JP2598990B2 - Cyan dye-forming coupler and silver halide photographic material containing the same - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a novel cyan dye-forming coupler used for a silver halide color photographic material and the like, and a silver halide photographic light-sensitive material containing the coupler. .

(Prior art) A silver halide photosensitive material is exposed to light and then subjected to a color development process so that a developing agent such as an aromatic primary amine oxidized by the silver halide reacts with a dye-forming coupler to develop a color. An image is formed. Generally, in this method, a color reproduction method using a subtractive color method is often used, and in order to reproduce blue, green, and red, yellow, magenta, and cyan color images having complementary colors are formed.

(Problems to be Solved by the Invention) As cyan image forming couplers, phenols or naphthols are often used. However,
There have been some problems in the storability of color images obtained from phenols and naphthols conventionally used. For example, U.S. Pat.Nos. 2,367,531, 2,369,929
No. 2,423,730 and 2,801,171 color images obtained from 2-acylaminophenol cyan couplers described in the specification, etc., generally have poor heat fastness, U.S. Pat.
Color images obtained from 2,5-diacylaminophenol cyan couplers described in 772,162 and 2,895,826,
In general, light fastness is poor, and 1-hydroxy-2-naphthamide cyan couplers are generally light and heat (particularly wet heat).
Both aspects of robustness are inadequate.

To improve the disadvantages of such cyan dye-forming couplers, for example, U.S. Patent Nos. 4,327,173 and 4,564,586
5-hydroxy-6-acylaminocarbostyril cyan coupler described in U.S. Pat.
3-Dihydro-1,3-benzimidazol-2-one couplers and the like have been developed. These couplers are excellent in light fastness and heat fastness. These couplers are specific couplers having a heteroatom in a coloring nucleus, but any ring having a dissociating group for coloring is equivalent to phenol.

On the other hand, couplers in which a heteroatom is introduced into a ring having a dissociating group are disclosed only in 3-hydroxypyridine and 2,6-dihydroxypyridine in U.S. Pat. No. 2,293,004. However, the absorption wavelength of the absorption obtained from the 3-hydroxypyridine described in this U.S. Patent is on the very short wavelength side, and the absorption peak is broad. Furthermore, the 3-hydroxypyridine is also water-soluble. Therefore, 3-hydroxypyridine cannot be used as a so-called cyan coupler.

Accordingly, an object of the present invention is to provide U.S. Pat.
5-hydroxy-6-acylaminocarbostyril cyan coupler described in U.S. Pat.
No. 0,423, 4-hydroxy-5-acylaminooxyindole coupler, 4-hydroxy-5-acylamino-2,3-dihydro-1,3-benzimidazole-2
-It has the same excellent light fastness and heat fastness as on couplers and the like, and also has excellent absorption characteristics of the coloring dye, that is, the absorption waveform is sharp, and the color reproducibility can be improved, that is, the color is reproduced. Above, visible absorption in the unnecessary short wavelength region is small, and the color reproduction region can be widened. An object of the present invention is to provide a novel cyan coupler in which a hetero atom is introduced into a ring having a dissociating group.

[Means for solving the problem]

The present invention provides a cyan dye-forming coupler represented by the following general formula [I].

(Wherein, R ₁ represents an aliphatic group, an aromatic group or a heterocyclic group; R ₂ represents an aliphatic group, an aromatic group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkenyloxy group, an amino group, Selected from the group consisting of acyl groups, ester groups, amide groups, sulfamide groups, imide groups, ureido groups, aliphatic or aromatic sulfonyl groups, aliphatic or aromatic thio groups, hydroxy groups, cyano groups, carboxy groups, and halogen atoms. Represents a group or an atom that can be substituted on the pyridine ring to be substituted (provided that, when R ₂ is a hydrogen group, it is at the meta position with respect to the N atom of the heterocyclic ring); Represents a leaving group; Y represents a divalent linking group containing at least one amide bond and / or ester bond; Z represents a hydroxyl group or an arylsulfonamide group;
Represents 0, 1 or 2; when n is 2, two R ₂ may be the same group or atom or different groups or atoms, and two R ₂ form a ring When n is 1 or more, R ₁ and R ₂ may form a ring; R ₁ , R ₂ and X
Is at least one of R ₁ , R ₂ or X in the general formula [I]
May be contained as one or more substituents. ).

Further, the present invention provides at least one compound represented by the above formula [I].
A silver halide photographic light-sensitive material containing two cyan dye-forming couplers.

Hereinafter, the cyan coupler represented by formula (I) will be described in detail.

In the general formula [I], R ₁ preferably has 1 to 1 carbon atoms.
36 aliphatic groups, preferably an aromatic group having 6 to 36 carbon atoms (eg, phenyl, naphthyl), a heterocyclic group (eg, 3-
Pyridyl, 2-furyl, morpholino).

In this specification, the term "aliphatic group" refers to a linear, branched or cyclic aliphatic hydrocarbon group, and includes saturated and unsaturated groups such as alkyl, alkenyl, and alkynyl groups. . Representative examples include methyl, ethyl, butyl, dodecyl, octadecyl, eicosenyl, iso-propyl, tert-butyl, tert-octyl, t
ert-dodecyl, cyclohexyl, cyclopentyl, allyl, vinyl, 2-hexadecenyl, propargyl.

The term "aromatic group" refers to a monocyclic or polycyclic fused aromatic hydrocarbon group, and the term "heterocyclic group" refers to not only carbon atoms but also heteroatoms such as O, S, N, and P. A cyclic group containing at least one ring in the ring, a 3 to 8 membered ring, preferably 5 or 6
In addition to one having a single member ring, a heterocyclic ring may be condensed, or a heterocyclic ring may be condensed with a benzene ring. It also includes a cyclic group having no aromaticity.

The aliphatic group, aromatic group and heterocyclic group represented by R ₁ further include an alkyl group, an aryl group, a heterocyclic group, an alkoxy group (for example, methoxy, 2-methoxyethoxy), and an aryloxy group (for example, 2,4- Di-tert-amylphenoxy, 2
-Chlorophenoxy, 4-cyanophenoxy), alkenyloxy group (eg, 2-propenyloxy), amino group (eg, butylamino, dimethylamino, anilino,
N-methylanilino), an acyl group (eg, acetyl, benzoyl), an ester group (eg, butoxycarbonyl,
Phenoxycarbonyl, acetoxy, benzoyloxy, butoxysulfonyl, toluenesulfonyloxy), amide group (eg, acetylamino, ethylcarbamoyl, dimethylcarbamoyl, methanesulfonamide, butylsulfamoyl), sulfamide group (eg, dipropylsulfamoylamino), Imide groups (eg, succinimide, hydantoinyl), ureido groups (eg, phenylureido, dimethylureide), aliphatic or aromatic sulfonyl groups (eg, methanesulfonyl, phenylsulfonyl), aliphatic or aromatic thio groups (eg, ethylthio, phenylthio) ), A hydroxy group, a cyano group, a carboxy group, a nitro group, a sulfo group, a halogen atom and the like.

Next, in the general formula [I], R ₂ represents a group that can be substituted on the pyridine ring, and preferred specific examples thereof include an aliphatic group (eg, methyl, ethyl, butyl, dodecyl, etc.) and an aromatic group ( For example, phenyl, naphthyl), a heterocyclic group (eg, 3-pyridyl, 2-furyl), an alkoxy group (eg, methoxy, 2-methoxyethoxy), an aryloxy group (eg, 2,4-di-tert-amylphenoxy, -Chlorophenoxy, 4-cyanophenoxy),
An alkenyloxy group (eg, 2-propenyloxy),
Amino group (eg, butylamino, dimethylamino, anilino, N-methylanilino), acyl group (eg, acetyl, benzoyl), ester group (eg, butoxycarbonyl, phenoxycarbonyl, acetoxy, benzoyloxy, butoxysulfonyl, toluenesulfonyloxy), amide Groups (eg, acetylamino, ethylcarbamoyl, dimethylcarbamoyl, methanesulfonamide, butylsulfamoyl), sulfamide groups (eg, dipropylsulfamoylamino), imide groups (eg, succinimide, hydantoinyl groups), ureido groups, aliphatic or Examples thereof include an aromatic sulfonyl group, an aliphatic or aromatic thio group, a hydroxy group, a cyano group, a carboxy group, and a halogen atom.

Specific examples of the groups listed above are the same as specific examples illustrated in R _1. R ₂ can also be present on a nitrogen atom in the pyridine ring, in which case, examples of R ₂ include an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, a sulfonyl group, an aliphatic group, Examples include an aromatic oxy group or an amino group. At this time, when the ortho or para position of the nitrogen atom in the pyridine ring is a hydroxyl group, those in which the hydroxyl group is expressed as a tautomer as a cyclic ketone are also included in the present invention.

Further, when X in the general formula [I] represents a coupling-off group (hereinafter, referred to as a leaving group), examples thereof include an activated carbon that is coupled via oxygen, nitrogen, sulfur, or a carbon atom; Group, a group bonding to an aromatic group, an aromatic or heterocyclic sulfonyl group, a group bonding to an aliphatic, aromatic or heterocyclic carbonyl group, a halogen atom, an aromatic group An aliphatic group, an aromatic group or a heterocyclic group contained in these leaving groups may be substituted with a substituent allowed by R ₁ , and when these substituents are two or more, may going be the same, may have a substituent which these substituents are further allowed to R _1.

Specific examples of the coupling-off group include a halogen atom (eg, fluorine, chlorine, bromine), an alkoxy group (eg, ethoxy, dodecyloxy, methoxyethylcarbamoylmethoxy, carboxypropyloxy, methylsulfonylethoxy), an aryloxy group (eg, 4-chlorophenoxy, 4-methoxyphenoxy, 4-carboxyphenoxy), acyloxy groups (eg, acetoxy,
Tetradecanoyloxy, benzoyloxy), aliphatic or aromatic sulfonyloxy group (eg, methanesulfonyloxy, toluenesulfonyloxy), acylamino group (eg, dichloroacetylamino, heptafluorobutyrylamino), aliphatic or aromatic sulfone Amido group (for example, methanesulfonamino, p-toluenesulfonylamino), alkoxycarbonyloxy group (for example, ethoxycarbonyloxy, benzyloxycarbonyloxy), aryloxycarbonyloxy group (for example, phenoxycarbonyloxy), aliphatic / aromatic or heterocyclic Ring thio group (eg, ethylthio, phenylthio, tetrazolylthio), carbamoylamino group (eg, N-methylcarbamoylamino, N-phenylcarbamoylamino), 5 Alternatively, a 6-membered nitrogen-containing heterocyclic group (eg, imidazolyl, pyrazolyl, triazolyl, tetrazolyl, 1,2-dihydro-2-oxo-1-pyridyl), an imide group (eg, succinimide, hydantoinyl), an aromatic azo group (eg, phenylazo ), And these groups may be further substituted with a group permitted as a substituent of R ₁ . As the leaving group bonded via a carbon atom, there is a bis-type coupler obtained by condensing a 4-equivalent coupler with an aldehyde or a ketone. The leaving group of the present invention may contain a photographically useful group such as a development inhibitor and a development accelerator.

In the general formula [I], Y is a divalent linking group containing at least an amide bond or an ester bond, and specifically, And the like. Here, R ₃ and R ₄ represent a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group.

It is preferred that there is no substituent on the nitrogen atom in the pyridine ring in the general formula [I]. In the general formula [I], preferred Y is And more preferably -NHCO- (attached to the pyridine ring via a nitrogen atom).

