JPH01315736A - Cyan dye forming coupler and silver halide photographic sensitive material containing same - Google Patents

Abstract

PURPOSE:To improve the light resistance, the thermal durability and the absorption characteristic of a coloring dye by incorporating a specified cyan coupler in the photosensitive material. CONSTITUTION:The coupler is shown by formula I. In the formula, R1 is an aliphatic or an aromatic group, etc., R2 is a group or an atom capable of substituting to a pyridine ring, X is hydrogen atom or a group capable of being released a coupling, Y is a divalent linking group contg. one or more of amide bindings and/or ester bindings, Z is dissociation group as hydroxide group, (n) is 0-2. One or more of the groups R1, R2 and X may contain an oligomer or a polymer contg. pyridyl group, one or more of the group R1, R2, X and Z may bind to a ballast group. The coupler shown by the formula is composed of a compd. shown by formula II.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a novel cyan dye-forming coupler used in silver halide color photographic materials and the like, and a silver halide photographic light-sensitive material containing the coupler. .

(Prior art) After exposing a silver halide light-sensitive material to light, a color development process is performed, whereby a developing agent such as an aromatic primary amine oxidized by silver halide reacts with a dye-forming coupler, resulting in color development. An image is formed.

-fn In this method, a subtractive color reproduction method is often used, and in order to reproduce blue, green, and red, color images of yellow, magenta, and cyan, which are complementary colors, are formed, respectively.

(Problems to be Solved by the Invention) Phenols or naphthols are often used as cyan image forming couplers.

However, several problems remain in the storage stability of color images obtained from conventionally used phenols and naphthols. For example, U.S. Patent No. 2.367.5
No. 31, No. 2.369.929, No. 2.423.73
The color images obtained from the 2-acylaminophenolic cyan couplers described in U.S. Pat.
72.162 and 2,895.826
．． Color images obtained from 5-diacylaminophenol cyan couplers are inferior to -a in light fastness, and 1-hydroxy-2-natutamidocyan couplers are generally poor in both light and heat (especially thermal) fastness. It is enough.

To improve the drawbacks of such cyan dye-forming couplers, for example, U.S. Pat.
, 564, 586.
Acylaminocarbostyryl cyan couplers and the 4-hydroxy-
5-acylaminooxindole coupler, 4-hydroxy-5-acylamino-2,3-dihydro-1,3
-benzimidazole-2-one couplers and the like have been developed. These couplers have excellent light and heat fastness. These couplers are specific couplers having a heteroatom in the color-forming mother nucleus, but any ring having a dissociative group for color-forming is equivalent to phenol.

On the other hand, U.S. Pat. No. 2.293.004 discloses only 3-hydroxypyridine and 2,6-hydroxypyridine as couplers in which a heteroatom is introduced into a ring with a dissociative group. The absorption wavelength of the absorption obtained from 3-hydroxypyridine described in the patent specification is on the very short wavelength side, and the absorption peak is also broad. Furthermore, this 3-hydroxypyridine is also water-soluble. Therefore, 3-hydroxypyridine could not be used as a so-called cyan coupler.

Therefore, an object of the present invention is to obtain the
No. 4,564.586, 5-hydroxy-
6-acylaminocarbostyryl cyan couplers and the 4-hydroxy-5-acylaminooxindole couplers described in U.S. Pat. No. 4,430,423, 4-
Hydroxy-5-acylamino-2,3-dihydro-1
, 3-benzimidazol-2-one couplers, etc., as well as excellent light resistance and heat fastness, as well as excellent absorption characteristics for coloring dyes, that is, sharp absorption waveforms and improved color reproducibility. To provide a novel cyan coupler in which a heteroatom is introduced into a ring with a dissociative group. It is in.

[Failure to solve the problem]

The present invention is a cyan dye-forming coupler represented by the following formula (1).

(In the formula, L represents an aliphatic group, an aromatic group, or a heterocyclic group; R2 represents a group or atom that can be converted into a pyridine 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 dissociative group; n is 0
, ■ or 2; When n is 2, the two R2 may be the same group or atom or different groups or atoms, and the two R2 may form a ring; n is 1
In the above case, R1 and R2 may form a ring<:R3
, R2 and X may also contain one or more pyridyl residues from which R3, R2 or When R2 is a hydroxyl group and the hydroxyl group is bonded at the ortho or para position to the nitrogen atom of the pyridyl ring, another R2 can be bonded to the nitrogen atom of the pyridyl ring, in which case the ortho position Alternatively, the hydroxyl group bonded to the para position can also become a ketone due to tautomerism. ) regarding.

Furthermore, the present invention provides at least one compound represented by the above formula 1"I"
This invention relates to a silver halide photographic material containing two cyan dye-forming couplers.

The cyan coupler represented by general formula (1) will be described in detail below.

In general formula (1), R3 preferably has 1 to 3 carbon atoms.
6 aliphatic groups, preferably aromatic groups having 6 to 36 carbon atoms (e.g. phenyl, naphthyl), heterocyclic groups (e.g.
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, icosenyl,
iso-7” lopyl, ter t-butyl, ter
These are t-octyl, tert-dodecyl, cyclohexyl, cyclopentyl, allyl, vinyl, 2-hexadecenyl, and propargyl.

In addition, "aromatic group" refers to a monocyclic or polycyclic condensed aromatic hydrocarbon group, and "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 of the following in the ring, and a 3- to 8-membered ring, preferably a 5- or 6-membered ring, may be fused with other heterocycles, and a heterocycle may be fused with a benzene ring. You can. It also includes cyclic groups that do not have aromaticity.

The aliphatic group, aromatic group and heterocyclic group representing R1 can further include an alkyl group, an aryl group, a heterocyclic group, an alkoxy group (e.g. methoxy, 2-methoxyethoxy), an aryloxy group (e.g. 2,4-di tert-amylphenoxy, 2-chlorophenoxy, 4-cyanophenoxy)
, alkenyloxy group (e.g. 2-propenyloxy)
, amino groups (e.g. butylamino, dimethylamino, anilino, N-methylanilino), acyl groups (e.g. acetyl, benzoyl), ester groups (e.g. butoxycarbonyl, phenoxycarbonyl, acetoxy, benzoyloxy, butoxysulfonyl, toluenesulfonyloxy), Amide groups (e.g. acetylamino, ethylcarbamoyl, dimethylcarbamoyl, methanesulfonamide, butylsulfamoyl), sulfamide groups (e.g. dipropylsulfamoylamino), imide groups (e.g. succinimide, hydantoinyl), ureido groups (e.g. phenylureido) , dimethylureido), aliphatic or aromatic sulfonyl groups (e.g. methanesulfonyl, phenylsulfonyl), aliphatic or aromatic thio groups (e.g. ethylthio, phenylthio), hydroxy groups,
It may be substituted with a group selected from a cyano group, a carboxy group, a nitro group, a sulfo group, a halogen atom, etc.

Next, in -i formula CI), R2 represents a group that can be substituted on the pyridine ring, and preferred specific examples thereof include aliphatic groups (e.g., methyl, ethyl, butyl, dodecyl, etc.), aromatic groups (e.g., phenyl, naphthyl), heterocyclic groups (e.g. 3-pyridyl, 2-furyl), alkoxy groups (
(e.g. methoxy, 2-methoxyethoxy), aryloxy groups (e.g. 2,4-di-tert-amylphenoxy, 2-chlorophenoxy, 4-cyanophenoxy)
, alkenyloxy group (e.g. 2-propenyloxy)
, amino groups (e.g. butylamino, dimethylamino, anilino, N-methylanilino), acyl groups (e.g. acetyl, benzoyl), ester groups (e.g. butoxycarbonyl, phenoxycarbonyl, acetoxy, benzoyloxy, butoxysulfonyl, toluenesulfonyloxy), Amide groups (e.g. acetylamino, ethylcarbamoyl, dimethylcarbamoyl, methanesulfonamide, butylsulfamoyl), sulfamide groups (e.g. dipropylsulfamoylamino), imide groups (e.g. succinimide, hydantoinyl groups), ureido groups,
aliphatic or aromatic sulfonyl group, aliphatic or aromatic thio group, hydroxy group, cyano group, carboxy group,
Examples include halogen atoms.

The specific examples of the group Q listed above are the same as the specific examples exemplified for R1. R2 can also be present on the nitrogen atom in the pyridine ring, in which case examples of R2 include aliphatic groups, aromatic groups, heterocyclic groups, acyl groups, sulfonyl groups, aliphatic or aromatic groups. Examples include oxy group and amino group. In this case, when the ortho or para position of the nitrogen atom in the pyridine ring is a hydroxyl group, the present invention also includes a tautomerized hydroxyl group expressed as a cyclic ketone.

Furthermore, when X in -i formula (1) represents a coupling-off group (hereinafter referred to as a "separation group"), examples thereof include coupling activated carbon via oxygen, nitrogen, sulfur or a carbon atom, and aliphatic Groups that bond to group groups, aromatic groups, heterocyclic groups, aliphatic/aromatic or heterocyclic sulfonyl groups, groups that bond to aliphatic/aromatic or heterocyclic carbonyl groups, halogen atoms, aromatic groups An azo group, etc., and the aliphatic, aromatic, or heterocyclic group contained in these leaving groups may be substituted with a substituent allowed for R4 (when there are two or more of these substituents, may be the same or different, and these substituents may further have a substituent permissible for R+.

Specific examples of coupling-off groups include halogen atoms (e.g. fluorine, chlorine, bromine), alkoxy groups (e.g. ethoxy, dodecyloxy, methoxyethylcarbamoylmethoxy, carboxypropyloxy, methylsulfonylethoxy), aryloxy groups (e.g. 4-chlorophenoxy, 4-methoxyphenoxy, 4-carboxyphenoxy), acyloxy groups (e.g. acetoxy, tetrazocallyoxy, benzoyloxy), aliphatic or aromatic sulfonyloxy groups (e.g. methanesulfonyloxy, toluenesulfonyloxy) , acylamino groups (e.g. dichloroacetylamino, heptafluorobutyrylamino), aliphatic or aromatic sulfonamido groups (e.g. methanesulfonamino, p-)luenesulfonylamino), alkoxycarbonyloxy groups (e.g. ethoxycarbonyloxy, benzyl oxycarbonyloxy), iri-oxycarbonyloxy groups (e.g. phenoxycarbonyloxy), aliphatic, aromatic or heterocyclic thio groups (e.g. ethylthio, phenylthio,
tetrazolylthio), carbamoylamino groups (e.g. N
-methylcarbamoylamino, N-phenylcarbamoylamino), 5- or 6-membered nitrogen-containing heterocyclic groups (e.g. imidazolyl, pyrazolyl, triazolyl, tetrazolyl, 1,2-dihydro-2-oxo-1-pyridyl), imide groups (e.g. succinimide, hydantoinyl), aromatic azo groups (e.g. phenylazo), etc.
These groups may be further substituted with a group allowed as a substituent for R.

In addition, as a leaving group bonded through a carbon atom, there is a bis-type coupler obtained by condensing an equivalent coupler with an aldehyde or a ketone. It may contain a functionally useful group.

-JIQ In formula (T), Y is a divalent linking group containing at least an amide bond or an ester bond, and specifically, 13O□-N- and R4 are hydrogen atoms, aliphatic groups, aromatic groups, or Represents a heterocyclic group.

In addition, it is preferable that there is no substituent on the nitrogen atom in the pyridine ring in the - binding margin [■]°. -Tsujirai CI), preferred Y is preferably -NHCO- (bonded to the pyridine ring through the nitrogen atom).

