JP2748071B2 - Color development processing method of silver halide color photographic light-sensitive material for photography - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a silver halide color photographic light-sensitive material. More specifically, the present invention relates to a halogenated photographic material which is capable of rapid color development, has low sensitivity reduction, and has excellent graininess. The present invention relates to a method for processing a silver color photographic light-sensitive material.

[0002]

2. Description of the Related Art In recent years, processing of silver halide color photographic light-sensitive materials (hereinafter, sometimes referred to as "light-sensitive materials") has been required to process more and more rapidly. In recent color paper processing, rapid processing of about 45 seconds has been generally performed in color development by introducing a silver chloride emulsion. However, in color negatives for photography, around 3 minutes and 15 seconds has been used as a general color development time since 1972 as a general color development time. This is because the high silver chloride emulsion introduced into the color paper can be developed faster than silver bromide or silver iodobromide used in color negatives for photography in terms of speeding up color development. This is because it is difficult to introduce high silver chloride since sufficient sensitivity is required in the color negative. Therefore, in order to shorten the development time of a color negative, various attempts have been made to increase the development speed by increasing the development activity of a color developer.
For example, the pH of the color developer is increased, the temperature is increased, the concentration of the developing agent is increased, and a development accelerator is used. Examples of the development accelerator include thioether compounds described in JP-B-37-16088 and JP-B-37-5987, U.S. Pat.No. 3,813,247, and p-type compounds described in JP-A-52-49829 and JP-A-50-15554. There are known phenylenediamine compounds, quaternary ammonium salts described in JP-A-50-137726, and amine compounds described in U.S. Pat. No. 2,494,903. However, when these means were used, it was found that there were problems such as fogging, although the color developability was improved, and that sensitivity equal to or higher than that before speeding up could not be obtained. Furthermore, the present inventor has found that even if the developing time is adjusted so as to obtain a sensitivity equal to or higher than that before the speeding-up, the graininess is deteriorated in most cases. In a photosensitive material for photography, such a decrease in sensitivity and deterioration of graininess are important problems.

As a method for improving the graininess during rapid development, for example, as described in Japanese Patent Application Laid-Open No. 62-157030, color development is performed by using silver halide having a defined amount of silver iodide. 12
It is known to take less than 0 seconds. However, in order to obtain a sufficient coloring density, it is necessary to increase the coloring temperature, and it has been found that when the temperature is increased to 43 ° C. or more as described in the patent, the fog increases.

A method for improving graininess in the presence of high bromide ions is described, for example, in Japanese Patent Publication No. Hei 3-15734. The patent discloses a silver halide emulsion having a silver iodide content of 4 mol% or less and a bromide ion concentration of 15.1 to prevent fluctuations in relative sensitivity due to improvement in graininess and fluctuations in processing time. This is a method of processing with a color developing solution of 5 mmol / L or more.
The solution has been attempted by using a photosensitive material having the above composition, and it has not been shown that the speed is positively increased. That is, it was found that when color development was performed within 2 minutes as described in the present invention, sufficient color development could not be obtained.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to process a silver halide color photographic light-sensitive material for photography, which is capable of rapid color development, has reduced sensitivity and less fog, and has excellent graininess. It is to provide a method.

[0006]

The above object is achieved by the following color developer. That is, in a method of color developing a silver halide color photographic light-sensitive material for photography in 2 minutes or less using a color developing solution, the half-wave potential when the color developing solution uses a standard hydrogen electrode as a reference electrode is +250.
mV or less of a color developing agent, 25 mmol or more of bromide ions per liter of the color developer, and 0.1 g or more of a compound represented by the formula (A) per liter of the color developer. Processing temperature of developer is 4
This was achieved by a color developing method for a silver halide color photographic light-sensitive material, wherein the temperature is 3 ° C. or higher.
Formula (A)

[0007]

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(In the formula, R represents an alkyl group having 1 to 4 carbon atoms.) Generally, it is known that a developing agent having a low oxidation-reduction potential has a high developing activity and that development is accelerated by increasing the processing temperature. Have been. On the other hand, bromide ions are known to significantly slow development. According to the present invention, it is possible to obtain rapid and good photographic properties in both sensitivity and granularity by using the compound having the opposite action and the compound represented by the formula (A).

In the development, electrons are transferred from a developing agent to silver halide using fine silver particles (called a latent image) generated on the silver halide by exposure as a medium, and silver ions in the silver halide are converted into silver ions. This is an electrochemical reaction in which an electrode is a so-called latent image, which receives electrons and becomes a silver atom to increase the thickness of silver particles by being integrated with the latent image. Therefore, in the above process, the developing agent is oxidized and silver ions are reduced. That is, when the oxidation-reduction potential of the developing agent is sufficiently lower than the oxidation-reduction potential of silver halide, the reaction is expected to be fast, that is, the development is fast. However, these developing agents having a low oxidation-reduction potential have a high activity, so that the silver halide in the unexposed portion is also easily reduced, so that fogging is likely to occur. Sensitivity also tends to decrease. What is desired at the time of development is that development of the image area is fast while development of the fog area is slow. In view of the above, the present invention increases the developing speed of the image area by using a developing agent having a lower oxidation-reduction potential as compared with a commonly used color negative developing agent (Example-1 Table 2 Comparative Compound A). At the same time, the occurrence of fogging is suppressed and good photographic properties can be quickly obtained.

Hereinafter, the present invention will be described in detail. The color developing agent used in the present invention is a color developing agent having a half-wave potential of +240 mV or less at pH 10 when a standard hydrogen electrode is used as a reference electrode. The half-wave potential of the developing agent shown here is determined by Photographic Science and Engineering, Vol. 8, No. 3, page 125 (1964).
Are the values described in. However, the value described in the document is a European convention generally used in the field of electrochemistry at present, that is, the stronger the reducing agent is, the smaller the potential is, or the larger the potential is, the stronger the reducing agent is. In this specification, the sign is reversed with the sign of the sign being followed. In addition, even if a color developing agent whose chemical structure is not described in the literature, at the measurement pH of 10, the Journal of the
The half-wave potential can be measured by using the measurement method described in American Chemical Society 73, 3100 (1951). When the half-wave potential of the color developing agent measured in this way is +240 mV or less, it goes without saying that the compound is included in the color developing agent of the present invention. The color developing agent used in the present invention is preferably a color developing agent represented by the following formula [D] and having a half-wave potential of +240 mV or less.