In formula (I), preferred X is a hydrogen atom, a halogen atom, an aliphatic or aromatic oxy group, an aliphatic or aromatic thio group, an aliphatic or aromatic oxycarbonyloxy group, an aliphatic or aromatic acyloxy group,
It is an aliphatic or aromatic sulfonyloxy group.

In formula (I), when R ₁ and R ₂ and R ₂ form a ring together, the number of ring members is preferably a 5- to 7-membered ring, more preferably a 5- or 6-membered ring. N or O
It may be a ring containing atoms and may or may not have aromaticity.

Z represents a dissociating group having an acid dissociation constant PKa of 5 to 12,
It represents a sulfonamide group which may be substituted with a hydroxyl group, an aliphatic, aromatic or heterocyclic group, and an active methine group having at least one, preferably two electron-absorbing groups (eg, an acyl group and a cyano group).

Z is preferably a hydroxyl group or an aromatic sulfonamide group, and particularly preferably a hydroxyl group.

—Y—R ₁ is the 2-position or 5
It is preferably in the -position. The coupler of the present invention in which —Y—R ₁ is present at the 2-position is particularly preferable because the azomethine dye derived from the coupler has a sharp absorption and a high molecular extinction coefficient.

The coupler represented by the general formula [I] has a so-called ballast group having 8 or more carbon atoms in at least one of R ₁ , R ₂ , X and Z for the purpose of stably introducing it into a color photographic light-sensitive material. preferable.

The coupler of the present invention represented by the general formula [I] includes R ₁ ,
At least one of R ₂ and X is R ₁ ,
A pyridyl group from which R ₂ or X has been eliminated may also contain one or more substituents. That is, the coupler of the present invention is:
At least one of R ₁ , R ₂ and X is And oligomers and polymers containing a pyridyl group represented by Here, among the couplers of the present invention, those having one pyridyl group from which R ₁ , R ₂ or X has been removed in the general formula [I] are called dimers and those containing two pyridyl groups are called trimers. Examples of the polymer include vinyl polymers containing at least one of the above three types of pyridyl groups in R ₁ , R ₂ or X. The number average degree of polymerization of the polymer is, for example, about 10 to 1,000. There can be.

Hereinafter, specific examples of the cyan coupler of the present invention are shown, but the present invention is not limited thereto.

Hereinafter, the synthesis method of the present invention will be described.

The coupler of the present invention can be synthesized, for example, by the route shown in the following scheme.

Y ′ represents an amino group or a carboxyl group, R ₂ ,
n has the same meaning as described above, and X 'represents a hydrogen atom or a halogen atom. When Y 'is an amino group, it is reacted with an acid chloride. When Y' is a carboxyl group, a bond is formed with an amine by a known dehydration condensation method to introduce a diffusion-resistant group (Ballast). . If necessary, the leaving group (X) may be introduced before or preferably after the introduction of the diffusion-resistant group.

The starting material, 3-hydroxypyridine derivative, was obtained from Beilsteins Handbuch der Organischen Chem.
ie) or by the method described in the literature cited therein.

Next, a specific method for synthesizing the coupler of the present invention will be described.

Synthesis Example 1 (exemplary coupler (1)) 11.0 g of 2-amino-3-hydroxypyridine was dissolved in 100 ml of acetonitrile and 20 ml of dimethylacetamide.
With heating under reflux, 38.9 g of 2- (2 ', 4'-di-tert-amylphenoxy) -lacnic acid chloride was added dropwise. After the addition, the mixture was refluxed for another 2 hours and cooled. The reaction mixture was dissolved in ethyl acetate (250 ml), water (250 ml) was added, and the mixture was neutralized and separated. After further washing the ethyl acetate layer with water, the solvent was distilled off under reduced pressure. The residue was dissolved by adding 200 ml of acetonitrile, and then cooled to crystallize. The crystals were collected by filtration to obtain 35.1 g of coupler (1). Melting point: 80-83 ° C Elemental analysis: C 72.59%, H 8.69%, N 6.72% Calculated: C 72.78%, H 8.80%, N 6.79% Synthesis example 2 (exemplified coupler (2)) exemplified coupler (1) 2- (2 ', 4'-di-te used in
(rt-amylphenoxy) -lactide chloride is replaced by an equimolar amount of 2- (2 ', 4'-di-tert-amylphenoxy)
2-Hexanoic acid chloride was used in a similar manner to 2-
{2 '-(2 ", 4" -di-tert-amylphenoxy)-
Hexanoic acid amide-3-hydroxypyridine was obtained.

25 g of 2- {2 ′-(2 ″, 4 ″ -di-tert-amylphenoxy) -hexanoic acid amide} -3-hydroxypyridine obtained above was dissolved in 200 ml of methylene chloride, and 8.4 g of sulfuryl chloride was added at room temperature. The mixture was added dropwise with stirring. Twenty minutes after the addition, the reaction solution was poured into water, extracted with methylene chloride, and concentrated. The residue was purified by silica gel column chromatography to give 18 g of the coupler (2) as an oil.

Synthesis Example 3 (Exemplified Coupler (3)) Synthesis of 3- [2 ′-(2 ″, 5 ″ -di-tert-amylphenoxy) -butanoic acid amide] -5-methoxypyridine 3-amino-5-methoxypyridine , 10 g dissolved in dimethylacetamide 30 ml, triethylamine 13.5 ml,
27.3 g of 2- (2,5-di-tert-amylphenoxy) -butanoic acid chloride was added dropwise while stirring in an aqueous solution. After reacting for 20 minutes, the reaction solution was poured into water and extracted with ethyl acetate. After drying over anhydrous sodium sulfate, concentration and purification by silica gel column chromatography gave 15 g of 3-
[2 '-(2 ", 5" -di-tert-amylphenoxy)-
Butanoic acid amide] -5-methoxypyridine was obtained as an oil.

Synthesis of Exemplary Coupler (3) 9 g of 3- [2 '-(2 ", 5" -di-tert-amylphenoxy) -butanoic acid amide] -5-methoxypyridine obtained above and 3 g of ethyl mercaptan were added to DMF. While melting and cooling with ice melting, 2.1 g of 60% sodium hydride was gradually added. After the addition, the mixture was stirred at 80 ° C. for 2 hours, the reaction solution was poured into water, acidified with acetic acid, and extracted with ethyl acetate. The organic layer was dried over anhydrous sodium sulfate, concentrated, and the residue was purified by silica gel column chromatography to obtain 4.2 g of the title compound (coupler (3)) (white powder).

Synthesis Example 4 (Exemplified Coupler (5)) 65.5-amino-3-picoline 25.5 g was mixed with acetonitrile 100
Then, 30.5 g of pivalic acid chloride was added dropwise at room temperature, and after completion of the addition, the mixture was heated under reflux for 30 minutes and then cooled. 100m
The mixture was poured into 1 l of water, adjusted to pH 8 with sodium carbonate, and extracted with chloroform. The solvent was distilled off under reduced pressure to obtain 44.7 g of crystalline 6-pivaloylamino-3-picoline. This was suspended in 500 ml of chloroform, and 44 g of m-chloroperbenzoic acid was added little by little. After the addition, the mixture was stirred for 2 hours and left overnight. After concentration under reduced pressure, the residue was dissolved in ethyl acetate and washed with an aqueous sodium carbonate solution. The solvent was distilled off under reduced pressure to obtain 44.5 g of solid 6-pivaloylamino-3-picoline oxide. This was dissolved in 200 ml of chloroform, and 54 ml of acetic anhydride was added. Under ice cooling, 43 g of bromine was diluted with 100 ml of chloroform and added dropwise. After dropping, at room temperature 3
0 minutes later, 23 g of sodium acetate was added, and the mixture was heated under reflux for 3 hours.
After adding a small amount of water and neutralizing with sodium carbonate, the chloroform layer was separated and concentrated under reduced pressure. The residue was separated by silica gel column chromatography (solvent: 5% methanol, chloroform) to obtain 28 g of 5-bromo-6-pivaloylamino-3-picoline oxide. This was dissolved in 80 ml of methanol, 0.15 mol of sodium methoxide was added, and the mixture was heated under reflux for 40 hours. After cooling, neutralize with oxalic acid,
After concentration, the residue was dissolved in chloroform to remove insolubles. The solvent was distilled off under reduced pressure to obtain 26 g of 5-methoxy-6-pivaloylamino-3-picoline oxide. This was added to 200 ml of methanol and 50 ml of 6N hydrochloric acid, and heated under reflux for 52 hours. After neutralizing the hydrochloric acid, it was extracted with chloroform. After evaporating the solvent under reduced pressure, 200 ml of acetonitrile was added, and 33.8 g of 2- (2 ', 4'-di-tert-amylphenoxy) -lacnic acid chloride was added dropwise under reflux with heating. The crystals precipitated by cooling were collected by filtration, and 35.4 g of 5-methoxy-6-
{2- (2 ', 4'-Di-tert-amylphenoxy) butyroylamino} -3-picoline oxide was obtained. Dissolve this in 500 ml of chloroform and add phosphorus trichloride at room temperature.
5 g was added and the mixture was heated under reflux for 1 hour. After cooling, the mixture was poured into 500 g of ice, adjusted to pH 10 with aqueous ammonia, and extracted with ethyl acetate. The solvent was distilled off under reduced pressure to give oily 5-methoxy-6-
31.8 g of {2- (2 ', 4'-tert-amylphenoxy) butyroylamino} -3-picoline was obtained. This was dissolved in 200 ml of chloroform, and 22.5 g of boron tribromide was added dropwise under ice-cooling, and the temperature was gradually raised to room temperature, and stirring was continued at room temperature for 2 hours. The reaction mixture was poured into ice water, neutralized with sodium carbonate and extracted with chloroform. The residue obtained by evaporating the solvent under reduced pressure was fractionated by silica gel column chromatography (solvent,
Chloroform). Recrystallization from ethyl acetate-acetonitrile gave 22.6 g of coupler (5). Melting point 91-95
° C Elemental analysis: C 73.13%, H 8.79%, N 6.62% Calculated: C 73.20%, H 8.98%, N 6.57% Synthesis example 5 (exemplary coupler (6)) Synthesis of example coupler (5) (synthesis) 2- used in Example 4)
Instead of (2 ', 4'-di-tert-amylphenoxy) lactic acid chloride, its molar equivalent of 2- (2', 4'-di-te
rt-Amylphenoxy) hexanoic acid chloride, and otherwise in the same manner, 19.6 g of 5-hydroxy-6- {2-
(2 ', 4'-tert-Amylphenoxy) hexanoylamino} -3-picoline was obtained. This was dissolved in 80 ml of methylene chloride, 12.4 g of sulfuryl chloride was added dropwise at room temperature, and the mixture was stirred for 1 hour. After stirring, the reaction solution was poured into water, extracted with methylene chloride, concentrated, and the residue was purified by silica gel column chromatography to obtain 14.1 g of coupler (6).

Synthesis Example 6 (Exemplified Coupler (7)) 2- used in synthesis of Exemplary Coupler (6) (Synthesis Example 5)
Instead of (2 ', 4'-di-tert-amylphenoxy) hexanoic acid chloride, the same mole of 2- (3-n-pentadecylphenoxy) lactic acid chloride was used, and the other procedure was to synthesize coupler (6). The coupler (7) was obtained in the same manner.

