DE900781C - Diffusion-resistant yellow color formers of the benzimidazole class - Google Patents

Description

The invention relates to non-diffusing fax forming components of the 2-phenyl-benzimidazole class, which have improved properties in terms of solubility and are capable of forming color Develop yellow dye images with better spectral properties and extremely fine Deliver grain.

In the current practice of color photography, after the most widely used Process a monopack with differently sensitized halogen silver emulsion layers arranged one on top of the other used, each of which has a dye component which is non-diffusible to the emulsion contains that in the development of the exposed monopack with a developer from a primary aromatic amine subtractively colored dye images; d. H. blue-green (cyan), blue-red (magenta) and delivers yellow images.

The commonly used yellow component consists of an open chain ketomethylene compound, such as ao Acetoacetanilide, benzoylacetoacetanilide, and the like. For most purposes, those represented by such components produced dye images satisfactorily, although they what the spectral properties and that As far as grain is concerned, it still leaves something to be desired. Another disadvantage in using this grain

components consists in their low solubility and, in particular, in their low stability in solution. It has now been found that the yellow color formers which are commonly used are used Disadvantages of forming dye images with improved spectral properties and fine Grain can be eliminated by taking care of the formation of the yellow image in the color-forming development process a 2-phenyl-benzimidazole is used,

ίο The one in the melted benzene ring is water-soluble making group, on the nitrogen atom in the i-position of the heterocyclic ring a diffusion-proof making radical and on the phenyl ring which is bonded to the carbon atom in the 2-position, one Contains acetamide residue. These color formers deliver by color-forming development with developers from p-phenylenediamine-type azomethine dye images are very desirable, and they also have an essential one better solubility compared to the ketomethylene compounds used in the color development process generally used.

Photographic emulsions containing yellow color formers of the aforementioned kind and processing such emulsions by color-forming development to produce improved yellow ones Dye images thus form the aim and purpose of the present invention.

The color formers proposed according to the invention can be represented by the following structural formula

CR- (R ₁ ) W /

in which R is a phenyl radical of which one carbon atom is bonded directly to the carbon atom of the heterocyclic ring, such as phenyl, halophenyl such as chlorophenyl, or bromophenyl and the like, alkylphenyl such as toluyl, ethylphenyl and the like, alkoxyphenyl as methoxyphenyl, ethoxyphenyl u. the like., R _{1 is} the radical-NH · CO · CH ₂ · a, R ₂ and an alkyl chain having at least 10 carbon atoms, such as decyl, undecyl, dodecyl, myristyl, tetradecyl, pentadecyl, octadecyl. etc. ., R _{3 is} a water-solubilizing group such as SuIf0, carboxy or the like, A is an alkyloyl radical such as acetyl, propionyl, butyryl and the like, aroyl such as benzoyl, naphthoyl and the like, cyano or carbathoxy and η ι or 2 is.

Examples of compounds encompassed by the above formula are the following:

i. 2- (4'-Benzoylacetaminophenyl) -i-octadecylbenzimidazole-5-sulfonic acid

G ₁₈ H ₃₇

HOoS

NH-CO-CHo-CO

2. z-i ^ -Benzoylacetaminophenyy-i-laurylbenzimidazole-s-sulfonic acid;

3. z - ^ '- BenzoylacetaminophenylI-i-myristylbenzimidazole-s-sulfonic acid;

4. a - ^ '- Benzoylacetaminophenylj-i-octadecylbenziimdazole-s-sulfonic acid

C ₁₈ H ₃₇

.N.

HO ₈ S

NH-CO-CH ₀₁ -CO

5 · 2 - [(3 '»S'-DibenzoylacetaminoJ-phenyy-i-octadecylbenzimidazole-s-sulfonic acid ⁵⁵ C, _R H ₃₇

NH-CO-CHj-CO

HO ₅ S

NH · CO · CH ₉ · CO ■

6. 2 - [(3'-Benzoylacetamino-4'-chloro) -phenyl] -i-octadecylbenzamidazole-5-sulfonic acid

HO ₃ S

NH-CO-CH ₈ -CO '

7-2 - [(3'-Benzoylacetamino-4'-methoxy) -phenyl] -i-octadecylbenzimidazole-5-sulfonic acid