[0011]

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In the general formula [D], R ₁ and R
₂ represents a hydrogen atom, an alkyl group, an aryl group, and a heterocyclic group, respectively. R ₃ , R ₄ , R ₅ and R
₆ represents a hydrogen atom or a substituent, respectively. R ₁ and R ₂ , R ₁ and R ₃ , R ₃ and R ₄ , R ₂ and R ₅ and R ₅
And R ₆ may together form a ring.

Hereinafter, the general formula [D] will be described in more detail. The alkyl group, aryl group and heterocyclic group represented by R ₁ and R ₂ are linked by an alkenyl group, an alkynyl group, a hydroxyl group, a nitro group, a cyano group, a halogen atom or other oxygen, nitrogen, sulfur or carbonyl group. May be substituted with the following substituents. Examples of such a substituent include the groups and atoms described below as substituents for R ₃ , R ₄ , R ₅ and R ₆ . Preferably, a hydroxy group, a sulfonamide group,
It is a carbamoyl group, a sulfamoyl group or a ureido group, more preferably a hydroxy group or a sulfonamide group.

R ₁ and R ₂ are more particularly a hydrogen atom,
Alkyl group (a linear, branched or cyclic alkyl group having 1 to 16 carbon atoms such as methyl, ethyl, propyl, isopropyl, t-butyl, 2-hydroxyethyl,
Hydroxypropyl, 2-methanesulfonamidoethyl, 3-methanesulfonamidopropyl, 2-methanesulfonylethyl, 2-methoxyethyl, cyclopentyl, 2-acetamidoethyl, 2-carboxyethyl,
2-carbamoylethyl, 3-carbamoylpropyl,
n-hexyl, 2-hydroxypropyl, 4-hydroxybutyl, benzyl, 2-carbamoylaminoethyl,
3-carbamoylaminopropyl, 4-carbamoylaminobutyl, 4-carbamoylbutyl, 2-carbamoyl-1-methylethyl, 4-nitrobutyl, 3-sulfamoylaminopropyl, 4-sulfamoyl), an aryl group (for example, phenyl, Naphthyl, p-methoxyphenyl) and a heterocyclic group (eg, 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzotriazolyl, imidazolyl, pyrazolyl, pyrrolidinyl, morphonyl).

[0015] R ₁ and R _2, at least one of, preferably represents an alkyl group, R ₁ and R ₂ are both alkyl groups are more preferred.

When R ₁ and R ₂ are each an alkyl group, the number of carbon atoms is preferably 8 or less, preferably 5 or less.
More preferably, the number is not more than the number. R ₃ , R ₄ , R ₅ and R ₆ are preferably a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a cyano group, a nitro group, a hydroxyl group, a carboxyl group, Alkoxy group, aryloxy group, acylamino group, alkylamino group, anilino group,
Ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group,
Sulfonamide group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyl group, silyloxy group, aryloxycarbonylamino group, imide group, heterocyclic thio Group, sulfinyl group, phosphoryloxy group, aryloxycarbonyl group, and acyl group.

More specifically, R ₃ , R ₄ , R ₅ and R ₆
Is a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom), an alkyl group (a linear, branched or cyclic alkyl group having 1 to 16 carbon atoms, which is an alkenyl group, an alkynyl group, a hydroxyl group, a nitro group, It may be substituted with a cyano group, a halogen atom or other substituents linked by an oxygen atom, a nitrogen atom, a sulfur atom or a carbonyl group, for example, methyl, ethyl, propyl, isopropyl, t-butyl, 2-hydroxy Ethyl, 3-hydroxypropyl, 2-methanesulfonamidoethyl, 3-methanesulfonamidopropyl, 2-methanesulfonylethyl, 2-methoxyethyl, cyclopentyl, 2-acetamidoethyl, 2-carboxyethyl, 2-carbamoylethyl, 3 -Carbamoylpropyl, n-hexyl, 2-hydroxyp Pills, 4-hydroxybutyl,
2-carbamoylaminoethyl, 3-carbamoylaminopropyl, 4-carbamoylaminobutyl, 4-carbamoylbutyl, 2-carbamoyl-1-methylethyl, 4-nitrobutyl), alkenyl group (for example, vinyl, 1-butenyl, 3- Hydroxy-1-propenyl), alkynyl group (eg, ethynyl, 1-propynyl), aryl group (eg, phenyl, naphthyl, p-
Methoxyphenyl), a heterocyclic group (eg, 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzotriazolyl, imidazolyl, pyrazolyl), a cyano group, a nitro group, a hydroxyl group, a carboxyl group, an alkoxy group (eg, , Methoxy, ethoxy, 2-methoxyethoxy, 2-methanesulfonylethoxy), an aryloxy group (for example, phenoxy), an acylamino group (for example,
Acetamido, 2-methoxypropionamido), alkylamino group (for example, N, N-dimethylamino, N,
N-diethylamino), anilino group (for example, anilino,
m-nitroanilino), a ureido group (eg, methylureide, N, N-diethylureide), a sulfamoylamino group (eg, dimethylsulfamoylamino),
Alkylthio groups (eg, methylthio, ethylthio),
Arylthio group (eg, phenylthio), alkoxycarbonylamino group (eg, methoxycarbonylamino, ethoxycarbonylamino), sulfonamide group (eg, methanesulfonamide), carbamoyl group (eg, N, N-dimethylcarbamoyl, N-ethyl) Carbamoyl), a sulfamoyl group (eg, dimethylsulfamoyl), a sulfonyl group (eg, methanesulfonyl, ethanesulfonyl), an alkoxycarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl), a heterocyclic oxy group (eg, 1-phenyltetra Zolyl-5-oxy, 2-tetrahydropyranyloxy), azo group (for example, phenylazo, 2-hydroxy-4-propanoylphenylazo), acyloxy group (for example, acetoxy), Moyloxy group (for example, N, N-dimethylcarbamoyloxy), silyl group (for example, trimethylsilyl), silyloxy group (for example, trimethylsilyloxy), aryloxycarbonylamino group (for example, phenoxycarbonylamino), imide group (for example, N -Succinimide), a heterocyclic thio group (for example, 2-benzothiazolylthio, 2-
Pyridylthio), a sulfinyl group (eg, ethanesulfinyl), a phosphoryloxy group (eg, dimethoxyphosphoryloxy), an aryloxycarbonyl group (eg, phenoxycarbonyl), and an acyl group (eg, acetyl, benzoyl).

