JP2726779B2 - Yellow dye-forming coupler and silver halide color photographic light-sensitive material containing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel acylacetamide type yellow dye-forming coupler and a silver halide color photographic light-sensitive material containing the same.

[0002]

2. Description of the Related Art A silver halide color photographic light-sensitive material reacts with an oxidized aromatic primary amine developing agent and a dye-forming coupler (hereinafter referred to as a coupler) by developing a color after the exposure of the material. Thus, a color image is formed.

Generally, in this method, a color reproduction method based on a subtractive color method is used, and in order to reproduce blue, green, and red, yellow, magenta, and cyan color images having complementary colors are formed. An acylacetamide coupler and a malondianilide coupler are used as a yellow dye-forming coupler (hereinafter referred to as a yellow coupler) for forming a yellow image, and a 5-pyrazolone coupler and a pyrazolotriazole coupler are used as a magenta coupler for forming a magenta image. A phenol coupler and a naphthol coupler are generally used as a cyan coupler for forming a cyan image.

The yellow dye, magenta dye and cyan dye obtained from these couplers have a silver halide emulsion layer or a silver halide emulsion layer having a color sensitivity to radiation which is complementary to the radiation absorbed by the dye. It is generally formed in an adjacent layer.

By the way, yellow couplers, particularly acylacetamide couplers such as benzoylacetoanilide couplers and pivaloylacetoanilide couplers are generally used for image formation. The former generally has a high coupling activity with an oxidized aromatic primary amine developing agent during development, and has a large molecular extinction coefficient of a yellow dye to be produced. It is mainly used for negative films, and the latter is mainly used for color paper and color reversal films because of its excellent spectral absorption characteristics and fastness of yellow dye.

[0006]

In the hue of a yellow image obtained from a yellow coupler, a hue having a sharp absorption at a long wavelength end, in other words, a hue having a small unnecessary absorption in a green light region and a high color purity is desired. .

On the other hand, it is desired that the yellow image has a sufficient absorbance in the blue light region (about 400 to 500 nm) and has a filter effect over the entire blue light region. Therefore, a yellow dye which gives a spectral spectrum with a large half width in a spectral absorption spectrum is desirable. G. FIG. H. Brown et al. A
m. Chem. Soc, 79, 2919 (1957) discloses that a yellow azomethine dye derived from an acylacetoanilide-type yellow coupler is substituted with a halogen atom, a methoxy group, a dimethylamino group or a phenoxy group at the ortho position of the anilino group. It is shown that the sharpness at the long wavelength end is improved and sharp spectral absorption is obtained.

[0008] Since then, the technique of substituting a chlorine atom at the ortho position of the anilino group has been widely applied to benzoylacetanilide type yellow couplers and pivaloylacetoanilide type yellow couplers, and most of them have been used for color negative films, color reversal films and color papers. It is used in any photosensitive material.

However, the half width in the spectral absorption spectrum of the yellow image is not sufficiently large.
Improvement was desired.

Therefore, an object of the present invention is to provide a spectral absorption characteristic of a yellow image in which the absorption at the long wavelength end is good.
Another object of the present invention is to provide a yellow coupler which gives a yellow image having a sufficiently large half width.

[0011]

SUMMARY OF THE INVENTION The object of the present invention is to provide an N-
This can be achieved by a (8-quinolyl) -acyl acetamide type yellow dye-forming coupler and a silver halide color photographic light-sensitive material containing the same.

Hereinafter, the N- (8-quinolyl) -acyl acetamide type yellow dye-forming coupler of the present invention (hereinafter referred to as the yellow coupler of the present invention) will be described in detail.

The yellow coupler of the present invention is preferably represented by the following general formula (1).

[0014]

Embedded image (Wherein, R ¹ is an aryl group, an alkyl group, or an amino group, R ² is a group that can be substituted on a quinoline ring, X is a hydrogen atom or a coupling-off group, and m is an integer of 0 to 6. However, when m is plural, plural R ² may be the same or different.) Here, examples of R ² include a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, and an alkoxycarbonyl group. Group, aryloxycarbonyl group, carbonamido group, sulfonamido group, carbamoyl group, sulfamoyl group, alkylsulfonyl group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, alkoxysulfonyl group,
There are acyloxy group, nitro group, heterocyclic group, cyano group, acyl group, amino group, imide group, alkylsulfonyloxy group, arylsulfonyloxy group, carboxyl group, sulfo group, and hydroxyl group (hereinafter referred to as substituent group A). Examples of the leaving group X include a heterocyclic group, an aryloxy group, an arylthio group, an acyloxy group, an alkylsulfonyloxy group, an arylsulfonyloxy group, a heterocyclic oxy group, and a halogen atom, which are bonded to a coupling active site with a nitrogen atom. .

Here, when the substituent in the general formula (1) or below is an alkyl or contains an alkyl group, unless otherwise specified, the alkyl group may be a straight-chain, branched or cyclic, substituted or unsubstituted alkyl group. Or an alkyl group which may contain an unsaturated bond.

When the substituent in the general formula (1) or below is an aryl group or contains an aryl group, the aryl group is an optionally substituted monocyclic or condensed-ring aryl group unless otherwise specified. means.

When the substituent in the general formula (1) or below is a heterocyclic group or contains a heterocyclic group, the heterocyclic group is selected from O, N, S, P, Se and Te unless otherwise specified. Or a 3- to 8-membered optionally substituted monocyclic or fused ring heterocyclic group containing at least one heteroatom in the ring.

Hereinafter, each substituent in the general formula (1) will be described in detail.

R ¹ is preferably an aryl group having a total number of carbon atoms (hereinafter referred to as C number) of 6 to 30 (preferably 6 to 16) (for example, phenyl, 4-methoxyphenyl, 4-butoxyphenyl, 4-sec-butoxy). Phenyl, 4-chlorophenyl, o-tolyl, 4-dimethylaminophenyl, 2-acetamidophenyl, 1-naphthyl, 2-methoxyphenyl), C number of 4-36 (preferably 4-1)
6) alkyl groups (for example, t-butyl, 1,1-dimethylpropyl, 1-methylcyclopropan-1-yl, 1
-Ethylcyclopropan-1-yl, 1-methylcyclobutan-1-yl, 1-methylcyclopentan-1-yl, bicyclo [1.1.1] pentan-1-yl, bicyclo [2.1.1] Hexane-1-yl, bicyclo [2.2.1] heptan-1-yl, bicyclo [2.
2.2] Octane-1-yl, tricyclo [3.1.
1.0 ^3,6 ] heptan-6-yl, tricyclo [3.
3.0.0 ^3,7 ] nonan-3-yl, tricyclo [3.
3.1.0 ^3,7 ] nonan-3-yl, bicyclo [2.
1.0] pentan-1-yl, bicyclo [3.1.0]
Hexane-1-yl, bicyclo [4.1.0] heptane-1-yl, bicyclo [2.2.0] hexan-1-yl, bicyclo [3.2.0] heptane-1-yl, bicyclo [ 3.3.0] octan-1-yl) or an amino group having a C number of 0 to 30 (preferably 2 to 24) (for example, dimethylamino, pyrrolidino, piperidino, morpholino,
1-indolinyl, anilino, N- (2-chlorophenyl) amino, N- (2-methoxyphenyl) amino, N
-(2-chloro-5-dodecyloxycarbonylphenyl) aminophenyl).

