US3585035A - Silver halide photographic elements containing phenol or naphthol carboxylic acid amide couplers - Google Patents

Abstract

IMPROVED CYAN IMAGES ARE PRODUCED BY PHOTOGRAPHIC COLOR DEVELOPMENT WHEN THE CYAN COUPLER IS A SUBSTITUTED 1-PHENOL-2-CARBOXYLIC ACID AMIDE OF THE FOLLOWING FORMULA

2-(R-NH-CO-N(-R)-(CH2)N-NH-CO-)PHENOL

WHEREIN N=1-6 AND R IS ALKYL OR ARYL.

Description

United States Patent Olhce Claims priority, applicatitsmzGermany, Dec. 2, 1966,

4 47 Int. Cl. cine 7/00 US. CI. 96-55 5 Claims ABSTRACT OF THE DISCLOURE Improved cyan images are produced by photographic color development when the cyan coupler is a substituted 1-phenol-2 carboxylic acid amide of the following formula wherein n: l6 and R is alkyl or aryl.

This is a continuation of my copending application Ser. No. 686,723, filed Nov. 29, 1967, for Improved Colour- Photographic Images, now abandoned.

This invention relates to a process for producing photographic color images by colorforming development, and to a photographic material for carrying out this process.

It is common practice to produce the cyan partial image by means of photographic materials containing color couplers of the phenol or naphthol series. Although many cyan couplers are known, none of them satisfies all the various requirements for such couplers. On the contrary, most color couplers sufier certain serious disadvantages. Lack of stability of the residual coupler which was not coupled with the color developer in producing the dye image, often leads to discoloration in the white areas of the image. Moreover, the dyes produced upon colorforming development usually show undesirably high side absorptions. Many couplers yield dyes in the form of relatively coarse dye grains, whilst, with others, the coupling reaction is too slow. Generally speaking, the cyan dyes obtained by oolorforming development show inadequate fastness to light, and unsatisfactory resistance to hydrolysis and undesired sensitivity to reducing agents.

It is among the objects of the present invention to provide cyan couplers which form upon colorforming development dyes with improved absorption properties and increased resistance to chemicals.

I now have found that compounds corresponding to the following formula 3,585,035 Patented June 15, 1971 for example by hydroxyl, phenyl, halogen such as chlorine or carboxyl, and the like; (II) aryl in particular a radical of the phenyl series, which phenyl group may be substituted for example by halogen such as fluorine, chlorine or bromine, alkyl in particular short-chain alkyl with up to 3 carbon atoms, such as methyl or ethyl, substituted alkyl, for example halogen-substituted alkyl, such as trifluoromethyl, carboxyl, esterified carboxyl, alkoxy with preferably up to 5 carbon atoms or aroxy such as phenoxy, sulto;

R may represent for example 4 chlorophenyl, 4 ethoxyphenyl, 4 methylphenyl, 2 methylphenyl, 2.4 dimethylphenyl, 3.5 dimethylphenyl, 3.5 dicarboxyphenyl, 4 carboxyphenyl, 2 ethoxyphenyl or 3,5 bistrifluoromethylphenyl radicals:

R represents (1) alkyl with up to 18 carbon atoms such as methyl, ethyl or stearyl, which alkyl radicals may be substituted for example by a hydroxyl group, a halogen atom such as fluorine, chlorine or bromine, or a sulfo group; (II) an alkenyl radical with up to 17 carbon atoms; (III) an aryl radical preferably a radical of the phenyl series, which aryl group may be substituted, for example by alkyl with up to 18 carbon atoms such as methyl or dodecyl, (IV) an amino group and in partic ular an alkylor aryl-substituted amino group such as stearylamino, dodecylphenylamino or myristylamino, (V) an alkoxy radical or (VI) an aroxy radical preferably phenoxy in which case the phenyl group may be substituted for example with alkyl with up to 18 carbon atoms, halogen such as fluorine, chlorine or bromine, alkoxy, carboxy, esterified carboxyl or sulfo;

12 represents hydrogen or the ring members, necessary for completing a fused aryl ring preferably a phenyl ring or a fused tetrahydrocarbocyclic ring preferably a tetrahydrobenzene ring;

n=l to 6 and preferably 3.