[0018] R ₃ and R ₅ are preferably both hydrogen atoms, R _3, and still more preferably R ₄ and R ₅ are both hydrogen atoms. Preferred R ₆ is a hydrogen atom,
It is an alkyl group or an alkoxy group, more preferably an alkyl group, and among them, a methyl group and an ethyl group are particularly preferable.

R ₁ and R ₂ , R ₁ and R ₃ , R ₃ and R ₄ , R
₂ and R ₅ and R ₅ and R ₆ may each form a ring. The number of rings formed may be one, or two or more. The number of members in each ring is not limited, but among them, 5-, 6- and 7-membered rings are preferred.

Specific examples of the case where R ₁ and R ₂ form a ring include, for example,

[0021]

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(Wherein * represents the bonding position of R ₁ or R ₂ ), and when each atom on these main chains can further have a substituent, R ₃ , R ₄ , R ₅ and R ₆ may have substituents in the permissible range.

Specific examples of the case where R ₁ and R ₃ and R ₂ and R ₅ form a ring include, for example,

[0024]

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(In the formula, * represents the bonding position of R ₁ or R _{2 in} the formula [D], and ** represents R
It represents the bonding position of ₃ or R _5. ), And when each atom on the main chain can further have a substituent, it may have a substituent within the range permitted by R ₃ , R ₄ , R ₅ and R ₆ . .

Specific examples of the case where R ₃ and R ₄ and R ₅ and R ₆ form a ring include, for example,

[0027]

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(In the formula, * represents a bonding position to the benzene ring. Each bonding position may be R ₃ or R ₅ , or may be R ₄ or R _6. ) When each atom on the main chain can further have a substituent, it may have a substituent within the range permitted by R ₃ , R ₄ , R ₅ and R ₆ .

The color developing agent used in the present invention preferably has a half-wave potential of +235 mV or less, more preferably +230 mV or less, and even more preferably +225 mV or less. Specific examples of the color developing agent of the present invention are shown below, but are not limited thereto.

[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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Since the color developing agent of the present invention is very unstable when stored as a free amine, it is generally produced and stored as a salt of an inorganic acid or an organic acid and first added to a processing solution. It is preferable to use free amine. Examples of the inorganic and organic acids that form the color developing agent of the present invention include hydrochloric acid, sulfuric acid, phosphoric acid, p-toluenesulfonic acid, methanesulfonic acid, and naphthalene-1,5-disulfonic acid.

The color developing agent of the present invention is, for example, Journal of the American Chemical Society 73
Can be synthesized according to the method described on page 3100 of the volume.

The color developer containing the color developing agent of the present invention is preferably an aqueous alkaline solution. The color developing agent of the present invention may be used alone or in combination of two or more. Known aromatic primary amine color developing agents, dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, and aminophenols such as N-methyl-p-aminophenol are also known. May be used in combination with the black-and-white developing agent. The color developing agent of the present invention is added in an amount of 2 × 10 ^-4 mol to 1 × 10 ^-1 mol, preferably 1 × 10 ^-3 mol to 5 × 10 ^-2 mol, per liter of the processing solution.

The color developer of the present invention contains at least 25 mmol of bromide ion per liter of the color developer.
This may be achieved by the amount of the photosensitive material eluted by the processing, or may be added to the color developer. For example may in general also be a (photosensitive material 1 m ² per 150ml or less in the present invention) performed when more than a bromide ion concentration of the low replenishment processing the photographic light-sensitive material with a color developer. At the bromide ion concentration, color development was significantly suppressed, and when p-phenylenediamine other than the present invention was used as a developing agent,
Sufficient sensitivity cannot be obtained. It was also found that the use of the above-mentioned development accelerator did not restore the sensitivity of the foot on sensitometry. In the present invention, the bromide ion concentration in the color developer is 30 mmol per liter of the color developer.
Or more, preferably 65 mmol or less, more preferably 35 mmol or more,
It is preferably 60 mmol or less. When bromide ions of 65 mmol or more are present, the development is suppressed too much to make it impossible to recover the color. When the amount is 25 mmol or less, the effect of the color developing agent of the present invention is not clear, and problems such as an increase in fog occur.

When directly added to the color developer, the bromine ion supplying substance may be an inorganic substance or an organic substance as long as it is a compound which can become bromine ions in the color developer. Preferred are inorganic compounds such as sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide, magnesium bromide, manganese bromide, nickel bromide, cadmium bromide, cerium bromide, odor Thallium bromide and the like can be mentioned, and among these, preferred compounds are potassium bromide and sodium bromide.

Next, the compound represented by the formula (A) will be described. R represents an alkyl group having 1 to 4 carbon atoms. Preferably it is a methyl group. The compounds represented by the formula (A) are shown below, but the present invention is not limited thereto.

[0045]

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The amount of the compound represented by the formula (A) of the present invention is 0.1 g or more, preferably 0.5 g or less, per liter of color developer. More preferably, it is 0.2 g or more and 0.4 g or less. The processing temperature of the color developer of the present invention is 43 ° C. or higher. If it is lower than this, the effect of the developing agent of the present invention is not sufficiently exhibited. The processing temperature is preferably 60 ° C. or less from the viewpoint of handling and stability of the color developer. It is more preferably in the range of 43 ° C to 50 ° C.

