US2133937A

US2133937A - Color photography

Info

Publication number: US2133937A
Application number: US125894A
Authority: US
Inventors: Edmund B Middleton; Andrew B Jennings
Original assignee: DuPont Film Manufacturing Corp
Current assignee: DuPont Film Manufacturing Corp
Priority date: 1937-02-15
Filing date: 1937-02-15
Publication date: 1938-10-18
Anticipated expiration: 1955-10-18
Also published as: GB497463A

Description

Patented Oct. 18, 1938 UNITED STATES,

PATENT OFFICE COLOR PHOTOGRAPHY Edmund B. Middleton and Andrew B. Jennings,

New Brunswick, N. Film Manufacturing assignors to Du Pont I a.

rporation, New York,

N. Y., acorporation of Delaware No Drawing. Application February 15, 1937, Serial No. 125,894

21 Claims. (on. 95-88) vide a color-photographic element derived from color-forming compounds which, in combination a with certain classes of developing agents, will form dyes in situ with photographic images. A further object is to produce such dyes by colorforming development. Another object is to produce partial color-records in which the individual records are of improved spectral quality for color photography.

It has been formerly taught to prepare colored photographs by developing exposed silver salt emulsion layers in certain developing agents whose oxidation products are water-insoluble dyes. Thus, a silver halide layer, bearing a latent image, can be developed in an alkaline indoxyl solution, whereupon a silver image is produced along with a blue dye image in situ with the silver. The silver image can be removed by Farmers Reducer revealing the dye image. In like manner, a photographic record can be developed in chlor-indoxyl to produce a green image and in thio-indoxyl for a red image.

It is also known, for the purposeof preparing color pictures, to develop exposed silver halide layers by agents whose oxidation products are not colored but which will chemically unite or couple with other organic agents, called colorformers to form intensely colored dyes. These color-formers are not photographic developers, are generally water-insoluble and produce dyes in situ with, and simultaneously with the deposition of the metallic silver image. The developers used for these proposed processes are of the diamino-aryl class, such as paraphenylendiamine' or its substitution products, such as for example, di-methyl or di-ethyl-para-phenylene-diamine. Color-forming compounds already proposed include, for example, thymol, benzoyl acetone, phenacyl chloride and para-nitrobenzyl cyanide.

These prior processes, however, have failed to produce colored images having the correct spectral qualities for color photography. Moreover, these prior color-formers tend to have a harmful eflect on the sensitivity of silver halide emulsions, so that, for these reasons, the color-formers already known have not provided a practical means for color photography.

The present invention has demonstrated that acylacetaminoarylmorpholines, in conjunction with aromatic amino developing agents, form satisfactory dye images. The acylacetamino-arylmorpholines are aminoarylmorpholines wherein an amino hydrogen is replaced by the radicle of an acyl acetic acid, e. g., acetoacetic acid,

malonic acid, cyanacetic acid, furoylacetic acid, benzolylacetic acid and naphthoylacetic acid. The aminoarylmorpholines include the orthometa-and para-aminophenylmorpholines, aminophenylthiomorpholines, aminonaphthylmorpholines, aminonaphthylthiomorpholines and their substitution products.

Aoeto-aoet-p-aminopbcuylmorpholine HN.COCH:.OOCHI N J H, d: H;

H: H: Aoeto-acet-4-amino-2-5-diethoxy-phenyl-morphoiine HN.COOH1.COCH| Acoto-acet-p-amino-m-chlor-phonyl-morpholino HI|-I.COCH;.COOH;

N C H1 Cm (5H1 3H2 Aoeto-aoeto-p-amino-phenyl-thiomorpholiue HN.COCH:.COCH;

N :21: 1 on E \Q/ g The preferred color-formingcompounds above described may be used either in developers or as an addition to silver halide emulsions.