In general 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 sulfotrioxy group.

-M In formula [I], when R1, R2, and R2 form a ring, the preferable number of ring members is 5 to 7 members,
5- and 6-membered rings are more preferred, and the ring may contain an N or O atom outside the carbocyclic ring, and may or may not have aromaticity.

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

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

-Y-R, is the 2-position or 5-position counting from N of the pyridine ring
It is preferably in the - position. The coupler of the present invention in which -Y-R, is present at the 2-position is particularly preferred because the azomethine dye derived from the coupler exhibits sharp absorption and has a high molecular extinction coefficient.

The coupler represented by the general formula CI) preferably has a so-called ballast group having 8 or more carbon atoms in at least one of R, R2, and xlZ for the purpose of stably introducing it into a color photographic light-sensitive material.

- the coupler of the present invention is represented by R1,
At least one of R2 and
9, R2 or X may contain one or more pyridyl groups as substituents. That is, the coupler of the present invention includes oligomers and polymers in which at least one of R1, R2 and X contains a pyridyl group represented by the following. Here, among the couplers of the present invention, - binding allowance (
Of I), the pyridyl group from which RISR2 or X has been removed is
Those containing one are called dimers, and those containing two are called trimers. In addition, as the polymer, R1, R2 or
Examples include vinyl polymers containing at least one of the above three types of pyridyl groups, and the number average degree of polymerization of the polymer is, for example, about 10 to 1. It can be o o o.

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

Cs1l+ r (L) 1;l U (L; Hz tear-υυ1) H i-Cat (*OCN C1! 13 L, E The synthesis method of the present invention will be explained below.

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

Y' represents an amino group or a carboxyl group, Rz,
n has the same meaning as above, and X' represents a hydrogen atom or a halogen atom. When Y / is an amino group, it is reacted with acid chloride, and when Y' is a carboxyl group,
A bond is created with amines by a known dehydration condensation method, and a diffusion-resistant group (Ballast) is introduced. Furthermore, if necessary, the radical (X) may be introduced before or preferably after the introduction of the diffusion-resistant group.

The 3-hydroxypyridine derivative as a starting material is manufactured by Peilstein Handpuch der Organissien.
Chemie (Beilsteins Handbuchde)
r Organischen Chemie) or the literature cited therein.

A specific method for synthesizing the coupler of the present invention will be described below.

Synthesis Example 1 (Exemplary coupler (1)) 2-Amino-3-hydroxypyridine 1). 0g to 100nl of acetonitrile and 20ml of dimethylacetamide
2-(2',4'-dit) while heating under reflux.
er t-amylphenoxy)-rough acid loride 38
．． 9 g was added dropwise. After the dropwise addition, the mixture was further refluxed for 2 hours and cooled. The reaction mixture was dissolved in 250 mf of ethyl acetate and 2
After adding 50 mff to neutralize the mixture, the liquid was separated. After further washing the ethyl acetate layer with water, the solvent was distilled off under reduced pressure. After adding 200 ml of acetonitrile to the residue and dissolving it, it was cooled and crystallized. The crystals were filtered to obtain 35.1 g of coupler (1). Melting point: 80-83°C Elemental analysis: C72, 59%, H8, 69%, N6
．． 72% calculated value: C72, 78%, H8, 80%, N
6.79% Synthesis Example 2 (Exemplary Coupler (2)) 2-(2',4'-Gt used in Exemplary Coupler (1))
2-(2'-( 2', 4'-G tert-
Amylphenoxy)-hexanoic acid amido)-3-hydroxypyridine was obtained.

The obtained 2-(2'-(2", 4#-Gter t
25 g of -amylphenoxy)-hexanoic acid amide)-3-hydroxypyridine was dissolved in 200 nffi of methylene chloride, and 8.4 g of sulfuryl chloride was added dropwise at room temperature with stirring. After 20 minutes of dropwise addition, the reaction solution was poured into water, extracted with methylene chloride, and concentrated. The residue was purified by silica gel column chromatography to obtain 18 g of coupler (2) as an oil.

Synthesis Example 3 (Illustrative coupler (3)) 3-2'-(2'',5'-di-tert-amylphenoxy)-butane "amido-5-methoxy" threaded 3-amino-5-methoxy 10 g of pyridine and 30 ml of dimethylacetamide. Triethylamine 13.5mj
l! 27.3 g of 2-(2,5-di-tert-amylphenoxy)-butanoic acid chloride was added dropwise to the solution while stirring in the 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 with silica gel column chromatography yielded 15 g of 3-[2'-(21,
5#-tert-amylphenoxy)-butanoic acid amide]-5-methoxypyridine was obtained as an oil.

3-[2'-(2', 5'-G ter t obtained above)
-amylphenoxy)-butanoic acid amide] -5-methoxypyridine, 9 g and ethyl mercaptan, 3 g, in DMF
While cooling with water, 2.1 g of 60% sodium hydride was gradually added.

After the addition, stir at 80°C for 2 hours, pour the reaction solution into water,
After acidification with acetic acid, extraction was performed with ethyl acetate. After drying the organic layer over anhydrous sodium sulfate, it was concentrated, and the residue was purified using silica gel column chromatography.
The title compound (coupler (3)) of g was obtained (white powder)
.

Synthesis Example 4 (Illustrative coupler (5)) Dissolve 25.5 g of 6-amino-3-picoline in acetonitrile 100II1), and dissolve 30 g of pivalic acid chloride.
．． 5 g was added dropwise to room temperature, heated under reflux for 30 minutes after completion of the addition, and then cooled. Pour into 100++1) water, p)1
8 with sodium carbonate, and extracted with chloroform. The solvent was distilled off under reduced pressure to obtain 44.7 g of crystalline 6-
Bivaloylamino-3-picoline was obtained. This material was suspended in 500 nl 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 then left in the apparatus overnight. After concentrating under reduced pressure, it 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-bivaloylamino-3-picoline oxide. Add this to 200 ml of chloroform
ml, and 54IIIl of acetic anhydride was added. After cooling with water, 43 g of bromine was diluted in 10,100 r of chloroform and added dropwise. After 30 minutes at room temperature after the completion of the dropwise addition, 2 ml of sodium acetate was added.
3 g was added and 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 fractionated using silica gel column chromatography (5% methanol, chloroform) and 28
g of 5-bromo-6-bivaloylamino-3-picoline oxide was obtained. Dissolve this in 80ml of methanol and add 0.15mol of sodium methoxide.
The mixture was heated under reflux for 40 hours. After cooling, the mixture was neutralized with oxalic acid, concentrated, and dissolved in chloroform to remove insoluble materials. The solvent was distilled off under reduced pressure, and 5-methoxy-6-bivaloylamino-3
-26 g of picoline oxide were obtained. 200mj of this stuff with methanol! and 50 m6 of 6N hydrochloric acid and heated under reflux for 52 hours. After neutralizing the hydrochloric acid, the mixture was extracted with chloroform. After distilling off the solvent under reduced pressure, 200ml of acetonitrile was added.
Add A and heat under reflux to produce 2-(2'.

33.8 g of 4'-tert-amylphenoxy)-rough acid chloride was added dropwise. The crystals precipitated by cooling were filtered and 35.4 g of 5-methoxy-6-(2
-(2',4'-di-tert-amylphenoxy)butyroylamino)-3-picoline oxide was obtained. This stuff is 500nL of chloroform! 55 g of phosphorus trichloride was added at room temperature, and the mixture was heated under reflux for 1 hour. After cooling, pour into 500g of ice water and adjust the pH to 1 with ammonia water.
0 and extracted with ethyl acetate. The solvent was distilled off under reduced pressure to obtain an oily 5-methoxy-6(2(2',4'-
tert-amylphenoxy)butyroylamino)-3
- 31.8 g of picoline were obtained. Dissolve this in 200 nl of chloroform and add 22.5 g of boron tribromide under water cooling.
was added dropwise, 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 then extracted with chloroform. The residue obtained by evaporating the solvent under reduced pressure was fractionated using silica gel column chromatography (solvent: chloroform) and recrystallized from ethyl acetate-acetonitrile to obtain 22.6 g of coupler (5). Melting point 91-95℃ Elemental analysis value: C73, 13%, 88.7
9%, H6, 62% Calculated value: C73, 20%, H8,9
8%, H6, 57% Synthesis Example 5 (Exemplary coupler (6)
) 2-( used in the synthesis of exemplary coupler (5) (Synthesis Example 4)
2',4'-di-tert-amylphenoxy) rough acid loride, the same molar amount of 2-(2',4'
19.6 g of 5-hydroxy-6-(2-(2') was prepared in the same manner as above, using -tert-amylphenoxy)hexanoyl chloride.

4'-tert-amylphenoxy)hexanoylamino)-3-picoline was obtained. This product 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 using silica gel column chromatography.
A coupler (6) of g was obtained.

Synthesis Example 6 (Exemplary Coupler (7)) 2-( used in the synthesis of Exemplary Coupler (6) (Synthesis Example 5)
Instead of 2',4'-di-tert-amylphenoxy)hexanoyl chloride, the same molar amount of 2-(3-n
-pentadecylphenoxy) rough acid loride, and in the same manner as in the synthesis of coupler (6), except for the synthesis of coupler (7).
) was obtained.

Synthesis Example 7 (Exemplary Coupler (8)) Using the same molar amount of 6-amino-3-ethylpyridine instead of 6-amino-3-picoline used in the synthesis of Exemplary Coupler (5) (Synthesis Example 4), Also 2-(2', 4'-
In place of the rough acid loride (di-tert-amylphenoxy), the same molar amount of 2-(2',4'-di-tert)
Using t-amylphenoxy)hexanoyl chloride,
Coupler (8) was obtained in the same manner as in the synthesis of coupler (5).

Synthesis Example 8 (Exemplary Coupler (9)) 2-( used in the synthesis of Exemplary Coupler (8) (Synthesis Example 7)
2',4'-diter t-amylphenoxy)hexanoyl chloride is converted into the same mole of 2-(2',4')
-Gter t-octylphenoxy)octanoic acid chloride in the same manner as for coupler (8), except that
5-ethyl-3-hydroxy-2- (2-(2', 4
'-di-tert-octylphenoxy)octanoylamino)pyridine was obtained.