In the present invention, the color developer has a general formula
It is desirable to contain at least one of the compounds represented by (1). General formula (1) L _1- (A ₁ -L ₂ ) _r -A ₂ -L ₃ (wherein L ₁ and L ₃ may be the same or different and each represents an alkyl group or a heterocyclic group. However, L ₁
And at least one of L ₃ is —OM ₁ , —SO ₃ M ₁ ,
_{-PO 3 M 2 M 3, -NR} 1 (R 2), - N + R 3 (R 4) (R
^{_{5) · X 1 -, -SO}} 2 NR 6 (R 7), - NR 8 SO
₂ R ₉ , -CONR ₁₀ (R ₁₁ ), -SO ₂ R ₁₄ , -CO
OM ₁ or an alkyl or heterocyclic group substituted with a heterocyclic group. L ₂ represents an alkylene group, an arylene group, an aralkylene group, a heterocyclic linking group or a linking group obtained by combining them. A ₁ and A ₂ may be the same or different and each represents —S—, —O—, —NR ₁₂ —, —C
O- or a group obtained by arbitrarily combining them. However, at least one of A ₁ and A _{2 in} the molecule represents —S—. r represents an integer of 1 to 10. When r is 2 or more, (A ₁ -L ₂ ) may be the same or different. M ₁ , M
₂ and M ₃ may be the same or different and each represents a hydrogen atom or a counter cation. R _{1 to} R ₁₂ may be the same or different and each represents a hydrogen atom, an alkyl group, an aryl group,
An aralkyl group or an alkenyl group, X ₁ ^- represents a counter anion. )

Here, the general formula (1) will be described in detail. L ₁ and L _{3 each} represent a substituted or unsubstituted C ₁ -C 1
10 alkyl groups (as unsubstituted alkyl groups, for example, methyl, ethyl, propyl, hexyl, isopropyl), or substituted or unsubstituted C 1-10 heterocyclic groups (as unsubstituted hetero rings, for example, Pyridyl, furyl, thienyl, imidazolyl) and the like. Provided that at least one -OM ₁ of L ₁ and L _3, -S
O ₃ M ₁ , —PO ₃ M ₂ M ₃ , —NR ₁ (R ₂ ) (hydrochloride,
It may be in the form of a salt such as acetate, for example, unsubstituted amino, methylamino, dimethylamino, N-methyl-N-hydroxyethylamino, N-ethyl-N-carboxyethylamino), -N ⁺ R ₃ (R _{4 ) (R 5) · X 1} - ( e.g., trimethylammonio _{chloride), - SO 2 NR 6 (} R 7)
(E.g., unsubstituted sulfamoyl, _{dimethylsulfamoyl), - NR 8 SO 2 R} 9 ( e.g., methanesulfonamido, benzenesulfonamide), - CONR ₁₀ (R
₁₁₎ [for example, unsubstituted carbamoyl, N- methylcarbamoyl, N, N- bis (hydroxyethyl) carbamoyl], -SO ₂ R ₁₄ (e.g., methanesulfonyl, 4-
Chlorophenyl sulfonyl), a Hajime Tamaki (e.g., representing a pyridyl, imidazolyl, thienyl, an alkyl group or a heterocyclic group substituted by tetrahydrofuranyl) or -COOM _1.

M ₁ , M ₂ and M ₃ are a hydrogen atom or a counter cation (for example, an alkali metal atom such as a sodium atom or a potassium atom, an alkaline earth metal atom such as a magnesium atom or a calcium atom, ammonium, triethylammonium) , Etc.).

R _{1 to} R _{12 each} represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms (eg, methyl, ethyl, propyl, hexyl, isopropyl); An aryl group (eg, phenyl, 4-methylphenyl, 3-methoxyphenyl), a substituted or unsubstituted aralkyl group having 7 to 12 carbon atoms (eg, benzyl, phenethyl) or a substituted or unsubstituted aralkyl group having 2 to 10 carbon atoms; Alkenyl groups (eg,
Vinyl, propenyl, 1-methylvinyl);
^- represents counter anion (e.g., chloride ion, halide ions such as bromide ion, nitrate ion, sulfate ion, acetate ion, p- toluenesulfonate ion) a. L ₂
Is a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms (for example, methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, 1-methylethylene, 1-hydroxytrimethylene); Arylene groups of the formulas 6 to 12 (for example,
Phenylene, naphthylene), a substituted or unsubstituted aralkylene group having 7 to 12 carbon atoms (eg, 1,2-xylylene), a substituted or unsubstituted heterocyclic linking group having 1 to 10 carbon atoms (eg,

[0051]

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Represents the following. A ₁ and A ₂ are -S-, -O
_{-, - NR 12 -, -} CO- or they represent any combination groups, the groups in any combination for example -CO
_{NR 13 -, - NR 14 CO} -, - NR 15 CONR 10 -, -
COO-, -OCO-, and the like. R _{13 to} R ₁₆ have the same meaning as R ₁₂ . At least one of A ₁ and A _{2 in} the molecule represents —S—.

R represents an integer of 1 to 10. When r is 2 or more, (A ₁ -L ₂ ) may be the same or different.

When each of L ₁ , L ₂ , L ₃ , and R _{1 to} R ₁₆ has a substituent, the substituent may be a lower alkyl group having 1 to 4 carbon atoms (eg, methyl or ethyl), 6 ~
10 aryl groups (eg, phenyl, 4-methylphenyl), aralkyl groups having 7 to 10 carbon atoms (eg, benzyl), alkenyl groups having 2 to 4 carbon atoms (eg, propenyl), alkoxy groups having 1 to 4 carbon atoms (Eg, methoxy, ethoxy), a halogen atom (eg, a chlorine atom or a bromine atom), a cyano group, a nitro group, a carboxylic acid group (which may be in the form of a salt), a hydroxy group and the like.

