US3615606A

US3615606A - Colorphotographic material

Info

Publication number: US3615606A
Application number: US741880A
Authority: US
Inventors: Walter Schulte; Helmut Mader; Willibald Pelz; Fritz Nittel; Erich Reckziegel
Original assignee: Agfa Gevaert AG
Current assignee: Agfa Gevaert AG
Priority date: 1967-07-10
Filing date: 1968-07-02
Publication date: 1971-10-26
Anticipated expiration: 1988-10-26
Also published as: BE717841A; DE1597464A1; FR1573578A; NL6809746A; CH496969A; GB1248924A; DE1597464B2

Abstract

IN WHICH R1 represents an alkyl radical; R2 represents an alkoxy radical, an alkylthio radical, a secondary or tertiary alkylamino group, a halogen, an alkyl radical, arylthio; R3 represents a substituent in the 4- or 5-position, which is: sulfonamide, carbamoyl, acylamino, an alkylsulfonyl; R4 represents hydrogen, an alkyl or alkoxy radical, halogen, sulfonamide or carbamoyl alkyl or alkylsulfonyl.

A light-sensitive photographic material containing in a silver halide emulsion layer a yellow coupler of the following formula:

Description

United States Patent [72] Inventors Walter Schulte Opladen; Helmut Mader, Leverkusen; Willibald Pelz, Opladen; Fritz Nittel, Cologne, Stammheim; Erich Reckziegel, Leverkusen,

all of Germany [21] Appl. No. 741,880

[22] Filed July 2, 1968 [45] Patented Oct. 26, 1971 [73] Assignee AFGA Gevaert Aktiengesellschaft Leverkusen, Germany [32] Priority July- 10, 1968 [33] Germany [54] COLORPHOTOGRAPHIC MATERIAL 9 Claims, No Drawings [52] US. Cl 96/100 [51] Int. Cl G03 1/40 [50] Field of Search 96/100 [56] References Cited UNITED STATES PATENTS 3,393,040 7/1968 Verbrugghe et al. 96/ 1 00 X FOREIGN PATENTS 1,039,965 8/1966 Great Britain 96/100 Primary Examiner-Norman G. Torchin Assistant Examiner-John L. Goodrow Attorney-Connolly and Hutz ABSTRACT: A light-sensitive photographic material containing in a silver halide emulsion layer a yellow coupler of the following formula:

R represents an alkoxy radical, an alkylthio radical, a secondary or tertiary alkylamino group, a halogen, an alkyl radical, arylthio;

R represents a substituent in the 4- or 5-position, which is: sulfonamide, carbamoyl, acylamino, an alkylsulfonyl;

R represents hydrogen, an alkyl or alkoxy radical, halogen, sulfonamide or carbamoyl alkyl or alkylsulfonyl.

color-forming developer. The resulting dye should, as far as possible, absorb only the desired spectral region since every side absorption in other spectral regions is disadvantageous. Furthermore, the resulting dyes should be light stable and stable even under the extreme conditions such as relatively high temperature and atmospheric moisture, found in the tropics. The color couplers themselves which are incorporated in the light-sensitive layer, should, also, of course possess sufficient stability under tropical conditions. The yellow couplers hitherto known do not meet requirements in practice in particular with regard to the last mentioned property. Furthermore, for economical reasons, only those color couplers which can be prepared by a simple method are of interest.

An object of this invention is to provide couplers which, are stable under tropical conditions and to light, and which can be produced in high yields and in pure form. We now have found that compounds of benzoyl acetanilide type of the following formula are especially suitable for use as yellow couplers in photographic silver halide emulsion layers:

R2 A-NH-C ooH,-o o O-R1 l L 5 6 soar in which R represents an alkyl radical preferably containing one to 18 carbon atoms;

R represents 1. an alkoxy radical preferably containing up to 18 carbon atoms;

2. an alkylthio radical preferably containing up to 18 carbon atoms;

3. a secondary or tertiary alkylamino group preferably containing up to 18 carbon atoms or a preferably saturated fiveor six-membered nitrogen-containing heterocyclic ring such as pyrrolidine or piperidine linked to the benzene nucleus through the nitrogen atom;

4. a halogen atom such as chlorine or bromine or an alkyl radical; the alkyl groups of the above substituents may contain further substituents, e.g. halogen atoms, to form in particular, a trifluoromethyl group, or phenyl radicals;