This product 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 dissolved in acetic acid 4
The mixture was dissolved in 0 mf and acetic anhydride 15++ff, and 2.3 ml of concentrated nitric acid was added dropwise while cooling with water. The mixture was further stirred at room temperature for 6 hours. The mixture was poured into ice water, neutralized with sodium carbonate, and then extracted with ethyl acetate. The solvent was distilled off under reduced pressure, and the residue was dissolved in 100 mA of ethanol, followed by 50 ml of water. was added, and 10 g of sodium hydrosulfide was added little by little while heating under reflux. The reaction mixture was refluxed until the yellow color almost disappeared, and then cooled. Water was added to the reaction mixture, and the precipitated crystals were filtered. This crystal was dissolved in dimethylacetamide 30II1) and acetonitrile 100+nj2, and 5.3% of 0-chlorobenzoyl chloride was dissolved at 60°C.
g was added dropwise. After refluxing for 6 hours and cooling, an aqueous sodium hydroxide solution was added to neutralize. The precipitated crystals were filtered and recrystallized from acetonitrile to obtain the coupler (16
) 9.8 g was obtained. Melting point: 125-128°C Elemental analysis: C67.71%, H7.03%, N7
．． 60% calculated value: C67, 89%, H7, 12%, N
7.42% Synthesis Example 10 (Exemplary coupler (17))
5-hydroxy-1,2,3,4-tetrahydro-1,
16.4 g of 7-naphthyridin-2-one was added to 50 tons of acetic acid.
sll and 20n+1 acetic anhydride, 1.9 ml of concentrated nitric acid was added dropwise under water cooling, and the mixture was stirred at room temperature for 3 hours. The reaction mixture was poured into ice water, neutralized with sodium carbonate, and then extracted with ethyl acetate. The residue obtained by distilling off the solvent under reduced pressure was dissolved in 300 ml of ethanol, and 150 mff1 of an aqueous solution of 40 g of sodium hydrosulfide was gradually added thereto, followed by heating under reflux for 30 minutes. Return to room temperature, add 45 liters of water
0II1) and the precipitated crystals were collected by filtration. This crystal is dimethylacetamide 50n+J! and 150ml of acetonitrile! 2-(2゜4-di-tert-amylphenoxy)butyric acid chloride 31, dissolved in and heated under reflux.
1 g was added dropwise. After the addition, the mixture was further refluxed for 3 hours. Return to room temperature and add 300mj of ethyl acetate! After neutralizing by adding 300 ml of water, the mixture was separated, and the ethyl acetate layer was further washed with water and dried with sodium sulfate. The residue obtained by distilling off the solvent under reduced pressure was purified by silica gel column chromatography (chloroform/ethyl acetate = 5/1), and then purified with hexane-
Crystallization was performed from a mixed solvent of ethyl acetate to obtain 4 g of the desired coupler 07126.

Synthesis Example 1) (Exemplary Coupler (19)) Instead of 2-(2',4'-di-tert-amylphenoxy)-butanoic acid chloride used in Synthesis Example 3, the same molar amount of 2-
(2',4'-di-tert-amylphenoxy)
3-(2'-(2',4'-di-tert-amylphenoxy))hexanoylamino) was synthesized using hexanoyl chloride and in the same manner as for the synthesis of coupler (3).
-5-hydroxypyridine was obtained. 12.0 later
g of acetic acid and 15 mj of acetic anhydride! 2.2 ml of concentrated nitric acid was added dropwise while 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, water was added (501)1), and 10 g of sodium hydrosulfide was added little by little while heating under reflux.The mixture was refluxed until the yellow color of the reaction mixture almost disappeared, and then cooled. The precipitated crystals were filtered. 9.8 g of this crystal was 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 resulting residue was purified by silica gel column chromatography to obtain 8.3 g of coupler (19).

Synthesis Example 12 (Exemplary Coupler (20)) Instead of 2-(2',4'-di-tert-amylphenoxy)-butanoic acid chloride used in Synthesis Example 3, the same molar amount of 2-(
3-(2'-(2"-chloro-4" t
ert-amylphenoxy)quinoylamino)-5-
Hydroxypyridine was obtained. 12g of this stuff and 40g of acetic acid
fflf and acetic anhydride 15mj! Dissolve it in water and cool it with 2.2mj of concentrated nitric acid! was dripped. After stirring at room temperature for 6 hours,
The mixture was poured into ice water, neutralized with sodium carbonate, and then extracted with ethyl acetate. The residue obtained by distilling off the solvent under reduced pressure was diluted with 10% ethanol.
Dissolve in 100r and add 50+sJ of water! In addition, 12 g of sodium hydrosulfide was added little by little while heating under reflux.The reaction mixture was refluxed until the yellow color almost disappeared, and then cooled, and the precipitated crystals were filtered. 8g of this crystal
was dissolved in acetonitrile 30II1), and pyridine 1
．． 7＋＋＋j! and heated under reflux, 4.6g of p-bromobenzenesulfonyl chloride was added to 10% of acetonitrile.
It was dissolved in ml and added dropwise. After dropping and refluxing for 3 hours,
After cooling, the reaction mixture was poured into water and extracted with ethyl acetate.

After distilling off the solvent, the residue was purified by silica gel column chromatography to obtain 6.1 g of coupler (20).

Synthesis Example 13 (Exemplary Coupler (26)) In place of 2-(2',4'-di-tert-amylphenoxy)butanoic acid chloride used in Synthesis Example 3, the same molar amount of phenyl chloroformate was used; 3-Hydroxy-5-phenoxycarbonylaminopyridine was obtained in the same manner as in the synthesis of coupler (3) (Synthesis Example 3). 20 g of this was dissolved in 80 ml of acetic acid and 20 ml of acetic anhydride, and 5.5 mf of concentrated nitric acid was added dropwise while cooling with water. 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 distilling off the solvent under reduced pressure was diluted with ethanol 1
00 mA, water was added to the solution at 100 mA, and 20 g of sodium hydrosulfide was added little by little while heating under reflux. The reaction mixture was refluxed until the yellow color almost disappeared, then cooled, 100 m6 of water was added, and the precipitated crystals were filtered.

18g of this crystal is mixed with 80mj of acetonitrile! -Dissolved in 40 ml of dimethylacetamide, added 33.6 g of 3-(1'-dodecylsulfonyl-2'-butanoylamino)benzoyl chloride, and stirred at 50°C for 1 hour. After the reaction was completed, 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 and the residue was diluted with methylene chloride 200+nj! Dissolved in sulfuryl chloride l1 at room temperature
g was added dropwise and stirred for 3 hours. The reaction solution was poured into water, extracted with methylene chloride, and the solvent was distilled off. The resulting residue was purified by column chromatography, resulting in 12.4 g of 2-
Chloro-6-(1'-dodecylsulfonyl-2'-butanoylamino)-5-hydroxy-3-phenoxycarbonylaminopyridine was obtained. Dissolve 12g of this in 50ml of chloroform and heat at room temperature to 1.1mJ! of concentrated nitric acid was added dropwise, and the reaction mixture was stirred 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 is ethanol 200++j! Raney nickel Ig and 1.1 g of acetaldehyde were added thereto, and catalytic hydrogenation was performed in an autoclave. After the catalyst was filtered off, it was poured into water, and the precipitated crystals were filtered.

When this crude crystal was recrystallized from acetonitrile, 6 g
A coupler (26) was obtained.

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

r (A) r H (D) 2-amino-5-nitropyridine (154.1 g.

Bromine (62.6cc, 1.2mol) was added dropwise to a THF (300ml) solution of 1.1mol) at room temperature,
I stirred it for an hour. The reaction mixture was added to 3,000 g of water, the precipitated crystals were filtered, and acetotrile (500 n+
Recrystallization from 1) gave 2-amino-3-bromo-5-nitropyridine (A) (194.4 g, 80%).

Under a nitrogen stream, pyridine (20 cc) was added to a solution of 2-amino-3-bromo-5-nitropyridine (A) (21.8 g, 0.1 moi in acetonitrile (300 nt#) at room temperature, followed by benzoyl Chloride (
24.4g (0.2mol) was added dropwise and stirred for 3 hours.

Add dilute hydrochloric acid (0, IN), extract twice with ethyl acetate,
It was dried with anhydrous sodium sulfate. The solvent was distilled off under reduced pressure,
Recrystallization from methanol yielded 3-bromo-2-dibenzoylamino-5-nitropyridine (B) (28.7 g,
89%) was obtained.

Reduced iron (42.6g, 0.76n+offi),
Water (42.6ml) Ammonium chloride (4.3g,
81 mm of isopropyl alcohol (300 m
f) ILJ solution was heated under reflux for 10 minutes. To this mixed solution was added 3-bromo-2-dibenzoylamino-5-nitropyridine (B) (42.6 g + 10 On + m
ol) was added and heated under reflux for 30 minutes. The reaction solution was filtered through Celite, and the filtrate was distilled off under reduced pressure. After performing benzene azeotropy twice, the residue was treated with acetonitrile (30(1)), pyridine (10 cc), 2-(2', 4'-jet)
-amylphenoxy)butanoyl chloride (33,8
g + 100 moj) was added and stirred for 1 hour. Dilute hydrochloric acid (0, IN) 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 5-(2-(2',4'-
di-t-amylphenoxy)butanoylamino)-2-
Dibenzoylamino-3-promopyridine (C) was obtained.

Acetonitrile (300 ml) of the obtained compound (C)
28% aqueous ammonia (20 cc) was added to the W solution at room temperature, and the mixture was stirred for 15 minutes. Water was added and extracted twice with ethyl acetate. It was washed with dilute hydrochloric acid (0, IN) and saturated brine, 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-bromopyridine (D)
(19.9 g, yield from compound (B): 34%) was obtained.

Compound (D) (19.9 g, 33.5 mm) under a nitrogen stream
28% methanol solution of sodium methoxide (7.1 ml!, 36.9 ml)
mol), anhydrous cuprous chloride (332 mg, 3.4 mmol)
8-Hydroxyquinoline (486 possible, 3.4
+u+oj was added, and 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 brine 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%) was obtained.

Under nitrogen flow, (E) (3.9g+ 7.2 mn+
Lithium iodide (4.0 g, 29.6 mmol) was applied to a solution of 2.4.6-collidine (30 m/) and heated under reflux for 3 hours. After cooling, dilute hydrochloric acid (0, IN
) and extracted twice with ethyl acetate. The organic layer was washed with saturated brine and dried with anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure and recrystallized from acetonitrile to obtain the illustrative coupler (
41) (2.9 g, 76%) was obtained.

Most of the couplers of the present invention are oil-soluble, and it is generally preferable to dissolve them in a high boiling point solvent (if necessary, use a low boiling point solvent together), emulsify and disperse them in an aqueous gelatin solution, and add them to a silver halide emulsion. . In addition, in the case where it is soluble in an alkaline aqueous solution, it can be dissolved in an alkaline aqueous solution together with a developing agent and other additives and used for image formation as so-called external mold development.

On the other hand, oxidative camping is carried out with an oxidizing agent (e.g. persulfate, silver nitrate, nitrous acid or its salts) together with a developing agent and an alkali (with addition of an organic solvent if necessary); 1] where X is a hydrogen atom, p-
Pigments can be synthesized by condensation using nitrosoanilines and alkali or acetic anhydride, which can be used as cyan dyes for various uses (for example, as dyes for filters, paints, inks, images and information recording, or printing). Can be used.

When added to a silver halide emulsion, it is possible to adjust and improve color development or storage stability by using hydroquinone-induced stopper, ultraviolet absorber, known anti-fading agent, etc., if necessary.

The high boiling point solvent can be used as long as it 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 higher) that can dissolve the coupler. As phosphoric acid ester M (
For example, tricresyl phosphate, trioctyl phosphate, tricyclohexyl phosphate), if
I esters (e.g. dibutyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, dodecyl benzoate, bis(2-ethylhexyl) sebacate)
, ethers, (including epoxies), amides, and amines, and these may be cyclic ones, and also high-boiling organic solvents used in the oil-in-water dispersion method described below. Can be used.

Next, the silver halide color photographic material of the present invention will be explained.

In the silver halide color photographic light-sensitive material of the present invention, at least 1N of the cough light-sensitive material contains a cyan dye-forming coupler represented by the above-mentioned margin (1).

The silver halide color photographic light-sensitive material of the present invention includes, for example,
It can be a multilayer, multicolor photographic material with at least two different spectral sensitivities on the support. Multilayer natural color photographic materials usually have at least one red-sensitive emulsion layer, one green-sensitive emulsion layer and one blue-sensitive emulsion layer on a support. The arrangement order of these layers can be arbitrarily selected as necessary.

