US3685995A

US3685995A - Yellow-forming coupler compounds and color photographic elements containing same

Info

Publication number: US3685995A
Application number: US26350A
Authority: US
Inventors: Makoto Yoshida; Momotoshi Tsuda; Yasushi Oishi; Kiyoshi Nakazyo
Original assignee: Fuji Photo Film Co Ltd
Current assignee: Fujifilm Holdings Corp
Priority date: 1969-04-07
Filing date: 1970-04-07
Publication date: 1972-08-22
Anticipated expiration: 1989-08-22
Also published as: FR2043023A5; DE2016585A1; CH548622A; BE748592A; GB1261156A; JPS4815872B1; CA970200A

Abstract

NOVEL YELLOW-FORMING COUPLER COMPOUNDS, REPRESENTED BY THE FORMULA 1-((2-X,Y-PHENYL)-NH-CO-CH2-CO-),3-(R''-CO-NH-),4-(R-O-)BENZENE WHEREIN X REPRESENTS A HALOGEN ATOM, A LOWER ALKOXYL GROUP, A DIALKYLAMINO GROUP OR AN ARYLOXY GROUP; Y REPRESENTS A HYDROGEN ATOM, A HALOGEN ATOM, A TRIFLUOROMETHYL GROUP A CYANO GROUP, AN ALKYL GROUP HAVING LESS THAN 8 CARBON ATOMS, AN ALKOXYL GROUP, AN ARYLOXY GROUP, AN ACYL GROUP, A CARBAMYL GROUP, AN ACYLAMINO GROUP, A SULFOAMINO GROUP, A SULFOAMOYL GROUP, A CARBOALKOXYL GROUP, OR AN AMINO GROUP; R REPRESENTS AN ALKYL GROUP HAVING 1 TO 5 CARBON ATOMS; AND -COR'' REPRESENTS AN ACYL GROUP HAVING 9 TO 28 CARBON ATOMS, AND METHODS OF THEIR PREPARATION ARE DISCLOSED. COLOR PHOTOGRAPHIC LIGHT-SENSITIVE ELEMETNS CONTAINING THESE COMPOUNDS ARE ALSO DISCLOSED.

Description

Aug. 22, 1972 MAKOTO YOSHIDA ETAL 3,685,995

YELLOW-FORMING COUPLER COMPOUNDS AND COLOR PHOTOGRAPHICM ELEMENTS CONTAINING SAME Filed April 7, 1970 F IG, i

WAVE LENGTH (MILLIMICRONS) INVENTORS MAKOTO YOSHIDA d a V MOMOTOSHI TSUDA 460 560 660 YASUSH! OISHI WAVE LENGTH (MILLIMICRONS) K'YOSHI NAKAZYO g m ifm M, BY 71% 4 Mar aK.

ATTORNEYS United States Patent O US. Cl. 96-100 13 Claims ABSTRACT OF THE DISCLOSURE Novel yellow-forming coupler compounds, represented by the formula NHCOR Y I NHOOCH2G OOR I X (I) wherein X represents a halogen atom, a lower al'koxyl group, a dialk'ylamino group or an aryloxy group; Y represents a hydrogen atom, a halogen atom, a trifluoro methyl group, a cyano group, an alkyl group having less than 8 carbon atoms, an alkoxyl group, an aryloxy group, an acyl group, a carbamyl group, an acylamino group, a sulfoamino group, a sulfoamoyl group, a carboalkoxyl group, or an amino group; R represents an alkyl group having 1 to carbon atoms; and -COR represents an acyl group having 9 to 28 carbon atoms, and methods of their preparation are disclosed. Color photographic light-sensitive elements containing these compounds are also disclosed.

BACKGROUND OF THE INVENTION (1) Field of the invention The present invention relates to a color photographic light-sensitive element containing a novel yellow-forming coupler.

(2) Description of the prior art For forming a color photographic image based on a subtractive color process, couplers, which form cyan, magenta and yellow dyes respectively by the coupling thereof with the oxidation product of a developing agent, a N,N-di-substituted paraphenylenediamine compound, formed simultaneously when silver halide emulsion grains are developed by said developing agent, are generally employed.

In general, as the yellow-forming coupler the acylacetanilide derivatives are well known.

The yellow dye image formed in a color photography by a subtractive color process absorbs usually blue light of a wavelength range of from about 400 millimicrons to about 500 millimicrons. In the preferable spectral absorption characteristics of the yellow image, the image has a strong absorption in the above-mentioned range of wave lengths but has less absorption in the green range and the red range having wave lengths longer than 500 millimicrons.

In the case where the couplers are incorporated in silver halide emulsions having corresponding spectral sensitivities repsectively during the production of multiplelayer type color photographic light-sensitive elements, the couplers must possess diffusion resistance or ballasting property for preventing the migration of each of the couplers in a silver halide emulsion layer into another emulsion layer, whereby the coupler is mixed with other couplers to degrade the color reproducing property. For

Patented Aug. 22, 1972 ice this purpose, it is necessary to introduce a ballasting group, having more than 8 carbon atoms and capable of reducing the diffusion resistance into the coupler molecule.

For incorporating such a ballasted coupler in a photographic emulsion layer, two methods are known. These methods are an aqueous solution method and an oil solution method. In the former method, the ballasted coupler has a water-solubilizing group and is incorporated in the silver halide emulsion as an alkaline solution thereof in water, whereas in the latter method the coupler is dissolved in an organic solvent and the resultant solution is added to a silver halide emulsion as an emulsified dispersion of the fine colloidal particles thereof in an aqueous medium. The yellow-forming coupler incorporated in a photographic emulsion layer by the aforesaid oil-solution method can give dye images with better spectral absorption characteristics and higher stability to moisture than those of the yellow coupler incorporated by the water-solution method. The coupler employed in the above-mentioned oil-solution method must be readily soluble in an organic solvent for preparing the dispersion and to be less crystallizable in the solvent.