Synthesis Example 7 (Example Coupler (8)) 6- used in synthesis of Example Coupler (5) (Synthesis Example 4)
Instead of amino-3-picoline, the same molar amount of 6-amino-3-ethylpyridine was used, and 2- (2 ', 4'-
Instead of di-tert-amylphenoxy) lactic acid chloride, the same molar amount of 2- (2 ', 4'-di-tert-amylphenoxy) hexanoic acid chloride was used, and the others were used for the synthesis of coupler (5). A coupler (8) was obtained in the same manner.

Synthesis Example 8 (Exemplified Coupler (9)) 2- used in synthesis of Exemplary Coupler (8) (Synthesis Example 7)
(2 ', 4'-Di-tert-amylphenoxy) hexanoic acid chloride is converted to the same molar amount of 2- (2', 4'-di-tert-yl).
-Octylphenoxy) octoic acid chloride was replaced with 5-ethyl-3- by a method similar to that of coupler (8).
Hydroxy-2- {2- (2 ', 4'-di-tert-octylphenoxy) octanoylamino} pyridine was obtained.
This was chlorinated with sulfuryl chloride in methylene chloride to obtain coupler (9).

Synthesis Example 9 (exemplary coupler (16)) 12.0 g of the exemplary coupler (3) obtained in Synthesis Example 3 was mixed with 40 ml of acetic acid.
And 15 ml of acetic anhydride, and 2.3 ml of concentrated nitric acid was added dropwise under cooling with water. Stirred at room temperature for a further 6 hours. The mixture was poured into ice water, neutralized with sodium carbonate, and extracted with ethyl acetate. The residue obtained by evaporating the solvent under reduced pressure was dissolved in 100 ml of ethanol, 50 ml of water was added, and 10 g of sodium hydrosulfite was added little by little under reflux with heating. The reaction mixture was refluxed until the yellow color almost disappeared, and then cooled. After adding water to the reaction mixture, the precipitated crystals were collected by filtration. The crystals were dissolved in 30 ml of dimethylacetamide and 100 ml of acetonitrile, and 5.3 g of o-chlorobenzoyl chloride was added dropwise at 60 ° C. After refluxing for 6 hours, the mixture was cooled and neutralized with an aqueous sodium hydroxide solution. The precipitated crystals were collected by filtration and recrystallized from acetonitrile to give 9.8 g of coupler (16).
I got Melting point 125-128 ° C Elemental analysis: C 67.71%, H 7.03%, N 7.60% Calculated: C 67.89%, H 7.12%, N 7.42% Synthesis example 10 (exemplified coupler (17)) 5-hydroxy-1 , 2,3,4-Tetrahydro-1,7-naphthyridin-2-one (16.4 g) was dispersed in 50 ml of acetic acid and 20 ml of acetic anhydride, and 7.9 ml of concentrated nitric acid was added dropwise under cooling with water, followed by stirring at room temperature for 3 hours. The reaction mixture was poured into ice water, neutralized with sodium carbonate, and extracted with ethyl acetate. The residue obtained by evaporating the solvent under reduced pressure was dissolved in 300 ml of ethanol, 150 ml of an aqueous solution of 40 g of sodium hydrosulfite was gradually added thereto, and the mixture was heated under reflux for 30 minutes. Return to room temperature, 450m water
In addition to l, the precipitated crystals were collected by filtration. The crystals were dissolved in 50 ml of dimethylacetamide and 150 ml of acetonitrile,
Under reflux with heating, 31.1 g of 2- (2,4-di-tert-amylphenoxy) butyric acid chloride was added dropwise. Reflux for an additional 3 hours. After returning to room temperature, 300 ml of ethyl acetate and 300 ml of water were added and neutralized, followed by separation, and the ethyl acetate layer was further washed with water,
It was dried with sodium sulfate. The residue obtained by evaporating the solvent under reduced pressure was purified by silica gel column chromatography (chloroform / ethyl acetate = 5/1), and then crystallized from a mixed solvent of hexane-ethyl acetate to give the desired coupler ( 1
7) 26.4 g was obtained.

Synthesis Example 11 (exemplary coupler (19)) Instead of 2- (2 ', 4'-di-tert-amylphenoxy) -butanoic acid chloride used in Synthesis Example 3, the same mole of 2- (2', 4- (2 '-(2 ", 4" -di-tert-amylphenoxy)) is obtained in the same manner as in the synthesis of coupler (3) except that 4'-di-tert-amylphenoxy) hexanoic acid chloride is used. ) Hexanoylamino} -5-hydroxypyridine was obtained. 12.0 g of this was dissolved in 40 ml of acetic acid and 15 ml of acetic anhydride, and 2.2 ml of concentrated nitric acid was added dropwise under cooling with water.
After stirring at room temperature for 6 hours, the mixture was poured into ice water, neutralized with sodium carbonate, and extracted with ethyl acetate. The residue obtained by evaporating the solvent under reduced pressure was dissolved in 100 ml of ethanol, and 50 ml of water was added.
Under reflux with heating, 10 g of sodium hydrosulfite was added little by little. The reaction mixture was refluxed until almost no yellowish color disappeared, then cooled, and the precipitated crystals were collected by filtration. 9.8 g of these crystals were dispersed in 80 ml of toluene, 3.2 g of p-cyanophenyl isocyanate was added, and the mixture was stirred at 80 ° C. for 3 hours. The reaction mixture was poured into water, extracted with ethyl acetate, the solvent was distilled off under reduced pressure, and the obtained residue was purified by silica gel column chromatography to give 8.3 g of coupler (19).
I got

Synthesis Example 12 (Exemplified Coupler (20)) Instead of 2- (2 ', 4'-di-tert-amylphenoxy) -butanoic acid chloride used in Synthesis Example 3, the same mole of 2- (2'- Chloro-4'-tert-amylphenoxy) hexanoic acid chloride was used, except that 3- {2 '-(2 "-chloro-
4 ″ -tert-amylphenoxy) hexinoylamino｝-
5-Hydroxypyridine was obtained. 12 g of this acetic acid 40 m
l and 15 ml of acetic anhydride, and 2.2 ml of concentrated nitric acid was added dropwise under cooling with water. After stirring at room temperature for 6 hours, the mixture was poured into ice water, neutralized with sodium carbonate, and extracted with ethyl acetate. The residue obtained by distilling off the solvent under reduced pressure was dissolved in 100 ml of ethanol, and 50 ml of water was added.
Was added in small portions. The reaction mixture was refluxed until almost no yellowish color disappeared, then cooled, and the precipitated crystals were collected by filtration. 8 g of this crystal was dissolved in 30 ml of acetonitrile, 1.7 ml of pyridine was added, and 4.6 g of p-bromobenzenesulfonyl chloride was dissolved in 10 ml of acetonitrile and added dropwise under reflux with heating. After the dropwise addition, the mixture was refluxed for 3 hours, cooled, poured into water and extracted with ethyl acetate. After evaporating the solvent, the residue was purified by silica gel column chromatography, and 6.
1 g of coupler (20) was obtained.

Synthesis Example 13 (Exemplified Coupler (26)) Instead of 2- (2 ′, 4′-di-tert-amylphenoxy) butanoic acid chloride used in Synthesis Example 3, the same mole of phenyl chloroformate was used. Others are the same as in the synthesis of coupler (3) (Synthesis Example 3) in the same manner as in 3-hydroxy-5-
Phenoxycarbonylaminopyridine was obtained. This one
20 g was dissolved in 80 ml of acetic acid and 20 ml of acetic anhydride, and 5.5 ml of concentrated nitric acid was added dropwise under ice cooling. After stirring at room temperature for 4 hours, the mixture was poured into ice water, neutralized with sodium carbonate, and extracted with ethyl acetate. The residue obtained by evaporating the solvent under reduced pressure was dissolved in 100 ml of ethanol, 100 ml of water was added, and 20 g of sodium hydrosulfite was added little by little under reflux with heating. The reaction mixture was refluxed until the yellow color almost disappeared, and then cooled,
100 ml of water was added, and the precipitated crystals were collected by filtration. 18g of this crystal
Was dissolved in 80 ml of acetonitrile-40 ml of dimethylacetamide, 33.6 g of 3- (1'-dodecylsulfonyl-2'-butanoylamino) benzoyl chloride was added, and the mixture was stirred at 50 ° C. for 1 hour. After completion of the reaction, the mixture was poured into water, 9 g of sodium acetate was added, and the mixture was extracted with ethyl acetate. The solvent was distilled off, the residue was dissolved in methylene chloride (200 ml), 11 g of sulfuryl chloride was added dropwise at room temperature, and the mixture was stirred for 3 hours. The reaction solution was poured into water, extracted with methylene chloride, the solvent was distilled off, and the residue obtained was purified by column chromatography.
-Chloro-6- (1'-dodecylsulfonyl-2'-butanoylamino) -5-hydroxy-3-phenoxycarbonylaminopyridine was obtained. 12 g of this product was dissolved in 50 ml of chloroform, and 1.1 ml of concentrated nitric acid was added dropwise at room temperature.
Stir at room temperature for 3 hours. The reaction mixture was poured into water, extracted with chloroform, and the solvent was distilled off. The residue obtained here was dissolved in 200 ml of ethanol, 1 g of Raney nickel and 1.1 g of acetaldehyde were added, and the mixture was subjected to catalytic hydrogenation in an autoclave. After the solvent was removed by filtration, it was poured into water, and the precipitated crystals were collected by filtration. The crude crystals were recrystallized from acetonitrile to obtain 6 g of coupler (26).

Synthesis Example 14 (Example Coupler (41)) Example Coupler (41) was synthesized according to the following scheme.

2-amino-5-nitropyridine (154.1 g, 1.1 mol)
(62.6cc, 1.2mol) in THF (300ml) solution at room temperature
Was added dropwise and stirred for 1 hour. Water the reaction mixture (3 l)
, And the precipitated crystals were filtered and acetonitrile (500m
Recrystallization from l) gave 2-amino-3-bromo-5-nitropyridine (A) (194.4 g, 80%).

Under a nitrogen stream, 2-amino-3-bromo-5-nitropyridine (A) (21.8 g, 0.1 mol) in acetonitrile (300 m
l) To the solution was added pyridine (20 cc) at room temperature, followed by dropwise addition of benzoyl chloride (24.4 g, 0.2 mol),
I stirred for 3 hours.

Dilute hydrochloric acid (0.1N) was added, extracted twice with ethyl acetate, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the residue was recrystallized from methanol to obtain 3-bromo-2-dibenzoylamino-5-nitropyridine (B) (28.7 g, 89%).

Reduced iron (42.6 g, 0.76 mol), water (42.6 ml), ammonium chloride (4.3 g, 81 mmol) in isopropyl alcohol (300
ml) The solution was heated to reflux for 10 minutes. To this mixed solution, 3-bromo-2-dibenzoylamino-5-nitropyridine (B) (42.6 g, 100 mmol) was added, and the mixture was heated under reflux for 30 minutes.
The reaction solution was filtered through celite, and the filtrate was distilled off under reduced pressure. After benzene azeotropic distillation twice, acetonitrile (30
0 ml) pyridine (10 cc), 2- (2 ', 4'-di-t-amylphenoxy) butanoyl chloride (33.8 g, 100 mol
l) and stirred for 1 hour. Dilute hydrochloric acid (0.1N) was added, extracted twice with ethyl acetate, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and recrystallized from acetonitrile to give 4- (2- {2 ', 4'-di-t-amylphenoxy} butanoylamino) -2-dibenzoylamino-3.
-Bromopyridine (C) was obtained.