R ² is preferably a halogen atom (F, C
l, Br, I), C number 1-30 (preferably 1-16)
Alkyl group having 1 to 30 (preferably 1 to 18) C, aryloxy group having 6 to 30 (preferably 6 to 24) C, and 2 to 30 (preferably 2 to 2)
0) an alkoxycarbonyl group, a C 7-30 (preferably 7-20) aryloxycarbonyl group, a C 1
~ 30 (preferably 2-24) carbonamido groups, C
A sulfonamide group having a number of 1 to 30 (preferably 1 to 24), an imide group having a C number of 4 to 30 (preferably 4 to 24),
Represents a nitro group or a cyano group.

M is preferably an integer of 0 to 4, more preferably an integer of 0 to 2. R ² is preferably substituted at positions 3, 4, 5 and 6 with respect to the quinoline ring.

X is preferably a hydrogen atom, a halogen atom,
An aryloxy group having 6 to 36 carbon atoms, an acyloxy group having 2 to 36 carbon atoms, a sulfonyloxy group having 1 to 36 carbon atoms, a heterocyclic group having a nitrogen atom having 2 to 36 carbon atoms, which is bonded to a coupling active site, A heterocyclic oxy group of the number 2 to 36, a C number of 6 to 36
Or a heterocyclic thio group having 2 to 36 carbon atoms.

X particularly preferably represents a heterocyclic group or an aryloxy group bonded to the coupling active site with a nitrogen atom.

When X represents a heterocyclic group, X is preferably a 5- to 7-membered monocyclic or condensed heterocyclic group which may be substituted, and examples thereof include succinimide, maleimide and Phthalimide, diglycolimide, pyrrole, pyrazole, imidazole, 1,2,4
-Triazole, tetrazole, indole, indazole, benzimidazole, benzotriazole, imidazolidine-2,4-dione, oxazolidine-2,4
-Dione, thiazolidine-2,4-dione, imidazolidine-2-one, oxazolidine-2-one, thiazolidine-2-one, benzimidazolin-2-one, benzoxazolin-2-one, benzothiazolin-2-one , 2-pyrrolin-5-one, 2-imidazoline-5
On, indoline-2,3-dione, 2,6-dioxypurine, parabanic acid, 1,2,4-triazolidine-
3,5-dione, 2-pyridone, 4-pyridone, 2-pyrimidone, 6-pyridazone-2-pyrazone, 2-amino-1,3,4-thiazolidine, 2-imino-1,3,4
-Thiazolidine-4-one, and these heterocycles may be substituted. Examples of the substituent of these heterocycles include a substituent selected from the above-mentioned substituent group A.

When X represents an aryloxy group, X preferably represents an aryloxy group having 6 to 30 carbon atoms;
It may be substituted with a group selected from the group of substituents mentioned above when X is a heterocyclic ring. Examples of the substituent of the aryloxy group include a halogen atom, a cyano group, a nitro group, a carboxyl group, a trifluoromethyl group, an alkoxycarbonyl group, a carbonamide group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group,
An arylsulfonyl group or a cyano group is preferred.

X is most preferably represented by the following general formula (2) or (3).

[0027]

Embedded image In the general formula (2), Z represents —O—CR ⁶ R ⁷ —, —S—
^{CR 6 R 7 -, - NR} 8 -CR 6 R 7 -, - NR 8 -N
^{R 9 -, - NR 8 -CO} -, - CR 6 R 7 -CR 10 R 11
- or -CR ¹² = CR ¹³ - represent. Where R ⁶ ,
R ^7, R ¹⁰ and R ¹¹ represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group or an amino group, R ⁸ and R ⁹
Represents a hydrogen atom, an alkyl group, an aryl group, an alkylsulfonyl group, an arylsulfonyl group or an alkoxycarbonyl group, and R ¹² and R ¹³ represent a hydrogen atom, an alkyl group or an aryl group. R ¹² and R ¹³ may combine with each other to form a benzene ring. R ⁶ and R ⁷ , R ⁷
And R ⁸ , R ⁸ and R ⁹ or R ⁶ and R ¹⁰ may combine with each other to form a ring (eg, cyclobutane, cyclohexane, cycloheptane, cyclohexene, pyrrolidine, piperidine).

Among the heterocycles represented by the general formula (2),
Particularly preferred is a compound of the formula (2) wherein Z is -OC.
^{R 6 R 7 -, - NR} 8 -CR 6 R 7 - or -NR ⁸ -
It is a heterocyclic group which is NR ⁹ —.

The heterocyclic group represented by the formula (2) has a C number of 2 to 30, preferably 4 to 20, more preferably 5 to 5.
~ 16.

[0030]

Embedded image In the general formula (3), at least one of R ³ and R ⁴ is a halogen atom, a cyano group, a nitro group, a trifluoromethyl group, a carboxyl group, an alkoxycarbonyl group, a carbonamide group, a sulfonamide group, a carbamoyl group,
It is a group selected from a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group and an acyl group, and the other may be a hydrogen atom, an alkyl group or an alkoxy group. R ⁵ represents a group having the same meaning as R ³ or R ^4, n represents an integer of 0 to 2. The C number of the aryloxy group represented by the general formula (3) is 6 to 30, preferably 6
~ 24, more preferably 6 ~ 15.

The coupler represented by the general formula (1) forms a dimer or a multimer which bonds to each other via a divalent or divalent or higher valent group at the substituent R ¹ , R ² or X. Is also good. In this case, the number of carbon atoms may be out of the specified range for each substituent.

When the coupler represented by the general formula (1) forms a multimer, a homo- or copolymer of an addition polymer ethylenically unsaturated compound (yellow color-forming monomer) having a yellow dye-forming coupler residue is a typical example. And preferably represented by the following general formula (4).

[0033]

Embedded image G _i in the general formula (4) is a repeating unit derived from the color forming monomer, a group represented by the general formula (5) shown by the following chemical formula 5, H _j is derived from the non-color forming monomer A group that is a repeating unit, i represents a positive integer, j represents 0 or a positive integer,
gi and hj each represents a weight fraction of G _i or H _j. Here when i or j is two or more, G _i or H
_j represents that it contains a plurality of types of repeating units.

[0034]

Embedded image In the general formula (5), R ¹⁴ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a chlorine atom, and A represents —CONH—, —C
OO- or a substituted or unsubstituted phenylene group, B represents a substituted or unsubstituted alkylene group, a phenylene group or an aralkylene group, L is -CONH-,
-NHCONH-, -NHCOO-, -NHCO-,-
OCONH-, -NH-, -COO-, -OCO-,-
CO -, - O -, - S -, - SO 2 -, - NHSO
₂ -, or represents a -SO ₂ NH-. a, b, and c are 0
Or an integer of 1. Q represents a yellow coupler residue obtained by removing one hydrogen atom from R ¹ , R ² or X of the compound represented by the general formula (1).