A preferred layer arrangement is, from the support side, a red-sensitive layer, a green-sensitive layer and a blue-sensitive layer in that order, a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer in that order, or a blue-sensitive layer, a red-sensitive layer and a green-sensitive layer in that order. Further, any color-sensitive emulsion layer can be replaced by two or more emulsion layers having substantially the same color sensitivity but different sensitivities (Sub emu-1sion I).
ayers) to improve the reach sensitivity,
The graininess may be further improved by using a three-layer structure. Furthermore, a non-photosensitive layer may be present between two or more emulsion layers having the same color sensitivity. A configuration may also be adopted in which emulsion layers of different color sensitivity are inserted between emulsion layers of the same color sensitivity. In particular, a reflective layer made of fine grain silver halide may be provided under the high-sensitivity blue-sensitive layer to improve the sensitivity, and a yellow filter layer may also be provided.

Generally, the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler, and part or all of the cyan-forming coupler has the general formula ( A cyan coupler shown in 1) is used. However, depending on the case, different combinations may be used. For example, infrared-sensitive layers may be combined for pseudo-color photography or for laser exposure of thick objects. The cyan coupler of this invention is typically added to the red-sensitive emulsion layer or its adjacent layer as the primary coupler. It can also be used as a main coupler in other blue-sensitive, green-sensitive or infrared-sensitive emulsion layers, or can be used in combination with the main coupler.

The standard amount of cyan coupler used in the present invention is in the range of 0.001 to 1 mol, preferably 0,003 to 0.3 mol, per 1 mol of photosensitive silver halide. .

Further, 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 color sensitivity different from the emulsion layer to which the cyan coupler is added. Further, a known cyan coupler may be used in combination in the same layer or in another layer to the extent that the effects of the present invention are not impaired. Cyan couplers, magenta couplers, and yellow couplers that may be used in combination include E PO231832A 2
General formulas (1) to (V) shown on pages 4 and 5 of the specification
Examples of the cyan coupler include the cyan couplers shown on pages 12 to 24 of the same specification, and examples of the magenta couplers include those shown on pages 25 of the same specification.
As the Mazek coupler on pages 43 to 43, and the yellow coupler on pages 44 to 64 of the same specification, the yellow couplers can be used.

The color photosensitive material of the present invention can be applied to various fields. Color negative film for general use or motion pictures,
It is preferably used for color reversal films for slides or televisions. It can also be used for color paper, color positive film, color reversal paper, etc. The present invention is also applicable to black-and-white window optical materials utilizing trichromatic coupler mixtures, such as those described in Research Disclosure 17123 (July 1978).

Furthermore, the silver halide emulsion forming the light-sensitive material of the present invention is not particularly limited (a variety of conventionally known emulsions can be used). ) can be used.Specifically, the above-mentioned publication 5, immediately above right column line 10~ can be used.
Silver halide listed in line 7 of the lower left column, batch report 5, directly below left column 8
Silver halide emulsions described in line 3 of the lower right column on page 7, couplers described in line 4 of the lower right column of the publication, line 4 of the lower right column on page 8, line 2 of the lower left column on page 8,
Various additives such as color antifoggants described in the same publication 8, right bottom left column, line 3 to page 9, top left column, line 1) 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 silver halide is preferably an internal latent image type direct positive silver bromide, or a color reversal paper. When used as silver halide, silver iodobromide (silver iodide content preferably 2-15 mol%) is used as silver halide.
) is preferred.

Furthermore, when the silver halide color photosensitive material of the present invention is used as color paper (window material for color printing),
As the silver halide emulsion, one consisting of silver chlorobromide or silver chloride that does not substantially contain silver iodide can be preferably used. Here, it means that it does not substantially contain silver iodide.
Silver iodide content is 1 mol% or less, preferably 0.2 mol%
Say the following: The halogen composition of the emulsion may be different or the same among the grains, but if an emulsion having the same halogen composition among the grains is used, it is easy to make the properties of each grain uniform. In addition, regarding the halogen composition distribution inside silver halide emulsion grains, there are grains with a so-called uniform structure in which the composition is the same in every part of the halide root grain, and grains with a so-called uniform structure where the composition is the same in all parts of the silver halide grain, and a core inside the silver halide grain and a shell surrounding it. (Shell) [-layer or multiple layers] A particle with a so-called layered structure in which the halogen composition is different, or a structure having a non-layered portion with a different halogen composition inside or on the surface of the particle (if it is on the surface of the particle, the edge of the particle , a structure in which portions of different compositions are joined on a corner or surface) can be appropriately selected and used. In order to obtain high sensitivity, it is more advantageous to use one of the latter than particles with a uniform structure, and it is also preferable from the viewpoint of pressure resistance. When silver halide grains have the above-mentioned structure, even if the boundaries between parts with different halogen compositions are clear boundaries, the boundaries may be unclear due to the formation of mixed crystals due to compositional differences. It is also possible to actively have continuous structural changes.

Regarding the halogen composition of these silver chlorobromide emulsions, any silver bromide/silver chloride ratio can be used. This ratio can vary widely depending on the purpose, but those with a chlorinated root ratio of 2% or more can be preferably used.

Furthermore, so-called high-silver chloride emulsions having a high silver chloride content are preferably used in light-sensitive materials suitable for rapid processing. The salt/silver chloride content of these high silver chloride emulsions is preferably 90 mol% or more, more preferably 95 mol% or more.

Such a high silver chloride emulsion preferably has a structure in which the localized silver bromide layer is provided inside and/or on the surface of the silver halide grains in a layered or non-layered manner as described above. The halogen composition of the localized phase preferably has a silver bromide content of at least 10 mol%, and more preferably exceeds 20 mol%. These localized layers can be located inside the grains or on the edges, corners, or surfaces of the grain surfaces, and one preferred example is one in which they are epitaxially grown on a part of the corner of the grains.

On the other hand, in order to minimize the decrease in sensitivity when a photosensitive material is subjected to pressure, even in high silver chloride emulsions with a silver chloride content of 90 mol% or more, grains with a uniform structure with a small distribution of halogen composition within the grains are used. It is also preferable to use

Furthermore, it is also effective to further increase the silver chloride content of the silver halide emulsion for the purpose of reducing the amount of replenishment of the development processing solution.

In such cases, the silver chloride content is between 98 mol% and 99 mol%.
．． Emulsions of almost pure silver chloride, such as 9 mol %, are also preferably used.

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

The particle size distribution thereof is preferably so-called monodisperse, with a coefficient of variation (standard deviation of particle size divided by average particle size) of 20% or less, preferably 15% or less. At this time, in order to obtain a wide latitude, it is preferable to blend the above-mentioned monodispersed emulsions in the same layer or to apply multilayer coating.

The shape of silver halide grains contained in photographic emulsions is regular (cubic, tetradecahedral, or octahedral).
lar) those with crystal shapes, those with irregular crystal shapes such as spherical, plate-like, etc.
Alternatively, a composite form of these can be used. Moreover, it may be made of a mixture of crystals having various crystal forms. In the present invention, among these, grains containing 50% or more, preferably 70% or more, more preferably 90% or more of particles having the above-mentioned regular crystal form are preferred.

In addition to these, the average aspect ratio (yen equivalent diameter/
Emulsions in which the projected area of tabular grains having a thickness of 5 or more, preferably 8 or more, exceeds 50% of the total grains can also be preferably used.

Various polyvalent metal ion impurities can be introduced into the silver halide emulsion used in the present invention during the process of emulsion grain formation or physical ripening.

Examples of compounds used include cadmium, zinc, lead,
Salts such as copper and thallium, or iron, which is a group II element,
Examples include salts or complex salts of ruthenium, rhodium, palladium, osmium, iridium, platinum, and the like. In particular, the above-mentioned Group Ⅰ elements can be preferably used. The amount of these compounds added varies over a wide range depending on the purpose, but is preferably from 10@-9 to 10@-2 mol relative to silver halide.

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

Regarding the chemical sensitization method, sulfur sensitization typified by the addition of unstable sulfur compounds, noble metal sensitization typified by gold sensitization, or reduction sensitization can be used alone or in combination. Regarding compounds used for chemical sensitization, see the lower right column on page 18 of the specification of JP-A-62-215272.
Those described in the upper right column of page 22 are preferably used.

In the present invention, the coupler (1) can be introduced into the optical material by various known dispersion methods.

For example, an oil-in-water dispersion method is mentioned, and examples of high boiling point solvents used in this dispersion method are described in US Pat. No. 2.322.027 and the like.

Specific examples of high-boiling organic solvents with a boiling point of 175°C or higher at normal pressure 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(l,1-diethylpropyl) phthalate, etc.), phosphoric acid or phosphonic acid Acid esters (trifel phosphate, tricresyl phosphate, 2-
ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, triptoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexyl phenyl phosphonate, etc.), benzoic acid esters (2-ethylhexyl benzoate,
dodecyl benzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), amides p (N,N-diethyldodecanamide, N,N-diethyl laurylamide, N-tetradecylpyrrolidone, etc.), alcohols or phenols (iso stearyl alcohol, 2,4
-LerL-amylphenol, etc.), fatty acid carboxylic acid 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.). Further, as an auxiliary solvent, the boiling point is about 30°C or higher, preferably 50°C or higher.
Organic solvents having a temperature of 160°C or higher can be used, and typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohegisanone,
-Ethoxyethyl acetate, dimethylformamide and the like.

When the coupler of general formula (1) of the present invention is dispersed by an oil-in-water dispersion method, the high-boiling point organic solvent used is at least one of the following - Tsuzuriyo (VI) or (■), or a combination thereof. Particularly preferred is the combined use of a co-solvent (eg ethyl acetate).

The weight ratio of the high boiling point organic solvent to the coupler is 1.0 or less, preferably 0.6 or less, more preferably 0.4 or less. That is, a method of dispersing using only an auxiliary solvent is also preferable.

General formula (Vl) In the formula, R6 and R62 may be the same or different and each represents an alkyl group, a cycloalkyl group, an alkenyl group, or an atomyl group, and the number of carbon atoms in the group represented by R61 and R&Z is The total number is 4-30.

-Spelling margin (■) In the formula, R7-R7ts R and s may be the same or different and each represents an alkyl group, cycloalkyl group, alkenyl group or aryl group, R1)-, R7□
,R? The total number of carbon atoms in the group represented by 3 is 12 to 60.

Specific examples of latex dispersion processes, effects, and latex for impregnation include U.S. Pat. It is described in.

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D, Corner 17643, page 28, and Kaiko 1B716, 6
It is described from the right column on page 47 to the left column on page 648.

The color photographic material according to the present invention is described in the above-mentioned RD, 17643, pages 28-29, and 6th page of Open Air 18716.
51. Development processing can be carried out by the usual methods described in the left column to right column.

It is preferable that the silver halide color photographic light-sensitive material of the present invention undergoes a water washing and/or stabilization step after the desilvering treatment.

The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the washing water, the number of washing tanks (number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set over a wide range. Among these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is
Urnalof the 5ociety of Mo
tion Picture and Televisi
onEngineers Vol. 64, P, 248-25
3 (May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned document, the amount of water used for washing can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria will breed, and the generated suspended matter will adhere to the photosensitive material. The problem arises. As a solution to such problems in the color light emitting material ρ treatment of the present invention,
The method for reducing calcium ions and magnesium ions described in JP-A-62-288838 can be effectively used. In addition, chlorine-based disinfectants such as isothiazolone compounds, cyabendazoles, and chlorinated sodium isocyanurate described in JP-A No. 57-8.542, and other benzotriazoles, "Bacterial and fungicidal agents" by Hiroshi Horiguchi, It is also possible to use germicides described in "Sterilization, Disinfection, and Antifungal Technology of Microorganisms" published by the Sanitation Technology Association, and "Encyclopedia of Antibacterial and Antifungal Agents" published by the Japan Antibacterial and Antifungal Society.