To a solution of the obtained compound (C) in acetonitrile (300 ml) was added 28% aqueous ammonia (20 cc) at room temperature, and the mixture was stirred for 15 minutes. Water was added, and the mixture was extracted twice with ethyl acetate.
The extract was washed with dilute hydrochloric acid (0.1N) and saturated saline and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the residue was recrystallized from acetonitrile. g, yield from compound (B): 34%).

Under a nitrogen stream, a 28% methanol solution of sodium methoxide (7.1 ml, 36.9 mmol) was added to a methanol solution of compound (D) (19.9 g, 33.5 mmol), and anhydrous cuprous chloride (332 mg, 3.4 mmol)
l) Add 8-hydroxyquinoline (486 mg, 3.4 mmol),
The mixture was heated under reflux for 3 hours.

Dilute hydrochloric acid was added, and the mixture was extracted twice with ethyl acetate. The organic layer was washed with saturated saline and dried over anhydrous sodium sulfate.

The solvent was distilled off under reduced pressure and recrystallized from acetonitrile to give 5- (2- {2 ', 4'-di-t-amylphenoxy} butanoylamino) -2-benzoylamino-3-methoxypyridine (E). (10.4 g, 57%).

Lithium iodide (4.0 g, 29.6 mmol) was added to a solution of (E) (3.9 g, 7.2 mmol) in 2,4,6-collidine (30 ml) under a nitrogen stream.
And heated to reflux for 3 hours. After cooling, dilute hydrochloric acid (0.1
N) and extracted twice with ethyl acetate. The organic layer was washed with saturated saline and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure and recrystallized from acetonitrile to obtain Exemplified Coupler (41) (2.9 g, 76%).

Many couplers of the present invention are oil-soluble and are generally preferably dissolved in a high-boiling solvent (using a low-boiling solvent if necessary), emulsified and dispersed in an aqueous gelatin solution, and added to a silver halide emulsion. . In the case of being soluble in an aqueous alkali solution, it can be dissolved in an aqueous alkali solution together with a developing agent and other additives, and can be used for image formation as so-called external development.

On the other hand, oxidative coupling with an oxidizing agent (for example, a persulfate, silver nitrate, nitrous acid or a salt thereof) using a developing agent and an alkali (adding an organic solvent as necessary) or a compound of the general formula [I Wherein X is a hydrogen atom is p
-Dyes can be synthesized by condensation using nitrosoanilines and alkali or acetic anhydride, and these can be used as cyan dyes for various applications (for example, filters, paints,
Inks, images and dyes for information recording or printing)
Can be used.

When added to a silver halide emulsion, if necessary, a hydroquinone derivative, an ultraviolet absorber, or a known anti-fading agent may be used in combination to achieve adjustment and improvement of colorability or storage stability.

The high boiling point solvent has a melting point of 100 ° C. or lower (preferably 80 ° C. or lower) and a boiling point of 140 ° C. or higher (preferably 160 ° C. or lower).
Any of the above can be used as long as the coupler can be dissolved at a temperature of not less than ℃, and examples thereof include phosphate esters (for example, tricresyl phosphate, trioctyl phosphate,
Tricyclohexyl phosphate), organic acid esters (eg, dibutyl phthalate, dioctyl phthalate,
Dicyclohexyl phthalate, dodecyl benzoate,
Bis (2-ethylhexyl) sebacate), ethers, (including epoxy), amides, and amines, and these may be cyclic. Furthermore, a high-boiling organic solvent used in the oil-in-water dispersion method described below can also be used.

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

In the silver halide color photographic light-sensitive material of the present invention, at least one layer of the light-sensitive material contains a cyan dye-forming coupler represented by the general formula (I).

The silver halide color photographic material of the present invention can be, for example, a multilayer multicolor photographic material having at least two different spectral sensitivities on a support. The multilayer natural color photographic material usually has at least one red-sensitive emulsion layer, one green-sensitive emulsion layer and one blue-sensitive emulsion layer on a support. In these layers, the arrangement order is arbitrarily examined as necessary. The preferred layer arrangement is from the support side in the order of red-sensitive, green-sensitive and blue-sensitive layers, blue-sensitive layer, green-sensitive layer and red-sensitive layer or in order of blue-sensitive, red-sensitive and green-sensitive layers. The emulsion layer of any color sensitivity may be composed of two or more emulsion layers (Sub emulsion Iayers) having substantially the same color sensitivity and different sensitivities to improve the reaching sensitivity. The graininess may be further improved as a configuration. Further, a non-photosensitive layer may be present between two or more emulsion layers having the same color sensitivity.
An emulsion layer having a different color sensitivity may be inserted between emulsion layers having the same color sensitivity. A reflective layer of fine silver halide or the like may be provided below the high-sensitivity layer, particularly the high-sensitivity blue-sensitive layer, to improve the sensitivity, or a yellow filter layer may be provided.

The cyan-forming coupler is generally contained in the red-sensitive emulsion layer, the magenta-forming coupler is contained in the green-sensitive emulsion layer, and the yellow-forming coupler is contained in the blue-sensitive emulsion layer. The cyan coupler represented by I) is used. However, a different combination may be adopted depending on the case. For example, a combination of infrared-sensitive layers may be used for pseudo color photography or semiconductor laser exposure. The cyan coupler of the present invention is typically added as a main coupler to the red-sensitive emulsion layer or an adjacent layer.
In addition, it can be used as a main coupler in a blue-sensitive, green-sensitive or infrared-sensitive emulsion layer or can be used in combination with a main coupler.

The standard use amount of the cyan coupler of the present invention is in the range of 0.001 to 1 mol, preferably 0.003 to 0.3 mol, per 1 mol of the light-sensitive silver halide.

The cyan coupler of the present invention can be used in combination with a magenta coupler or a yellow coupler in an emulsion layer having a different color sensitivity from the emulsion layer to which the cyan coupler is added. Further, a known cyan coupler may be used in the same layer or in another layer to the extent that the effects of the present invention are not impaired. These may be used in combination with a cyan coupler, a magenta coupler,
Examples of the yellow coupler include the couplers represented by the general formulas (I) to (V) shown on pages 4 and 5 of EP0231832 A2. As the cyan coupler and the magenta coupler on pages 12 to 24 of the specification, magenta couplers on pages 25 to 43 of the same specification and the yellow coupler on pages 44 to 64 of the same specification as the yellow coupler can be used.

The color light-sensitive material of the present invention can be applied to various fields. It is preferably used for color negative films for general use or movies, and color reversal films for slides or televisions. It can also be used for color paper, color positive film and color reversal paper. The present invention can also be applied to black-and-white photosensitive materials utilizing a mixture of three-color couplers described in Research Disclosure 17123 (July 1978).

Further, as the silver halide emulsion and the like forming the light-sensitive material of the present invention, various conventionally known silver halide emulsions can be used without any particular limitation. For example, JP-A-61-198236 (U.S. Pat.
7,436) can be used. Specifically, silver halide described in page 5, upper right column, line 10 to lower left column, line 7 of the above publication, page 5 lower left column, line 8 to page 7, lower right column 3,
The silver halide emulsion described in the row, page 7, lower right column, line 4,
Various additives such as couplers described on page 8, lower left column, line 2, and color fog inhibitors described on page 8, lower left column, line 3 to page 9, upper left column, line 11 can be used.

In particular, when the silver halide color light-sensitive material of the present invention is used as a direct positive color film or a direct positive color paper, the internal latent image type direct positive silver bromide is preferable as the silver halide. When used as silver halide, silver iodobromide (preferably with a silver iodide content of 2 to 15 mol%) is preferred as the silver halide.

When the silver halide color light-sensitive material of the present invention is used as a color paper (light-sensitive material for color printing), the silver halide emulsion is composed of silver chlorobromide or silver chloride containing substantially no silver iodide. Those can be preferably used. Here, "contains substantially no silver iodide" means that the silver iodide content is 1 mol% or less, preferably 0.2 mol% or less. The halogen composition of the emulsion may be different or the same between grains. However, when an emulsion having the same halogen composition between grains is used, it is easy to make the properties of each grain uniform. Regarding the 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) [Layer or plural layers] and a so-called laminated type particle having a different halogen composition, or a structure having a non-layered portion having a different halogen composition inside or on the surface of the particle (when the particle is on the particle surface, the edge of the particle, Particles having a structure in which portions having different compositions are joined on corners or surfaces) 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, and this is also preferable from the viewpoint of pressure resistance. In the case where the silver halide grains have the above-described structure, even if the boundary between different portions in the halogen composition is a clear boundary, it is an unclear boundary by forming a mixed crystal due to a composition difference. It is also possible to employ a structure in which a continuous structural change is positively provided.

Regarding the halogen composition of these silver chlorobromide milk materials, those having an arbitrary silver bromide / silver chloride ratio can be used. Although this ratio can take a wide range according to the purpose, a silver chloride ratio of 2% or more can be preferably used.

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

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

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

It is also effective to further increase the silver chloride content of the silver halide emulsion in order to reduce the replenishment amount of the developing solution. In such a case, the silver chloride content is 98 mol% to 9 mol%.
An almost pure silver chloride emulsion having a content of 9.9 mol% is also preferably used.

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

The particle size distribution is preferably a so-called monodisperse coefficient of variation (a standard deviation of the particle size divided by the average particle size) of 20% or less, and preferably 15% 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 photographic emulsions have a regular (regular, cubic, tetradecahedral or octahedral) shape.
r) Those having a crystal form, those having an irregular crystal form such as spheres, plates, etc., or those having a complex form thereof can be used. Also,
It may be composed of a mixture having various crystal forms. In the present invention, among these, particles containing the above-mentioned particles having a regular crystal form in an amount of 50% or more, preferably 70% or more, more preferably 90% or more are good.

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

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

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

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

In the present invention, the coupler of the general formula (I) can be introduced into the light-sensitive material by various known dispersion methods. For example, an oil-in-water dispersion method is mentioned, and examples of the high boiling point solvent used in the dispersion method are described in US Pat. No. 2,322,027.

Specific examples of high-boiling organic solvents having a boiling point at normal pressure of 175 ° C. or higher used in the oil-in-water dispersion method include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis (2,4-di-t-amylphenyl) phthalate, bis (2,4-di-t-amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate, etc., phosphoric acid or phosphonic acid ester (Trifel phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2
-Ethylhexylphenylphosphonate), benzoic esters (such as 2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate), amides (N, N-diethyldodecaneamide, N, N-diethyllauramide), N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,4-di-tert-
Fatty acid carboxylic esters (bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (N, N-dibutyl-2-) Butoxy-5-tert
-Octylaniline, etc.), hydrocarbons (paraffin,
Dodecylbenzene, diisopropylnaphthalene, etc.). The auxiliary solvent has a boiling point of about 30 ° C.
Above, preferably 50 ° C. or more and about 160 ° C. or less of an organic solvent can be used, typical examples are ethyl acetate, butyl acetate,
Examples include ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, and dimethylformamide.

When the coupler of the general formula (I) of the present invention is dispersed by an oil-in-water dispersion method, the high-boiling organic solvent used for the dispersion is at least one of the following general formulas (VI) or (VII), or a combination thereof. Solvent (for example, ethyl acetate)
Particularly preferred is the combination of The ratio of the high-boiling organic solvent to the coupler is 1.0 or less by weight, preferably 0.6 or less, more preferably 0.4 or less. That is, a method of dispersing with only the auxiliary solvent is also preferable.

