JP2552916B2 - Color developing composition and processing method using the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for processing a silver halide color photographic light-sensitive material, and in particular, the stable production of a color developing solution is improved, and the deterioration of the color developing solution with time is improved. The present invention relates to an improved processing method for tar contamination, and further relates to a processing method which is excellent in color developability and has stable photographic performance in continuous processing.

(Prior Art) A color developing solution containing an aromatic primary amine color developing agent has been conventionally used for forming a color image, and now plays a central role in a color photographic image forming method. There is. However, the above color developer has a problem that it is very easily oxidized by air or metal, and when a color image is formed using the oxidized developer, the stain is increased and the sensitivity and gradation are changed. Therefore, it is well known that desired photographic characteristics cannot be obtained.

In addition, the deterioration phenomenon described above tends to be further accelerated with the recent rapid processing at high temperature and the low replenishment of the replenisher. As a result, fatigue of the liquid due to high temperature, coloring of the developer due to long-term retention of the processing liquid for low replenishment due to low replenishment, and accumulation of decomposed products of the developing agent, causing a serious problem of adverse effects on the photosensitive material. There is.

Conventionally, so-called preservatives have been developed to prevent the deterioration of the liquid as described above, but generally these preservatives largely impair the color forming property. Especially, hydroxylamine and sulfite ion, which are widely used in general, are suitable for high silver chloride content photosensitive materials used for rapid processing in recent years.
Has a significant adverse effect.

To address these problems, substituted hydrazine having a substituent has been investigated as a preservative. For example, JP-A-63-17
Examples thereof include alkyl-substituted hydrazines described in JP-A Nos. 0642, 63-170643, JP-A-1-97953, European Patent Application Publication Nos. 0285010 and 0254280. Although some of these substituted hydrazines have little effect on photographic properties,
Not always enough.

(Problems to be Solved by the Invention) Accordingly, the first object of the present invention is to provide a color developing solution which is excellent in stability and can be used for long-term solution storage or during continuous processing of silver halide color photographic light-sensitive materials. (EN) It is intended to provide a treatment method which is less likely to deteriorate the main drug and which is excellent in preventing contamination by its oxidative decomposition product (tar).
A second object of the present invention is to provide a method for processing the above light-sensitive material which is excellent in color developability and stain prevention.

(Means for Solving the Problems) The above object could be achieved by the method described below. That is, (1) a color developing composition containing a compound represented by the following general formula (I).

(2) A method of processing a silver halide color photographic light-sensitive material, which comprises processing the silver halide color photographic light-sensitive material with a color developer in the presence of a compound represented by the following general formula (I).

Achieved by

General formula (I) (In the formula, L represents an alkylene group, an alkenylene group, an arylene group, Represents a divalent linking group formed by combining them alone or in combination, A represents a phosphonic acid residue, a phosphinic acid residue, a phosphonate residue, or a phosphonamide residue, and R represents a hydrogen atom, an alkyl group. Represents a group, a carbamoyl group, an acyl group or an alkoxycarbonyl group, and X is
It represents an amino group, an acylamino group, an alkoxycarbonylamino group, or a ureido group. ) As alkyl-substituted hydrazine, dimethylhydrazine, diethylhydrazine, alkoxyalkylhydrazine and the like are well known, and other known compounds are disclosed in JP-A-63-170642.
No. 63-170643, JP-A-1-97953, and European Patent Application Publication Nos. 0285010 and 0254280, which are specific even when compared to a carboxy group or a sulfo group, which are relatively preferable substituents of substituted alkyl. It was totally unexpected that the substituted hydrazine having a phosphonic acid residue was excellent in stability with time of liquid, antifouling property, photographic variation in processing (eg, stain, sensitivity).

Phosphonic acid residues are generally well known as substituents for substituted alkyls, but are not known as substituents for hydrazine, especially as a preservative for color developers at all in the past. The effect was proved for the first time in the present invention.

This effect means "preservation performance" in a broad sense, meaning (prevention of deterioration of color developing agents) and (prevention of liquid coloring and tar formation).
And (prevention of inhibition of color formation and prevention of stain),
That is, it shows excellent performance in terms of both "photographic performance".

 The general formula (I) will be described in more detail.

In the formula, L is an optionally substituted alkylene group, alkenyl group, arylene group, Or Represents a divalent linking group constituted by or alone,
An alkylene group having 1 to 6 carbon atoms which may be substituted is preferable. Examples of the substituent include a hydroxy group, a carboxy group, a sulfo group, an amino group, an acyl group, an acylamino group, a carbamoyl group, an alkylsulfonyl group, an alkylsulfonylamino group and a sulfamoyl group. Preferred are a hydroxy group, a carboxy group, and a sulfo group. A
Represents a phosphonic acid residue, a phosphinic acid residue, a phononic acid ester residue, or a phosphonamide residue, and a phosphonic acid residue is a preferred example. R represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted carbamoyl group, a substituted or unsubstituted acyl group, a substituted or unsubstituted alkoxycarbonyl group, and a hydrogen atom, a substituted or unsubstituted An alkyl group (preferably having 1 to 6 carbon atoms) is mentioned as a preferred example. As the substituent, a phosphonic acid residue, a phosphinic acid residue, a hydroxy group, a carboxy group,
Sulfo group, amino group, acyl group, acylamino group, carbamoyl group, alkylsulfonyl group, alkylsulfonylamino group, sulfamoyl group, alkyl group, aryl group and the like, phosphonic acid residue, phosphinic acid residue, hydroxy group, A carboxy group and a sulfo group are preferable examples. X represents an optionally substituted amino group, an optionally substituted acylamino group, an optionally substituted alkoxycarbonylamino group, or an optionally substituted ureido group. Examples of the substituent include an alkyl group and an aryl group, and these substituents may be substituted with a hydrophilic group such as a phosphonic acid residue, a phosphinic acid residue, a hydroxy group, a carboxy group and a sulfo group. Preferred examples of X are an optionally substituted amino group and an optionally substituted acylamino group. Further, L and R may be connected to each other to form a ring.

(7) H ₂ NNHCH ₂ PO ₃ H ₂ (8) H ₂ NNH (CH ₂ ) ₂ PO ₃ H ₂ (9) H ₂ NNH (CH ₂ ) ₃ PO ₃ H ₂ (13) H ₂ NNHCH ₂ CH (PO ₃ H ₂ ) ₂ (24) H ₂ NNHCH ₂ PO ₂ H ₂ (30) CH ₃ NHCONHNHCH ₂ PO ₃ H ₂ (31) CH ₃ CONHNHCH ₂ PO ₃ H ₂ (42) CH ₃ NHCONHNH-CH ₂ PO ₃ H ₂ (43) CH ₃ CONHNHHCH ₂ PO ₃ H ₂ (50) H ₂ O ₃ PCH ₂ NHNHCH ₂ PO ₃ H ₂ (52) (H ₂ O ₃ P) ₂ CHCH ₂ NHNHCH ₂ CH (PO ₃ H ₂ ) ₂ (53) H ₂ O ₃ P (CH ₂ ) ₂ NHNH (CH ₂ ) ₂ PO ₃ H ₂ The content of these compounds in the color developer is 0.5 g to 50 g, preferably 1.0 g to 30 g, per color developer.
It is more preferably 1.5 g to 20 g.

These compounds may be present in the light-sensitive material.
Further, not only the color developing solution but also the bleaching and bleach-fixing solution or the washing agent or the stabilizing agent as an alternative to the washing agent, when it is allowed to be present by bringing in or adding from the pre-bath, the main agent and its oxidant present in each solution. Etc., and good performance can be given.

Synthetic examples of these compounds are as follows, taking the exemplified compounds (1) and (4) as examples.

Other compounds can be easily synthesized according to these methods or using known methods.

Synthesis Example 1 32.6 g of formalin was added to a hydrochloric acid aqueous solution of 6.8 g of hydrazine hydrochloride and 18.0 g of phosphorous acid, and the mixture was heated under reflux for 2 hours. The generated crystals were recrystallized from water and methanol to give 7.8 g of compound (1).
(36%) was obtained.

Synthesis Example 2 5.0 g of hydrazine hydrate and 1-chloroethylphosphonic acid 2
An aqueous solution of sodium hydroxide (8.9 g) was heated under reflux for 10 hours.
The generated crystals were recrystallized from water and methanol to obtain 7.4 g (33%) of compound (4).

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

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

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

The color developing solution according to the present invention is represented by the following general formula [A] from the viewpoint that it is possible to more effectively prevent the occurrence of stains and gradation changes during continuous processing, and to improve the effects of the present invention. The compound is more preferably used.

General formula [A] (Wherein, R ₁₁ is a hydroxyalkyl group having 2 to 6 carbon atoms;
₁₂ and R ₂₃ are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group having 2 to 6 carbon atoms, a benzyl group or a formula Where n is an integer of 1 to 6, X and X'are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or 2 to 6 carbon atoms.
Is a hydroxyalkyl group. The compound represented by the general formula [A] is a known compound described in, for example, "Chemical Dictionary" published by Kyoritsu Shuppan Co., Ltd., published on Mar. 15, 1938, and can be easily produced by those skilled in the art. Or it can be obtained.

Preferred specific examples of the compound represented by the general formula [A] are as follows.

(A-1) Ethanolamine (A-2) Diethanolamine (A-3) Triethanolamine (A-4) Di-isopropanolamine (A-5) 2-Methylaminoethanol (A-6) 2-Ethylaminoethanol (A-7) 2-Dimethylaminoethanol (A-8) 2-Diethylaminoethanol (A-9) 1-Diethylamino-2-propanol (A-10) 3-Diethylamino-1-propanol (A-11) 3- Dimethylamino-1-propanol (A-12) Isopropylaminoethanol (A-13) 3-Amino-1-propanol (A-14) 2-Amino-2-methyl-1,3-propanediol (A-15) Ethylenediaminetetraisopropanol (A-16) Benzylethanolamine (A-17) 2-Amino-2- (hydr Roxymethyl)-
1,3-Propanediol (A-18) 1,3-Diaminopropanol (A-19) 1,3-Bis (2-hydroxyethylmethylamino) -propanol These compounds represented by the general formula [A] are From the viewpoint of the effect of the present invention, it is preferably used in the range of 3 g to 100 g per color developing solution, and more preferably 6 g to 60 g.
Used in the g range.

In the color developer according to the present invention, the occurrence of stains and the gradation change during continuous processing are more effectively prevented, and the effects of the present invention are better exhibited.
And the compounds represented by [B-II] are more preferably used.

General formula [BI] General formula [B-II] In the formula, R ₁₄ , R ₁₅ , R ₁₆ and R ₁₇ are each a hydrogen atom,
Halogen atom, a sulfonic acid group, an alkyl group having a carbon number of 1 to 7, -OR _18, -COOR _19, Or, it represents a phenyl group. R ₁₈ , R ₁₉ , R ₂₀ and R ₂₁ each represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. However, when R ₁₅ represents an —OH group or a hydrogen atom, R ₁₄ represents a halogen atom, a sulfonic acid group, an alkyl group having 1 to 7 carbon atoms, —OR ₁₈ , —COOR ₁₉ , Alternatively, it represents a phenyl group.

The alkyl group represented by R ₁₄ , R ₁₅ , R ₁₆ and R ₁₇ includes those having a substituent, for example, a methyl group, an ethyl group, is
o-propyl group, n-propyl group, t-butyl group, n-
Butyl group, hydroxymethyl group, hydroxyethyl group,
Examples include methylcarboxylic acid group, benzyl group, and R
_The alkyl group represented by ₁₈ , R ₁₉ , R ₂₀ and R ₂₁ has the same meaning as described above, and further includes an octyl group and the like.

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

The following are typical examples of the chelating agent of the present invention, but the chelating agent is not limited to these.

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

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, nitrilo-N, N, N-tris (methylenephosphonic acid), ethylenediamine-N, N, N ', N'-tetrakis (methylenephosphonic acid) ), 1,3-diamino-2-propanoltetraacetic acid, transcyclohexanediaminetetraacetic acid, nitrilotripropionic acid, 1,2-diaminopropanetetraacetic acid, hydroxyethyliminodiacetic acid, glycol etherdiaminetetraacetic acid, hydroxyethylenediaminetriacetic acid. , Ethylenediamine ortho-hydroxyphenylacetic 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.

Among these chelating agents, ethylenediaminetetraacetic acid, ethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, 1,3-diaminopropanoltetraacetic acid, ethylenediamine-N, N, N ', N'-tetrakis (methylenephosphonic acid) are preferred. Hydroxyethyliminodiacetic acid is good.

Two or more of these chelating agents may be used in combination, 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 Patent Publication Nos. 37-16088 and 37-598.
No. 7, No. 38-7826, No. 44-12380, No. 45-9019, and thioether compounds represented by U.S. Pat. No. 3,813,247, etc., p shown in JP-A Nos. 52-49829 and 50-15554. -Phenylenediamine compounds, JP-A-50-13
7726, JP-B-44-30074, JP-A-56-156826 and JP-A-52-43429, quaternary ammonium salts, p-aminophenols described in U.S. Pat.Nos. 2,610,122 and 4,119,462, and U.S. Pat. Patent No. 2,494,903, same
3,128,182, 4,230,796, 3,253,919, Japanese Patent Sho 4
1-11431, U.S. Pat. Nos. 2,482,546, 2,596,926 and 3,582,346, etc., amine compounds described in JP-B-3.
Nos. 7-16088, 42-25201, U.S. Pat.No. 3,128,183,
JP-B-41-11431, JP-B-42-23883 and U.S. Pat.
Polyalkylene oxides represented by 532, 501, etc.,
In addition, 1-phenyl-3-pyrazolidones, hydrozines, mesoionic compounds, ionic compounds, imidazoles, etc. can be added as necessary.

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

Chlorine ions and bromine ions are required in the color developer for the purpose of preventing fog. In the present invention, the chlorine ion content is preferably 1.0 × 10 ^{-2 to} 1.5 × 10 ^-1 mol / l, and more preferably 4 × 10 ^-2 to 1 × 10 ^-1 mol / l. When the chlorine ion concentration is more than 1.5 × 10 ^-1 mol / l, it is not preferable to delay the development and quickly obtain a high maximum concentration. Also, 3.
If it is less than 5 × 10 ^-2 mol / l, stains are generated, and further, fluctuation in photographic properties (particularly minimum density) due to continuous processing becomes large, which is not preferable.

In the present invention, the color developer preferably contains bromide ions in an amount of 3.0 × 10 ⁻⁵ mol / l to 1.0 × 10 ⁻³ mol / l. More preferably, it is 5.0 × 10 ^{−5 to} 5 × 10 ⁻⁴ mol / l. Particularly preferably, it is 1 × 10 ^{−4 to} 3 × 10 ⁻⁴ mol / l. When the bromine ion concentration is more than 1 × 10 ^-3 mol / l, the development is delayed, the maximum concentration and sensitivity are lowered, and when the bromine ion concentration is less than 3.0 × 10 ^-5 mol / l, stain is generated, and the continuous processing is involved. It is not preferable because it causes photographic variation (especially minimum density).

Here, chlorine ions and bromine ions may be added directly to the developing solution or may be eluted from the light-sensitive material during the development processing.

When added directly to the color developer, examples of the chlorine ion supplying substance include sodium chloride, potassium chloride, ammonium chloride, nickel chloride, magnesium chloride, manganese chloride, calcium chloride, and cadmium chloride. Among them, preferred is sodium chloride. , Potassium chloride.

It may also be supplied in the form of a salt against the optical brightener added to the developer. As a source of bromide ions, sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide, madanesium bromide, manganese bromide, nickel bromide, cadmium bromide, cerium bromide, thallium bromide Among them, potassium bromide and sodium bromide are preferable.

When it is eluted from the light-sensitive material during development, both chlorine ions and bromine ions may be supplied from the emulsion or may be supplied from sources other than the emulsion.

In the present invention, any antifoggant can be added in addition to chlorine ion and bromine ion, if necessary. As the antifoggant, an alkali metal halide such as potassium iodide and an organic antifoggant can be used. Examples of 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 phosphonic acid, aliphatic carboxylic acid, aromatic carboxylic acid may be added.

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

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

Further, the color developing solution of the present invention has a liquid opening ratio (air contact area (cm ² ) / liquid volume (cm ³ )) which is relatively superior to the combinations other than the present invention under any condition. ,
From the viewpoint of stability of the color developing solution, the liquid opening ratio is 0 to 0.
1 cm ^-1 is preferred. 0.001 for continuous processing
preferably in the range of cm ^-1 ~0.05cm ^-1, more preferably 0.00
It is a 2cm ^-1 ~0.03cm ^-1.

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

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

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 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
3-8 are preferable and 4-7 are especially 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. Particularly, addition of ammonium sulfite is preferable.

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

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

The bleach-fixing solution of the present invention has a processing time of 10 seconds to 120 seconds, preferably 20 seconds to 60 seconds. The replenishment rate is 30 per 1 m ² of light-sensitive material.
It is ml-250 ml, preferably 40 ml-150 ml. Generally, as the replenishment amount is decreased, stain is increased and desilvering failure is likely to occur, but according to the present invention, the replenishment amount of the bleach-fixing solution can be reduced without causing such a problem. You can

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

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

According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced, but due to the increase in the residence time of water in the tank, bacteria propagate, and the suspended matter produced adheres to the photosensitive material, etc. Problem arises. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, the method of reducing calcium and magnesium described in Japanese Patent Application No. 61-131632 can be used very effectively. Further, isothiazolone compounds and siabendazoles described in JP-A-57-8542, chlorinated germicides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc., Hiroshi Horiguchi, "Chemistry of Antibacterial and 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, "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 water temperature and washing time can be set variously depending on the characteristics of the light-sensitive material, the use, etc., but generally 15 to 45 ° C for 20 seconds to 2 minutes, preferably 25 to 40 ° C for 30 seconds to 1 minute 30 seconds. Is selected.

Even in such a short time water washing, according to the present invention,
Good photographic characteristics can be obtained without increasing stain.

Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such stabilizing treatment, JP-A-57-8543 and JP-A-58-14834 are used.
No. 59, No. 184343, No. 60-220345, No. 60-238832
No. 60, No. 60-239784, No. 60-239749, No. 61-4054,
All known methods described in JP-A-61-118749 and the like can be used. Especially 1-hydroxyethylidene-1,1-
A stabilizing bath containing diphosphonic acid, 5-chloro-2-methyl-4-isothiazolin-3-one, a bismuth compound, an ammonium compound and the like is preferably used.

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

The processing step time of the present invention is defined as the time from the contact of the light-sensitive material with the color developing solution to the final bath (generally washing with water or stabilizing bath). The processing step time is 3 minutes. The effect of the present invention can be remarkably exhibited in a rapid processing step of 30 seconds or less, preferably 3 minutes or less.

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

As the silver halide emulsion used in the present invention, an emulsion composed of silver chlorobromide or silver chloride containing substantially no silver iodide can be preferably used. Here, "contains substantially no silver iodide" means that the silver iodide content is 1 mol% or less, preferably 0.2 mol% or less. The halogen composition of the emulsion may be different or the same between grains, but if an emulsion having the same halogen composition among grains is used, it is easy to make the properties of each grain uniform. Regarding the halogen composition distribution inside the silver halide emulsion grains, the so-called uniform structure grains having the same composition in any part of the silver halide grains, or the core inside the silver halide grains and the shell surrounding it. Particles having a so-called laminated structure having a halogen composition different from that of the (shell) [one or more layers], or
Particles with a structure in which the halogen composition is different in a non-layered manner inside or on the surface of the particle (when the surface of the particle is bonded to the edges, corners or surfaces of the different composition) are appropriately selected and used. be able to. In order to obtain high sensitivity, it is advantageous to use either of the latter two rather than the particles having a uniform structure, and it is also preferable from the viewpoint of pressure resistance. When the silver halide grains have the structure as described above, the boundary between different portions in the halogen composition is an unclear boundary because a mixed crystal is formed due to the composition difference even if the boundary is clear. It may also be one that positively has a continuous structural change.

Regarding the halogen composition of these silver chlorobromide emulsions, any silver bromide / silver chloride ratio can be used. This ratio can take a wide range depending on the purpose, but a silver chloride ratio of 2% or more can be preferably used.

A so-called high silver chloride emulsion having a high silver chloride content is preferably used for a light-sensitive material suitable for rapid processing. The silver chloride content of these high silver chloride emulsions is preferably 90 mol% or more,
More preferably 95 mol% or more.

In such a high silver chloride emulsion, a structure having a silver bromide localized layer in the inside and / or on the surface of the silver halide grain in a layered or non-layered manner as described above is preferable.
The halogen composition of the localized phase preferably has a silver bromide content of at least 10 mol%, more preferably more than 20 mol%. These localized layers can be present inside the particles, on the edges, corners, or on the surface of the particles, and one preferable example is a layer epitaxially grown on the corners of the particles.

On the other hand, in order to minimize sensitivity deterioration when the light-sensitive material is subjected to pressure, even in a high-silver chloride emulsion having a silver chloride content of 90 mol% or more, grains of a uniform structure with a small distribution of halogen composition in the grains should be formed. It is also preferably used.

It is also effective to further increase the silver chloride content of the silver halide emulsion for the purpose of reducing the replenishment amount of the developing solution. In such a case, the silver chloride content is 98 mol% to 10
An emulsion of substantially pure silver chloride such as 0 mol% is also preferably used.

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

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

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

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

The silver chlorobromide emulsion used in the present invention is a chimi by P. Glafkides.
e et Phisique Photographique (Paul Montel, 196
7 years), Photographic Emulsion Chemistry by GF Duffin
(Focal Press, 1966), VL Zelikman et al M
aking and Coating Photographic Emuldion (Focal Pre
ss, 1964) and the like. That is, any of an acidic method, a neutral method, an ammonia method, etc. may be used, and a method of reacting a soluble silver salt with a soluble halogen salt may be any method such as a one-sided mixing method, a simultaneous mixing method, and a combination thereof. You may use. It is also possible to use a method of forming particles in an atmosphere in which silver ions are excessive (so-called reverse mixing method). As one form of the simultaneous mixing method, a method of keeping pAg in a liquid phase where silver halide is formed constant, that is, a so-called controlled double jet method can be used.
According to this method, a silver halide emulsion having a regular crystal form and a nearly uniform grain size can be obtained.

The silver halide emulsion used in the present invention can be introduced with various polyvalent metal ion impurities in the process of emulsion grain formation or physical ripening. Examples of compounds used include salts of cadmium, zinc, lead, copper, thallium, etc., or salts or complex salts of Group VIII elements iron, ruthenium, rhodium, palladium, osmium, iridium, platinum and the like. it can. Especially above VI
Group II elements can be preferably used. The addition amount of these compounds may vary over a wide range depending on the purpose, but is preferably 10 ^-9 to 10 ^-2 mol with respect to the silver halide.

The silver halide emulsion used in the present invention is usually chemically and spectrally sensitized.

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

Spectral sensitization is performed for the purpose of imparting spectral sensitivity in a desired light wavelength region to the emulsion of each layer in the light-sensitive material of the present invention. In the present invention, it is preferable to add a dye-spectral sensitizing dye that absorbs light in the wavelength range corresponding to the desired spectral sensitivity. Examples of the spectral sensitizing dye used at this time include Heterocyclic compo by FM Harmer.
unds-Cyanine dyes and related compounds (John Wil
ey & Sons [New York, London], 1964). As specific examples of the compound and the spectral sensitization method, those described in the above-mentioned JP-A No. 62-215272, page 22, upper right column to page 38 are preferably used.

To the silver halide emulsion used in the present invention, various compounds or their precursors are added for the purpose of preventing fog during the production process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. be able to. As specific examples of these compounds, those described on pages 39 to 72 of the above-mentioned JP-A No. 62-215272 are preferably used.

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

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

A cyan coupler preferably used in the present invention,
The magenta coupler and the yellow coupler are represented by the following general formulas (C-I), (C-II), (M-I), (M-II) and (Y).

General formula (C-I) General formula (C-II) General formula (MI) General formula (M-II) General formula (Y) In the general formulas (C-I) and (C-II), R ₁ , R ₂
And R ₄ represents a substituted or unsubstituted aliphatic, aromatic or heterocyclic group, R ₃ , R ₅ and R ₆ represent a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group or an acylamino group, R ₃ may represent a nonmetallic atom group forming a nitrogen-containing 5-membered ring or 6-membered ring together with R ₂ . Y ₁ and Y ₂ represent a hydrogen atom or a group capable of splitting off during the coupling reaction of the oxidized product of the developing agent. n represents 0 or 1.

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

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

In the general formula (CI), preferred R ₁ is an aryl group,
A heterocyclic group, a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an acylamino group, an acyl group,
A carbamoyl group, a sulfonamide group, a sulfamoyl group, a sulfonyl group, a sulfamide group, an oxycarbonyl group, and an aryl group substituted with a cyano group are more preferable.

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

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

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

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

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

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

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

Among the pyrazoloazole couplers represented by the general formula (M-II), the imidazo [1,2-b] pyrazoles described in U.S. Pat. No. 4,500,630 have small yellow sub-absorption of a coloring dye and light fastness. Are preferred and are
The pyrazolo [1,5-b] [1,2,4] triazoles described in 4,540,654 are particularly preferred.

In addition, a pyrazolotriazole coupler in which a branched alkyl group as described in JP-A-61-65245 is directly linked to the 2-, 3- or 6-position of a pyrazolotriazole ring, JP-A-61-652.
A pyrazoloazole coupler containing a sulfonamide group in the molecule as described in JP-A No. 46, a pyrazoloazole coupler having an alkoxyphenyl sulfonamide ballast group as described in JP-A-61-147254, and a European patent. It is preferable to use a pyrazolotriazole coupler having an alkoxy group or an aryloxy group at the 6-position as described in (Publication) Nos. 226,849 and 294,785.

In formula (Y), R ₁₁ represents a halogen atom, an alkoxy group, a trifluoromethyl group or an aryl group, and R ₁₂ represents a hydrogen atom, a halogen atom or an alkoxy group. A is —NHCOR ₁₃ , —NHSO ₂ —R ₁₃ , —SO ₂ NHR ₁₃ , —
COOR ₁₃ , Represents However, R ₁₃ and R ₁₄ each represent an alkyl group, an aryl group, or an acyl group. Y ₅ represents a leaving group. R ₁₂
And the substituents of R ₁₃ and R ₁₄ are the same as the substituents allowed for R ₁ , and the leaving group Y ₅ is preferably of a type that leaves at either an oxygen atom or a nitrogen atom. The nitrogen atom elimination type is particularly preferable.

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

The couplers represented by the general formulas (C-I) to (Y) are usually contained in the silver halide emulsion layer constituting the photosensitive layer in an amount of 0.1 to 1.0 mol, preferably 0.1 to 1.0 mol per mol of silver halide.
~ 0.5 mol is contained.

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

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

As the high-boiling organic solvent, the following general formula (A) is preferable.
The high boiling point organic solvent represented by (E) is used.

General formula (A) Formula _{(B) W 1 -COO-W} 2 Formula (C) General formula (D) Formula (E) W ₁ -O-W ₂ (In the formula, W ₁ , W ₂ and W ₃ each represent a substituted or unsubstituted alkyl group, cycloalkyl group, alkenyl group, aryl group or heterocyclic group, W ₄ is W ₁ , OW ₁ or SW
Represents ₁ , and n is an integer of 1 to 5, and when n is 2 or more, W ₄ may be the same or different, and in the general formula (E), W ₁ and W ₂ are condensed rings. May be formed).

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

For details of these high-boiling organic solvents, see JP-A-62-62.
-215272, from page 137, lower right column to page 144, upper right column.

Further, these couplers are impregnated with a loadable latex polymer (for example, US Pat. No. 4,203,716) in the presence or absence of the above high boiling point organic solvent, or dissolved in a water-insoluble and organic solvent-soluble polymer. It can be emulsified and dispersed in a hydrophilic colloid aqueous solution.

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

The light-sensitive material produced using the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative or the like as a color antifoggant.

Various anti-fading agents can be used in the light-sensitive material of the present invention. That is, as an organic anti-fading agent for cyan, magenta and / or yellow images, hydroquinones,
6-hydroxychromans, 5-hydroxycoumarans, spirochromans, p-alkoxyphenols,
Typical examples are hindered phenols centered on bisphenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines and ether or ester derivatives obtained by silylating and alkylating the phenolic hydroxyl groups of these compounds. Can be mentioned. Further, a metal complex represented by a (bissalicylaldoximato) nickel complex and a (bis-N, N-dialkyldithiocarbamato) nickel complex can also be used.

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

Hydroquinones are U.S. Patent Nos. 2,360,290 and 2,41
8,613, 2,700,453, 2,701,197, 2,72
No. 8,659, No. 2,732,300, No. 2,735,765, No. 3,9
82,944, 4,430,425, British Patent 1,363,921,
In US Pat. Nos. 2,710,801 and 2,816,028, etc., 6-
Hydroxychromans, 5-hydroxycoumarans, and spirochromans are described in U.S. Pat. Nos. 3,432,300 and 3,573,0.
No. 50, No. 3,574,627, No. 3,698,909, No. 3,764,
No. 337, JP-A-52-152225, etc., spiroindanes in US Pat. No. 4,360,589, p-alkoxyphenols in US Pat. No. 2,735,765, British Patent No. 2,066,975,
JP-A-59-10539 and JP-B-57-19765 disclose hindered phenols in U.S. Pat. No. 3,700,455 and JP-A-52-72.
No. 224, U.S. Pat.No. 4,228,235, Japanese Patent Publication No. 52-6623 and the like, gallic acid derivatives, methylenedioxybenzenes, aminophenols are respectively U.S. Pat.No. 3,457,079,
No. 4,332,886, Japanese Patent Publication No. 56-21144, etc., hindered amines are described in U.S. Patent Nos. 3,336,135 and 4,268,593.
No., British Patent Nos. 1,326,889, 1,354,313, 1,
No. 410,846, Japanese Patent Publication No. 51-1420, JP-A No. 58-114036, No. 59-53846, No. 59-78344, etc., metal complexes are U.S. Pat.Nos. 4,050,938, 4,241,155, British patents. Second 02
7,731 (A). These compounds can achieve the object by usually coemulsifying 5 to 100% by weight of the corresponding color coupler with the coupler and adding them to the photosensitive layer. In order to prevent the deterioration of the cyan dye image due to heat and especially light, it is more effective to introduce an ultraviolet absorber into the cyan coloring layer and the layers on both sides adjacent to the cyan coloring layer.

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

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

Further, it is particularly 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 k ₂ 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 k ₂ is larger than this range, the compound itself becomes unstable and may react with gelatin or water to decompose. On the other hand, if k ₂ is smaller than this range, the reaction with the remaining aromatic amine-based developing agent is slow, and as a result, side effects of the remaining aromatic amine-based developing agent may not be prevented.

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

General formula (FI) R _1- (A) _n -X General formula (F II) In the formula, R ₁ and R ₂ each represent an aliphatic group, an aromatic group, or a heterocyclic group. n represents 1 or 0. A represents a group which 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 represents that an aromatic amine-based developing agent is added to the compound of the general formula (F II). Represents a promoting group. Where R ₁ and X, Y and R ₂
Alternatively, B and 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 the general formulas (FI) and (F II) are described in JP-A-63-158545, JP-A-62-283338, EP-A-298321 and EP-277589. Those described are preferred.

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 EP-A-255722, JP-A-62-143048 and JP-A-62-143048.
Those described in 229145, Japanese Patent Application No. 63-136724, No. 62-214681, European Patent Publication No. 298321, No. 277589 and the like are preferable.

Details of the combination of the compound (G) and the compound (F) are described in European Patent Publication No. 277589.

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

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

In the present invention, gelatin may be lime-treated,
It may be either treated with an acid or not. Details of the gelatin manufacturing method are described in Arthur Weuice, The Macromolecular Chemistry of Gelatin (Academic Press, 1964).

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

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

Other reflective supports include specular or secondary
Supports having a metal surface that is diffusely reflective can be used. The metal surface has a spectral reflectance of 0.5 in the visible wavelength range.
The above is preferable, and it is preferable that the metal surface is roughened or is made to be diffuse reflective by using metal powder. As the metal, aluminum, tin, silver, magnesium, or an alloy thereof is used, and the surface may be the surface of a metal plate, a metal foil, or a metal thin layer obtained by rolling, vapor deposition, or plating.
Among them, it is preferable to obtain the metal by vapor-depositing a metal on another substrate. It is preferable to provide a water resistant resin, especially a thermoplastic resin layer, on the metal surface. An antistatic layer may be provided on the side of the support of the present invention opposite to the side having the metal surface. For details of such a support, see, for example, JP-A-61-210346.
No. 63-24247, No. 63-24251 and No. 63-24255.

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

As the light-reflecting substance, a white pigment should be sufficiently kneaded in the presence of a surfactant, and the surface of the pigment particles should not be mixed.
It is preferable to use one treated with a tetrahydric alcohol.

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

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

(Examples) Hereinafter, the present invention will be described with reference to Examples, but the present invention is not limited thereto.

Example 1 A multilayer color photographic paper having the following layer structure was prepared on a paper support laminated on both sides with polyethylene. The coating liquid was prepared as follows.

Preparation of 1st layer coating solution Yellow coupler (ExY) 19.1g and color image stabilizer (Cp
d-1) 4.4 g and color image stabilizer (Cpd-7) 0.7 g were dissolved by adding ethyl acetate 27.2 cc and solvent (Solv-1) 8.2 g, and this solution was dissolved in 10% sodium dodecylbenzenesulfonate 8c.
It was emulsified and dispersed in 185 cc of 10% gelatin aqueous solution containing c. On the other hand, a silver chlorobromide emulsion (cubic, 3: 7 mixture of 0.88 μm average grain size and 0.70 μm average grain size (silver molar ratio). The variation coefficient of grain size distribution is 0.08 and 0.10, and each emulsion is silver bromide.
The following blue-sensitive sensitizing dyes were added to the large-sized emulsion at 2.0 × 10 ⁻⁴ mol per mol of silver, and 0.2 × 10 ⁻⁴ mol was added to the small-sized emulsion. , 2.5 × 10 ⁻⁴ mol of each was added, and then sulfur-sensitized. The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a first coating solution having the composition shown below.

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. The gelatin hardener for each layer is 1-
Oxy-3,5-dichloro-s-triazine sodium salt was used.

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

Blue-sensitive emulsion layer (Each mol of silver halide is 2.0 × 10 ^-4 mol for large size emulsion, and each is for small size emulsion.
2.5 × 10 ^-4 mol) Green sensitive emulsion layer (For large emulsions per mol of silver halide,
4.0 × 10 ^-4 mol, 5.6 × 10 ^-4 mol for small emulsions and (For large emulsions per mol of silver halide,
7.0 × 10 ^-5 mol, and 1.0 × 10 ^-5 for small size emulsions
Mol) Red-sensitive emulsion layer (For large emulsions per mol of silver halide,
0.9 × 10 ^-4 mol, or 1.1 × 10 ^-4 for small emulsions
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.

Further, 1- (5-methylureidophenyl) -5-mercaptotetrazole was added to each of the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer per mol of silver halide.
8.5 × 10 ^-5 mol, 7.7 × 10 ^-4 mol and 2.5 × 10 ^-4 mol were added.

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

The following dyes were added to the emulsion layer to prevent irradiation.

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

Support Polyethylene laminated paper [Polyethylene on the first layer side contains white pigment (TiO ₂ ) and bluish dye (ultraviolet)] First layer (blue sensitive layer) Said silver chlorobromide emulsion 0.30 Gelatin 1.86 Yellow coupler (ExY ) 0.82 Color image stabilizer (Cpd-1) 0.19 Solvent (Solv-1) 0.35 Color image stabilizer (Cpd-7) 0.06 Second layer (color mixing prevention layer) Gelatin 0.99 Color mixing inhibitor (Cpd-5) 0.08 Solvent ( Solv-1) 0.16 Solvent (Solv-4) 0.08 Third layer (green-sensitive layer) Silver chlorobromide emulsion (cubic, 1: 3 mixture of 0.55 μm average particle size and 0.39 μm average particle size (Ag mol) The coefficient of variation of the grain size distribution is 0.10 and 0.08, and AgBr0.
0.12 Gelatin 1.24 Magenta coupler (ExM) 0.20 Color image stabilizer (Cpd-2) 0.03 Color image stabilizer (Cpd-3) 0.15 Color image stabilizer (Cpd-4) 0.02 Color image stabilizer (Cpd-9) 0.02 Solvent (Solv-2) 0.40 Fourth layer (ultraviolet absorbing layer) Gelatin 1.58 Ultraviolet absorbing agent (UV-1) 0.47 Color mixture inhibitor (Cpd-5) 0.05 Solvent (Solv) -5) 0.24 Fifth layer (red-sensitive layer) Silver chlorobromide emulsion (cubic, 1: 4 mixture of 0.58 µm and 0.45 µm in average grain size, Ag molar ratio) Variation in grain size distribution The coefficients are 0.09 and 0.11, AgBr0 for each emulsion.
0.23 Gelatin 1.34 Cyan coupler (ExC) 0.32 Color image stabilizer (Cpd-6) 0.17 Color image stabilizer (Cpd-7) 0.40 Color image stabilizer ( Cpd-8) 0.04 Solvent (Solv-6) 0.15 Sixth layer (UV absorbing layer) Gelatin 0.53 UV absorber (UV-1) 0.16 Color mixing inhibitor (Cpd-5) 0.02 Solvent (Solv-5) 0.08 Seventh layer (Protective layer) Gelatin 1.33 Polyvinyl alcohol acrylic modified copolymer (degree of modification
17%) 0.17 Liquid paraffin 0.03 Next, the following processing solutions were prepared. The composition is as follows.

Color developer Water 600 ml Ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid 2.0g Potassium bromide 0.015g Potassium chloride 3.1g Triethanolamine 10.0g Potassium carbonate 27g Optical brightener (WHITEX ・ 4B Sumitomo Chemical Co., Ltd. 1.0g Additive Refer to Table 1 N-Ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 5.0g Water was added to 1000 ml pH (25 ° C ) 10.05 Bleach-fixing solution Water 400 ml Ammonium thiosulfate (70%) 100 ml Sodium sulfite 17 g Ethylenediaminetetraacetic acid iron (III) ammonium 55 g Ethylenediaminetetraacetate disodium 5 g Ammonium bromide 40 g Water 1000 ml pH ( 25 ℃) 6.0g Rinse solution Ion-exchanged water (3ppm or less for each of calcium and magnesium) Prepare part of the above color developer in each beaker so that the opening ratio will be 0.015cm ^-1. Aged at 35 ° C for 35 days.

A sensitometer (FWH type manufactured by Fuji Photo Film Co., Ltd.) was used as the above color light-sensitive material, and gradation exposure of a three-color separation filter for sensitometry was performed. The exposure was performed so that the exposure amount was 250 CMS with the exposure time of 0.1 seconds.

After the exposure, treatment was carried out according to the following steps using the (fresh solution) immediately after preparation of the solution prepared above and the aged color developing solution (aging solution). Processing process Temperature Time Color development 38 ℃ 45 seconds Bleach fixing 35 ℃ 45 seconds Rinse 35 ℃ 20 seconds Rinse 35 ℃ 20 seconds Rinse 35 ℃ 20 seconds Dry 80 ℃ 60 seconds Process with fresh color developing solution (fresh solution) Increase in minimum density Dmin of yellow when processed with color developer (aged solution) aged with respect to minimum density (Dmin) of yellow and sensitivity of magenta (log E of exposure dose giving density 0.5) (△ Dmin) and magenta sensitivity change (△ S)
Was calculated. The residual amount of the main drug in the aged liquid was fixed by high performance liquid chromatography. The results are shown in Table 1.

As is clear from Table 1, according to the configuration of the present invention, Δ
It can be seen that the values of Dmin and ΔS are small, and fluctuations in photographic properties are suppressed. (Nos. 6 to 21) Further, it can be seen that the reduction of the residual amount of the main drug is greatly improved by using the compound of the present invention and sufficient performance can be obtained.

In particular, by comparing No. 3 and No. 21, No. 4 and No. 17, and No. 5 and No. 7, the values of ΔDmin and ΔS were found when a substituent such as phosphonic acid was substituted on the hydrorazine analog. Was small, and the decrease in the remaining amount of main business could be greatly improved.

Example 2 Additives No. 6 and No. 7 in Table 1 of Example-1 were used as the specific exemplified compounds (14), (15), (17) of the present invention,
In the processing liquids changed to (30), (31), (32), (35), and (52), the color development temperature was set to 35 ° C., and otherwise the same as in Example-1.

As a result, good results were obtained according to the constitution of the present invention as compared with the case where the additive was N, N dimethylhydrazine as in Example-1.

Example 3 A multi-layer color photographic paper having the following layer constitution was produced on a paper support which was laminated on both sides with polyethylene and the surface of which was subjected to a corona discharge treatment. The coating liquid was prepared as follows.

Preparation of 1st layer coating solution 60.0g of yellow coupler (ExY) and anti-fading agent (Cp
d-1) 28.0 g of ethyl acetate 150 cc and solvent (Solv-
3) Add 1.0 cc and 3.0 cc of solvent (Solv-4) and dissolve, then add 10 cc of this solution containing sodium dodecylbenzene sulfonate.
% Gelatin aqueous solution (450 cc) and then dispersed with an ultrasonic homogenizer. The resulting dispersion is 420 g of silver chlorobromide emulsion (0.7 mol% of silver bromide) containing the following blue-sensitive sensitizing dye.
To prepare a coating solution for the first layer.

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. As a gelatin hardening agent for each layer 1,2-
Bis (vinylsulfonyl) ethane was used.

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

Blue-sensitive emulsion layer; Anhydro-5,5'-dichloro-3,3'-
Disulfoethylthiacyanine hydroxide Green-sensitive emulsion layer; Anhydro-9-ethyl-5,5'-diphenyl-3,3'-disulfoethyloxacarbocyanine hydroxide Red-sensitive emulsion layer; 3,3'-diethyl- 5-methoxy-9,11-
Neopentyl thiadicarbocyanine iodide The following substances were used as stabilizers for each emulsion layer.

The following dyes were used as the anti-irradiation dye.

[3-carboxy-5-hydroxy-4- (3- (3
-Carboxy-5-oxo-1- (2,5-bisulfonatophenyl) -2-pyrazolin-4-ylidene) -1-propenyl) -1-pyrazolyl] benzene-2,5-disulfonate-disodium salt N, N '-(4,8-dihydroxy-9,10-dioxo-3,7
-Disulfonatoanthracene-1,5-diyl) bis (aminomethanesulfonate) -tetrasodium salt [3-cyano-5-hydroxy-4- (3- (3-cyano-5-oxo-1- ( 4-sulfonate phenyl)
-2-pyrazolin-4-ylidene) -1-bentanyl)
-1-Pyrazolyl] benzene-4-sulfonate-sodium salt (Layer constitution) The composition of each layer is shown below. Numbers represent coating weight (g / m ² ). The silver halide emulsion represents the coating amount in terms of silver.

Support Paper support laminated on both sides with polyethylene and corona discharge treated on the surface. First layer (blue sensitive layer) Silver chlorobromide emulsion (AgBr 0.7 mol%, cubic, average grain size 0.9 μm) 0.29 Gelatin 1.80 Yellow coupler (ExY) 0.60 Anti-fading agent (Cpd-1) 0.28 Solvent (Solv-3) 0.01 Solvent (Solv-4) 0.03 Second layer (color mixing prevention layer) Gelatin 0.80 Color mixing inhibitor (Cpd-2) 0.055 Solvent ( Solv-1) 0.03 Solvent (Solv-2) 0.15 Third layer (green-sensitive layer) Silver chlorobromide emulsion (AgBr 0.7 mol%, cubic, average grain size 0.45 μm) 0.18 Gelatin 1.86 Magenta coupler (ExM) 0.27 Anti-fading agent (Cpd-3) 0.17 Anti-fading agent (Cpd-4) 0.10 Solvent (Solv-1) 0.2 Solvent (Solv-2) 0.03 Fourth layer (anti-color mixing layer) Gelatin 1.70 Anti-fading agent (Cpd-2) ) 0.065 UV absorber (UV-1) 0.45 UV absorber (UV-2) 0.23 Solvent Solv-1) 0.05 Solvent (Solv-2) 0.05 Fifth layer (red sensitive layer) Silver chlorobromide emulsion (AgBr 4 mol%, cubic, average grain size 0.5 μm) 0.21 Gelatin 1.80 Cyan coupler (ExC-1) 0.26 Cyan coupler (ExC-2) 0.12 Anti-fading agent (Cpd-1) 0.20 Solvent (Solv-1) 0.16 Solvent (Solv-2) 0.09 Color accelerator (Cpd-5) 0.15 Sixth layer (UV absorbing layer) Gelatin 0.70 UV absorber (UV-1) 0.26 UV absorber (UV-2) 0.07 Solvent (Solv-1) 0.30 Solvent (Solv-2) 0.09 7th layer (protective layer) Gelatin 1.07 (ExY) Yellow coupler α-pivalyl -Α- (3-Benzyl-1-hydantoinyl) -2-chloro-5- [β- (dodecylsulfonyl) butyramide] acetanilide (ExM) magenta coupler 7-chloro-6-isopropyl-3- {3-[(2 −
Butoxy-5-tert-octyl) benzenesulfonyl]
Propyl} -1H-pyrazolo [5,1- C ] -1,2,4-triazole (ExC-1) cyan coupler 2-pentafluorobenzamide-4-chloro-5
[2- (2,4-di-tert-amylphenoxy) -3-methylbutylamidophenol (ExC-2) cyan coupler 2,4-dichloro-3-methyl-6- [α- (2,4-di −
tert-Amylphenoxy) butyramide] phenol (Cpd-2) Anti-color mixing agent 2,5-di-tert-octylhydroquinone (Cpd-3) Anti-fading agent 7,7'-dihydroxy-4,4,4 ', 4'-tetramethyl-
2,2'-spirochroman (Cpd-4) anti-fading agent N- (4-dodecyloxyphenyl) -morpholine (Cpd-5) color development accelerator p- (p-toluenesulfonamide) phenyl-dodecane (Solv-1) Solvent Di (2-ethylhexyl) phthalate (Solv-2) solvent Dibutylphthalate (Solv-3) solvent Di (i-nonyl) phthalate (Solv-4) solvent N, N-diethylcarbonamide-methoxy-2,4-di −
t-Amylbenzene (UV-1) UV absorber 2- (2-hydroxy-3,5-di-tert-amylphenyl) benzotriazole (UV-2) UV absorber 2- (2-hydroxy-3,5) -Di-tert-butylphenyl) benzotriazole These samples were subjected to imagewise exposure and subjected to continuous processing (running test) using a paper processor until replenishing twice the tank capacity for color development in the following processing steps. went.

In addition, the sample was exposed to light by the method described in Example 1 and processed before and after the running test.

The composition of each processing solution is as follows.

Bleach-fix solution (tank solution and replenisher are the same) Water 400 ml Ammonium thiosulfate (70%) 100 ml Sodium sulfite 17g Ethylenediaminetetraacetic acid iron (III) ammonium 55 g Ethylenediaminetetraacetate dinatrium 5 g Glacial acetic acid 9 g Add water 1000 ml pH (25 ℃) 5.40 Stabilizer (same as tank and replenisher) Formalin (37%) 0.1 g Formalin-sulfite adduct 0.7 g 5-Chloro-2-methyl-4-isothiazolin-3-one 0.02 g 2-Methyl-4-isothiazolin-3-one 0.01 g Copper sulfate 0.005 g Water was added to 1000 ml pH (25 ° C) 4.0 The minimum concentration (Dmin) of each of yellow, magenta and cyan after running was measured, and Then, the gradation change (Δγ) of cyan after the end of running with respect to cyan at the start of the running test was calculated. However, the gradation is represented by the density change from the point where the density is 0.5 to the density point on the high exposure side of 0.3 with logE.

The results are shown in Table 2. As is clear from Table 2, by using the compound of the present invention, the Dmin of yellow, magenta and cyan and especially the gradation change are significantly smaller than those of other alkyl-substituted hydrazines (No. 10 to 33), Or, in the combined use of the additive I such as triethanol, the combined use with the compound of the present invention is compared with the combined effect of the comparative examples (No. 1 vs. No. 2 to 5, No. 6, 8 vs. No. 7, 9). Effect (No.10, 11, 12 vs. No. 13, 1
4, 15 or No. 16, 17, 18, No. 28, 29 vs. No. 30, 31 or 3
2, 33) is large. In particular, compounds A-3 and B described in the text
It can be seen that even better results can be obtained by using the compound of the present invention in combination among the two such as -I-2. (No.1
0, 11, 12 vs. No. 13, 14, 15 vs. No. 24, 25, 26) Example-4 The light-sensitive material prepared in Example-1 was subjected to sensitometric exposure as described in Example-1. Also, a part of the color developer described below is adjusted to have an aperture ratio of 0.02 cm ^-1 ,
For 20 days. Step Temperature Time Color development 35 ° C. 45 seconds blix 35 ° C. 45 sec Rinse 35 ° C. 20 sec Rinse 35 ° C. 20 sec Rinse 35 ° C. 20 seconds Drying 80 ° C. 60 seconds Color developer Water 700 ml Ethylenediaminetetraacetic acid 2.0g 1,2-Dihydroxybenzene-3,5-disulfonic acid dinatrium salt 0.6g Potassium bromide See Table 3 Potassium chloride See Table 3 Optical brightener (4,4'-diaminostilbene type) 1.5g Triethanol Amine 10 g Sodium sulfite See Table 3 Additive See Table 3 N-Ethyl-N (β-methanesulfonamidoethyl) -3-methyl- 4 -aminoaniline sulfate 5.5 g Water was added to 1000 ml pH (25 ° C) 10.05 Similar to Example-1, change in magenta sensitivity before and after aging (ΔS) and minimum concentration of magenta after aging liquid treatment (Dmi
n) was measured. Further, the gradation change of yellow (Δγ) and the maximum density of magenta (Dmax) after the liquid treatment with time were measured in the same manner as in Example-3. The result (△ S), (Dmin) is the third
Table (1) shows (Δγ) and (Dmax) in Table 3 (2).

From Table 3 (1), when diethylhydroxylamine and compounds a, b, and c are used, the ΔS and Dmin values are large (No. 1 to 9), whereas when the compound of the present invention is used, It can be seen that the value is small (No. 10 to 18). Also in the constitution of the present invention, ΔS is large when the amount of potassium bromide and potassium chloride is large (No. 14), and Dmin is large when the amount is small (No. 10). Therefore, the concentration range shown in (No. 11 to 13) is preferable. It can be seen that this change is not so remarkable in Comparative Examples (Nos. 5 to 1, Nos. 2 to 4).

Next, from Table 3 (2), it can be seen that according to the constitution of the present invention, magenta coloring property is excellent in all regions of the sulfurous acid concentration. (No.25 ~ 2 against No.19 ~ 21, No.22 ~ 24
7, No. 28 to 30) Further, in the constitution of the present invention, it is found that the less sodium sulfite, the smaller Δγ is particularly preferable.
5 ~ 27, No. 28 ~ 30) Example-5 Imagewise exposure was given to the light-sensitive material prepared in Example-1.
Using a paper processor, in the following processing steps, continuous processing (running test) was carried out until the tank capacity for color development was doubled. In addition, it was exposed to light by the method described in Example 1 separately, and processed before and after the running test.

Further, the liquid opening ratio of the color developing solution is 0.005 cm ^-1 on average on both of the above.

 The composition of each processing solution is as follows.

Bleach-fixing solution (same as tank solution and replenisher) Water 400 ml Ammonium thiosulfate (70%) 100 ml Sodium sulfite 17 g Ethylenediaminetetraacetic acid iron (III) ammonium 55 g Ethylenediaminetetraacetic acid dinatrium 5 g Glacial acetic acid 9 g 1000 ml pH (25 ° C) 5.40 Rinse solution (tank solution and replenisher are the same) Ion-exchanged water (calcium and magnesium are 3 ppm or less).

The minimum densities (Dmin) of yellow, magenta, and cyan after the completion of the running test were measured, and the gradation change (Δγ) of cyan at the end of running with respect to cyan at the start of the running test was calculated. However, the gradation is represented by the density change from the point where the density is 0.5 to the density point on the high density side of 0.3 with logE.

In addition, the liquid state of the color developer after running is Indicated by.

The results are shown in Table 4. As is apparent from Table 4, according to the constitution of the present invention, the replenishment amount of the color developing solution is at least (51 ml / m ² ), the increase in stain is very small, and the liquid is good. I understand. Further, a large relative preferable replenishing amount of 40ml~110ml / m ² range, that is, Comparative Examples towards 109 ml / m ² and 51 ml / m ² as compared to when the effect is the replenishing amount of 155 ml / m ² of the present invention It is possible to exert an effect.

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Claims (4)

(57) [Claims] 1. A color developing composition comprising a compound represented by the following general formula (I). General formula (I) (In the formula, L represents an alkylene group, an alkenylene group, an arylene group, Represents a divalent linking group formed by combining them alone or in combination, A represents a phosphonic acid residue, a phosphinic acid residue, a phosphonate residue, or a phosphonamide residue, and R represents a hydrogen atom, an alkyl group. Represents a group, a carbamoyl group, an acyl group or an alkoxycarbonyl group, and X is
It represents an amino group, an acylamino group, an alkoxycarbonylamino group, or a ureido group. ) 2. A method of processing a silver halide color photographic light-sensitive material, which comprises processing the silver halide color photographic light-sensitive material with a color developer in the presence of a compound represented by the following general formula (I). General formula (I) (In the formula, L represents an alkylene group, an alkenylene group, an arylene group, Represents a divalent linking group formed by combining them alone or in combination, A represents a phosphonic acid residue, a phosphinic acid residue, a phosphonate residue, or a phosphonamide residue, and R represents a hydrogen atom, an alkyl group. Represents a group, a carbamoyl group, an acyl group or an alkoxycarbonyl group, and X is
It represents an amino group, an acylamino group, an alkoxycarbonylamino group, or a ureido group. ) 3. The processing method according to claim 2, wherein the color developing solution contains at least one compound represented by the general formula [A]. General formula [A] (Wherein, R ₁₁ is a hydroxyalkyl group having 2 to 6 carbon atoms;
₁₂ and R ₂₃ are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group having 2 to 6 carbon atoms, a benzyl group or a formula Where n is an integer of 1 to 6, X and X'are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or 2 to 6 carbon atoms.
Is a hydroxyalkyl group. ) 4. Chloride ions in the color developer are 3.5 × 1.
0 ^{-2 to} 1.5 x 10 ^-1 mol / l and 3.0 x 1 bromine ion
The treatment method according to claim (2), characterized in that the treatment method comprises 0 ^{-5 to} 1.0 × 10 ^-3 mol / l.