JPH05127327A - Yellow dyestuff forming coupler and silver halide photographic sensitive material containing the coupler - Google Patents

Abstract

PURPOSE:To obtain an yellow picture with the long-wave end of absorption cut sharply and having a sufficient large half width by using an N-(8-quinolyl)- acylacetamide type yellow dyestuff forming coupler. CONSTITUTION:This N-(8-quinolyl)-acylacetamide type yellow forming coupler is shown by the formula. In the formula, R<1> is an aryl, alkyl or amine group, R<2> is a group capable of being substituted for a quinoline ring, (m) is an integer of 0 to 6, and the plural R<2>s can be the same or different when (m) is the plural. When the substituent is an alkyl or contains an alkyl, the alkyl can be substituted by a straight chain, a branched chain or a ring or contains an unsaturated bond unless otherwise specified. When the substituent is an aryl or contains an aryl, the aryl can be a single or condensing ring capable of being substituted unless otherwise specified.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention 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 a dye-forming coupler (hereinafter referred to as "coupler") which is oxidized by an aromatic primary amine developing agent which is oxidized by a coloring phenomenon after exposing the material to light. By doing so, a color image is formed.

Generally, in this method, a color reproduction method by 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. Acylacetamide couplers and malondianilide couplers as yellow dye-forming couplers (hereinafter referred to as yellow couplers) for forming yellow color images, and 5-pyrazolone couplers and pyrazolotriazole couplers as magenta couplers for forming magenta color images, Phenol couplers and naphthol couplers are generally used as cyan couplers for forming cyan images.

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

By the way, yellow couplers, particularly acylacetamide couplers represented by benzoylacetanilide couplers and pivaloylacetanilide couplers are generally used for image formation. The former generally has a high activity of coupling with an oxidized product of an aromatic primary amine developing agent at the time of development, and a large molecular absorption coefficient of a yellow dye to be formed, and therefore a high sensitivity is required for a color photosensitive material for photographing, particularly a color photosensitive material. It is mainly used for negative films, and the latter is mainly used for color paper and color reversal films because of its excellent yellow dye spectral absorption characteristics and fastness.

[0006]

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

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

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 pivaloylacetanilide type yellow couplers, and most of them are color negative films, color reversal films and color papers. It is put to practical use in any photosensitive material.

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

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

[0011]

The object of the present invention is to provide N-
(8-quinolyl) -acylacetamide type yellow dye forming coupler, and a silver halide color photographic light-sensitive material containing the same.

The N- (8-quinolyl) -acylacetamide 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 below.

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

[0014]

[Chemical 1] (In the formula, R ¹ is an aryl group, an alkyl group, or an amino group, R ² is a group capable of substituting for 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.) Examples of R ² are halogen atom, alkyl group, aryl group, alkoxy group, aryloxy group, alkoxycarbonyl. Group, aryloxycarbonyl group, carbonamido group, sulfonamide 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 (above substituent group A) Examples of the leaving group X include a heterocyclic group bonded to a coupling active position at a nitrogen atom, an aryloxy group, an arylthio group, an acyloxy group, an alkylsulfonyloxy group, an arylsulfonyloxy group, a heterocyclic oxy group, and a halogen atom. ..

Here, when the substituent in the general formula (1) or less is alkyl or includes an alkyl group, unless otherwise specified, the alkyl group may be a linear, branched or cyclic substituent. And an alkyl group which may be unsaturated or may contain an unsaturated bond.

When the substituent in the general formula (1) or less is an aryl group or contains an aryl group, the aryl group is a monocyclic or condensed ring aryl group which may be substituted, unless otherwise specified. means.

When the substituent in the general formula (1) or less is a heterocyclic group or includes a heterocyclic group, the heterocyclic group is selected from O, N, S, P, Se and Te unless otherwise specified. It means a 3- to 8-membered optionally substituted monocyclic or condensed-ring heterocyclic group containing at least one hetero atom in the ring.

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

R ¹ is preferably an aryl group (for example, phenyl, 4-methoxyphenyl, 4-butoxyphenyl, 4-sec-butoxy) having 6 to 30 (preferably 6 to 16) total carbon atoms (hereinafter referred to as C number). Phenyl, 4-chlorophenyl, o-tolyl, 4-dimethylaminophenyl, 2-acetamidophenyl, 1-naphthyl, 2-methoxyphenyl), C number 4-36 (preferably 4-1).
6) alkyl groups (eg 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] Hexan-1-yl, bicyclo [2.2.1] heptan-1-yl, bicyclo [2.
2.2] Octan-1-yl, tricyclo [3.1.
^1.03,6 ] 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]
Hexan-1-yl, bicyclo [4.1.0] heptan-1-yl, bicyclo [2.2.0] hexan-1-yl, bicyclo [3.2.0] heptan-1-yl, bicyclo [ 3.3.0] Octane-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 to 30 (preferably 1 to 16)
Alkyl group, C number 1 to 30 (preferably 1 to 18) alkoxy group, C number 6 to 30 (preferably 6 to 24) aryloxy group, C number 2 to 30 (preferably 2 to 2)
0) alkoxycarbonyl group, C number 7 to 30 (preferably 7 to 20) aryloxycarbonyl group, C number 1
To 30 (preferably 2 to 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 0-4, more preferably an integer of 0-2. The substitution position of R ² is preferably the 3, 4, 5 and 6 positions with respect to the quinoline ring.

X is preferably a hydrogen atom, a halogen atom,
C6 to C36 aryloxy group, C2 to C36 acyloxy group, C1 to C36 sulfonyloxy group, C2 to C36 nitrogen atom-bonded heterocyclic group, C Heterocyclic oxy group of the number 2-36, C number 6-36
Is an arylthio group or a heterocyclic thio group having a C number of 2 to 36.

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

When X represents a heterocyclic group, X is preferably a 5- to 7-membered monocyclic or condensed-ring heterocyclic group which may be substituted, and examples thereof include succinimide, maleinimide, 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, imidazolidin-2-one, oxazolidin-2-one, thiazolidin-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
-Thiazolidin-4-one, these heterocycles being optionally substituted. Examples of the substituents on these heterocycles include substituents selected from the above substituent group A.

When X represents an aryloxy group, X preferably represents an aryloxy group having a C number of 6 to 30,
It may be substituted with a group selected from the substituent group mentioned when X is a heterocycle. As the substituent of the aryloxy group, a halogen atom, a cyano group, a nitro group, a carboxyl group, a trifluoromethyl group, an alkoxycarbonyl group, a carbonamido group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group,
Arylsulfonyl group or cyano group is preferable.

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

[0027]

[Chemical 2] Z in the general formula ^{(2) -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 represent 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, and 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
R ⁸ 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 Z in the general formula (2) is —O—C.
^{R 6 R 7 -, - NR} 8 -CR 6 R 7 - or -NR ⁸ -
It is a heterocyclic group which is NR ⁹ —.

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

[0030]

[Chemical 3] In 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 carbonamido group, a sulfonamide group, a carbamoyl group,
It is a group selected from a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group or 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, and n represents an integer of 0-2. The C number of the aryloxy group represented by the general formula (3) is 6 to 30, preferably 6
-24, and more preferably 6-15.

The coupler represented by the general formula (1) forms a dimer or a multimer of the substituents R ¹ , R ² or X which are bonded to each other through a divalent or divalent or higher valent group. Good. In this case, the number of carbon atoms shown in each of the above substituents may be out of the specified range.

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

[0033]

[Chemical 4] In the general formula (4), G _i is a repeating unit derived from a color forming monomer, is a group represented by the general formula (5) shown in the following chemical formula 5, and H _j is derived from a non-color forming monomer. A repeating unit, i is a positive integer, j is 0 or a positive integer,
gi and hj represent the weight fraction of G _i or H _j , respectively. Here, when i or j is plural, G _i or H
_j represents that it contains multiple types of repeating units.

[0034]

[Chemical 5] In 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 represents -CONH-,
-NHCONH-, -NHCOO-, -NHCO-,-
OCONH-, -NH-, -COO-, -OCO-,-
CO -, - O -, - S -, - SO 2 -, - NHSO
₂ -, or represents a -SO ₂ NH-. a, b, c are 0
Or represents 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).

Non-color-forming, ethylene-type monomers which do not couple with the oxidation product of the aromatic primary amine developing agent which gives the repeating unit H _j include acrylic acid, α-chloroacrylic acid and α-alkylacrylic acid (for example, Methacrylic acid) Amides or esters derived from these acrylic acids (eg, acrylamide, methacrylamide, n-butyl acrylamide, t-butyl acrylamide, diacetone acrylamide, 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-hydroxymethacrylate), vinyl esters (eg vinyl acetate, vinyl propionate and vinyl laurate),
Acrylonitrile, methacrylonitrile, aromatic vinyl compounds (eg 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 acid ester, N-vinyl-2-pyrrolidone, N-vinyl pyridine and 2- and -4-vinyl pyridine.

Acrylic acid esters, methacrylic acid esters and maleic acid esters are particularly preferred. Two or more kinds of non-color-forming ethylene type monomers used here can be used together. For example, methyl acrylate and butyl acrylate, butyl acrylate and styrene, butyl methacrylate and methacrylic acid, methyl acrylate and diacetone acrylamide, etc. can be used.

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

For the yellow polymer coupler represented by the general formula (4), the sum of gi is 10% to 100%.
(Preferably 30% to 70%), and the total sum of hj is 9
It is 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 5000 or less can also be used.