[0035] As the repeating units H oxidation product of an aromatic primary amine developing agent to give _j and uncoupled non-color forming ethylenic monomers are acrylic acid, alpha-chloro acrylic acid, alpha-alkyl acrylic acid (e.g. Methacrylic acid) amides or esters derived from these acrylic acids (e.g., acrylamide, methacrylamide, n-butylacrylamide, t-butylacrylamide, diacetoneacrylamide, methyl acrylate, ethyl acrylate, n-propyl acrylate,
n-butyl acrylate, t-butyl acrylate, i
so-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate,
n-butyl methacrylate and β-hydroxy methacrylate), vinyl esters (eg, vinyl acetate, vinyl propionate and vinyl laurate),
Acrylonitrile, methacrylonitrile, aromatic vinyl compounds (such as styrene and its derivatives such as vinyltoluene, divinylbenzene, vinylacetophenone and sulfostyrene), itaconic acid, citraconic acid,
There are crotonic acid, vinylidene chloride, vinyl alkyl ether (for example, vinyl ethyl ether), maleic ester, N-vinyl-2-pyrrolidone, N-vinyl pyridine and 2- and -4-vinyl pyridine.

Particularly preferred are acrylic esters, methacrylic esters, and maleic esters. The non-color-forming ethylene type monomer used here can be used in combination of two or more kinds. For example, methyl acrylate and butyl acrylate, butyl acrylate and styrene, butyl methacrylate and methacrylic acid, and methyl acrylate and diacetone acrylamide can be used.

As is well known in the field of polymer couplers, the ethylenically unsaturated monomer to be copolymerized with the vinyl monomer corresponding to the general formula (5) may be in the form of a copolymer to be formed, for example, a solid , Liquid, micellar and physical and / or chemical properties such as solubility (solubility in water or organic solvents), compatibility with binders of photographic colloid compositions such as gelatin, its flexibility It can be selected so that the properties, thermal stability, coupling reactivity with a developing agent, diffusion resistance in a photographic colloid, etc. are favorably affected.
These copolymers may be random copolymers or copolymers having a specific sequence (eg, block copolymer, alternating copolymer).

With respect to the yellow polymer coupler represented by the general formula (4), the sum of gi is 10% to 100%.
(Preferably 30% to 70%), and the sum of hj is 9
0% to 0% (preferably 70% to 30%).

The number average molecular weight of the yellow polymer coupler used in the present invention is usually on the order of thousands to hundreds of thousands, but oligomeric polymer couplers of 5,000 or less can also be used.

The yellow coupler used in the present invention is
A lipophilic polymer soluble in an organic solvent (eg, ethyl acetate, butyl acetate, ethanol, methylene chloride, cyclohexanone, dibutyl phthalate, tricresyl phosphate), but a hydrophilic polymer miscible with a hydrophilic colloid such as an aqueous gelatin solution. Or a polymer having a structure and properties capable of forming micelles in a hydrocolloid.

The yellow polymer coupler used in the present invention is obtained by dissolving a lipophilic polymer coupler obtained by polymerization of a vinyl monomer to give a coupler unit represented by the above general formula (5) in an organic solvent, into gelatin. It may be made by emulsifying and dispersing in the form of a latex in an aqueous solution, or may be made directly by an emulsion polymerization method.

A method for emulsifying and dispersing a lipophilic polymer coupler in the form of a latex in an aqueous gelatin solution is described in US Pat. No. 3,451,820, and emulsion polymerization is described in US Pat. Nos. 4,080,211 and 3,370, US Pat. No. 952 can be used.

Specific examples of each substituent in the general formula (1) are shown below. (I) Examples of R ¹ are shown below.

[0044]

Embedded image

[0045]

Embedded image (Ii) Examples of R ² are shown in Chemical formulas 8 and 9 below.

[0046]

Embedded image

[0047]

Embedded image (Iii) Examples of X are shown below.

[0048]

Embedded image

[0049]

Embedded image

[0050]

Embedded image

[0051]

Embedded image Specific examples of the yellow coupler of the present invention are shown in the following formulas 14 to 19, but the present invention is not limited to these.

[0052]

Embedded image

[0053]

Embedded image

[0054]

Embedded image

[0055]

Embedded image

[0056]

Embedded image

[0057]

Embedded image The yellow coupler of the present invention represented by the general formula (1) can be synthesized, for example, by a synthesis route shown in the following formula (20).

[0058]

Embedded image Here, 8-aminoquinolines a and β-ketoesters b can be synthesized by a conventionally known method.

Compound c is synthesized by reacting compounds a and b without solvent or in a hydrocarbon solvent. The reaction temperature is usually from 100 to 200C, preferably from 120 to 160C. When X is not H, compound e is synthesized by introducing a leaving group X after chlorination or bromination. Compound c in a solvent such as dichloroethane, carbon tetrachloride, chloroform, methylene chloride, tetrahydrofuran,
The compound is converted to a chloro-substituted product d with sulfuryl chloride, N-chlorosuccinimide or the like, or a bromo-substituted product d with bromine or N-bromosuccinimide. At this time, the reaction temperature is -20C to 70C, preferably -10C to 50C.

Next, the chloro-substituted or bromo-substituted product d and the leaving group protonated product HX are combined with methylene chloride, chloroform, tetrahydrofuran, acetone, acetonitrile, dioxane, N-methylpyrrolidone, N, N'-
In a solvent such as dimethylimidazolidin-2-one, N, N-dimethylformamide, N, N-dimethylacetamide, the reaction temperature is -20C to 150C, preferably -10C.
By reacting at 〜100 ° C., the coupler e of the present invention can be obtained. At this time, triethylamine, N
Bases such as -ethylmorpholine, DBU, tetramethylguanidine, potassium carbonate, sodium hydroxide, sodium hydrogen carbonate and the like may be used.

The following synthesis examples of the coupler of the present invention are shown below.

Synthesis Example 1 Synthesis of Illustrative Coupler (1) 5.9 g of 8-aminoquinoline and 11 g of ethyl pivaloyl acetate were mixed and heated and stirred at 140 ° C. for 4 days in a nitrogen stream. After distilling off ethyl pivaloyl acetate under reduced pressure, 5.5 g of the objective exemplified coupler (1) was obtained by crystallization from a mixed solvent of n-hexane and ethyl acetate.
Obtained. The structure of this compound is represented by ¹ HNMR spectrum, M
It was confirmed by ASS spectrum and elemental analysis. The melting point of this compound was 79 to 80 ° C.

Synthesis Example 2 Synthesis of exemplified coupler (3) 11.6 g of 8-aminoquinoline and 23.8 of ethyl 1-methylcyclopropan-1-ylcarbonyl acetate
g were mixed and heated and stirred at 140 ° C. under reduced pressure with an aspirator. Four hours later, ethyl 1-methylcyclopropan-1-ylcarbonyl acetate was distilled off under reduced pressure, and then methanol was added for crystallization to obtain 15.6 g of the desired exemplified coupler (3). The structure of this compound was confirmed by ¹ HNMR spectrum, MASS spectrum and elemental analysis. The melting point of this compound was 137.
138 ° C.

Synthesis Example 3 Synthesis of Illustrative Coupler (5) 15 g of 8-hydroxy-5-nitroquinoline obtained by nitration of 8-hydroxyquinoline, 15 ml of ethanol and 110 ml of 28% aqueous ammonia were placed in an autoclave and placed in an autoclave.
Stirred at 80 ° C. for 5 hours. After leaving overnight, it is taken out of the autoclave, filtered and washed with water to give 8-amino-5.
11.5 g of -nitroquinoline were obtained.

8-amino-5-nitroquinoline 11.5
g and 31.4 g of ethyl pivaloyl acetate,
The mixture was stirred at 150 ° C. for 5 hours under reduced pressure using an aspirator. After cooling the reaction solution, 10 g of activated carbon and 200 ml of ethyl acetate were added, and the mixture was stirred for 30 minutes, filtered, and the filtrate was concentrated. By crystallization with addition of n-hexane, N- (5-nitro-
15 g of 8-quinolyl) -pivaloylacetamide was obtained.

15 g of N- (5-nitro-8-quinolyl) -pivaloylacetamide was iron-reduced with 20 g of iron powder, 20 ml of water and 300 ml of isopropanol, filtered, and concentrated to give N- (5-amino-8-). 12 g of (quinolyl) -pivaloylacetamide were obtained.

12 g of N- (5-amino-8-quinolyl) -pivaloylacetamide was dissolved in 100 ml of N, N-dimethylacetamide and stirred at room temperature under stirring with 2- (2,4-dimethyl-tert-pentylhexyl). ) 15.2 g of butanoyl chloride were added dropwise. After stirring for 2 hours, 200 ml of ethyl acetate and 500 ml of water were added for extraction and concentration. By adding 200 ml of methanol to the concentrate and crystallizing,
18.7 g of the objective exemplified coupler (5) was obtained. The structure of this compound was confirmed by ¹ HNMR spectrum, MASS spectrum and elemental analysis.

The melting point of this compound is 111-114 ° C.
Met.

Synthesis Example 4 Synthesis of Illustrative Coupler (7) 9.0 g of Illustrative Coupler (5) was dissolved in 50 ml of methylene chloride, and 2.6 g of bromine was added dropwise under ice cooling. 1 except ice bath
After stirring for an hour, the mixture was washed with water. 5.9 g of 5,5-dimethyloxazoline-2,4-dione, 3.1 of triethylamine
g was dissolved in 50 ml of methylene chloride, and the methylene chloride solution previously washed with water was added dropwise over 30 minutes while stirring at room temperature. Stir for 5 hours and leave overnight. After the reaction, the reaction mixture was washed with an alkali and then with dilute hydrochloric acid, concentrated, and crystallized by adding 80 ml of methanol to obtain 6.2 g of the desired exemplified coupler (7). The structure of this compound was confirmed by ¹ HNMR spectrum, MASS spectrum and elemental analysis. In addition, the melting point of this compound was 159 to 161 ° C.

Synthesis Example 5 Synthesis of Illustrative Coupler (8) 5,5-Dimethyloxazolidine in Synthesis Example 4
1-benzyl-5 instead of 5.9 g of 2,4-dione
Except that 7.9 g of ethoxyimidazolidin-2,4-dione was used, 8.1 g of the desired exemplified coupler (8) was obtained in the same manner as in Synthesis Example 4. The structure of this compound is ¹
Confirmed by 1 H NMR spectrum, MASS spectrum and elemental analysis. The melting point of this compound is 141 to 14
4 ° C.

The present invention can be applied to various silver halide photosensitive materials. The silver halide emulsion and other materials (for example, additives) and photographic constituent layers (for example, layer arrangement) applied in the present invention, and processing methods and processing additives applied for processing this light-sensitive material include: And the following patent publications, in particular the European patent EPO, 355, 660 A2
No. (JP-A-2-139544) are preferably used. Photographic components, etc. JP-A-62-215272 JP-A-2-33144 EPO, 355,660A2 Silver halide emulsion 10th page, upper right column, line 6 to page 28 upper right column, line 16 to 45 page 53 lines to 47 12 5th line on the lower left column of the page, 11th line on the lower right column of the 29th page, 3rd line of the page, 4th from the lower right column of the 12th page, 4th page from the 2nd line to 5th line 47th line from the 20th line to the 13th upper left line Column 17 line 22 line silver halide solvent line 12 lower left column line 6 -----line 14 and page 13 upper left column line 3 from bottom to page 18 lower left column last line chemical sensitizer 12 From the lower left column of the page 3 to the lower right column on page 29 Line 12 to page 47 From the fourth line to the ninth line to the lower right column from the lower end to the last line Line 5 and the lower right column of the page 18 Lines 1 to 22 Line 9 from bottom right of upper right column Spectral sensitizer Page 22 Line 830 from bottom right of upper right column Line 1 from top left column to line 10 to page 47 to line 15 (spectral sensitization method) Line to line 38 to end line 13 Line Emulsion stabilizer Page 39, Upper left column, Line 1 to Page 30, Upper left column, Line 14 to Page 47, Line 16 to 19 Page 72, Upper right column, Last line Upper right column, Line 1, Line Image accelerator page 72, lower left column, line 1 to page 91, upper right column, line 3 ------ Color coupler page 91, upper right column, line 4 to page 3, upper right column, line 14 to page 4, line 15 to 27 (cyan, Line 121, upper left column, line 6 Line 18 upper left column, last line and line, magenta, page 30, upper right column, line 6 to page 5, line 30 to 28 yellow cap, page 35, lower right column, line 11, page last line, Line 45, lines 29-31, page 47, lines 23-63, page 50 Color enhancer page 121, upper left column, line 7-page 125, upper right column, line 1 ------ UV absorber page 125 Upper right column, second line 37 page, lower right column, line 14 to page 65, line 22 to 31 to 127, lower left column, last line 38 page upper left column, line 11 Line fading inhibitor 127 page, lower right column, first line 36 Page 12 upper right column line 12 to page 4 line 30 to 5 (image stabilizer) 137 page 137 lower left column line 8 page 37 upper left column line 19 page 23 line, page 29 line 1 to page 45 line 25 Line 45, lines 33 to 40, page 65 lines 2 to 21, high boiling point and / or page 137, lower left column, line 9, page 35 Lower column, line 14 to page 64, line 1 to 51 or low-boiling organic solvent ~ page 144, upper right column, last line, page 36, lower left column, lower 4th line Medium line, for photo additives, page 144, lower left column 1, Line 27, lower right column, line 10 to 63, line 51 to 64 scatter method-page 146, upper right column, line 7 28, upper left column, last line and page 56, line 35, lower right column, line 12 to 36 Page 7, upper right column, line 7 Hardening agent Page 146, upper right column, line 8 to page 155, lower left column, line 4 ------ Developing agent precursor 155, page 155 lower left column, line 5 --- --- Sir to page 155, lower right column 2 Line Developing inhibitor release, page 155, lower right column, line 3 --- --- Compound -9th line support 155 page, lower right column, line 19, page 38 upper right column, line 18-66, line 29-67 156 pages, upper left column, 14 lines 39 pages, upper left column, 3 lines, page 13 line Item Sensitive material layer composition 156 pages, upper left column, 15 lines 28 pages, upper right column, 1 line-45 pages, 41 lines-52 to 156 pages, lower right Column 14 line 15 Line line Dye 156 page lower right column 15 line 38 page upper left column line 12-66 page 18 line 22-184 page lower right Last line Upper right column 7th line Line item Color mixing inhibitor 185 page upper left column 1st line 36 page upper right column 8th line 64 pages 57th line 65-188 page lower right column 3 lines 11th line 1st page Eye Tone adjuster page 188, lower right column, line 4 --- --- to line 8 Stain preventive agent, page 188, lower right column, line 9 page 37, upper left column, last line to page 65, line 32 to pages 66 to 193 Lower right column, line 10 Lower right column, line 13 Page 17 Line 17 Surfactant Page 201, lower left column, line 1 Page 18, upper right column, line 1 --- --- 210, upper right column, last line 24, right lower column, last line Line 27 Line 10 from bottom left bottom column to line 9 to bottom right column line 9 Fluorine-containing compound Page 210 Line 1 bottom left column line 1 Line 25 top left column line 1 to (Antistatic agent, coating ~ page 222, bottom left column line 5 Line 27, lower right column, line 9 Cloth aid, lubricant, eye as an anti-adhesion agent) Binder 222, lower left column, line 6, page 38 upper right column, line 8 to 66, line 23 to 28 (hydrophilicity) Colloid) ~ page 225, upper left column, last line, line 18 line Item Thickener, page 225, upper right column, line 1 --- − To 227, upper right column, line 2 Antistatic agent: 227, upper right column, line 3 −− −− to page 230, upper left column, line 1 Polymer Latec 230, upper left column, line 2 −−−−− to page 239, last line Item Matting agent Page 240, upper left column, first line --- --- to page 240, upper right column, last line Photo processing method Page 3, upper right column, line 7 to page 39, upper left column, line 4 to page 67, line 14 to 69 (processing Process and Addition, page 10, upper right column, line 5, page 42, upper left column, last line, page 28, etc. The above cited reference in Japanese Patent Application Laid-Open No. Includes amendments made to the procedure amendment dated on March 16.

