JP3244383B2 - Color developing agent, processing composition and color image forming method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel silver halide color photographic developing agent, a processing composition containing the developing agent, and a color image forming method using the processing solution. The present invention relates to a color photographic developing agent having rapid processing suitability and capable of obtaining an image with less fog, a processing composition containing the developing agent, and a color image forming method using the processing solution.

[0002]

2. Description of the Related Art In recent years, along with the increase in over-the-counter processing called mini-labs and the increase in the number of color negative films used in the news photography field, development processing has been completed in a shorter time, and prints can be provided to customers immediately, Demands for publication in such places have increased rapidly. In particular, there is a particularly high demand for shortening the processing time for processing a color negative film, which requires a longer time than color paper. In a color photographic light-sensitive material mainly composed of a silver iodobromide emulsion such as a color negative film, the processing time can be reduced by changing the color developing agent. Among them, 4- (N
Such as -ethyl-N-δ-hydroxybutylamino) -2-methoxyaniline and 4- (N-ethyl-N-β-hydroxyethylamino) -2-methoxyaniline described in JP-A-53-69035. It has been found that changing the 2-position to a methoxy group makes it possible to significantly reduce the processing time. U.S. Pat. No. 2,304,95
No. 3 having an alkoxy group having a water-soluble group at the 2-position, for example, 2- (hydroxyethoxy) -4-diethylaminoaniline, 2- (2,3-dihydroxypropoxy) -4- (N-propyl-N It has been found that a developing agent such as -benzylamino) aniline also contributes to shortening of the processing time.

However, when a color photographic light-sensitive material mainly composed of a silver iodobromide emulsion is developed with the compounds described in these specifications, it has been found that it has some disadvantages. Since the image density of the unexposed area is high, that is, the fog is large, and the image density of yellow and cyan in the exposed area is not sufficient as compared with magenta, so that the color balance of the three colors is poor.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned circumstances, and has as its object to have rapid processing aptitude, low fog density, and low yellow and cyan image densities. An object of the present invention is to provide a sufficient color developing agent, and to provide a processing solution of a silver halide color photographic light-sensitive material and a color image forming method using the developing agent.

[0005]

The object of the present invention is to provide a color developing agent represented by the following general formula (DB) and a general formula (DB)

[0006]

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(Wherein, R ₁ represents an alkyl group having at least one hydroxy group, R ₂ and R ₃ represent an alkyl group which may have a substituent, and R ₄ represents a substituent. , R ₁ , R ₂ and R ₃ have a total of 2 to 4 hydroxy groups and a total of R ₁ , R ₂ and R ₃ carbon atoms of 5 to 11. n is 0 to 3. And / or a color photographic processing composition comprising at least one color developing agent described above, and / or an image-exposed silver halide color photographic light-sensitive material. The invention has been achieved by a color image forming method and a processing composition, wherein the development is performed with a processing solution containing at least one of the above color developing agents.

JP-A-5-113635, JP-A-53-113
The alkoxy-type developing agents described in US Pat. No. 69,035 and US Pat. No. 2,304,953 have rapidity, but have poor color balance of three colors and large fog. As a result of intensive studies on the alkoxy-type developing agent, it was found that it could not be predicted from the prior art. As a result of synthesizing various compounds having different hydrophilicity / hydrophobicity of the developing agent and evaluating various photographic properties, it was found that the drawbacks of the conventional alkoxy-type developing agent can be largely improved by making the developing agent more hydrophilic. Specifically, the hydroxyl group 2
It has been found that the above problems can be specifically solved by having four carbon atoms and reducing the number of carbon atoms of R ₁ , R ₂ and R ₃ to 11 or less.

The advantages of the color image forming method using the color developing agent represented by the general formula (DB) are that rapid processing is possible, the fog density is low, and three colors of yellow, magenta and cyan in the rapid processing. Excellent balance, excellent light fastness of yellow, good compatibility with hydroxylamine preservatives, and little influence on photographic properties. These are effects that cannot be expected from conventional knowledge.

In the present invention, R ₁ , R ₂ , R ₃ , R ₄ and n in the compound represented by formula (DB) will be described in detail below. R ₁ represents an alkyl group having at least one hydroxy group, preferably has 2 to 6 carbon atoms, and more preferably has 2 to 5 carbon atoms. It may further have a substituent, examples of the substituent include a hydroxy group, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, a nitro group, a carboxy group, a sulfo group, an alkoxy group, an aryloxy Group, acylamino group, amino group,
Alkylamino group, anilino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonylamino 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, phosphonyl group,
An aryloxycarbonyl group and an acyl group. Preferred examples of the substituent include a hydroxy group, an alkyl group, an aryl group, a carboxy group, a sulfo group, an acylamino group, an amino group, an alkylamino group, a ureido group, a sulfamoylamino group, an alkoxycarbonylamino group,
A sulfonylamino group, a carbamoyl group, a sulfamoyl group, a carbamoyloxy group, and an imide group. More preferred examples of the substituent include a hydroxy group, a carboxy group, a sulfo group, a ureido group, a sulfonylamino group, a carbamoyl group, and a sulfamoyl group.

R ₁ is preferably, for example, 2-hydroxyethyl, 3-hydroxypropyl, 3-hydroxycyclopentyl, 2-hydroxypropyl, 4-hydroxybutyl, 5-hydroxypentyl, 6-hydroxyhexyl, 4-hydroxypentyl , 3-hydroxybutyl, 4-hydroxy-4-methylpentyl, 4-hydroxycyclohexyl, 2-hydroxy-2-methylpropyl, 3-hydroxy-2-methylpropyl, 2-
Hydroxy-3-carboxypropyl, 2-hydroxy-3-sulfopropyl, 2,3-dihydroxypropyl, 3,4-dihydroxybutyl, 2,3,4-trihydroxybutyl, 2- (hydroxymethyl) -3-hydroxy Propyl, 2- (hydroxymethyl) -4-hydroxybutyl. More preferred examples of R ₁ include 2-hydroxyethyl, 3-hydroxypropyl,
2-hydroxypropyl, 4-hydroxybutyl, 3-
Hydroxy-2-methylpropyl, 2,3-dihydroxypropyl, 3,4-dihydroxybutyl, 2,3,4
-Trihydroxybutyl, 2- (hydroxymethyl)-
3-hydroxypropyl, 2- (hydroxymethyl)-
4-hydroxybutyl.

R ₂ and R ₃ represent an optionally substituted linear, branched or cyclic alkyl group. Examples of the substituent include a hydroxy group, a halogen atom (for example, a fluorine atom and a chlorine atom), an aryl group (preferably having 6 to 7 carbon atoms, for example, phenyl and m-hydroxyphenyl), and a heterocyclic group (having 1 carbon atom). 5- or 6-membered saturated or unsaturated heterocyclic ring containing at least one oxygen atom, nitrogen atom or sulfur atom of at least 5 is preferable, for example, 2-furyl,
2-thienyl, 2-pyrimidinyl, imidazolyl, pyrazolyl), alkoxy group (preferably having 1 to 7 carbon atoms, for example, methoxy, ethoxy, 2-hydroxyethoxy,
2-methanesulfonylethoxy), an aryloxy group (preferably having 6 to 7 carbon atoms, for example, phenoxy, p-
Hydroxyphenoxy), an acylamino group (1 to 1 carbon atoms)
7 are preferred, for example, acetamido, 2-methoxypropionamide, p-hydroxybenzoylamide),
Alkylamino group (preferably having 1 to 7 carbon atoms, for example,
Dimethylamino, diethylamino, 2-hydroxyethylamino), anilino group (preferably having 6 to 7 carbon atoms, for example, anilino, m-nitroanilino, m-hydroxyanilino), and ureido group (preferably having 1 to 7 carbon atoms) Ureide, methylureide, N, N-diethylureide, 2-methanesulfonamidoethylureide),
Sulfamoylamino group (preferably having 0 to 7 carbon atoms, for example, dimethylsulfamoylamino, methylsulfamoylamino, 2-methoxyethylsulfamoylamino), alkylthio group (preferably having 1 to 7 carbon atoms, for example, , Methylthio, ethylthio, benzylthio), an arylthio group (preferably having 6 to 7 carbon atoms, for example, phenylthio, 2-carboxyphenylthio, 4-hydroxyphenylthio), and an alkoxycarbonylamino group (preferably having 2 to 7 carbon atoms) Methoxycarbonylamino, ethoxycarbonylamino, 3-methanesulfonylpropoxycarbonylamino), sulfonylamino group (preferably having 1 to 7 carbon atoms, for example, methanesulfonamide, p-toluenesulfonamide, 2-methoxyethanesulfonamide), Rubamoyl group (preferably having 1 to 7 carbon atoms, for example, carbamoyl, N, N-dimethylcarbamoyl, N-ethylcarbamoyl), and sulfamoyl group (preferably having 0 to 7 carbon atoms, for example, sulfamoyl, dimethylsulfamoyl, ethylsulfur) Famoyl), a sulfonyl group (preferably an aliphatic sulfonyl group having 1 to 5 carbon atoms or an aromatic sulfonyl group having 6 to 7 carbon atoms, for example, methanesulfonyl, ethanesulfonyl, 2-chloroethanesulfonyl), an alkoxycarbonyl group (carbon Numbers 1 to 7 are preferable, for example, methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl), a heterocyclic oxy group (5-membered or 6-membered containing at least one oxygen atom, nitrogen atom or sulfur atom having 1 to 5 carbon atoms) A membered saturated or unsaturated heterocyclic oxy group that forms a ring That the type of number and elemental heteroatoms may be a plurality, even one for example, 1-phenyl-tetrazolyl-5-oxy, 2
-Tetrahydropyranyloxy, 2-pyridyloxy), an azo group (preferably having 1 to 7 carbon atoms, for example, phenylazo, 2-hydroxyphenylazo, 4-sulfophenylazo), and an acyloxy group (preferably having 1 to 7 carbon atoms) For example, acetoxy, benzoyloxy, 4-hydroxybutanoyloxy), a carbamoyloxy group (preferably having 1 to 7 carbon atoms, for example, N, N-dimethylcarbamoyloxy, N-methylcarbamoyloxy, N-
Phenylcarbamoyloxy), silyl group (3 to carbon atoms)
7, for example, trimethylsilyl, isopropyldiethylsilyl, t-butyldimethylsilyl), a silyloxy group (preferably having 3 to 7 carbon atoms, for example, trimethylsilyloxy, triethylsilyloxy), and an aryloxycarbonylamino group (having 7 carbon atoms). Preferably, for example, phenoxycarbonylamino, 4-hydroxyphenoxycarbonylamino), imide group (4 to 7 carbon atoms)
For example, N-succinimide), a heterocyclic thio group (a 5- or 6-membered saturated or unsaturated heterocyclic thio group containing at least one oxygen atom, nitrogen atom or sulfur atom having 1 to 5 carbon atoms) The number of heteroatoms and the types of elements that constitute the ring may be one or more. For example, 2-benzothiazolylthio, 2-pyridylthio), a sulfinyl group (preferably having 1 to 7 carbon atoms) For example, methanesulfinyl, benzenesulfinyl, ethanesulfinyl), a phosphonyl group (preferably having 2 to 7 carbon atoms, for example, methoxyphosphonyl, ethoxyphosphonyl, phenoxyphosphonyl), an aryloxycarbonyl group (preferably having 7 carbon atoms, For example, phenoxycarbonyl, 3-hydroxyphenoxycarbonyl), an acyl group (1-7 carbon atoms are preferred) Properly, for example, acetyl, benzoyl, 4-hydroxybenzoyl).

R ₂ and R ₃ are preferably, for example, methyl, ethyl, n-propyl, isopropyl, t-butyl, n-pentyl, 2-hydroxyethyl, 3-hydroxypropyl, hydroxyethoxyethyl, benzyl,
2-methanesulfonamidoethyl, 3-methanesulfonamidopropyl, 2-methanesulfonylethyl, 2-methoxyethyl, 2-acetamidoethyl, 2-carbamoylethyl, 3-carbamoylpropyl, 2,3-dihydroxypropyl, 3,4 -Dihydroxybutyl, 2-
Hydroxypropyl, 4-hydroxybutyl, 4-carbamoylbutyl, 2-carbamoyl-1-methylethyl, 4-nitrobutyl, 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl, 2-sulfoethyl, 4-sulfobutyl, -Sulfamoylethyl, 3-sulfamoylpropyl, 4-sulfamoylbutyl, 2-ureidoethyl, 3-ureidopropyl,
2-imidazolylmethyl. More preferred examples of R ₂ and R ₃ include methyl, ethyl, n-propyl, and 2
-Hydroxyethyl, 3-hydroxypropyl, 2-methanesulfonamidoethyl, 3-methanesulfonamidopropyl, 2-carboxyethyl, 4-sulfobutyl,
3-carbamoylpropyl, 4-sulfamoylbutyl, 2-ureidoethyl.

R ₄ represents a substituent. In this case, the substituent has the same meaning as the substituent described for R ₂ and R ₃ . n is 0
Represents an integer from to 3. n is preferably 0 to 1, and more preferably n is 0.