General formula (VI) In the formula, R ₆₁ and R ₆₂ may be the same or different, each represents an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group, and the total number of carbon atoms of the groups represented by R ₆₁ and R ₆₂ is 4 to There are 30.

General formula (VII) In the formula, R ₇₁ , R ₇₂ , and R ₇₃ may be the same or different and each represent an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group, and R ₇₁ , R ₇₂ , and a group represented by R ₇₃ The total number of carbon atoms is 12-60.

The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in U.S. Pat. No. 4,199,363, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.

Suitable supports that can be used in the present invention include, for example, those described above.
From page 28 of RD.No.17643, and from the right column of page 647 of No.18716
It is described in the left column on page 648.

The color photographic light-sensitive material according to the present invention is described in RD.
Developing can be carried out by a usual method described in 17643, pp. 28-29, and No. 18716, 651, left column to right column.

The silver halide color photographic light-sensitive material of the present invention generally undergoes a washing and / or stabilizing step after desilvering. The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, depending on the material used, such as a coupler), the application, the rinsing water temperature,
It can be set in a wide range depending on the number of washing tanks (number of stages), a replenishment method such as countercurrent flow, forward flow, and other various conditions. Of these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent method is described in the Journal of the Society of Motion Picture and T
It can be determined by the method described in elevision Engineers, Vol. 64, pp. 248-253 (May, 1955).

According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced, but bacteria increase due to an increase in the residence time of water in the tank, and the generated suspended matter adheres to the photosensitive material. Problem arises. In the processing of the color light-sensitive material of the present invention, the method of reducing calcium ions and magnesium ions described in JP-A-62-288838 can be used very effectively as a solution to such a problem. Further, isothiazolone compounds and thiabendazoles described in JP-A-57-8542, chlorine-based disinfectants such as chlorinated sodium isocyanurate, and other benzotriazoles, etc., written by Hiroshi Horiguchi, "Bactericidal and Fungicide Chemistry" ,
Sanitizing agents described in "Sterilization, Sterilization and Antifungal Technology of Microorganisms" edited by the Society of Sanitary Engineers, and "Dictionary of Antifungal Agents" edited by the Japan Society of Antifungals and Fungi can also be used.

In the processing of the light-sensitive material of the present invention, the pH of the washing water is from 4 to
9, and preferably 5 to 8. Washing water temperature,
The washing time can also be variously set depending on the characteristics of the photosensitive material, the application, etc., but is generally 20 to 10 minutes at 15 to 45 ° C., preferably 25 to 45 ° C.
A range of 30 seconds to 5 minutes at 40 ° C is selected. Further, the light-sensitive material of the present invention can be processed directly with a stabilizing solution instead of the above-mentioned washing. In such a stabilization process,
Known methods described in JP-A-57-8,543, JP-A-58-14,834 and JP-A-60-220,345 can all be used.

Further, after the above-mentioned water washing treatment, a stabilization treatment may be further carried out. For example, a stabilizing bath containing formalin and a surfactant used as a final bath of a color light-sensitive material for photography can be mentioned. . Various chelating agents and fungicides can also be added to this stabilizing bath.

The overflow solution resulting from the washing and / or replenishment of the stabilizing solution can be reused in another step such as a desilvering step.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up the processing.
In order to incorporate the color developing agent, it is preferable to use various precursors of a color developing agent. For example, indoaniline-based compounds described in U.S. Pat. Salt complexes and urethane compounds described in JP-A-53-135,628 can be mentioned.

The silver halide color light-sensitive material of the present invention may contain various 1-phenyl-3
-Pyrazolidones may be incorporated. Typical compounds are described in JP-A-56-64339, JP-A-57-144,547 and JP-A-58-1.
No. 15,438.

The various processing solutions in the present invention are used at 10 ° C to 50 ° C. Usually, a temperature of 33 ° C to 38 ° C is standard, but a higher temperature promotes the processing and shortens the processing time, and conversely, lowers the temperature to achieve the improvement of the image quality and the stability of the processing solution. be able to. Further, in order to save silver of the light-sensitive material, a process using cobalt intensification or hydrogen peroxide intensification described in West German Patent No. 2,226,770 or US Pat. No. 3,674,499 may be performed.

The silver halide light-sensitive material of the present invention is disclosed in U.S. Pat.
No. 500,626, JP-A-60-133,449, JP-A-59-218443,
It is also applicable to the photothermographic materials described in JP-A-61-238056 and European Patent No. 210,660A2.

 Hereinafter, the present invention will be further described with reference to examples.

Example 1 2.0 g of the coupler (1) of the present invention was dissolved in 20 ml of ethyl acetate and 15 ml of ethanol, and 3 g of sodium carbonate was dissolved in 30 ml of water and added. After stirring, 2.4 g of 4- (ethyl, methanesulfonamidoethylamino) -o-toluidine monohydrate sesquisulfate was added, and 2.7 g of ammonium persulfate was dissolved in 16 ml of water and added dropwise. After stirring at room temperature for 30 minutes, 100 ml of water was added to carry out liquid separation. 3 layers of ethyl acetate
After washing with water repeatedly, the extract was dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure at room temperature. Immediately, it was dissolved in a small amount of chloroform, and a cyan fraction was taken through a silica gel column. The solvent was distilled off under reduced pressure at room temperature to obtain a dark blue powdery pigment.

For comparison, dyes were synthesized using couplers (2) and (5) and the following comparative couplers (C-1) and (C-2) in the same manner as described above.

Table 1 shows the results of measuring the solution absorption spectrum of the dye. FIG. 1 shows the spectra of the coupler (1) and the comparative coupler (C-1).

As can be seen from FIG. 1 and Table 1, the absorption of the dye obtained from the coupler of the present invention is very sharp, has a vivid hue, and has a high molar extinction coefficient (ε).

Comparative coupler (C-1) Comparative coupler (C-2) Example 2 10 g of coupler (1) of the present invention and 10 g of dibutyl phthalate
And a solution obtained by heating 20 ml of ethyl acetate to 50 ° C. is a 1% aqueous solution of sodium dodecylbenzenesulfonate.
It was emulsified and dispersed in 80 g of a gelatin solution containing 8 ml.

Next, this emulsified dispersion was mixed with a red-sensitive silver chlorobromide emulsion (Br 50
%) Of 145 g (containing 7 g of Ag), and sodium dodecylbenzenesulfonate was added as a coating aid, followed by coating on a paper support laminated on both sides with polyethylene. The coating amount of the coupler was set to 400 mg / m ² . On this layer, a protective layer of Zenitine (gelatin 1 g / m ² ) was applied.

Instead of the above coupler (1), the same moles of couplers (2), (3), (5), (16), (17) and (26)
Was used to prepare a film by the same operation. These were designated as Samples B to G in order. As comparative examples, comparative couplers (C-1), (C-2), (C-3) and (C-
Samples HL were prepared using 4) and (C-5).

Each sample was exposed using a continuous wedge for sensitometry and then subjected to the following development processing.

Color development processing step (33 ° C) 1 color development 3 minutes 30 seconds 2 bleaching fix 1 minute 30 seconds 3 water washing 2 minutes 30 seconds The processing steps used in each step are as follows.

Color developer Benzyl alcohol 15.0ml Diethylene glycol 8.0ml Ethylenediaminetetraacetic acid 5.0g Sodium sulfite 2.0g Anhydrous potassium carbonate 30g Hydroxylamine sulfate 3.0g Potassium bromide 0.6g 4-Amino-N-ethyl-N- (β-methanesulfonamide Ethyl) -m-toluidine sesquisulfate monohydrate 5.0g Add water 1 (pH 10.2) Comparative coupler Bleaching-fixing solution Ethylenediaminetetraacetic acid 4.0 g Ethylenediaminetetraacetic acid ferric 40 g salt Sodium sulfite 5.0 g, sodium thiosulfate (70%) 150 ml After water treatment, the samples coated with the coupler of the present invention were all vivid. It showed a cyan or blue hue.

Next, the robustness of the sample after the treatment was examined. That is, Table 2 shows the residual ratio of the dye concentration when left at 100 ° C. in a dark place for 10 days and when exposed to light with a xenon fade meter (100,000 lux) for one week.

Table 2 shows that the couplers of the present invention have the same robustness as the corresponding carbocyclic couplers (A, B and H, D and I, E and J, F and K, G and L).

Example 3 On a paper support laminated on both sides with polyethylene,
A multilayer silver halide photosensitive material 101 having the following layer structure was prepared.

As a gelatin hardener for each of the following layers, 1-oxy-
3,5-Dichloro-s-triazine sodium salt was used.

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

Blue-sensitive emulsion layer (Per mol of silver halide, 2.0 × 10 ^-4 mol for large-size emulsion and 2.5 × ^10-4 mol for small-size emulsion, respectively)
× 10 ^-4 mol) Green-sensitive emulsion layer (Per mole of silver halide, for large emulsions
4.0 × 10 ^-4 mol, 5.6 × 10 ^-4 mol for small size emulsion) and (Per mole of silver halide, for large emulsions
7.0 × 10 ^-5 mol, and 1.0 × 10 ^-5 for small size emulsions
Mol) Red-sensitive emulsion layer (Per mole of silver halide, for large emulsions
0.9 × 10 ^-4 mol, and 1.1 × 10 ^-4 for small size emulsions
The following compounds were added to the red-sensitive emulsion layer in an amount of 2.6 × 10 ^-3 mol per mol of silver halide.

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

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

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

Support Polyethylene laminated paper [The first layer side polyethylene contains white pigment (TiO ₂ ) and blue dye (ultra blue)] First layer (blue sensitive layer) Silver chlorobromide emulsion 0.30 Zetirane 1.86 Yellow coupler ( ExY) 0.82 Color image stabilizer (Cpd-1) 0.19 Solvent (Solv-3) 0.35 Color image stabilizer (Cpd-7) 0.06 Second layer (color mixture prevention layer) Zetirane 0.99 Color mixture inhibitor (Cpd-5) 0.08 Solvent (Solv-1) 0.16 Solvent (Solv-4) 0.08 Third layer (green sensitive layer) Silver chlorobromide emulsion (cubic, 1: 3 mixture of 0.55 μm and 0.39 μm) (Ag (Molar ratio) The coefficient of variation of the grain size distribution was 0.10 and 0.08, and each emulsion was AgBr0.
0.12 Gelatin 1.24 Magenta coupler (ExM) 0.20 Color image stabilizer (Cpd-3) 0.15 Color image stabilizer (Cpd-4) 0.02 Color image stabilizer (Cpd-2) 0.03 Solvent (Solv-2) 0.40 Fourth layer (ultraviolet absorbing layer) Gelatin 1.58 Ultraviolet absorber (UV-1) 0.47 Color mixture inhibitor (Cpd-5) 0.05 Solvent (Solv-5) 0.24 Fifth layer (red Layer) Silver chlorobromide emulsion (cubic, 1: 4 mixture of 0.58 µm average grain size and 0.45 µm grain size (Ag molar ratio), variation coefficient of grain size distribution is 0.09 and 0.11, AgBr0 for each emulsion) .
0.23 Gelatin 1.34 Cyan coupler (C-1) 0.15 Cyan coupler (C-2) 0.18 Color image stabilizer (Cpd-6) 0.17 Color image stabilizer (Cpd-8) 0.04 Color image stabilizer (Cpd-7) 0.40 Solvent (Solv-6) 0.15 Sixth layer (ultraviolet absorbing layer) Gelatin 0.53 Ultraviolet absorbing agent (UV-1) 0.16 Color mixing inhibitor (Cpd-5) 0.02 Solvent (Solv) -5) 0.08 Seventh layer (protective layer) Gelatin 1.33 Acrylic modified copolymer of polyvinyl alcohol (degree of modification
17%) 0.17 Liquid paraffin 0.03 (ExY) yellow coupler (ExM) Magenta coupler (Cpd-1) Color image stabilizer (Cpd-3) Color image stabilizer (Cpd-5) Color mixing inhibitor (Cpd-4) Color image stabilizer (Cpd-2) Color image stabilizer (Cpd-6) color image stabilizer (Cpd-7) Color image stabilizer (Cpd-8) Color image stabilizer (UV-1) UV absorber (Solv-1) solvent (Solv-2) solvent (Solv-3) solvent O = PO-C ₉ H ₉ (ios)] ₃ (Solv-4) solvent (Solv-5) solvent (Solv-6) solvent Samples 102 to 108 Coupler (C-1) of the fifth layer of Sample 101 (comparative),
(C-2) is (1), (5), (6), (9), (1)
Sample 1 except for the equivalent molar substitution of 6), (17) and (26)
A sample was prepared in the same manner as in 01. Each of these is a sample
102 to 108 (the present invention).