Further, among the color couplers described in the above documents, the yellow coupler is described in JP-A-63-231451.
No. 63-123047, No. 63-241547 and JP-A-1-1734
It is also preferable to use so-called short-wave yellow couplers described in JP-A Nos. 99, 1-213648 and 1-250944.

When the present invention is used for a color paper, the cyan coupler may be a diphenylimidazole cyan coupler described in JP-A-2-33144, or a cyan coupler described in European Patent EPO, 333,185A2.
-Hydroxypyridine cyan couplers (among others, couplers (42) listed as specific examples, 4-equivalent couplers obtained by imparting a chlorine leaving group to 2-equivalent couplers, and couplers (6) and (9) are particularly preferred) and JP-A-64-322
No. 60, a cyclic active methylene cyan coupler (among others, coupler examples 3, 8, and
34 is particularly preferred).

As the silver halide used in the present invention, silver chloride, silver bromide, silver chlorobromide, silver iodochlorobromide, silver iodobromide and the like can be used. For the purpose of processing, the content of silver chloride containing substantially no silver iodide is 90 mol% or more, more preferably 95% or more, especially 98%.
The use of the above silver chlorobromide or silver chloride emulsions is preferred.

The light-sensitive material according to the present invention may further comprise a hydrophilic colloid layer in order to improve the sharpness of an image, etc., in accordance with EP-A-337,490-A2.
Dyes capable of being decolorized by treatment (among which are oxonol dyes) described on page 76 are added so that the optical reflection density at 680 nm of the photosensitive material becomes 0.70 or more, or the water-resistant resin layer of the support is used. 12% by weight or more (more preferably 14% by weight or more) of titanium oxide surface-treated with dihydric or tetrahydric alcohols (for example, trimethylolethane) or the like.
It is preferable to include them.

When the present invention is used for a light-sensitive material such as color paper which emphasizes dye preservability, a compound for improving color image preservability as described in European Patent EPO, 277,589A2 is used together with a coupler. Is preferred.
In particular, combination use with a pyrazoloazole coupler is preferred.

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

The light-sensitive material according to the present invention is provided with a fungicide such as that described in JP-A-63-271247 to prevent various molds and bacteria that propagate in the hydrophilic colloid layer and deteriorate the image. It is preferred to add an agent.

As a support used in the light-sensitive material according to the present invention, a white polyester-based support or a layer containing a white pigment was provided on a support having a silver halide emulsion layer for a display. A support may be used. In order to further improve the sharpness, an antihalation layer is preferably provided on the support on the side where the silver halide emulsion layer is coated or on the back surface. In particular, the transmission density of the support is set to 0.3 so that the display can be viewed with both reflected light and transmitted light.
It is preferable to set in the range of 5 to 0.8.

The photosensitive material according to the present invention may be exposed to visible light or infrared light. The exposure method may be low-illuminance exposure or high-illuminance short-time exposure. In the latter case, a laser scanning exposure method in which the exposure time per pixel is shorter than 10 ^-4 seconds is preferred.

Further, upon exposure, US Pat.
It is preferable to use the band stop filter described in U.S. Pat. This removes light mixing,
The color reproducibility is significantly improved.

The technology and inorganic / organic materials which can be preferably used or used together when the present invention is used for a color photographic light-sensitive material for high-sensitivity photography are described in EP 436,933.
No. 8A2, and in the patents cited below. 1. 1. Layer structure: page 146, line 34 to page 147, line 25 Silver halide emulsion: page 147, line 26 to 148
Page 12 line 3. Yellow coupler: page 137, line 35 to 146
Page 33, line 149, lines 21-23. Magenta coupler: page 149, lines 24 to 28; EP 421,453 A1, page 3, line 5 to
Page 25, line 55 5. Cyan coupler: page 149, lines 29 to 33;
5. From page 3, line 28 to page 40, line 2 of EP 432, 804A2. Polymer coupler: page 149, lines 34-38; EP 113,334 A2, page 113, 39
Line-page 123, line 37 7. Colored coupler: page 53, line 42 to page 137, line 34, page 149, line 39 to line 45 Other functional couplers: page 7, line 1 to page 53, line 41, page 149, line 46 to page 150, line 3; EP 435,334A2, page 3, lines 1 to 29
Page 50, line 9. 9. Antiseptic / antifungal agent: page 150, lines 25-28. 10. Formalin scavenger: page 149, lines 15-17. Other additives: page 153, lines 38 to 47; EP 421,453 A1, page 75, line 21 to page 84, line 56, page 27, line 40 to page 37, page 4
Line 0 12. 12. Dispersion method: page 150, lines 4 to 24 Support: page 150, lines 32 to 34 14. Film thickness / film physical properties: page 150, lines 35 to 49 15. Color development step: page 150, line 50 to page 151, line 47 Desilvering step: page 151, line 48 to page 152, 53
Line 17. Automatic developing machine: page 152, line 54 to page 153, 2
Line 18. Washing / stabilizing step: page 153, lines 3 to 37 The yellow coupler of the present invention may be used in any layer in the light-sensitive material, but is preferably a blue-sensitive silver halide emulsion layer or adjacent thereto. Used for non-photosensitive layers. When the yellow coupler of the present invention is added to the non-photosensitive layer, the amount of the yellow coupler is preferably 0.001 to 1 mol per mol of the silver halide in the adjacent photosensitive layer.
2 mol%, more preferably 0.005 to 1
Mol% range.