The yellow coupler used in the present invention is
Even a lipophilic polymer soluble in an organic solvent (eg, ethyl acetate, butyl acetate, ethanol, methylene chloride, cyclohexanone, dibutyl phthalate, tricresyl phosphate) is a hydrophilic polymer miscible with a hydrocolloid such as an aqueous gelatin solution. Alternatively, it may be 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-type monomer which gives the coupler unit represented by the general formula (5) in an organic solvent to obtain gelatin. It may be prepared by emulsion-dispersing it in the form of a latex in an aqueous solution, or may be prepared directly by an emulsion polymerization method.

A method of emulsion-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 an emulsion polymerization is described in US Pat. Nos. 4,080,211 and 3,370. The method described in 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 in Chemical Formulas 6 and 7 below.

[0044]

[Chemical 6]

[0045]

[Chemical 7] (Ii) Examples of R ² are shown in Chemical Formulas 8 and 9 below.

[0046]

[Chemical 8]

[0047]

[Chemical 9] (Iii) Examples of X are shown in Chemical Formulas 10 to 13 below.

[0048]

[Chemical 10]

[0049]

[Chemical 11]

[0050]

[Chemical 12]

[0051]

[Chemical 13] Specific examples of the yellow coupler of the present invention are shown in Chemical Formulas 14 to 19 below, but the present invention is not limited thereto.

[0052]

[Chemical 14]

[0053]

[Chemical 15]

[0054]

[Chemical 16]

[0055]

[Chemical 17]

[0056]

[Chemical 18]

[0057]

[Chemical 19] The yellow coupler of the present invention represented by the general formula (1) can be synthesized, for example, by the synthetic route shown in the following chemical formula 20.

[0058]

[Chemical 20] Here, 8-aminoquinolines a and β-ketoesters b can be synthesized by a conventionally known method.

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

Next, the chloro-substituted product or bromo-substituted product d and the proton adduct of the leaving group, H-X, 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 and the like, reaction temperature is -20 ° C to 150 ° C, preferably -10 ° C.
The coupler e of the present invention can be obtained by reacting at -100 ° C. At this time, triethylamine, N
-A base such as ethylmorpholine, DBU, tetramethylguanidine, potassium carbonate, sodium hydroxide or sodium hydrogen carbonate may be used.

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

Synthesis Example 1 Synthesis of Exemplified 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 under a nitrogen stream. After the ethyl pivaloyl acetate was distilled off under reduced pressure, 5.5 g of the target exemplary coupler (1) was obtained by crystallizing from an n-hexane-ethyl acetate mixed solvent.
Obtained. The structure of this compound is ¹ H NMR spectrum, M
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 ethyl 1-methylcyclopropan-1-ylcarbonylacetate 23.8
g were mixed, and the mixture was heated and stirred at 140 ° C. under reduced pressure with an aspirator. After 4 hours, ethyl 1-methylcyclopropan-1-ylcarbonylacetate was distilled off under reduced pressure, and methanol was added to the residue for crystallization to obtain 15.6 g of the target exemplary coupler (3). The structure of this compound was confirmed by ¹ HNMR spectrum, MASS spectrum and elemental analysis. The melting point of this compound is 137.
Was 138 ° C.

Synthesis Example 3 Synthesis of Exemplified 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.
The mixture was stirred at 80 ° C for 5 hours. After leaving it overnight, it was taken out from 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 are mixed,
The mixture was stirred under reduced pressure with an aspirator at 150 ° C. for 5 hours. After cooling the reaction solution, 10 g of activated carbon and 200 ml of ethyl acetate were added, stirred for 30 minutes, filtered, and the filtrate was concentrated. By adding n-hexane and crystallizing, 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 obtain N- (5-amino-8-). 12 g of quinolyl) -pivaloyl acetamide was obtained.

12 g of N- (5-amino-8-quinolyl) -pivaloylacetamide was dissolved in 100 ml of N, N-dimethylacetamide and 2- (2,4-dimethyl-tert-pentylphenoxy) was stirred at room temperature. ) 15.2 g of butanoyl chloride was 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 crystallization,
18.7 g of the desired exemplary 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 to 114 ° C.
Met.

Synthesis Example 4 Synthesis of Exemplified Coupler (7) 9.0 g of Exemplified Coupler (5) was dissolved in 50 ml of methylene chloride, and 2.6 g of bromine was added dropwise under ice cooling. 1 excluding ice bath
After stirring for an hour, it was washed with water. 5,5-dimethyloxazoline-2,4-dione 5.9 g, triethylamine 3.1
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 let stand overnight. After the reaction, the reaction product was washed with an alkali and then with dilute hydrochloric acid, concentrated, and added with 80 ml of methanol for crystallization to obtain 6.2 g of the desired exemplary coupler (7). The structure of this compound was confirmed by ¹ HNMR spectrum, MASS spectrum and elemental analysis. The melting point of this compound was 159 to 161 ° C.

Synthesis Example 5 Synthesis of Exemplified Coupler (8) 5,5-Dimethyloxazolidine-in Synthesis Example 4
1-Benzyl-5-instead of 5.9 g of 2,4-dione
By the same procedure as in Synthesis Example 4 except that 7.9 g of ethoxyimidazolidine-2,4-dione was used, 8.1 g of the desired exemplary coupler (8) was obtained. The structure of this compound is ¹
It was confirmed by 1 HNMR spectrum, MASS spectrum and elemental analysis. The melting point of this compound is 141-14.
It was 4 ° C.

The present invention can be applied to various silver halide light-sensitive 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 the processing method and processing additives applied for processing the light-sensitive material are , The following patent publications, in particular European patent EPO, 355, 660A2
Those described in JP-A-2-139544 are preferably used. Photographic elements, etc. JP-A-62-215272 JP-A-2-33144 EPO, 355,660A2 Silver halide emulsion Page 10 upper right column, line 6 to page 28 upper right column, line 16 to 45 page 53 line to 47 12 Page lower left column 5th line and page 29 Lower right column 11th line and page 3rd line, Page 12 Lower right column Lower 4th page Page 30 2nd line to 5th line 47 Page 20th line to line 13th page upper left Column 17 Line 22 Line Silver halide solvent Page 12 Lower left column Line 6 to line ---------- Page 14 and Page 13 Upper left column Line 3 from bottom to page 18 Lower left column Last line Chemical sensitizer 12 Page bottom left column Bottom 3 Page 29 Bottom right column Line 12 to page 47 Line 4 to line 9 Bottom right column Bottom to end line Line 5 and page 18 Bottom right column Line 1 to page 22 Top right column, bottom line 9 Spectral sensitizer page 22 Top right column, bottom page 8 30 Top left column, line 1 to page 47 Line 10 to line 15 (spectral sensitization method) Line to page 38 End line line 13 Line Emulsion stabilizer Page 39 Upper left column 1st line to Page 30 Upper left column 14th line to Page 47 Page 16 Line 16 to 19 Page 72 Upper right column Last line Upper right column 1st 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, Page 121 Upper left column 6th line Page 18 Upper left column Last line and line, Magenta, Page 30 Upper right column 6th line to 5th page 30th line to 28 Yellow cap Page 35 Right lower column 11th line Last page, Page 45, lines 29-31, page 47, lines 23-63, line 50, color enhancer, page 121, upper left column, line 7 to 125, upper right column, line 1 -----, UV absorber, page 125 Upper right column, second line, page 37, lower right column, lines 14 to 65, page 22, lines 31 to 127, lower left column, end line 38, upper left column, line 11, line Fade prevention agent, page 127, lower right column, line 1 36 Page upper right column 12th line to 4th page 30th line to 5 (image stabilizer) to 137 page lower left column 8 line 37 upper left column 19th line page 23th line, page 29 1st line to 45 page 25 line Page 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 Bottom line, line 14 to page 1, line 1 to 51, or low-boiling organic solvent, page 144, upper right column, end line, page 36, left lower column, bottom to fourth line, medium line, photographic additives, page 144, lower left column 1, Line 27 Page lower right column 10 line to 63 page 51 line to 64 Dispersion to 146 Page upper right column 7 line 28 Page upper left column Last line and page 56 line 35 Page right lower column 12 line 36 Page upper right column, line 7 Hardener 146 Page upper right column, line 8 to page 155 Page lower left column, line 4 --- --- Developing agent precursor 155 Page lower left column, line 5 --- 155 Page lower right column 2 Line Develop development inhibitor release Page 155 Lower right column 3rd line −−−− Compound 9th line Support 155 Page lower right column 19th line 38 Upper right column 18th line to 66th line 29th line to 67th line Page 156 Upper left column Line 14 Page 39 Upper left column Line 3 Page 13 Line 13 Sensitive material layer composition Page 156 Upper left column Line 15 Page 28 Upper right column Line 1-Page 45 Line 41-52-Page 156 Lower right Column 14 line 15 line Dye 156 page lower right column 15 line 38 upper left column line 12 to page 66 line 18 to 22 to page 184 lower right column Last line Upper right column 7th line Line 5 Color mixing inhibitor Page 185 Upper left column 1st line Page 36 Upper right column 8th line-64th page 57th line-65-188 Page lower right column 3rd line 11th line 1st line Gradation control agent Page 188 Lower right column, line 4 −−−− to line 8 Anti-staining agent Page 188 Lower right column, line 9 Page 37 Upper left column Last line to page 65 Line 32 to page 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 Page upper right column, end line Page 24 Right lower column, end line Page 27 Page 27 Bottom left column 10th line from bottom to bottom right column 9th line Fluorine-containing compounds Page 210 Bottom left column 1st line Page 25 Top left column 1st line ~ (Antistatic agent, Coating ~ 222 Page 5 left bottom column 5th line) Page 27, lower right column, line 9 As cloth aids, lubricants, adhesives, etc.) Binder 222 Page, lower left column, line 6 Page 38 Upper right column, line 8 to page 66, line 23 to 28 (hydrophilicity Colloid) ~ Page 225 Upper left column Last line 18th line Line 25 Thickener 225 Page upper right column First line --- --Page 227, upper right column, second line, antistatic agent, page 227, upper right column, third line --- --- to page 230, upper left column, first line, Polymer Latec 230 page, upper left column, second line -----, page 239, last line Eye matting agent Page 240 Upper left column 1st line --- --- Page 240 Upper right column Last line Photo processing method Page 3 Upper right column 7th line ~ Page 39 Upper left column 4th line ~ Page 67 14th line ~ 69 (Process Process and addition Page 10, upper right column, line 5, page 42, upper left column, end line, page 28, line, etc.) The above cited Japanese Patent Laid-Open No. 62-215272 cited at the end of this publication. It also includes the contents amended by the amendment to the procedure dated 16th of March.