The above photosensitive material was exposed through an optical wedge and processed in the following steps.

Processing temperature / time Replenisher ^* Tank capacity Color development 35 ° C 45 seconds 161ml 17l Bleaching and fixing 30-35 ° C 45 seconds 215ml 17l Rinse 30-35 ° C 20 seconds −10l Rinse 30-35 ° C 20 seconds −10l Rinse 30-35 ° C 20 sec 350 ml 10l drying 70 to 80 ° C. 60 seconds * replenishment rate is composition (3 and a tank countercurrent system. to rinse →) each processing solution per photosensitive material 1 m ² is as follows.

Bleach-fix solution (same as tank solution and replenisher) Water 400 ml Ammonium thiosulfate (70%) 100 ml Sodium sulfite 17 g Ammonium iron (III) ethylenediaminetetraacetate 55 g Disodium ethylenediaminetetraacetate 5 g 40 g ammonium bromide Add 1000 ml pH ( 25 ° C) 6.0 Rinse solution (same for tank solution and replenisher) Deionized water (3ppm for calcium and magnesium respectively)
Hereinafter, Samples 102 to 108 using the coupler of the present invention were all superior in color reproducibility as compared with Comparative Sample 101.

Example 4 A paper support (thickness: 10) laminated on both sides with polyethylene
A color photographic light-sensitive material was prepared by coating the following first to fourteenth layers on the front side (0 micron) and the fifteenth to sixteenth layers on the back side. Titanium oxide (4 g / m ² ) is used as a white pigment in the polyethylene on the first layer,
m including ² of ultramarine as a bluing dye (chromaticity of the surface of the support is L ^*, a ^*, b ^* system in 88.0, -0.20, was -0.75.).

(Composition of photosensitive layer) The components and the coating amount (g / m ² , unit) are shown below. For silver halide, the coating amount is shown in terms of silver. The emulsion used for each layer was prepared according to the method for preparing emulsion EM1. However, as the emulsion of the fourteenth layer, a Lippmann emulsion which did not undergo surface chemical sensitization was used.

1st layer (antihalation layer) Black colloidal silver 0.10 gelatin ... 0.70 2nd layer (intermediate layer) gelatin ... 0.70 3rd layer (low-sensitivity red-sensitive layer) Red sensitizing dye (ExS-1,2, Silver bromide spectrally sensitized in 3) (average grain size 0.25μ, size distribution [coefficient of variation] 8)
%, Octahedral) ... 0.04 Silver chlorobromide (5 mol% silver chloride, average grain size 0.40μ, size distribution) spectrally sensitized with red sensitizing dye (ExS-1, 2, 3)
0.08 Gelatin 1.00 Cyan coupler (ExC-1,2,3 1: 1: 0.2) ... 0.30 Anti-fading agent (Cpd-1,2,3,4 equivalent) ... 0.18 Stain inhibitor (Cpd-5) ...... 0.003 Coupler dispersion medium (Cpd-6) ... 0.03 Coupler solvent (Solv-1,2,3 equivalent) ... 0.12 4th layer (highly sensitive red sensitive layer) Red increase Silver bromide (average grain size 0.60μ, size distribution 15%, octahedron) spectrally sensitized with dyes (ExS-1, 2, 3)…
… 0.14 Gelatin… 1.00 Cyan coupler (ExC-1,2,3 1: 10: 0.2)… 0.30 Anti-fading agent (Cpd-1,2,3,4 equivalent)… 0.18 Coupler dispersion medium (Cpd) −6)… 0.03 Coupler solvent (Solv-1,2,3 equivalents)… 0.12 5th layer (intermediate layer) Gelatin… 1.00 Chromatic mixture inhibitor (Cpd-7)… 0.08 Color mixture inhibitor solvent (Colv 0.16 polymer latex (Cpd-8) 0.10 6th layer (low-sensitivity green-sensitive layer) Silver bromide spectrally sensitized with green sensitizing dye (ExS-4) (average) (Particle size 0.25μ, size distribution 8%, octahedron) ......
04 Silver chlorobromide spectrally sensitized with green sensitizing dye (ExS-4) (silver chloride 5 mol%, average grain size 0.40μ, size distribution)
0.06 Gelatin ... 0.80 Magenta coupler (ExM-1,2,3 equivalent) ... 0.11 Anti-fading agent (Equivalent to Cpd-9,26) ... 0.15 Stain inhibitor (Cpd) −10,11,12,13 in 10: 7: 7: 1 ratio)…
... 0.025 Coupler dispersion medium (Cpd-6) ... 0.05 Coupler solvent (Solv-4,6 equivalent) ... 0.15 7th layer (highly sensitive green-sensitive layer) Spectral sensitization with green sensitizing dye (ExS-4) Silver bromide (average grain size 0.65μ, size distribution 16%, octahedron) …… 0.
10 Gelatin ... 0.80 Magenta coupler (ExM-1,2,3 equivalent) ... 0.11 Anti-fading agent (Equivalent to Cpd-9,26) ... 0.15 Stain inhibitor (Cpd-10,11,12,13) In a 10: 7: 7: 1 ratio)…
... 0.025 Coupler dispersion medium (Cpd-6) ... 0.05 Coupler solvent (Solv-4,6 equivalent) ... 0.15 8th layer (intermediate layer) Same as 5th layer 9th layer (yellow filter layer) Yellow colloidal silver (Particle size 100 mm) ... 0.12 Gelatin ... 0.70 Color-mixing inhibitor (Cpd-7) ... 0.03 Color-mixing inhibitor solvent (Colv-4,5 equivalent) ... 0.10 Polymer latex (Cpd-8) ... 0.07 10th layer (intermediate layer) Same as 5th layer 11th layer (low-sensitivity blue-sensitive layer) Silver bromide spectrally sensitized with blue sensitizing dye (ExS-5,6) (average grain size 0.40μ, size distribution 8%, octahedron) ... 0.
07 Silver chlorobromide (silver chloride 8mol%, average grain size 0.60μ, size distribution) spectrally sensitized with blue sensitizing dye (ExS-5,6)
11%, octahedral) 0.14 Gelatin 0.80 Yellow coupler (ExY-1,2 equivalent) 0.35 Anti-fading agent (Cpd-14) 0.10 Stain inhibitor (Cpd-5,15: 0.005 Coupler dispersion medium (Cpd-6) ... 0.05 Coupler solvent (Solv-2) ... 0.10 12th layer (high-sensitivity blue-sensitive layer) Blue sensitizing dye (ExS-5,6) Spectrally sensitized silver bromide (average grain size 0.85μ, size distribution 18%, octahedron) ... 0.
15 Gelatin… 0.60 Yellow coupler (ExY-1,2 equivalent)… 0.30 Anti-fading agent (Cpd-14)… 0.10 Stain inhibitor (Cpd-5,15 in 1: 5 ratio)… 0.007 Coupler Dispersion medium (Cpd-6) ... 0.05 Coupler solvent (Solv-2) ... 0.10 13th layer (ultraviolet absorbing layer) Gelatin ... 1.00 Ultraviolet absorber (Cpd-2, 4, 16 equivalents) ... 0.50 Inhibitor (Cpd-7, 17 equivalents) ... 0.03 Dispersion medium (Cpd-6) ... 0.02 Ultraviolet absorber solvent (Solv-2, 7 equivalents) ... 0.08 Irradiation prevention dye (Cpd-18, 19) , 20,21,27 to 10:
10: 13: 15: 20 ratio) ...... 0.05 14th layer (protective layer) Fine grain silver chlorobromide (silver chloride: 97 mol%, average size: 0.1μ)
…… 0.03 Acrylic modified copolymer of polyvinyl alcohol (molecular weight
50,000) …… 0.01 Polymethyl methacrylate particles (average particle size 2.4μ)
(And silicon oxide (average particle size 5μ) equivalent) 0.05 gelatin 1.80 gelatin hardener (H-1, H-2 equivalent) 0.18 15th layer (back layer) gelatin ... 2.50 UV absorption Agent (Solv-2,4,16 equivalent) ...... 0.50 Dye (Equivalent of Cpd-18,19,20,21,27) ... 0.06 16th layer (backside protective layer) Polymethyl methacrylate particles (average particle Size 2.4
μ) and hydrogen silicon oxide (average particle size 5μ) equivalents ... 0.
05 Gelatin …… 2.00 Gelatin hardener (H-1, H-2 equivalent) …… 0.14 How to make emulsion EM-1 15 minutes at 75 ° C while vigorously stirring an aqueous solution of potassium bromide and silver nitrate into an aqueous gelatin solution And octahedral silver bromide particles having an average particle size of 0.35 μm. At this time silver 1
0.3 g of 3,4-dimethyl-1,3-thiazoline-2 per mole
-Thion was added. To this emulsion, 6 mg of sodium thiosulfate and 7 mg of chloroauric acid (tetrahydrate) per mol of silver were sequentially added, and heated at 75 ° C. for 80 minutes to perform chemical sensitization. Using the particles thus obtained as a core, the particles were further grown in the same precipitation environment as in the first time, and finally had an average particle diameter of 0.7 μm.
Octahedral monodispersed core / shell silver bromide emulsion was obtained. The coefficient of variation of the particle size was about 10%. To this emulsion, 1.5 mg of sodium thiosulfate and 1.5 mg of chloroauric acid (tetrahydrate) per mole of silver were added, and heated at 60 ° C. for 60 minutes to perform chemical sensitization to obtain an internal latent image type silver halide emulsion. Obtained.

In each photosensitive layer, ExZK-1 and ExZK-2 were used as nucleating agents at 10 ^-3 and 10 ^-2 % by weight, respectively, of silver halide, and Cpd-22 was used as a nucleating accelerator at 10 ^-2 % by weight. . Further, alkanol XC (Dupon) and sodium alkylbenzene sulfonate were used as emulsifying and dispersing aids for each layer, and succinic acid ester and Magefac F-120 (manufactured by Dainippon Ink and Chemicals) were used as coating aids. (Cpd-23, 24, 25) was used as a stabilizer in the layer containing silver halide and colloidal silver. This sample was designated as a sample number. The compounds used in the examples are shown below.

