JP2866945B2 - Color developing composition and processing method using the same - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a method for processing a silver halide color photographic light-sensitive material, and more particularly, to improving the stability of a color developer and deteriorating the color developer over time. The present invention relates to a processing method in which tar contamination is improved, and a processing method which is excellent in color developability and provides stable photographic performance during 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 currently plays a central role in a color photographic image forming method. I have. However, the above color developing solution has a problem that it is very easily oxidized by air or metal, and when a color image is formed using the oxidized developing solution, stains increase, sensitivity and gradation change. It is well known that desired photographic characteristics cannot be obtained due to the

In addition, with the recent rapid processing at high temperatures and the low replenishment of the replenisher, the above-mentioned deterioration phenomenon tends to be further accelerated. As a result, the coloration of the developer due to the long-term retention of the processing solution in the processing tank and the accumulation of decomposition products of the developing agent due to the fatigue and low replenishment of the solution due to high temperatures have a serious problem on photosensitive materials. Has become.

So-called preservatives have been developed in order to prevent such deterioration of the liquid, but these preservatives generally have a large inhibition on the coloring property. Particularly, hydroxyamine and sulfite ions, which are generally widely used, have a remarkable adverse effect on photosensitive materials having a high silver chloride content used in rapid processing in recent years.

To address these problems, substituted hydroxylamines having substituents have been investigated as preservatives. For example, WO 87/05434, 87/06026, U.S. Pat.
And dialkyl-substituted hydroxylamines described in JP-A-801,516 and JP-A-63-4234. Although some of these substituted hydroxylamines have less influence on photographic properties than unsubstituted hydroxylamines,
Most of them have insufficient preservative performance.

The preservative performance generally means the ability to prevent the decomposition of the color developing agent, but broadly also means the ability to prevent liquid coloring and tar. Conventionally known sulfite ions are mainly effective in preventing liquid coloring and tar, but have little ability to prevent the decomposition of color developing agents such as the above-mentioned hydroxylamines. Therefore, in general, hydroxylamines and sulfite ions are used in combination, and they can prevent the decomposition of the color developing agent and the screens for liquid coloring and tar formation. However, as described above, sulfite ions greatly inhibit color development, and it is preferable that the amount of sulfite ions be limited as much as possible.

As compounds replacing sulfites, alkanolamines described in JP-A-54-3532 and polyethyleneimines described in JP-A-56-94349 have been proposed, but these compounds are sufficient. No effect could be obtained. Further, examples of the tar inhibitor include diphenyl oxide disulfonates described in U.S. Pat. No. 4,567,776, but they are not satisfactory. In other words, it can be said that there is no technology that satisfies all "preservation performance" in a broad sense including prevention of decomposition of a color developing agent and prevention of liquid coloring and tar formation, and "photographic performance" such as inhibition of color development and increase in stain. .

(Problems to be Solved by the Invention) Accordingly, a first object of the present invention is to provide a color developing solution which is excellent in stability and which can be used for color development over a long period of time or during continuous processing of a silver halide color photographic light-sensitive material. It is an object of the present invention to provide a color developing composition in which deterioration of a base drug is small and which is excellent in prevention of contamination by an oxidized decomposition product (tar), and a processing method using the same. It is a second object of the present invention to provide a color developing composition having excellent color developing properties and stain preventing ability, and a processing method using the same.

(Means for Solving the Problems) The above object was achieved by the composition and method described below. (1) A color developing composition containing at least one compound represented by the following general formula (I).

(2) A method of processing a silver halide color photographic material using a color developer in the presence of a compound represented by the following general formula (I): General formula (I) (Wherein, L represents an alkylene group, A represents a phosphonic acid residue, a phosphinic acid residue, a phosphonamide residue or a phosphonic acid ester residue, and R represents a hydrogen atom, an alkyl group, an acyl group, a carbamoyl group or Represents an alkoxycarbonyl group, and n represents 0 or 1.) As the hydroxylamine having an alkyl substitution,
Diethylhydroxylamine, dimethylhydroxylamine, alkoxyalkylhydroxyamine and the like are well known, and others are disclosed in JP-A-63-4234 and U.S. Pat.
The substituted hydroxylamine of the phosphonic acid group as shown by the general formula (1) of the present invention is specifically superior to the carboxy group and the sulfo group, which are relatively preferred substituted alkyl substituents as described in 801516. That was completely unexpected.

Phosphonic acid is generally known as a substituent of a substituted alkyl, but hardly known as a substituent of hydroxylamine, and has never been known as a preservative of a color developer at all in the past, The effect has been found for the first time in the present invention.

This effect is "preservation performance" in a broad sense that means (prevention of deterioration of color developing agent) and (prevention of liquid coloring and tar formation).
And (prevention of inhibition of color development and prevention of generation of stain), that is, excellent photographic performance.