In the general formula (1), preferably, L ₁ and L ₃
At least one of —OM ₁ , —SO ₃ M ₁ , and —PO _{3
M 2 M 3, -NR 1 (} R 2), - N + R 3 (R 4) (R 5) · X 1
^- represents a heterocyclic group or an alkyl group having 1 to 6 carbons substituted with -COOM _1,, L ₂ represents an alkylene group having 1 to 6 carbon atoms. A ₁ and A ₂ represent —S—, —O
— Or —NR ₁₂ —. However, at least one of A ₁ and A ₂ is -S-. R ₁ , R ₂ , R ₃ ,
R ₄ , R ₅ and R ₁₂ represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and r represents an integer of 1 to 6. r is 2
In the above case, (A ₁ -L ₂ ) may be the same or different. In the general formula (1), L ₁ and L ₃ are more preferably -O
M ₁ , —SO ₃ M ₁ , —PO ₃ M ₂ M ₃ , or —CO
An alkyl group having 1 to 4 carbon atoms substituted with OM ₁ ,
A ₁ and A ₂ represent —S—, and r represents an integer of 1 to 3. Hereinafter, specific examples of the compound of the present invention are shown, but the present invention is not limited thereto.

[0056]

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[0057]

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[0058]

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[0059]

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The compounds of the present invention represented by the general formula (1) are described in Journal of Organic Chemistry (J. Org. Chem.) 30, 2867 (1965),
2846 (1962), Journal of American Chemical Society (J. Am. Chem. Soc.) 69, 23
30 (1947) and the like can be easily synthesized. In the present invention, the amount of the compound represented by the general formula (1) used in the color developer is 1 × per liter of the color developer.
10 ^-6 to 1 × 10 ^-1 mol, preferably 1 × 10 ^-5.
５5 × 10 ^-2 mol.

The color developer of the present invention comprises a pH buffer such as an alkali metal carbonate, borate or phosphate, a chloride salt in addition to the specified amount of bromine ion concentration of the present invention.
It may contain a development inhibitor or an antifoggant such as an iodide salt, a benzimidazole, a benzothiazole or a mercapto compound. And hydroxylamines such as hydroxylamine, diethylhydroxylamine, N-methyl-hydroxylamine, N, N-bis (sulfonatoethyl) hydroxylamine, sulfites, bisulfites, and N, N-biscarboxymethylhydrazine. Hydrazines, phenylsemicarbazides, triethanolamine, various preservatives such as catecholsulfonic acids, ethylene glycol, organic solvents such as diethylene glycol, benzyl alcohol,
Development accelerators such as polyethylene glycol, quaternary ammonium salts, amines, dye-forming couplers, competitive couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity-imparting agents, aminopolycarboxylic acids, aminopolyphosphones Various chelating agents such as acids, alkylphosphonic acids and phosphonocarboxylic acids can be added. Examples of the chelating agent include ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid,
Cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N, N, N-tetramethylenephosphonic acid And ethylenediamine-di (o-hydroxyphenylacetic acid) and their salts.

The replenishment amount of the color developer is preferably smaller from the viewpoint of reducing the processing waste liquid. Therefore, it is preferably 300 ml or less, more preferably 250 ml or less, more preferably 200 ml or less per square meter of the photosensitive material. The lower limit is preferably not less than the amount of the photosensitive material brought into the next bath, and is about 50 to 100 ml. The contact area between the photographic processing solution and air in the processing tank can be represented by the aperture ratio defined below. That is, aperture ratio (cm ^-1 ) = [contact area between processing solution and air (c
m ^2)] ÷ [processing solution volume (cm ^3)] The above aperture is preferably 0.1 cm ^-1 or less, more preferably 0.001~0.05cm ^-1.
As a method of reducing the aperture ratio in this way, in addition to providing a shield such as a floating lid on the photographic processing liquid surface of the processing tank, a method using a movable lid described in JP-A-1-82033, And a slit developing method described in JP-A-216050. The reduction of the aperture ratio is preferably applied not only to color development but also to all subsequent steps such as bleaching, bleach-fixing, fixing, washing and stabilization. The time of the color development processing is set to 2 minutes or less, but is preferably 10 seconds or more, 90 seconds or less, more preferably 15 seconds or more and 60 seconds or less in the present invention. The light-sensitive material subjected to the color development processing of the present invention is usually subjected to desilvering processing, washing and / or stabilizing processing. These processes may be performed in any manner. For example, JP-A-4-73748, page 31, upper left column 1
It is described from line 7 to page 33, lower left column, line 6. The light-sensitive material subjected to the color development processing of the present invention may be any silver halide color photographic light-sensitive material having a sensitivity for photography, such as that described in JP-A-4-73748. In general, a photographic material for photographing may be provided with at least one of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive silver halide emulsion layer on a support. There is no particular limitation on the number and order of the emulsion layers and the non-light-sensitive layers. A typical example is a silver halide photographic light-sensitive material having at least one light-sensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. The light-sensitive layer is a unit light-sensitive layer having color sensitivity to any of blue light, green light, and red light, and in a multilayer silver halide color photographic light-sensitive material, generally, The arrangement is such that a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer are arranged in this order from the support side. However, depending on the purpose, the order of installation may be reversed, or the order of installation may be such that different photosensitive layers are sandwiched between layers of the same color sensitivity.

The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is about 0.2
Silver iodobromide or silver iodochlorobromide containing 〜30 mol% of silver iodide. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 10 mol% of silver iodide, wherein at least one of the color-sensitive layers has an iodine content of less than 10 mol% of silver chloride. This is a photosensitive material containing a silver chlorobromide emulsion. Particularly, silver iodobromide is most preferable in terms of adjusting the balance between yellow, magenta, and cyan colors.

[0064]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. Example 1 On a subbed cellulose triacetate film support,
Each layer having the composition shown below was applied in multiple layers to prepare a sample 101 as a multilayer color photosensitive material. (Composition of photosensitive layer) The main materials used for each layer are classified as follows: ExC: cyan coupler UV: ultraviolet absorber ExM: magenta coupler HBS: high boiling point organic solvent ExY: yellow coupler H: gelatin Curing agent ExS: Sensitizing dye The number corresponding to each component indicates the coating amount in g / m ² , and for silver halide, it indicates the coating amount in terms of silver. However, as for the sensitizing dye, the coating amount is shown in mol unit with respect to 1 mol of silver halide in the same layer.