In the general formula (DB), R ₁ , R ₂ , R ₃ ,
Preferred combinations of R ₄ and n are described below. n is 0, R ₁ is an alkyl group having 2 to 6 carbon atoms and having at least one hydroxy group, and a carboxy group, a sulfo group, a ureido group, a sulfonylamino group, a carbamoyl group which may be further substituted; , A sulfamoyl group, and R ₂ and R ₃ may be the same or different, and may be a linear, branched, or cyclic alkyl group which may be substituted. A carboxy group, a sulfo group, a ureido group, a sulfonylamino group, a carbamoyl group, and a sulfamoyl group; R ₁ , R ₂ , and R _{3 each} have a total of 2 to 3 hydroxy groups; and R ₁ , R ₂ , and R ₃ A combination in which the total number of carbon atoms is 5 to 11 is preferable.

As a more preferred combination, m is 0, and R ₁ is an alkyl group having 2 to 5 carbon atoms and one hydroxy group, specifically, 2-hydroxyethyl,
3-hydroxypropyl, 4-hydroxybutyl, 3-
Hydroxy-2-methylpropyl, one of R _2, R ₃ is an alkyl group having 1 to 4 carbon atoms and the other is an alkyl group having one hydroxyl group in the 2 to 5 carbon atoms, R ₁ , R ₂ and R ₃ are preferably a combination in which the total number of carbon atoms is 6 to 9. As a more preferable combination,
m is 0, and R ₁ is an alkyl group having 2 to 5 carbon atoms and having 2 to 3 hydroxy groups, specifically, 2,3-
Dihydroxypropyl, 3,4-dihydroxybutyl,
2,3,4-trihydroxybutyl, 2- (hydroxymethyl) -3-hydroxypropyl and 2- (hydroxymethyl) -4-hydroxybutyl, wherein R ₂ and R ₃ are an alkyl group having 1 to 4 carbon atoms. And the total number of carbon atoms of R ₁ , R ₂ and R ₃ is preferably 6 to 9.

Next, specific examples of the representative developing agent represented by formula (DB) in the present invention are shown, but the invention is not limited thereto.

[0018]

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[0019]

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[0020]

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[0021]

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[0022]

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[0023]

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[0024]

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[0025]

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[0026]

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[0027]

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Since the compound represented by the general formula (DB) 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.
It is preferable that free amine is first obtained when added to the processing solution. Examples of the inorganic and organic acids that form the salt of the compound of the formula (DB) include hydrochloric acid, sulfuric acid, phosphoric acid, and p
-Toluenesulfonic acid, methanesulfonic acid, naphthalene-1,5-disulfonic acid and the like. Among these, a salt of sulfuric acid or p-toluenesulfonic acid is preferable, and salt formation as a salt with sulfuric acid is most preferable. The color developing agent of the present invention can be easily synthesized by the following synthesis examples or a method analogous thereto. Further, for example, it can be synthesized according to the method described in Journal of the American Chemical Society 73, 3100-3125 (1951). Synthesis Example-1 According to the following formula, the exemplified compound (DB-3) of the present invention was synthesized.

[0029]

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Synthesis of (1-b) 82.6 g of m-dimethylaminophenol (1-a) and potassium carbonate 207 in 500 ml of dimethylacetamide
g and heated and stirred at 85 ° C., and 132.6 g of 3-chloro-1,2-propanediol was gradually added. Further 85
The mixture was stirred with heating at 2 ° C. for 2 hours, cooled to room temperature, poured into water, extracted with ethyl acetate, washed with saturated saline, dried over sodium sulfate, and concentrated. This was purified by silica gel column chromatography to obtain 79.7 g of (1-b) (yield: 56%). Synthesis of (1-c) In a mixed solvent of 200 ml of methanol and 400 ml of water, 79.7 g of (1-b) and 94.3 ml of concentrated hydrochloric acid were added, and while stirring under ice cooling, 60 ml of an aqueous solution of 25.3 g of sodium nitrite was added. Was gradually added. After stirring for 1 hour, 64.4 g of sodium hydrogencarbonate was added, and inorganic substances were removed by filtration through Celite. The filtrate was concentrated, purified by silica gel column chromatography, and crystallized using methanol to obtain 59.7 g of (1-c). (Yield 67%) Synthesis of Exemplified Compound (DB-3) (1-c) 59.7 g and 10% palladium carbon 0.5 g
Was added to 500 ml of ethanol and contacted with hydrogen for 2 hours in an autoclave. Then, the catalyst was separated by filtration using celite as a filter aid, and the filtrate was added dropwise to an ethanol solution of 80.1 g of 1,5-naphthalenedisulfonic acid tetrahydrate. The precipitated crystals are collected by filtration, and the target exemplary compound (DB
86.1 g of 1,3-naphthalenedisulfonic acid salt of -3) was obtained as white crystals. (Yield 71%) Melting point 219-2
23 ° C.

Synthesis Example 2 According to the same synthesis route as Synthesis Example 1, 1,5-naphthalenedisulfonic acid salt of Exemplified Compound (DB-21) of the present invention was obtained as white crystals. Melting point 214-220 [deg.] C.

The color developing agent of the present invention can be used alone or in combination with other known p-phenylenediamine derivatives. Representative examples of the compounds to be combined are shown below, but are not limited thereto. N, N-diethyl-p-phenylenediamine (P-1), 4-amino-
3-methyl-N, N-diethylaniline (P-2), 4
-Amino-3-methyl-N-ethyl-N- (3-hydroxypropyl) aniline (P-3), 4-amino-N-
Ethyl-N- (2-hydroxyethyl) aniline (P-
4), 4-amino-3-methyl-N-ethyl-N- (2
-Hydroxyethyl) aniline (P-5), 4-amino-3-methyl-N-ethyl-N- (2-methanesulfonamidoethyl) aniline (P-6), N- (2-amino-5-N , N-diethylaminophenylethyl) methanesulfonamide (P-7), N, N-dimethyl-p-phenylenediamine (P-8), 4-amino-3-methyl-N-ethyl-N- (2-methoxy Ethyl) aniline (P-9), 4-amino-3-methyl-N-ethyl-N
-(4-hydroxybutyl) aniline (P-10), 4-
Amino-3-methyl-N-ethyl-N- (2-butoxyethyl) aniline (P-11). As the compound to be combined, P-3, P-5, P-6 or P-10 is particularly preferable among the above-mentioned p-phenylenediamine derivatives.
Further, these p-phenylenediamine derivatives and salts such as sulfates, hydrochlorides, sulfites, p-toluenesulfonates, nitrates, naphthalene-1,5-disulfonates are generally used. . The treatment composition may be in a liquid state or a solid state (for example, a powdery state or a granular state). These compounds can be used in combination of two or more depending on the purpose. The amount of the aromatic primary amine developing agent to be used is preferably 0.001 mol to 0.2 mol, more preferably 0.005 mol to 0.1 mol per liter of the color developer.
1 mole.

In the color developer, compounds described in JP-A-63-5341, JP-A-63-106655 or JP-A-4-144446 may be used as compounds for directly preserving the aromatic primary amine color developing agent. Various hydroxylamines, hydroxamic acids described in JP-A-63-43138, hydrazines and hydrazides described in JP-A-63-146041, 63-44657 and 63-58.
No. 443, α-hydroxyketones and α-aminoketones described in JP-A-63-44656, and various sugars described in JP-A-63-36244. Also, in combination with the above compounds, JP-A-63-4235, JP-A-63-24254 and JP-A-63-24
Nos. 1647, 63-146040, 63-278
Monoamines described in No. 41 and No. 63-25654, No. 63-30845, No. 63-14640,
Diamines described in JP-A-63-43139 and the like;
Nos. 21647, 63-26655 and 63-4
Polyamines described in No. 4655, and 63-53551.
No. 63-43140.
Alcohols described in JP-A-63-53549, oximes described in JP-A-63-56654, and alcohols described in JP-A-63-56654.
Tertiary amines described in 239,47 can be used. Other preservatives include JP-A-57-44148.
And various metals described in JP-A-57-53749; salicylic acids described in JP-A-59-180588;
Alkanolamines described in No. 3582, 56-9
If necessary, polyethyleneimines described in No. 4349, aromatic polyhydroxy compounds described in U.S. Pat. No. 3,746,544, and the like may be contained. In particular, when hydroxylamines are used, the above-mentioned alkanolamines and aromatic polyhydroxy compounds are preferably used in combination.
Particularly preferred preservatives are described in JP-A-3-144446.
And hydroxylamines represented by the general formula (I), and among them, compounds having a methyl group, an ethyl group, a sulfo group or a carboxy group are preferable. These preservatives may be added in an amount of 20 to 200 mmol, preferably 30 to 150 mmol per liter of color developer.
Millimoles.

It is preferable that the developer of the photosensitive material for printing contains chlorine ions in an amount of 3.0 × 10 ^{-2 to} 1.5 × 10 ^-1 mol / l. Particularly preferably 3.5 × 10
^{−2 to} 1.0 × 10 ⁻¹ mol / l. If the chloride ion concentration is more than 1.5 × 10 ^{-1 to} 1.0 × 10 ^-1 mol / l, it has the disadvantage of delaying the development, and in order to achieve the object of the present invention, which is rapid and has a high maximum concentration. Not preferred. On the other hand, if it is less than 3.0 × 10 ⁻² mol / l, it is not preferable in preventing fog. In the present invention, the color developer preferably contains 0.5 × 10 ⁻⁵ mol / L to 1.0 × 10 ⁻³ mol / L of bromine ions. More preferably, it is 3.0 × 10 ^{−5 to} 5 × 10 ⁻⁴ mol / l. When the bromine ion concentration is higher than 1 × 10 ⁻³ mol / l, the development is delayed, and the maximum concentration and sensitivity are reduced. When the bromide ion concentration is lower than 0.5 × 10 ⁻⁵ mol / l, fog is sufficiently prevented. Can not.

The chlorine ions and bromine ions may be added directly to the color developer or may be eluted from the light-sensitive material into the color developer during the development. When directly added to a color developer, examples of the chloride ion supplying material include sodium chloride, potassium chloride, ammonium chloride, lithium chloride, magnesium chloride, and calcium chloride. Further, it may be supplied from a fluorescent whitening agent added to the color developer. As a bromine ion supply substance,
Examples include sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide, and magnesium bromide. When eluted from the light-sensitive material during the development processing, both chlorine ions and bromine ions may be supplied from the emulsion or may be supplied from sources other than the emulsion.

Other color developing solutions include those described in
Various additives described in No. 144446 can be used. For example, carbonic acids, phosphoric acids, boric acids, hydroxybenzoic acids, and the like described on page (9) of the same patent can be used as a buffer for maintaining pH. It is preferable that the pH of the color developer is maintained at 9.0 to 12.5 using these buffers. More preferably, it is 9.5 to 11.5. Examples of the antifoggant include halide ions and organic antifoggants described on page (10). In particular, when the concentration of the developing agent in the color developer is as high as 20 mmol / L or more, or when high-temperature processing is performed at 40 ° C. or more, the bromide ion concentration is preferably somewhat high, and is preferably 17 mmol / L.
It is preferably from liter to 60 mmol. If necessary, halogen can be removed by using an ion-exchange resin or an ion-exchange membrane to control the concentration in a preferable range. As a chelating agent, aminopolycarboxylic acid,
Aminopolyphosphonic acid, alkylphosphonic acid and phosphonocarboxylic acid are preferably used. For example, 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-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof as representative examples. The following compounds can be used. Preferred chelating agents include compounds having biodegradability. Examples of this are disclosed in JP-A-63-146998 and JP-A-63-19929.
5, JP-A-63-267750, JP-A-63-26
No. 7751, JP-A-2-229146, JP-A-3-3-1
No. 86841, German patent 3739610, European patent 46
No. 8325 and the like. Further, development inhibitors such as benzimidazoles, benzothiazoles or mercapto compounds, development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, amines, dye-forming couplers, competitive couplers, 1-phenyl- If necessary, an auxiliary developing agent such as 3-pyrazolidone, a viscosity-imparting agent, or various surfactants such as alkylsulfonic acid, arylsulfonic acid, aliphatic carboxylic acid, and aromatic carboxylic acid may be added.

An optional development accelerator can be added to the color developer if necessary. As a development accelerator, JP-B-37
-16088, 37-5987 and 38-782
Nos. 6, 44-12380, 45-9019 and U.S. Pat. Nos. 3,813,247, and JP-A-52-49829 and JP-A-50-49829.
P-phenylenediamine compound represented by JP-A-15554, JP-A-50-137726, JP-B-44-3
0074, JP-A-56-156826 and JP-A-52-286.
Quaternary ammonium salts represented by 43429 and the like; U.S. Pat. Nos. 2,494,903 and 3,128,182
Nos. 4,230,796 and 3,253,919
No., JP-B-41-11431, U.S. Pat. No. 2,48
Nos. 2,546, 2,596,926 and 3,58
No. 2,346, etc .;
No. 16088, No. 42-25201, U.S. Pat.
128,183, JP-B-41-11431, 42
Polyalkylene oxides described in U.S. Pat. No. 23883 and U.S. Pat. No. 3,532,501, and other 1-phenyl-3-pyrazolidones, imidazoles, and the like can be added as necessary.