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

L represents an alkylene group which may be substituted, and is preferably an alkylene group having 1 to 6 carbon atoms which may be substituted.
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. A represents a phosphonic acid residue, a phosphinic acid residue, a phosphonamide residue or a phosphonate ester residue. A is preferably a phosphonic acid residue. R represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted acyl group, a substituted or unsubstituted carbamoyl group, or a substituted or unsubstituted alkoxycarbonyl group. Examples of the substituent include a phosphonic acid residue, a phosphinic acid residue, 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, a sulfamoyl group, and an alkyl group. And an aryl group. R is preferably a hydrogen atom, a substituted or unsubstituted alkyl group, and examples of the substituent include a phosphonic acid residue, a phosphinic acid residue, a hydroxy group, a carboxy group,
Sulfo groups are mentioned as preferred examples. L and R may combine to form a ring.

A or R shown in the general formula (I) may be a salt of an alkali metal (for example, sodium or potassium).

Specific compounds are shown below, but the present invention is not limited to these compounds.

(14) HONHCH ₂ PO ₃ H ₂ (15) HONH (CH ₂ ) ₂ PO ₃ H ₂ (16) HONH (CH ₂ ) ₃ PO ₃ H ₂ (20) HONHCH ₂ CH (PO ₃ H ₂ ) ₂ (31) HONHCH ₂ PO ₂ H ₂ (34) HONH (CH ₂ ) ₂ PO ₂ H ₂ The content of these compounds in a color developer is 0.5 g to 50 g, preferably 1.0 g to 30 g, per color developer.
More preferably, it is 1.5 g to 20 g. These compounds may be present in the light-sensitive material. It is preferable to add the dye to a color developer because the stability of the dye itself can be greatly improved.

In addition to the color developing solution, even if it is added to a bleaching and bleach-fixing solution or a washing solution or a stabilizing solution alternative to washing or brought in from a pre-bath, the oxidized form of the main agent present in each solution is not affected. It works and can give good performance.

Examples of the synthesis of these compounds are as follows, taking specific exemplified compounds (1) and (4) as examples. Other compounds can also be easily synthesized by known methods.

Synthesis Example 1 32.6 g of formalin was added to an aqueous hydrochloric acid solution of 7.2 g of hydroxyamine hydrochloride and 18.0 g of phosphorous acid, and the mixture was heated under reflux for 2 hours. The resulting crystals are recrystallized from water with methanol to give compound (1)
9.2 g (42%) were obtained.

Synthesis Example 2 An aqueous sodium hydroxide solution of 7.2 g of hydroxyamine hydrochloride and 28.9 g of 1-chloroethylphosphonic acid was heated under reflux for 10 hours. The resulting crystals were recrystallized from water and methanol to obtain 8.7 g (35%) of compound (4).

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

D-1 N, N-diethyl-p-phenylenediamine D-2 2-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- (methanesulfonamido) ethyl] -aniline D-7 N (-2-amino-5-diethylaminophenylethyl) methanesulfonamide D-8 N, N-dimethyl-p-phenylenediamine D-9 4- Amino-3-methyl-N-ethyl-N-methoxyethylaniline D-10 4-Amino-3-methyl-N-ethyl-N-β
-Ethoxyethylaniline D-11 4-amino-3-methyl-N-ethyl-N-β
-Butoxyethylaniline Among the above p-phenylenediamine derivatives, particularly preferred is 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 (Exemplified Compound D-
5).

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

In the color developing solution according to the present invention, a compound represented by the following general formula [A] is more preferably used from the viewpoint of further improving the effects of the present invention.

General formula [A] (Wherein, R ₁₁ is a hydroxyalkyl group having 2 to 6 carbon atoms;
₁₂ and R ₂₃ are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group having 2 to 6 carbon atoms, a benzyl group or a formula Wherein 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.
Represents a hydroxyalkyl group. 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 above general formula 6A] The effect of the present invention is preferably used in the range of 3 g to 100 g, more preferably 6 g to 50 g, per color developing solution.

In the color developing solution according to the present invention, the following general formulas [BI] and [B-
The compound represented by II] is more preferably used.

General formula [BI] General formula [B-II] Wherein R ₁₄ , R ₁₅ , R ₁₆ and R ₁₇ are each a hydrogen atom,
Halogen atom, a sulfonic acid group, an alkyl group having a carbon number of 1 to 7, -OR _18, -COOR _19, Or, it represents a phenyl group. Also, R ₁₈ , R ₁₉ , R ₂₀ and R
₂₁ represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. However, when R ₁₅ represents —OH or a hydrogen atom, R ₁₄ represents a halogen atom, a sulfonic acid group,
To 7 alkyl groups, —OR ₁₈ , —COOR ₁₉ , Or, 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,
Methyl carboxylic acid group, benzyl group, etc.
_18, the alkyl group R _19, R ₂₀ and R ₂₁ represent the same meaning as defined above, can be further octyl group and the like exemplified.