The pH of the washing water in the processing of the photosensitive material of the present invention is 4 to 4.
9, preferably 5 to 8.

The washing water temperature and washing time can be set in various ways depending on the characteristics of the photosensitive material, its use, etc., but generally it is 20 seconds to 10 seconds at 15 to 45°C.
minutes, preferably in the range of 30 seconds to 5 minutes at 25-40°C. Furthermore, the photosensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water. In such stabilization treatment, Japanese Patent Application Laid-open No. 57-8.543,
All of the known methods described in No. 58-14.834, No. 60-220, and No. 345 can be used.

Further, following the water washing treatment, a further stabilization treatment may be carried out, and an example thereof is a stabilizing bath containing formalin and a surfactant, which is used as a final column of color photosensitive materials for photographic printing. can.

Various chelating agents and antifungal agents can also be added to this stabilizing bath.

The overflow liquid resulting from the water washing and/or replenishment of the stabilizing liquid can also be reused in other processes such as the grudge removal process.

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 processing. In order to incorporate the color developing agent, it is preferable to use various precursors of the color developing agent. For example, U.S. Patent No. 3.342.59
Indoaniline compounds described in No. 7, No. 3,342.
No. 599, Research Disclosure 14.850
Schiff base-type compounds described in No. 15.159 and aldol compounds described in No. 13.924, U.S. Patent No. 3
．． Metal salt complex described in No. 719.492, JP-A-53-1
Examples include urethane compounds described in No. 35.628.

The silver halide color optical material of the present invention may contain various types of l-phenyl-3, if necessary, for the purpose of promoting color development.
- Pyrazolidones may be incorporated. Typical compounds are disclosed in JP-A No. 56-64, No. 339, and No. 57-144.54.
No. 7, and No. 58-1) No. 5,438.

Various treatment liquids in the present invention are used at 10°C to 50°C. Normally, the standard temperature is 33°C to 38°C, but higher temperatures can be used to accelerate processing and shorten processing time, or lower temperatures can be used to improve image quality and stability of the processing solution. be able to. Also, because of the nodal line of the photosensitive material, West German Patent No. 2.226.770 or U.S. Patent No. 3
．． A treatment using cobalt intensification or hydrogen peroxide intensification as described in No. 674.499 may also be carried out.

Further, the silver halide photoluminescent material of the present invention is disclosed in U.S. Patent No. 4,
It can also be applied to the heat-developable photosensitive materials described in JP-A No. 500,626, JP-A-60-133.449, JP-A-59-218443, JP-A-61-238056, European Patent Application No. 210.66OA2, etc. .

The present invention will be further explained below with reference to Examples.

Example 1 Coupler of the invention (li 2. Og to ethyl acetate 20
ml and dissolved in ethanol 15 mA, sodium carbonate 3
g was dissolved in 30 ml of water and added. While stirring, 4
-(ethyl, methanesulfonamidoethylamino)-0
-) After adding 2.4 g of luidine monohydrate sesquisulfate, 2.7 g of ammonium persulfate was dissolved in 16 ml of water and added dropwise. After stirring at room temperature for 30 minutes, add 10 ml of water.
0mj! was added and separated. After washing the ethyl acetate layer three times with water, it was dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure at room temperature. It was immediately dissolved in a small amount of chloroform and passed through a silica gel column to collect a cyan fraction. When the solvent was distilled off under slight pressure at room temperature, a dark blue powdery dye was obtained.

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 above.

Table 1 shows the results of measuring the solution absorption spectrum of the dye. Further, the spectra of coupler (1) and comparative coupler <C-1) are shown in FIG.

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, it has a vivid hue, and it also has a high molar extinction coefficient (ε).

Comparative coupler (C-1) Comparative coupler (C-2) Example 2 Coupler of the present invention (IHOg, dibutyl phthalate 10
g and ethyl acetate 20+l! The solution obtained by heating to 50° C. was emulsified and dispersed in 80 g of gelatin solution containing 8 ml of 1% aqueous sodium dodecylbenzenesulfonate solution.

Next, this emulsified dispersion was mixed into a red-sensitive silver chlorobromide emulsion (Br50
%) (containing 7 g of Ag), sodium dodecylbenzenesulfonate was added as a coating aid, and the mixture was coated on a paper support laminated on both sides with polyethylene.

The coupler coating amount was set at 400 mg/m''.A gelatin protective layer (gelatin Ig/m') was coated on top of this layer, and this was designated as Sample A.

The same molar coupler (2) instead of the above coupler (1)
, (3), (5), (16), (17) and (26)
A film was prepared using the same procedure. These were designated as samples B to G in this order. Also, as comparative examples, comparative couplers (C-1), (C-2), (C-3), (C-4
) and (C-5) to prepare sample) 1-L.

After each sample was exposed to light using a continuous wedge for sensitometry, the following development treatment was performed.

Color development process (33℃) 1 Color development ・・・・・・3 minutes 30 seconds 2 Bleach fixing ・・・・・・1 minute 30 seconds 3 Washing with water
......2 minutes 30 seconds The processing steps used in each step are as follows.

Color developer benzyl alcohol 15.0 kl diethylene glycol ゛8. Omj2 Ethylenediaminetetraacetic acid 5.0g Sodium sulfite
2.0g anhydrous potassium carbonate
30 g Hydroxylamine 6La salt 3.0 g Potassium bromide 0.6 g 4-Amino-N-ethyl-N- (β-methanesulfonamidoethyl)-m-toluidine sesquisulfate monohydrate 5.0 g Add water
1 N (pH 10,2) comparative coupler 2 (C-5) Bleach-fix solution ethylenediaminetetraacetic acid 4.0g ethylenediaminetetraacetic acid ferric 40g salt sodium sulfite 5.0g sodium thiosulfate (70%) 1501) + J water In addition
1) After treatment, all samples coated with the coupler of the present invention exhibited a bright cyan to blue hue.

Next, the robustness of the sample after treatment was investigated.

That is, when left at 100°C in the dark for 10 days,
Table 2 shows the residual rate of dye density when exposed to light for one week using a xenon fade meter (100,000 lux).

Table 2 It can be seen from Table 2 that the couplers of the present invention have the same robustness as the corresponding carbocyclic couplers (
Comparison of A, B and H, D and ■, E and JSF, G and L)
.

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

The gelatin hardening agent for each layer below is l-oxy-3
, 5-dichloro-5-) riazine sodium salt was used.

The following spectral sensitizing dyes were used in each layer.

Blue-sensitive emulsion layer (2.0xlO-' mol each for large-sized emulsions and 2.5x10-' mol each for small-sized emulsion per mole of silver halide); green-sensitive emulsion layer (silver halide); per mole, 4.0xlO-' moles for large size emulsions and 5.6 for small size emulsions.
X10-' mole) and (per mole of silver halide, for large size emulsions ?, 0X10-' mole and for small size emulsions 1
．． 0x10-' mole) red-sensitive emulsion layer (per mole of silver halide, 0.9x10-' mole for large size emulsions and 1 for small size emulsions)
．． For the red-sensitive emulsion layer, the following compound was added in an amount of 2.6 x 10-' mol per mol of silver halide.

Further, for the blue-sensitive emulsion layer, green-sensitive emulsion layer, and red-sensitive emulsion layer, 1-(5-methylureidophenyl)-5-mercaptotetrazole was added at 8.5×10 −' mol per mol of the halogenated material, and 7. 7 x 10-' moles, 2.5
X10-' moles were added.

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

SO3Na 503Na and (Layer Structure) The composition of each layer is shown below. Numbers are applied (g/i)
The silver halide emulsion represents the coating amount in terms of silver.

Support polyethylene laminate paper [The polyethylene on the first layer side contains a white pigment (TiO2) and a bluish dye (ulmarine blue)] -th layer (blue-sensitive layer) Said silver chlorobromide emulsion 0.30 Gelatin 1.86 Yellow Coupler (ExY) 0.82 Color image stabilizer (Cpd-1) 0.19? Container (Solv-3)
0.35 color image stabilizer (Cpd-7)
0.06 Fifth layer (color mixing prevention layer) Gelatin 0.99 Color mixing prevention agent (Cpd-5) 0.08 Solvent (Solv-1) 0.16
Solv-4
0.08 3rd F! (Green-sensing layer) Silver chlorobromide emulsion (cubic, 1:3 mixture of average grain sizes of 0.55 μm and 0.39 μm (Ag molar ratio). The coefficient of variation of grain size distribution is 0. 10 and 0.0
8. Each emulsion contained 0.8 mol% of AgBr locally on the grain surface) 0.12 Gelatin
1.24 magenta coupler (Ex
M) 0.20 color image stabilizer (Cpd-
3) 0.15 color image stabilizer (Cpd
-4) 0.02 color image stabilizer (Cp
d-2) 0.03 solvent (Solv
-2) 0.40 Fourth layer (ultraviolet absorption layer) Gelatin 1.58 Ultraviolet absorber (UV-1) 0.47 Color mixing inhibitor (Cpd-5) 0.05 Solvent (Solv-5) 0.2
4 Fifth layer (red-sensitive layer) Silver chlorobromide emulsion (cubic, 1:4 mixture (Ag molar ratio) of one with an average grain size of 0.58 μm and one with an average grain size of 0.45 μm. Coefficient of variation of grain size distribution are 0.09 and 0.1
), each emulsion locally contained 6 mol% of hegBrO on the grain surface) 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 (Cp
d-8) 0.04 color image stabilizer (C
pd-7) 0.40 Solvent (Sol
v-6) 0.15 6th layer (
Ultraviolet absorption N) Gelatin 0.53 Ultraviolet absorber (UV-1) 0.16 Color mixing inhibitor (Cpd-5) 0.02 Solvent (Solv-5) 0.0
8 Seventh layer (protection N) Gelatin 1.33 Acrylic modified copolymer of polyvinyl alcohol (denaturation degree 17%)
) 0.17 liquid paraffin
0.03 (ExY) 1:1 mixture (molar ratio) with yellow coupler (ExM) 1:1 mixture (molar ratio) of magenta coupler (Cpd-1) Color image stabilizer (Cpd-3) Color image stabilizer (Cpd-5) Color mixture inhibitor H (Cpd-4) Color image stabilizer (Cpd-2) Color image stabilizer (Cpd-6) 2:4:4 mixture (weight ratio) of color image stabilizer (Cpd- 7) Color image stabilizer + CI! -C8←7 C0JICJv (n) Average molecular weight 60,000 (Cpd-8) Color image stabilizer 0■ 0■ (υv-1) 4:2:4 mixture of ultraviolet absorbers (weight ratio) (Solv-1) Solvent (Solv-2)? 2:1 mixture of 8 solvents (volume ratio) (Solv-3) Solvent (Solv-4) Solvent (Solv-5) Heat the solvent C00C*H+ (CHz) s ■ C00CsH+y (Solv-6) Solvent samples 102 to 108 Coupler in the fifth layer of sample 101 (comparison) <C-1),
(C-2) to (1), (5), (6), (9), QII
OSQ? ) and (26) were substituted in equimolar amounts, but a sample was prepared in the same manner as sample 101. These were designated as samples 102 to 108 (invention), respectively.

After exposing the above photosensitive material through an optical wedge, it was processed in the following steps.

Processing process Seiren Toyosara Seinu Ketsuji”? Sandan color development 35℃ 45 seconds 161mj! 17f bleach fixing 30~35℃ 45 seconds 215mj! 1)
1 Rinse■ 30~35℃ 20 seconds -101 Rinse■ 30~35℃ 20 seconds -106 Rinse■ 30
~35℃ 20 seconds 350mj! 10j! dry
Drying: 70 to 80°C for 60 seconds *The replenishment amount was per 1rrl of the photosensitive material (3 tank countercurrent system was used for rinsing ① to ②).The composition of each processing solution was as follows.

, l-Satoki Arashi tank liquid replenishment liquid water
800ml! 8
00 mβ ethylenediamine-N,N.

N,N-tetramethylenephosphonic acid 1.5g 2.0g Triethanolamine 8.0g 12.0
g Sodium chloride 1.4 g - Potassium carbonate 25 g 25 g N-Ethyl τN-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate 5.0 g 7.0 gN
, N-bis(carboxymethyl)hydrazine 5.5 g 7.0 g Optical brightener (WHITEX 4B.

Add water 1000n+ 1 1000
m 1p)l (25℃>10.0
5 10.45 Bleach-fix solution (tank solution and replenisher solution are the same) water
400mj! Ammonium thiosulfate (70%)
100ml Sodium sulfite 17
gIron ethylenediaminetetraacetate (m) Ammonium 55g Disodium ethylenediaminetetraacetate 5g Add water
1000mlp1000℃) 6.0 Rinse solution (tank solution and refill solution are the same) Ion exchange water (calcium, magnesium 3p each)
pm or less) Samples 102 to 108 using the couplers of the present invention were all superior in color reproducibility compared to comparative sample 101.

Example 4 Paper support laminated on both sides with polyethylene (thickness 10
A color photographic window light material was prepared by coating the following 1st to 14th layers on the front side of the film (0 microns) and 5th to 6th layers on the back side. Titanium oxide (4g/rrr) was added as a white pigment to the polyethylene on the coating side of the first layer.
Contains 0.003g/nf of ultramarine blue as a dye (
The chromaticity of the surface of the support is 88. in L''', a''', b1 system.
They were 0, -0.20, and -0.75. ).

(Photosensitive layer composition) Ingredients and application below! (g/n?, unit).

Regarding silver halide, the coating amount is shown in terms of silver. The emulsion used in each layer was prepared according to the manufacturing method of emulsion EMI.

However, the emulsion for the 14th layer was a Lippmann emulsion that was not surface chemically sensitized.

1st F! (Antihalation N) Black colloidal silver −・−・−0,10 Gelatin −・・−0,70 2nd layer (intermediate layer) Gelatin −・−0,70 3rd layer (low sensitivity red sensitive layer) Red enhancement Silver bromide spectrally sensitized with a sensitive dye (ExS -1, 2, 3) (average grain size 0.25 μ, size distribution [coefficient of variation] 8%, octahedral) - - - - - 0.04 Red Silver chlorobromide (silver chloride 5 mol%, average grain size 0.40
μ, size distribution 10%, octahedron...---0,08 gelatin -...1.00 cyan coupler (ExC-1, 2, 3 1:1:0.2)
---0.30 Anti-fading agent (C
pd -1, 2, 3, 4 equivalents)・------・0.
18 Anti-stin agent (Cpd-5)---1-0.0
03 force puller dispersion medium (Cpd-6)・・・・・・-0
．． 03 coupler solvent (Solv-1, 2, 3 equivalents)...
・・・・・・0.12 4th layer (high sensitivity red-sensitive layer) Silver bromide (average grain size 0.60μ, size Distribution 15
%, octahedron) ・−・−0,14 gelatin
-・-・-1,00 cyan coupler (ExC-
1, 2, 3 (1:1). 2)・
・−・−・−・・0.30 Antifading agent (Cpd -1,
2, 3, 4 equivalents) ---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 Color mixing prevention agent (Cpd -7) −・・0.08 Color mixing prevention agent solvent (Solv-4, 5 equivalent) −・−・・・0.
16 Polymer latex (Cpd-8) ・-・-0,10 6th layer (low sensitivity green sensitive layer) Bromide 1 spectrally sensitized with green sensitizing dye (ExS-4)!
(Average particle size 0.25 μ, size distribution 8%, octahedral) -・-・-・0.04 green color enhancer dye (
Silver chlorobromide spectrally sensitized with ExS-4) (silver chloride 5 mol%, average particle size 0.40μ, size distribution 1O%, octahedral)...-0,06 Gelatin ------- -・0.80
Magenta coupler (ExM -1, 2, 3 equivalent) ---
・-・-=0.1) Anti-fading agent (equal amount of Cpd -9,26)・-・・-・
-・0.15 Anti-stinting agent (Cpd -10,1), 12,13 in a ratio of 10:7:1') -----------0
,025 force puller dispersion medium (Cpd-6)...
・0.05 coupler solvent (Solv-4,6 equivalent)-・
・・・-0.15 7th layer (high-range green sensitizing N) Silver bromide spectrally sensitized with green sensitizing dye (ExS-4)
Average particle size 0.65μ, size distribution 16%, octahedral) -...--0,1O gelatin ・
------・0.80 magenta coupler (ExM −
1,'2. 3 equivalents)...0.1) Anti-fading agent (Cpd -9,26 equivalents)...0
．． 15 Stin inhibitor (Cpd-10, 1), 12, 13 in 1
0 near:7:1 ratio)---0.025 force puller dispersion medium (Cpd-6)---0.05 coupler solvent (Solv-4,6 equivalent)--- -----・0.15 8th layer (middle layer) 9th layer (yellow filter layer) same as 5th layer Yellow colloid i (particle size 100)・---
--・・0.12 Gelatin −・−・・0.70 Color mixture prevention agent (Cpd -7) −・−・・−0,03 Color mixture prevention agent solvent (Solv −4, 5 equivalent) −・・−・0.
10 Polymer latex (Cpd-8)・−・−・0.07
10th layer (middle layer) Same as 5th layer 1) 7! (Low-sensitivity blue-sensitive layer) Silver bromide spectrally sensitized with blue mulching dye (ExS -5,6) (average grain size 0.40μ, size distribution 8%, octahedron) ・-・・-0, 07 Blue sensitizing dye (
Silver chlorobromide (silver chloride 8 mol%, average grain size 0.60μ, size distribution 1) spectrally sensitized with ExS-5,6)
%, octahedron) --- 0.14 Gelatin --- 0.80 Yellow coupler (ExY-1, 2 equivalents) --- = 0.35 Antifading agent (Cpd -14) --- −・・・−・0
．． 10 Stain inhibitor (Cpd-5, 15 in a 1:5 ratio)---0.007 Coupler dispersion medium (Cpd-6)---0.05
Coupler solvent (Solv-2) ------0,10
12th layer (high-sensitivity front window layer) 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 a 1:5 ratio) ------- 0.007 Coupler dispersion medium (Cpd -6) -0,0
5 coupler solvent (Solv-2) -----0,1
0 13th layer (ultraviolet absorbing layer) Gelatin ----1.00 Ultraviolet absorber (Cpd -2,4,16 equivalent) ---0,5
0 Color mixing prevention agent (Cpd -7,17 equivalent) ----0,
03 Dispersion medium (Cpd -6) --...0.0
2 UV absorber solvent (Solv-2,7 equivalent)...
-...-0,08 Anti-irradiation dye (Cpd -18°19.2
0.21.27 in 10:10:13:1510 ratio)
・・・・−・0.05 No. 141j (protective layer) Fine grain silver chlorobromide (silver chloride 97 mol%, average size 0.1
μ) −−−−−−・0.03 Acrylic modified copolymer of polyvinyl alcohol (molecular weight 50
．． 000 ) ・-・-= 0.01 polymethyl methacrylate particles (average particle size 2.4 μ) (and silicon oxide (average particle size 5 μ) equivalent amount
−・・・・−0,05 gelatin
-・・・-・1.80 Gelatin hardening agent (H-1, H-
2 equivalents) -------1.0.18 15th layer (back layer) Gelatin ---2.50
Ultraviolet absorber (Cpd -2, 4, 16 equivalent)・-・-
0,50 dye (equal amounts of Cpd-18, 19, 20, 21, 27)
・-・-・-0,06 16th layer (back protective layer) Polymethyl methacrylate particles (average particle size 2.4
μ) and silica hydrogen oxide (average particle size 5μ) equivalent amount
・・・・・・-= 0.05 gelatin
-・・・-・-・2.00 Gelatin hardening agent (H-1, 8-2 equivalent)・・・−・・0.14 How to make emulsion EM-1 Add an aqueous solution of potassium bromide and silver nitrate to gelatin Added to the aqueous solution simultaneously at 75°C for 15 minutes with vigorous stirring,
Octahedral silver bromide grains with an average grain size of 0.35 μm were obtained. In this case, 0.3 g of 3゜4-dimethyl-1,3 per mole of silver
-Thiazoline-2-thione was added. 1 silver in this emulsion
6 μ per mole of sodium periosulfate and 7 μ per mole of chloroauric acid (
Chemical aggravation treatment was carried out by sequentially adding tetrahydrate salt and heating at 75° C. for 80 minutes. Using the thus obtained grains as cores, they were further grown in the same precipitation environment as the first time, and finally an octahedral monodisperse core/shell silver bromide emulsion with an average grain size of 0.7μ was obtained. The coefficient of variation was approximately 10%. To this emulsion, 1.5 rvt of sodium thiosulfate and 1.5 μg of chloroauric acid (tetrahydrate) were added per mole of silver, and the emulsion was heated at 60°C for 60 minutes to carry out a chemical sensitization treatment, and the internal latent image type halogen A silver oxide emulsion was obtained.

Each photosensitive layer contains ExzK-1 and ExzK- as nucleating agents.
2 was used in an amount of 10-'' and 10-2% by weight, respectively, based on silver halide, and Cpd-22 was used as a nucleation accelerator in an amount of 10'' and 10-2% by weight, respectively. Further, in each layer, Alkanol
was used. (Cpd-23, 24, 25) was used as a stabilizer in the silver halide and colloidal silver containing layers. This sample was designated as the sample number. The compounds used in the examples are shown below.

xS-1 xS-2 xS-3 SUsNa :1) U3-xS
-4 -10 Cpd-1) Cpd-12 r〃 し2 Cpd-13 0M Cpd-14 Cpd-15 H Cpd-16 Cpd-17 ON il Cpd-18 Cpd-19 SOJ 503K pd-20 Cpd-21 Cpd-22 Cpd -23 H Cpd-24 H Cpd-25 Pd-27 XC-1 I XC-2 EXC-3 EXM-1 EXM-2 EXM-3 CHl ■ XY-1 rθ XY-2 Cθ 5olv -1 di(2-ethylhexyl ) Sebacate 5 olv-2) Linonyl phosphate 5 olv 3 Di(3-methylhexyl) phthalate 5 olv-4) Licrisyl phosphate Sol Sea 5
Dibutyl phthalate 5olv 6) Lioctyl phosphate Sol Sea 7 Di(2-ethylhexyl) phthalate H-1), 2-bis(vinylsulfonylacetamide)
Ethane H-24,6-dichloro-2-hydroxy-1,3,5
-) riazine Na salt ExZK -17-(3-ethoxythiocarbonylaminobenzamide)-9-methyl-10-promgyl-1.2,3.4-tetrahydroacridinium trifluoromethanesulfonateExZK-22[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 or more The sample prepared in this manner was designated as 201.