On the other hand, in order that the photographic emulsion layer have high sensitivity, good gradation and developing speed as well as a high yield when the coupler is converted into a yellow dye, it is necessary that the coupler incorporated in the silver halide emulsion layer have a coupling reactivity of a definite level with the oxidation product of a N,N-di-substituted para-phenylene diamine developing agent. However, a conventional yellow coupler incorporated in a photographic emulsion layer by the oil-solution method generally shows a low coupling reactivity.

Furthermore, color images obtained from conventional yellow-forming couplers heretofore known generally have a tendency to fade when they are exposed to intense light for a long period of time. This has been a big hindrance in storing the color photographs for a long period of time.

Thus, in the field of manufacturing color photographic light-sensitive elements, the yellow-forming couplers to be employed in the oil-solution system desirably should possess sufficient coupling reactivity, should have less green absorption, and should give rise to dye images which are fast to light.

For the purpose, various improvements by introducing various substituents to acylanilide compounds have been attempted. For example, it has been discovered previously that the introduction of a methyl group to the benzoyl ring of an a-benzoyl-Z-(alkoxy or halo)-5-acylaminoacetanilide or an a-benzoyl-2-(alkoxy or halo)-5-carboalkoxy acetanilide, as disclosed in Japanese patent application No. 3,236/ 1966, a lower alkoxy group to the 4-position of the benzoyl ring of an a-benzoyl 2. halo(4 or 5)- acylaminoacetanilide, as disclosed in Japanese patent application No. 3,985/ 1966, and an amino group to the 4-position of the benzoyl ring of an a-benzoyl 2 halo- (4 or 5)-acylaminoacetanilide, as disclosed in Japanese patent application No. 56,965/1968, is effective for improving the spectral absorption characteristics and the light-fastness of the color images obtained from the aforesaid acetanilides. In these compounds disclosed above, a ballasting group giving diffusion resistance to these compounds is positioned to the anilide ring thereof as an acylamino group or a carboalkoxyl group.

DESCRIPTION OF THE INVENTION Yellow-forming couplers have been investigated and as the result thereof, it has been discovered also that compounds represented by the following general Formula I, shown below, have particularly excellent properties as yellow-forming couplers suitable for the oilsolution system and having suflicient diffusion resistance ITIHCOR l X Formula I wherein X represents a halogen atom, a lower alkoxyl group, a dialkylamino group or an aryloxy group; Y represents a hydrogen atom, a halogen atom, a trifluoromethyl group, a cyano group, an alkyl group having less than 8 carbon atoms, an alkoxyl group, an aryloxy group, an acyl group, a carbamyl group, an acylamino group, a sulfoamino group, a sulfoamoyl group, a carboalkoxyl group, or an amino group; R represents an alkyl group having 1 to carbon atoms; and COR' represents an acyl group having 9 to 28 carbon atoms.

The substituent represented by Y is introduced to one of the 3-, 4- and 5-positions of the anilide ring. That is, a compound having group Y at the 6-position of the anilide ring has an extremely low coupling reactivity and provides a yollow image having a strong green absorption, and hence is unsuitable for the purposes of the present invention.

By the introduction of group Y to the 3-, 4- or 5-position of the anilide ring of the compound represented by general Formula I, the coupling reactivity of the coupler and the spectral absorption characteristics of color image can be improved without reducing the fastness of the color image obtained. The improvements in the introduction of two substituents X and Y on the anilide ring have been very difficult in the above-mentioned compounds of our previous invention each having a ballasting group at the anilide ring.

If the acyl group represented by COR' in the general Formula I has less than 9 carbon atoms, sufficient oilsolubility and diffusion resistance to the coupler does not result, while if the number of carbon atoms in the acyl group is larger than 28, the molecular weight of the coupler is so much increased that the blue absorption per unit weight or volume of the yellow dye formed is reduced, the solubility of the coupler itself is reduced due to the increased dispersing power based on the acyl group, and also the thickness of the photographic emulsion layer containing the coupler must be increased to provide a definite blue density to the photographic emulsion layer. As the acyl group represented by -COR' in the general Formula I, a substituted or unsubstituted aliphatic acyl group or the following groups are particularly suitable:

wherein R represents an alkyl group having 5 to 18 carbon atoms, R and R each represents an alkyl group having less than 9 carbon atoms, R represents a hydrogen atom or an alkyl group having less than 3 carbon atoms,

and n is a positive integer of 2 to 5.

By selecting the acyl group represented by COR' in the above-mentioned general Formula I properly, the

coupler can have sufficient oil solubility for being dispersed in the oil-solution system.

The above-described novel yellow-forming couplers of the present invention provide color images which are extremely stable when exposed to intense light. Moreover, the fading tendency in light of the color image obtained with the novel yellow-forming coupler of the present invention can be further reduced by providing an ultra violet absorption layer capable of absorbing selectively light, having wave lengths shorter than about 400 millimicrons, on the surface of the silver halide emulsion layer having the yellow image formed by the coupling of said coupler, on the side exposed to light. Suitable ultraviolet absorption layers are disclosed in Japanese patent application No. 19,299/1968.

The yellow coupler obtained from the novel yellowforming coupler of the present invention is resistant to the actions of heat and moisture. Thus, the color photograph obtained from the color photographic light-sensitive element of the present invention can be stored stably for a long period of time even under severe conditions with less discoloring and fading.

The yellow-forming coupler of this invention represented by the general Formula I can give a yellow image having spectral absorption characteristics suitable for the requirements of color reproduction in substractive color process. This advantage will be explained below in comparison with known yellow-forming coupler represented by the following general Formula II ITTHC OR wherein X and COR have the same meaning as described in regard to the general Formula I.

BRIEF DESCRIPTION OF THE ACCOMPANYING DRAWINGS In FIG. 1 of the accompanying drawings the spectral absorption curve (Curve 1) of an ethyl acetate solution of the yellow dye prepared by the oxidation coupling of the novel coupler having the general Formula I, 3-[04-(2', 4'-di-tert amylphenoxy)butylamido]-4-me.thoxybenzoylaceto-2-chloroanilide, and a developing agent, 4-amino-3- methyl-N,N-diethylaniline, and the spectral absorption curve (Curve 2) of an ethyl acetate solution of the yellow dye obtained by the oxidation coupling of a known coupler having the general Formula II, 3-(2',4'-di-tertamylphenoxy)acetoamido benzoylaceto-Z-chloroanilide, and the aforesaid developing agent are shown. As can be seen in the graph shown in FIG. 1, the yellow-forming coupler of the present invention provides a clear yellow dye having a spectral absorption curve sharper on the long wave length side than the absorption of the conventional coupler and having less green absorption of wave lengths longer than 500 millimicrons than the absorption of the conventional coupler.

DETAILED DESCRIPTION OF THE INVENTION It is advantageous that the organic solvent used for dissolving the coupler of the present invention in preparing a color photographic light-sensitive element be substantially water-immiscible and have a boiling point higher than C. at normal pressure. Such an organic solvent having a high boiling point and being immiscible with Water not only facilitates the emulsifying disperson of the coupler but also contributes to preventing the crystallization of the coupler, improves the spectral absorption characteristics of the color image, and improves the stability of the color image by staying in the emulsion layer together with the coupler.

Suitable organic solvents are carboxylic acid esters, phosphoric acid esters, carboxylic acid amides, ethers, and substituted hydrocarbons.

Specific examples of these organic solvents are di-nbutyl phthalate, di-iso-octyl azelate, dibutyl sebacate, tricresyl phosphate, N,N-diethyl caprylic amide, butyl-npentadecyl phenyl ether, and chlorinated parafiin.

For finely dispersing the coupler of the present invention in an aqueous medium, it is desirable to use a low boiling solvent or a high boiling water-miscible solvent alone or together with the above-described water-immiscible high boiling solvents. Suitable specific examples of these solvents are propylene carbonate, ethyl acetate, cyclohexanol, tetrahydrofur'an, cyclohexanone, dimethyl formamide, ethylene glycol monomethyl ether, and the like.

As the color developing agent used for converting the coupler of this invention effectively to an azomethine dye in the presence of light-exposed silver halide, a N,N-disubstituted-para-phenylenediamine derivative is preferred. Specific examples of these derivatives are N,N-dimethyl-p-phenylenediamine,

N,N-diethyl-p-phenylenediamine,

N-ethyl-N- (,B-hydroxyethyl -p-phenylenediamine,

4-amino-3-methyl-N,Ndiethyl-p-phenylenediamine,

4-amino-3 -methyl-N-ethyl-N- (fl-hydroxyethyl p-phenylenediamine,

4-amino-3-methyl-N-ethyl-N- B-methanesulfonamidoethyl) -p-phenylenediamine.

The salts of these phenylenediamines are also suitable.

For forming a blue-sensitive photographic emulsion layer having improved properties, the couplers represented by the general Formula I can be used alone in combinations of two or more such couplers, or together with other conventional yellow-forming couplers. Furthermore, it is sometimes advantageous to use the coupler represented by the general Formula I together with a known yellowforming coupler employed in the water-solution system.

The present invention can be applied to various kinds of light-sensitive elements with good results. For example, the invention can be applied to color photographic printing papers, color photographic positive films, color photographic negative films and color photographic reversal Compound A lTII-ICOCHQO- Compound B (32115 llVHC CH0- Compound C NHCOCHzOHzN CJHQ NHCOCHECO OCH3 OCHa Compound D IT HC O CHO- C H (tert) Nrr0ocH2c0--oom 0511mm) (LCHs Compound E IIIHCO CH2O 1 o1 NHCOCH2COOCH; 015mm I Cl Compound F C2H5 F3|C lIIHCOCHO- -C5H11(tert) -Nnooon2oo-o CH3 CsHMtert) Compound G (3 015 31 (C H gNOgS NHCOOH'JCHQN C4H9 NHCOCH2CO- -OCH3 Compound H (01% 0 ONE ITIHCOCH:O-Q C5Hn(see( l @mnooomoo-Q-o on; 0511mm Compound .T

I armonic-0511 (rm ONHCOCH2CO-OC2H5 (5211mm Compound K CzHs l CH3 0 IIIH o 0 on 0-o5m1 (tert) Nncoomoo o on, ofinlldert Compound N (ll H (n) C H1 O O O NHCOCHO- C Hn(tert) O-mrooomoo-Q-o on C5Hll( l?li) Compound 0 0211 NIICOCI{3COOCH3 C Hi1(tert) Compound P ozHmNo o r nooclsuu NHC o crI2oo -o out Compound Q CHzC 0 OH NHC O CHCH=CHCH33 -Nr1oooHto o -oorn Compound S (ca s) 2N 1S N C H3) 2 PREPARATION EXAMPLE 1 (la) Preparation of 4-methoxy-3-nitrobenzoylaceto-(2-chloro)anilide A 500 ml. three-necked flask was equipped with a stirrer, a thermometer, and a conduit for discharging alcohol produced as a by-product and in the flask were charged 134 g. of ethyl-4-methoxy-3-nitrobenzoyl acetate, 64 g. of o-chloroaniline, and 100 ml. of xylol and the system was heated to about 134 C. with stirring. The reaction was conducted for about one hour, and 18.5 g. of ethanol was recovered as the by-product. Thereafter, the system was cooled and 500 ml. of methanol was added to the product to crystallize the product, which was filtered 01f and washed with 300 ml. of methanol followed by drying to provide 141 g. (81.5% yield) of the crystals of the above-mentioned anilide having a melting point of 169-170 C.

(1-b) Preparation of 3-amino-4-methoxybenzoylaceto- (2-chloro) anilide Compound R Cal-I5 l NHCOCHO C H 1(tert) In a two liter three-necked flask equipped with a stirrer, a condenser, and a dropping funnel were charged 141 g. of the anilide obtained above and then 200 ml. of dimethylformamide. After heating the system with stirring to dissolve the anilide in the solvent, 140 g. of reduced iron and 300 ml. of ethanol were added to the solution followed by stirring. Thereafter, 300 ml. of concentrated hydrochloric acid was added dropwise through the drop ping funnel and the system reacted vigorously for minutes. After cooling the system gradually, the product was poured in 2 liters of ice-cooled water and the crystals (1-c) Preparation of 3-.(2,4 tert aniylphenoxy)acetamide 4 methoxy benzoylaceto 2 chloroanilicle (Compound A) In a one liter three-necked flask were charged 16 g. of the amino compound prepared above, 200 ml. of acetic acid, and 8 g. of anhydrous sodium acetate and the mixture was stirred. To the mixture was added 15.5 g. of o;-(2,4-di-tert-amylphenoxy)acetylchloride and the resultant mixture was stirred for 3 hours. The product was poured in ice-cooled water and the crystals thus formed were recovered by filtration, washed with water, and recrystallized from methanol to provide 20 g. (68% yield) of Compound A having a melting point of 164-165 C.

PREPARATION EXAMPLE 2 Preparation of 3-[ot- (2,4' di tert-amylphenoxy)butylamido]-4-methoxy-benzoylaceto-2-chloroanilide (Compound B) The same procedure as used in Preparation Example (1c) was followed using 16 g. of the amino compound prepared as in Preparation Example (l-b), 200 ml. of acetic acid, 8 g. of anhydrous sodium acetate, and 19 g. of ot-(2,4-di-tert-amylphenoxy)butyryl chloride to provide 18 g. (58% yield) of Compound B having a melting point of 110-111 C.

PREPARATION EXAMPLE 3 (3a) Preparation of 4-methoxy-3-nitrobenzoylaceto-(2-methoxy)anilide The same procedure as used in Preparation Example (l-a) was followed by using 62 g. of o-anisidine instead of o-chloraniline to provide 159 g. (92% yield) of the above-mentioned anilide having a melting point of 168- 169 C.

(3b) Preparation of 3-amino-4-methoxybenzoylaceto- Z-methoxy) anilide The same procedure as in Example l-b) was followed by using 142 g. of the nitro compound prepared by Example .(3-a) instead of 4-met-hoxy-3-nitrobenzoylaceto- (2-chloro) anilide to provide 81 g. of the amine having a melting point of 128 C. with a yield of 64%.

(3c) Preparation of 3 [m-(2,4-di-tert-amylphenoxy)- butylamido] 4 methoxy henzoylaceto- 2 -meth0xyanilide (Compound D) The same procedure as used in Preparation Example (1-c) was followed using 47 g. of the amino compound prepared as in Preparation Example (1-b), 300 ml. of acetic acid, 37 g. of anhydrous sodium acetate, and 57 g. of a-.(2,4-di-tert-amylphenoxy)butyryl chloride to provide 47 g. (47% yield) of the crystals of the above-mentioned anilide (Compound D) having a melting point of 89 C.

PREPARATION EXAMPLE 4 (4-a) Preparation of 4-methoxy-3-nitrohenzoylaceto- (2-chloro-S-tri-fluoromethyl)anilide The same procedure as used in Preparation Example (1a) was followed using 58 g. of 2-chloro-5-fluoromethylaniline instead of o-chloroaniline to provide 166 g. yield) of the aforesaid anilide having a melting point of 168169 C.

(4-b) Preparation of 3-amino-4-methoxybenzoylaceto- (2-chloro-5-tri-fluoron1ethyl)anilide The same procedure as used in Preparation Example (1-b) was followed by using 100 g. of the nitro compound prepared as in Preparation Example (4a), 100 ml. of dimethyl-formamide, 300 ml. of ethanol, 100 g. of reduced iron and 200 ml. of concentrated hydrochloric acid to provide 53 g. (57% yield) of the amine having a melting point of 154155 C.

(4-c) Preparation of 3 [a-(2,4-di-tert-amylphenoxy)- butyl-amido]-4-methoxybenzoylaceto 2 chloro 5- tri-fiuoromethyl-anilide (Compound F) The same procedure as used in Preparation Example (1-c) was followed using 53 g. of the amino compound prepared as in Preparation Example (4-b), 400 ml. of glacial acetic acid, 34 g. of anhydrous sodium acetate and 53 g. of or-(2,4-di-tertamylphenoxy)butyryl chloride to provide 61 g. (63.5% yield) of Compound 'F having a melting point of 149-150 C.