Particular utility is exhibited for example by the following color couplers:

The color couplers according to the invention are pre pared in a manner known per se. A process for their preparation is described in detail in the following:

Coupler II 372 g.(4 mols) of aniline and 26 ml. of glacial acetic acid are heated to 125 C. in a three-necked flask provided with a reflux condenser. 276 g.(5 .2 mols) of acrylonitrile are then added dropwise with stirring over a period of 5 hours at a bath temperature of around 130 C., causing the internal temperature to drop to 100 C. Stirring is continued while the bath temperature gradually rises until the internal temperature is 132l34 C. The reaction mixture is then distilled in vacuo. After the first runnings of unreacted material, 411 g. of crude product of B.P. =185190 C. are collected. The crude product is purified by stirring it with a mixture of 400 ml. of water and 400 ml. of hydrochloric acid, filtering off the undissolved component in the presence of active carbon and adding at 10-15 C. a solution of 200 g. of caustic soda in 1200 ml. of water. The product is filtered under suction and washed with water, dried in vacuo and then distilled under a high vacuum. 340 g. of pure ,B-anilinopropionitrile of B.P. =ll2-1 14 C. M.P. 54 C. are obtained.

43.8 g. (0.3 mol) of fl-anilinopropionitrile are stirred with 79.2 g. (0.3 mol) of naphthsalol (phenyl l-hydroxy- 2-naphthoate) in a three-necked fllask and fused at 120 C., the product being stirred for another 5 hours at 160 C. It is then cooled to 80 C. and stirred into water. The precipitate which forms is recrystallised from methanol in the presence of active carbon and then from benzene/ petroleum ether. 69 g. of 1-hydroxy-N-phenyl-N-betacyanoethyl-2-naphthoylamide melting at 128 l30 C. are obtained.

56 g. of ammonia gas are dissolved in a solution of 156 g. of 1 hydroxy N phenyl-N-betacyanoethyl-Z- naphthoylamide in 1560 ml. of methanol and 440 ml. of ethanol. The resulting solution is hydrogenated at 80 C./50 atms. in the presence of 78 g. of Raney nickel. On completion of hydrogenation, the product is separated from the catalyst by filtration. The filtrate which is still warm is then adjusted with concentrated hydrochloric acid to pH 4 and precipitated ammonium chloride is fiiltered off. Upon evaporation of the resulting solution to a small volume and cooling, a deposit is formed, which is filtered off under suction and stirred twice with soda solution. The free base thus precipitated in suction-filtered, dried and recrystallized from methanol. 120 g. of l-hydroxy-N- omegaphenylarninopropyl 2 naphthoylamide melting at 130-131 C. are obtained.

24 g. of 1 hydroxy N omegaphenylaminopropyl-Z- naphthoylamide (0.075 mol) are dissolved in ml. of dried tetrahydrofuran in a three-necked flask equipped with condenser and stirrer and 21.2 g. of stearyl isocyanate are added dropwise to the resulting solution. Stirring is continued for 5 hours at C., after which most of the solvent is distilled 01f again. The reaction mixture is crystallized by mixing with cold water. Thereafter, it is suction-filtered, the residue dried and finally recrystallized from methanol. 38 g. of coupler -II melting at 63-64 C., are obtained.

In order to vary R in the general formula the acrylonitrile may be reacted with a variety of amines. A report of such addition reactions can be found in Houben-Weyl, vol. nitrogen compounds II, page 274. Hitherto, these reactions have only been possible by the addition of catalysts such as carbazolpotassium (cf. Houben-Weyl) or choline hydrate (cf. Pietra, Gazzetta Chimica Italiana, volume 86, page 70 [1956] or by the addition of acids (cf. British patent specification No. 466,316 [1936]; Chemisches Zentralblatt 1937, II, 2750).

Coupler XVII N-(Z-hydroxyethyl)-ethylene diamine is fused with naphthsalol and the product reacted with stearyl isocyanate and coupler XVII is obtained.

Coupler XVIII Bromoethylamine hydrobromide is reacted with 2- methyl-aniline. The N-(Z-methylanilino)-ethylene diamine thus formed is melted twith naphthsalol, the resulting compound is reacted with dodecylphenylisocyanate and the color component is sulfonated in the final stage to form color coupler XVIII.

Coupler XIX The addition product of 4-ethoxyaniline and acrylonitrile is hydrogenated with Raney nickel in a solution of ammonia in methanol to give N-ethoxyphenyl trimethylene diamine which, after purification by vacuum distillation, is reacted with naphthsalol by melting therewith. A long chain fatty group is introduced by reaction with stearyl isocyanate.

Coupler XX Bromoethylamine hydrobromide is reacted in pyridine with 2,4-dimethyl aniline to form N-2,4-dimethylphenyl ethylene diamine which is melted with naphthsalol. A long chain fatty group is introduced into the reaction product by reaction with 3-lauryl0xypropylisocyanate.

Coupler XXI Tetramethylene diamine is reacted with 2-hydroxyethyliodide in pyridine to form N-(Z-hydroxyethyl)-tetramethylene-1,4-diamine.

Coupler XXII Bromoethylamine hydrobromide is reacted in pyridine with 3,5-dicarbethoxyaniline to form N-,(3,4-dicarbethoxyphenyl)-ethylene diamine. This reaction product is melted with naphthsalol at approximately C. After the next reaction with octadecyl isocyanate, the two ester groups are carefully hydrolysed.

The color couplers according to the invention may be incorporated in the light-sensitive silver halide emulsion layers in diffusion-resistant form. This can be performed in known manner by dissolving color couplers substituted by long alkyl radicals and water-solubilising groups, in the casting solution.

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 gelatinc, after which the resulting emulsion is dried, and allowed to swell again in water and is then mixed with the silver halide gelatine 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 solvent is evaporated off. The color couplers according to the invention may be used in any of these processes.

The new dye components may be added not only to the light-sensitive silver halide emulsion layer itself, but also to an adjacent non-sensitive layer. The concentration of the coupler in the light-sensitive halide emulsion layer is not critical and depends on the etfect desired, the type of silver halide emulsion etc. An amount of 1 g. to 15 g. per liter of emulsion ready for casting has generally proved sufficient.

The coupler may also be developed into the photographic material in conjunction with the color developer.

Light-sensitive layers containing the color couplers according to the invention will generally be used in multilayer materials although layers of this kind may of course also be used as a single layer on a suitable support.

Any color developers containing a primary amino group may be used for development, although those of the pphenylene diamine series are preferred. Examples of these are N,N-diethyl-p-phenylene diamine, N-monomethyl-pphenylene diamine, N,N-dimethyl-p-phenylene diamine, 2- amino-S-diethylaminotoluene and N-butyl-N-w-sulfobutyL p-phenylene diamine.

Suitable binding agents for the layers include conventional hydrophilic film formers such as proteins, in particular gelatine, polyvinyl alcohol, polyvinylpyrrolidone, cellulose derivatives such as carboxyalkyl cellulose, in particular carboxymethyl cellulose, derivatives of alginic acid and their alkali metal salts or esters.

The cyan couplers according to the invention are preferably added to red-sensitized photographic silver halide emulsions. In addition, emulsions of this kind may contain chemical sensitizers in the usual way. These layers may also be stabilized by use of conventional additives and in particular by the azaindene derivatives described by Birr in Z. wiss. Phot. 47 (1952), pages 2 to 28.

EXAMPLE 1 3 g. of color coupler XVII are made into a paste with 4 ml. of ethanol. 4% sodium hydroxide is added to the mixture in such a quantity that the pH-value rises to 89, after which the product is made up with water to 150 ml. giving a solution which is stirred into 300 g. of a photographic silver bromide gelatine emulsion. This emulsion was prepared by mixing 75 g. of a starting emulsion prepared from 70 g. of AgNO per kg. and 225 g. of 7.5% gelatine solution. The casting viscosity can be adjusted by adding a little water. This mixture is applied in the usual way onto a transparent cellulose acetate support and dried.

The photographic material thus prepared is imagewise exposed and then developed in a colorforming developing bath of the following composition:

G. N,N-diethyl-p-phenylenediamine hydrochloride 2.75 Anhydrous sodium sulfite 2 Potassium carbonate 75 Potassium bromide 0.5 Hydroxylamine hydrochloride 1.2 Sodium hexametaphosphate 1.0

Water up to 1000 ml.