The replenishing amount of the color developing solution in the case of photographic light-sensitive material is preferably not more than 1 m ² per 550 ml, 450 ml
The following are more preferable, and the 400 ml or less and the 80 ml or more are most preferable. By reducing or not including the bromide ion concentration in the replenisher, it can be reduced to 300 ml or less. In the case of a photosensitive material for printing, the replenishment amount of the color developing solution is suitably from 20 to 600 ml, preferably from 30 to 200 ml, more preferably from 40 to 100 ml, per m ^{2 of} the photosensitive material. The processing temperature of the color developer is preferably 35 ° C. or higher, and more preferably 40 ° C. or higher and 50 ° C. or lower, for a photosensitive material for photography. In the case of a photosensitive material for printing, the processing temperature of the color developer is 20 to 50 ° C., preferably 30 to 50 ° C.
45 ° C, most preferably 37-42 ° C. The processing time of the color developing solution is preferably 30 seconds to 3 minutes 15 seconds, and more preferably 30 seconds to 2 minutes 30 seconds in the case of a photosensitive material for photography. The processing time of the color developer is generally 3 minutes or less for a photosensitive material for printing, but is preferably 10 seconds to 1 minute, more preferably 10 seconds to 30 seconds. Here, the processing time (for example, the developing time) refers to the time from when the photosensitive material enters the target processing solution to when it enters the processing solution in the next bath.

It is preferable that the developer of the printing photosensitive material contains substantially no benzyl alcohol. The developer of the photosensitive material for printing must be substantially free of sulfite ions in order to suppress fluctuations in photographic characteristics due to continuous processing and to achieve the effects of the present invention. , And a sulfite ion concentration of 3.0 × 10 ⁻³ mol / liter or less). Preferably, it contains no sulfite ion at 1.0 × 10 ⁻³ mol / l or less, most preferably no sulfite ion at all. Here, however, a very small amount of sulfite ion used for preventing oxidation of a processing agent kit in which a developing agent is concentrated before preparing a working solution is excluded. In order to suppress a change in photographic characteristics due to a change in the concentration of hydroxylamine, the developer should be substantially free of hydroxylamine (here, substantially not containing a hydroxylamine concentration of 5.0 × 1).
0 is ^-3 mol / l or less. Is more preferred. Most preferably, it contains no hydroxylamine.

It is preferable to prevent evaporation of the liquid and oxidation of the air. The contact area between the photographic processing solution and air in the processing tank can be represented by an aperture ratio defined below. That is, aperture ratio = [contact area between treatment liquid and air (cm ² )] ÷ [capacity of treatment liquid (cm ³ )] The above-mentioned aperture ratio (cm ⁻¹ ) is preferably 0.05 or less, more preferably Preferably it is 0.0005-0.01.
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,
A slit developing method described in JP-A-63-216050 can be exemplified. Further, it is preferable that the processing solution in the replenishment tank of the color developer or the processing layer is shielded with a high boiling point organic solvent or a high molecular compound to reduce the contact area with air. Particularly, liquid paraffin, organosiloxane and the like are preferable. Reducing the aperture ratio can be applied not only to both color development and black-and-white development, but also to all subsequent steps such as bleaching, bleach-fixing, fixing, washing, stabilization, and the like. The developer can be regenerated and used. Regeneration of the developer means that the used developer is subjected to an anion exchange resin or electrodialysis, or the activity of the developer is increased by adding a processing chemical called a regenerant to be used again as a processing liquid. . In this case, the regeneration rate (the percentage of overflow in the replenisher)
It is preferably at least 70%, particularly preferably at least 90%. As a regeneration method, it is preferable to use an anion exchange resin. Particularly preferred anion exchange resin compositions and resin regeneration methods include those described in Diaion Manual (I) (14th edition, 1986) issued by Mitsubishi Kasei Kogyo. Among the anion exchange resins, JP-A-2-952 and JP-A-1-28115
The resin having the composition described in No. 2 is preferred.

The color-developed photosensitive material is usually desilvered. The desilvering process referred to here basically comprises a bleaching process and a fixing process, but is constituted by a bleach-fixing process in which these processes are performed simultaneously and a combination of these processes. Examples of the bleaching agent include iron salts; iron (III), cobalt (III)
And compounds of polyvalent metals such as chromium (IV) and copper (II); peracids; quinones; and nitro compounds. Representative bleaching agents include iron chloride; ferricyanide; dichromate; organic complex salts of iron (III) (eg, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diamino acid) Metal complex salts such as aminopolycarboxylic acids such as propanetetraacetic acid and glycol ether diaminetetraacetic acid); persulfates; bromates; permanganates; and nitrobenzenes. Of these, the aforementioned Japanese Patent Laid-Open No.
As described on page 144446 (11), ferric aminopolycarboxylic acid salts or salts thereof are preferably used. For example, ferric salts such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, and glycol etherdiaminetetraacetic acid can be used. In addition, complex salts such as citric acid, tartaric acid, and malic acid can be used as the bleaching agent. Among these, iron (III) complex salts of aminopolycarboxylic acid such as iron (III) complex salt of ethylenediaminetetraacetate and 1,3-diaminopropanetetraacetate complex salt are particularly preferable. These iron (III) complex salts of aminopolycarboxylic acid are particularly useful in a bleaching solution and a bleach-fixing solution.

In the bleaching solution, the bleach-fixing solution and the prebath thereof, a bleaching accelerator can be used if necessary.
Specific examples of useful bleach accelerators are described in the following specification: U.S. Pat. No. 3,893,858, West German Patent 1,290,812, JP-A-53-95630, Research. Disclosure No. 17129 (197
A compound having a mercapto group or a disulfide bond as described in US Pat. No. 3,706,5.
No. 61; thiourea derivatives described in JP-A-58-1623.
No. 5, iodide salt; West German Patent 2,748,430
No. 45-polyoxyethylene compounds;
Polyamine compounds described in No. 8836; bromide ions and the like can be used. Among them, a compound having a mercapto group or a disulfide group is preferable from the viewpoint of a large accelerating effect,
In particular, U.S. Patent No. 3,893,858, West German Patent No. 1,
Compounds described in JP-A-290,812 and JP-A-53-95630 are preferred. No. 4,552,8.
The compound described in No. 34 is also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color photographic material for photography.

In the desilvering bath, in addition to the bleaching agent, JP-A-3-1
P. 44446 (12), rehalogenating agent, p
H buffers and known additives can be used. The bleaching solution and the bleach-fixing solution preferably contain an organic acid in addition to the above compounds for the purpose of preventing bleaching stain. Particularly preferred organic acids are compounds having an acid dissociation constant (pka) of 2 to 6, specifically acetic acid, propionic acid, hydroxyacetic acid succinic acid, maleic acid, glutaric acid, fumaric acid, malonic acid, adipic acid and the like. Among them, succinic acid, maleic acid and glutaric acid are particularly preferred. The pH of the bleaching solution or the bleach-fixing solution is usually from 4.0 to 8.0, but the processing can be carried out at a lower pH in order to speed up the processing.

Examples of the fixing agent used in the fixing solution or the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodides. Use is common, especially ammonium thiosulfate being the most widely used. It is also preferable to use a combination of a thiosulfate with a thiocyanate, a thioether-based compound, thiourea, or the like. As a preservative of the fixing solution or the bleach-fixing solution, a sulfite, a bisulfite, a carbonyl bisulfite adduct, or a sulfinic acid compound described in EP-A-294769A is preferable. Further, for the purpose of stabilizing the liquid, it is preferable to add a chelating agent such as various aminopolycarboxylic acids or organic phosphonic acids. Preferred chelating agents include 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediamine-N, N, N ', N'-tetrakis (methylenephosphonic acid), nitrilotrimethylenephosphonic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexane Diaminetetraacetic acid, 1,2
-Propylenediaminetetraacetic acid. Among them, 1-hydroxyethylidene-1,1-diphosphonic acid and ethylenediaminetetraacetic acid are particularly preferred. The pKa of the fixing solution or the bleach-fixing solution is adjusted for pH adjustment.
It is preferable to contain a compound of 0 to 9.0. For example, it is preferable to add imidazoles such as imidazole, 1-methylimidazole, 1-ethylimidazole and 2-methylimidazole in an amount of 0.1 to 10 mol / l. The imidazole compound represents imidazole and its derivatives, and preferable substituents of imidazole include an alkyl group, an alkenyl group, an alkynyl group, an amino group, a nitro group, a halogen atom, and the like.
Further, the alkyl group, alkenyl group, and alkynyl group may be further substituted with an amino group, a nitro group, a halogen atom, or the like. The preferred total carbon number of the substituents of imidazole is 1 to 6, and the most preferred substituent is a methyl group.

Hereinafter, specific examples of the imidazole compound will be described, but the invention is not limited thereto. Imidazole, 1-methylimidazole, 2-methylimidazole, 4-methylimidazole, 4- (2-hydroxyethyl) -imidazole, 2-ethylimidazole, 2-
Vinylimidazole, 4-propylimidazole, 4-
(2-Aminoethyl) imidazole, 2,4-dimethylimidazole, 2-chloroimidazole. Of these,
Preferred compounds are imidazole, 2-methyl-imidazole, 4-methyl-imidazole, and the most preferred compound is imidazole.

The fixing solution or the bleach-fixing solution may further contain various fluorescent whitening agents; antifoaming agents; surfactants; polyvinylpyrrolidone; When a replenishment method is used in the processing, the replenishment amount of the fixing solution or the bleach-fixing solution is 100 to 3000 per m ² of the light-sensitive material.
ml is preferred, but more preferably 300 to 1800 m
l. Replenishment of the bleach-fixing solution may be carried out as a bleach-fixing replenisher, or by using an overflow solution of the bleaching solution and the fixing solution as described in JP-A-61-143755 and Japanese Patent Application No. 2-216389. You may. The total processing time of the desilvering step comprising a combination of bleaching, bleach-fixing and fixing of the photographic light-sensitive material is preferably 30 seconds to 3 minutes, more preferably 45 seconds to 2 minutes. The processing temperature is 30 to 60.
° C, preferably 35 to 55 ° C.

It is particularly preferred that the processing solution having bleaching ability is subjected to aeration during processing, since the photographic performance can be kept extremely stable. Any means known in the art can be used for aeration, and air can be blown into a processing solution having bleaching ability, or air can be absorbed using an ejector. When blowing air, it is preferable to release air into the liquid through a diffuser having fine pores. Such a diffuser is widely used for an aeration tank in activated sludge treatment. Regarding aeration, Z-1 issued by Eastman Kodak Company
21, Using Process C-41 Third Edition (198
2 years), and the items described on pages BL-1 and BL-2 can be used. In the processing using the processing solution having the bleaching ability of the present invention, it is preferable that the stirring is strengthened. The contents described in the second row from the lower left column can be used as they are.

Silver can be recovered from a processing solution having a fixing ability by a known method, and a regenerating solution having such a recovered silver can be used. Examples of the silver recovery method include an electrolysis method (described in French Patent No. 2,299,667), a precipitation method (Japanese Patent Application Laid-Open No. 52-73037, and German Patent No. 2,331,
No. 220), ion exchange method (JP-A-51-1711).
No. 4, German Patent 2,548,237) and a metal substitution method (UK Patent 1,353,805) are effective. These silver recovery methods are preferably performed in-line from the tank liquid because the rapid processing suitability is further improved. Further, the processing solution having the bleaching ability can be reused after collecting the overflow solution after use in the processing, correcting the composition by adding components, and then reusing it. Such a method of use is usually referred to as reproduction, but the present invention can also preferably perform such reproduction. Regarding the details of the reproduction, the matters described in pages 39 to 40 of Fujifilm Processing Manual, Fujicolor Negative Film, CN-16 processing (revised in August 1990) issued by Fuji Photo Film Co., Ltd. can be applied. The kit for adjusting the processing solution having the bleaching ability of the present invention may be a liquid or a powder, but when the ammonium salt is excluded, most of the raw materials are supplied in the form of a powder, and the hygroscopicity is low. Makes powder easier. From the viewpoint of reducing the amount of waste liquid, the regenerating kit is preferably a powder because it can be directly added without using excess water.

Regarding the regeneration of the processing solution having the bleaching ability,
In addition to the aeration described above, "Basics of photographic engineering-silver halide photography-" (edited by the Photographic Society of Japan, published by Corona, 1979)
Year) can be used. Specifically, in addition to electric field regeneration, a method for regenerating a bleaching solution using bromic acid, zinc acid, bromine, bromine precursor, persulfate, hydrogen peroxide, hydrogen peroxide using a catalyst, bromite, ozone, etc. No.
In the regeneration by electrolysis, the cathode and the anode are placed in the same bleaching bath, or the anode and the cathode are separated from each other by using a diaphragm for regeneration, and the bleaching solution, the developer and the And / or regenerating the fixing solution at the same time. The regeneration of the fixing solution and the bleach-fixing solution is carried out by electrolytic reduction of accumulated silver ions. Others
It is also preferable to remove the accumulated halogen ions with an anion exchange resin in order to maintain the fixing performance.