PREPARATION 'EXAMPLE 5 (5-a) Preparation of 4-chloro-3-nitro-pivaloylanilide In a one liter three-necked flask equipped with a stirrer, a condenser, and a dropping funnel were charged 147 g. of 4-chloro-3-nitroaniline, 500 ml. of acetone and 6 g. of triethylamine, and the mixture was stirred. Thereafter, 103 g. of pivaloyl chloride was added dropwise to the system through the dropping funnel and then the system was stirred for 2 hours at temperatures of 4050 C. After distilling off /2 of the acetone, the reaction product solution was poured in two liters of ice-cooled water acidified with hydrochloric acid to crystallize the product, which was recovered by filtration, washed with water and recrystallized from methanol to provide 119 g. (53% yield) of the pure crystals of the aforesaid anilide having a melting point of 103-l05 C.

(5-b) Preparation of 2-chloro-S-pivaloylamidianiline In a one liter autoclave were charged 119 g. of the nitro compound prepared as in Preparation Example (5-1), 300 ml. of ethanol, and about 5 g. of Raney nickel catalyst and the nitro compound was reduced at 80-85 C. under a hydrogen pressure of 70 kg./cm. After filtering off the nickel catalyst and distilling off /2 of the ethanol, the system was cooled and the crystals thus formed were recrystallized from ethanol to provide 83 g. (79% yield) of the above-mentioned aniline having a melting point of 152 C.

(5-c) Preparation of 4-methoxy-3-nitrobenzoylaceto-2- chloro-S-pivaloylamido aniline The same procedure as used in Preparation Example (1-a) was followed by using 83 g. of the 2-chloro-5- pivaloylamidoaniline prepared as in Preparation Example (5-b) to provide 137 g. (84% yield) of the abovementioned anilide having a melting point of 182-183 C.

(S-d) Preparation of 3-amino-4-methoxybenzoylaceto-Z- chloro-S-pivaloylamido anilide The same procedure as used in Preparation Example (l-b) was followed by using 137 g. of the nitro compound prepared as in Preparation Example (5-c), 200 ml. of dimethyl-formamide, 200 ml. of ethanol, 130 g. of reduced iron, and 400 ml. of concentrated hydrochloric acid to provide 85 g. (67% yield) of the anilide mentioned above having a melting point of 165 C.

(5-e) Preparation of 3-[a-(2',4'-di-sec-amylphenoxy)- acetamido] 4 methoxy-benzoylaceto 2 chloro-5- pivaloylamido-anilide (Compound H) In a one liter three-necked flask were charged 40 g. of the amino compound prepared as in Preparation Example (S-d), 400 ml. of acetone, and 12 g. of triethylamine with stirring and after adding 30 g. of a-(2,4-di-sec-amyl- PREPARATION EXAMPLE 6 (6a) Preparation of 4-methoxy-3-nitrobenzoylaceto- (2,5-di-methoxy) anilide The same procedure as used in Preparation Example (1-a) was followed by using 77 g. of 2,5-dimethoxyaniline instead of o-chloroaniline in the same example to provide 182 g. (97% yield) of the anilide having a melting point of 205 C.

(6b) Preparation of 3-amino-4-methoxybenzoylaceto- (2,5-di-methoxy anilide The same procedure as used in Preparation Example (l-b) was followed by using 182 g. of the nitro compound prepared as in Preparation Example (6a), 400 ml. of dimethylformamide, 400 ml. of ethanol, 180 g. of reduced iron, and 400 ml. of concentrated hydrochloric acid to provide 94 g. (57% yield) of the above-described anilide having a melting point of 138 C.

(6c) Preparation of 3-[a-(2',4-di-tert-amylphenoxy)- butyl amido] 4 methoxybenzoylaceto 2,5 dimethoxyanilide (Compound K) The same procedure as used in Preparation rExample (1c) was followed by using 52 g. of the amino compound prepared as in Preparation Example (l-b), 37 g. of anhydrous sodium acetate, 300 ml. of glacial acetic acid, and 57 g. of a-(2,4-di-tert-amylphenoxy)butyryl chloride to provide 60 g. (62% yield) of the above dimethoxyanilide having a melting point of C.

PREPARATION EXAMPLE 7 (7-a) Preparation of 4-methoxy-3-nitrobenzoylaceto- (Z-methoxy-5 N,N-diethylaminosulfo) anilide The same procedure as used in Preparation Example (1-a) using 129 g. of 2-methoxy-S-N,N-diethylaminosulfoaniline instead of o-chloroaniline in the example to provide 167 g. (70% yield) of the above anilide having a melting point of 198 C.

(7-b) Preparation of 3-amino-4-methoxybenzoylaceto- (Z-methoxy-5 N,N-diethylaminosulfo) anilide The same procedure as used in Preparation Example (1-b) was followed by using 167 g, of the nitro compound prepared as in Preparation Example (7-a), 300 ml. of dimethyl-formamide, 300 ml. of ethanol, g. of reduced iron, and 350 ml. of concentrated hydrochloric acid to provide 98 g. (62% yield) of the above-described anilide having a melting point of 137138 C.

(7-c) Preparation of 3 [a (2',4' di tert amylphenoxy) butyl amido] 4 methoxybenzoylaminosulfoanilide (Compound M) The same procedure as used in Preparation Example (1-c) was followed by using 67 g. of the amino compound prepared as in Preparation Example (7-b), 300' ml. of glacial acetic acid, 37 g. of anhdrous sodium acetate, and 57 g. of a-(2,4-di-tert-amylphenoxy)butyryl chloride to provide 72 g. (64% yield) of Compound M having a melting point of 1l0-112 C.

PREPARATION EXAMPLE 8 (8 a) Preparation of 4-methoxy-3-nitrobenzoylaceto- (Z-methoxy-S-methyl) anilide The same procedure as used in Preparation Example (l-a) was followed byusing 137 g. of 2-methoxy-5- methylaniline instead of o-chloroaniline in the example 11 to provide 168 g. (94% yield) of the aforesaid anilide having a melting point of 202203 C.

(8-b) Preparation of 3-amino-4-methoxy-benzoylaceto- (Z-methoxy-S-methyl)anilide The same procedure as used in Preparation Example (1-b) was followed by using 168 g. of the nitro compound prepared as in Preparation Example (8-a), 300 ml. of dimethylformamide, 300 ml. of ethanol, 150 g. of reduced iron, and 300 ml. of concentrated hydrochloric acid to provide 86 g. (56% yield) of the aforesaid anilide having a melting point of 105 C.

(8c) Preparation of 3-[ot-(2',4'-di-tert-amylphenoxy)- butylamido] 4 methoxybenzoylaceto-2-methoxy-5- methyl-anilide (Compound The same procedure as used in Preparation Example (1-c) was followed by using 49 g. of the amino compound prepared as in Preparation Example (8b), 300 ml. of glacial acetic acid, 37 g. of anhydrous sodium acetate, and 57 g. of a-(2,4-di-tert-amylphenoxy)-butyryl chloride to provide 56 g. (59% yield) of Compound 0 having a melting point of 107109 C.

Now, the present invention will be explained further by the following examples.

EXAMPLE 1 A solution prepared by refluxing a mixture of 30 g. of Compound B shown by the aforesaid structural formula, ml. of di-n-butyl phthalate, and 60 ml. of ethyl acetate was added to 600 ml. of an aqueous solution containing 50 g. of gelatin and 2.5 g. of sodium dodecylbenzene sulfonate with stirring and the resultant mixture was passed five times through a colloid mill, whereby the coupler was dispersed by emulsification together with the solvents.

The entire amount of the dispersion was added to 1.0 kg. of a silver halide emulsion containing 54 g. of silver iodobromide and 60 g. of gelatin and after adding ml. of an acetone solution of 3 triethylene phosphamide as a hardening agent and adjusting the pH of the emulsion to 6.0, the resultant silver halide emulsion was applied to a triacetyl cellulose film at a dry thickness of 7.0 microns. The light sensitive film thus prepared is designated hereinafter as Film U.

For comparison, the same procedure described above was repeated with the exception that a conventional coupler (a) having the general Formula II above-mentioned, 3-(2',4'-di-tert-amylphenoxy)acetamidobenzoylaceto 2- chloroanilide, was used instead of the coupler of the present invention and also the same amount of cyclohexanone was employed instead of ethyl acetate to prepare a control light-sensitive film, hereinafter designated Film Each of the light-sensitive films was subjected to graduated exposure for sensitometry and processed as follows:

Temperature, Time 0.) (min.)

(1) Color development (2) Washing. (3) First fixing l) \Vashing (5) Bleaching (ti) Washing (7) Second fixing (8) Washing.

The composition of the color developer used in the above color development was as follows:

The fixing solution and the bleaching solution used above were aqueous solutions, each containing sodium thiosulfate and a ferricyanide, respectively.

Films U and V each showed the maximum density of 2.85 and 2.95 respectively to blue light.

The spectral absorption curves of the colored images of these two films obtained by the above photographic procedures are shown in FIG. 2 of the accompanying drawings. As shown in FIG. 2, the spectral absorption curve of the color image obtained by using Film U (Curve 3) shows less absorption in the wave length region longer than 500 millimicrons as compared with the spectral absorption curve of the color image obtained by using Film V (Curve 4). According to the result, Film U gave a less reddish brilliant yellow image as compared with the color image of Film V.

The two photographic films thus processed were exposed for 40 hours to light from a xenon arc lamp of 1.5 watts and thereafter were measured on reduction in blue densities, the results of which are shown below:

FADTNG 0F YELLOW IMAGE BY LIGHT EXPOSURE* Film Coupler Initial density 1 0 (2.0) U B 18 (15) V A 35 (25) *Thc reduction in percentage of blue density to the initial density.

EXAMPLE 2 A mixture of 21 g. of the Coupler F shown before, 20 ml. of di-n-butyl phthalate, and 45 ml. of cyclohexanone was heated to 60 C. to dissolve the coupler and the solution thus prepared was added to 300 ml. of an aqueous solution containing 25 g. of gelatin and 1 g. sodium dodecylbenzene sulfonate, and stirred vigorously, whereby the coupler was dispersed together with the solvents.

The entire amount of the dispersion was added to 500 g. of a photographic emulsion containing 45 g. of silver iodobromide and 50 g. of gelatin and after adding to the mixture 30 ml. of a 3% acetone solution of triethylene phosphamide as a hardening agent and adjusting the pH of the mixture to 7.0, the resultant mixture was applied to a triacetyl cellulose film at a dry thickness of 6.0 microns.

The film was exposed and processed as in Example 1, whereby a yellow image having a high coupling density and an absorption maximum at 456 millimicrons was obtained. When the photograph thus processed was stored for 20 days under the conditions of 65 C. in temperature and 75% in relative humidity, substantially no reduction in blue density was observed.