The yellow coupler of the present invention can be used in combination with a known acylacetamide type yellow coupler other than the present invention. A desirable composition when used in combination is that the yellow coupler of the present invention is 20 to 100 of the total yellow coupler.
Mol%, more preferably in the range of 50 to 100 mol%.

The combination may be in the same layer or different layers.

The preferred amount of the yellow coupler of the present invention relative to silver halide is in the range of 0.005 to 2 mol, more preferably 0.01 to 0.5 mol, per mol of silver halide. It is.

Hereinafter, the present invention will be described in detail with reference to examples. Example 1 Synthesis of azomethine dye 6.1 g of the exemplified coupler (1) was dissolved in a mixed solvent of 100 ml of ethyl acetate and 100 ml of ethanol. Under stirring at room temperature, a solution of 11.9 g of sodium carbonate in 100 ml of water and 13 g of 4-amino-3-methyl-N-ethyl-N- (2-methanesulfonamidoethyl) aniline sulfate were sequentially added, and then 15.4 g of ammonium persulfate. Was added dropwise over 30 minutes. After stirring for 1 hour, the mixture was extracted with ethyl acetate and concentrated. The concentrate is separated and purified by column chromatography (filler: silica gel, developing solution: n-hexane / ethyl acetate = 2/1 mixture), and then crystallized from a mixed solvent of n-hexane / isopropanol to give an exemplary coupler. 5.5 g of the azomethine dye of (1)
Obtained. Melting point was 127-128 ° C.

The maximum absorption wavelength λ _max in the visible region of the spectral absorption spectrum of this compound measured in ethyl acetate
And the molecular extinction coefficient ε _{max at the} maximum absorption wavelength was 429.2 nm and 14,700 l · mol ⁻¹ · cm ⁻¹ , respectively.

The same operation was performed except that 6.1 g of the exemplified coupler (3) was used instead of 6.1 g of the exemplified coupler (1), and the azomethine dye of the exemplified coupler (3) was crystallized from ethanol. 8.6 g were obtained. Melting point is 15
It was 0 ° C. Note that λ _max and ε _max are 42
It was 4.2 nm and 19600 liter · mol ⁻¹ · cm ⁻¹ .

The measurement of the spectral absorption spectrum in Examples 1 and 2 was carried out using a self-recording spectrophotometer UV-260 manufactured by Shimadzu Corporation, and was about 2 × 10 ⁻⁵ mol / mol in ethyl acetate.
Performed at room temperature with a concentration of 1 liter.

Example 2 Comparison of spectral absorption characteristics The following characteristic values were selected for comparison of spectral absorption characteristics.

S ₆₀ and S ₈₀ were used as characteristic values indicating the sharpness at the long wavelength end in the spectral absorption spectrum.

S ₆₀ : ratio of the maximum absorption wavelength to the absorbance at the maximum absorption wavelength plus the absorbance at 60 nm. S ₈₀ : ratio of the maximum absorption wavelength to the absorbance at the maximum absorption wavelength plus the absorbance at 80 nm. It can be said that the smaller the value of both S ₆₀ and S ₈₀ , the sharper the absorption and the better the sharpness at the long wavelength end.

Next, the half width was used as a characteristic value indicating an effective filter effect in the blue light region. It is desirable that the half width is large.

The azomethine dye derived from the coupler of the present invention shown in Chemical formula 21 and the azomethine dye for comparison are shown below.
The spectral absorption spectrum was measured in ethyl acetate, and S ₆₀ , S ₈₀ and the half width determined from the spectrum are shown in Table 1.

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[0096]

[Table 1] In Table 1, three sets of A to D, EG, and H to J can be compared.

[0097] In to D, A and C although the half width is large, S ₆₀ value which represents the sharpness of the long wavelength end of the absorption, it is seen that S ₈₀ value is significantly larger undesirable absorption.
On the other hand, Ar is o- chlorophenyl group B is S ₆₀ value,
Half width of those S ₈₀ value indicates a relatively small value is decreased, not always preferred absorbent. The D of the present invention enables a relatively large half-value width with a small S ₆₀ value and S ₈₀ value.

A similar tendency can be seen in EG and HJ. Therefore, it is clear that the azomethine dye derived from the coupler of the present invention gives a spectral absorption spectrum with good sharpness at the long wavelength end and a large half width.

Example 3 After a corona discharge treatment was applied to the surface of a paper support laminated on both sides with polyethylene, a gelatin subbing layer containing sodium dodecylbenzenesulfonate was provided, and various photographic constituent layers were further coated. A multilayer color photographic paper (sample 1) having the layer configuration shown was prepared. The coating solution was prepared as follows.

Preparation of Fifth Layer Coating Solution 32.0 g of cyan coupler (ExC), color image stabilizer (C
pd-2) 3.0 g, color image stabilizer (Cpd-4) 2.0
g, color image stabilizer (Cpd-6) 18.0 g, color image stabilizer (Cpd-7) 40.0 g and color image stabilizer (Cpd-
8) To 5.0 g, 50.0 cc of ethyl acetate and solvent (S
olv-6) was added and dissolved, and this solution was added to 500 cc of a 20% aqueous gelatin solution containing 8 cc of sodium dodecylbenzenesulfonate, and then emulsified and dispersed with an ultrasonic homogenizer to prepare an emulsified dispersion. on the other hand,
Silver chlorobromide emulsion (cubic, 1: 4 of large size emulsion having an average grain size of 0.58 μm and small size emulsion of 0.45 μm)
Mixture (Ag mole ratio).

The coefficient of variation of the particle size distribution is in each case 0.
09 and 0.11, and in each size emulsion, 0.6 mol% of AgBr was locally contained in a part of the grain surface).
In this emulsion, the following red-sensitive sensitizing dye E was contained in an amount of 0.9 × 10 ^-4 mol per mol of silver for a large emulsion and 1.1 × 10 ^-4 mol for a small emulsion. Has been added. The emulsion was chemically ripened by adding a sulfur sensitizer and a gold sensitizer. The emulsified dispersion and the red-sensitive silver chlorobromide emulsion were mixed and dissolved to prepare a fifth layer coating solution having the following composition.

Coating solutions for the first to fourth, sixth and seventh layers were prepared in the same manner as the coating solution for the fifth layer. H-1 and H-2 were used as gelatin hardeners in each layer.

Further, each layer has Cpd-10 and Cpd-11.
Was added so that the total amount was 25.0 mg / m ² and 50.0 mg / m ² , respectively.

The following spectral sensitizing dyes were used for the silver chlorobromide emulsion in each photosensitive emulsion layer.

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[Table 2]

[0106]

[Table 3]

[0107]

[Table 4] Also, 1- (5-methylureidophenyl) -5-mercaptotetrazole was added to the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer in an amount of 8.5 × 10 ^-5 mol, ^7-7 mol per mol of silver halide. 0.7 × 10 ^-4 mol, 2.5 × 1
^0-4 moles were added.

Further, 4-hydroxy-6-methyl-1,3,3a, 7- was added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer.
Tetrazaindene was added in an amount of 1 × 10 ^-4 mol and 2 × 10 ^-4 mol, respectively, per mol of silver halide.

The following dyes were added to the emulsion layer to prevent irradiation (the number in parentheses indicates the coating amount).

[0110]

Embedded image (Layer Structure) The composition of each layer is shown below. The numbers indicate the application amount (g /
m ² ). The silver halide emulsion represents a coating amount in terms of silver.

[0111]

[Table 5]

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[Table 6]

[0113]

[Table 7]

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[Table 8]

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Embedded image The following known couplers were used as couplers for comparison.

[0122]

Embedded image Samples 2 to 10 were prepared by replacing the coupler so as to be equimolar to the yellow coupler ExY-1 of Sample 1.

First, each sample was subjected to gradation exposure of a three-color separation filter for sensitometry using a sensitometer (FWH type, manufactured by Fuji Photo Film Co., Ltd., color temperature of light source: 3200 ° K). The exposure at this time is 2 seconds with an exposure time of 0.1 second.
The exposure was performed so that the exposure amount became 50 CMS.

The exposed samples were subjected to continuous processing (running test) using a paper processor using the following processing steps and processing compositions until the replenishment was twice as large as the tank capacity for color development. Processing temperature Temperature Replenishment amount ^* Tank capacity Color development 35 ° C 45 seconds 161 ml 17 liter Bleach-fix 35 ° C 45 seconds 215 ml 17 liter Rinse (1) 35 ° C 20 seconds -10 liter Rinse (2) 35 ° C 20 seconds -10 liter rinse (3) 35 ° C. 20 seconds 360 ml 10 liter drying 80 ° C. 60 seconds (* replenishment rate per photosensitive material 1 m ²⁾ (rinse (3) → (1) 3 to a tank countercurrent system to) each processing The composition of the liquid is as follows.

(Color developing solution) (Tank solution) (Replenisher) Water 700 ml 700 ml Ethylenediaminetetraacetic acid 3.0 g 3.0 g 1,2-dihydroxybenzene-4,6-disulfonic acid disodium salt 0.5 g 0.5 g triethanolamine 12.0 g 12.0 g Potassium chloride 1.6 g-Potassium bromide 0.01 g-Potassium carbonate 27.0 g 27.0 g Optical brightener (WHITEX 4B manufactured by Sumitomo Chemical) 1.0 g 2.5 g Sodium sulfite 0.1 g 0.2 g Disodium-N, N-bis ( Sulfonate ethyl) Hydroxylamine 8.0 g 10.0 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 5.0 g 7.1 g Add water 1000 ml 1000 ml pH (25 ° C) 10.05 10.45 (Bleaching / fixing solution) (Same as tank solution and replenisher) Water 600ml Ammonium thiosulfate (700g / liter) 100ml Ammonium iron (III) ammonium ethylenediaminetetraacetate 55g Ethylenediamine Tetraacetic acid 5 g Ammonium bromide 40 g Nitric acid (67%) 30 g Add water 1000 ml pH (25 ° C) (with acetic acid and ammonia water) 5.8 (Rinse solution (the tank solution and the replenisher are the same)) Ion-exchanged water (calcium , Magnesium is 3ppm each
Hereinafter, the sensitometry curve of the processed sample in the blue separation exposure area was measured through a blue filter and a green filter. The ordinary yellow color density can be known from the sensitometric curve measured through the blue filter, and the magenta component of the yellow color portion can be known from the sensitometric curve measured through the green filter.

Table 9 shows the results.

[0127]

[Table 9] In the table, _Dmax is the maximum color density when the yellow density of the fog portion is set as a reference (0). In addition, D _G (B = 1.
5) is a magenta density based on the magenta fog density at an exposure amount that gives a yellow density of 1.5 when the yellow fog density is used as a reference. This value corresponds to the amount of the undesired magenta component in the yellow coloring portion,
The smaller the value, the better the hue of the yellow dye.

Table 9 can be compared among the compound groups of A, B and C according to the type of acyl group.

As can be seen from the comparison within the group A in Table 9, the couplers (7) and (10) of the present invention give almost the same yellow color density as the comparative couplers ExY1 to ExY1-3, and the magenta component of the couplers was It can be seen that the coupler has less hue. FIG. 1 shows an absorption spectrum of a yellow dye formed by using the coupler of the present invention and the coupler for comparison. The solid line shows the absorption spectrum distribution of the yellow dye formed using the exemplary coupler (7) of the present invention of Sample 4, and the broken line shows the yellow dye formed using the conventionally known comparative coupler ExY-1 of Sample 1. 2 shows the absorption spectrum distribution of the sample. As is apparent from the comparison of the absorption spectrum distributions shown in FIG. 1, the yellow dye formed using the exemplified coupler (7) of the present invention is formed using the conventionally known comparative coupler ExY-1. Compared to the yellow dye obtained, the "cut" of the absorption spectrum on the longer wavelength side was remarkably better than expected, and it was found that the color reproducibility of natural color photographs was particularly excellent, that is, the hue of the yellow dye was excellent. .

The same applies to groups B and C, and it is apparent that the coupler of the present invention has an excellent hue.

Example 4 On an undercoated cellulose triacetate film support,
Each layer having the composition shown below was applied in multiple layers to prepare a sample 101 as a multilayer color photosensitive material. (Composition of photosensitive layer) The main materials used for each layer are classified as follows: ExC: cyan coupler UV: ultraviolet absorber ExM: magenta coupler HBS: high boiling point organic solvent ExY: yellow coupler H: gelatin Hardener ExS: Sensitizing dye The number corresponding to each component indicates the coating amount expressed in g / m ² unit. For silver halide, it indicates the coating amount in silver. However, as for the sensitizing dye, the coating amount is shown in mol unit with respect to 1 mol of silver halide in the same layer. (Sample 101) First Layer (Antihalation Layer) Black Colloidal Silver Silver 0.18 Gelatin 1.40 ExM-1 0.18 ExF-1 2.0 × 10 ^-3 .

Second layer (intermediate layer) Emulsion G Silver 0.065 2,5-di-t-pentadecylhydroquinone 0.18 ExC-2 0.020 UV-1 0.060 UV-2 0.080 UV-3 0.10 HBS-1 0.10 HBS-2 0.020 Gelatin 1.40.

Third layer (low-sensitivity red-sensitive emulsion layer) Emulsion A silver 0.25 Emulsion B silver 0.25 ExS-1 6.9 × 10 ^-5 ExS-2 1.8 × 10 ^-5 ExS-3 3.1 × 10 ^-4 ExC-1 0.18 ExC-4 0.15 ExC-7 0.020 UV-1 0.070 UV-2 0.050 UV-3 0.070 HBS-1 0.060 Gelatin 0.87. Fourth Layer (Medium Speed Red Sensitive Emulsion Layer) Emulsion D Silver 0.80 ExS-1 3.5 × 10 ^-4 ExS-2 1.6 × 10 ^-5 ExS-3 5.1 × 10 ^-4 ExC-1 0.20 ExC-2 0.050 ExC-4 0.20 ExC-5 0.050 ExC-7 0.015 UV-1 0.070 UV-2 0.050 UV-3 0.070 Gelatin 1.30.

Fifth layer (high-sensitivity red-sensitive emulsion layer) Emulsion E silver 1.40 ExS-1 2.4 × 10 ^-4 ExS-2 1.0 × 10 ^-4 ExS-3 3.4 × 10 ^-4 ExC-1 0.097 ExC-2 0.010 ExC-3 0.065 ExC-6 0.020 HBS-1 0.22 HBS-2 0.10 Gelatin 1.63.

