JP2558502B2 - Processing method of silver halide color photographic light-sensitive material - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a silver halide color light-sensitive material, and more particularly to a method for processing a silver halide color light-sensitive material in which the replenishment amount of a color developer is remarkably reduced. About.

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

In color development 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, halogen ions generated by decomposition of silver halide are eluted and accumulated in the developing solution. 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 development finish characteristics due to a change in the component concentration. Means is needed.

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 high. 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. The 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, a reduction in the replenishment amount of the color developer has been strongly desired for the purpose of saving resources and reducing pollution as well as speeding up the development processing. However, if the replenishment amount of the color developing solution is simply reduced, the development activity is lowered and the rapidity is impaired due to the accumulation of eluate from the light-sensitive material, particularly bromine ion which is a strong development inhibitor, and various organic compounds. The problem arises.

As a solution to this, a development accelerating technique is required, and many speeding-up techniques for reducing the replenishment amount of the developer are being studied. For example, as one of the methods, there is known a speeding-up means for increasing the pH and the processing temperature of a color developer to promote development. However, this method has a serious problem that the fog is high, the stability of the developer is deteriorated, and the fluctuation of the photographic characteristics is increased during continuous processing. Further, as another accelerating technique, a method of adding various development accelerators is described, but the accelerating effect is insufficient and it is not satisfactory.

For the purpose of reducing the accumulation of bromine ion, which is a strong development inhibitor, and speeding up the development, JP-A-58-95345 and 59-232
342, 61-70552, and International Publication WO87 / 04534 disclose a method using a silver halide light-sensitive material having a high silver chloride content, which is effective for reducing the replenishment amount of a developer without impairing speeding up. Considered a means. However, when the continuous processing was carried out by actually reducing the replenishment amount of the developing solution, the rapidity was not impaired, but the photographic characteristics, especially the minimum density, the maximum density and the gradation were significantly changed with the continuous processing, Moreover, a new problem has been found that floating substances and tars are generated in the processing liquid, and further the image storability after the processing, especially the stain after the lapse of time is significantly increased.

At present, the replenishing amount of the color developing solution is somewhat different depending on the photosensitive material to be developed, but generally 180 to 1000 ml per 1 m ^{2 of} the photosensitive material to be processed is required. Because
If the replenishment amount is further reduced without impairing the rapidity, as described above, during continuous processing, the photographic characteristics may greatly fluctuate, floating matters and tars may be generated in the processing solution, or image storability after processing, especially This is because a very serious problem that the stain increases with the lapse of time occurs, and a technique that can fundamentally solve these problems has not been found.

(Problems to be Solved by the Invention) Therefore, a first object of the present invention is to maintain photographic characteristics, particularly maximum density, in continuous processing even if the replenishing amount of the color developing solution is remarkably reduced. It is intended to provide a development processing method in which variations in minimum density and gradation are small.

A second object of the present invention is to provide a processing method in which suspended matters and tar are not generated in the processing solution even when the replenishing amount of the color developing solution is significantly reduced.

A third object of the present invention is to provide a processing method capable of preventing an increase in image storability after processing, especially stain even after the replenishment amount of the color developing solution is remarkably reduced.

(Means for Solving the Problem) As a result of various investigations, the present inventors were able to achieve the above object by the method described below.

In a method of continuously processing a silver halide color photographic light-sensitive material with a color developing solution containing at least one aromatic primary amine color developing agent, an emulsion of high silver chloride containing 80 mol% or more of silver chloride is prepared. Have at least one layer,
The coated silver amount is 0.3 to 0.8 g / m ² , the total film thickness when dried is 7 μm to 13 μm, and the swelling degree is 10 in the color developing solution.
0% to 300%, and the content of calcium atoms is 14 mg / m
Under the condition of ² or less, the following general formulas (VIII), (IX),
A silver halide color photographic light-sensitive material containing a compound or saccharide represented by (X), (XI) or (XII),
The replenishing amount of the color developing solution is the silver halide photographic light-sensitive material 1
A method of processing a silver halide color photographic light-sensitive material, which comprises processing with a color development processing solution of ^{20 to} 150 ml per m ² .

General formula (VIII) 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.

General formula (IX) In the formula, A ²¹ is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted amino group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkoxy group, Or an unsubstituted aryloxy group, a substituted or unsubstituted carbamoyl group, a substituted or unsubstituted sulfamoyl group, an acyl group, a carboxy group, a hydroxyamino group, or a hydroxyaminocarbonyl group.

X ²¹ is -SO ₂ -, or represents -SO-. Y ²¹ represents a hydrogen atom or a group capable of becoming a hydrogen atom by a hydrolysis reaction.

General formula (X) 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.

General formula (XI) In the formula, R ⁴¹ is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a carboxyl group, a sulfo group, a carbamoyl group, a sulfamoyl group, an amide group, a sulfonamide group, a ureido group, an alkylthio group, It represents an arylthio group, a nitro group, a cyano group, an amino group, a formyl group, an acyl group, a sulfonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkoxysulfonyl group, and an aryloxysulfonyl group. When there are two or more R ⁴¹ , the types may be the same or different, and when they are adjacent to each other, they may be bonded to each other to form a ring. R ⁴² represents a hydrogen atom or a hydrolyzable group. Also, m,
n is an integer of 1 to 5, respectively.

General formula (XII) In the formula, R ⁵¹ represents a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, an alkoxy group, an aryloxy group or an amino group, and R ⁵² represents a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group. And R ⁵¹ and R ⁵² may form a carbocyclic or heterocyclic ring together. R ⁵¹ represents a hydroxyl group or a substituted or unsubstituted amino group.

In the present invention, the total thickness of the color photographic light-sensitive material when dried is 7 μm to 13 μm, more preferably 8 μm to 12 μm.
m.

If it is less than 7 μm, the film strength will decrease, and
If it is larger than μm, the effect of the present invention cannot be obtained.

The degree of swelling in the present invention is a scale showing the amount of equilibrium swelling when the light-sensitive material of the present invention is immersed in a color developing solution, more specifically, the color developing solution used in Example 1 to be described later and allowed to swell. , Is expressed by the following equation.

In the present invention, the degree of swelling may be in the range of 100% to 300%, but the range of 150% to 250% is particularly preferable.

In the present invention, if the total amount of calcium atoms in the light-sensitive material is 15 mg / m ² or less, the effect of the present invention will be further exerted. It is advantageous to use ICP (Inductively Conpied Plasma) emission spectrometry as a method for quantifying all calcium atoms in the light-sensitive material. This analysis method is based on the special issue No. 127 (published by Nankodo 1980) and VA Fassel: Anal, C.
hem., 46 1110A (1974) (Title Inductively Conpied Plas
ma Emission Spectroscopy) has detailed description.

Gelatin used as a binder in a silver halide color photographic light-sensitive material usually contains a considerable amount of calcium salt that comes from, for example, the bone of the raw material (thousands of ppm converted to calcium atoms). degree.

In the present specification, the amount of calcium salt is calculated as calcium atom unless otherwise specified). Therefore, a color photographic material that has been put into practical use usually contains 15 mg / m ² or more of calcium, although it depends on the gelatin coating amount.

As defining the calcium content in the photosensitive material,
For example, there is a description in JP-A-60-159850, which relates to fluctuations in photographic properties during continuous processing of a specific magenta coupler, and a color developer in which the replenishment amount of a high silver chloride color light-sensitive material is reduced. It was a totally unexpected fact that the fluctuation of photographic characteristics during the processing with use and the storage stability after processing, particularly the generation of floating matters and tar in the processing solution, were significantly prevented.

In the present invention, the calcium content in the light-sensitive material is 14 mg / m
^{The amount} is preferably ² or less, more preferably 12 mg / m ² or less, further preferably 11 mg / m ² or less.

Various methods are conceivable for realizing the embodiment of the present invention, and the following method can be mentioned, for example.

(1) A raw material gelatin having a low calcium content is used in the production of a light-sensitive material.

(2) Gelatin solution, emulsion, silver halide emulsion, and other additives containing gelatin are desalted in advance by noodles, washing with water, dialysis, etc. during the production of the light-sensitive material.

Among the above, the method (1) is preferable in terms of manufacturing stability of the light-sensitive material. In order to reduce the calcium content in gelatin and obtain so-called deionized gelatin (Ca content of 100 ppm or less), for example, treatment with Na ⁺ type or H ⁺ type ion exchange resin or dialysis treatment can be mentioned. In any case, gelatin having a low calcium content can be advantageously used in the present invention.

At the time of producing a light-sensitive material, gelatin is added in the form of a gelatin solution as a silver halide emulsion, an emulsion containing a coupler or the like or a simple binder. Therefore, the light-sensitive material of the present invention can be prepared by using gelatin having a low calcium content in all or part of these additives.

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 color developer used in the present invention will be described in detail.

The range of the replenishment amount of the color developing solution in the present invention is ^{20 to} 120 ml per m ^{2 of the} silver halide light-sensitive material. The replenishment amount of the developing solution to 120 ml or less is unrealistic in the prior art due to the above-mentioned problems, and was made possible for the first time by the present invention. The replenishment amount of 120 ml / photosensitive material 1 m ² is a value located at the boundary between the range which is possible for the first time by the present invention and the range which is possible by the combination of the prior arts other than the present invention. Also, depending on the light-sensitive material, if the developer replenishment amount is 20 ml / light-sensitive material 1 m ² or less, the carry-out amount of the processing liquid by the light-sensitive material exceeds the replenishment amount, and the processing liquid decreases, making it practical. Makes continuous processing impossible. The replenishment rate 20 ml / photosensitive material 1 m ² is slightly different depending photosensitive material, a take-out amount by the light-sensitive material of the processing solution and replenishing amount is indicative of the substantially equal amount.

It is more preferable that the developer used in the present invention does not substantially contain benzyl alcohol for the purpose of reducing fluctuations in photographic characteristics during continuous processing. Here, substantially not contained is preferably 2 ml / l or less, more preferably 0.5 ml / l.
The benzyl alcohol concentration is as follows, and most preferably, benzyl alcohol is not contained at all.

The developer used in the present invention more preferably contains substantially no sulfite ion. The sulfite ion has a function as a preservative of the developing agent, and at the same time, has a function of dissolving a silver halide and a function of reacting with an oxidized product of the developing agent to reduce the dye forming efficiency. It is presumed that such an effect is one of the causes of an increase in fluctuations in photographic characteristics that occur when the replenishment amount of the color developing solution is reduced. Here, the term "substantially free from" means that the concentration of sulfite ion is 5.0 × 10 ^-3 mol / l or less, and most preferably no sulfite ion is contained. However, in the present invention, a very small amount of sulfite ion used for preventing oxidation of a processing agent kit in which a developing agent is concentrated before preparing a working solution is excluded.

The developer used in the present invention preferably contains substantially no sulfite ion, and more preferably contains substantially no hydroxylamine. this is,
This is because hydroxylamine has a silver developing activity at the same time as having a function as a preservative of the developing solution, and it is considered that fluctuations in the concentration of hydroxylamine greatly affect photographic characteristics. The term "substantially free of hydroxylamine" as used herein means that the concentration of hydroxylamine is preferably 5.0 × 10 ^-3 mol / l or less, and most preferably it does not contain hydroxylamine at all.

It is more preferable that the developer used in the present invention contains an organic preservative in place of the hydroxylamine and the sulfite ion in view of stability of photographic properties during continuous processing and image storability after processing.

Here, the organic preservative refers to all organic compounds that reduce the deterioration rate of the aromatic primary amine color developing agent by being added to the processing solution of the color photographic light-sensitive material. That is, it is an organic compound having a function of preventing the oxidation of the color developing agent due to air, etc. Among them, hydroxylamines (excluding hydroxylamine), hydroxamic acids,
Hydrazines, hydrazides, phenols, α-hydroxyketones, α-aminoketones, sugars, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds Polycondensed amines are particularly effective organic preservatives. These are Japanese Patent Application No. Sho 61-147823,
61-173595, 61-165621, 61-188619, 61-
197760, 61-186561, 61-198987, 61-20186
No. 1, 61-186559, 61-170756, 61-188742,
No. 61-188741, U.S. Pat. Nos. 3,615,503 and 2,494,903, JP-A-52-143020, JP-B-48-30496, and the like.

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 it so that the concentration becomes / l.

The following are preferred as [hydroxylamine] s.

General formula (VIII) 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, a nitrogen atom, a sulfur atom and the like, and may be saturated or unsaturated.

It is preferable that R ¹¹ and R ¹² are an alkyl group or an alkenyl group, and the carbon number is preferably 1 to 10, and particularly preferably 1 to 5. 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 preferable hydroxamic acids.

General formula (IX) In the formula, A ²¹ is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted amino group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkoxy group, Or an unsubstituted aryloxy group, a substituted or unsubstituted carbamoyl group, a substituted or unsubstituted sulfamoyl group, an acyl group, a carboxy group, a hydroxyamino group, or a hydroxyaminocarbonyl group. Examples of the substituent include a halogen atom, an aryl group, an alkyl group, an alkoxy group, and the like.

A ²¹ is preferably a substituted or unsubstituted alkyl group, aryl group, amino group, alkoxy group, or aryloxy group. Particularly preferred examples are a substituted or unsubstituted amino group, an alkoxy group, and an aryloxy group. The number of carbon atoms is preferably 1-10.

X ²¹ is -SO ₂ -, or represents -SO-. Preferably X ²¹ is Is.

R ²¹ is a hydrogen atom, a substituted or unsubstituted alkyl group,
It represents a substituted or unsubstituted aryl group. At this time,
A ²¹ and R ²¹ may be linked to form a ring structure. The substituent is the same as the substituents mentioned in A ^21. Preferably R ²¹
Is a hydrogen atom.

Y ²¹ represents a hydrogen atom or a group capable of becoming a hydrogen atom by a hydrolysis reaction.

Compound example The following are preferred as hydrazines and hydrazides.

General formula (X) 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 the general formula (X), R ³¹ , R ³² and R ³³ represent a hydrogen atom or C ₁ -C
_It is preferably an alkyl group of ₁₀ , particularly preferably R ³¹ and R ³² are hydrogen atoms.

In the general formula (X), 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 carboxyl group, a sulfo group, a nitro group, an amino group, a phosphono group and the like. X ³¹ is preferably —CO— or —SO ₂ —, and most preferably —CO—.

_{X-2 NH 2 NHCH 2 4} SO 3 H X-3 NH 2 NHCH 2 2 OH _{X-6 NH 2 NHCOCH 3 X} -7 NH 2 NHCOOC 2 H 5 X-10 NH ₂ NHCONH ₂ X-12 NH ₂ NHSO ₃ H X-14 NH ₂ NHCOCONHNH ₂ X-15 NH ₂ NHCH ₂ CH ₂ CH ₂ SO ₃ H X-18 NH ₂ NHCH ₂ CH ₂ COOH The following are preferred as phenols.

General formula (XI) In the formula, R ⁴¹ is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a carboxyl group, a sulfo group, a carbamoyl group, a sulfamoyl group, an amide group, a sulfonamide group, a ureido group, an alkylthio group, It represents an arylthio group, a nitro group, a cyano group, an amino group, a formyl group, an acyl group, a sulfonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkoxysulfonyl group, and an aryloxysulfonyl group. When R ⁴¹ is further substituted, examples of the substituent include a halogen atom, an alkyl group, an aryl group, a hydroxyl group, an alkoxy group, and the like. When there are two or more R ⁴¹ , the types may be the same or different, and when they are adjacent to each other, they may be bonded to each other to form a ring. The ring structure 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 ⁴² represents a hydrogen atom or a hydrolyzable group. Further, m and n are integers from 1 to 5, respectively.

In formula (XI), preferred R ⁴¹ is an alkyl group, a halogen group, an alkoxy group, an alkylthio group, a carboxyl group, a sulfo group, a carbamoyl group, a sulfamoyl group, an amino group, an amide group, a sulfonamide group, a nitro group, and It is a cyano group. Among them, an alkoxy group, an alkylthio group, an amino group, and a nitro group are particularly preferable, and these are more preferably in the ortho position or the para position of the (OR ⁴² ) group. Further, the carbon number of R ⁴¹ is preferably from 1 to 10, particularly preferably from 1 to 6.

Preferred R ⁴² is a hydrogen atom or a hydrolyzable group having 1 to 5 carbon atoms. Further, when there are two or more (OR ⁴² ) groups, it is more preferable that they are located in the ortho position or the para position with respect to each other.

The following are preferred as α-hydroxyketones and α-aminoketones.

General formula (XII) In the formula, R ⁵¹ represents a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, an alkoxy group, an aryloxy group or an amino group, and R ⁵² represents a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group. And R ⁵¹ and R ⁵² may form a carbocyclic or heterocyclic ring together. R ⁵¹ represents a hydroxyl group or a substituted or unsubstituted amino group.

In formula (XII), R ⁵¹ is preferably a hydrogen atom, an alkyl group, an aryl group or an alkoxy group, and R ⁵²
Is preferably a hydrogen atom or an alkyl group.

Sugars are also preferred organic preservatives.

(Also referred to as carbohydrate) saccharide comprises monosaccharide and polysaccharide, many have the general formula C _n H _2m O _m. Monosaccharides generally refer to aldehydes or ketones of polyhydric alcohols (referred to as aldoses and ketoses, respectively) and their reduced derivatives, oxidized derivatives, dehydrated derivatives, and a wider range of derivatives such as amino sugars and thio sugars. The polysaccharide refers to a product obtained by dehydrating and condensing two or more of the aforementioned monosaccharides.

Among these sugars, more preferable ones are aldoses having a reducing aldehyde group, and derivatives thereof, and particularly preferable ones are those corresponding to monosaccharides.

XIII-1 D-oxylose XIII-2 L-arabinose XIII-3 D-ribose XIII-4 D-deoxyribose XIII-5 D-glycose XIII-6 D-galactose XIII-7 D-mannose XIII-8 glycosamine XIII-9 L-sorbose XIII-10 D-sorbit (sorbitol) Examples of the mol amines include the following.

General formula (XIV) 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. Further, as the substituent, a hydroxyl group, a sulfone group, a carboxyl group, a halogen atom, a nitro group,
Amino groups and the like can be mentioned.

XIV-1 NCH ₂ CH ₂ OH) ₃ XIV-2 H ₂ NCH ₂ CH ₂ OH XIV-3 HNCH ₂ CH ₂ OH) ₂ XIV-10 (HOCH ₂ CH _{2 2} NCH ₂ CH ₂ SO ₂ CH ₃ XIV-11 HNCH ₂ COOH) ₂ XIV-13 H ₂ NCH ₂ CH ₂ SO ₂ NH ₂ XIV-14 H ₂ N-CCH ₂ OH) ₂ The following diamines are preferred.

General formula (XV) In the formula, R ⁸¹ , R ⁸² , R ⁸³ , and R ⁸⁴ represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, or a heterocyclic group.

R ⁸⁵ represents a divalent organic group, specifically an alkylene group, an arylene group, an aralkylene group, an alkenylene group or a heterocyclic group.

R ⁸¹ , R ⁸² , R ⁸³ and R ⁸⁴ are particularly preferably a hydrogen atom and an alkyl group, and R ⁸⁵ is particularly preferably an alkylene group.

XV-2 (HOCH ₂ CH _{2 2} NCH ₂ CH ₂ NCH ₂ CH ₂ OH) ₂ XV-4 H ₂ NCH ₂ CH ₂ NCH ₂ CH ₂ OH) ₂ The following are preferable polyamines.

General formula (XVI) In the formula, R ⁹¹ , R ⁹² , R ⁹³ and R ⁹⁴ represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group or a heterocyclic group.

R ⁹⁵ , R ⁹⁶ , and R ⁹⁷ represent a divalent organic group, and specifically have the same meaning as R ^{85 in the} general formula (XV).

X ⁹¹ and X ₉₂ R represents a linking group composed of —O—, —S—, —CO—, —SO ₂ —, —SO— or a combination of these linking groups;
⁹⁸ has the same ^meaning as R ⁹¹ , R ⁹² , R ⁹³ and R ⁹⁴ . m represents 0 or an integer of 1 or more.

(The upper limit of m is not particularly limited and may be a high molecular weight as long as the compound is water-soluble, but usually m is preferably in the range of 1 to 3) XVI-2 (HOCH ₂ CH _{2 2} NCH ₂ CH ₂ OCH ₂ CH ₂ NCH ₂ CH ₂ OH) ₂ The following are preferred as quaternary ammonium salts.

General formula (XVI) (In the formula, R ¹⁰¹ represents an n-valent organic group, and R ¹⁰² , R ¹⁰³ and
R ¹⁰⁴ represents a monovalent organic group. The term "organic group" as used herein means a group having 1 or more carbon atoms, and specifically, an alkyl group, an aryl group, a heterocyclic group or the like. At least two groups out of R ¹⁰² , R ¹⁰³ and R ¹⁰⁴ may combine to form a heterocyclic ring containing a quaternary ammonium atom. n is an integer of 1 or more, and X ^e represents a counter anion. ) A particularly preferred monovalent group among R ¹⁰² , R ¹⁰³ and R ¹⁰⁴ is a substituted or unsubstituted alkyl group, and at least one of R ¹⁰² , R ¹⁰³ and R ¹⁰⁴ is a hydroxyalkyl group, an alkoxyalkyl group or a carboxyalkyl group. Most preferably, it is a group. n is preferably an integer of 1 to 3, more preferably 1 or 2.

The following are preferred as nitroxy radicals.

General formula (XVII) R ¹¹¹ and R ¹¹² each represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. Further, these alkyl group, aryl group or heterocyclic group may have a substituent. Examples of such a substituent include a hydroxy group, an oxo group, a carbamoyl group, an alkoxy group, a sulfamoyl group, a carboxy group, and a sulfo group. Examples of the heterocyclic group include a pyridyl group and a piperidyl group.

Preferably, R ¹¹¹ and R ¹¹² are a substituted or unsubstituted aryl group or a tertiary alkyl group (for example, a t-butyl group).

(Compound example) The following alcohols are preferable.

General formula (XIX) Wherein R ¹²¹ represents a hydroxy-substituted alkyl group;
¹²² represents an unsubstituted alkyl group or the same group as ^R121 . R
¹²³ represents a hydrogen atom or a group similar to ^R122 . X ¹²¹ is a hydroxy group, a carboxyl group, a sulfo group, a nitro group,
It represents an unsubstituted or hydroxy-substituted alkyl group, an unsubstituted or substituted amide group, and a sulfonamide group.

In the general formula (XIX), X ¹²¹ is preferably a hydroxy group, a carboxyl group, or a hydroxyalkyl group.

XIX-4 HO-CHCH ₂ OH) ₂ XIX-5 (HO-CH _{2 3} COOH XIX-6 CCH ₂ OH ₄ XIX-7 (HOCH _{2 3} C-CH ₃ XIX-8 (HOCH _{2 3} C-NHCOCH ₃ The following alcohols are preferable.

General formula (XX) In the formula, R ¹³¹ , R ¹³² and R ¹³³ each represent a hydrogen atom or an alkyl group, and n represents a positive integer up to 500.

The alkyl group represented by R ¹³¹ , R ¹³² and R ¹³³ preferably has 5 or less carbon atoms, and more preferably 2 or less carbon atoms. R ¹³¹ , R ¹³² and R ¹³³ are very preferably a hydrogen atom or a methyl group, most preferably a hydrogen atom.

n is preferably a positive integer of 3 or more and 100 or less, and more preferably 3 or more and 30 or less.

XX-1 HOCH ₂ CH ₂ O ₄ OH XX-2 CH ₃ OCH ₂ CH ₂ O ₃ OH XX-3 CH ₃ OCH ₂ CH ₂ O ₂ OCH ₃ XX-5 HOCH ₂ CH ₂ OCH ₃ XX-6 C ₂ H ₅ OCH ₂ CH ₂ O ₂ OH XX-7 HOCH ₂ CH ₂ O _n H Average molecular weight About 300 XX-8 HOCH ₂ CH ₂ O _n H Average molecular weight About 800 XX-9 HOCH ₂ CH ₂ O _n H average molecular weight about 3000 XX-10 HOCH ₂ CH ₂ O _n H average molecular weight about 8000 The following oximes are preferred.

General formula (XXI) In the formula, R ¹⁴¹ and R ¹⁴² represent a hydrogen atom, a substituted or unsubstituted alkyl group, and a substituted or unsubstituted aryl group, respectively. R ¹⁴¹ and R ¹⁴² may be the same or different, and these groups may be linked together.

Preferred as R ¹⁴¹ and R ¹⁴² in the general formula (XXI) are a halogen group, a hydroxyl group, an alkoxyl group, an amino group, a carboxyl group, a sulfo group, a phosphonic acid group, and an alkyl group substituted with a nitro group, and an unsubstituted group. Is an alkyl group.

The total number of carbon atoms in the general formula (XXI) is preferably 30 or less, more preferably 20 or less.

The following are preferable polyamines.

General formula (XXII) In the formula, X ¹⁵¹ and X ¹⁵² represent -CO- or -SO _2- , and R ¹⁵¹ , R ¹⁵² , R ¹⁵³ , R ¹⁵⁴ , R ¹⁵⁵ and R ¹⁵⁶ represent a hydrogen atom, an unsubstituted or substituted alkyl group. And R ¹⁵⁷ represent an unsubstituted or substituted alkylene group, an unsubstituted or substituted arylene group and an unsubstituted or substituted aralkylene group. m ¹ , m ² and n represent 0 or 1.

The following are preferred as _{XXII-6 H 2 NSO 2 NHSO} 2 NH 2 condensed ring amines.

General formula (XXIII) 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 formulas (XXIII), particularly preferred are the compounds represented by the general formulas (1-a) and (1-b).

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

In the general formula (1-a), X ¹ is preferably N. The carbon number 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 (XVI).

In the general formula (1-b), 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 (1-a) and (1-b), the compound represented by the general formula (1-a) is particularly preferable.

Many of the compounds of the general formulas (VIII) to (XXIII) according to the present invention can be easily obtained as commercial products.

Two or more kinds of the organic preservatives may be used in combination. A preferred combination is at least one compound of the general formulas (VIII) to (XIII) and at least one compound of (XIV) (XXIII).

More preferred combined use is at least one of the general formulas (VIII) and (XV) and at least one of the general formulas (XVI) and (XXIII).

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

The color developing solution used in the present invention contains a known aromatic primary amine color developing agent. A preferred example is p-phenylenediamine, and representative examples thereof are shown below, but 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 The use of D-4 is particularly preferred.

Further, these p-phenylenediamine derivatives may be salts such as sulfate, hydrochloride and p-toluenesulfonic acid salt. The amount of the aromatic primary amine developing agent to be used is preferably about 0.1 g to about 20 g, more preferably about 0.5 g 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 in the color developing solution as a precipitation preventing agent for calcium and magnesium, or for improving the stability of the color developing solution.

Specific examples are shown below, but the present invention is not limited thereto. Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, triethylenetetraminehexaacetic acid, N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid, 1,3- Diamino-2-propanoltetraacetic acid, transcyclohexanediaminetetraacetic acid, nitrilotripropionic acid, 1,2-
Diaminopropane tetraacetic acid, hydroxyethyliminodiacetic acid, glycol ether diamine tetraacetic acid, hydroxyethylenediamine triacetic acid, ethylenediamine orthohydroxyphenylacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxyethylidene-1,1- Diphosphonic acid, N, N'-bis (2-hydroxybenzyl), ethylenediamine-N, N'-diacetic acid 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
Nos. 38-7826, 44-12380, 45-9019, and thioether compounds represented by U.S. Pat. No. 3,813,247, and JP-A Nos. 52-49829 and 50-15554.
-Phenylenediamine compounds, JP-A-50-137726,
JP-B-44-30074, JP-A-56-156826 and JP-A-52-43429
, Etc., quaternary ammonium salts, US Pat.
P-aminophenols described in 2,610,122 and 4,119,462, U.S. Pat. Nos. 2,494,903, 3,128,182, and 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, etc., amine compounds described in Japanese Patent Publications 37-16088, 42-252.
01, U.S. Patent No. 3,128,183, Japanese Patent Publication No. 41-11431, 4
2-23883 and U.S. Pat. No. 3,532,501, and other polyalkylene oxides, other 1-phenyl-3-pyrazolidones, hydrazines, mesoionic compounds, ionic compounds, imidazoles, etc. are added as necessary. be able to.

An optional antifoggant can be added to the color developer used in the present invention, 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 the organic antifoggant include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole,
Representative examples thereof include nitrogen-containing heterocyclic compounds such as 5-chloro-benzotriazole, 2-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 amount of addition is 0-5 g / l, preferably 0.1-4 g / l.

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

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

The replenishing amount of the color developing solution of the present invention is 20 per 1 m ² of the light-sensitive material.
It is ml to 120 ml, preferably 30 ml to 100 ml. The replenishing amount referred to here indicates the amount of replenishment of a so-called color developing replenisher, and the amount of an additive or the like for correcting deterioration with time or concentration is outside the replenishing amount of the present invention.

The additive as used herein refers to, for example, water for diluting the concentrate, a preservative that easily deteriorates with time, or an alkaline agent that raises the pH.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. Further, in order to speed up the processing, a processing method of bleach-fixing processing after bleaching processing may be used. Further processing with two continuous bleach-fix baths,
The fixing treatment before the bleach-fixing treatment or the bleaching treatment after the bleach-fixing treatment can be optionally carried out according to the purpose.
Examples of bleaching agents include iron (III), cobalt (III),
Compounds of polyvalent metals such as chromium (VI) and copper (II), peracids, quinones, nitro compounds and the like are used. Typical bleaching agents are ferricyanide; dichromate; iron (II
I) or cobalt (III) organic complex salts such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3
-Aminopolycarboxylic acids such as diaminopropane tetraacetic acid and glycol ether diamine tetraacetic acid or complex salts such as citric acid, tartaric acid and malic acid; persulfates; bromates; permanganates; nitrobenzenes and the like can be used. it can. Of these, aminopolycarboxylic acid iron (II) including ethylenediaminetetraacetic acid iron (III) complex salts
I) Complex salts and persulfates are preferable from the viewpoint of rapid processing and prevention of environmental pollution. Furthermore, iron (III) aminopolycarboxylate
Complex salts are particularly useful in both bleaching solutions and bleach-fixing solutions. The pH of the bleaching solution or bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 4.5 to 8, but a lower pH can be used for speeding up the processing.

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath. Specific examples of useful bleaching accelerators are described in the following specifications: US Pat. No. 3,893,858, West German Patent 1,290,812, JP-A-53-9.
5,630, Research Disclosure No. 17,129 (July 1978), etc., compounds having a mercapto bond or a disulfide group; thiazolidine derivatives described in JP-A-50-140,129; US Pat. No. 3,706,561. Thiourea derivatives; iodide salts described in JP-A-58-16,235; polyoxyethylene compounds described in West German Patent 2,748,430; polyamine compounds described in JP-B-45-8836; bromide ion and the like can be used. Among them, compounds having a mercapto group or a disulfide group are preferable from the viewpoint of a large accelerating effect, and the compounds described in US Pat. No. 3,893,858, West German Patent 1,290,812 and JP-A-53-95,630 are particularly preferable. Further, the compounds described in US Pat. No. 4,552,834 are also preferable. It can be obtained by the method described in this May, 5 issue.

According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced, but due to the increase in the residence time of water in the tank, bacteria propagate, and the suspended matter produced adheres to the photosensitive material, etc. Problem arises. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, the method of reducing calcium ion and magnesium ion described in Japanese Patent Application No. 61-131632 can be very effectively used. Further, isothiazolone compounds and siabendazoles described in JP-A-57-8,542, chlorine-based bactericides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc., Hiroshi Horiguchi "Chemistry of antifungal agents" It is also possible to use the bactericides described in "Microbial Sterilization, Sterilization, and Antifungal Technology" edited by the Society of Hygiene Technology and "Encyclopedia of Antibacterial and Antifungal Agents" edited by the Society for Antibacterial and Antifungal Society of Japan.

The pH of washing water in the processing of the light-sensitive material of the present invention is 4-
9, preferably 5-8. The washing water temperature and washing time can also be variously set depending on the characteristics of the light-sensitive material, the use, etc., but generally 15-45 ° C. for 20 seconds-10 minutes, preferably 25-40 ° C. for 30 seconds.
A range of seconds-5 minutes is selected. Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such a stabilization process, Japanese Unexamined Patent Publication No.
All known methods described in Nos. -8,543, 58-14,834 and 60-220,345 can be used.

Further, there is a case where a stabilizing treatment is further performed 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. . Various chelating agents and fungicides can also be added to this stabilizing bath.

The overflow solution accompanying the above washing with water and / or supplementation of the stabilizing solution can be reused in other steps such as the desilvering step.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up the processing.
For incorporation, it is preferable to use various precursors of color developing agents. For example, indaniline compounds described in U.S. Pat. Examples thereof include salt complexes and urethane compounds described in JP-A-53-135,628.

The silver halide color light-sensitive material of the present invention contains various 1-phenyl-containing compounds, if necessary, for the purpose of promoting color development.
You may incorporate 3-pyrazolidones. Typical compounds are JP-A-56-64,339, JP-A-57-144,547, and JP-A-58-11.
No. 5,438 is described.

The various treatment liquids in the present invention are used at 10 ° C to 50 ° C. Normally, a temperature of 33 ° C to 38 ° C is standard, but a higher temperature accelerates the processing to shorten the processing time, and a lower temperature lowers the image quality to improve the stability of the processing liquid. be able to. Further, in order to save silver in the light-sensitive material, processing using cobalt intensification or hydrogen peroxide intensification described in West German Patent No. 2,226,770 or US Pat. No. 3,674,499 may be performed.

The method of the present invention can be applied to processing of color paper, color reversal paper, color direct positive paper and the like.

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

The silver halide emulsion of the present invention has a silver chloride content of 80 mol% or more, preferably 95 mol% or more, more preferably 98 mol% or more. 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. Preferably, the halogen composition of silver halide in all the light-sensitive emulsion layers is 80 mol% or more.

The silver halide grain used in the present invention may have a layer (core / shell grain) whose inner surface is different from the surface layer, may have a multi-phase structure having a joint structure, or may have a uniform phase as a whole. Good. Moreover, they may be mixed.

The average grain size of the silver halide grains used in the present invention (in the case of spherical or nearly spherical grains, the grain diameter is used; in the case of cubic grains, the ridge length is used as the grain size, and the average is based on the projected area. Is also expressed in terms of sphere.) Is preferably 2 μm or less and 0.1 μm or more, and particularly preferably 1.5 μm or less and 0.15 μm or more. The grain size distribution may be narrow or wide, but the value (variation rate) obtained by dividing the standard deviation value in the grain size distribution curve of the silver halide emulsion by the average grain size is within 20%, particularly preferably 15 It is preferred to use so-called monodisperse silver halide emulsions within the range of% in the present invention. Further, in order to satisfy the target gradation of the light-sensitive material, two or more kinds of monodisperse silver halide emulsions having different grain sizes in the emulsion layers having substantially the same color sensitivity (the above-mentioned monodispersity is the same). Those having a variation rate are preferable) can be mixed in the same layer or multilayer-coated in different layers. Further, two or more kinds of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion may be used as a mixture or as a mixture.

The silver halide grains used in the present invention have a regular shape such as a cube, an octahedron, a rhodohedron and a tetradecahedron.
It may be a compound having different crystal forms or a coexisting form thereof, may have an irregular crystal form such as a sphere, or may have a composite form of these crystal forms. Further, tabular grains may be used, and an emulsion in which tabular grains having a length / thickness ratio value of 5 or more, particularly 8 or more account for 50% or more of the total projected area of the grains may be used. It may be an emulsion composed of a mixture of these various crystal forms. These various emulsions may be either a surface latent image type which forms a latent image mainly on the surface or an internal latent image type which is formed inside the grain.

The coated silver amount of the silver halide emulsion of the light-sensitive material used in the method of the present invention is 0.8 g / m ² or less and 0.3 g / m ² or more in terms of silver amount. When the coated silver amount is 0.8 g / m ² or less, it is very preferable in terms of rapidity, processing stability, and image storage stability after processing (particularly suppression of yellow stain).

The photographic emulsion used in the present invention is Research Disclosure (RD) vol. 176 Item No. 17643 (I, II, III)
It can be prepared using the method described in section (December 1978).

The emulsion used in the present invention is usually one that has been physically ripened, chemically ripened and spectrally sensitized. Additives used in such processes are Research Disclosure Vol. 176, No. 17643 (December 1978) and Vol. 187,
No. 18716 (November 1979), and the relevant locations 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 locations described in the table below are shown.

Various color couplers can be used in the present invention. Here, the color coupler means a compound capable of forming a dye by a coupling reaction with an oxidized product of an aromatic primary amine developing agent. Typical examples of useful color couplers include:
There are naphthol or phenol compounds, pyrazolone or pyrazoloazole compounds and open-chain or heterocyclic ketomethylene compounds. Specific examples of these cyan, magenta and yellow couplers that can be used in the present invention are Research Disclosure (RD) 17643 (197).
(December 8) VII-D and the patent cited in 18717 (November 1979).

The color coupler incorporated in the light-sensitive material preferably has a ballast group or is polymerized to be diffusion resistant. The amount of coated silver can be reduced in the case of a two-equivalent color coupler in which a coupling active position is substituted by a leaving group, rather than a four-equivalent color coupler in which a hydrogen atom is present. A coupler in which the color-forming dye has a suitable diffusibility, a colorless coupler, or a DIR coupler which releases a development inhibitor upon coupling reaction or a coupler which releases a development accelerator can also be used.

A typical example of the yellow coupler that can be used in the present invention is an oil protect type acylacetamide coupler. A specific example is U.S. Pat.
No. 210, No. 2,875,057 and No. 3,265,506. In the present invention, the use of a 2-equivalent yellow coupler is preferable, and U.S. Pat. Nos. 3,408,194 and 3,44 are used.
No. 7,928, Nos. 3,933,501 and 4,022,620, etc., described in, for example, an oxygen atom-elimination type yellow coupler or JP-B No. 55-10739, U.S. Pat.No. 4,401,752, and No. 4,3
26,024, RD-18053 (April 1979), British Patent 1,425,
No. 020, West German Application Publication No. 2,219,917, No. 2,261,361
No. 2,329,587, No. 2,433,812 and the like, nitrogen atom-releasing yellow couplers described in JP-A No. 2,329,587 and No. 2,433,812 are typical examples. The α-pivaloyl acetanilide type coupler is excellent in the fastness, especially the light fastness, of the color forming dye, while the α-benzoyl acetanilide type coupler can obtain a high coloring density.

Specific examples of these yellow couplers are described below, but the preferred yellow couplers in the present invention are not limited to these.

Examples of magenta couplers that can be used in the present invention include oil-protection type indazolone type or cyanoacetyl type couplers, preferably 5-pyrazolone type or pyrazoloazole type couplers. The 5-pyrazolone-based coupler is preferably a coupler in which the 3-position is substituted with an arylamino group or an acylamino group, from the viewpoint of the hue and color density of the color forming dye, and a typical example thereof is U.S. Pat.
082, 2,343,703, 2,600,788, 2,90
No. 8,573, No. 3,062,653, No. 3,152,896 and No. 3,936,015. As a leaving group for a 2-equivalent 5-pyrazolone-based coupler, US Pat. No. 4,310,
Nitrogen atom leaving groups described in 619 or U.S. Pat.
The arylthio groups described in 51,897 are preferred. Further, the 5-pyrazolone type coupler having a ballast group described in European Patent No. 73,636 provides a color density.

A pyrazoloazole-based coupler is a 5-membered to 5-membered condensed nitrogen hetero coupler (hereinafter referred to as 5,5N heterocyclic coupler), and its coloring mother nucleus has isoelectronic aromaticity with naphthalene, and is usually azapentalene. Among the pyrazoloazole-based couplers having the chemical structure collectively referred to as “1H-imidazo [1,2-b] pyrazoles, 1H-
Pyrazolo [5,1-c] [1,2,4] triazoles, 1H-pyrazolo [1,5-b] [1,2,4] triazoles and 1H-
These are pyrazolo [1,5-b] tetrazoles.

Specific examples of these magenta couplers will be given below, but in the present invention, more preferable magenta couplers are not limited to these.

Cyan couplers that can be used in the present invention include oil-protection type naphthol-based and phenol-based couplers, naphthol-based couplers described in U.S. Pat.No. 2,474,293, preferably U.S. Pat.Nos. 4,052,212, 4,146,396, and No. 4,228,233 and No. 4,296,200
As a representative example, the oxygen atom-releasing two-equivalent naphthol-based couplers described in JP-A No. 1994-242242 can be mentioned. Further, specific examples of the phenol-based coupler are described in U.S. Patents 2,369,929 and 2,80.
1,171, 2,772,162, 2,895,826 and the like.

Among these, in the present invention, it is more preferable to use a cyan coupler of the general formula (C) in the red-sensitive emulsion layer from the viewpoint of stability of photographic characteristics during continuous processing.

General formula (C) (In the formula, R ¹ represents an alkyl group, a cycloalkyl group, an aryl group, an amino group or a heterocyclic group. R ² represents an acylamino group or an alkyl group having 2 or more carbon atoms. R ³ represents a hydrogen atom or a halogen atom. Represents an alkyl group or an alkoxy group, R ³ may combine with R ² to form a ring, Z ¹ represents a hydrogen atom, a halogen atom or an oxidized product of an aromatic primary amine color developing agent. Group which can be split off in the reaction of 1.) The preferable cyan coupler is not limited to this.

The graininess can be improved by using a coupler in which the color forming dye has an appropriate diffusibility. Such dye-diffusing couplers are described in U.S. Patent No. 4,366,237 and British Patent No.
Specific examples of magenta couplers are described in 2,125,570, and specific examples of yellow, magenta or cyan couplers are described in EP 96,570 and German Offenlegungsschrift 3,234,533.

The dye-forming coupler and the above-mentioned special coupler may form a dimer or higher polymer. Typical examples of polymerized dye forming couplers are described in US Pat. Nos. 3,451,820 and 4,080,211. Specific examples of polymerized magenta couplers are described in British Patent No. 2,102,173 and U.S. Patent No. 4,367,282.

The various couplers used in the present invention can be used in combination of two or more kinds in the same layer of the light-sensitive layer in order to satisfy the properties required for the light-sensitive material, and the same compound can be used in two or more different layers. Can also be introduced.

To introduce the coupler into the silver halide emulsion layer, known methods such as the method described in US Pat. No. 2,322,027 are used. For example, phthalic acid alkyl ester (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid ester (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid ester (eg acetyl citrate tributyl), Benzoic acid esters (eg octyl benzoate), alkyl amides (eg diethyl lauryl amide), fatty acid esters (eg dibutoxyethyl succinate, diethyl azelate), trimesic acid esters (eg tributyl trimesate) etc., or boiling point Organic solvents at about 30 ° C to 150 ° C, for example, lower alkyl acetates such as ethyl acetate and butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxy. After being dissolved in ethyl acetate, methyl cellosolve acetate, etc., it is dispersed in a hydrophilic colloid. The high boiling point organic solvent and the low boiling point organic solvent may be mixed and used.

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 organic solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027. Further, the process of the latex dispersion method as one of the polymer dispersion methods, effects, and specific examples of the latex for impregnation are described in US Pat. No. 4,199,363 and West German patent application (O.
LS) Nos. 2,541,274 and 2,541,230, etc., dispersing methods using organic solvent-soluble polymers are described in PCT JP87 / 00.
No. 492.

Examples of the organic solvent used in the above oil-in-water dispersion method include alkyl phthalates (dibutyl phthalate, dioctyl phthalate, etc.), phosphates (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate). Fate), citric acid ester (eg acetyl citrate tributyl), benzoic acid ester (eg octyl benzoate), alkylamide (eg diethyllaurylamide), fatty acid ester (eg dibutoxyethyl succinate, diethyl azelate), trimesine Acid esters (eg, tributyl trimesate) or the like, or an organic solvent having a boiling point of about 30 ° C. to 150 ° C., such as ethyl acetate,
A lower alkyl acetate such as butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate and the like may be used in combination.

The standard amount of the color coupler used is in the range of 0.001 to 1 mol per mol of the photosensitive silver halide,
Preferably 0.01 to 0.5 moles for yellow couplers,
It is 0.003 to 0.3 mol for the magenta coupler and 0.002 to 0.3 mol for the cyan coupler.

The photographic light-sensitive material used in the present invention is applied to a commonly used plastic film (cellulose nitrate, cellulose acetate, polyethylene terephthalate, etc.), a flexible support such as paper or a rigid support such as glass. For details on the support and coating method, see Research Disclosure Vol. 176 Item 17643 XV (P.27)
It is described in Section XVII (P.28) (December 1978 issue).

In the present invention, a reflective support is preferably used. The "reflective support" is one which enhances the reflectivity and makes the dye image formed on the silver halide emulsion layer clear, and such a reflective support includes titanium oxide, zinc oxide, Examples include those coated with a hydrophobic resin containing a light reflecting substance such as calcium carbonate and calcium sulfate dispersed therein, and those using a hydrophobic resin containing a light reflecting substance dispersed therein as a support.

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

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

(2) The processing method according to claim 1, wherein the color developing solution contains an organic preservative.

(3) The coating amount of silver halide color photographic light-sensitive material is
The treatment method according to claim 1, which is 0.80 g / m ² or less.

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

(Example-1) 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 the mixture was desalted. Add water and dispersed gelatin, adjust pH to 6.0, and average particle size 1.0 μm Coefficient of variation (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. After that, 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 in 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) was added in an amount of 5 × 10 ^-4 mol per mol of the emulsion, and a spectral sensitizing dye (Sen-3) was added to the silver halide emulsion (3).
^Was added in an amount of 0.9 × 10 ^-4 mol per mol of the emulsion.

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

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 liquid was prepared as follows.

1st layer coating liquid preparation Yellow coupler (E _X Y) 19.1 g ethyl acetate 27.2 cc
And 3.8 cc of solvent (Solv-1) were added and dissolved, and this solution was emulsion-dispersed in 185 cc of 10% gelatin aqueous solution containing 8 cc of 10% sodium dodecylbenzenesulfonate. On the other hand, a silver halide emulsion (1) to which a blue-sensitive sensitizing dye (Sen-1) was added at 5.0 × 10 ^-4 mol per mol of silver was prepared.
The emulsified dispersion and the emulsion were mixed and dissolved to prepare a first layer coating solution having the following composition.

The 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 hardening agent 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
Each of (5-methylureidophenyl) -5-mercaptoterrazole was added at 1.0 × 10 ⁻³ per mol of silver halide.
Mole was added.

Further, to the red light-sensitive emulsion layer, 2-amino-5-mercapto-1,3,4-thiadiazole was added in an amount of 2.5 × 10 ^-4 mol per mol of silver halide.

 The composition of each layer is shown below.

(Constituent layer) Support Paper support laminated on both sides with polyethylene [White pigment on the polyethylene of the first layer: TiO ₂ (2.7 g /
m ² ) and bluish dye (ultrasound)] 1st layer (blue sensitive layer) Silver halide emulsion (1) 0.26 Gelatin A 0.73 Gelatin B 0.40 Yellow coupler (ExY) 0.66 Solvent (Solv-1) 0.28 Second Layer (color mixing prevention layer) Gelatin A 0.31 Gelatin B 0.58 Color mixing 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) 0.29 Gelatin A 0.61 Gelatin B 0.47 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 absorbing layer) Gelatin A 0.63 Gelatin B 0.79 UV absorbing agent (UV-1) 0.52 Mixed color Inhibitor (Cpd-1) 0.06 Solvent (Solv-4) 0.26 Dye (T-2) 0.015 Fifth layer (red sensitive layer) Silver Genide Emulsion (3) 0.22 Gelatin A 0.96 Cyan coupler (Exc-1) 0.08 Cyan coupler (Exc-2) 0.03 Cyan coupler (Exc-3) 0.19 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 (UV absorbing layer) Gelatin A 0.21 Gelatin B 0.27 UV absorbing agent (UV-1) 0.18 Solvent (Solv-4) 0.08 Dye (T-2) 0.005 Seventh layer (protective layer) Gelatin C 1.33 Polyvinyl alcohol acrylic modified copolymer (degree of modification
17%) 0.05 Liquid paraffin 0.03 The structures of the compounds used are as follows: (Solv-4) solvent _{O = PO-C 9 H 19} -iso) 3 Gelatin A: Gelatin having a calcium content of 3000 ppm 〃 B: 〃 40 ppm 〃 〃 C: 〃 100 ppm 〃 The sample manufactured in this way was designated as Sample 101. The calcime content in the light-sensitive material was measured and found to be 10.6 mg / m ² . Next, samples 102 to 114 were prepared by changing the amount of the gelatin hardener used and the amount of the gelatin used in the first to seventh layers. The amount of gelatin used was changed in the same ratio from the first layer to the seventh layer. The total film thickness of Samples 102 to 114 when dried and the time of swelling using the color developing solution described later
The measurement results of the total film thickness at 38 ° C and the value of the swelling degree calculated from these values are shown. The calcium content of Samples 102 to 114 was 10.6 mg / m ² .

In addition, each sample was used after being left for 1 month at 25 ° C. and 60% relative humidity after coating.

The following experiment was conducted to examine the photographic characteristics of these coated samples.

First, the coated sample was subjected to gradation exposure for sensitometry using a sensitometer (FWH type manufactured by Fuji Photo Film Co., Ltd., color temperature of light source: 3200 ° K). The exposure at this time was performed so that the exposure amount was 250 CMS with an exposure time of 1/10 second.

Next, continuous processing (running test) was performed in the following processing steps and the following processing solution compositions until the tank capacity of the color developing solution was doubled.

The composition of each processing solution is as follows.

Bleach-fix solution (tank solution and replenisher are the same) Water 400ml Ammonium thiosulfate (70%) 100ml Sodium sulfite 17g Ethylenediaminetetraacetic acid iron (III) ammonium 55g Ethylenediaminetetraacetate disodium 5g Ammonium bromide 40g Glacial acetic acid 9g Add water 1000ml pH (25 ℃) 5.40 Rinse solution (same as tank solution and replenisher) Ion-converted water (calcium, magnesium, 3ppm each)
The following) The sensitometry is processed at the start and end of the running test, and the minimum density (Dmin) and maximum density (Dmax) and gradation (density 0.5) of blue (B), green (G) and red (R) are processed. The change in density due to continuous processing was measured using a Macbeth densitometer, and the results are shown in Table 2.

At the same time, the unexposed samples were processed at the end of the run for the evaluation of yellow, magenta, and cyanstin after processing, and each processed sample was stored at 80 ° C and 70% relative humidity for 10 days, and the changes after storage were evaluated. The results are shown in Table 2.

Further, the presence or absence of suspended matter and tar in the color developing solution at the end of running was visually confirmed. The results are shown in Table 2.

As can be seen from Table 2, Sample 1 with a swelling degree of less than 100%
01 and the sample 107 larger than 300%, the photographic characteristics by continuous processing remarkably fluctuated, and the stain after processing also remarkably increased, while the sample within the range of 100% to 300%
It can be seen that there is almost no change in photographic characteristics and an increase in stain after processing due to the continuous processing of 102 to 106, and it is particularly preferable that the range is from 150% to 250%. Further, even if the swelling degree is within the range of the present invention, the sample 108 having a total film thickness when dried of less than 7 μm remarkably changes in photographic characteristics due to continuous processing,
It was found that the surface of the sample of wet heat stain became sticky and the swelling strength was obviously reduced. Furthermore, in the case of the sample 114, the total film thickness during drying was more than 13 μm, the photographic characteristics after continuous processing remarkably fluctuated. It can be seen that the samples 109 to 113, which are in the range of 7 μm to 13 μm, are more preferable, and those of the range of 8 μm to 12 μm are more preferable.

In addition, in Samples 101 to 114, the generation of floating matters and tar was not observed at the end of running.

Example-2 Samples 101, 104, 107, 108 and 114 were used in the same manner as Samples 101, 104, 107, 108 and 114, except that the gelatin hardener used in Examples 1 to 104 was replaced with the following compound. Samples 201 to 205 were prepared respectively. The total amount of gelatin hardening agent added when the oil was swelled in the developer used in Example 1 was 10%.
Adjusted to be the same as 1, 104, 107, 108, 114. Sample 2
The calcium contents of 01 to 205 were all 10.6 mg / m ² .