Solv-1 Di (2-ethylhexyl) sebacate Solv-2 Trinonyl phosphate Solv-3 Di (3-methylhexyl) phthalate Solv-4 Tricresyl phosphate Solv-5 Dibutyl phthalate Solv-6 Trioctyl phosphate Solv-7 Di ( 2-ethylhexyl) phthalate H-1 1,2-bis (vinylsulfonylacetamide) ethane H-2 4,6-dichloro-2-hydroxy-1,3,5-triazine Na salt ExZK-17- (3-ethoxy) Thiocarbonylaminobenzamide) -9-methyl-10-prohagyl-1,2,3,4
-Tetrahydroacridinium trifluoromethanesulfonate ExZK-2 2- [4- {3- [3- {3- [5-} 3-
[2-Chloro-5- (1-dodecyloxycarbonylethoxycarbonyl) phenylcarbamoyl] -4-hydroxy-1-naphthylthio {tetrazol-1-yl]
Phenyl {ureido] benzenesulfonamido {phenyl] -1-formylhydrazine The sample prepared as described above was designated 201.

Next, the cyan coupler EXC- used for the third and fourth layers was used.
A sample prepared by equimolarly replacing all the amounts of 1, 2, and 3 with the cyan coupler (1) of the present invention was designated as 202.

Samples 203 to 207 were prepared in the same manner as in Sample 202 except that cyan couplers (5), (6), (9), (16) and (17) were used instead of cyan coupler (1). .

The samples 201 to 207 thus obtained were exposed through a red filter and then subjected to the following development processing.

When the spectral absorption of the obtained developed sample was measured, Samples 202 to 207 using the cyan coupler of the present invention were:
The sample 201 using the cyan coupler other than the present invention exhibited extremely sharp spectral absorption characteristics.

The replenishment method of the washing water is as follows: replenish the washing bath (3), replenish the washing bath (3), guide the overflow of the washing bath (3) to the washing bath (2), and overflow the washing bath (2). Was introduced into a washing bath (1), so-called countercurrent replenishment method. At this time, the amount of the bleach-fix solution brought into the washing bath (1) from the bleach-fix bath by the photosensitive material was 35 ml / m ² , and the ratio of the replenishment amount of the washing water to the carry amount of the bleach-fix solution was 9.1 times.

The composition of each processing solution was as follows.

Rinse water Both mother liquor and replenisher mixed with tap water filled with H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH-type anion exchange resin (Amberlite IR-400) Water was passed through the column to adjust the concentration of calcium and magnesium ions to 3 mg / l or less, and then 20 mg / l of sodium diisocyanurate and 1.5 g / l of sodium sulfate were added. The pH of this solution was in the range of 6.5 to 7.5.

Example 5 On a cellulose triacetate film support having an undercoat, each layer having the following composition was applied in multiple layers to prepare a sample 301 as a multilayer color photosensitive material.

(Composition of photosensitive layer) The number corresponding to each component indicates the coating amount expressed in g / m ² , and for silver halide, the coating amount is expressed in terms of silver. However, as for the sensitizing dye, the coating amount is shown in mol unit with respect to 1 mol of silver halide in the same layer.

(Sample 101) First layer (antihalation layer) Black colloidal silver Silver 0.18 Gelatin 1.40 Second layer (Intermediate layer) 2,5-Di-t-pentadecylhydroquinone 0.18 EX-1 0.07 EX-3 0.02 EX-12 0.002 U-1 0.06 U-2 0.08 U-3 0.10 HBS-1 0.10 HBS-2 0.02 Gelatin 1.04 Third layer (first red-sensitive emulsion layer) Emulsion A silver 0.25 Emulsion B silver 0.25 Sensitizing dye I 6.9 × 10 ^-5 Sensitizing dye II 1.8 × 10 ^-5 Sensitizing dye III 3.1 × 10 ^-4 EX-2 0.335 EX-10 0.020 HBS-1 0.060 Gelatin 0.87 Fourth layer (second red-sensitive emulsion layer) Emulsion G Silver 1.0 Sensitizing dye I 5.1 × 10 ^-5 sensitizing dye II 1.4 × 10 ^-5 sensitizing dye III 2.3 × 10 ^-4 EX-2 0.400 EX-3 0.050 EX-10 0.015 HBS-1 0.060 Gelatin 1.30 Fifth layer (third red Emulsion layer) Emulsion D silver 1.60 Sensitizing dye I 5.4 × 10 ^-5 Sensitizing dye II 1.4 × 10 ^-5 Sensitizing dye III 2.4 × 10 ^-4 EX-3 0.010 EX-4 0.080 EX-2 0.097 HBS-1 0.22 HBS-2 0.10 Gelatin 1.63 Layer 6 (Medium Interlayer) EX-5 0.040 HBS-1 0.020 Gelatin 0.80 7th layer (first green-sensitive emulsion layer) Emulsion A silver 0.15 Emulsion B silver 0.15 Sensitizing dye V 3.0 × 10 ^-5 Sensitizing dye VI 1.0 × 10 ^-4 Sensitizing dye VII 3.8 × 10 ^-4 EX-6 0.260 EX-1 0.021 EX-7 0.030 EX-8 0.025 HBS-1 0.100 HBS-3 0.010 Gelatin 0.63 Eighth layer (second green-sensitive emulsion layer) Emulsion C silver 0.45 Sensitizing dye V 2.1 × 10 ^-5 Sensitizing dye VI 7.0 × 10 ^-5 Sensitizing dye VII 2.6 × 10 ^-4 EX-6 0.094 EX-8 0.018 EX-7 0.0026 HBS-1 0.160 HBS-3 0.008 Gelatin 0.50 9 layers (third green-sensitive emulsion layer) Emulsion E silver 1.2 sensitizing dye V 3.5 × 10 ^-5 sensitizing dye VI 8.0 × 10 ^-5 sensitizing dye VII 3.0 × 10 ^-4 EX-13 0.015 EX-11 0.100 EX -1 0.025 HBS-1 0.25 HBS-2 0.10 gelatin 1.54 10th layer (yellow filter layer) yellow colloidal silver silver 0.05 EX-5 0.08 HBS-1 0.03 gelatin 0.95 11th layer (first blue-sensitive emulsion layer) Emulsion A silver 0.08 Emulsion B silver 0.07 Emulsion F silver 0.07 sensitization Containing ^{VIII 3.5 × 10 -4 EX-9} 0.721 EX-8 0.042 HBS-1 0.28 Gelatin 1.10 12th layer (2nd blue-sensitive emulsion layer) Emulsion G silver 0.45 Sensitizing dye ^{VIII 2.1 × 10 -4 EX-9} 0.154 EX -10 0.007 HBS-1 0.05 Gelatin 0.78 Layer 13 (third blue-sensitive emulsion layer) Emulsion H Silver 0.77 Sensitizing dye VIII 2.2 × 10 ^-4 EX-9 0.20 HBS-1 0.07 Gelatin 0.69 Layer 14 (First protection) Layer) Emulsion I Silver 0.5 U-4 0.11 U-5 0.17 HBS-1 0.05 Gelatin 1.00 Fifteenth layer (Second protective layer) Polymethyl acrylate particles (about 1.5 μm in diameter) 0.54 S-1 0.20 Gelatin 1.20 In addition to the above components, a gelatin hardener H-1 and a surfactant were added.

HBS-1 Tricresyl phosphate HBS-2 Di-n-butyl phthalate The sample manufactured as described above was designated as 301.

Next, the total amount of the cyan couplers EX-2 and EX-4 used in the third, fourth, and fifth layers was changed to the cyan coupler (1) of the present invention.
The sample prepared by replacing each layer with equimolar
And

Samples 303 to 307 were prepared in the same manner as Sample 302 except that cyan couplers (5), (6), (9), (16), and (17) were used instead of cyan coupler (1). did.

The obtained samples 301 to 307 were exposed through a red filter, and then subjected to the following development processing.

When the spectral absorption of the obtained developed sample was measured, Samples 302 to 307 using the cyan coupler of the present invention were:
The sample 301 using the cyan coupler other than the present invention showed extremely sharp spectral absorption characteristics.

Example 6 Preparation of Sample 401 A multilayer color photosensitive material comprising the following layers was prepared on an undercoated cellulose triacetate film support having a thickness of 127 μm to prepare Sample 401.