Next, the cyan coupler used for the third and fourth layers! XC-
A sample 202 was prepared by replacing all of the amounts of compounds 1, 2, and 3 with the cyan coupler (1) of the present invention in equimolar amounts.

Cyan coupler (5) instead of cyan coupler (1).

Samples 203 to 207 were prepared in the same manner as sample 202 except that +6), (9), Ql, and Qη were used.

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

When the spectral absorption of the developed sample was measured,
Samples 202 to 207 using cyan couplers of the present invention exhibited much sharper spectral absorption characteristics than sample 201 using cyan couplers other than the present invention.

Color development 80 seconds 38℃ 81 300m
l/rd bleach fixing 40〃33〃3〃300〃washing (1) 40# 33# 3#
-Water wash (2) 40"33# 3 -Water wash (3) 15" 33〃0.5〃320
〃Drying 30〃80〃 The method of replenishing the washing water is to replenish it to the washing bath (3) and
A so-called countercurrent replenishment system was adopted in which the overflow liquid of step 3) was led to the washing bath (2), and the overflow liquid of the washing bath (2) was led to the washing bath (1). At this time, the amount of bleach-fixing solution brought into the washing bath (1) from the bleach-fixing bath using the fluorescent material is 35 mj! /m, and the ratio of the amount of washing water replenishment to the amount of bleach-fix solution brought in was 9.1 times.

The composition of each treatment liquid was as follows.

Ullll Two-component diamine tetra 0.5g 0.5g
Kismethylene phosphonate diethylene glycol 10mj' 10m
1 Benzyl alcohol 12. Otsll 1
4.4 tsll potassium bromide 0.5
2g - Sodium chloride 0.06g
-Sodium sulfite 2.4 g 2.
9 gN,N-diethylhydro 4.0 g
4.8 g xylamine triethylenediamine (1,4,0 g 4.8 g
4-diazabicyclo[2°2.2]octane) 3-methyl-4-amino-5,6g 6.6 gN
-Ethyl-N-(β-methanesulfonamidoethyl) Aniline sulfate potassium carbonate 27.0 g 25.
0 g optical brightener (diamino) 1.0 g
1.2 g stilbene type) pH (25°C) 10.50 1
0.80 ethylenediaminetetraacetic acid, 4.0 g The same disodium dihydrate ethylenediaminetetraacetic acid, 46.0 gFe(II
I) ・Ammonium・Ammonium thiosulfate dihydrate 155mj! (700g
/1) p-Toluenesulfine 20.0 g Sodium acid sodium bisulfite 12.0 g Ammonium bromide 50.0 g Ammonium nitrate 30.0 g Add water to 1000 ml pH (25°C)
6.20 Washing water Both the mother liquor and the replenisher were filled with tap water and an H-type acidic cation exchange resin (Amberlite IR-120B, manufactured by Rohm and Haas) and an OH-type anion exchange resin (Amberlite IR-400, manufactured by Rohm and Haas). Water is passed through the hotbed column to increase the concentration of calcium and magnesium ions to 3■/! The following treatment was carried out, followed by the addition of 20 g/It of sodium isocyanurate dichloride and 1.5 g/II of sodium sulfate. The pl+ of this liquid is 6.
It was in the range of 5 to 7.5.

Example 5 On a subbed cellulose triacetate film support,
Sample 301, which is a multilayer color light-sensitive material, was prepared by coating each layer having the composition shown below with heavy nitrogen.

(Photosensitive layer composition) The numbers corresponding to each component indicate the coating amount expressed in g/d units, and for silver halide, the coating amount is expressed in terms of silver. However, for sensitizing dyes, silver halide 1 in the same layer
The coating amount is expressed in moles.

(Sample 101) 1st layer (antihalation N) Black colloidal silver Silver 0.18 Gelatin 1.40 2nd layer (middle N) 2.5-di-t-pentadecylhydroquinone 0.18EX-
10,07 E 1 red-sensitive emulsion layer) Emulsion A 0.25 Emulsion B
Silver 0.25 sensitizing dye T
6.9 XIO'''sensitizing dye n
1.8 Xl0-' Exacerbating Pigment III 3. I Xl0-'E
X -20,33S E Dye II 1.4 Xl0-' Sensitizing dye m 2.3 xlO'''
4EX -20,400 EX -30,050 EX -100,015 HB S -10,060 Gelatin 1.30 No. 5N
(Third red emulsion N) Emulsion D 1.60 Sensitizing dye 1 5.4 Xl0-' Sensitizing dye n 1.4 Xl0-' Sensitizing dye I [[2,4Xl0-' E X -30, 010 E X -40,080 E X -20,097 HB S -10,22 HB S -20,10 Gelatin 1.63 6th layer (middle layer) E .80 7th
Fj (1st green emulsion N) Emulsion A 0.15 Emulsion B
SI O,15 sensitizing dye V 3. OXl0-'sensitizing dyevit, oxio-'sensitizing dye■ 3.8 Xl0-'E
X -60,260 EX -10,021 EX -70,030 EX -80,025 HB S -10,100 8B S -30,010 Gelatin 0.63 No.
i! (Second green-sensitive emulsion layer) Emulsion C silver 0.45 Multiplying dye V' 2. lX10-
'Sensitizing dye Vl 7. OXl0
-'Sensitizing dye ■ 2.6 Xl0
-'E X -60,094 E X -80,018 E .2 Enhancing dye V 3.5 Xl0-' Sensitizing dye Vl 8. Oxto-S enhancement dye ■ 3. OXl0-'E
X -130,015 EX -1)0,10Q EX -10,025 HB S -10,25 HB S -20,10 Gelatin 1.54 No. 10
]'! (Yellow filter layer) Yellow colloidal silver
Silver 0.05EX -50,08 HB S -10,03 Gelatin 0.95 1st)
Layer (first blue-sensitive emulsion layer) Emulsion A 0.08 Emulsion B
Silver 0.07 emulsion F
Silver 0.07 sensitizing dye■
3.5 xlO-'EX-90,
721 EX -80,042 HB S -10,28 Gelatin 1.10 No. 12
Layer (second blue-sensitive emulsion layer) Emulsion G Silver 0.45 Sensitizing dye■ 2. I Xl0-'EX-
90,154 EX -100,007 HB S -10,05 Gelatin 0.78 No. 13
Layer (third blue emulsion layer) Emulsion H silver 0.77 Sensitizing dye ■ 2.2 Xl0-'
EX -90,20 HB S -10,07 Gelatin 0.69 No. 14
71 (First protective layer) Emulsion I Silver 0.5U -4
0,1) U -50,17 HB S -10,05 Gelatin 1.00 No. 15
Layer (second protection layer) Polymethyl acrylate particles (diameter approx. 1.5 urn) 0
．． 54S -10,20 Gelatin 1.20 In addition to the above components, gelatin hardening agent H-1 and a surfactant were added to each layer.

EX-1 ShiE EX-2 H (t)CJ*0CNH EX-3 H EX-4 H EX” C6H+5(n) ■ EX-5 EX-7 EX-8 EX-9 EX-10 H ■ H3 EX- 1) Shiy EX-12 czusosoρ EX-13 Shi2 CI! (t)cn++q U-3 (t)CJI* BS-2 Di-n-butyl phthalate B5-3 Sensitizing dye I (cnz) 4sO30 Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ HH CH2=CI-SO □-CHz C0NHCHzCH
z=CI-5ow-CHz-CONH-CHz The sample prepared in the above manner was designated as 301.

Next, the cyan couplers of the present invention (
A sample 302 was prepared by replacing the same moles of each layer with 1).

Cyan coupler (5) instead of cyan coupler (1)
.

(6), (91,QQ, (Samples 303 to 307 were each produced in the same manner as in the case of sample 302 except that ln was used.

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

When the spectral absorption of the developed sample was measured,
Samples 302 to 307 using cyan couplers of the present invention exhibited extremely sharper spectral absorption characteristics than sample 301 using cyan couplers other than the present invention.

Processing process amount *Replenishment amount: per 1m length of 35wm wide photosensitive material.

(Color developer) Mother solution (g) Replenisher (g) Hydroxyethylimino 5.0 6.0 Sodium sulfite diacetate 4.0 3.0 Potassium carbonate 30.0 37.0 Potassium bromide 1.3 0.5 Potassium iodide 1.2■ -Hydroxylamine 2.0 3.6 Sulfate 4- [N-ethyl-1,0X10-" mol 1.
Add 3X10-”mol N-β-hydroxyethylaminoco-2-methylaniline sulfate solution 1.ON 1.0
βp■ 10.00 10
．． 15 (Bleach solution) Mother liquor (g) Replenishment solution axis) 1.3-diaminopropane 130 190 acid ferric acetate complex salt 1,3-diaminopropane 3.0 4.0 Tetraacetic acid ammonium bromide 85 120
Acetic acid 5070 Ammonium nitrate 3040 Add water
1.0ffi 1. Oj! ! pH 4,3 pH 3,5 pH adjustment with acetic acid and ammonia (fixer) Mother liquor (g) Replenisher (g) 1-Hydroxyethylidene 5.0 ? ,0
-1.1-diphosphonic acid ethylene diamine acid acetic acid a O,5Q,7 disodium salt Sodium sulfite 10,0 12.
0 Sodium Bisulfite 8.0 10.
0 Ammonium thiosulfate 170. Orm l
200. Ova It aqueous solution (700g/N) Rodan ammonium too, o iso
,.

Thiourea 3.0 5.03
．． 6-Sythia 1.8- 3.0 5.0 Add octanediol water ゛ 1. Oll, OJI
Add ammonia acetate to pH 6,56,7 (stable solution) mother liquor, replenisher common formalin (37%) 1.2 ml)
5-chloro-2-methyl-4-6,0 ■ Isothiazolin-3-one 2-methyl-4-iso 3.0 ■ Thiazoline 3
-on surfactant 0.4 ethylene glycol 1.0 water added
1.01 pH 5,0-7,0 Example 6 Preparation of Sample 401 A multilayer color angry light material consisting of each layer having the following composition was prepared on an undercoated cellulose triacetate film support with a thickness of 127μ. It was designated as sample 401.

1st layer: antihalation layer - black colloid 0.25 g/
rd ultraviolet absorber U-10,04g/rrr ultraviolet absorber U-20,1g/rd ultraviolet absorber U 3 0.1 g/rr
l High boiling point organic solvent 0-1 0.1cc/nf
Gelatin layer containing (dry film thickness 2μ) 2nd layer: Intermediate layer A -142,5*/n? Compound H-10.05g/I Emulsion A Silver I O.05g/
ml high boiling point organic solvent 0 2 0.05cc/
Gelatin layer containing rrl (dry film thickness 1μ) 3rd layer: 1st red-light emulsion layer
Monodisperse silver iodobromide emulsion spectrally sensitized with 2■/d)
Amount of silver - 0.15 g/rrr (contains iodine! 4 mol%, average particle size 0.20 μ, coefficient of variation related to particle size (hereinafter simply referred to as variation coefficient) 12%) Aggravation dye S - 1 (0,51■/, rrf) and S-2
Monodisperse internal latent image type silver iodobromide emulsion spectrally sensitized at (0,03■/d) Weight: 0.20 g/rd (Iodine content: 4
Mol%, average particle size 0.40μ, distance from latent image to particle surface 100 people.