6. Arylthio preferably phenylthio particularly alkyl substituted phenyl, halogensubstituted phenyl;

7. Aroxy preferably phenoxy particularly alkyl substituted phenyl, halogen substituted phenyl 8. Aralkoxy preferably benzyloxy or substituted benzyloxy such as halogen substituted or alkyl sub stituted benzyloxy;

R represents a substituent in the fouror five-position,

preferably in the five-position, which is:

l. sulfonamide in which the amide group may be substituted by alkyl radicals which preferably contain one to 18 carbon atoms;

2. carbamoyl in which the amide group may be substituted by alkyl radicals which have preferably one to 18 carbon atoms;

3. acylamino, acylamino,-preferably monoacylamino, in which the acyl groups are preferably derived from aliphatic carboxylic or sulfonic acids which have up to 18 carbon atoms, or

4. a alkylsulfonyl which preferably contains up to 18 carbon atoms;

R represents hydrogen, an alkyl or alkoxy radical preferably containing up to five carbon atoms, halogen such as chlorine or bromine, sulfonamide or carbamoyl in which the amide groups may be substituted by alkyl radicals which preferably contain up to 18 carbon atoms or alkylsulfonyl, preferably containing up to l8 carbon atoms.

In the above general formula, the benzene rings, especially the benzene ring present in the amide part of the color coupler molecule, may contain any other substituents in addition to those already mentioned, e.g., alkyl or alkoxy groups, or halogen atoms.

Examples of suitable color couplers are shown in the following table:

| SOaH benzene ring of the amide part of the molecule so that sulfona- COUPLER l 3-Nitro-4-methoxybenzesulfonie acid-N-stearyl amide 81 g. of stearylamine and 40 ml. of triethylamine are dissolved in 800 ml. of tetrahydrofuran. A solution of 75 g. of 3nitro-4- methoxybenzenesulfochloride in 200 ml. of tetrahydrofuran are added dropwise with stirring and the reaction mixture is stirred for 1 hour at room temperature. The mixture is stirred into a mixture of ice and water, suction filtered and recrystallized from dioxane.

Yield: 140 g., m.p. 102 C.

3-Amino-4-methoxybenzenesulfonic acid-N-stearyl amide 130 g. of the above nitro compound are hydrogenated in 1,600 ml. of methanol at '50 atmospheres and 50 C. with Raney nickel. The product is filtered while hot and cooled to C. The precipitated amine is suction filtered, washed with methanol and dried in air. Yield: 100 g., m.p. 89 C.

34 g. of the above amine are heated to 140 C. in 25 ml. of triethylamine and 300 ml. of chlorobenzene, and a solution of 25 g. of the acetic acid ethyl ester in 100 ml. of chlorobenzene is added dropwise with stirring, The reaction mixture is refluxed for 4 hours. It is then cooled to 0 C. and the product is precipitated with methanol. After suction filtration and washing with methanol, the product ,is recrystallized from alcohol.

Yield: 58 g. m.p. 140 C.

38 g. of the product are slowly introduced into 230 ml.of sulfuric acid monohydrate at room temperature. The reaction mixture is stirred for about 1 hour and heated to40 C. until a sample precipitated with ice is not soluble in alkali. The mixture is then stirred into ice and the precipitated coupler is suction filtered, washed with 'witer'ina' recrystallized from methanol.

Yield: 28 g., m.p. l30l40C. with decomposition.

COUPLER 4 3-Nitro-4-chlorobenzenesulfone-N-methyl-N-stearyl amide 136 g. of methylstearylamine are dissolved in 700 ml. of tetrahydrofuran and a solution of 128 g. of 4-chlor-3- nitrobenzenesulfochloride in 300 ml. of tetrahydrofuran is added dropwise, The reaction mixture is stirred for 30 minutes and then poured into 2 liters of iced water. The product which precipitates out is suction filtered and recystallized from alcohol. Yield: 138 g.,m.p. 89C.

3-Nitro-4-methylbenzylamino-N-methyl-N-stearylbenezene-sulfonamide, 260 g. of the above product and 144 g. of methylbenzylamine are refluxed for 6 hours in 400 ml. of

-isopropanol. The precipitated product is suction filtered,

washed with H 0 and recrystallized from methanol. Yield: 178 g., m.p. l30 C.

REDUCTION 180 g. of the above compound in 2 l. of ethanol are hydrogenated in the presence of Raney nickel at 50 C. and 50 atmospheres pressure. The catalyst is removed by filtration under suction, the solution is cooled to 0 C. and the precipitated product is suction filtered and washed with ethanol.