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

Specific examples of the chelating agent of the present invention are shown below, but are not limited thereto.

(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-tricarboxylic acid Hydroxynaphthalene-6-carboxylic acid (B-II-4) 2,3-dihydroxy-8-isopropyl-naphthalene (B-II-5) 2,3-dihydroxy-8-chloro-naphthalene-6
Sulfonic acid Among the above compounds, particularly preferred compounds used in the present invention include 1,2-dihydroxybenzene-3,5-
Examples thereof include disulfonic acid, which can be used as an alkali metal salt such as a sodium salt and a potassium salt. ((BI-2 of Specific Exemplary Compound) In the present invention, the compounds represented by the above general formulas [BI] and [BI
The compound of formula (I) is used in an amount of 5 mg to 15 mg 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 is preferably pH 9
To 12, more preferably 9 to 11.0, and the color developer may further contain a compound of a known developer component.

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

The amount of the buffer added to the color developer was 0.1 mol / mol.
It is preferably at least 0.1 mol / -0.4 mol / m.

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

Specific examples are shown below, but the present invention is not limited thereto. Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, triethylenetetraminehexaacetic acid, nitrilo-N, N, N-tris (methylenesulfonic 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 ether diaminetetraacetic acid, hydroxyethylenediaminetriacetic acid , Ethylenediamine orthohydroxyphenylacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1
-Hydroxyethylidene-1,1-diphosphonic acid, N, N'-
Bis (2-hydroxybenzyl) ethylenediamine-N,
N'-diacetic acid, catechol-3,4,6-trisulfonic acid, catechol-3,5-disulfonic acid, 5-sulfosalicylic acid, 4-sulfosalicylic acid.

Of these chelating agents, preferably ethylenediaminetetraacetic acid, ethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, 1,3-diaminopropanoltetraacetic acid, ethylenediamine-N, N, N ', N'-tetrakis (methylenephosphonic acid) Hydroxyethyl iminodiacetic acid is preferred.

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

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

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

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

Preferably, the color developer is substantially free of benzyl alcohol. Substantially means per color developer
2.0 ml or less, more preferably not containing at all. The one containing substantially no phthalocyanine reduces fluctuations in photographic properties during continuous processing, particularly an increase in stain, and can provide more preferable results.

Chloride ions and bromine ions are required in the color developer for the purpose of preventing fog and the like. In the present invention, the content is preferably 1.0 × 10 ^{-2 to} 1.5 × 10 ^-1 mol / mol, more preferably 4 × 10 ^-2 to 1 × 10 ^-1 mol / chlorine. If the chloride ion concentration is more than 1.5 × 10 ^-1 mol / mol, it is not preferable to delay development and quickly obtain a high maximum concentration. If it is less than 3.5 × 10 ^-2 mol / s, stain is generated, and furthermore, the photographic property fluctuation (particularly the minimum density) accompanying continuous processing is undesirably large.

In the present invention, bromine ions are preferably contained in the color developer at 3.0 × 10 ⁻⁵ mol / to 1.0 × 10 ⁻³ mol /. More preferably, it is 5.0 × 10 ^{−5 to} 5 × 10 ⁻⁴ mol /. Particularly preferably, it is 1 × 10 ^{−4 to} 3 × 10 ⁻⁴ mol /. If the bromine ion concentration is higher than 1 × 10 ^-3 mol /,
Delays development, lowers maximum density and sensitivity, 3.0 × 10 ^-5
If it is less than mol / mol, stains are formed, and photographic fluctuations (particularly minimum density) due to continuous processing are not preferred.

Here, chlorine ions and bromine ions may be directly added to the developer or may be eluted from the photosensitive material during the development processing.

When directly added to a color developer, examples of the chloride ion supply material include sodium chloride, potassium chloride, ammonium chloride, nickel chloride, magnesium chloride, manganese chloride, calcium chloride, and cadmium chloride, with sodium chloride being preferred. , Potassium chloride.

Further, it may be supplied in the form of a salt of a fluorescent whitening agent added to the developer. Sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide, madanedium bromide, manganese bromide, nickel bromide, cadmium bromide, cerium bromide, thallium bromide Among them, preferred are potassium bromide and sodium bromide.

When eluted from the photosensitive material at the time of development, both chloride ions and bromine ions may be supplied from the emulsion, or may be supplied from sources other than the emulsion.

In the present invention, an optional antifoggant can be added in addition to chlorine ions and bromine ions, if necessary. As antifoggants, alkali metal halides such as potassium iodide and organic antifoggants can be used. Examples of organic antifoggants include benzotriazole, 6
-Nitrobenzimidazole, 5-nitroindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-
Representative examples include 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 /, preferably 0.1 to 6 g /.