With respect to Samples 201 to 205, the photographic characteristics at the time of continuous processing, the stain after the processing, and the generation of floating matters and tars in the processing liquid at the end of the running were examined in exactly the same manner as in Example 1. The effect was obtained.

Example 3 Samples 301 to 305 were prepared in exactly the same manner as Sample 104, except that the gelatin in the first to seventh layers in Sample 104 of Example 1 was changed as shown in Table 3.

When the film thickness of Samples 301 to 305 and the degree of swelling with the color developing solution of Example 1 were measured, it was the same as that of Sample 104.

With respect to Samples 301 to 305, the photographic characteristics during continuous processing and the stain after processing were examined in exactly the same manner as in Example 1. All were as good as Sample 104.

Further, Table 3 shows the results of examining the generation states of suspended solids and tar in the treatment liquid at the end of running of Samples 301 to 305 in the same manner as in Example 1. Samples 301 to 303 with a calcium content of 15 mg / m ² or less had almost no problem.
In Samples 304 and 305 with mg / m ² or more, a large amount of suspended solids and tar were generated.

(Example 4) Samples 401 to 401 were prepared in the same manner as in Sample 104 except that the yellow, magenta and cyan couplers used in the first layer, the third layer and the fifth layer of Sample 104 of Example 1 were changed as shown in Table 4. Made 410. (Coupler was replaced by equimolar amount) As for Samples 401 to 410, the photographic characteristics during continuous processing, the stain after processing, and the generation of floating matters and tars at the end of running were examined in the same manner as in Example 1, and all samples were good.

(Example 5) The organic preservative A (X) of the coupler developer used in Example 1
-19) and B (XIV-1) were replaced with the compounds shown in Table 5 to prepare color developers (1) to (22).

Sample 104 was continuously processed in the processing steps of Example 1 using the color developing solutions (1) to (22), and stains after the photographic characteristic processing and the generation of floating matters and tars in the processing solution at the end of running were generated. I checked. Developers (1), (2) containing hydroxylamine and developers (2) containing sulfite,
In the case of (3), the effect was diminished and the photographic characteristics (particularly the maximum density and gradation) fluctuated slightly, but a developer containing neither organic sulfite nor hydroxylamine (containing an organic preservative ( In 4) to (22), the photographic characteristics hardly changed, the preservability after the treatment was good, and the generation of floating matters and tar in the treatment liquid at the end of the running was not observed. In particular, color developers (4), (5), which are a combination of hydroxylamines or hydrazines and amines,
In (7), (11) to (14), (21) and (22), the effect was remarkable as in Example 1.

(Example 6) The first layer, the third layer, and the fifth layer of the sample 104 used in Example 1
Samples 601 to 604 were prepared in the same manner as sample 104 except that the coating silver amount of the layer was changed as shown in Table 6. (Unit is g / m ² ) After imagewise exposure of the above-mentioned light-sensitive material, continuous processing (running test) using a paper processor until replenishment with twice the color developing tank capacity with the following processing steps and processing solutions
I went. Processing temperature Temperature Time Replenishment amount ^* Tank capacity Color development 39 ℃ 60 seconds 30ml 4l Bleach fixing 30-36 ℃ 45 seconds 215ml 4l Stable 30-37 ℃ 20 seconds −2l Stable 30-37 ℃ 20 seconds −2l Stable 30-37 ℃ 20 seconds −2l Stable 30 to 37 ℃ 30 seconds 250ml 2l Dry 70 to 85 ℃ 60 seconds * per 1 m ^{2 of} light-sensitive material (stabilized → 4 tank countercurrent method) The composition of each processing solution is as follows. On the street.

Bleach-fix solution (same as tank solution and replenisher) Water 400ml Ammonium thiosulfate (70%) 100ml Sodium sulfite 17g Ethylenediaminetetraacetic acid iron (III) ammonium 55g Ethylenediaminetetraacetate disodium 5g Glacial acetic acid 9g Water is added to 1000ml pH (25 ℃) 5.40 Stabilizer (same as tank solution and replenisher) Formalin (37%) 0.1g Photographic characteristics during continuous processing, stains in the processing and floating substances and tar generation in the processing solution at the end of running Example 1 0.8 g / m ² or less of the sample 603 and 60 compared to the amount of coated silver 0.80 g / m ² greater than the sample 601 and 602 were examined in the same manner as
4 was superior in photographic characteristics especially during continuous processing.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-62-65040 (JP, A) JP-A-1-298351 (JP, A) JP-A-62-178956 (JP, A) JP-A-60- 159850 (JP, A) JP 61-70552 (JP, A) JP 63-4234 (JP, A) JP 63-43138 (JP, A) JP 63-44656 (JP, A) JP-A-63-41850 (JP, A) JP-B-48-30496 (JP, B1)

Claims (1)

(57) [Claims] 1. A method of continuously processing a silver halide color light-sensitive material with a color developing solution containing at least one aromatic primary amine color developing agent, which comprises a high chloride content of 80 mol% or more of silver chloride. It has a silver emulsion in at least one layer, the amount of coated silver is 0.3 to 0.8 g / m ² , the total film thickness when dried is 7 μm to 13 μm, and the swelling degree in a color developing solution is 100% to 300%. %, And the content of calcium atoms is 14
A silver halide color photographic light-sensitive material that is less than mg / m ²
The replenishing amount of the color developing solution is the silver halide photographic light-sensitive material 1
Under the condition of 20 to 120 ml per m ² , the following general formula (VII
I), (IX), (X), (XI) or (XII) or a color developing solution containing a color developer containing a saccharide or a processing method for processing a silver halide color photographic light-sensitive material. General formula (VIII) In the formula, R ¹¹ and R ¹² represent a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkenyl group, an unsubstituted or substituted aryl group, or a heteroaromatic group. R
¹¹ and R ¹² do not become hydrogen atoms at the same time and may be linked to each other to form a heterocycle together with a nitrogen atom. General formula (IX) In the formula, A ²¹ is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted amino group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkoxy group, Or an unsubstituted aryloxy group, a substituted or unsubstituted carbamoyl group, a substituted or unsubstituted sulfamoyl group, an acyl group, a carboxy group, a hydroxyamino group, or a hydroxyaminocarbonyl group. X ²¹ is -SO ₂ -, or represents -SO-. Y ²¹ represents a hydrogen atom or a group capable of becoming a hydrogen atom by a hydrolysis reaction. General formula (X) In the formula, R ³¹ , R ³² , and R ³³ are hydrogen atoms, substituted or unsubstituted,
Represents an alkyl group, an aryl group, or a heterocyclic group,
R ³⁴ represents a hydroxy group, a hydroxyamino group, a substituted or unsubstituted 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, and C,
It is composed of H, O, N, S and halogen atoms 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. General formula (XI) In the formula, R ⁴¹ represents a hydrogen atom, a halogen atom, an alkyl group,
Aryl group, alkoxy group, aryloxy group, carboxyl group, sulfo group, carbamoyl group, sulfamoyl group, amide group, sulfonamide group, ureido group, alkylthio group, arylthio group, nitro group, cyano group, amino group, formyl group, acyl Represents a group, a sulfonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkoxysulfonyl group, and an aryloxysulfonyl group. When there are two or more R ⁴¹ , the types may be the same or different, and when they are adjacent to each other, they may be bonded to each other to form a ring. R ⁴² represents a hydrogen atom or a hydrolyzable group. Also, m, n
Are integers from 1 to 5, respectively. General formula (XII) In the formula, R ⁵¹ represents a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, an alkoxy group, an aryloxy group or an amino group, and R ⁵² represents a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group. And R ⁵¹ and R ⁵² may form a carbocyclic or heterocyclic ring together. R ⁵¹ represents a hydroxyl group or a substituted or unsubstituted amino group.