The exposed and developed material is bleached, fixed and rinsed with Water in the usual way. A cyan dye image with an absorption maximum at 686 m is obtained.

Similar results are obtained with color components XX.

EXAMPLE 2 3 g. of color coupler II are dissolved in 15 ml. of ethyl acetate at 5560 C. The resulting solution is added to 50 ml. of 5% gelatine to which 8 g. of lauryl sulfate per kg. have been added as stabilizer, and the resulting mixture is emulsified. 50 g. of the photographic silver bromide gelatine emulsiondescribed'in Example 1 are 6 added to this emulsion while it is still warm. The mixture is diluted with 100 ml. of 7.5% gelatine solution and then applied in the usual way onto a cellulose acetate support and dried.

After exposure and development in the developer solution described in Example 1, bleaching, fixing and rinsing with water in the usual way, a cyan dye image is obtained which has an absorption maximum at 673 me.

After exposure, a dye image may also be obtained by use of the following developer solution:

Benzyl alcohol3.8 ml.

Sodium hexametaphosphate-2 g.

Anhydrous sodium sulfite2 g.

Sodium hydroxide 10% )--5.5 ml.

2-amino-5 [N ethyl N (s methylsulfonamidoethyl)'- amino]-toluene-sesquisulfate monohydrate-S g.

Potassium bromide-l g.

Sodium carbonate monohydrate50 g.

Water up to 1000 ml.

pH-value at 21 C. 10.75

After bleaching, fixing and rinsing with water in the usual way, a cyan dye image is obtained which has an absorption maximum at 698 m Comparison of this dye with cyan dyes of the kind commonly used in the art for example the dye obtained from l-hydroxy-Z-naphthoyl stearylamide, with the abovementioned developer shows that the color grain of the dye according to the invention is appreciably finer.

The dye is not affected after standing for 24 hours at 60 C. and 96% relative atmospheric humidity. In contrast, 40% of the comparison dye is destroyed at a density of 0.5 under such conditions.

If a sample is allowed to stand for 24 hours at 14 mm. pressure and C., the dye is not affected, whilst 30% of the comparison dye is destroyed at a density of 0.5.

If the dye is exposed to light together with the comparison dye, no changes are visible in the dye from the color coupler according to the invention, whereas the comparison dye is partially bleached out.

What is claimed is:

1. In a process of making color photographic images by exposing a light-sensitive photographic material comprising at least one light-sensitive silver halide emulsion layer, color-forming development in the presence of a color coupler, bleaching and fixing, the improvement consisting of performing the colorforming development in the presence of a cyan coupler of the formula:

in which R is a hydrogen or halogen atom or a sulfo group which may be present in salt form;

R is a hydrogen;

R is an alkyl group or a radical of the phenyl series;

R represents an alkyl substituted amino group or an aryl substituted amino group;

b represents hydrogen atom or the ring members neces sary for completing a fused phenyl ring which may be tetrahydrogenated; and

rv=1 to 6.

2. A process as claimed in claim 1, wherein n=3.

3. A process as claimed in claim 1, wherein before the exposure the color coupler is added to a photographic emulsion layer, which is sensitized to red.

8 4. A light-sensitive photographic material comprising necessary for completing a fused phenyl ring which at least one silver halide emulsion layer, which contains may be tetrahydrogenated; and a cyan coupler of the following formula: 11:1 to 6.

OH 5. A light-sensitive photographic material as claimed 1] (i 5 in claim 4, wherein n=3. b- CN CH u N"" R 2) l 4 References Cited b- 2 3 UNITED STATES PATENTS 10 3,135,609 6/1964 Klinger 96-1OO R1 3,328,419 6/1967 Anderson 96100 1n whlch 3,337,344 8/1967 Kimura et a1. 96100 1 15 a hydrogen, halogen or a sulfo group which y 3,418,129 12/1968 Kimura et a1. 96100 be present in salt form; R is hydrogen; J. TRAVIS BROWN, Primary Examiner R is an alkyl group or a radical of the phenyl series; 15 R represents an alkyl substituted amino group or an C X- aryl substituted amino group; 9610() b represents a hydrogen atom or the ring members