In the desilvering step, it is preferable that the stirring is strengthened as much as possible. As a specific method of strengthening the stirring, a method described in JP-A-62-183460, in which a jet of a processing solution is made to impinge on the emulsion surface of a light-sensitive material, or a method described in JP-A-62-183460.
No. 2-183461, a method of increasing the stirring effect by using a rotating means, and furthermore, by moving a photosensitive material while bringing a wiper blade provided in a liquid into contact with an emulsion surface, thereby causing a turbulent flow on the emulsion surface to further stir. A method for improving the effect and a method for increasing the circulating flow rate of the entire processing liquid can be given. Such a stirring improving means is effective for any of a bleaching solution, a bleach-fixing solution and a fixing solution. It is considered that improving the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film, and as a result, increases the desilvering speed. The above-mentioned means for improving the stirring is more effective when a bleaching accelerator is used, and can significantly increase the accelerating effect or eliminate the fixing inhibiting effect of the bleaching accelerator. Automatic developing machines used in the light-sensitive material of the present invention are described in JP-A-60-191257 and JP-A-60-19
It is preferable to have the photosensitive material conveying means described in JP-A Nos. 1258 and 60-191259. As described in the above-mentioned JP-A-60-191257, such a conveying means can significantly reduce the carry-in of the processing solution from the pre-bath to the post-bath, and is highly effective in preventing the performance of the processing solution from deteriorating. Such an effect is particularly effective for reducing the processing time in each step and reducing the replenishing amount of the processing solution.

Generally, a water washing step is performed after the desilvering treatment. A stabilizing step may be performed instead of the washing step. In such a stabilization process, Japanese Patent Application Laid-Open No. 57-8543 is disclosed.
And all known methods described in JP-A-58-14834 and JP-A-60-220345 can be used. Also,
A washing step and a stabilizing step may be performed such that a stabilizing bath containing a dye stabilizer and a surfactant is used as a final bath. The washing solution and the stabilizing solution may contain a hard water softener such as inorganic phosphoric acid, polyaminocarboxylic acid, and organic aminophosphonic acid.

The amount of water in the washing step and the like depends on the characteristics of the photosensitive material (for example, depending on the material used such as a coupler), the application, the liquid temperature, the number of tanks (the number of stages), the replenishment method such as countercurrent, forward flow, and various other methods. It can be set in a wide range depending on conditions. The number of stages is preferably 2 to 4 stages. The replenishment amount is 1 to 50 times, preferably 1 to 30 times the amount brought in from the previous bath per unit area.
And more preferably 1 to 10 times. As a method of efficiently reducing the replenishment amount, a so-called multi-chamber washing method in which a washing tank or a stabilizing bath is divided by a partition wall, and the photosensitive material is processed in a liquid without passing through a slit portion of a wiper blade or the like to enter the air. Alternatively, a stable treatment is preferably used.

According to the above-mentioned multi-stage countercurrent method or multi-chamber washing method, the amount of washing water can be greatly reduced. However, due to an increase in the residence time of the water in the tank, bacteria are propagated and the generated suspended matter is exposed to light. Problems such as adhesion to materials occur. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, a method of previously reducing calcium ions and magnesium ions described in JP-A-62-288838 can be used very effectively. It is also effective to use water previously sterilized with a germicide such as chlorinated sodium isocyanurate. In addition, for washing water, etc., isothiazolone compounds and cyabendazoles described in JP-A-57-8,542, known chlorine-based bactericides, other benzotriazoles, etc.
(1986) Sankyo Publishing, Sanitary Technology Association, "Microbial Sterilization, Sterilization, and Antifungal Technology" (1982) Industrial Technology Association, Japan Society of Antimicrobial and Fungicide, "Encyclopedia of Antifungal Agents" (1986) The bactericides described can also be used.

The pH of the washing water and the stabilizing solution is from 4 to 9, preferably from 5 to 8. The temperature and time can also be variously set depending on the characteristics of the photosensitive material, the application, and the like.
10 seconds to 10 minutes at 5 to 45 ° C, preferably 25 to 40 ° C
Selects a range from 15 seconds to 5 minutes. 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 stabilization treatment, any of the known methods described in JP-A-57-8543, JP-A-58-14834, and JP-A-60-220345 can be used.

The stabilizing solution contains a compound for stabilizing a dye image, for example, benzaldehydes such as formalin and m-hydroxybenzaldehyde, formaldehyde bisulfite adduct, hexamethylenetetramine and its derivatives, hexahydrotriazine and its derivatives, N-methylol compounds such as dimethylol urea and N-methylol pyrazole, organic acids and pH buffers are included. The preferable addition amount of these compounds is from 0.001 to 0.02 mol per liter of the stabilizing solution. The lower the concentration of free formaldehyde in the stabilizing solution, the less the formaldehyde gas is scattered. From these viewpoints, examples of the dye image stabilizer include N-methylolazoles described in JP-A-4-270344, such as m-hydroxybenzaldehyde, hexamethylenetetramine and N-methylolpyrazole, and N, N'-bi (1 , 2,4-triazol-1-ylmethyl) piperazine, etc.
Azolylmethylamines described in 3753 are preferred.
In particular, azoles such as 1,2,4-triazole and 1,4-bis (1,2,4-triazol-1-ylmethyl) described in JP-A-4-359249 (corresponding to EP-A-519190A2). ) A combination of azolylmethylamine and its derivatives such as piperazine is preferred because of high image stability and low formaldehyde vapor pressure.
Further, if necessary, ammonium compounds such as ammonium chloride and ammonium sulfite, metal compounds such as Bi and Al, a fluorescent brightener, a hardener, and US Pat.
No. 6,583, and a preservative that can be contained in the above-mentioned fixing solution or bleach-fixing solution, for example, a sulfinic acid compound described in JP-A 1-231051 is also preferable. .

The washing water and the stabilizing solution may contain various surfactants in order to prevent unevenness of water droplets during drying of the processed photosensitive material. Among them, a nonionic surfactant is preferably used, and an alkylphenol ethylene oxide adduct is particularly preferable. Octyl, nonyl, dodecyl and dinonylphenol are particularly preferred as the alkylphenol, and the number of moles of ethylene oxide added is particularly preferably 8 to 14. It is also preferable to use a silicon-based surfactant having a high defoaming effect.

It is preferable that the washing water and the stabilizing solution contain various chelating agents. Preferred chelating agents include aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N, N'-trimethylenephosphonic acid, diethylenetriamine-N, N,
Organic phosphonic acids such as N ', N'-tetramethylenephosphonic acid, and a hydrolyzate of a maleic anhydride polymer described in EP 345,172 A1 can be mentioned.

The overflow solution accompanying the washing and / or replenishment of the stabilizing solution can be reused in other steps such as a desilvering step. In the processing using an automatic developing machine or the like, when each of the above processing solutions is concentrated by evaporation,
In order to correct the concentration by evaporation, it is preferable to replenish an appropriate amount of water or a correction solution or a processing replenisher. There is no particular limitation on a specific method for performing water replenishment. Among them, a monitor water tank separate from the bleaching tank described in JP-A Nos. 1-254959 and 1-254960 is installed, and water in the monitor water tank is provided. The amount of evaporation of water in the bleaching tank is calculated from the amount of evaporation of water, and the amount of water in the bleaching tank is replenished in proportion to the amount of evaporation.
The evaporation correction method using a liquid level sensor or an overflow sensor described in JP-A Nos. 3-249644, 3-249645 and 3-249646 is preferable.
Tap water may be used as the water for correcting the evaporation of each processing solution, but it is preferable to use deionized water or sterilized water which is preferably used in the above-mentioned washing step.

The water treated and / or stabilized with a reverse osmosis membrane can be used effectively. As the material of the reverse osmosis membrane, cellulose acetate, crosslinked polyamide, polyether, polysulfone, polyacrylic acid, polyvinylene carbonate, or the like can be used. Feeding the pressure in the use of these films, preferred conditions by preventing deterioration in water permeate flow and stain preventing effect is 2 to 10 kg / cm ^2, particularly preferred conditions are 3~7kg / cm ^2.

The treatment with the reverse osmosis membrane is preferably performed on water in the second and subsequent tanks for such multistage countercurrent washing and / or stabilization. Specifically, the water in the second tank in the case of the two-tank configuration, the second or third tank in the case of the three-tank configuration, and the water in the third or fourth tank in the case of the four-tank configuration is treated with a reverse osmosis membrane and permeated. Water in the same tank (a tank from which water was collected for reverse osmosis membrane treatment; hereinafter referred to as a collection tank)
Alternatively, it is carried out by returning to a water washing and / or stabilizing tank located thereafter. Furthermore, concentrated water washing and / or
Alternatively, returning the stabilizing solution to the bleach-fix bath upstream of the collection tank is one measure.

It is preferable that the various treatment liquids are used at 10 ° C. to 50 ° C. Normally, a temperature of 33 ° C to 38 ° C is standard, but a higher temperature promotes the processing and shortens the processing time. be able to.

Each processing solution can be commonly used for processing two or more kinds of photosensitive materials. For example, by processing the color negative film and the color paper using the same processing liquid, the cost of the processing machine can be reduced and the processing can be simplified.

The present invention can be applied to various color light-sensitive materials such as color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers. In addition, Tokuhei 2-32615, Jitsuhei 3-39784
It is also suitable for a film unit with a lens described in (1).

The light-sensitive material may have at least one light-sensitive layer provided on a support. 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. It is. The photosensitive layer is a unit photosensitive layer having color sensitivity to any of blue light, green light, and red light, and in a photosensitive material for photographing a multi-layer silver halide color photograph, the unit photosensitive layer is generally used. 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, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between layers of the same color sensitivity. A non-light-sensitive layer may be provided between the silver halide light-sensitive layers and as the uppermost layer and the lowermost layer. These may contain a coupler, a DIR compound, a color mixing inhibitor and the like described below. As described in DE 1,121,470 or GB 923,045, a plurality of silver halide emulsion layers constituting each unit photosensitive layer are composed of a high-speed emulsion layer and a low-speed emulsion layer.
It is preferable to arrange them so that the photosensitivity becomes lower gradually toward the support. Also, JP-A-57-112751, 62-200350,
As described in JP-A-62-206541 and JP-A-62-206543, a low-sensitivity emulsion layer may be provided on the side remote from the support, and a high-sensitivity emulsion layer may be provided on the side close to the support. As specific examples, from the farthest side from the support, a low-sensitivity blue-sensitive layer (BL) / a high-sensitivity blue-sensitive layer (BH) / a high-sensitivity green-sensitive layer (GH) / a low-sensitivity green-sensitive layer (GL) / High-sensitivity red-sensitive layer (RH) / low-sensitivity red-sensitive layer (RL), or BH / BL / GL / GH / RH / RL, or BH / BL / GH / GL / RL / RH And so on. Further, as described in JP-B-55-34932, the blue-sensitive layer / GH / RH / GL is arranged from the side farthest from the support.
/ RL can be arranged in this order. JP-A-56-2573
8. As described in JP-A-62-63936, the layers can be arranged in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support.

As described in JP-B-49-15495, the upper layer is a silver halide emulsion layer having the highest sensitivity, the middle layer is a silver halide emulsion layer having a lower sensitivity, and the lower layer is a layer having a higher sensitivity. An example is an arrangement in which a silver halide emulsion layer having a low sensitivity is arranged, and three layers having different sensitivities are sequentially reduced in sensitivity toward a support. Even when such a three-layer structure having different photosensitivity is used,
As described in JP-A-59-202464, in the same color-sensitive layer, a medium-speed emulsion layer / a high-speed emulsion layer / a low-speed emulsion layer may be arranged in this order from the side away from the support. Others
High-speed emulsion layers / low-speed emulsion layers / medium-speed emulsion layers, or low-speed emulsion layers / medium-speed emulsion layers / high-speed emulsion layers may be arranged in this order. The arrangement may be changed as described above even in the case of four or more layers. US to improve color reproduction
4,663,271, 4,705,744, 4,707,436, JP-A-62-1
A donor layer (CL) having a multilayer effect having a spectral sensitivity distribution different from that of the main photosensitive layer such as BL, GL, and RL described in the specifications of 60448 and 63-89850, is arranged adjacent to or close to the main photosensitive layer. Is preferred.

In a general photosensitive material for printing (color printing paper), silver halide emulsion grains are spectrally sensitized by blue-sensitive, green-sensitive, and red-sensitive spectral sensitizing dyes in the order of the above-described color forming layers. It can be constituted by coating on the support in the order described above. However, the order may be different. In other words, from the viewpoint of rapid processing, it is preferable that the photosensitive layer containing the silver halide grains having the largest average grain size be the uppermost layer. It may be preferable to do so. The photosensitive layer and the color hue may not have the above correspondence, and at least one infrared-sensitive silver halide emulsion layer may be used.

Preferred silver halides for use in the photographic light-sensitive material include silver iodobromide containing about 30 mol% or less of silver iodide,
It is silver iodochloride or silver iodochlorobromide. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 10 mol% silver iodide. Silver halide grains in photographic emulsions include those having regular crystals such as cubic, octahedral and tetradecahedral, those having irregular crystal forms such as spheres and plates, twin planes, etc. Or a composite form thereof. The silver halide may be fine grains having a grain size of about 0.2 μm or less or large grains having a projected area diameter of about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion. Dispersion coefficient 15% or less, 1
Monodispersed particles of 0% or less are preferred. Silver halide photographic emulsions include, for example, Research Disclosure (hereinafter, referred to as “Research Disclosure”).
No. 17643 (December 1978), pp. 22-23,
"I. Emulsion preparation and type
s) ", and No. 18716 (November 1979), p. 648,
No. 307105 (November 1989), pages 863 to 865, and the like.