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

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

Replenishing amount of color developer during continuous processing the photographic material 1 m ² per 20～220Ml, preferably 25~160ml is particularly preferably
30 ml to 110 ml is preferable in that the effects of the present invention can be effectively exhibited.

Further, the color developer of the present invention has a liquid opening ratio (air contact area (cm ² ) / liquid volume (cm ³ )) which is relatively superior to a combination outside the present invention in any state. ,
From the viewpoint of the stability of the color developer, the liquid aperture 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.

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

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

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

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

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

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

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

Further, the bleach-fixing solution may contain other various types of fluorescent whitening agents, antifoaming agents, surfactants, and organic solvents such as polyvinylpyrrolidone and methanol.

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

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

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

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

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

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

According to the multi-stage counter-current method described in the above-mentioned document, the amount of washing water can be greatly reduced.However, due to an increase in the residence time of water in the tank, bacteria propagate, and the generated suspended matter adheres to the photosensitive material. Problem arises. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, the method of reducing calcium and magnesium described in Japanese Patent Application No. 131632/1986 can be used very effectively. Also, isothiazolone compounds and thiabendazoles described in JP-A-57-8542, chlorine-based disinfectants such as chlorinated sodium isocyanurate, and other benzotriazoles, etc. It is also possible to use the disinfectant described in "Sterilization, disinfection and antifungal technology of microorganisms" edited by the Sanitary Technology Association, and "Encyclopedia of Antifungal and Antifungal Agents" edited by the Japan Society of Antifungals and Fungi.

The pH of the washing water in the processing of the light-sensitive material of the present invention is 4 to 9
And preferably 5 to 8. The washing temperature and washing time can also be variously set depending on the characteristics of the photosensitive material, application, etc., but are generally in the range of 15 to 45 ° C for 20 seconds to 2 minutes, preferably in the range of 25 to 40 ° C for 30 seconds to 1 minute 30 seconds. Is selected.

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

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

Further, after the water washing treatment, a stabilization treatment may be further performed, and examples thereof include a stabilizing bath containing formalin and a surfactant used as a final bath of a color light-sensitive material for photography. .

The processing time of the present invention is defined as the time from when the photosensitive material comes into contact with the color developer until it leaves the final bath (generally, a washing or stabilizing bath). The effect of the present invention can be remarkably exhibited in a rapid processing step of 30 seconds or less, preferably 3 minutes or less.

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

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

Regarding the halogen composition of these silver chlorobromide emulsions, any silver halide / silver chloride ratio can be used. Although this ratio can take a wide range according to the purpose, a silver chloride ratio of 2% or more can be preferably used.

Further, a so-called high silver chloride emulsion having a high silver chloride content is preferably used as a photosensitive material suitable for rapid processing. The silver chloride content of these high silver chloride emulsions is preferably at least 90 mol%,
95 mol% or more is more preferable.

Such high silver chloride emulsions preferably have a structure in which a silver bromide localized layer is formed in a layered or non-layered form as described above on the inside and / or on the surface of silver halide grains.
The halogen composition of the localized phase is preferably at least 10 mol% in terms of silver bromide content, and more preferably more than 20 mol%. These localized layers can be on the inside of the grain, on the edge, corner, or plane of the grain surface. One preferred example is a layer grown epitaxially on the corner of the grain.

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

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

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

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

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

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

The silver chlorobromide emulsion used in the present invention is described by P. Glafkides.
mie et Phisique Photographique (Paul Montel, 1
967), Photographic Emulsion Chemi by GFDuffin
stry (Focal Press, 1966), VLZelikman et a
lMaking and Coating Photographic Emuldion (Foc
al Press, 1964). 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 and a soluble halide is a one-sided mixing method,
Any method such as a simultaneous mixing method and a combination thereof may be used. A method of forming particles in an atmosphere containing excess silver ions (a so-called reverse mixing method) can also be used. As one type of the double jet method, a method of maintaining a constant pAg in a liquid phase in which silver halide is formed, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a nearly uniform grain size can be obtained.

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

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

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

Spectral sensitization is performed for the purpose of imparting spectral sensitivity to a desired light wavelength range to the emulsion of each layer in the light-sensitive material of the present invention. In the present invention, it is preferable to add a dye that absorbs light in a wavelength range corresponding to the intended spectral sensitivity—a spectral sensitizing dye. The spectral sensitizing dye used at this time is, for example, Heterocyclic com by FM Harmer.
pounds -Cyanine dyes and related compounds (John
Wiley & Sons [New York, London], 1964). Specific examples of the compounds and the spectral sensitization method are described in the above-mentioned JP-A-62-215272.
What is described in the upper right column of page 22 to page 38 of the specification of Unexamined-Japanese-Patent No. 2000-216, is preferably used.

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

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

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

Cyan coupler preferably used in the present invention,
The magenta coupler and the yellow coupler are represented by the following 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 (CI) and (C-II), R ₁ , R ₂
And R ₄ represents a substituted or unsubstituted aliphatic, aromatic or heterocyclic group; R ₃ , R ₅ and R ₆ represent a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group or an acylamino group; ₃ may represent a non-metallic atomic group forming a 5- or 6-membered nitrogen-containing ring together with R ₂ . Y ₁ and Y _{2 each} represent a hydrogen atom or a group capable of leaving during a coupling reaction with an oxidized form of a developing agent. n represents 0 or 1.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

These couplers may be impregnated with a loadable latex polymer (for example, U.S. Pat.No. 4,203,716) in the presence or absence of the high-boiling organic solvent or dissolved in a water-insoluble and organic solvent-soluble polymer. 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 the use of an acrylamide polymer is particularly preferred for stabilizing a color image.

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

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

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

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

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

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

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

That is, the compound (F) which forms a chemically inert and substantially colorless compound by chemically bonding with the aromatic amine-based developing agent remaining after the color developing process and / or the aromatic compound remaining after the color developing process. The compound (G) which forms a chemically inert and substantially colorless compound by chemically bonding with an oxidized form of an aromatic amine color developing agent can be used simultaneously or alone, for example, in storage after processing. It is preferable in order to prevent the generation of stains and other side effects due to the formation of a coloring dye due to the reaction between the color developing agent or its oxidized product and the coupler remaining in the film.

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

If k ₂ is greater than this range, the compound itself becomes unstable, resulting in decomposition reacts with gelatin or water. On the other hand, if k ₂ is smaller than this range, the reaction with the remaining aromatic amine-based developing agent is slow, and as a result, the side effect 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 forms a chemical bond by reacting with an aromatic amine-based developer, and X represents a group which is eliminated by reacting with an aromatic amine-based developer. B represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, or a sulfonyl group, and Y represents that an aromatic amine-based developing agent is added to the compound of the general formula (F II). Represents a promoting group. Here, R ₁ and X, Y and R ₂ or B may be bonded to each other to form a cyclic structure.

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

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

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

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

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

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

The light-sensitive material prepared according to the present invention contains a 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.

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

In the present invention, gelatin is lime-treated,
Either one treated with an acid may be used. The details of the method for producing gelatin are described in Arthur Wuice, 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 a polyethylene terephthalate which is usually used for a photographic light-sensitive material, or a reflective support can be used. For the purposes of the present invention, the use of a reflective support is more preferred.

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

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

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

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

The occupied area ratio (%) per defined unit area of the white pigment fine particles is most typically obtained by dividing the observed area into adjacent 6 μm × 6 μm unit areas and projecting the unit area. It can be obtained by measuring the occupied area ratio (%) (R _i ) of the fine particles. Variation coefficient 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 / Can be obtained by

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

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

Preparation of first layer coating solution 19.1 g of yellow coupler (ExY) and color image stabilizer (Cp
d-1) To 4.4 g and 0.7 g of the color image stabilizer (Cpd-7), 27.2 cc of ethyl acetate and 8.2 g of (solvent (Solv-1) were added and dissolved.
This solution is 10% sodium dodecylbenzenesulfonate
It was emulsified and dispersed in 185 cc of a 10% aqueous gelatin solution containing 8 cc.
On the other hand, a silver chlorobromide emulsion (cubic, 3: 7 mixture (average grain ratio) of 0.88 μm and 0.70 μm) (silver molar ratio) The coefficient of variation of the particle size distribution is 0.08 and 0.10, and each emulsion is silver bromide The following blue-sensitive sensitizing dyes were added in an amount of 2.0 × 10 ^-4 mol per mol of silver per mol of silver and 0.2 × 10 ^-4 mol per mol of silver. , Each of which was subjected to sulfur sensitization after addition of 2.5 × 10 ^-4 mol. The above-mentioned emulsified dispersion and this emulsion were mixed and dissolved to prepare a first coating solution having the following composition.

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

 The following were used as spectral sensitizing dyes for each layer.

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

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

Also, 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 × 10 mol, respectively, per mol of silver halide. ×
10 ^-4 mol was added.

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

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

Support Polyethylene laminated paper [The first layer of polyethylene contains white pigment (TiO ₂ ) and blue dye (ultra blue)] First layer (blue-sensitive layer) Silver chlorobromide emulsion 0.30 Gelatin 1.86 Yellow coupler (ExY 0.82 Color image stabilizer (Cpd-1) 0.19 Solvent (Solv-1) 0.35 Color image stabilizer (Cpd-7) 0.06 Second layer (color mixture prevention layer) Gelatin 0.99 Color mixture inhibitor (Cpd-5) 0.08 Solvent ( Solv-1) 0.16 Solvent (Solv-4) 0.08 Third layer (green sensitive layer) Silver chlorobromide emulsion (cubic, 1: 3 mixture of 0.55 μm average and 0.39 μm emulsion (Ag mole) The coefficient of variation of the grain size distribution is 0.10 and 0.08, and each emulsion is AgBr
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 average grain size and 0.45 µm grain size (Ag mole ratio). Particle size distribution) Coefficient of variation is 0.09 and 0.11, AgBr 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 (ultraviolet absorbing layer) Gelatin 0.53 Ultraviolet absorber (UV-1) 0.16 Color mixing inhibitor (Cpd-5) 0.02 Solvent (Solv-5) 0.08 Seventh layer (Protective layer) Gelatin 1.33 Acrylic modified copolymer of polyvinyl alcohol (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 600ml Ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid 2.0g Potassium bromide 0.015g Potassium chloride 3.1g Triethanolamine 10.0g Potassium carbonate 27g Fluorescent brightener (WHITEX / 4B Sumitomo Chemical 1.0g Additive See Table 1 N-ethyl-N- (β-methanesulfonamidoethyl
) -3-Methyl-4-aminoaniline sulfate 5.0 g Add water 1000 ml pH (25 ° C) 10.05 Bleaching fixer Water 400 ml Ammonium thiosulfate (70%) 100 ml Sodium sulfite 17 g Ethylene (III) ammonium ethylenediaminetetraacetate 55 g Disodium ethylenediaminetetraacetate 5g Add ammonium bromide 40g water 1000ml pH (25 ℃) 6.0g Rinse liquid Ion exchange water (calcium and magnesium are 3ppm each)
Hereinafter, a part of the color developer was prepared in a beaker so that the aperture ratio became 0.02 cm ^−1, and aged at 38 ° C. for 20 days.

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

After exposure, each was processed according to the following steps using the above prepared fresh solution (fresh solution) and the aged color developing solution (aging solution).

Processing temperature time Color development 38 ° C 45 seconds Bleaching and fixing 35 ° C 45 seconds Rinse 35 ° C 20 seconds Rinse 35 ° C 20 seconds Rinse 35 ° C 20 seconds Dry 80 ° C 60 seconds When processed with fresh color developer (fresh solution) Of the minimum density of yellow (Dmin) and the sensitivity of magenta (the logarithmic logE of the exposure amount giving a density of 0.5) and the increase in the minimum density of yellow Dmin (処理Dmin) and the change in magenta sensitivity (感 度 S)
Was calculated. The remaining amount of the main drug in the aged solution 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,
It can be seen that the values of Dmin and ΔS are small, and the fluctuation of photographic properties is suppressed. (Nos. 6 to 20) Also, it can be seen that sufficient performance can be obtained by using the compound of the present invention for the residual amount of the main drug.

Example 2 The additive shown in Table 1 of Example 1 was diethylhydroxylamine, and the compound examples (20), (22), (24), (26),
In the processing solution changed to (32) or (35), the temperature of color development was set to 35 ° C., and the other conditions were the same as in Example-1.

As a result, similar to Example 1, good results were obtained according to the configuration of the present invention as compared with the case where the additive was diethylhydroxylamine.

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 solution was prepared as follows.

Preparation of first layer coating solution 60.0 g of yellow coupler (ExY) and anti-fading agent (Cp
d-1) In 28.0 g, 150 cc of ethyl acetate and a solvent (Solv-
3) Add 1.0 cc and 3.0 cc of a solvent (Solv-4) to dissolve the solution, and add this solution containing sodium dodecylbenzenesulfonate to 10%.
% Gelatin aqueous solution, and dispersed with an ultrasonic homogenizer. The resulting dispersion was treated with 420 g of a 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.

Coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. 1,2-
Bis (vinylsulfonyl) ethane was used.

The following were used as spectral sensitizing dyes for each layer.

Blue-sensitive emulsion layer; anhydro-5,5'-dichloro-3,3'-
Disulfoethyl thiacyanine 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-
Neopentylthiadicarbocyanine iodide The followings were used as stabilizers for each emulsion layer.

Further, the following substances were used as the irradiation preventing dye.

[3-carboxy-5-hydroxy-4- (3- (3-
Carboxy-5-oxo-1- (2,5-bisulfonatophenyl) -2-pyrazolin-4-indene) -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 -Sulfonatophenyl)-
2-pyrazolin-4-indene) -1-bentanyl)-
[1-Pyrazolyl] benzene-4-sulfonate-sodium salt (layer constitution) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents a coating amount in terms of silver.