As preferred color-forming developers, the following produce excellent results:

Formula 1 i Diethyi-p-phenylenediamine hydrochloride 2 gm" Sodium suiiite, anhydrous gm 5 Sodium carbonate, anhydrous -gm wat to liter 1 To which is added aceto-acet-p-amino- I phenyl morpholine gm 1.0 Ethyl al 00.; 100

Formula 2 Diethyl-p-phenylenediamine hydrochloride I gm 2 Sodium sulflte, anhydrous gm 5 Sodium carbonate, anhydrous gm 20 Water to liter 1 To which is added aceto-acet-4-amino-2-5- diethow-phenyl-morpholine gm 1.0 lithyl alc cc 100 In place of the di-alkyl-substituted p-phenylenediamine, the mono-alkylated substitution produce may be used or the un-substituted p-phenylenediamine may be' used as well as the bases and/or acid salts of these developing agents. In place of the ethyl alcohol, methyl alcohol or acetone may be used, and, if desired, the organic solvent for the color-forming compound may be dispensed with entirely. A

If it is desired to add the color-forming compound directly to the emulsion, a preferred procedure is as follows: 10 grams of the color- !ormer is dissolved in 200 mls. of ethyl alcohol 'to which is added about 50 grams of gelatin in 500 mls. of water and then thoroughly mixed.

This color-forming solution is then added, with vigorous stirring, to 1 liter of silver-gelatinoemulsion. Emulsions containing these colorforming compounds may be coated as layers on one or both sides of a photographic support either as individual or superposed emulsion layers.

While it is preferred to employ silver-gelatinoemulsions, other emulsions comprising other well known sensitizers and binding agents may also be used. Examples of these are the well known silver collodion emulsion, albuminoid emulsion, or bichromated emulsion.

In the form of color-forming developers, the above described compounds may also be used to re-develop bleached silver images. Thus, a silver image may be bleached in potassium ferrocya-' nide or a mixture of chromic and hydrobrornic acids and re-exposed, whereupon the bleached image can be re-developed to silver and a dye image by the color-forming developers above described. After development, the silver is removed by any of the well known reducers such as Farmers Reducer.

While the foregoing specification sets forth the preferred exempliilcations of the present invenline.

2. A color-forming photographic developer comprising an aromatic amino photographic developing agent and an acetoacetaminoarylmorpholine. 3. A color-forming photographic developer comprising an aromatic amino photographic developing agent and an acylacetaminophenylmorpholine.

4. A color-forming photographic developer comprising an aromatic amino photographic developing agent and an acetoacetaminophenylmorpholine.

5. A color-forming photographic developer comprising an aromatic amino photographic de- 12. A color-forming photographic emulsion comprising a binding agent, ahalogen salt of .silver and an acetoacetaminoarylmorpholine.

13. A color-forming photographic emulsion comprising a binding agent, a halogen salt of silver and an acylacetaminophenylmorpholine.

14. A color-forming photographic emulsion comprisinga binding agent, a halogen salt of silver and an acetoacetaminophenylmorpholine.

15. A color-forming photographic emulsion comprising a binding agent, a halogen salt of silver and acetoacet-p-aminophenylmorpholine.

16. A color-forming photographic emulsion comprising a binding agent, a silver halide and an acetoacet 4. amino-2,5-diethoxyphenylmorpholine.

17. A color-forming photographic emulsion comprising a binding agent, a silver halide and {in acetoacet-p-amino 2 chlorophenylmorphono.

18. A color-forming photographic layer comprising a sensitized gelatino-silver-halide emulsion and an acylacetaminoarylmorpholine.

19. A color-forming photographic layer comprising a sensitized gelatino-silver-halide emulsion and an acetoacetaminoarylmorpholine.

20. A color-forming photographic layer comprising a sensitized gelatino-silver-halide emulsion and an acylacetaminophenylmorpholine.

21. A color-forming. photographic layer comprising a sensitized gelatino-siiver-halide emulsion and an 'acetoacetaminophenylmorpholine.

22. A color-forming photographic layer comprising a sensitized gelatino-silver-halide emulsion and acetoacet-p-aminophenylmorpholine.

23. A color-forming photographic developer comprising an N-di-alkyl-p-phenylene diamine and an acylaoetaminoarylmorpholine.

24. A color-forming photographic developer comprising an N-di-alkyl-p-phenylene diamine and an acetoacetaminoarylmorpholine.

25. A color-forming photographic developer 27. A color-forming photographic developer comprising an N-di-alkyl-p-phenylene diamine comprising an N-di-alkyl-p-phenylene diamine and an acylacetaminophenylmorpholine. and acetoacet-p-aminophenylmorpholine. 26. A color-forming photographic developer 5 comprising an N-di-alkyl-p-phenylene diamine EDMUND B. MIDDLETON.

and an acetoacetaminophenylmorpholine. ANDREW B. JENNINGS.