(Sample 101) First Layer (Antihalation Layer) Black Colloidal Silver Silver 0.18 Gelatin 1.40 ExM-1 0.18 ExF-1 2.0 × 10 ^-3 HBS-1 0.20

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Third layer (low-sensitivity red-sensitive emulsion layer) Emulsion A silver 0.25 Emulsion B silver 0.25 ExS-1 6.9 × 10 ^-5 ExS-2 1.8 × 10 ^-5 ExS-3 3.1 × 10 ^-4 ExC-1 0.17 ExC-3 0.030 ExC-4 0.10 ExC-5 0.020 ExC-7 0.0050 ExC-8 0.010 Cpd-2 0.025 HBS-1 0.10 Gelatin 0.87

Fourth Layer (Medium Speed Red Sensitive Emulsion Layer) Emulsion D Silver 0.70 ExS-1 3.5 × 10 ^-4 ExS-2 1.6 × 10 ^-5 ExS-3 5.1 × 10 ^-4 ExC-1 0.13 ExC-2 0.060 ExC-3 0.0070 ExC-4 0.090 ExC-5 0.025 ExC-7 0.0010 ExC-8 0.0070 Cpd-2 0.023 HBS-1 0.10 Gelatin 0.75

Fifth layer (high-sensitivity red-sensitive emulsion layer) Emulsion E silver 1.40 ExS-1 2.4 × 10 ^-4 ExS-2 1.0 × 10 ^-4 ExS-3 3.4 × 10 ^-4 ExC-1 0.12 ExC-3 0.045 ExC-6 0.020 ExC-8 0.025 Cpd-2 0.050 HBS-1 0.22 HBS-2 0.10 Gelatin 1.20

Sixth layer (intermediate layer) Cpd-1 0.10 HBS-1 0.50 Gelatin 1.10

Seventh layer (low-sensitivity green-sensitive emulsion layer) Emulsion C Silver 0.35 ExS-4 3.0 × 10 ^-5 ExS-5 2.1 × 10 ^-4 ExS-6 8.0 × 10 ^-4 ExM-1 0.010 ExM-2 0.33 ExM-3 0.086 ExY-1 0.015 HBS-1 0.30 HBS-3 0.010 Gelatin 0.73

Eighth Layer (Medium Speed Green Sensitive Emulsion Layer) Emulsion D Silver 0.80 ExS-4 3.2 × 10 ^-5 ExS-5 2.2 × 10 ^-4 ExS-6 8.4 × 10 ^-4 ExM-2 0.13 ExM-3 0.030 ExY-1 0.018 HBS-1 0.16 HBS-3 8.0 × 10 ^-3 Gelatin 0.90

Ninth layer (high-sensitivity green-sensitive emulsion layer) Emulsion E silver 1.25 ExS-4 3.7 × 10 ^-5 ExS-5 8.1 × 10 ^-5 ExS-6 3.2 × 10 ^-4 ExC-1 0.010 ExM-1 0.030 ExM-4 0.040 ExM-5 0.019 Cpd-3 0.040 HBS-1 0.25 HBS-2 0.10 Gelatin 1.44

Tenth layer (yellow filter layer) Yellow colloidal silver silver 0.030 Cpd-1 0.16 HBS-1 0.60 gelatin 0.60

Eleventh layer (low-sensitivity blue-sensitive emulsion layer) Emulsion C Silver 0.18 ExS-7 8.6 × 10 ^-4 ExY-1 0.020 ExY-2 0.220 ExY-3 0.500 ExY-4 0.020 HBS-1 0.28 Gelatin 1.10

12th layer (Medium speed blue-sensitive emulsion layer) Emulsion D Silver 0.40 ExS-7 7.4 × 10 ^-4 ExC-7 7.0 × 10 ^-3 ExY-2 0.050 ExY-3 0.10 HBS-1 0.050 Gelatin 0.78

Thirteenth layer (high-sensitivity blue-sensitive emulsion layer) Emulsion F Silver 1.00 ExS-7 4.0 × 10 ^-4 ExY-2 0.10 ExY-3 0.10 HBS-1 0.070 Gelatin 0.86

Fourteenth layer (first protective layer) Emulsion G silver 0.20 UV-4 0.11 UV-5 0.17 HBS-1 5.0 × 10 ^-2 gelatin 1.00

15th layer (second protective layer) H-1 0.40 B-1 (1.7 μm in diameter) 5.0 × 10 ^-2 B-2 (1.7 μm in diameter) 0.10 B-3 0.10 S-1 0.20 Gelatin 1.20

Further, W-1 to W-3, B-4 to B- may be added to each layer to improve the storage stability, processability, pressure resistance, fungicidal and bacteriostatic properties, antistatic properties and coatability. 6, F
-1 to F-17, and iron salts, lead salts, gold salts, platinum salts,
Contains iridium and rhodium salts.

[0081]

[Table 1]

In Table 1, (1) Emulsions A to F were prepared according to the examples of JP-A-2-19938.
Reduction sensitization was performed using thiourea dioxide and thiosulfonic acid during the preparation of the particles. (2) Emulsions A to F were prepared according to the examples in JP-A-3-237450.
Gold sensitization, sulfur sensitization and selenium sensitization were performed in the presence of the spectral sensitizing dye and sodium thiocyanate described in each photosensitive layer. (3) For preparing tabular grains, low molecular weight gelatin is used according to the examples of JP-A-1-158426. (4) Dislocation lines as described in JP-A-3-237450 have been observed in tabular grains and normal crystal grains having a grain structure using a high-pressure electron microscope.