Coefficient of variation 14%) Emulsion B Silver amount---0.05g
/ IA-10,60■/d Compound H60,01g/rrl Coupler C-10,13g/rrl' Coupler C-20,033g/rd Coupler C-100,1g/rrl High boiling point organic solvent 0 2 0.02 cc /r
Gelatin N containing ri (dry 1! thickness 0.7μ) 4th layer:
Second red-sensitive emulsion layer sensitizing dyes S-1 (1,1 /d) and 5-2 (0,04
Monodisperse silver iodobromide emulsion spectrally sensitized with
Silver amount----0,53g/rt? (
Iodine content 3 mol%, average particle size 0.55 □ μ,
Coefficient of variation 16%) A -40,02■/- Coupler 〇-10,40g/rd Coupler C-20,07g/rrr Coupler C~9 0.05 glrd
High boiling point organic solvent 0-2 0.22 cc/
Gelatin layer containing m (dry film thickness 1.7μ) 5th layer: 3rd layer
Red-light emulsion layer sensitizing dyes S-1 (1,1 qr/m) and S-2 (0,0
41) Monodisperse silver iodobromide emulsion spectrally sensitized at 1r/m) Silver amount: -0.53g/rd(
(Iodine content: 2 mol%, average particle size: 0.07μ, coefficient of variation: 17%) A-71, 2 mg/rri Coupler C-60, 35 g/m Coupler C-80, 20 g/rrr High-boiling organic solvent 0-2 0. 06 cc/+
Gelatin layer containing d (dry film thickness 1.8μ) 6th layer: Intermediate layer A-1010■/d A-1) 5tri/rrr Compound H-10, 1glrd High boiling point organic solvent 0-2 0.1 cc/ rr
gelatin N containing r (dry film thickness 1μ) 7th layer: 1st green emulsion layer sensitizing dye S-3 (2,2*/rrr) and S-4 (1,
Monodisperse silver iodobromide emulsion spectrally sensitized at 0■/d)
1! Amount・・・・・・0.5 glcd (Iodine content 3 mol%, average grain size 0.35μ, coefficient of variation 19%) Emulsion B fl! Amount-・-・〜・0.0
5g/mA -50,12mg/rrl Compound H-60,01g/rrr Compound H-50,005g/rrr Coupler C-30,27g/d Gelatin layer containing high-boiling organic solvent O-20,05cc/rd (dried) Film thickness 0.7 μ) 8th calendar: 2nd green emulsion layer sensitizing dye S-3 (0.29 g/rr?) and S-4 (0
, 3■/nf) spectrally sensitized monodisperse internal latent image type silver iodobromide emulsion primate!・------...0.5 glcd (Iodine content 2.5 mol%, average particle size 0.5 μ, coefficient of variation 18%, distance from latent image to particle surface 100 people) A -60,2 ■/d Compound H-60,01g/rr? Coupler C-30,2glcd High boiling point organic solvent 0-2 0.13 cc/r
Gelatin N containing d (dry film thickness 1.7μ) 9th layer: 3rd layer
Green-sensitive emulsion layer sensitizing dyes S-3 (0,9*/rrr> and S-4 (0,
31) Tabular silver iodobromide emulsion spectrally sensitized with IIr/rrr) Silver amount: 0.5 g/
nl (average thickness of 0 particles, 0.10μ, in which particles containing 12 mol% of iodine and having a diameter/thickness ratio of 7 or more occupy 50% of the projected area of all particles) A-21,5■/d Coupler〇- 40.2g/nf 1 solvent with high boiling point 0-2 0.03 cc/r
Gelatin layer containing d (dry film thickness 1.7μ) No. 107!
: Intermediate layer compound H-40, 1g/rr? Gelatin layer containing high boiling point organic solvent 0-2 0.1 cc/m (dry film thickness 0.05μ) 1st) layer: Yellow filter layer Yellow colloidal silver Silver amount - 0,12 g/
Compound A-150,22g/Compound resistant H-10,02g/mr Compound H-20,03glrd High-boiling organic solvent 0-2 0.04 cc/n
Gelatin layer containing l (dry film thickness lμ) 12th N: First blue emulsion layer Tabular silver iodobromide emulsion spectrally sensitized with sensitizing dye S-5 (1.0 g/rd) Silver amount -・...0.6 g/rd (Grains with an iodine content of 3 mol% and a diameter/thickness ratio of 7 or more occupy 50% of the projected area of all grains. Average grain thickness o, ioμ) Emulsion A Silver amount 0.1 g/mA
-70,5■/d Coupler C-50,5glnr Gelatin layer containing high boiling point organic solvent 0-2 0.1 cc/m (dry film thickness 1.5μ) 13th layer: 2nd blue-sensitive emulsion layer sensitization Tabular silver iodobromide emulsion spectrally sensitized with dye s-5 (2,0 g/m) Silver amount -1,1 g/cd (iodine content 2
．． Particles with a diameter/thickness ratio of 5 mole percent and a diameter/thickness ratio of 7 or more account for 50% of the total particle projected area. Average thickness of particles 0.15
μ) A-1210tvz/rr? Coupler C-71, 2g/rrr Coupler C-80, 2g/nf High boiling point organic solvent 0-2 0.07 cc/c
Gelatin layer containing d (dry film thickness 3μ) 14th layer: 1st layer 8iN A-130,10■/d Ultraviolet absorber U-10,02g/rrf Ultraviolet absorber U-20,03g/rrr Ultraviolet absorber tJ-30
,03g/rrrUV absorber U-40,29glr
d High boiling point organic solvent 0 2 0.28cc/r
Gelatin layer containing rr (dry film thickness 2μ) 15th layer: Fine grain silver iodobromide emulsion covered with the surface of the second protective layer Silver amount: 0.1 g/rrl (iodine content if mol) %, average particle size 0.06μ) A-610+ng/n? Polymethyl methacrylate particles 0.1 g/rrr
(Average particle 1.5μ) Gelatin N containing A-30.2g/rd A-91.0μ/d (dry film thickness 0.8μ) In addition to the above composition, each layer contained antifoggant A-16. , gelatin hardener H
-3, and a surfactant were added.

Preparation of Emulsions A and B A silver bromide cubic emulsion with an average grain size of 0.15 μm was prepared by the Chondrald double jet method and fogged (formed into an emulsion) with hydrazine and a gold complex under low pAg.

Emulsion B was obtained by shelling silver bromide to a thickness of 250 mm on the surface of emulsion A thus prepared.

The compounds used to prepare the samples are shown below.

C-10H CH3 ■ C-601( COOC,Hy (iso) H H OOH t-C4H* H t-CaH* H t-CJ* H-1 H H H H CH2=CH5O□CHzCONHCHzCO2,CH
30□CHzCONHCHzH H (C!Iz) asOx O S-2 O CJs COxCH-COx A-8 C*F+tSO□NCHzCOOK CJfuCJs L;zHsA
-12 A-13 SO, Na H HI The sample prepared as above was designated as 401.

Next, cyan coupler C used for the third, fourth, and fifth layers.
Sample 402 was prepared by replacing the entire amounts of -1, C-2, C-6, and C-8 with the cyan coupler (1) of the present invention in equal moles in each layer.

Cyan coupler (5) instead of cyan coupler (1)
, (6), (9), (16), and (17) are used.
Samples 403 to 407 were prepared in the same manner as sample 402.
was created.

The obtained samples 401 to 407 were exposed through a red filter and then subjected to the following development treatment.

When the spectral absorption of the developed sample was measured,
Samples 402 to 407 using cyan couplers of the present invention exhibited extremely sharper spectral absorption characteristics than sample 401 using cyan couplers other than the present invention.

几工、ll・′
Second development: 6 minutes, washing with water at 38℃
2〃 3B-Reverse 2〃
38〃Color development 6〃 38〃Adjustment 2〃 38〃Bleaching
6〃 38〃Settlement 4〃
38〃Washing 4〃 38〃Stable
1〃25〃The composition of each treatment liquid was as follows.

Xing Erli Yeongkei Nitrilo-N,N,N-)limethylene 2.0g Phosphonic acid pentasodium salt Sodium sulfite 30g Hydroquinone monosulfone H20g Potassium potassium carbonate 33 g1
-phenyl-4-methyl-4-human 2. Og roxymethyl-3-pyrazolidone Potassium bromide 2.5g Potassium thiocyanate 1.2g Potassium iodide 2.0g
10001) IN, pH 9,
60 pH was adjusted with hydrochloric acid or potassium hydroxide.

Inverted hill Nitrilo-N,N,N-trimethylene 3.0 g Phosphonic acid pentasodium salt Stannous chloride dihydrate 1. Ogp-aminophenol 0.1 g Sodium hydroxide 8 g Glacial acetic acid
15mA'U more
10100O! pH 6.00 pH was adjusted with hydrochloric acid or sodium hydroxide.

2ヱL! (!JL Nitrilo-N,N,N-trimethylene 2.0 g Phosphonic acid pentasodium salt Sodium sulfite 7.0 g Trisodium phosphate dodecahydrate 36 g Potassium bromide 1.0 g Potassium iodide 90 g Water Sodium oxide 3.0 g Citrazic acid
1.58N-ethyl-N-(β
-Methanesulfo 1) -3-methyl-4-aminoaniline sulfate 3.6-cythiaoctane-1.8-di 1.0g All 7 was added to 1000mlpH
1), 80 pH was adjusted with hydrochloric acid or potassium hydroxide.

Star! Wataru Ethylenediamine Tetraacetic acid/Sodium 8. Ogmu salt・
Sodium sulfite dihydrate 12 gl-
Add thioglycerin 0.4mi' loOQmfpH6,2
0 pH was adjusted with hydrochloric acid or sodium hydroxide.

Bleach solution ethylenediamine 4-acetic acid 2-sodium 2. Ogmu salt・
Dihydrate ethylenediamine tetraacetic acid/Fe(III) 120
g ammonium dihydrate potassium bromide 100 g ammonium nitrate 10 g water
Et 10100O! pH5
, 70 9H was prepared with hydrochloric acid or sodium hydroxide.

Add 80 g of sodium thiosulfate, 5.0 g of sodium sulfite, and 5.0 g of sodium bisulfite.
1000m100O6,6Q p1) was adjusted with hydrochloric acid or aqueous ammonia.

Genjo Coffin Holimarin (37%) 5.0mff
1 Polyoxyethylene ~ p-monononyl 0.5ml phenyl ether (average degree of polymerization 10) Add water to 10100O!
No pH adjustment

[Brief explanation of the drawing]

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

Claims (2)

[Claims] (1) A cyan dye-forming coupler represented by the following general formula [I]. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (In the formula, R_1 represents an aliphatic group, aromatic group, or heterocyclic group; R_2 represents a group or atom that can be substituted for the pyridine ring; X is hydrogen represents an 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 dissociative 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 the two R_2 may form a ring; when n is 1 or more, R_1 and R_2 may form a ring. may be; at least one of R_1, R_2 and X,
In the general formula [I], R_1, R_2, or X may contain one or more pyridyl residues as a substituent; Another R_2 can be bonded to the nitrogen atom of the pyridyl ring if it is bonded to the ortho or para position to the nitrogen atom of the ring, in which case the hydroxyl group bonded to the ortho or para position is It can also become a ketone due to tautomerism. ) (2) A silver halide photographic material containing at least one cyan dye-forming coupler represented by formula [I] according to claim (1).