Support 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 particle 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 mixture prevention layer) Gelatin 0.80 Color mixture inhibitor (Cpd-2) 0.055 Solvent ( Solv-1) 0.03 Solvent (Solv-2) 0.15 Third layer (green-sensitive layer) Silver chlorobromide emulsion described above (AgBr 0.7 mol%, cubic, average particle 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 (color mixture prevention layer) Gelatin 1.70 Color mixture inhibitor (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 described above (AgBr 4 mol%, cubic, average particle 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 development accelerator (Cpd-5) 0.15 Sixth layer (ultraviolet 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) butylamide] 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-aluminophenoxy) -3-methylbutyramide phenol (ExC-2) cyan coupler 2,4-dichloro-3-methyl-6- [α- (2,4-di −
tert-Amylphenoxy) butyramide] phenol (Cpd-1) Anti-fading agent (Cpd-2) color-mixing inhibitor 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-toluenesulfonamido) phenyl-dodecane (Solv-1) Solvent Di (2-ethylhexyl) phthalate (Solv-2) solvent Dibutyl phthalate (Solv-3) solvent Di- (i-nonyl) phthalate (Solv-4) solvent N, N-diethylcarbonamide-methoxy-2,4- Jee
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 the following processing step replenished twice the tank capacity for color development. went.

Further, exposure was performed by the method described in Example 1 separately, and processing was performed before and after the running test.

Processing process temperature time replenishment amount ^* tank capacity development 35 ° C 45 seconds 161ml 17 Bleaching and fixing 30-36 ° C 45 seconds 215ml 17 Stable 30-37 ° C 20 seconds -10 Stable 30-37 ° C 20 seconds -10 Stable 30-37 ° C 20 seconds - 10 stable 30 to 37 ° C. 30 seconds 248 ml 10 drying 70 to 85 ° C. 60 seconds * replenishment rate per photosensitive material 1 m ² (. was a four-tank counter-current system to a stable →) the composition of each processing solution It is as follows.

Aniline sulfate 5.0 g 7.0 g Add water 1000 ml 1000 ml pH (25 ° C) 10.05 10.45 Bleaching fixer (same as tank solution and replenisher) Water 400 ml Ammonium thiosulfate (70%) 100 ml Sodium sulfite 17 g Iron ethylenediaminetetraacetate (III ) Ammonium 55g Disodium ethylenediaminetetraacetate 5g Glacial acetic acid 9g Add water 1000ml pH (25 ℃) 5.40 Stabilizer (same as tank solution and replenisher) Formalin (37%) 0.1g Formalin-sulfuric acid adduct 0.7g 5- Chloro-2-methyl-4-isothiazoline-3-
ON 0.02g 2-Methyl-4-isothiazolin 3-one 0.01g Copper sulfate 0.005g Add water 1000ml pH (25 ℃) 4.0 Measure the minimum concentration (Dmin) of yellow, magenta and cyan after running, In addition, the change in gray level (△ γ) of cyan after the end of running with respect to cyan at the start of the running test was calculated. However, the gradation was represented by a density change from a point representing a density of 0.5 to a density point on the high exposure side of 0.3 logE.

The results are shown in Table 2. As can be seen from Table 2, the use of the compounds of the present invention makes the Dmin and especially the gradation change of yellow, magenta and cyan significantly smaller than those of other alkyl-substituted hydroxylamines (Nos. 10 to 33). Or the combination use of additive I such as triethanol, the combination curing of the comparative example (No. 1 vs. No. 2-5, No. 6, 8 vs. No. 7, 9)
Compared with the compound of the present invention (No. 10, 11, 12 vs. N
o.13, 14, 15 or No. 16, 17, 18, No. 28, 29 vs. No. 30, 3
1 or Nos. 32 and 33) are large. In particular, compound A 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 of the two compounds such as -3 and BI-2. (No. 10, 11, 12 vs. No. 13, 14, 15 vs. No. 24, 25, 2
6) Example-4 The light-sensitive material prepared in Example-1 was subjected to sensitometric exposure as described in Example-1. A part of the following color developer was similarly aged for 20 days. Processing was performed in the following steps using the color developing solution before and after aging.

Step Temperature Time Color developing 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 700ml Ethylenediaminetetraacetic acid 2.0 g 1, 2 -Dihydroxybenzene-3,5-disulfonic acid disodium salt 0.6 g Potassium bromide See Table 3 Potassium chloride See Table 3 Fluorescent brightener (4,4-diaminostilbene) 1.5 g Triethanolamine 10 g Sodium sulfite See Table 3 Additives See Table 3 N-Ethyl-N (β-methanesulfonamidoethyl)
-3-Methyl-4-aminoaniline sulfate 5.5 g Add water 1000 ml pH (25 ° C.) 10.05 Change magenta sensitivity before and after aging (ΔS) and magenta after aging treatment as in Example-1 Minimum concentration (Dmi
n) was measured. Further, in the same manner as in Example-3, the gradation change of yellow (Δγ) and the maximum density of magenta (Dmax) after the aging treatment were measured. (△ S) and (Dmin) of the result are 3rd
Table (1) shows (Δγ) and (Dmax) in Table 3 (2).