First layer: antihalation layer Black colloidal 0.25 g / m ² UV absorber U-1 0.04g / m ² UV absorber ^U-2 0.1 g / m 2 UV absorber U-3 0.1 g / m ² High-boiling organic Gelatin layer containing 0.1 cc / m ² of solvent O-1 (dry thickness 2 μm) Second layer: Intermediate layer A-14 2.5 mg / m ² Compound H-1 0.05 g / m ² Emulsion A Silver amount 0.05 g / m ² High boiling organic solvent O-2 Gelatin layer containing 0.05 cc / m ² (dry film thickness 1 μm) Third layer: First red-sensitive emulsion layer Sensitizing dyes S-1 (0.47 mg / m ² ) and S-2 (0.02mg / m ²⁾
Amount of silver monodisperse silver iodobromide emulsion spectrally sensitized with 0.15 g /
m ² (Iodine content: 4 mol%, average particle size: 0.20 μ, variation coefficient relating to particle size (hereinafter simply referred to as variation coefficient): 12%) Sensitizing dyes S-1 (0.51 mg / m ² ) and S-2 ( 0.03mg / m ²⁾
Amount of monodispersed internal latent image type silver iodobromide emulsion spectrally sensitized with: 0.20 g / m ² (iodine content 4 mol%, average grain size 0.40 μ, distance from latent image to grain surface 100 mm, Coefficient of variation 14%) Emulsion B Silver amount: 0.05 g / m ² A-1 0.60 mg / m ² Compound H-6 0.01 g / m ² Coupler-C-1 0.13 g / m ² Coupler-C-2 0.033 g / m ² coupler-C-10 0.1 g / m ² High boiling organic solvent O-2 Gelatin layer containing 0.02 cc / m ² (dry film thickness 0.7 μm) 4th layer: 2nd red-sensitive emulsion layer Sensitizing dye S -1 (1.1mg / m ²⁾ and ^{S-2 (0.04mg / m 2} )
Amount of silver monodisperse silver iodobromide emulsion spectrally sensitized with 0.53 g /
m ² (iodine content 3 mol%, average particle size 0.55 μ, coefficient of variation 16%) A-4 0.02 mg / m ² coupler C-1 0.40 g / m ² coupler C-2 0.07 g / m ² coupler C-9 Gelatin layer containing 0.05 g / m ² high boiling organic solvent O-2 0.22 cc / m ² (1.7 μm dry film thickness) Fifth layer: Third red-sensitive emulsion layer Sensitizing dye S-1 (1.1 mg / m ²⁾ ) And S-2 (0.04 mg / m ² )
Amount of silver monodisperse silver iodobromide emulsion spectrally sensitized with 0.53 g /
m ² (Iodine content 2 mol%, average particle size 0.07 μ, coefficient of variation 17%) A-7 1.2 mg / m ² Coupler C-6 0.35 g / m ² Coupler C-8 0.20 g / m ² High boiling organic solvent Gelatin layer containing O-2 0.06 cc / m ² (dry film thickness 1.8 μm) 6th layer: Intermediate layer A-10 10 mg / m ² A-11 5 mg / m ² Compound H-1 0.1 g / m ² Gelatin layer containing 0.1 cc / m ² of a high boiling point organic solvent O-2 (1 μm dry film thickness) 7th layer: 1st green-sensitive emulsion layer Sensitizing dyes S-3 (2.2 mg / m ² ) and S-4 ( Monodispersed silver iodobromide emulsion spectrally sensitized at 1.0 mg / m ² ) Amount of silver: 0.5 g / m ² (Iodine content: 3 mol%, average grain size: 0.35 μ, Coefficient of variation: 19%) Emulsion B: Silver content ^{...... 0.05 g / m 2 A-} 5 0.12 mg / m 2 compound H-6 0.01 g / m ² compound H-5 0.005 g / m ² coupler C-3 0.27 g / m ² high-boiling organic solvent O-2 0.05 Gelatin layer containing cc / m ² (dry film thickness 0.7 μm) Eighth layer: Second green-sensitive emulsion layer Sensitizing dye S-3 (0.29 g / Amount of monodisperse internal latent image type silver iodobromide emulsion spectrally sensitized with m ² ) and S-4 (0.3 mg / m ² ): 0.5 g / m ² (iodine content 2.5 mol%, average Particle size 0.5μ, Coefficient of variation 18%, distance from latent image to particle surface 100 表面) A-6 0.2 mg / m ² Compound H-6 0.01 g / m ² Coupler C-3 0.2 g / m ² High boiling organic solvent O-2 Gelatin layer containing 0.13 cc / m ² (dry film thickness 1.7 μm) Ninth layer: Third green-sensitive emulsion layer Sensitizing dyes S-3 (0.9 g / m ² ) and S-4 (0.3 mg / m ² ) Amount of tabular silver iodobromide emulsion spectrally sensitized with m ² ): 0.5 g / m ² (Iodine content: 2 mol%, diameter / thickness ratio of 7 or more, Occupies 50% of the average particle thickness
0.10μ) A-2 1.5 mg / m ² Coupler C-4 0.2 g / m ² High boiling organic solvent O-2 Gelatin layer containing 0.03 cc / m ² (dry film thickness 1.7μ) 10th layer: Intermediate layer Compound H-4 0.1 g / m ² High boiling organic solvent O-2 Gelatin layer containing 0.1 cc / m ² (dry film thickness 0.05 μm) 11th layer: yellow filter layer Yellow colloidal silver Silver amount: 0.12 g / m ² Compound A-15 0.22 g / m ² Compound H-1 0.02 g / m ² Compound H-2 0.03 g / m ² High boiling organic solvent O-2 Gelatin layer containing 0.04 cc / m ² (dry film thickness 1 μm) 12 layers: 1st blue-sensitive emulsion layer Tabular silver iodobromide emulsion spectrally sensitized with sensitizing dye S-5 (1.0 mg / m ² ) Silver amount: 0.6 g / m ² (iodine content: 3 mol% The grains having a diameter / thickness ratio of 7 or more occupy 50% of the projected area of all grains.
0.10μ) Emulsion A Silver amount 0.1 g / m ² A-7 0.5 mg / m ² Coupler C-5 0.5 g / m ² High boiling organic solvent O-2 Gelatin layer containing 0.1 cc / m ² (dry film) 13th layer: 2nd blue-sensitive emulsion layer Tabular silver iodobromide emulsion spectrally sensitized with sensitizing dye S-5 (2.0 g / m ² ) Silver amount: 1.1 g / m ² ( iodine content 2.5 mole%, the ratio is 7 or more particles of diameter / thickness account for 50 percent of the total grain projected area. the average thickness of the particle 0.15μ) a-12 10 mg / m 2 coupler C-7 1.2 g / m ² Coupler C-8 0.2 g / m ² High boiling organic solvent O-2 Gelatin layer containing 0.07 cc / m ² (dry film thickness 3 μm) 14th layer: 1st protective layer A-13 0.10 mg / m ² UV absorber U-1 0.02 g / m ² UV absorber U-2 0.03 g / m ² UV absorber U-3 0.03 g / m ² UV absorber U-4 0.29 g / m ² High boiling organic solvent O- Gelatin layer containing 0.28 cc / m ² (dry film thickness 2μ) 15th layer: 2nd protective layer Grain silver iodobromide emulsion silver amount: 0.1 g
/ m ² (iodine content 1 mole%, average grain size 0.06μ) A-8 10 mg / m 2 of polymethyl methacrylate particles 0.1 g / m ² (average particle 1.5μ) A-3 0.2 g / m 2 A-9 Gelatin layer containing 1.0 mg / m ² (dry thickness 0.8 μm) In addition to the above composition, an antifoggant A-16, a gelatin hardener H-3, and a surfactant were added to each layer.

Preparation of Emulsions A and B A silver bromide cubic emulsion having an average grain size of 0.15 μm was prepared by a controlled double jet method, and was fogged with hydrazine and a gold complex under a low pAg (hereinafter referred to as Emulsion A). .

Emulsion B was prepared by subjecting the surface of emulsion A thus prepared to silver bromide with a shell having a thickness of 250 °.

 The compounds used to make the samples are shown below.

The sample prepared as described above was designated as 401.

Next, the cyan couplers (C-1), (C-2), (C-6) and (C-8) used in the third, fourth and fifth layers were all replaced with the cyan coupler (1) of the present invention in equimolar amounts. The sample thus prepared was designated as 402.

Samples 403 to 407 were prepared in the same manner as Sample 402 except that cyan couplers (5), (6), (9), (16), and (17) were used instead of cyan coupler (1). did.

After exposing the obtained samples 401 to 407 through a red filter, the following phenomenon treatment was performed.

When the spectral absorption of the obtained developed sample was measured, Samples 402 to 407 using the cyan coupler of the present invention showed much sharper spectral absorption characteristics than Sample 401 using the cyan coupler other than the present invention. Processing time Time First temperature development 6 minutes 38 ° C Rinse 2〃 38〃 Inversion 2〃 38〃 Color development 6〃 38〃 Adjustment 2〃 38〃 Bleaching 6〃 38〃 Fixing 4〃 38〃 Rinse 4〃 38〃 Stable 1〃 twenty five〃 The composition of each processing solution was as follows.

First developer Nitrilo-N, N, N-trimethylenephosphonic acid pentasodium salt 2.0 g Sodium sulfite 30 g Hydroquinone potassium monosulfonate 20 g Potassium carbonate 33 g 1-phenyl-4-methyl-4-hydroxymethyl-3
-Pyrazolidone 2.0 g Potassium bromide 2.5 g Potassium thiocyanate 1.2 g Potassium iodide 2.0 g Water was added to 1000 ml pH 9.60 pH was adjusted with hydrochloric acid or potassium hydroxide.

Reversal liquid Nitrilo-N, N, N-trimethylenephosphonic acid pentasodium salt 3.0 g Stannous chloride dihydrate 1.0 g p-aminophenol 0.1 g Sodium hydroxide 8 g Glacial acetic acid 15 ml Add water 1000 ml pH 6.00 pH , Hydrochloric acid or sodium hydroxide.

Color developer Nitrilo-N, N, N-trimethylenephosphonic acid / pentasodium salt 2.0 g Sodium sulfite 7.0 g Trisodium phosphate / 12 hydrate 36 g Potassium bromide 1.0 g Potassium iodide 90 g Sodium hydroxide 3.0 g Citrazinic acid 1.5 g N -Ethyl-N- (β-methanesulfonamidoethyl)
-3-Methyl-4-aminoaniline sulfate 11 g 3,6-dithiaoctane-1,8-diol 1.0 g Water was added to the mixture, and the pH was adjusted with hydrochloric acid or potassium hydroxide.

Conditioning liquid 8.0 g of ethylenediamine tetraacetic acid, disodium salt, dihydrate
Sodium sulfite 12g 1-thioglycerin 0.4ml Water was added to 1000ml pH 6.20 pH was adjusted with hydrochloric acid or sodium hydroxide.

Bleach Ethylenediamine tetraacetic acid, disodium salt, dihydrate 2.0 g
Ethylenediaminetetraacetic acid ・ Fe (III) ・ ammonium ・
Dihydrate 120 g Potassium bromide 100 g Ammonium nitrate 10 g Water was added to 1000 ml pH 5.70 pH was adjusted with hydrochloric acid or sodium hydroxide.

Fixer Sodium thiosulfate 80 g Sodium sulfite 5.0 g Sodium bisulfite 5.0 g Water was added to 1000 ml pH 6.60 pH was adjusted with hydrochloric acid or aqueous ammonia.

Stabilizing liquid Holimarin (37%) 5.0ml Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.5ml Add water 1000ml No pH adjustment

[Brief description of the drawings]

FIG. 1 shows absorption spectra of the dyes obtained from the coupler (1) and the comparative coupler (C-1).

Continued on the front page (72) Inventor Shigeru Yamazaki 210 Nakanakanuma, Minamiashigara, Kanagawa Prefecture Inside Fujisha Shin Film Co., Ltd. Document JP-A-58-102936 (JP, A) JP-A-1-250949 (JP, A) JP-A-1-295257 (JP, A) JP-A-2-62539 (JP, A) JP-A-61-2 36745 (JP, A)

Claims (5)

(57) [Claims] 1. A cyan dye-forming coupler represented by the following general formula [I]. (Wherein, R ₁ represents an aliphatic group, an aromatic group, or a heterocyclic group; R ₂ represents an aliphatic group, an aromatic group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkenyloxy group, an amino group, Selected from the group consisting of acyl groups, ester groups, amide groups, sulfamide groups, imide groups, ureido groups, aliphatic or aromatic sulfonyl groups, aliphatic or aromatic thio groups, hydroxyl groups, cyano groups, carboxyl groups, and halogen atoms. Represents a group or atom which can be substituted on the pyridine ring (however, when R ₂ is a hydroxyl group, it shall be at the meta position to the N atom of the heterocyclic ring); X represents a hydrogen atom or a coupling-off group Y represents a divalent linking group containing at least one amide bond and / or ester bond; Z represents a hydroxyl group or an arylsulfonamide group; n represents 0,
1 or 2; when n is 2, two R ₂ may be the same group or atom or different groups or atoms, and two R ₂ may form a ring if n is 1 or more, may form a ring with R ₁ and R _2; R _1, R ₂ and X of at least one, but R _1, R ₂ or X of formula (I) The removed pyridine residue may also contain one or more substituents. ) 2. The cyan dye-forming coupler according to claim 1, wherein Z is a hydroxyl group. (3) R ₂ is an aliphatic group, an aromatic group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkenyloxy group,
Selected from the group consisting of amino groups, acyl groups, ester groups, amide groups, sulfamide groups, imide groups, ureido groups, aliphatic or aromatic sulfonyl groups, aliphatic or aromatic thio groups, cyano groups, carboxyl groups, and halogen atoms. The cyan dye-forming coupler according to claim 1, which represents a group or atom that can be substituted on the pyridine ring. 4. Z is a hydroxyl group, and R ₂ is an aliphatic group,
The cyan dye-forming coupler according to claim 1, which represents a group or an atom that can be substituted on a pyridine ring selected from the group consisting of an alkoxy group, an aryloxy group, an ester group, an amide group, an aliphatic thio group and a halogen atom. 5. A silver halide photographic light-sensitive material containing at least one cyan dye-forming coupler represented by formula [I] according to any one of claims (1) to (4).