EXAMPLE 3 A solution prepared by heating a mixture of 15.5 g. of the Compound K shown above, 8 ml. of di-n-butyl phthalate, and 30 ml. of butyl acetate was added to an aqueous solution containing 10 g. of gelatin and 0.7 g. of sodium dodecylbenzene sulfonate. The mixture was stirred for 15 minutes vigorously in a high speed mixer, whereby the coupler was dispersed finely.

The entire amount of the dispersion was mixed with 1 kg. of a blue-sensitive photographic emulsion containing 45 g. of silver chlorobromide and 70 g. of gelatin and, after adding 30 ml. of a 3% acetone solution of triethylene phosphamide as a hardening agent and adjusting the pH thereof to 6.0, the resulting mixture was applied to a triacetyl cellulose film in a dry thickness of 6.5 microns.

To the emulsion layer prepared were applied a rcd-sensitive emulsion containing the cyan-forming coupler b having the structure shown below, a green-sensitive emulsion containing the magenta-forming coupler 0 having the structure shown below, and finally a protective layer of gelatin to provide a color photographic light-sensitive element.

Coupler b (|)H C ONHC 18H37 Coupler c CsHn(tert)-OCHONH I 051111 (ten) NHCONH? 'ClH3 The color photographic positive film thus prepared was exposed through a color negative and processed as in Example 1 to provide a clear color positive. In particular, the yellow image of the color positive showed excellent heat and moisture resistance.

EXAMPLE 4 A solution prepared by heating a mixture of 20 g. of the Compound M shown above, 30 ml. of tricresyl phosphate, and 50 ml. of ethyl acetate was mixed with 250 ml. of an aqueous solution containing 1.5 g. of sodium dodecyl sulfate and 20 g. of gelatin and the mixture was stirred vigorously for 30 minutes in a homogenizer, whereby the coupler was finely dispersed together with the solvents.

The entire amount of the dispersion was added to 540 .g. of a blue-sensitive photographic emulsion containing 30 g. of silver chlorobromide and 35 g. of gelatin and, after adding thereto 30 ml. of a 3-acetone solution of triethylene phosphamide and 2 g. of polyvinyl pyrrolidone, the resultant mixture was applied to a baryta-coated paper in a dry thickness of 4.5 microns.

To the blue-sensitive emulsion layer thus prepared were further applied a green-sensitive photographic emulsion containing the magenta-forming coupler shown above, a red-sensitive emulsion containing the cyan-forming coupler b shown above, and finally a gelatin layer containing an equal amount of the following three ultraviolet absorbers .(d), (e), and (f) in a total area concentration of 2.0 g./m. to provide a color photographic printing paper, hereinafter designated Color Printing Paper W:

Ultraviolet Absorber (d) C 4Ho( r Ultraviolet Absorber (e) '14 Ultraviolet Absorber (f) O 4H (tort) I CH After image-exposing the color printing paper, it was developed in a Color Developer B having the following composition for 12 minutes at 24 C. and thereafter subjected to the same fixing, bleaching and washing procedures as in Example 1.

Color Developer B:

Water-l00 ml.

Sodium hexa-metaphosphate2.0 g.

Sodium sulfite (anhydrous)1.0 g.

Benzyl alcohol-l2.0 ml.

Sodium carbonate (mono-hydrate)27.5 g.

Hydroxylarnine sulfate-2.5 g.

4-amino-3-methyl-N-ethyl-N- B-methanesulfoamidoethyl)-aniline sesquisulfate (mono-hydrate) 4.0 g.

When Color Printing Paper W containing the novel Coupler M of the present invention was exposed to blue light and then developed, a brilliant yellow image having an absorption maximum at 449 milimicrons was obtained.

After exposing the yellow image, obtained by processing the color printing paper, to light from an intense xenon arc lamp for 60 hours, the reduction in blue reflection density was measured, the results of which are shown in the following table:

Fading of Yellow Image by Light Exposure* Initial density Percent reduction of density as compared with the initial value These results showed that the color image obtained by using the novel coupler of the present invention was excellent in light fastness. That is to say, it was confirmed that the yellow forming coupler of the present invention gave a color image having a long life.

The above examples illustrate that the yellow-forming coupler of the present invention represented by the abovementioned general Formula I has a function of providing a sufficiently high color density by color development as well as the properties of providing a clear and less reddish color image fast to heat, moisture, and light.

What is claimed is:

1. In a light-sensitive material for producing a colored image comprising a support and a silver halide emulsion layer thereon the improvement which comprises the layer containing a yellow-forming coupler having the formula Color Printing Paper W Coupler M wherein X is a member selected from the group consisting of a halogen atom, a lower alkoxy group, a di-alkylamino group and an aryloxy group; wherein Y is a member selected from the group consisting of a hydrogen atom, a halogen atom, a trifiuoromethyl group, a cyano group, an alkoxy group, an alkyl group, an aryloxy group, an acyl group, a carbamyl group, an acylamino group, a sulfonamino group, a sulfoamoyl group, and a carboxy alkoxy group; wherein OR represents an alkoxy group containing from 1 to 5 carbon atoms; wherein COR represents an acyl group containing from 9 to 28 carbon atoms; and wherein said Y is located at one of the 3-, 4- and 5-positions of the anilide nucleus.

15 2. The light-sensitive material as claimed in claim 1, wherein X is a chlorine atom.