From Table 3 (1), when diethylhydroxylamine or the compounds D, E, and F were used, the ΔS and Dmin values were large (Nos. 1 to 11), whereas when the compound of the present invention was used, It can be seen that the values are small (Nos. 12 to 20). Also in the constitution of the present invention, ΔS is large when the amount of potassium bromide and potassium chloride is large (No. 16), and Dmin is large when the amount is small (No. 12). Therefore, the concentration range is preferably represented by (No. 13 to 15). This change is not so remarkable in the comparative example (No. 5, No. 2 to No. 4).

Next, from Table 3 (2), it can be seen that according to the constitution of the present invention, the magenta coloring property is excellent in all regions of the sulfurous acid concentration. (No.21-23, No.24-26 vs. No.27-2
9, Nos. 30 to 32) In the structure of the present invention, it is found that the smaller the amount of sodium sulfite, the smaller the value of Δγ and the more preferable. (N
o.27-29, No.32-32) Example-5 The photosensitive material prepared in Example-1 was subjected to imagewise exposure,
Continuous processing (running test) was performed using an automatic developing processor for color paper in the following processing steps until the tank was replenished with twice the capacity of the color developing tank. Further, exposure was performed by the method described in Example 1 separately, and processing was performed before and after the running test.

Processing process temperature Time replenishment amount ^* Tank capacity Color development 37 ° C 45 seconds 150ml 17 38 ° C 45 seconds 100ml 17 40 ° C 45 seconds 55ml 17 Bleaching and fixing 35 ° C 45 seconds 215ml 17 rinse 35 ° C 20 seconds 10 rinse 35 ° C 20 seconds 10 rinse 35 ° C. 20 seconds 250 ml 10 drying 80 ° C. 60 seconds * photosensitive material 1 m ² replenishing amount per.

 A three-tank countercurrent system was used for rinsing.

The liquid developer has a liquid aperture ratio of 0.005 cm ^-1 on average.

 The composition of each processing solution is as follows.

Bleach-fix solution (same as tank solution and replenisher) Water 400ml Ammonium thiosulfate (70%) 100ml Sodium sulfite 17g Ammonium iron (III) ethylenediaminetetraacetate 55g Disodium ethylenediaminetetraacetate 5g Glacial acetic acid 9g Add water 1000ml pH (25 ℃) 5.40 Rinse solution (same as tank solution and replenisher) Deionized water (calcium, magnesium, 3ppm or less).

The respective minimum densities (Dmin) of yellow, magenta, and cyan after the running test were measured, and the change in the tone of cyan (△ γ) after the running was completed with respect to the cyan at the start of the running test. However, the gradation was represented by a density change from a point representing a density of 0.5 to a density point on the higher density side of 0.3 logE.

Also, the color developer after running is 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 developer is at least (55 ml / m ² ), and the rise of stain is very small and the liquid is good. Further, a large relative preferable replenishing amount of 40ml~110ml / m ² range, that is, Comparative Examples towards 109 ml / m ² and 55 ml / m ² as compared to when the effect is the replenishing amount of 150 ml / m ² of the present invention The effect can be achieved.

Continuation of front page (56) References JP-A-63-5341 (JP, A) JP-A-63-48548 (JP, A) JP-A-63-204258 (JP, A) JP-A-63-88548 (JP, A) JP-A-63-129341 (JP, A) JP-A-63-106655 (JP, A) JP-A-63-63044 (JP, A) Patent 2,671,042 (JP, B2)

Claims (2)

(57) [Claims] 1. A color developing composition comprising at least one compound represented by the following general formula (I). General formula (I) (Wherein, L represents an alkylene group, A represents a phosphonic acid residue, a phosphinic acid residue, a phosphonamide residue or a phosphonic acid ester residue, and R represents a hydrogen atom, an alkyl group, an acyl group, a carbamoyl group or Represents an alkoxycarbonyl group, and n represents 0 or 1.) 2. A processing method for processing a silver halide color photographic light-sensitive material with a color developer, wherein the processing is performed with a color developer in the presence of at least one compound represented by the following general formula (I). Characteristic processing method of silver halide color photographic light-sensitive material. General formula (I) (Wherein, L represents an alkylene group, A represents a phosphonic acid residue, a phosphinic acid residue, a phosphonamide residue or a phosphonic acid ester residue, and R represents a hydrogen atom, an alkyl group, an acyl group, a carbamoyl group or Represents an alkoxycarbonyl group, and n represents 0 or 1.)