Yield: 130 g., m.p. 55-57 C.

A mixture of 33 g. or 4-methoxybenzoyl acetic acid ethyl ester and 200 ml. of chlorobenzene are added dropwise to a solution of 56 g. of the above product and 30 ml. of triethylamine in 300 ml. of chlorobenzene at C. The reactions mixture is then heated for 4 hours at 140 C. with stirring, during which time a small amount of chlorobenzene and alcohol distil off. The mixture is then concentrated by evaporation under vacuum and the residue is recrystallized from ethanol.

Yield: 62 g., m.p. 4344 C.

30 g. of the product are added slowly to 180 ml. of sulfuric acid monohydrate. The reaction mixture is then stirred for one hour at 30 to 35 C. and poured onto ice. The precipitated product is suction filtered. After it has been washed with water, it is recrystallized from methanol.

Yield: 20 g.

The other couplers may be prepared in analogous manner.

The color couplers to be used in accordance with the present invention are incorporated in the silver halide emulsion by known methods. They are preferably added before casting in the form of a solution, e.g. in the form of a solution, e.g. in the form of a solution of their alkali metal salts, to the blue-sensitive silver halide emulsion.

According to another known method, solutions of the color couplers which are hydrophobic, may be emulsified if desired in the presence of so-called oil formers, in gelatin, after which the resulting emulsion is dried, and allowed to swell again in water and is then mixed with the silver halide gelatin emulsion. Other processes are known according to which the solution of the color coupler in an organic solvent is mixed directly with the silver halide emulsion, and the silvent is evaporated off. The color couplers according to the invention may be used in any of these processes. The binders which may be used for the layers are the known hydrophilic film-forming agents such as proteins, especially gelatin, polyvinyl alcohol, polyvinyl pyrrolidone, cellulose derivatives such as carboxyalkyl-cellulose, especially carboxamethylcellulose, derivatives of alginic acid and their alkali metal salts or esters.

The layers may in addition be stabilized by known additives, in particular the azaindene derivatives described in the publication by Birr in Z. wiss. Phot. 47 [952), pages 2-28.

' The layer support is transparent or opaque depending on the purpose for which the light-sensitive material is to be used and maybe made of paper, glass, cellulose esters such as cellulose nitrate or cellulose triacetate, polyesters, polystyrene or other high molecular weight natural or synthetic materials.

The yellow couplers according to the invention are usually incorporated with the light-sensitive layer itself. In addition, they may also be added to a layer which is not light sensitive and which is in contact with the blue-sensitized layer, or with a layer of colloid which is separated from the blue-sensitized layer by a water-permeable layer of colloid.

The yellow couplers of the present invention can be applied for colorphotographic materials to be used for a negative-positive process as well as for a colorphotographic reversal process.

Any color-forming developers which contain a primary amino group may be used for the development step. Those of the p-phenylenediamine type, e.g. N,N-diethyl-p-phenylenediamine, monomethyl-p-phenylenediamine, N,N'- dimethyl-p-phenylenediamine, Z-amino-S- diethylaminotoluene and N-butyl-Nw-sulfobutyl-p-phenylenediamine are preferred.

EXAMPLE 1 4 mols of coupler 8 are dissolved in water containing a small amount of alcohol and sodium hydroxide solution. The total volume of the solution is about 100 ml. and the pH should range between 7 and 9. The coupler solution prepared in this way is added to 50 ml. of a photographic silver bromide gelatine emulsion which contains 7 percent of gelatin and 0.5 mol of silver bromide per kg. of emulsion. ml. of 7.5 percent gelatin solution, 5 ml. of a 1 percent methanolic solution f 4.h d .6 h l l3 3 7- i d 6 l of R an alkylsulfamyl group containing up to four carbon aqueous saponin solution (l percent) and 3 ml. of aqueous atoms chrome acetate solution (0.5 percent) are added to this cou- 2. Light-sensitive photographic material as defined in claim pler-containing emulsion which is then cast on a support of wherein is m hy cellulose triacetate to form a layer about 5 p. in thickness. The 5 g e e photographic material as defined in claim pH of the layer is about 6.5-7 percent. 1 wherein 3 is a Sulfonamide p- After dryin th materi l i x o ed th gh a grey t 4. Light-sensitive photographic material as defined in claim wedge and developed for 8 minutes in a developer solution of 2 wherein 3 is a monomethylsulfonamide g pthe following composition. 1 0 5. Light-sensitive photographic material as defined in claim 2.75 g. of N,N-diethyl-p-phenylenediaminosulfate, l whe rein R stands for alkoxy containing up to 1 8 carbon 1.2 g. of hydroxylaminohydrochloride, atoms or a tertiary alkyl amino group, the alkyl radicals of 2 g, of anhydrou N $0 which contain up to 18 carbon atoms. 2 g. of sodium metaphosphate, 6. Light-sensitive photographic material as defined in claim 75 g. of potassium carbonate, 1 5 2 in which the color couplerhas the following formula: 2 g. of potassium bromide and water up to l 1. Further processing includes treatment in the following CH3 CHE baths:

N BLEACHING BATH NH-c-cm-c-ocm 3 g. of ethylenediaminotetracetic acid, H ll 50 g. of potassium ferricyanide, 0 O 0 H g. of potassium bromide, l g. of disodium phosphate, Q2NH CH3 19 g. of monopotassium phosphate, water up to l l. 2 The fixing bath consists of a solution of 200 g. of sodium thiosulfate in 1 1. ofwaten 7. Light-sensitive photographic material as defined in claim The processing times after development are as follows: 3 in which the color coupler has the 8 formula: 15 minutes washing 5 minutes bleaching bath v "Has 5 minutes washing 5 minutes fixing bath NH C CHT C O 0H, 10 minutes washing. I I] I] A yellow image of the step wedge is obtained. 0 0 g 11 If the yellow image is exposed to 96 percent relative humidity for one day at 60 C., no reduction is found at a density of I 0.5 and 1.5.

- 8. Light-sensitive photographic material as defined in claim EXAMPLE 2 3 in which the color coupler has the following formula: The same procedure is employed as carried out in example 1 except that the coupler used in coupler 4. A yellow image OCH: with maximum density 2.6 and gradation 3.4 is obtained.

When the film is stored under the conditions used in exam- HFC ple 1, no reduction 15 found at dens ty and l g I;

We claim: 0 N u 80 1i 1. Light-sensitive photographic material comprising at least I one silver halide emulsion layer which contains a yellow cou- CH3 pler of the following formula:

R2 9. Light-sensitive photographic material as defined in claim I 2, in which the color coupler has the following fonnula:

l Ra SOaH N wherein: I

R, methyl; NHC-C H;C'OCH: R I

1 an alkoxy radical containing up to 18 carbon atoms; or 30:11 2 a secondary or tertiary alkylamino group containing up I to 18 carbon atoms is one of the alkyl residues; and z 4 v UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION PATENT NO. 3, 615,606 DATED October 26, 1971 INVENTOMS) WALTER SCHULTE et al It is certified that error appears in the above-identified patent and that said Letters Patent is hereby corrected asshown below: on the title page Column 1, in the Priority date, cancel "1968" and insert 1967 The Priority date line should read as follows:

[32] Priority July 10, 1967.

Column 9, line 61, cancel "is" and insert in Column 6, line 67, cancel "acetate" and insert acetic acid esters line 67 should read as follows:

"benzoyl acetic acid ester in the presence of a suitable base such as" Same column, line 68 cancel "acetic acid ester" and insert sodium acetate line 68, should read as follows "triethylamine, pyridine or sodium acetate".

Column 7, line 33, before "acetic" insert p-methoxybenzoyl and line 33 should read as follows:

"25q. of the p-methoxybenzoyl acetic acid ethyl ester in 100 ml.

of chlorobenzene.

Signed and Scaled this Twenty-ninth D a y f March I 983 |SAL| Armc- GERALD J. MOSSINGI'IOFF Arresting Officer Commissioner of Parents and Trademarks

Claims

2. Light-sensitive photographic material as defined in claim 1, wherein R1 is methyl.
3. Light-sensitive photographic material as defined in claim 1 wherein R3 is a sulfonamide group.
4. Light-sensitive photographic material as defined in claim 2 wherein R3 is a monomethylsulfonamide group.
5. Light-sensitive photographic material as defined in claim 1 wherein R2 stands for alkoxy containing up to 18 carbon atoms or a tertiary alkyl amino group, the alkyl radicals of which contain up to 18 carbon atoms.
6. Light-sensitive photographic material as defined in claim 2 in which the color coupler has the following formula:
7. Light-sensitive photographic material as defined in claim 3 in which the color coupler has the following formula:
8. Light-sensitive photographic material as defined in claim 3 in which the color coupler has the following formula:
9. Light-sensitive photographic material as defined in claim 2, in which the color coupler has the following formula: