US2884325A - Process for the production of a yellow mask image in magenta-colored photographic images - Google Patents

Description

V Ap fl 1959 BURGARDT EIAL 7 2,384,325

PROCESS FOR THE PRODUCTION OF A YELLOW MASK IMAGE IN MAGENTA-COLORED PHOTOGRAPHIC IMAGES Filed-March 3, 1955 v EXPOSURE AND COLOR FORMING DE VELOPEMEN T NEGATIVE MAGENTA COLOR IMAGE PLUS SILVER 'IMAGE [REACT/0N- WITH PYRROLE ALDEHYDE POSITIVE YELLOW MASK/N6 IMAGE POSITIVE YELLOW MASK/N6 IMAGE I INVENTORS. .L OTHAR BURGARDT, EHCH RECKZIEGEL, OTTMAR WAHL.

A TYTORNEYS United States Patent PROCESS FOR THE PRODUCTION OF A YELLOW MASK IMAGE IN MAGENTA-COLORED PHO- TOGRAPHIQ IMAGES Lothar Burgardt, Leverkusen-Bayerwerk, Erich Reckziegel, Leverknsen, and Ottmar Wahl, Opladen, Germany, assignors to Agfa Aktiengesellschaft Application March 3, 1955, Serial No. 492,053

Claims priority, application Germany March 5, 1954 7 Claims. (Cl. 96-9) This invention relates to a process for the correction of photographic color images and more particularly to a process for the correction of magenta photographic images produced by the process of color forming development. It is known that azomethine dyes, which are generally used for the production of magenta-colored images according to the process of color forming development, do not have a perfect absorption. They absorb light in the green range of the spectrum as well as some of the light in the blue range of the spectrum. This fact obviously leads to a color defect in the negative-positive process. This applies, for example, to magenta dyestuffs which are formed by color-forming development from pyrazolones. It is also known that it is possible to compensate for this undesirable secondary absorption in the blue range of the spectrum by means of a masking image, the absorption of which corresponds to the secondary absorption of the said negative image.

Such masking images may be produced by transforming the color couplers contained in a silver halide layer after color forming development into yellow dyestuffs. For this purpose, a process has already been proposed which is characterised in that the light-sensitive material, which contains a diffusion-resisting pyrazolone or a similar compound containing an active methylene group as magenta color-former, is treated after exposure and color development with an aromatic aldehyde of the benzene or naphthalene series which contains an auxochromic group, or with a functional derivative of such an aldehyde. The residual color coupler in such a case is transformed by the aldehyde to form a yellow dyestulf, which serves as a color mask for correcting the undesired secondary absorption of the image dye. Appropriate compounds for carrying out this process are monoand di-substituted p-aminobenzaldehydes and the anils, arylhydrazones or bisulphite reaction products of such aldehydes, which are alkali-soluble as a result of suitable substituents, for example, sulphonic groups. The yellow masking image dyes obtained by this process have the disadvantage, however, that their absorption is not restricted to the blue part of the spectrum, but also extend to the green part thereof. However, an undesirable flattening of the gradation of the magenta image dyestufi is caused by this absorption in the green part of the spectrum.

It has now been found that for the production of yellow masking images for magenta-colored images produced in photographic layers containing color couplers by the method of color forming development, it is possible with particular advantage to use aldehydes of pyrrole, indole and carbazone and their functional derivatives, more especially the anils of these aldehydes.

These aldehydes are particularly suitable, because they lead to styryl dyestuffs, which are of shorter wavelength in their absorption than the corresponding dyes with substituted aminobenzaldehydes and therefore cannot be the cause of a disadvantageous flattening in the gradation of the magenta dyestufi image.

; ample,

The aforementioned heterocyclic aldehyes are particularly valuable for the purpose in question, because the use thereof, independently of the duration of their action on the photographic material does not lead to overmasking, i.e. a positive yellow image with higher density than that of the secondary absorption of the magenta image dyestuffs formed from pyrazolones. The secondary absorptions of these magenta image dyestuffs and the yellow masking dyes which are formed have in fact substantially the same color density.

The production of the said aldehydes is carried out in accordance with known processes. Pyrrole aldehydes, indole aldehydes and N-substituted carbazole aldehydes are adapted to be manufactured easily with good yields according to the method of Vilsmeier and Haack (Berichte der deutschen chemischen Gesellschaft 60, 119). Pyrrole aldehydes and indole aldehydes are also available by other methods, for example, the Reimer- Tiemann synthesis (for example, Berichte der deutschen chemischen Gesellschaft 61, 1078). By treatment of suitable aldehydes with conventional sulphonating agents, it is possible for sulphonic acids to be prepared therefrom. Examples of suitable aldehydes which may be mentioned, inter alia, are: u-pyrrole aldehyde, 2.4-diphenylpyrrole-S-aldehyde, ,G-indole aldehyde, indole-3- aldehyde-carboxylic acid, 1-methyl-2-phenylindole-3- aldehyde, N- (carboxyethyl)-carbazole-3-aldehyde, N- ethyl-carbazole-3-aldehyde-sulphonic acid and N-ethylcarbazole-3-aldehyde. The anils are produced according to known processes. Particularly suitable for this purpose are those aniline derivatives which carry positive substituents, such as, for example, hydroxy-, alkoxyor dialkylamino-groups. Sparingly soluble aldehydes, on the other hand, are transformed into alkali-soluble compounds by reaction with aniline-sulphonic acids.

The process according to the invention is particularly suitable for the production of yellow masking images in photographic multi-layer materials which contain color couplers for the production of yellow, magenta and cyan color couplers in three superimposed silver halide layers which are sensitive to diflferent regions of the spectrum. Appropriate couplers for the production of magneta images are the well known pyrazolones-S, for ex- 1 (4-phenoxy-5-sulphophenyl)-3-heptadecyl-5- pyrazolone. There may also be used other couplers such as cyanacetyl compounds. The process is illustrated in the accompanying drawing and is further explained by the following examples.

Example 1 The following multi-layer light sensitive material is used:

A transparent support is coated with a layer of a red sensitive silver halide emulsion containing 20 grams per litre of the cyan color forming coupler having the formula:

CH3.N. 0171135 OH NH.OO

SO H

Upon this layer there is applied a layer of a green sensitive silver halide emulsion layer containing per litre 15 grams of the magenta color forming coupler 1-(4- phenoxy'sulphophenyl)-3-heptadecyl-5-pyrazolone. On this layer a yellow filter layer of colloidal silver and thereupon an optically not sensitized silver halide layer 3 is coated, which contains per litre the following yellow color forming coupler:

This film is exposed to an object to be reproduced and developed in a developer solution of the following composition:

COOH

OOH

Diethyl-p-phenylene-diamine-hydrochloride 3 g.

After rinsing, the material is bathed in an 0.5% slightly alkaline solution of m-"nethoxy-anil of fl-indolealdehyde- 2-carboxylic acid. The film is then bleached, fixed and washed in the conventional manner. The material thus treated now contains a positive yellow color image serving as a mask in the green-sensitive layer, in addition to its cyan, magenta and yellow negative component images. The ,B-indolealdehyde-Z-carboxylic acid is obtained from e-indole-carboxylic acid ethyl ether according to the process disclosed in J. Am. Chem. Soc. 68 (1946), 1156.

Example 2 Instead of the said solution of m-methoxy-anil of [3- indole-aldehyde-Z-carho-xylic acid referred to in Example 1, there may equally well be employed an 0.5-1% weakly alkaline solution of m-dimethyl amino-anil of N-ethylcarbazole-3-aldehyde-sulphonic acid for the production of the yellow masking image.

N-ethyl-carbazole-3-aldehyde sulphonic acid is obtained in the following manner:

To a mixture of 1.1 mols of N-formyl-N-methylaniline and 2 mols of phosphoroxychloride there are 'added by degrees while stirring 1 mol of N-ethylcarhazole. The reaction mixture is kept for 12 hours at 3035 C. and thereafter introduced into water at 40-45 C. The oil formed is stirred until crystallization takes place. The reaction product is isolated and recrystallized from ethanol.

Yield of N-ethylcarbazolaldehyde, 200 g. RP. 81 C.

700 g. of N-ethylcarbazolaldehyde are sulfonated with a mixture of 1.7 litres of concentrated sulphuric acid and 300 mol of oleum 20% at C.

Example 3 Instead of the said solution of m-methoxy-anil of fi-indole-aldehyde-Z-carboxylic acid referred to in Example 1, there is employed an 0.5 Weakly alkaline solution of m-hydroxyanil of ot-pyrrole aldehyde for the production of the masking image. The a-pyrrol-aldehyde is obtained according to the process disclosed in Berichte der- Deutschen Chemischen Gesellschaft 51 (1928), 1078.

Example 4 A multi-layer material, in which the bottom red-sensitive silver halide layer with blue-green component has coated thereon a green-sensitive silver halide layer with yellow component, above which is a yellow filter layer and an unsensitised silver halide layer with a pyrazolone as magenta dyestuif former, is exposed and developed as in Example 1.

After being rinsed, the material is treated with an 0.5-1% weakly alkaline solution of the m-sulphanil of N- ethyl-carbaZole-3-aldehyde, bleached, fixed and washed. In addition to the negative blue-green and yellow images in the bottom coating and middle coating, the film now contains a negative magenta image in the top coating, opposite-whichis a yellow masking image.

4 Example 5 Instead of the solution mentioned in Example 4 for the production of a yellow masking image, there may equally well be employed a weakly alkaline solution of a sulphanil of 1-methyl-2-phenyl-indole-3-aldchyde. This aldehyde is obtained by the process disclosed in German patent specification 614,325.

Example 6 Instead of the solution mentioned in Example 4, the masking image may be produced by using the weakly alkaline solution of m-hydroxyanil of 2.4-diphenyl-pyrrol- S-aldehyde. This aldehyde is obtained by the process disclosed in J. Chem. Soc. (London) 1943, p. 596.

Any other theoretically possible arrangement or association of the layers may be chosen for this process, apart from the multi-layer materials described in the examples.

Example 7 For the production of a duplicate negative, three positive black-and-white separation records produced from a multi-color negative are successively exposed by means of three partial color record filters on to a multi-layer material which has a bottom red-sensitive silver halide layer with a cyan color forming coupler, above this a greensensitive silver halide layer with a yellow color forming coupler and a top layer of an unsensitised silver halide layer with a pyrazolone as magneta color forming coupler, all layers containing tartrazinc as filter dyestutf instead of using a separate filter layer. The color forming couplers may be the same as those disclosed in Example 1. The material thus exposed is developed in a developer of the following composition:

Diethyl-p-phenylene-diamine-hydrochloride g 3 Anhydrous soda g 60 Potassium bromide g 2 Anhydrous sodium sulphite g 2 Water cc 1,000

is thereafter rinsed and bathed in an 0.5 Weakly alkaline solution of p-sulphanil of B-indole aldehyde (see I. Am. Chem. Soc. 68 (1946), p. 1156). After bleaching, fixing and rinsing, the multi-layer material contains a negative blue-green image in the bottom coating, a negative yellow image in the middle coating and a negative magenta image with a yellow masking image in the top coating.

What we claim is:

1. A process for the production of a yellow masking image for a magenta-colored image comprising develop ing an imagewise-exposed silver halide emulsion layer, containing a magenta color-forming coupler having an active methylene group, with a primary aromatic amino developing agent to form a magenta dye image, and reacting the residual color-forming coupler with an aldehyde to produce a yellow styryl dyestufi masking image, said aldehyde being selected from the group consisting of pyrrolealdehydes, indole-aldehydes, carbazole aldehydes and anils thereof.

2. The process of claim 1 wherein the magenta colorforming coupler is a pyrazolone.

3. A process for the production of a yellow masking image for a magenta-colored image which comprises developing an imagewise-exposed photographic material comprising a transparent base and a plurality of superimposed silver halide emulsion layers coated on said base, one of said layers containing a magenta-color-forming coupler having an active methylene group, with a primary aromatic amino developing agent to form a magenta dye image in said layer containing said magenta color-forming coupler, and reacting the residual colorforming coupler with an aldehyde to produce a yellow styryl dyestuif image, said aldehyde being selected from the group consisting of pyrrole aldehydes, indole aldehydes, carbazole aldehydes and anils thereof,

5 6 4. The process of claim 3 wherein one of said layers 7. The process of claim 1 wherein said aldehyde concomprises a red-sensitive silver halide layer containing a (aims a Sulfonic acid group bonded to a cyclic carbon cyan color-forming coupler, another of said layers comatomprlses a green-sensitwe sllver halide layer sltuated above References Cited in the file of this patent said red-sensitive layer, and a third layer comprises an 5 unsensitized silver halide layer situated above said green- UNITED STATES PATENTS sensitive layer, one of said last-mentioned layers con- 1,731,966 Ballauf 0 taining pyrazolone as a magenta color-forming coupler. 1,398,445 e Z et a1. Feb. 21, 1933 5. The process of claim 1 wherein said aldehyde con- 10 1,954,452 Mannes et P 1934 tains a hydroxyl group bonded to a cyclic carbon atom. 2,252,718 Mannes et 191 1941 6. The process of claim 1 wherein said aldehyde congsgg ii.

tams a carboxyl group bonded to a cycllc carbon atom. 2,704709 p g Mar. 1955

Claims (1)

1.A PROCESS FOR THE PRODUCTION OF A YELLOW MASKING IMAGE FOR A MAGENTA-COLORED IMAGE COMPRISING DEVELOPING AN IMAGEWISE-EXPOSED SILVER HALIDE EMULSION LAYER, CONTAINING A MAGENTA COLOUR-FORMING COUPLER HAVING AN ACTIVE METHYLENE GROUP, WITH A PRIMARY AROMATIC AMINO DEVELOPING AGENT TO FORM A MEGENTA DYE IMAGE, AND REACTING THE RESIDUAL COLOR-FORMING COUPLER WITH AN ALDEHYDE TO PRODUCE A YELLOW STYRYL DYESTUFF MASKING IMAGE, SAID SLDEHYDE BEING SELECTED FROM THE GROUP CONSISTING OF PYRROLEADLDSHYDES, INDOLE-ALDEHYDES, CARBAZOLE ALDEHYDES AND ANILS THEROF.

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