Sixth layer (intermediate layer) Cpd-1 0.040 HBS-1 0.020 gelatin 0.80.

Seventh layer (low-sensitivity green-sensitive emulsion layer) Emulsion C Silver 0.30 ExS-4 2.6 × 10 ^-5 ExS-5 1.8 × 10 ^-4 ExS-6 6.9 × 10 ^-4 ExM-1 0.021 ExM-2 0.26 ExM-3 0.030 ExY-1 0.025 HBS-1 0.10 HBS-3 0.010 Gelatin 0.63.

Eighth Layer (Medium Speed Green Sensitive Emulsion Layer) Emulsion D Silver 0.55 ExS-4 2.2 × 10 ^-5 ExS-5 1.5 × 10 ^-4 ExS-6 5.8 × 10 ^-4 ExM-2 0.094 ExM-3 0.026 ExY-1 0.018 HBS-1 0.16 HBS-3 8.0 × 10 ^-3 gelatin 0.50.

Ninth layer (high-sensitivity green-sensitive emulsion layer) Emulsion E Silver 1.55 ExS-4 4.6 × 10 ^-5 ExS-5 1.0 × 10 ^-4 ExS-6 3.9 × 10 ^-4 ExC-1 0.015 ExM-1 0.013 ExM-4 0.065 ExM-5 0.019 HBS-1 0.25 HBS-2 0.10 Gelatin 1.54.

Tenth layer (yellow filter layer) Yellow colloid layer Silver 0.035 Cpd-1 0.080 HBS-1 0.030 Gelatin 0.95.

Eleventh layer (low-sensitivity blue-sensitive emulsion layer) Emulsion C Silver 0.18 ExS-7 8.6 × 10 ^-4 ExY-1 0.040 ExY-2 0.73 HBS-1 0.28 Gelatin 1.10.

Twelfth Layer (Medium Speed Blue Sensitive Emulsion Layer) Emulsion D Silver 0.40 ExS-7 7.4 × 10 ^-4 ExC-7 8.0 × 10 ^-3 ExY-2 0.15 HBS-1 0.050 Gelatin 0.78.

13th layer (high-sensitivity blue-sensitive emulsion layer) Emulsion F Silver 0.70 ExS-7 2.8 × 10 ^-4 ExY-2 0.20 HBS-1 0.070 Gelatin 0.69.

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

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

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

[0146]

[Table 10] In Table 10, (1) Emulsions A to F were subjected to reduction sensitization during the preparation of grains using thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-191938. (2) Emulsions A to F were subjected to gold sensitization, sulfur sensitization and selenium sensitization in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate according to the examples of Japanese Patent Application No. 2-34090. It has been subjected. (3) For preparing tabular grains, low molecular weight gelatin is used according to the examples of JP-A-1-158426. (4) Dislocation lines as described in Japanese Patent Application No. 2-34090 have been observed in tabular grains and normal crystal grains having a grain structure using a high voltage electron microscope.

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[0159]

Embedded image After the above-described color photographic light-sensitive material is subjected to gray exposure so as to give a density of 0.5, the cumulative replenishment amount of the developing solution is reduced to 3% of the tank capacity by the method described below using an automatic developing machine.
The processing (running processing) was performed until the number became double. (Processing method) Step Processing time Processing temperature Replenishment amount Tank capacity Color development 3 minutes 15 seconds 38 ° C 22 ml 20 liter Bleaching 3 minutes 00 seconds 38 ° C 25 ml 40 liter Rinse 30 seconds 24 ° C 1200 ml 20 liters Fixing 3 Min 00 sec 38 ℃ 25ml 30 liter Rinse with water (1) 30sec 24 ℃ From (2) to (1) 10 liter countercurrent piping system Rinse with water (2) 30sec 24 ℃ 1200ml 10 liter Stability 30sec 38 ℃ 25 ml 10 liter Drying 4 minutes 20 seconds 55 ° C Replenishment amount per 35 mm width 1 m length Next, the composition of the processing solution is described.

(Color developing solution) Tank solution (g) Replenisher (g) Diethylenetriaminepentaacetic acid 1.0 1.1 1-hydroxyethylidene-1,1-diphosphonic acid 3.0 3.2 Sodium sulfite 4.0 4.4 Potassium carbonate 30.0 37.0 Potassium bromide 1.4 0.3 Iodine 1.5 mg potassium hydroxide-hydroxylamine sulfate 2.4 2.8 4- (N-ethyl-N-β-hydroxyethylamino) -2-methylaniline sulfate 4.5 6.2 Add water 1.0 liter 1.0 liter pH 10.05 10.15

(Bleaching solution) Tank solution (g) Replenisher (g) Ethylenediaminetetraacetic acid sodium ferric trihydrate 100.0 120.0 Ethylenediaminetetraacetic acid disodium salt 10.0 11.0 3-mercapto-1,2,4-triazole 0.08 0.09 Ammonium bromide 140.0 160.0 Ammonium nitrate 30.0 35.0 Ammonia water (27%) 6.5 ml 4.0 ml Add water 1.0 liter 1.0 liter pH 6.0 5.7.

(Fixing solution) Tank solution (g) Replenisher (g) Ethylenediaminetetraacetic acid disodium salt 0.5 0.7 Ammonium sulfite 20.0 22.0 Ammonium thiosulfate aqueous solution (700 g / L) 290.0 mL 320.0 mL Add water 1.0 L 1.0 L pH 6.7 7.0.

(Stabilizing solution) Common to tank solution / replenisher (g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.2 Disodium ethylenediaminetetraacetate 0.05 1,2 , 4-Triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 Water and 1.0 liter pH 8.5.

Next, the yellow coupler ExY of Sample 101 was used.
Samples 102 to 105 were prepared in which ExY-3 and the coupler of the present invention were replaced with ExY-3 in such a manner that -2 all became equimolar amounts.

Each of the samples 101 to 105 was exposed to blue-separated light having passed through a blue filter, treated with the above-mentioned running solution, and measured for sensitometric curves. The blue light density D of each sample at an exposure amount at which the density of the sample 101 is 1.0 when the blue light density is based on the fog area.
_B is shown in Table 11.

The sample 101 at the same exposure was used as a reference (±
0.00) green density ΔD _G (B = 1.0)
Table 11 also shows them.

The smaller the ΔD _G (B = 1.0), the better the hue of the yellow dye, and it can be said that the coupler is preferable in terms of color reproduction.

[0168]

[Table 11] As is clear from Table 11, the coupler of the present invention has a smaller ΔD _G (B = 1.0) (absolute value is larger as a negative value) than the comparative examples in each compound group, and is a coupler preferable in color reproduction. I can say that there is.

[Brief description of the drawings]

FIG. 1 is an absorption spectrum diagram of a yellow dye formed using the coupler of the present invention and a coupler for comparison.

Claims (2)

(57) [Claims] 1. An N- (8-quinolyl) -acyl acetamide type yellow dye-forming coupler. 2. A silver halide color photographic material comprising at least one N- (8-quinolyl) -acyl acetamide type yellow dye-forming coupler.