Further, tabular grains having an aspect ratio of about 3 or more can be used in the present invention. Tabular grains are described in Gutoff, Photographic Science and Engineering (Gutoff, Photographic Science and E).
ngineering), Vol. 14, pp. 248-257 (1970), US 4,43
4,226, GB 2,112,157. The crystal structure may be uniform, the inside and outside may have different halogen compositions, or may have a layered structure. Silver halides having different compositions may be joined by an epitaxial junction, or may be joined to a compound other than silver halide such as, for example, silver rhodanate or lead oxide. Also, a mixture of particles of various crystal forms may be used. The above emulsion may be either a surface latent image type in which a latent image is mainly formed on the surface, an internal latent image type in which the latent image is formed inside the grains, or a type having a latent image on both the surface and the inside. It is necessary that
Among the internal latent image type emulsions, core / shell type internal latent image type emulsions described in JP-A-63-264740 may be used, and the preparation method is described in JP-A-59-133542. The thickness of the shell of this emulsion varies depending on the development process, but is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

As the silver halide emulsion, usually, those subjected to physical ripening, chemical ripening and spectral sensitization are used. Additives used in such a process are described in RD17643, RD17616 and RDRD 307105, and the relevant portions are summarized in the table below. In the light-sensitive material of the present invention, two or more types of emulsions having at least one characteristic different from each other in the grain size, grain size distribution, halogen composition, grain shape and sensitivity of the photosensitive silver halide emulsion are mixed in the same layer. Can be used. U.S. Pat. Preferably, it is applied to a substantially light-insensitive hydrophilic colloid layer. The term "silver halide particles having a fogged interior or surface" refers to silver halide grains that can be uniformly (non-imagewise) developed regardless of unexposed portions and exposed portions of the photosensitive material. . The silver halide forming the internal nucleus of the core / shell type silver halide grains whose inside is fogged may have a different halogen composition. The silver halide having the inside or surface of the grain fogged includes silver chloride, silver chlorobromide,
Both silver iodobromide and silver chloroiodobromide can be used. The average grain size of these fogged silver halide grains is preferably 0.01 to 0.75 μm, particularly preferably 0.05 to 0.6 μm. The particles may be regular particles or polydisperse emulsions, but are preferably monodisperse.

Non-photosensitive fine grain silver halide can also be used. Non-photosensitive fine grain silver halide is silver halide fine grains that are not exposed during imagewise exposure to obtain a dye image and are not substantially developed in the developing process, and are preferably not fogged in advance. . Fine grain silver halide has a silver bromide content of 0 to 10
0 mol%, and may contain silver chloride and / or silver iodide as needed. Preferably, it contains 0.5 to 10 mol% of silver iodide. The fine grain silver halide has an average grain size (average value of the circle equivalent diameter of the projected area) of 0.01 to 0.5 μm.
m is preferable, and 0.02 to 0.2 μm is more preferable. Fine grain silver halide does not need to be optically sensitized, nor does it require spectral sensitization. However, prior to adding this to the coating solution, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, or mercapto-based compound or a zinc compound in advance. Colloidal silver can be contained in the layer containing fine silver halide grains. Coated silver amount of the photographic light-sensitive material is preferably not more than ^{6.0g / m 2, 4.5g / m} 2
The following are most preferred.

In the light-sensitive material for printing, it is preferable to use silver chloride, silver chlorobromide, or silver chloroiodobromide particles in which 95 mol% or more is silver chloride. In particular, silver chlorobromide or silver chloride substantially free of silver iodide can be preferably used in order to shorten the development processing time. Here, "contains substantially no silver iodide" means that the silver iodide content is 1 mol% or less, preferably 0.2 mol% or less. On the other hand, 0.01 to 3 mol% of the emulsion surface described in JP-A-3-84545 is used for the purpose of increasing the high illuminance sensitivity, increasing the spectral sensitization sensitivity, or increasing the stability over time of the photosensitive material. In some cases, high silver chloride grains containing silver iodide are preferably used. 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 halogen composition distribution inside the silver halide emulsion grains, grains having a so-called uniform structure having the same composition in any part of the silver halide grains, a core inside the silver halide grains and a shell surrounding the core are used. (shell)
[Single or plural layers] grains having a so-called laminated structure having different halogen compositions from each other or a structure having a non-layered portion having a different halogen composition inside or on the surface of the grains. Particles having a structure in which portions having different compositions are bonded to each other) can be appropriately selected and used. In order to obtain high sensitivity, it is advantageous to use one of the latter two particles rather than particles having a uniform structure, which 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.

The high silver chloride emulsion preferably has a structure in which the silver bromide localized phase is in a layered or non-layered form as described above 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 is preferably 20 mol%.
Is more preferable. These localized phases can be inside the grains, at the edges, corners or planes of the grain surfaces. One preferred example is a phase that is epitaxially grown at the corners of the grains. 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 9
Emulsions of almost pure silver chloride, such as 8 mol% to 100 mol%, are also preferably used.

Average grain size of silver halide grains contained in the silver halide emulsion (the grain size is defined as the diameter of a circle equivalent to the projected area of the grain, and the number average is calculated)
Is preferably 0.1 μm to 2 μm. The particle size distribution is preferably a so-called monodisperse coefficient of variation (a standard deviation of the particle size distribution divided by the average particle size) of 20% or less, preferably 15% or less, more preferably 10% or less. . 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 the photographic emulsion may have a regular crystal form such as cubic, tetradecahedral or octahedral, or irregular (irreactive) such as spherical or tabular.
gular) The one having a crystal form or the one having a complex form thereof can be used. Further, it may be composed of a mixture of those having various crystal forms. In the present invention, among these, the particles having the above-mentioned regular crystal form should be contained in 50% or more, preferably 70% or more, more preferably 90% or more. In addition to these, 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 areas exceed 50% of all grains can be preferably used.

The localized phase of silver halide grains or a substrate thereof may contain a foreign metal ion or a complex ion thereof. Preferred metals are Group VIII and VIII of the periodic table.
It is selected from metal ions or metal complexes belonging to Group IIb, lead ions and thallium ions. Ion selected from iridium, rhodium, iron, etc. or its complex ion for the localized phase, and metal ion selected from osmium, iridium, rhodium, platinum, ruthenium, palladium, cobalt, nickel, iron, etc. for the substrate Alternatively, the complex ions can be used in combination. Further, the type and concentration of the metal ion can be changed depending on the localized phase and the substrate. A plurality of these metals may be used. In particular, it is preferable that the iron and iridium compounds be present in the silver bromide localized phase.

These metal ion-providing compounds are added to a gelatin aqueous solution serving as a dispersion medium when silver halide grains are formed.
The silver halide grains of the present invention may be dissolved in an aqueous halide solution, an aqueous silver salt solution or another aqueous solution, or in the form of silver halide fine particles containing metal ions in advance and dissolving the fine particles. Include in the localized phase and / or other particle portions (substrates). The metal ions used in the present invention can be contained in the emulsion grains either before, during or immediately after grain formation. This can be changed depending on where the metal ions are contained in the particles.

The silver halide emulsion is usually subjected to chemical sensitization and spectral sensitization. Chemical sensitization includes chemical sensitization using a chalcogen sensitizer (specifically, sulfur sensitization represented by addition of an unstable sulfur compound, selenium sensitization by a selenium compound, and tellurium sensitization by a tellurium compound). ), Noble metal sensitization typified by gold sensitization, or reduction sensitization, or the like can be used alone or in combination. Compounds used for chemical sensitization are disclosed in
Those described in the lower right column on page 18 to the upper right column on page 22 of JP-A-2-215272 are preferably used. The effect of the constitution of the light-sensitive material of the present invention is more remarkable than when a gold-sensitized high silver chloride emulsion is used. The emulsion used in the present invention is a so-called surface latent image type emulsion in which a latent image is mainly formed on the grain surface.

Various compounds or their precursors may be added to the silver halide emulsion for the purpose of preventing fog during the production process, storage or photographic processing of the photographic material, or stabilizing photographic performance. Can be. As specific examples of these compounds, those described on pages 39 to 72 of JP-A-62-215272 are preferably used. Further, a 5-arylamino-1,2,3,4-thiatriazole compound (the aryl residue has at least one electron-withdrawing group) described in EP0447647 is also preferably used.

Spectral sensitization is performed for the purpose of imparting spectral sensitivity to a desired light wavelength region to the emulsion of each layer in the photosensitive material. Examples of spectral sensitizing dyes used for spectral sensitization in blue, green, and red regions include, for example, Heterocyclic co
mpounds-Cyanine dyes and related compounds (John W
iley & Sons New York, London, 1964). Specific examples of the compounds and the spectral sensitization method are described in the above-mentioned JP-A-62-21.
No. 5,272, page 22, upper right column to page 38 are preferably used. In particular, as the red-sensitive spectral sensitizing dye for silver halide emulsion grains having a high silver chloride content, spectral sensitizing dyes described in JP-A-3-123340 are disclosed in terms of stability, strength of adsorption, and exposure temperature. It is very preferable from the viewpoint of the dependency.

In order to efficiently spectrally sensitize the infrared region, JP-A-3-15049, page 12, upper left column to page 21, lower left column, JP-A-3-20730, page 4, lower left column to page 15, lower left column, European Patent EP0 , 420, 011, page 4, lines 21-6
Page 54, line 4, page 12, EP 0,420,012
Lines to 10 pages, 33 lines, European Patent EP 0,443,466
And sensitizing dyes described in U.S. Pat. No. 4,975,362 are preferably used.

The spectral sensitizing dye may be added to the emulsion at any stage in the preparation of the emulsion which has been known to be useful. In other words, before the silver halide emulsion is formed, during the grain formation, immediately after the grain formation, before entering the washing step, before the chemical sensitization, during the chemical sensitization, and immediately after the chemical sensitization, until the emulsion is cooled and solidified, during the preparation of the coating solution. , You can choose from. Most commonly, it is performed after completion of chemical sensitization but before coating, but US Pat.
As described in JP-A-628969 and JP-A-4222566, spectral sensitization may be carried out simultaneously with chemical sensitization by simultaneous addition with a chemical sensitizer.
It can be carried out prior to chemical sensitization as described in No. 28, or it can be added before completion of precipitation of silver halide grains to start spectral sensitization. It is also possible to add the spectral sensitizing dye separately, as taught in U.S. Pat. No. 4,225,666, i.e. to add part prior to chemical sensitization and to add the remainder after chemical sensitization. It is possible at any time during silver halide grain formation, including the method taught in U.S. Pat. No. 4,183,756. Among them, it is particularly preferable to add a sensitizing dye before the washing step of the emulsion or before the chemical sensitization.

The addition amount of these spectral sensitizing dyes may vary over a wide range depending on the case, and may be 0.5 to 0.5 mol per mol of silver halide.
The range is preferably from × 10 ^-6 mol to 1.0 × 10 ^-2 mol.
More preferably, 1.0 × 10 ⁻⁶ mol to 5.0 × 10 ^−3.
Range of moles. In the present invention, particularly when a sensitizing dye having spectral sensitization sensitivity from the red region to the infrared region is used, the compounds described in JP-A-2-157747, page 13, lower right column to page 22, lower right column may be used in combination. preferable. By using these compounds, the preservability of the photographic material, the stability of processing and the supersensitizing effect can be specifically enhanced. Among them, it is particularly preferable to use the compounds of the general formulas (IV), (V) and (VI) in the patent in combination. These compounds are used in an amount of from 0.5 × 10 ^-5 mol / mol of silver halide.
5.0 × 10 ⁻² mol, preferably 5.0 × 10 ⁻⁵ mol
An amount of 5.0 × 10 ⁻³ mol is used, and 0.1 to 10,000 times, preferably 0.5 to 5 times, per mol of the sensitizing dye.
There is an advantageous usage in the range of 000 times.

For the purpose of preventing irradiation and halation and improving safelight safety, the photosensitive material is coated with a hydrophilic colloid layer in European Patent EP03374.
Dyes which can be decolorized by treatment (among others, oxonol dyes and cyanine dyes) described on pages 27 to 76 of the specification of 90A2 can be added. Some of these water-soluble dyes deteriorate color separation and safelight safety when used in an increased amount. As dyes that can be used without deteriorating color separation, water-soluble dyes described in Japanese Patent Application Nos. 03-310143, 03-310189, and 03-310139 are preferable.

Instead of the water-soluble dye or in combination with the water-soluble dye, a colored layer which can be decolorized by the treatment is used. The colored layer that can be decolorized by the processing used may be in direct contact with the emulsion layer, or may be arranged so as to be in contact with an intermediate layer containing a processing color mixture inhibitor such as gelatin or hydroquinone. This colored layer is preferably provided below the emulsion layer (on the side of the support) that develops the same primary color as the colored color. It is possible to install all the colored layers corresponding to each primary color individually, or to arbitrarily select and install only a part of them. It is also possible to provide a colored layer which is colored corresponding to a plurality of primary color gamuts. The optical reflection density of the colored layer is the wavelength range used for exposure (400 nm to 700 nm in the visible light range in normal printer exposure, and the wavelength of the scanning exposure light source used in scanning exposure).
It is preferable that the optical density value at the wavelength having the highest optical density is 0.2 or more and 3.0 or less. More preferably 0.5 or more and 2.5 or less, particularly 0.8 or more and 2.0
The following is preferred.

For forming a colored layer, a conventionally known method can be applied. For example, Japanese Patent Application Laid-Open No. 2-282244-3
The dyes described on page 8 from the upper right column of the page and JP-A-3-79
No. 31, page 3, upper right column to page 11, lower left column, a method in which a solid fine particle dispersion is contained in a hydrophilic colloid layer, a method in which an anionic dye is mordanted to a cationic polymer, and a dye is halogenated. Examples thereof include a method of adsorbing fine particles such as silver and fixing it in a layer, and a method of using colloidal silver as described in JP-A-1-239544. As a method of dispersing the fine powder of the dye in a solid state, for example, a method of containing a fine powder dye which is substantially water-insoluble at least at pH 6 or less but is substantially water-soluble at least at pH 8 or more is disclosed in 2-30824
No. 4, pages 4-13. Also, for example,
A method of mordanting an anionic dye into a cationic polymer is described in JP-A-2-84637, pp. 18-26. For a method for preparing colloidal silver as a light absorber, see U.S. Patent Nos. 2,688,601 and 3,45.
No. 9,563. Among these methods, a method of incorporating a fine powder dye and a method of using colloidal silver are preferred.

As a binder or protective colloid that can be used in the light-sensitive material, gelatin is advantageously used, but other hydrophilic colloids can be used alone or together with gelatin. As a preferable gelatin, it is preferable to use a low calcium gelatin having a calcium content of 800 ppm or less, more preferably 200 ppm or less. In order to prevent various fungi and bacteria that propagate in the hydrophilic colloid layer and deteriorate the image, it is preferable to add a fungicide as described in JP-A-63-271247.

When exposing the photosensitive material for printing to a printer, it is preferable to use a band stop filter described in US Pat. No. 4,880,726. As a result, light color mixing is removed, and color reproducibility is significantly improved. The exposed light-sensitive material can be subjected to conventional color development processing, but it is preferable to perform bleach-fix processing after color development for the purpose of rapid processing. In particular, when the high silver chloride emulsion is used, the pH of the bleach-fix solution is preferably about 6.5 or less, and more preferably about 6 or less, for the purpose of accelerating desilvering.

The photographic additives which can be used are also described in the RD, and the relevant places are indicated in the following table. Type of additive RD17643 RD18716 RD307105 Chemical sensitizer page 23 648 page right column page 866 2. Sensitivity enhancer page 648, right column 3. Spectral sensitizer, pages 23 to 24, page 648, right column 866 to 868 Super sensitizer, page 649, right column 4. Brightener 24 page 647, right column page 868 5 Light absorbers, pages 25 to 26, page 649, right column, page 873 Filters, page 650, left column Dyes, ultraviolet absorbers 6. Binders, page 26, page 651, left column 873 to 874 7. Plasticizers, page 27, page 650, right Column 876 Lubricant 8. Coating aid, pages 26 to 27 Page 650 Right column 875 to 876 Surfactant 9. Static 27 page 650 650 Right column 876 to 877 Inhibitor 10. Mast agent 878 to 879

Various dye-forming couplers can be used in the light-sensitive material, and the following couplers are particularly preferred. Yellow coupler: a coupler represented by formulas (I) and (II) of EP 502,424A; a coupler represented by formulas (1) and (2) of EP 513,496A (especially Y-28 on page 18); Claim 1 of -134523
A coupler represented by the general formula (I) of US Pat. No. 5,066,576, column 1, lines 45 to 55;
Couplers represented by general formula (I) in paragraph 0008 of JP-A-4-274425; couplers described in claim 1 on page 40 of EP 498,381A1 (especially D-35 on page 18); formulas on page 4 of EP 447,969A1 (Y)
(Particularly Y-1 (page 17), Y-54 (page 41));
Couplers represented by formulas (II) to (IV) in columns 7, 36 to 58 of US Pat. Acylacetanilide type couplers,
Pivaloyl acetanilide type coupler having a halogen atom or an alkoxy group at the ortho position of the anilide ring, EP0447969A, JP-A-5-107701
, An acyl group described in JP-A-5-113624, etc.
Acylacetanilide-type couplers which are cycloalkanecarbonyl groups substituted at the position, European Patent EP-0448252
No. A, and a malondianilide type coupler described in EP-0524540A and the like.

Magenta coupler; JP-A-3-39737 (L-57 (1
L-68 (lower right of page 12), L-77 (lower right of page 13); EP 456,
257, A-4 -63 (p. 134), A-4 -73, -75 (p. 139); EP 486,
965 M-4, -6 (p. 26), M-7 (p. 27); Paragraph 0 of Japanese Patent Application No. 4-234120
M-45 of 024; M-1 of paragraph 0036 of Japanese Patent Application No. 4-36917;
No. 2631, paragraph 0237, M-22. As a 5-pyrazolone-based magenta coupler, International Publication Nos. WO 92/18901, WO
Arylthio-eliminated 5-pyrazolone-based magenta couplers described in Nos. 92/18902 and WO92 / 18903. As a pyrazoloazole type coupler, JP-A-61-1
Pyrazoloazole couplers containing a sulfonamide group in the molecule as described in JP-A-65246;
Pyrazoloazole couplers having an alkoxyphenylsulfonamide ballast group as described in EP 147254, EP 226,849A and EP 294,7
A pyrazoloazole coupler having an alkoxy group or an aryloxy group at the 6-position as described in No. 85A.

Cyan coupler: CX-1, described in JP-A-4-04843
3,4,5,11,12,14,15 (pages 14 to 16); C-7,1 of JP-A-4-43345
0 (page 35), 34, 35 (page 37), (I-1), (I-17) (pages 42 to 43); the general formula (Ia) or (Ia) of claim 1 of Japanese Patent Application No. 4-236333. A coupler represented by Ib). Polymer coupler: P-1, P-5 (p. 11) of JP-A-2-44345.
Phenol couplers, naphthol couplers, diphenylimidazole cyan couplers described in JP-A-2-33144, 3-hydroxypyridine cyan couplers described in EP 0 333 185 A2, and JP-A 64-32260. Cyclic active methylene cyan couplers described, EP 04562
No. 26A1, a pyrrolopyrazole type cyan coupler described in EP-A-0 484 909, a pyrroloimidazole type cyan coupler described in EP 0484909, and EP 0488.
Pyrrolotriazole-type cyan couplers described in JP-A-248 and EP0491197A1.

Examples of couplers in which the coloring dye has an appropriate diffusibility include US Pat. No. 4,366,237, GB 2,125,570, EP 96,873B,
Those described in DE 3,234,533 are preferred. Couplers for correcting unnecessary absorption of color-forming dyes are yellow colored cyan couplers represented by the formulas (CI), (CII), (CIII) and (CIV) described on page 5 of EP 456,257A1 (especially on page 84). YC-86), the EP
Yellow colored magenta coupler ExM-7 (202
), EX-1 (page 249), EX-7 (page 251), magenta colored cyan coupler CC-9 (column 8) described in US 4,833,069,
CC-13 (column 10), US 4,837,136 (2) (column 8), WO92
Colorless masking couplers of formula (A) of claim 1 of U.S. Pat. Examples of compounds (including couplers) that release a photographically useful compound residue by reacting with an oxidized developing agent include the following. Development inhibitor releasing compound: EP 378,2
Compounds represented by formulas (I), (II), (III) and (IV) described on page 11 of 36A1 (especially T-101 (page 30), T-104 (page 31), T-113 (36 page),
T-131 (p. 45), T-144 (p. 51), T-158 (p. 58)), EP436, 938A2
Compounds of the formula (I) described on page 7 (particularly D-49 (5
1)), a compound represented by formula (1) of Japanese Patent Application No. 4-134523 (particularly, paragraph (0027) of paragraph 0027), a compound represented by formulas (I), (II), Compounds represented by (III) (especially on page 29)
I- (1)); Bleaching accelerator releasing compounds: compounds represented by the formulas (I) and (I ′) on page 5 of EP 310,125A2 (particularly, (60) and (6) on page 61)
1)) and a compound represented by formula (I) of claim 1 of Japanese Patent Application No. 4-325564 (particularly, paragraph (0022) (7)); a ligand releasing compound: represented by LIG-X described in claim 1 of US Pat. No. 4,555,478. Compounds (especially compounds on lines 21-41 of column 12); leuco dye releasing compounds: compounds 1-6 of columns 3-8 of US 4,749,641; fluorescent dye releasing compounds: represented by COUP-DYE of claim 1 of US 4,774,181. Compounds (especially columns 7 to 10)
Compounds of formulas (1) to (11); Development accelerator or fogging agent release compounds: compounds represented by formulas (1), (2) and (3) in column 3 of US Pat. No. 4,656,123 (especially (I-22) in column 25) and EP 450,6
ExZK-2, p. 75, lines 36-38 of 37A2; a compound which releases a group which becomes a dye only when it is cleaved: a compound represented by formula (I) in claim 1 of US Pat. No. 4,857,447 (especially, Y- 1 to
Y-19).

As the additives other than the coupler, the following are preferable. Dispersion medium of oil-soluble organic compound: P-3,5, JP-A-62-215272
16,19,25,30,42,49,54,55,66,81,85,86,93 (140-144
Page); Latex for impregnation of oil-soluble organic compounds: US 4,199,3
63. Latex according to 63; oxidized developing agent scavenger: a compound represented by the formula (I) in columns 54 to 62 of column 2, US Pat. No. 4,978,606 (especially I-, (1), (2), (6), (12 ) (Column 4 ~
5), US Pat. No. 4,923,787, columns 5 to 10 of formula (particularly compound 1 (column 3); stain inhibitor: EP 298321A 4
Formulas (I) to (III) on page 30-33, especially I-47, 72, III-1, 27 (24
-48 pages); Anti-fading agent: A-6, 7, 20, 21, 23, 24, EP 298321A
25,26,30,37,40,42,48,63,90,92,94,164 (pp.69-118),
US 5,122,444 columns 25-38 II-1 to III-23, especially III-
10, EP 471347A, pages 8-12, I-1 to III-4, especially II-2, US
5,139,931 columns 32-40 A-1 to 48, especially A-39,42; Materials that reduce the amount of color enhancer or color mixture inhibitor used:
EP 411324A, pages 1 to 24, I-1 to II-15, especially I-46; Formalin Scavenger: EP 477932A, pages 24 to 29, SCV-1 to
28, especially SCV-8; hardener: H-1,4 on page 17 of JP-A-1-214845,
6,8,14, US 4,618,573, columns 13 to 23 of formulas (VII) to (XI
Compound (H-1 to 54) represented by I), JP-A-2-214852-8
Compounds (H-1 to 76) represented by the formula (6) at the lower right of the page, especially H-1
4, compounds described in claim 1 of US Pat. No. 3,325,287; development inhibitor precursors: P-24,37,39 of JP-A-62-168139 (6 to
Compounds described in claim 1 of US 5,019,492, especially 28, 29 of column 7; Preservatives, fungicides: I-1 to III-43 of columns 3 to 15 of US 4,923,790, especially II-1, 9,10,18, III-25;
Stabilizers, antifoggants: US 4,923,793 columns 6 to 16
I-1 to (14), especially I-1,60, (2), (13), compounds 1 to 65 in columns 25 to 32 of US 4,952,483, especially 36: Chemical sensitizer: triphenylphosphine selenide, especially Compound 50 of Kaihei 5-40324; Dye: JP-A-3-156450, pages 15-18, a-1 to b-20,
In particular, a-1, 12, 18, 18, 27, 35, 36, b-5, V-1 to 23 on pages 27 to 29, especially FI-1, F-II on pages 33 to 55 of V-1, EP 445627A. -43, especially
FI-11, F-II-8, III-1 to 36 on pages 17 to 28 of EP 457153A,
In particular, III-1,3, a microcrystalline dispersion of Dye-1 to 124 of 8-26 of WO 88/04794, compounds 1 to 22 of EP 319999A, pages 6 to 11, especially compound 1, a compound of formula (1) of EP 519306A Compounds D-1 to 87 represented by (3) to (3) (pages 3 to 28), compounds 1 to 22 represented by the formula (I) of US Pat. No. 4,268,622 (columns 3 to 10), US Pat.
Compounds (1) to (31) represented by the formula (I)
9); UV absorber: Compounds (18b) to (18r), 101 to 427 (pages 6 to 9) represented by formula (1) of JP-A-46-3335, represented by formula (I) of EP 520938A Compounds (3) to (66) (pages 10 to 44) and compound HBT-1 to 10 (page 14) represented by formula (III), EP 52
Compounds (1) to (31) represented by the formula (1) of 1823A (columns 2 to 9).

The support used for the photographic material for printing may be any support such as glass, paper and plastic film on which a photographic emulsion layer can be coated, and the most preferred is a reflective support. The term "reflective support" used in the present invention refers to a support which enhances reflectivity to sharpen a dye image formed in a silver halide emulsion layer. Such a reflective support includes a support. A substrate coated with a hydrophobic resin dispersedly containing a light-reflecting substance such as titanium oxide, zinc oxide, calcium carbonate, calcium sulfate, etc. Is included. For example, polyethylene coated paper,
Polyethylene terephthalate-coated paper, polypropylene-based synthetic paper, transparent support provided with a reflective layer or combined with a reflective substance, such as a glass plate, polyethylene terephthalate, polyester film such as cellulose triacetate or cellulose nitrate, polyamide film, polycarbonate Film, polystyrene film, vinyl chloride resin and the like. As the reflective support used in the present invention, a paper support coated on both sides with a water-resistant resin layer,
Preferably, at least one of the water-resistant resin layers contains white pigment fine particles.

The water-resistant resin of the reflective support is a resin having a water absorption (weight%) of 0.5, preferably 0.1 or less, for example, polyolefin such as polyethylene, polypropylene and polyethylene polymer, vinyl polymer and the like. Copolymers (polystyrene, polyacrylate and copolymers thereof), polyesters (polyethylene terephthalate, polyethylene isophthalate, etc.) and copolymers thereof. Particularly preferred are polyethylene and polyester. As the polyethylene, high-density polyethylene, low-density polyethylene, linear low-density polyethylene, and a blend of these polyethylenes can be used. The melt flow rate (hereinafter abbreviated as MFR) of these polyethylene resins before processing is preferably in the range of 1.2 g / 10 min to 12 g / 10 min as measured under the condition 4 in Table 1 of JIS K7210. The MFR of the polyolefin resin before processing refers to the MFR of the resin before kneading a bluing agent and a white pigment.
Indicates FR.

The mixing ratio of the water-resistant resin to the white pigment is 98/2 to 30/70 (water-resistant resin / white pigment) by weight, preferably 95/5 to 50/50, and particularly preferably 90/10. 60/40. 2% by weight of white pigment
If it is less than 70%, the contribution to whiteness is insufficient, and if it exceeds 70% by weight, the surface smoothness of the photographic support is insufficient, and a photographic support having excellent gloss is obtained. Can not. These water-resistant resin layers are 2 to 200
It is preferred to coat the substrate with a thickness of μm, more preferably 5 to 80 μm. If the thickness is more than 200 μm, the brittleness of the resin will be emphasized, causing problems such as cracking. If the thickness is less than 2 μm, the waterproofness, which is the original purpose of the coating, is impaired, and the whiteness and the surface smoothness cannot be satisfied at the same time. The thickness of the resin or the resin composition coated on the surface of the substrate other than the photosensitive layer application surface side is 5 to 100.
μm is preferred, and more preferably 10 to 50 μm. If the thickness exceeds this range, the brittleness of the resin is emphasized, and problems such as cracking occur in physical properties. If the ratio is less than the above range, the waterproof property which is the original purpose of the coating is impaired and the physical properties are too soft, which is not preferable.

In the reflective support, the cost and the support are such that the water-resistant resin coating layer on the photosensitive layer coating side is a reflective support comprising two or more water-resistant resin coating layers having different white pigment contents. May be more preferable from the viewpoint of the suitability for the production of the compound. In this case, among the water-resistant resin coating layers having different white pigment contents, the content of the white pigment of the water-resistant resin coating layer closest to the substrate is at least one of the water-resistant resin coating layers above the layer. It is preferably lower than the content of the white pigment. In a more preferred embodiment, among the water-resistant resin coating layers having different white pigment contents in the reflection support, the reflection support having the highest white pigment content in the water-resistant resin coating layer closest to the photosensitive layer, or The support comprises at least three water-resistant resin coating layers, and any of the intermediate layers other than the water-resistant resin coating layer closest to the photosensitive layer of the multilayer water-resistant resin coating layer and the water-resistant resin coating layer closest to the substrate And a reflective support having the highest content of a white pigment.

The content of the white pigment in each layer in the multilayer water-resistant resin layer is from 0% by weight to 70% by weight, preferably 0% by weight.
-50% by weight, more preferably 0-40% by weight. The content of the layer having the highest white pigment content in the multilayer water-resistant resin layer is 9% by weight to 70% by weight, preferably 15% by weight to 50% by weight, more preferably 20% by weight to 40% by weight. It is. When the content of the white pigment in this layer is less than 9% by weight, the sharpness of the image is low, and when it exceeds 70% by weight, cracking of the melt-extruded film occurs. The thickness of each layer of the multilayer water-resistant resin layer is 0.5 μm to 5 μm.
0 μm is preferred. For example, in the case of a multilayer water-resistant resin layer having a two-layer structure, the thickness of each layer is preferably 0.5 μm to 50 μm, and the total thickness of the layers is in the above range (2 to 200 μm).
μm). In the case of a three-layer structure, the thickness of the uppermost layer is 0.5 μm to 10 μm, and the thickness of the intermediate layer is 5 μm.
５０50 μm, and the thickness of the lower layer (the layer closest to the substrate) is 0.5
-10 μm is preferred. The thickness of the uppermost layer and the lowermost layer is 0.5
If it is not more than μm, the effect of the highly filled white pigment in the intermediate layer is likely to cause die lip streaks. On the other hand, when the thickness of the uppermost layer, the lowermost layer, particularly the uppermost layer is 10 μm or more, the sharpness is reduced.

It is preferable that the fine white pigment particles are uniformly dispersed without forming an aggregate of particles in the reflection layer.
The size of the distribution can be determined by measuring the occupied area ratio (%) (Ri) of the fine particles projected onto a unit area. The variation coefficient of the occupied area ratio (%) can be obtained by the ratio s / R of the standard deviation s of Ri to the average value (R) of Ri. In the present invention, the coefficient of variation of the occupied area ratio (%) of the pigment fine particles is preferably 0.15 or less, more preferably 0.12 or less. Particularly preferred is 0.08 or less. A support having a diffuse reflection surface of the second kind can be used. The second type diffuse reflection is obtained by giving irregularities to a surface having a mirror surface, dividing the surface into minute mirror surfaces facing different directions, and dispersing the orientation of the divided fine surface (mirror surface). Diffuse reflection. The unevenness of the surface of the second type diffuse reflection surface has a three-dimensional average roughness of 0.1 to 2 μm, preferably 0.1 to 1.2 μm with respect to the center plane. The frequency of the unevenness on the surface is preferably 0.1 to 2000 cycles / mm, and more preferably 50 to 600 cycles / mm for unevenness having a roughness of 0.1 μm or more. For more information on such supports,
It is described in JP-A-2-239244.

A suitable support for the light-sensitive material is described, for example, in RD. 17643, page 28; 18716, page 647, right column, 648
It is described in the left column of the page and on page 879 of the same 307105.

In the photographic light-sensitive material, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is preferably 23 μm or less, more preferably 20 μm or less, and 13 to 17 μm
Is particularly preferred. Further, the film swelling speed T _1/2 is preferably 5 to 15 seconds. T _1/2 is the time required for the film thickness to reach 1/2 when the saturated film thickness is 90% of the maximum swollen film thickness reached when the color developing solution is processed at 30 ° C. for 3 minutes and 15 seconds. Is defined.
T _1/2 can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after coating. The swelling ratio is 150-350%
Is preferred. The swelling ratio can be calculated from the maximum swelling film thickness under the conditions described above by the formula: (maximum swelling film thickness-film thickness) / film thickness. The photosensitive material can be provided with a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μm to 20 μm on the side opposite to the side having the emulsion layer. The back layer preferably contains the above-described light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, and surfactant. The swelling ratio of the back layer is preferably from 150 to 500%.

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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 Preparation of Multilayer Color Photosensitive Material Each layer having the following composition was applied to prepare Sample 101 which is a multilayer color photographic 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 the silver halide indicates the coating amount in terms of silver. However, with respect to the sensitizing dye, the coating amount is shown in mol units 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 1.60 ExM-1 0.11 ExF-1 3.4 × 10 ^-3 ExF-2 (Solid Disperse Dye) 0.03 ExF-3 (Solid Disperse Dye) ) 0.04 HBS-1 0.16

Second layer (intermediate layer) ExC-2 0.055 UV-1 0.011 UV-2 0.030 UV-3 0.053 HBS-1 0.05 HBS-2 0.02 Polyethyl acrylate latex 8.1 × 10 ^-2 gelatin 1.75

Third layer (low-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion A silver 0.46 ExS-1 5.0 × 10 ^-4 ExS-2 1.8 × 10 ^-5 ExS-3 5.0 × 10 ^-4 ExC-1 0.16 ExC-3 0.045 ExC-5 0.0050 ExC-7 0.001 ExC-8 0.010 Cpd-2 0.005 HBS-1 0.090 Gelatin 0.87

Fourth layer (medium-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion Silver 0.70 ExS-1 3.0 × 10 ^-4 ExS-2 1.2 × 10 ^-5 ExS-3 4.0 × 10 ^-4 ExC-1 0.22 ExC-2 0.055 ExC-5 0.007 ExC-8 0.009 Cpd-2 0.036 HBS-1 0.11 Gelatin 0.70

Fifth layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion E 1.62 ExS-1 2.0 × 10 ^-4 ExS-2 1.0 × 10 ^-5 ExS-3 3.0 × 10 ^-4 ExC-1 0.133 ExC-3 0.040 ExC-6 0.040 ExC-8 0.014 Cpd-2 0.050 HBS-1 0.22 HBS-2 0.10 Gelatin 0.85

Sixth layer (intermediate layer) Cpd-1 0.07 HBS-1 0.04 Polyethyl acrylate latex 0.19 Gelatin 2.30

7th layer (low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion A silver 0.24 silver iodobromide emulsion B silver 0.10 silver iodobromide emulsion C silver 0.14 ExS-4 4.0 × 10 ^-5 ExS-5 1.8 × 10 ^-4 ExS-6 6.5 × 10 ^-4 ExM-1 0.005 ExM-2 0.30 ExM-3 0.09 ExY-1 0.015 HBS-1 0.26 HBS-3 0.006 Gelatin 0.80

Eighth Layer (Medium Speed Green Sensitive Emulsion Layer) Silver Iodobromide Emulsion D Silver 0.94 ExS-4 2.0 × 10 ^-5 ExS-5 1.4 × 10 ^-4 ExS-6 5.4 × 10 ^-4 ExM-2 0.16 ExM-3 0.045 ExY-1 0.008 ExY-5 0.030 HBS-1 0.14 HBS-3 8.0 × 10 ^-3 Gelatin 0.90

Ninth layer (high-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion E 1.29 ExS-4 3.7 × 10 ^-5 ExS-5 8.1 × 10 ^-5 ExS-6 3.2 × 10 ^-4 ExC-4 0.011 ExM-1 0.016 ExM-4 0.046 ExM-5 0.023 Cpd-3 0.050 HBS-1 0.20 HBS-2 0.08 Polyethyl acrylate latex 0.26 Gelatin 0.82

Tenth layer (yellow filter layer) Yellow colloidal silver silver 0.010 Cpd-1 0.10 ExF-5 (solid disperse dye) 0.06 ExF-6 (solid disperse dye) 0.06 ExF-7 (oil-soluble dye) 0.005 HBS-1 0.055 gelatin 0.70

Eleventh layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion A silver 0.25 silver iodobromide emulsion C silver 0.25 silver iodobromide emulsion D silver 0.10 ExS-7 8.0 × 10 ^-4 ExY-1 0.010 ExY-2 0.70 ExY-3 0.055 ExY-4 0.006 ExY-6 0.075 ExC-7 0.040 HBS-1 0.25 Gelatin 1.60

12th layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion F silver 1.30 ExS-7 3.0 × 10 ^-4 ExY-2 0.15 ExY-3 0.06 HBS-1 0.070 Gelatin 1.13

13th layer (first protective layer) UV-2 0.08 UV-3 0.11 UV-4 0.26 HBS-1 0.09 Gelatin 1.20

Fourteenth layer (second protective layer) Silver iodobromide emulsion Silver 0.10 H-1 0.30 B-1 (diameter 1.7 μm) 5.0 × 10 ^-2 B-2 (diameter 1.7 μm) 0.10 B-3 0.10 S-1 0.20 Gelatin 1.75

Further, W-1 to W-3, B-4 to B-3 may be added to each of the layers in order to improve the storability, processability, pressure resistance, fungicidal / antibacterial properties, antistatic properties and coatability. -6,
F-1 to F-17 and iron salts, lead salts, gold salts, platinum salts,
Contains iridium, palladium and rhodium salts.

[0117]

[Table 1]

In Table 1, (1) Emulsions A to F were prepared according to the examples in JP-A-2-91938.
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 of 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) Low molecular weight gelatin is used for the preparation of tabular grains according to the examples of JP-A-1-158426. (4) Dislocation lines described in JP-A-3-237450 are observed in the tabular grains using a high-pressure electron microscope.

Preparation of Dispersion of Organic Solid Disperse Dye ExF-2 shown below was dispersed by the following method. That is, water 2
1.7 ml and 3 ml of a 5% aqueous solution of sodium p-octylphenoxyethoxy ethanesulfonate and 0.5 g of a 5% aqueous solution of 0.5 g of p-octylphenoxypolyoxyethylene ether (polymerization degree 10) were placed in a 700 ml pot mill, and the dye ExF- 2 and 5.0 ml of zirconium oxide beads (diameter 1 mm) were added, and the contents were dispersed for 2 hours. For this dispersion, a BO type vibration boat mill manufactured by Chuo Koki was used. After dispersion, take out the contents, 12.5%
8 g of an aqueous gelatin solution was added, and the beads were removed by filtration.
A gelatin dispersion of the dye was obtained. The average particle size of the fine dye particles was 0.44 μm.

Similarly, solid dispersions of ExF-3, ExF-4 and ExF-6 were obtained. The average particle diameter of the fine dye particles is 0.24 μm, 0.45 μm, and 0.52 μm, respectively.
m. ExF-5 is published in European Patent Application (EP)
The particles were dispersed by a microprecipitation dispersion method described in Example 1 of Japanese Patent No. 0,549,489A. The average particle size was 0.06 μm.

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(Processing step) Process Processing time Processing temperature Replenishment amount * Tank capacity Color development 3 minutes 40.0 ° C 200 ml 2.0 liter Bleaching 30 seconds 45.0 ° C 130 ml 0.7 liters Fixing (1) 30 seconds 45.0 ° C 100 ml 0.7 liters Settling (2) 30 seconds 45.0 ° C 70 ml 0.7 liter Rinse (1) 15 seconds 45.0 ° C-0.4 liter Rinse (2) 15 seconds 45.0 ° C-0.4 liter Rinse (3) 15 seconds 45.0 ° C 400 ml 0.4 liter drying 20 sec 80 ° C. * the replenishing amount is 2 tank countercurrent from the photosensitive material 1 m ² per (washing (4 tank countercurrent multistage cascade from 3) to the fixing (2)) (fixing (2) to the fixing (1) Multistage cascade)

The composition of the processing liquid is shown below. (Color developing solution) Tank solution (g) Replenisher (g) Diethylenediaminetetraacetic acid 4.0 4.0 4,5-Dihydroxybenzene-1,3-disulfonic acid 0.5 0.5 Sodium sulfite 3.9 6.5 Potassium carbonate 37.5 39.0 Potassium bromide 2.7- Potassium iodide 1.3 mg-N-methylhydroxylamine hydrochloride 4.5 5.5 2-Methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate (p-5) 5.0 9.0 1.0 liter 1.0 liter pH (prepared with potassium hydroxide and sulfuric acid) 10.05 10.25

(Bleaching solution) Tank solution (mol) Replenisher (mol) 1,3-diaminopropanetetraacetic acid ferric chloride ammonium monohydrate 0.33 0.50 ferric nitrate nonahydrate 0.30 4.5 ammonium bromide 0.80 1.20 Ammonium nitrate 0.20 0.30 Acetic acid 0.67 1.0 Add water 1.0 liter 1.0 liter pH (prepared with aqueous ammonia) 4.5 4.0

(Fixing solution) Common to tank solution and replenisher (g) Ammonium sulfite 28 Aqueous solution of ammonium thiosulfate (700 g / L) 280 mL Imidazole 15 Ethylenediaminetetraacetic acid 15 Water and 1.0 L pH [prepared with aqueous ammonia and acetic acid] 5.8

(Washing water) Common to tank liquid and replenisher tap water is H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH-type anion exchange resin (Amberlite IR-400). The mixture was passed through a mixed-bed column packed with to treat the calcium and magnesium ion concentrations at 3 mg / l or less, and then 20 mg / l of sodium diisocyanurate and 0.15 g / l of sodium sulfate were added. The pH of this solution was in the range of 6.5 to 7.5.

(Stabilizing solution) Common to tank solution and replenishing solution 1,2-benzisothiazolin-3-one 0.1 polyoxyethylene-p-monononyl 0.2 phenyl ether (average degree of polymerization: 10) , Adjusted with hydrochloric acid) 8.50

Sample 101 was subjected to imagewise exposure, and was subjected to continuous processing until the replenishment amount of the bleach-fixing solution in the above-mentioned processing step became three times the tank dose. The running treatment liquid thus obtained is referred to as treatment 201. Next, the same color developer except that the color developing agent P-5 sulfate in the color developing solution was changed to an equimolar amount of the comparative color developing agent shown in Table 2 and the color developing agent of the present invention. Is prepared and the same continuous processing is performed to obtain each running processing solution (processing 202).
213). The promptness of the treatment was evaluated as follows. First, after subjecting the sample 101 to wedge exposure, the color developing process is changed from 1 minute to 3 minutes in increments of 10 seconds, and the process is performed using each running processing solution (processing 202 to 213) [running process step (a). )], And the optical densities of the yellow, magenta, and cyan images of the obtained samples were measured. Next, after subjecting the sample 101 to the same wedge exposure, the sample 101 was subjected to a processing in a comparative development processing step (b) described below, and the optical densities of the yellow, magenta, and cyan images were measured in the same manner. The density curve of the magenta image obtained in the comparative development processing step (b) was compared with each of the above-described processing at intervals of 10 seconds, and the color development time required to obtain a magenta density equal to or higher than that was obtained. Next, using the sample at the time when the magenta density gave the same density, the degree of reduction in the density of the yellow and cyan images was evaluated. 1. Magenta density
The yellow and cyan densities of each sample at an exposure amount giving 0 are obtained, and compared with the yellow and cyan densities obtained in the comparative development processing step (b), the density values (a negative value indicates a decrease in density,
The positive value indicates an increase in the concentration). The fog density of yellow was measured using this sample, and the difference from the fog density of yellow obtained in the comparative development processing step (b) is shown in Table 2. Color developing agent for comparison

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Comparative development processing step (b) (Processing method) Process Processing time Processing temperature Color development 3 minutes 15 seconds 38 ° C. Bleaching 1 minute 00 seconds 38 ° C. Bleaching and fixing 3 minutes 15 seconds 38 ° C. Water washing (1) 40 seconds 35 ° C water washing (2) 1 minute 00 seconds 35 ° C Stabilized 40 seconds 38 ° C Drying 1 minute 15 seconds 55 ° C

Next, the composition of the processing solution will be described. (Color developing solution) (Unit g) Diethylenetriaminepentaacetic acid 1.0 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 Sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide 1.4 Potassium iodide 1. 5 mg hydroxylamine sulfate 2.4 4- [N-ethyl-N- (β-hydroxyethyl) amino] -2-methylaniline sulfate [P-5] 4.5 Add water and add 1.0 liter pH ( Adjusted with potassium hydroxide and sulfuric acid) 10.05

(Bleaching solution) (Unit g) Ammonium ferric ethylenediaminetetraacetate dihydrate 120.0 Ethylenediaminetetraacetic acid disodium salt 10.0 Ammonium bromide 100.0 Ammonium nitrate 10.0 Bleaching accelerator 0.005 mol _{(CH 3) 2 N-CH} 2 -CH 2 -SS-CH 2 -CH 2 -N (CH 3) 2 · 2HCl aqueous ammonia (27%) of 15.0 ml water was added to 1.0 l pH (ammonia (Adjust with water and nitric acid) 6.3

(Bleach-fixing solution) (unit: g) Ferric ammonium ethylenediaminetetraacetate dihydrate 50.0 Disodium ethylenediaminetetraacetate 5.0 Sodium sulfite 12.0 Aqueous ammonium thiosulfate solution (700 g / liter) 240.0 Milliliter ammonia water (27%) 6.0 milliliters add water 1.0 liter pH (adjusted with ammonia water and acetic acid) 7.2

(Rinse water) Tap water was washed with an H-type strongly acidic cation exchange resin (Amberlite IR- manufactured by Rohm and Haas Company).
120B) and water through a mixed-bed column filled with an OH-type anion exchange resin (Amberlite IR-400) to treat the calcium and magnesium ion concentrations to 3 mg / l or less, followed by isocyanuric dichloride 20 mg / liter of sodium and 0.15 g / liter of sodium sulfate were added. The pH of this solution was in the range of 6.5 to 7.5.

(Stabilizing solution) (Unit g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.2 Disodium ethylenediaminetetraacetate 0.05 1, 2,4-triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 1.0 liter with water added pH 8.5

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[Table 2]

From Table 2, it can be seen that the color developing agent of the present invention having an alkoxy group or the comparative compounds 1 to 5 has a magenta developing time which is much shorter than that of P-5 having a methyl group (processing No. 201). It can be seen that the density of the image can be obtained. It can be seen that Comparative Compounds 1 to 5 have excellent quickness, but hardly produce yellow density and cyan density, and have high yellow fog density. Comparative compound 3 has two hydroxy groups but is hydrophobic as a compound because the total number of carbon atoms of R ₁ , R ₂ and R ₃ is 13 and is large. As a result, it can be understood that the yellow density and the cyan density are hardly produced, and the fog density of yellow is also increased. With the color developing agent of the present invention, the color developability of yellow density and cyan density was greatly improved, and the fog density of yellow was able to be suppressed. In the developing agent of the general formula (DB), R ₁ has at least one hydroxy group, and the total of the hydroxy groups substituted on R ₁ , R ₂ and R ₃ is 2 to 4, and R ₁ and R The total number of carbon atoms in R ₂ , R ₃ is 5 to 11, but R ₁ , R ₂ , R ₃
It is understood that the range of the total number of carbon atoms is particularly preferably 7 to 9. [Process numbers 207 to 213] As in the color developing agent of the present invention, it is extremely important to have two or more hydroxy groups and to suppress the total number of carbon atoms of R ₁ , R ₂ and R ₃ . By using the developing agent of the present invention, the processing speed was improved, the yellow and cyan densities were secured, and at the same time, the yellow fog density could be suppressed low. Such properties cannot be inferred from the color developing agents listed in Comparative Examples.

Example 2 After the sample 101 in Example 1 was exposed, development processing was performed by the following processing method using the exemplified compound (DB-2) of the present invention as a color developing agent in a color developing solution. However, the desired gradation can be obtained while the color development time is as short as 60 seconds, and the fog density is low. Further, instead of the exemplary compound (DB-2), the exemplary compound (D
B-6), exemplified compound (DB-7), exemplified compound (DB
-12), exemplified compound (DB-13), exemplified compound (D
B-15), Exemplified Compound (DB-16), Exemplified Compound (DB-17), Exemplified Compound (DB-18), and Exemplified Compound (DB-20) could be used to obtain similar results. .

Development Process and Composition of Processing Solution Processing Time Temperature Color development 45 ° C. 60 seconds Bleaching and fixing 45 ° C. 60 seconds Washing with water (1) Washing with 40 ° C. 15 seconds (2) Washing with 40 ° C. 15 seconds Stable 40 ° C 15 seconds Drying 80 ° C 30 seconds (Water washing was performed in a three-tank countercurrent method from (3) to (1).)

Liquid composition (color developing solution) Tank solution (g) Diethylenetriaminepentaacetic acid 4.0 1-hydroxyethylidene-1,1 diphosphonic acid 3.0 Sodium sulfite 4.0 Potassium carbonate 50.0 Potassium bromide 4.0 Potassium iodide 1.3 mg Hydroxylamine sulfate 4.0 Color developing agent (DB-2) 20.0 1.0 liter by adding water pH (prepared with potassium hydroxide and sulfuric acid) 10.05 (Bleach-fixing solution) (Unit mol) Chelating agent represented by formula A 0.17 Ferric nitrate 9 Hydrate 0.15 Ammonium thiosulfate 1.25 Ammonium sulfite 0.10 Metacarboxybenzenesulfinic acid 0.05 Add water 1.0 liter pH (prepared with acetic acid and ammonia) 5.8 (Washing water) Tap water is replaced with H-type strongly acidic cation exchange resin (Rohm and Haas Co.) Amberlite IR-120B)
And OH type anion exchange resin (Amberlite IR-
400) to treat the calcium and magnesium ion concentrations to 3 mg / L or less, followed by 20 mg of sodium diisocyanurate dichloride.
/ L and 0.15 g / l of sodium sulfate were added. The pH of this solution was in the range of 6.5 to 7.5. (Stable liquid) Tank liquid (g) 1,2-Benzoisothiazolin-3-one 0.1 Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.2 Add water and add 1.0 liter pH [Ammonia water, hydrochloric acid Adjustment) 8.50

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By using the color developing agent of the present invention, it is possible to obtain an image which is suitable for rapid processing, has a sufficient image density for all of yellow, magenta and cyan and has a low fog density.

──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Masato Taniguchi 210 Nakanakanuma, Minamiashigara-shi, Kanagawa Fujisha Shin Film Co., Ltd. (56) References JP-A-5-197109 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) G03C 7/413

Claims (3)

(57) [Claims] 1. A color developing agent represented by the following general formula (DB). General formula (DB) In the formula, R ₁ represents an alkyl group having at least one hydroxy group, R ₂ and R ₃ represent an alkyl group which may have a substituent, and R ₄ represents a substituent. Where R
The sum of the hydroxyl groups substituted on ₁ , R ₂ and R ₃ is 2
And the total number of carbon atoms of R ₁ , R ₂ and R ₃ is 5 to 1
It is one. n represents an integer of 0 to 3. 2. A color photographic processing composition comprising at least one color developing agent according to claim 1. 3. A silver halide color photographic light-sensitive material which has been subjected to image exposure, wherein at least one of the color developing agents according to claim 1 is used.
A color image forming method, comprising developing with a processing solution containing a seed.