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The processing steps and processing recipe for processing the above sample are shown below. Processing process Process time Processing temperature Color development See Table 2 See Table 2 Bleaching 50 seconds 38.0 ° C Bleaching and fixing 50 seconds 38.0 ° C Fixed 50 seconds 38.0 ° C Rinse 30 seconds 38.0 ° C Stable (1) 20 seconds 38.0 ℃ Stability (2) 20 seconds 38.0 ℃ Drying 1 minute 60 ℃

The composition of the processing liquid is shown below. (Color developer) (g) Diethylenetriaminepentaacetic acid 2.0 1-hydroxyethylidene-1,1-diphosphonic acid 3.3 Potassium carbonate 37.5 Potassium bromide See Table 2 Potassium iodide 1.3 mg Hydroxylamine sulfate 2.4 Sodium sulfite 4.5 Color developing agent (compound of general formula (D)) Refer to Table 2 Compound (A-1) 0.3 Add water and add 1.0 liter pH 10.25

(Bleaching solution) (g) Ammonium ferric salt of 1,3-propylenediaminetetraacetic acid 144.0 Ammonium bromide 84.0 Ammonium nitrate 17.5 Hydroxyacetic acid 63.0 Acetic acid 54.2 Water was added. 1.0 liter pH (adjusted with aqueous ammonia) 3.80

(Bleaching-fixing solution mother liquor) A mixture of the above-mentioned bleaching solution mother liquor and the following fixing solution mother liquor in a ratio of 15:85.

(Fixing solution) (g) Ammonium sulfite 19.0 Aqueous solution of ammonium thiosulfate (700 g / L) 280 mL Imidazole 28.5 Ethylenediaminetetraacetic acid 12.5 Add water, 1.0 L pH (adjusted with aqueous ammonia and acetic acid) 7 .40

(Washing water) Tap water was replaced with H-type strongly acidic cation exchange resin (Amberlite IR- manufactured by Rohm and Haas Company).
120B) and a mixed bed column filled with an OH type strongly basic anion exchange resin (Amberlite IRA-400) to reduce the calcium and magnesium ion concentrations to 3
mg / L or less, followed by 20 mg / L of sodium diisocyanurate and 15 mg of sodium sulfate.
0 mg / liter was added. The pH of this solution is 6.5-
It was in the range of 7.5.

(Stabilizing solution) (Unit g) Formalin (37%) 1.2 ml Sodium p-toluenesulfinate 0.3 g Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.2 Ethylenediaminetetraacetic acid Disodium salt 0.05 Add water and 1.0 liter pH 7.2

The sample 101 was subjected to a gradation exposure to perform the processing. The sample obtained by the treatment was subjected to density measurement of yellow, magenta, and cyan, which are the coloring pigments of the B, G, and R layers, to obtain characteristic curves. From this characteristic curve, the minimum density (Dmin) and the maximum density (Dmax) of yellow
) And Dmin + of yellow, magenta and cyan
The logarithm of the reciprocal of the exposure at the point giving the density of 0.2 was calculated, and this was calculated as the sensitivity (S).

In Table 2, No. 1 did not accelerate color development, and the standard processing showed that only No. 1 had a main agent concentration of 1
The concentration was 6 mmol / liter, and after No. 2, a concentration of 35 mmol / liter was used. The color developers of Nos. 21, 22, and 23 do not contain the compound represented by the formula (A). The above sensitivity, minimum density, and maximum density were represented by differences (ΔS, ΔDmin, ΔDmax) with reference to No. 1. The results are shown in Table 2. No. 2 to N for No. 1
In the case of o.6, even if the processing temperature was raised to 45 ° C., sufficient color was not obtained, and when the KBr concentration was low, Dmin
It turns out that the value of becomes large. Furthermore, it can be seen that, even when the color developing agent of the present invention is used, when KBr and the processing temperature are outside the embodiments of the present invention, Dmin increases and sufficient color formation cannot be obtained. In contrast, according to the present invention, sufficient color development and sensitivity can be obtained with a development time of 1 minute and 30 seconds, and Dmin
Can be prevented (Nos. 10 to 20). However, when the compound represented by the formula (A) is not used, Dmin is high and good photographic properties cannot be obtained (Nos. 21, 22, and 23).

[0107]

[Table 2]

[0108]

[Table 3]

Example 2 The sample 101 prepared in Example 1 was subjected to stepwise exposure for evaluating graininess, and the color developing agent, the amount of potassium bromide, and the temperature were changed as shown in Table 3 to obtain a sample. The same processing as in Example 1 was performed. However, in processing No. 1, (Dmin + 0.
The color development time was adjusted so that the logE density at the position 3) was the same in each treatment. The sample obtained by the treatment had an RMS value indicating the granularity of 48 (Dmin + 0.3) for each of the yellow, magenta, and cyan dye density portions.
The measurement was performed using a μm aperture. The results are shown in Table 3. As is evident from Table 3, when the color developing agent of the present invention was not used, not only it took time to obtain the same sensitivity as No. 1, but also the RMS value was deteriorated. Recognize. Furthermore, even when the color developing agent of the present invention is used, when the KBr concentration is low, the granularity of the fog portion is added and the RMS value is deteriorated. On the other hand, according to the configuration of the present invention, good results can be obtained (Nos. 7 to 10).

[0110]

[Table 4]

Example 3 Using the sample 110 of Example 2 in JP-A-3-194439, replenishing the color developing solution using an automatic developing machine after the imagewise exposure using a solution having the following processing step and processing solution composition: Continuous processing was performed until the cumulative replenishment amount of the liquid became three times the mother liquor tank capacity.

Processing process Step Processing time Processing temperature Replenishment amount Tank capacity Color development 60 seconds 50 ° C 80 ml 5 liter Bleaching 40 seconds 45 ° C 140 ml 3 liter Bleaching and fixing 30 seconds 45 ° C-3 liters Fixing 30 seconds 45 ℃ 420 ml 3 liters Rinse with water 15 seconds 38.0 ℃ 980 ml 2 liters Stable (1) 15 seconds 38.0 ℃-2 liters Stable (2) 15 seconds 38.0 ℃ 560 ml 2 liters Dry 1 minute 60 ℃ Amount per 1 m ^{2 of} photosensitive material Washing water was a countercurrent system from (2) to (1), and all overflows of washing water were introduced into the fixing bath. To replenish the bleach-fix bath, connect the upper part of the bleach tank and the lower part of the bleach-fix tank of the automatic processor, and connect the upper part of the fix tank and the lower part of the bleach-fix tank with pipes. All the overflow generated by the supply was introduced into the bleach-fix bath. Incidentally, the amount of carryover of the developing solution into the bleaching step, the amount of carryover of the bleach-fixing step of the bleaching solution, bring volume to the washing step of the amount carried and fixing solution to the fixing step of the bleach-fixing solution photosensitive material 1 m ² respectively per 70ml, 50ml, 50ml, 5
It was 0 ml. The crossover time is 5 seconds in each case, and this time is included in the processing time of the previous step.