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

When the present invention is used for a color paper, as a cyan coupler, in addition to the diphenylimidazole type cyan coupler described in JP-A-2-33144, a cyan coupler described in European Patent EPO, 333,185A2 can be used.
-Hydroxypyridine-based cyan couplers (among others, couplers (42) listed as specific examples are 4-equivalent couplers having a chlorine leaving group to make them 2-equivalent, and couplers (6) and (9) are particularly preferable) and Japanese Patent Laid-Open No. 64-322
Cyclic active methylene-based cyan couplers described in No. 60 (among others, coupler examples 3 and 8 listed as specific examples,
Is particularly preferred).

The silver halide used in the present invention may be silver chloride, silver bromide, silver chlorobromide, silver iodochlorobromide, silver iodobromide, etc. For the purpose of processing, the content of silver chloride containing substantially no silver iodide is 90 mol% or more, further 95% or more, and particularly 98%.
Use of the above silver chlorobromide or silver chloride emulsions is preferred.

Further, in the light-sensitive material of the present invention, a hydrophilic colloid layer is added to the photosensitive colloid layer for the purpose of improving the sharpness of an image, etc., in EP No. 337,490A2 of EP No. 27-.
A dye which can be decolorized by treatment (among others, an oxonol dye) described on page 76 is added so that the optical reflection density at 680 nm of the light-sensitive material is 0.70 or more, or the water-resistant resin layer of the support. 12% by weight or more (more preferably 14% by weight or more) of titanium oxide surface-treated with a dihydric or tetrahydric alcohol (eg, trimethylolethane)
It is preferably contained.

When the present invention is used in a light-sensitive material such as a color paper in which importance is attached to the dye preservability, a color image preserving improving compound as described in European Patent EPO, 277,589A2 is used together with a coupler. Preferably.
In particular, it is preferably used in combination with a pyrazoloazole coupler.

That is, compound (F) and // which chemically bond with the aromatic amine developing agent remaining after the color development processing to form a chemically inactive and substantially colorless compound.
Alternatively, the compound (G) which chemically bonds with an oxidized product of an aromatic amine color developing agent remaining after the color developing treatment to form a chemically inactive and substantially colorless compound is used simultaneously or alone. Are preferable, for example, in order to prevent stain generation and other side effects due to the formation of a coloring dye by the reaction of the coupler with the color developing agent remaining in the film or the oxidant thereof during storage after processing.

The light-sensitive material according to the present invention has a mildewproofing agent as described in JP-A-63-271247 in order to prevent various molds and bacteria which propagate in the hydrophilic colloid layer and deteriorate the image. It is preferable to add an agent.

As the support used in the light-sensitive material of the present invention, a white polyester support for display or a layer containing a white pigment is provided on the support having a silver halide emulsion layer. A support may be used. Further, in order to further improve the sharpness, it is preferable to apply an antihalation layer on the silver halide emulsion layer coated side or the back side of the support. In particular, the transmission density of the support is 0.3 so that the display can be viewed with both reflected and transmitted light.
It is preferably 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, and in the latter case, a laser scanning exposure method in which the exposure time per pixel is shorter than 10 ⁻⁴ seconds is preferable.

Also, upon exposure, US Pat. No. 4,88
It is preferable to use the band stop filter described in No. 0,726. This removes the light mixture,
Color reproducibility is significantly improved.

Techniques and inorganic / organic materials which can be preferably used or used in combination when the present invention is applied to a color photographic light-sensitive material for high-sensitivity photography are described in European Patent 436,93.
It is described in the following section of 8A2 and in the patents cited below. 1. Layer structure: Page 146, line 34 to Page 147, line 25. Silver halide emulsion: pp. 147, line 26-148.
Page 12th line 3. Yellow coupler: Page 137, line 35 to line 146
3. Line 33, page 149, lines 21-23. Magenta coupler: page 149, line 24 to line 28; European Patent No. 421,453A1, page 3, line 5 to
Page 25, Line 55 5. Cyan coupler: page 149, lines 29-33;
5. European Patent No. 432,804A2, page 3, line 28 to page 40, line 2. Polymer couplers: page 149, lines 34-38; EP 435,334A2, page 113, 39.
Line 1-Page 123, Line 37 7. Colored coupler: page 53, line 42 to page 137, line 34, page 149, line 39 to line 45 8. Other functional couplers: page 7, line 1 to page 53, line 41, page 149, line 46 to page 150, line 3; European Patent 435,334A2, page 3, line 1 to line 29
Page 50 line 9. Antiseptic / antifungal agent: Page 150, lines 25-28 10. Formalin Scavenger: Page 149, lines 15-17. 11. Other additives: p. 153, lines 38 to 47; EP 421,453A1, p. 75, line 21 to p. 84, line 56, p. 27, line 40 to p. 37, 4
Line 0 12. Dispersion method: Page 150, lines 4 to 24 13. Support: Page 150, lines 32 to 34 14. Film thickness / film properties: Page 150, lines 35 to 49 15. Color development step: page 150, line 50 to page 151, line 47. 16. Desilvering process: page 151, line 48 to page 152, 53
Line 17. Automatic processor: Page 152, Line 54-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 light-sensitive silver halide emulsion layer or adjacent thereto. Used in non-photosensitive layer. When the yellow coupler of the present invention is added to the non-photosensitive layer, the preferable amount of the silver halide in the adjacent photosensitive layer is 0.001 to 1 mol of silver halide.
It is in the range of 2 mol%, and more preferably 0.005 to 1
It is in the range of mol%.

The yellow coupler of the present invention can be used in combination with a known acylacetamide type yellow coupler other than the present invention. When used in combination, the yellow coupler of the present invention preferably has a composition of 20 to 100 of all yellow couplers.
It is in the range of mol%, and more preferably in the range of 50 to 100 mol%.

The combination may be the same layer or different layers.

The amount of the yellow coupler of the present invention to be used with respect to silver halide is preferably 0.005 to 2 mol, and more preferably 0.01 to 0.5 mol, per mol of silver halide. Is.

The present invention will be described in detail below 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. 100 ml of water solution 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 mixed solution), and then crystallized from an n-hexane-isopropanol mixed solvent to give an exemplary coupler. 5.5 g of the azomethine dye of (1)
Obtained. The melting point was 127 to 128 ° C.

The maximum absorption wavelength λ _max in the visible region in the spectroscopic absorption spectrum of this compound measured in ethyl acetate
And the molecular extinction coefficient ε _{max at the} maximum absorption wavelength were 429.2 nm and 14700 liter · mol ⁻¹ · cm ⁻¹ , respectively.

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

The spectral absorption spectra in Examples 1 and 2 were measured by using a self-recording spectrophotometer UV-260 type manufactured by Shimadzu Corporation in about 2 × 10 ^-5 mol / ethyl acetate.
Performed at room temperature at a concentration of 1 liter.

Example 2 Comparison of Spectral Absorption Characteristics The following characteristic values were selected in order to compare the spectral absorption characteristics.

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

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

Next, the full width at half maximum was used as a characteristic value showing an effective filter effect in the blue light region. Larger half width is desirable.

The azomethine dyes and the azomethine dyes for comparison, which are derived from the couplers of the present invention shown in Chemical formula 21,
The spectral absorption spectrum was measured in ethyl acetate, and S ₆₀ , S ₈₀ and half-value width obtained from the spectrum are shown in Table 1.

[0095]

[Chemical 21]

[0096]

[Table 1] In Table 1, it is possible to compare three sets of A to D, E to G, and H to J.

In A to D, although A and C have large half-value widths, S ₆₀ and S ₈₀ values representing breakage of long wavelength end of absorption are remarkably large, which is an unfavorable absorption.
On the other hand, B in which Ar is an o-chlorophenyl group has an S ₆₀ value,
Although the S ₈₀ value shows a relatively small value, the full width at half maximum becomes small, and it cannot be said that the absorption is preferable. The D of the present invention enables a small S ₆₀ value, an S ₈₀ value and a relatively large half width.

Similar tendencies can be seen in E to G and H to J. Therefore, it is clear that the azomethine dye derived from the coupler of the present invention gives a good absorption at the long wavelength end and gives a spectral absorption spectrum having a wide half width.

Example 3 The surface of a paper support laminated on both sides with polyethylene was subjected to a corona discharge treatment, and then a gelatin subbing layer containing sodium dodecylbenzene sulfonate was provided, and various photographic constituent layers were further coated to prepare a A multilayer color photographic paper (Sample 1) having the layer structure shown was produced. The coating liquid was prepared as follows.

Preparation of coating liquid for fifth layer Cyan coupler (ExC) 32.0 g, 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) 5.0 g, ethyl acetate 50.0 cc and solvent (S
14.0 g of olv-6) was added and dissolved, and this solution was added to 500 cc of a 20% gelatin aqueous solution containing 8 cc of sodium dodecylbenzenesulfonate, and then emulsified and dispersed by an ultrasonic homogenizer to prepare an emulsified dispersion. on the other hand,
Silver chlorobromide emulsion (cubic, 1: 4 of large size emulsion with average grain size 0.58 μm and small size emulsion of 0.45 μm)
Mixture (Ag molar ratio).

The coefficient of variation of the particle size distribution is 0.
09 and 0.11, 0.6 mol% of AgBr was locally contained in a part of the grain surface in each size emulsion).
In this emulsion, the red sensitizing dye E shown below is 0.9 × 10 ^-4 moles per 1 mole of silver for large size emulsions and 1.1 × 10 ^-4 moles for small size emulsions. Has been added. The chemical ripening of this emulsion was performed by adding a sulfur sensitizer and a gold sensitizer. The above emulsified dispersion and this red-sensitive silver chlorobromide emulsion were mixed and dissolved to prepare a coating solution for the fifth layer having the composition shown below.

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

In addition, Cpd-10 and Cpd-11 are provided in each layer.
Were added so that the total amounts were 25.0 mg / m ² and 50.0 mg / m ² , respectively.

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

[0105]

[Table 2]

[0106]

[Table 3]

[0107]

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

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

In order to prevent irradiation, the following dyes (in parentheses represent coating amount) were added to the emulsion layer.

[0110]

[Chemical formula 22] (Layer constitution) The composition of each layer is shown below. Numbers are coating amount (g /
m ² ) is represented. The silver halide emulsion represents the coating amount in terms of silver.

[0111]

[Table 5]

[0112]

[Table 6]

[0113]

[Table 7]

[0114]

[Table 8]

[0115]

[Chemical formula 23]

[0116]

[Chemical formula 24]

[0117]

[Chemical 25]

[0118]

[Chemical formula 26]

[0119]

[Chemical 27]

[0120]

[Chemical 28]

[0121]

[Chemical 29] The known couplers shown below were used as the couplers for comparison.

[0122]

[Chemical 30] The above couplers were replaced so as to be equimolar to the yellow coupler ExY-1 of Sample 1 to prepare Samples 2 to 10.

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

The exposed sample was subjected to continuous processing (running test) using a paper processor using a solution having the following processing step and processing composition until replenishment of twice the tank capacity for color development. Treatment process Temperature Time Replenishment amount ^* Tank capacity Color development 35 ℃ 45 seconds 161 ml 17 liter Bleach fixing 35 ℃ 45 seconds 215 ml 17 liters Rinse (1) 35 ℃ 20 seconds -10 liters Rinse (2) 35 ℃ 20 seconds -10 Liter rinse (3) 35 ℃ 20 seconds 360 ml 10 liter Dry 80 ℃ 60 seconds (* Replenishment amount per 1 m ^{2 of} light-sensitive material) (Rinsing (3) → (1) 3 tank countercurrent method) Each processing The composition of the liquid is as follows.

(Color developer) (Tank liquid) (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 12.0g Potassium chloride 1.6g-Potassium bromide 0.01g-Potassium carbonate 27.0g 27.0g Optical brightener (WHITEX 4B Sumitomo Chemical Co., Ltd.) 1.0g 2.5g Sodium sulfite 0.1g 0.2g Disodium-N, N-bis ( Sulfonatoethyl) hydroxylamine 8.0g 10.0g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 5.0g 7.1g Water is added to 1000ml 1000ml pH (25 ° C) 10.05 10.45 (Bleaching fixer) (same as tank solution and replenisher) Water 600ml Ammonium thiosulfate (700g / l) 100ml Ethylenediamineiron (III) tetraacetate ammonium 55g Ethylenediamine Tetraacetic acid 5g Ammonium bromide 40g Nitric acid (67%) 30g Add water 1000ml pH (25 ℃) (with acetic acid and ammonia water) 5.8 (Rinse solution (tank solution and replenisher are the same)) Ion exchange water (calcium And magnesium are 3ppm each
The following) The sensitometric curve of the blue separation exposed portion of the processed sample was measured through a blue filter and a green filter. The normal yellow color density can be known from the sensitometric curve measured through the blue filter, and the magenta component of the yellow color part can be known from the sensitometric curve measured through the green filter.

The results are shown in Table 9.

[0127]

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

Table 9 can be compared within the respective compound groups A, B and C depending on the kind of the acyl group.

As is clear from the comparison in Group A of Table 9, the couplers (7) and (10) of the present invention give yellow color densities almost equal to those of the comparative couplers ExY1 to 3, and the magenta component thereof is the comparative coupler. It can be seen that the coupler has less hue and excellent hue.

The same applies to Groups B and C, and it is clear that the couplers of the present invention have excellent hue.

Example 4 On a subbed cellulose triacetate film support,
Each layer having the composition shown below was applied in multiple layers to prepare Sample 101, which is a multilayer color light-sensitive material. (Photosensitive layer composition) The main materials used for each layer are classified as follows; ExC: Cyan coupler UV: UV absorber ExM: Magenta coupler HBS: High boiling point organic solvent ExY: Yellow coupler H: Gelatin Curing agent ExS: Sensitizing dye The numbers corresponding to the respective components indicate the coating amount expressed in g / m ² , and for silver halide, the coating amount in terms of silver. However, with respect to the sensitizing dye, the coating amount is shown in mol unit per 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. 4th 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 Sensitivity 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.

9th 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.

10th 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-sensitive 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.

Thirteenth 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.

14th 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.

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

Further, in order to improve the storability, processability, pressure resistance, antifungal / antibacterial property, antistatic property and coating property of each layer, W-1 to W-3, B-4 to B are appropriately added. -6, F
-1 to F-17 and iron salt, lead salt, gold salt, platinum salt,
It contains iridium salt and rhodium salt.

[0146]

[Table 10] In Table 10, (1) Emulsions A to F were reduction-sensitized at the time of grain preparation 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 the preparation of 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.

[0147]

[Chemical 31]

[0148]

[Chemical 32]

[0149]

[Chemical 33]

[0150]

[Chemical 34]

[0151]

[Chemical 35]

[0152]

[Chemical 36]

[0153]

[Chemical 37]

[0154]

[Chemical 38]

[0155]

[Chemical Formula 39]

[0156]

[Chemical 40]

[0157]

[Chemical 41]

[0158]

[Chemical 42]

[0159]

[Chemical 43] The color photographic light-sensitive material as described above was exposed to gray so as to give a density of 0.5, and then the cumulative replenishment amount of the developing solution was 3 times the tank volume by the method described below using an automatic developing machine.
Processing (running processing) was performed until the number of times doubled. (Treatment method) Process Treatment time Treatment temperature Replenishment amount Tank capacity Color development 3 minutes 15 seconds 38 ℃ 22 ml 20 liters Bleach 3 minutes 00 seconds 38 ℃ 25 ml 40 liters Water wash 30 seconds 24 ℃ 1200 milliliters 20 liters Fixed 3 Minutes 00 seconds 38 ℃ 25 ml 30 liters Water wash (1) 30 seconds 24 ℃ From (2) to (1) 10 liter countercurrent piping system Water wash (2) 30 seconds 24 ℃ 1200 ml 10 liters Stability 30 seconds 38 ℃ 25 ml 10 liter Dry 4 min 20 sec 55 ° C Replenishment amount per 35 mm width 1 m length The composition of the treatment liquid is described below.

(Color developer) Tank liquid (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 Potassium iodide 1.5 mg-hydroxylamine sulfate 2.4 2.8 4- (N-ethyl-N-β-hydroxyethylamino) -2-methylaniline sulfate 4.5 6.2 Water was added to 1.0 liter 1.0 liter pH 10.05 10.15.

(Bleaching solution) Tank solution (g) Replenishing solution (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.

(Fixer) 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 / liter) 290.0 ml 320.0 ml 1.0 liter 1.0 liter pH by adding water 6.7 7.0.

(Stabilizing Solution) Common Tank Solution / Replenishing Solution (g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether (Average degree of polymerization 10) 0.2 Ethylenediaminetetraacetic acid disodium salt 0.05 1,2 , 4-triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 Water was added to 1.0 liter pH 8.5.

Next, the yellow coupler ExY of sample 101
Samples 102 to 105 were prepared by substituting ExY-3 and the coupler of the present invention so that all of -2 had an equimolar amount.

The above samples 101 to 105 were exposed to blue separation light passing through a blue filter and treated with the above running treatment liquid, and then sensitometric curves were measured. For the sample 101, the blue light density D of each sample at the exposure amount at which the blue light density is 1.0 when the fog portion is the reference
_B is shown in Table 11.

The sample 101 with the same exposure amount was used as a reference (±
0.00) green density ΔD _G (B = 1.0)
The results are also shown in Table 11.

It can be said that the smaller the ΔD _G (B = 1.0), the more excellent the hue of the yellow dye and the more preferable the coupler in terms of color reproduction.

[0168]

[Table 11] As is clear from Table 11, the couplers of the present invention have smaller ΔD _G (B = 1.0) (larger absolute value as a negative value) than the comparative examples in each compound group, and are preferred couplers for color reproduction. Can be said to be.

Claims (2)

[Claims] 1. An N- (8-quinolyl) -acylacetamide type yellow dye-forming coupler. 2. A silver halide color photographic light-sensitive material containing at least one yellow dye-forming coupler according to claim 1.