HO ₃ S

8. 2 - [(3'-Benzoylacetamino-4'-methoxy) -phenyl] -i-decylbenzimidazole-5-sulfonic acid;

9. 2- (4'-Acetoacetaminophenyl) -i-octadecylbenzimidazole-5-sulfonic acid

H0, S

NH-CO-CH ₂ -CO-CH ₃ ;

10. 2- (4'-Acetoacetaminophenyl) -i-octadecylbenzimidazole-5-carboxylic acid;

11. 2- (4'-Carbethoxyacetaminophenyl) -i-octadecylbenzimidazole-5-sulfonic acid

HO ₃ S

NH-CO-CH ₂ -CO-OC ₈ H ₅ ;

12. 2- (4'-Cyanoacetaminophenyl) -i-octadecylbenzimidazole-5-sulfonic acid

HO ₃ S

NH-CO-CHj-CN

The color formers are prepared by heating a 2- (4'-aminophenyl) -i-long-chain alkylbenzimidazole-5-sulfonic or carboxylic acid with an acyl acetate ester with mixing or by heating the aforementioned components in the presence of pyridine to a temperature of about 100 to 130 ⁰ C are heated.

The starting benzimidazole, on the other hand, is produced by adding a 3 - amino - 4 - long alkyl chain
Aminobenzenesulfonic or carboxylic acid with the desired nitrobenzene carboxylic acid chloride in the presence of pyridine or any other suitable
Acid binder is heated and the nitro compound 125 is then reduced to the corresponding amine.

The preparation of the intermediate is the same as that described in U.S. Patent 2,530,349 Process, with the difference that the i-oxy-2-naphthoyl chloride by the desired Replaced nitrobenzoyl chloride and then reduced the product obtained to the corresponding amine will.

The emulsions intended for the production of the desired yellow image are prepared, by adding a small amount of the color former, for example about 0.5 g, in 100 ecm of a photographic Halide silver emulsion dispersed, the emulsion is coated on a carrier and then dried. The film containing the emulsion can be produced by the negative-positive process or by the reversal process processed, whereby for the color development a primary aromatic amine developer, such as p-diethylaminoanuine or the like. Is used.

The invention is further described by the following examples; However, she is neither on this Examples are still limited to the details described therein.

example 1

CirH,

HOoS

NH-CO-CH ₉ -CO

30 parts of 2- (4'-aminophenyl) -1-octadecylbenzimidazole-5-sulfonic acid and 15 parts of benzoylacetate are mixed in a Werner-Pfleiderer mixer and Heated for 4 hours to a vapor pressure of 3.5 kg / cm.

The crude product is purified by being taken up in 125 parts of methanol and heated to reflux (65 ⁰ C) Va hour. After cooling to 30 to 35 ^° C., the product is collected on a filter, washed with 50 parts of methanol, sucked dry and then air-dried.

0.5 g of the purified product are in 100 ecm a photographic silver bromide emulsion. The emulsion will be translucent on a Layer carrier applied and dried. After exposure, the film is in a color-forming developer developed, which from an aqueous solution of 10 parts of sodium sulfite, 15 parts of p-diethylaminoaniline, 2.5 parts of sodium carbonate and 70 parts of potassium bromide. That way it becomes Silver and dye image formed. After removing the silver by fading in a potassium ferricyanide solution and subsequent fixing becomes a vivid yellow dye image with very fine grain obtain.

Example 2

30 parts of 2 - (4 '- aminophenyl) -1 - octadecylbenzimidazole-5-sulfonic acid, 15 parts of benzoylacetester and 200 parts of pyridine are heated to 110 to 4 hours Heated to 120 ° C. The reaction mixture is diluted with 100 parts of water and then into a mixture from 100 parts of concentrated hydrochloric acid and 1000 parts Entered ice water. The crude product is collected on a filter, twice with cold water washed, vacuumed as dry as possible and air dried.

The crude product is purified by taking it up in 200 parts of methanol and heating it under reflux (65 ° C.) ^x / ₂ hours. After cooling to 20 to 25 ^° C., the product is collected on a filter, washed with 75 parts of methanol, sucked dry and then dried in the air. The product is the same as that of example r and can be used as indicated there.

Example 3

HO, S

NH-CO-CH ₂ -CO

This product is made in the same way as in Example ί from 30 parts of 2- (3'-aminophenyl) -i-octadecylbenzimidazole-5-sulfonic acid and 15 parts of benzoyl acetic ester hergesteUt.

By dispersing the color former in a photographic silver bromide emulsion and processing the Emulsion as in Example 1, a strong yellow dye image with very fine grain is obtained.

Example 4

HO ₃ S

NH-CO-CH ₂ -CO '

NH-CO-CH ₉ -CO '

The product is made from 28 parts of 2- (3 ', 5'-diaminophenyl) -i-octadecylbenzimidazole-5-sulfonic acid according to the procedure of Example ι and 25 parts Benh

zoyl acetic ester produced.

When the above color former is used to form an azomethine dye image, so will Obtained dye images that ι according to Example

and 3 obtained are similar.
Example 5

HO ₃ S

NH-CO-CH ₂ CO

This product is made in the same way as in Example ι from 30 parts of 2 - [(3'-amino-4'-chloro) -phenyl] -i-octadecylbenzimidazole-5-sulfonic acid and 15 parts of benzoylacetester.

By using the above color former as in Example 1, a vivid yellow azomethine dye image is obtained generated. These dye images are particularly notable for the fineness of their grain.

Example 6

H0, S

As in Example 1, this product is made up of 32 parts 2 - [(3'-Amino-4'-methoxy) -phenyl] -i-octadecylbenzimidazole-5-sulfonic acid and 18 parts of benzoylacetester.

NH · CO -CHo-CO

By using the above color former as in Example 1, a vivid yellow azomethine dye image is obtained generated. These dye images are particularly notable for the fineness of their grain.

Example 7

HO ₃ S

NH-CO-CH ₂ -CO-CH ₃

This product is used in a similar way to Example 1 Way from 27 parts of 2- (4'-aminophenyl) -i-octadecylbenzimidazole-5-sulfonic acid and 15 parts of acetoacetester.

By using the above color former as in Example 1, a vivid yellow azomethine dye image is obtained generated. These dye images are particularly notable for the fineness of their grain.

Example 8

'18 ^J

HO ₃ S

= - NH • CO • CH ₂ • CO -OC ₂ H ₅ .

This product is made from 27 parts as in Example ι 2- (4'-aminophenyl) -i-octadecylbenzimidazole-5-sulfonic acid and 12 parts of diethyl malonate.

By using the above color former as in Example 1, a vivid yellow azomethine dye image is obtained generated. These dye images are particularly notable for the fineness of their grain.

HOoS

Example 9

-NH-CO-CH ₂ -CN,

37 parts of 2 - (4 '- aminophenyl) -1 - octadecylbenzimidazol-5-sulfonic acid and 50 parts Cyanacetester are heated for 4 hours at 145 to 150 ⁰ C. 75 parts of methanol and 75 parts of ethyl acetate are added to the cooled reaction mixture. The product is collected on a filter, washed with 75 parts of ethyl acetate, sucked dry and then air dried.

By using the above color former as in Example 1, a vivid yellow azomethine dye image is obtained generated. These dye images are particularly notable for the fineness of their grain.

Claims (4)

PATENT CLAIMS: i. Photographic silver halide emulsion for color photography, characterized in that it is a compound of the following formula as a diffusion-resistant yellow color former R, CR- (R ₁ ) M contains, in which R a phenyl radical, R ₁ the group -NH-CO-CH ₂ -A, R ₂ an alkyl radical with at least 10 carbon atoms, R ₃ a water-solubilizing group, η the Number 1 or 2 and A is an alkyloyl, aroyl, cyano or carbethoxy group. 2. Photographic halogen silver emulsion according to claim 1 for color photography, thereby ge go indicates that it is the compound 2- (4'-benzoylacetaminophenyl) as a non-diffusing yellow color former -1 - octadecylbenzimidazole -5 - contains sulfonic acid. 3. Photographic halogen silver emulsions according to Claim ι for color photography, characterized in that it is used as a diffusion-resistant yellow color former the compound 2- (3'-benzoylacetaminophenyl) -1-octadecylbenzimidazole-5-sulfonic acid contains. 4. Photographic halogen silver emulsion according to claim 1 for color photography, characterized in that that they use the compound 2 - [(3 ', 5'-Dibenzoylacetamino) -phenyl] -i-octadecylbenzimidazole-5-sulfone- contains acid. 5660 12.53