The composition of the processing liquid is shown below. (Color developer) Mother liquor (g) Replenisher (g) Diethylenetriaminepentaacetic acid 4.0 4.0 1-hydroxyethylidene-1,1-diphosphonic acid 3.3 3.3 Potassium carbonate 37.5 37.5 Potassium bromide 6.5 (54.6 mmol)-Potassium iodide 1.3 mg -Hydroxylamine sulfate 2.4 5.0 Sodium sulfite 4.0 6.0 Color developing agent (see Table 4) 40 mmol 64 mmol Compound of general formula (1) (see Table 4) 1.5 mmol 1.5 mmol Compound (A-1) 0.3 0.05 Add water 1.0 liter 1.0 liter pH 10.25 10.95

(Bleaching solution) Mother liquor (g) Replenisher (g) 1,3-propylenediaminetetraacetic acid ferric ammonium ammonium monohydrate 144.0 206.0 ammonium bromide 84.0 120.0 ammonium nitrate 17.5 25.0 hydroxyacetic acid 63.0 80.0 acetic acid 54.2 80.0 1.0 liter 1.0 liter pH (adjusted with ammonia water) 3.80 3.60

(Bleaching-fixing solution mother liquor) A mixture of the above-mentioned bleaching solution mother liquor and the following fixing solution mother liquor in a ratio of 15:85.

(Fixing solution) Mother liquor (g) Replenisher (g) Ammonium sulfite 19.0 57.0 Ammonium thiosulfate aqueous solution (700 g / L) 280 ml 840 ml Imidazole 28.5 85.5 Ethylenediaminetetraacetic acid 12.5 37.5 Add water 1.0 L 1.0 L pH (ammonia water) , Adjusted with acetic acid) 7.40 7.45

(Washing water) Common tap water was used as a H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and an OH-type strongly basic anion exchange resin (Amberlite IRA-). 4
00) to reduce the concentration of calcium and magnesium ions to 3 mg / l or less, followed by 20 mg / l of sodium diisocyanurate dichloride.
Liters and 150 mg / liter of sodium sulfate were added. The pH of this solution was in the range of 6.5 to 7.5.

(Stabilizer) Common to mother liquor and replenisher (unit: g) Formalin (37%) 1.2 ml Sodium p-toluenesulfinate 0.3 g Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization: 10) 0 0.2 Ethylenediaminetetraacetic acid disodium salt 0.05 Add water and add 1.0 liter pH 7.2

After the end of the continuous processing, the same gradation exposure as in Example 1 is applied, and the sensitivity (S) at the point (Dmin + 0.2) of the yellow (Dmin) and (Dmax) and the Dmin + 0.2 of each of the yellow, magenta and cyan dyes is obtained. I asked. Further, the RMS value of magenta was measured in the same manner as in Example-2. However, No. 1 of Example 1
Is a standard process, and color development is 60
It was evaluated as photographic performance when performed in seconds. The results are shown in Table 4. Table 4 shows that when the color developing agent was Comparative Example A (the same compound as in Example 1), the sensitivity was low and the value of Dmax was low. On the other hand, in the case of the color developing agent of the present invention, sensitivity or Dmax equal to or higher than that of the standard No. 1 can be given. Also, the RMS value is good. General formula
It can be seen that when the compound (1) is used, better performance can be obtained especially in combination with the color developing agent of the present invention. (No. 7-10)

[0120]

[Table 5]

[0121]

According to the present invention, sensitivity, Dmin, Dmax,
It can be processed quickly without deteriorating photographic properties such as RMS.

Claims (2)

(57) [Claims] 1. A method for performing color development processing of a silver halide color photographic light-sensitive material for photographing in 2 minutes or less using a color developer, wherein a half-wave potential when the color developer uses a standard hydrogen electrode as a reference electrode. Contains +240 mV or less of a color developing agent, 25 mmol or more of bromide ions per liter of the color developer and 0.1 g or more of the compound represented by the formula (A) per liter of the color developer.
And a processing temperature of the color developing solution is 43 ° C. or higher. Formula (A) (In the formula, R represents an alkyl group having 1 to 4 carbon atoms.) 2. A color developing process for a silver halide color photographic light-sensitive material for photography according to claim 1, wherein said color developer contains at least one compound represented by the general formula (1). Method. General formula (1) L _1- (A ₁ -L ₂ ) _r -A ₂ -L ₃ (wherein L ₁ and L ₃ may be the same or different and each represents an alkyl group or a heterocyclic group. At least one -OM _1, -SO ₃ M _1, of, L ₁ and L ₃ -
_{PO 3 M 2 M 3, -NR} 1 (R 2), - N + R 3 (R 4) (R 5)
^{_{· X 1 -, -SO 2 NR}} 6 (R 7), - NR 8 SO 2 R 9,
—CONR ₁₀ (R ₁₁ ), —SO ₂ R ₁₄ , —COOM _1, or an alkyl or heterocyclic group substituted with a heterocyclic group. L ₂ represents an alkylene group, an arylene group, an aralkylene group, a heterocyclic linking group or a linking group obtained by combining them. A ₁ and A ₂ may be the same or different and each represents —S—, —O—, —NR ₁₂ —, —CO— or a group obtained by arbitrarily combining them. However, at least one of A ₁ and A _{2 in} the molecule represents —S—. r represents an integer of 1 to 10. When r is 2 or more, (A ₁ -L
₂ ) may be the same or different. M ₁ , M ₂ and M ₃ may be the same or different and each represents a hydrogen atom or a counter cation. R ₁ to R ₁₂ represent each hydrogen atom may be the same or different, an alkyl group, an aryl group, an aralkyl group or an alkenyl group, X ₁ ^- represents a counter anion. )