US2186733A - Color photography - Google Patents

Description

Patented Jan. 9, 1940", I

UNITED STATES,

@1108 PHOTOGRAPHY Wilhelm Schneider and Alfred Walnut:

Germany, salmon, by memo assignments, 5 Me Anaco Corporation, Binghamton. N. 1., a

corporation of Delaware o Drawing. Application September 18, 1987. sa-hi9 No. 184,409.11: Germany October I,

is calm. (01. 05-0) Our present invention relates to color photography and more particularly to improved color components for the process of color development.

It has for an object to provide color components which are soluble in water and which are fast to diffusion with respect to the silver halide emulsion.

A further object of the invention is to provide a new and improved process for preparing color formers having these properties.

A further object is to provide silver halide emulsions containing the color components fast to diffusion.

A further object is to provide an improved film for color photography having superposed silver halide emulsion layers, each layer containing a color component fast to diflusion.

A known process for producing color photographic and cinematographic pictures uses silver halide emulsion layers which contain color formers. The production of the picture varies with the kind of color former used. As described in U. 8. Patents 1,102,028 and 1,055,155 there may be used color formers which yield color pictures during the development with certain developing substances. For producing multi-color pictures it has been proposed to superimpose lightsensitive. layers containing various coupling bodies, the layers being separated from each other: by intermediate layers so that difiusion oi the coupling bodies from the light-sensitive layers may be prevented. It hasbeen found,however, that this expedient for preventing difiusion is not sufliciently successful in practice. In U. S. Patents 2,179,228, 2,178,612, and 2,179,244 and U. S. patent applications Ser. No. 94,340 filed August 5, 1936, and Ser. No. 159,518, filed August 17, 1937, there are described dyestuil' components which are fast to diffusion. I

The present invention is based on the observation that, color formers of good fastness to diffusion are obtainable by the introduction into the molecule of the dyestufi component as a substituent, a constituent or a conversion product of a natural resin. The conversion products, however, are limited to those in which the' general structure of the natural resin is substantially retained. The constituent or conversion product of the natural resin must contain a reactive group, for instance a carboxyl group or a hydroxyl group, with the aid of which the color former can be caused to enter into chemical combination. Suitable resinous products are, for example, a-pimarabietic acid, fl-pimarabietic acid, pinabietic acid, abietic acid, dihydropinabietic acid, siaresinolic acid, sumaresinolic acid, a-amyrin and various resinoles and bitter substances, for example the humulone of hops.

The compounds of the resinous product with the dyestuil former may be made in known manner, either by producing an ester-like or acid amide-like union between the hydroxyor the amino-group of the dyestuif former and the acid 5 group of the resin acid or by producing an etherlike union, for instance between the hydroxygroup of the resinole and the 'hydroxy-group oi the dyestufl former. For further guidance to those skilled in the art reference is here made to the examples, which disclose in detail the actual process to be followed. They do not, however, limit the invention to the specific data disclosed there, but all such equivalent processes are within the ambit of the invention as fall within the scope of the annexed claims.

-As dyestuil components into which the residue of the resin product is to be introduced there may be named, for example, aminonaphthols,

When the dyestufi component of this kind, that is to say containing a resin constitution, is added to a photographic silver halide emulsion the 001- or picture may be produced, according to the nature of the dyestufi' component, by color development or through the intermediary of diazo-compounds or by the silver bleaching-out process. The procedure may be that described in any of the following: U. S. Patent 2,179,228 and U. S. patent application Ser. No. 141,093, filed May 6, 1937, and in any of the U. S. patents or U. S. patent applications enumerated on page 1, column 1, lines 35 to 38. Or the components located in multi-layer film may be converted into azo-dyes following development and fixing by treatment with a diazo compound such as a carbonic acid solution of tetrazotized benzidine disulfonic acid.

' to oduce the dye image.

The dyestuff formers used in the foregoing process are, in consequence of the groups in the dyestufi molecules which lend solubility in water,

of themselves or in the form of their salts soluble in water and may therefore be incorporated without difliculty in the photographic silver halide emulsion at any point in the process of the production. The resinous substituent makes the dyestufl component fast to diffusion. It must be observed, however, that the chlorides of the resin acids must be used as homogeneous compounds.

The silver halide emulsions made in accordance process, for example by mordant dyeing or toning.

The emulsions may be prepared in any other manner, for example differently sensitized emulsions having diflerent dyestufl formers may be brought in the term 01 small particles on the surface 01' the carrier.'

The iollowing examples illustrate the invention:

(1) 30 grams or the purest colophony are converted in known manner into abietic acid chloride and the benzene solution of this is added in drops to a solution of 18 grams or ,1-amino-5- naphthol in 100 cc. 0! pyridine so that by application of external heat the benzene dropped in is continuously distilled off. when all the aminonaphthol has entered into reaction with the abietic chloride the product is precipitated by means of ice anda'iter the mass has been rendered acid to Congo by hydrochloric acid it is filtered and the solid matter washed. 1 The latter is the dyestufi component which is to be added to the silver halide emulsion.

(2) grams of 3f-amino-5'-sulio- -phenyl- 3-methyl-5-pyrazolone are dissolved in 100 cc. of pyridine. Into the solution there is dropped a solution of grams 0! abietic acid chloride in benzene, the addition being so made that the benzene is continuously distilled oil. When all the aminosuliophenylpyrazolone has entered into reaction the whole is precipitated by means of ice, then made acid to Congo by means of hydrochloric acid and filtered, the solid matter being washed neutral with water.

20 grams of the dyestuif component thus obtained are added to 1 kilo oi emulsion and the latter is then poured to form a layer. After exposure the layer is developed with a solution alkaline with sodium carbonate of aminodimethylaniline, whereby there is obtained a red color image in addition to the silver image. The latter is removed in known manner, whereby the red color image remains.

If the exposed silver halide emulsion layer is developed not with aminodimethylanillne but with an ordinary black-and-white developer and the silver image is converted into a silver antidiazotate of s-naphthyl-amine, for example as described in U. S. patent application Ser. No. 10,704, filed March 12, 1935, and finally this antidiazotate silver image is treated with a weak acid solution, a yellow picture is obtained.

Instead of converting the silver image into the diazo-image there may be produced throughout the whole layer a uniform red dyestui! by treating the layer with a solution of tetrazotized benzidine disulfonic acid and destroying the red dyestuff at the places of the silver image by the silver bleaching out process with use oi! known agents.

(3) A three-layer film for three-color photography is made in the following manner.

1 kilo of silver bromide emulsion is mixed with 15 grams of para-abietylaminobenzoylacetic acid anilide-para-carboxylic acid. In the layer 01 this emulsion there may be produced by means or color development a yellow dyestufl image.

Also dyestufl images which may be produced with aid 01 diam-compounds are yellow.

. thereto by For making the second-emulsion layer 1 kilo or silver bromide emulsion is mixed with a sensitizer for green and then with'lii grams of a solution 01 3-abietylamino-fi-sulio-l-phenyl-S- methyl-fi-pyrazolone. In this layer there is produced by color development a purple dyestui! image.

For making the third emulsion layer 1 rub of silver bromide emulsion is mixed with a sensitizer for red and with a solution of 15 grams of l abietylamino 5 hydroxynaphthalene-B-carboxylic acid. In this layer chromogenic development produces a blue-green dyestufl image.

I! desired the several layers oi. emulsion may be alternated with filter layers.

What we claim is:

1. A photographic silver color photography comprising naphthol.

2. A photographic silver halide emulsion for color photography comprising 3-abietyl-amino- 5-sulio-1-phenyl-3-methyl-fi-pyrazolene.

3. A silver halide emulsion for color photography containing a color former having a natural resin linked thereto by a homopolar linkage.

4- A silver halide emulsion tor color photography containing a color former having .a natural resin linked thereto by a homopolar linkage, said natural resin being a member oi! the group consisting of pimarabietic acid, pinabietic abietic acid, slaresinolicand sumareslnolic acids, amyrins, resinoles and humulones.

5. A silver halide emulsion for color photography containing a natural resin-acid-amide 0! a color former.

6. A process which comprises developing with an aromatic amino developer a silver halide emulsion for color photography containing a color former having a natural resin linked thereto by homopolar linkages.

7. A process which comprises developing with an aromatic amino developer, a. silver halide emulsion for color photography containing a color former having a natural resin linked therehalide emulsion tor abietyl-aminoto by homopolar linkage, said natural resin being acid,. 30

a member of the group consisting of pimarabietic" acid, pinabietic acid, and sumaresinolic acids, amyrins, humulones.

8. A process which comprises developing with an aromatic amino developer, a silver halide emulsion for color photography containing a natural resin-acid amide of a color former.

9. The silver halide emulsion defined in claim 3 wherein the homopolar linkage is selected from the class consisting of an ether-, an ester-, and an acid amide linkage. I

10. The silver halide emulsion defined in claim abietic acid, siaresinolicresinoles and 5 wherein the resin acid is abietic acid.

11. The silver halide emulsion defined in claim- 5 wherein the color former is a pyrazolone and the resin acid is'abietic acid.

12. A photographic silver halide gelatine emulsion Iorcolor photography comprising abietylaminosuliophenylpyrazolone. 1

13. A silver halide emulsion for color photography containing a color former having linked a homopolar linkage a resinous substance selected' from stantially retained. I

the class consisting of a 7. natural resin and its derivatives in which the molecular structure of said natural resin is sub-