3. The lightsensitive material as claimed in claim L wherein X is a methoXy group.

4. The light-sensitive material as claimed in claim 1, wherein said OR is selected from the group consisting of and O O (EEO- wherein R is an alkyl group containing from to 18 carbon atoms; wherein R and R each is an alkyl group containing less than 9* carbon atoms; wherein R is selected from the group consisting of a hydrogen atom and an alkyl group containing from 1 to 3 carbon atoms; and wherein n represents an integer of from 2 to 5.

5. A light-sensitive material for producing a colored image comprising a support and a silver-halide emulsion layer thereon containing a yellow-forming coupler selected from the group consisting of 3-acylamino-4-methoxybenzoylaceto-Z-chloroanilide,

3-acylamino-4-methoXybenzoylaceto-2-methoxyanilide, 3-acylarnino-4-rneth0Xybenzoylaceto-Z-chloro-S-trifluoromethyl-anilide, 3-acylamino-4-methoxybenzoylaceto-Z-chloro-5- pivaloylarnino-anilide, 3-acylamino-4-methoxybenzoylaceto-2,5-dimethoxyanilide, 3-acylamino-4-methoxybenzoylaceto-2-methoxy-5- N,N-di- (lower alkyl)-aminosulfonanilide, 3-acylamino-4-methoxybenzoylaceto-2-methoxy5 methylanilide, 3-acylamino-4-methoxybenzoylaceto-2,4-dichloroanilide, and 3-acylamino-4-methoxybenzoylaceto-2-chloro-5-N,N-

di- (lower alkyl -amino sulfonanilide, in which each acylamino group contains from 9 to 28 carbon atoms.

6. A light-sensitive material as claimed in claim 5, in which each acylamino group is selected from the group consisting of o artino-Qua and l 6 wherein R is an alkyl group containing from 5 to 18 carbon atoms; wherein R and R each is an alkyl group containing less than 9 carbon atoms; wherein R is selected from the group consisting of a hydrogen atom and an alkyl group containing from 1 to 3 carbon atoms; and wherein n represents an integer of from 2 to 5.

7. A method of producing a colored image by developing an exposed silver-halide emulsion layer with an aromatic primary amino develeping agent in the presence of a yellow-forming coupler having the formula NHCOR Y I wherein X is a member selected from the group consisting of a halogen atom, a lower alkoxy group, a di-alkylamino group and an aryloxy group; wherein Y is a member selected from the group consisting of a hydrogen atom, a halogen atom, a trifiuoromethyl group, a cyano group, an alkoxy group, an alkyl group, an aryloxy group, an acyl group, a carbamyl group, an acylamino group, a sulfonamino group, a sulfoamoyl group, and a carboXyalkoxy group; wherein OR represents an alkoxy group containing from 1 to 5 carbon atoms; wherein COR represents an acyl group containing from 9 to 28 carbon atoms; and wherein said Y is located at one of the 3-, 4- and 5-positions of the anilide nucleus.

8. A method of producing a colored image as claimed in claim 7, wherein X represents a chlorine atom.

9. A method of producing a colored image as claimed in claim 7, wherein X represents a methoxy group.

10. A method of producing a colored image as claimed in claim 7, wherein said OR group is selected from the a group consisting of and wherein R is an alkyl group containing from 5 to 18 carbon atoms; wherein R and R each is an alkyl group containing less than 9 carbon atoms; wherein R is selected from the group consisting of a hydrogen atom and an alkyl group containing from 1 to 3 carbon atoms; and wherein n represents an integer of from 2 to 5.

11. A method of producing a colored image by developing an exposed silver halide emulsion layer with an aromatic primary amino developing agent in the presence of a yellow-forming coupler selected from the group consisting of 3-acylamino-4-methoXybenzoylaceto-2-chloroanilide,

3-acylarnino-4-methoxybenzoylaceto-Z-methoxyanilide,

3-acylamino 4 methoxybenzoylaceto-2-chloro-5-trifiuoromethylanilide,

3-acylamino-4-methoxybenzoylaceto 2 chloro-S-pivaloylaminoanilide,

3-acylamino-4-methoxybenzoylaceto 2,5 dimethoxyanilide,

3-acylamino 4 methoxybenzoylaceto-Z-methoxy-S- N,N-di (lower alkyl) -aminosulfonanilide,

3-acylamino 4 methoXybenzoylaceto2-methoxy-5- methylanilide,

and

wherein R is an alkyl group containing from 5 to 18 carbon atoms; wherein R and R each is an alkyl group containing less than 9 carbon atoms; wherein R is selected from the group consisting of a hydrogen atom and an alkyl group containing from 1 to 3 carbon atoms; and wherein n represents an integer of from 2 to 5.

13. In a light-sensitive material for producing a colored image comprising a support and a silver halide emulsion layer thereon the improvement which comprises the layer containing a yellow-forrning coupler having the formula NHCOR Y wherein X is a member selected from the group consisting of a halogen atom, a lower alkoxy group, a di-alkylamino group and an aryloXy group; wherein Y is a member selected from the group consisting of a halogen atom, a trifiuoromethyl group, a cyano group, an alkoxy group, an alkyl group, an aryloxy group, an acyl group, a carbamyl group, an acylamino group, a sulfonamino group, a sulfoamoyl group, and a carboxylalkoxy group; wherein OR represents an alkoxy group containing from 1 to 5 carbon atoms; wherein COR represents an acyl group containing from 9 to 28 carbon atoms; and wherein said Y is located at one of the 3-, 4- and 5- positions of the anilide nucleus.

References Cited UNITED STATES PATENTS 3,133,815 5/1964 Greenhalgh 96100 1. TRAVIS BROWN, Primary Examiner R. E. FIGHTER, Assistant Examiner U.S. Cl. X.R. 9655; 260-562