH (25 ℃) 10.05 Bleach-fixing Liquid water 400 ml Ammonium thiosulfate (70%) 100 ml Sodium sulfite 17 g Ethylenediaminetetraacetic acid iron (III) ammonium 55 g Ethylenediaminetetraacetic acid disodium 5 g Ammonium bromide 40 g Glacial acetic acid 9 g Water added 1000 ml pH (25 ° C) 5.40 Rinse solution (tank) Solution and replenisher are the same) Ion-exchanged water (calcium and magnesium are each 3ppm or less)
² ) / volume (cm ^-3 )) 0.02 cm ^{-1 in} a container at room temperature 1
After a lapse of months, the change in the minimum density before and after the aging, the maximum density after the aging, and the residual silver amount were measured in the same manner as in Reference Example 1, and the results are shown in Table 2.

According to Table 2, as can be seen from Experiment Nos. 4 to 7 using the treatment of the present invention in Sample A using the hardener of the present invention, the minimum density difference before and after the aging of the color developing solution was very high. Small, high maximum density, improved developability. Further, the amount of residual silver is small and the desilvering property is improved.

According to the present invention, it is found that when the bromine ion concentration in the color developing solution is 3 × 10 ⁻⁵ to 1 × 10 ⁻³ mol / l, it is particularly preferable in terms of prevention of stain generation and reduction of residual silver amount.

Reference Example 3 Samples E to K were prepared in the same manner as Samples A and D of Reference Example 1, except that the halogen composition of the emulsion was changed as shown in Table 3.

As in Reference Example 1, the addition amount of the hardening agent of Samples J and K was adjusted so that the swollen film thickness was almost the same as that of Sample E.

For these coated samples, in the same manner as in Reference Example 1,
Grayscale exposure for sensitometry was applied.

The sample was processed with the following processing steps and the following processing compositions using an automatic developing machine for paper.

 The composition of each processing solution is as follows.

Color developer Water 800 ml Ethylenediamine-N, N, N-N-tetramethylenephosphonic acid 3.0 g Organic preservative A (V-19) 0.03 mol Sodium chloride 3.0 g Potassium carbonate 25 g N-ethyl-N- (β-methane Sulfonamide
Cyl) -3-methyl-4-aminoaniline sulfate 5.0 g Triethanolamine 10.0 g Optical brightener (4,4′-diaminostilbene type) 2.0 g Sodium sulfite See Table 4 1000 ml pH with water ( 10.05 Bleach-fixing solution Water 400ml Ammonium thiosulfate (70%) 100ml Sodium sulfite 17g Ethylenediaminetetraacetic acid iron (III) ammonium 55g Ethylenediaminetetraacetic acid disodium 5g Ammonium bromide 40g Glacial acetic acid 9g Water added 1000ml pH (25 ℃ ) 5.40 Rinse solution (tank solution and replenisher are the same) Ion-exchanged water (calcium and magnesium are each 3ppm or less) Maximum concentration of blue (B) in the above sensitometry (Dma
x) and the minimum density (Dmin) were measured using a Macbeth densitometer, and the results are shown in Table 4.

At the same time, the light-sensitive material was uniformly exposed so as to obtain 90% of developed silver with respect to the coated silver amount, and then processed, and the developed silver amount and the residual silver amount were measured by fluorescent X-ray. Is shown in Table 4.

Reference Example 4 As in Sample E of Reference Example 3, except that the hardener I-3
Was changed to I-5, I-7, I-12, II-5 and treated with the developer of Experiment No. 1 of the same reference example, the maximum density was high, the minimum density was low, and the residual silver Good photographic properties were obtained with a small amount.

Claims (1)

(57) [Claims] 1. A color developer containing a silver halide color photographic light-sensitive material having a red-sensitive emulsion layer, a green-sensitive emulsion layer and a blue-sensitive emulsion layer and containing at least one aromatic primary amine color developing agent. In the method of treating with
At least 1 silver halide emulsion containing 80 mol% or more
Has a total coating silver amount of 0.80 g / m ² or less, and
At least 1 represented by the following general formula (I) or (II)
A silver halide color photographic light-sensitive material containing one type of hardener has a sulfite ion concentration of 3 × 10 ⁻³ mol / l or less and a chlorine ion concentration of 3.5 × 10 ^{−2 to} 1.5 × 10 ^−1. Mol / l,
A method of processing a silver halide color photographic light-sensitive material, which comprises processing with a color developer having a bromine ion concentration of 3 × 10 ⁻⁵ to 1 × 10 ⁻³ mol / l. (In the formula, X ₁ is a halogen atom, an N-methylolamino group,
Glycidoxy group, Y ₁ is H, halogen atom, -OH, -OM
(M is an alkali metal ion), an amino group, a substituted amino group, an alkyl or phenyl ether group, an alkyl or phenyl thioether group, a sulfonamide or an alkyl sulfonamide group. Z ₁ is selected from the same group as Y _1, may be the same or different from Y _1. )