US1762033A - Process of preparing pictures to be produced by tanning action - Google Patents

Description

a instance 7 pigment-printing,

Patented June. 3, J

UNITED; mus PATENT mc mnxmmmn PAUL scnmn'r, nunonr zAim, BADEN-IBIEBRIOH, GERMANY, nssrenoas ro CORPORATION OE GERMANY rnocnss or ranrmme rrc'runns To an rnonucnnsx :mmrnve acrron No Drawing Application filed August 7,

aration of pictures to be produced by the action of tanning substances.

In certain photo printingprocesses (for printing, ozotypic printing or the like) and also in many other arts of printing (copper' deep printing, photo-lithography, photo-printing, etc.), the la ers prepared with salts of chromic acid ta e a prominent place in spite of the disadvantages they show, the .most serious drawback being that, notwithstanding the many attempts made in this respect (see for instance Namias, Eders Jahrbuch, 1904, page 142), it has not beenpossible to stabilize the colloid layer sensitized with chromates before exposure to light so as to render them suitable for technical pur oses. 1n

Colloid layers sensitized by means 0 salts of chromic acid are not only unfit for being stored for some time, for even in the course of a few hours the said layers may under unfavorable atmospheric-conditions undergo so extensive alterations that it is no longer possible to obtain invariably good results by using them for-the above mentioned purposes. 7

Although attempts have been made to substitute for the chromates other bodies (see Strasser German Patent No. 160,729, issued April 10, 1905) the use of suchother bodies has not been, adopted in practice owing to the unsatisfactory photographic results they gave. c

We have now found that the decomposition products of diazo compounds which are formed during exposure to light are capable, when subjected to reaction with chromates or any other substance, in the presence of a colloid, of'producing a tanning action. By the term tanning action is here to be understood that action by which the solubil-- ity or the swelling u of colloids is diminished. A similar actlon to that of a bichromate can be produced by other oxidation agents for instance ammonium hypobromite, and likewise diazo compounds of great coupling capacity. In using stable diazo comounds as for instance orthoor para-hyroxyor amino-diazo compounds it has being ex 1928, Serial No. 298,1 26, and m Germany August 22, 1927.

been found that layers sensitizedtherewith are, when not yet exposed'to light, of abetter stability than layers prepared from chromates. Moreover the new process is applicable to a much greater variety of pur poses because sensitized papers prepared according to this process can be kept in store fit-for immediate use so that the need not be freshly sensitized whenever they are to be employed. The reat number of available diazo compoun s enables one, .by conveniently varym the proces, to modify extensivelythe gradation of the light-sensitive layers.

The diazo compounds in question may be incorporated into the colloid layer when it is b mg repared or by subsequentl plache a er in a bath prepared rom a so ution o the respective diazo compound, if reguired, with a stabilizer or. sensitizer adde thereto. 'The said diazo compounds may also be applied alone on a suitable base for instance paper, films, metal-foils or the him), then exposed to light under a correspondin original and finally pressed upon a colloi layer moistened with a solution of a chromate.

Diazo compounds may be used with advantage instead of chromates in all reproducing processes where a tanning effect 1s to be producedon colloid la er by chromates reduced by the action of t e light. Among those processes may be mentioned: Pi mentprinting, copper-deep rinting, photo ithography, phototypy, ge atine-printing, gum-v been washed. In certain cases' it is advan AND wmnnnrxamena, or, HALLE & co. AKTIENGESELLSGBAFT, A

tageous to color the layers before and alsov after washing them. -Furthermore a varnis then the layer developed wit warm waterfand, if desired, dusted over with a color dust in order to intensify the picture.

there may be rolled on the layers in question, after osed to light, a fatty color, or only The following examples serve to illustrate our invention, but are notintended to limit it thereto. v

1. Pigment paper is placed in a bath prepared with a solution, at 18 C. temperature, of 4; parts of hydrofluoborate of l-diazoldimethylaminobenzene in 100 parts of water and left therein until it is thoroughly moistened; the paper is then pressed upon a well nitrocellulose with a gelatine layer of a cleaned glass-plate and dried and, afterdrying, it is detached from the latter. The said diazo. compound may be obtained by diazotizing 1-amino-4;-dimethylaminobenzene in the presence of a hydrofluoboric-acid. After drying, the dried pigment paper is exposed to light under a negative, then placed together with a suitable piece of transfer paper in a 2 per cent solution of potassium bichromate, until the pigment paper becomes stretched, the pigment paper and transfer paper are then taken from the bath, pressed upon each other and the picture is developed by dissolving therefrom the gelatine which has not been exposed to light in water of about 40 C. temperature in the manner in which pigment-pictures are usually de veloped.

2. 4: parts of 4-diaz o-3-methyltdimethylanilinsulfate obtained by diazotizing 4- amino-3-methyl-1-dimethylanilin in a sulfuric solution, are dissolved in 100 parts of water and this solution is spread on wellsized paper having a smooth surface. After drying, the paper so treated is exposed to light under a diapositive decomposed through a dotted screen. The paper after exposure to light is pressed upon pigment paper moistened with a 0.25 per cent solution of potassium bichromate and pressed out, such as it is used for copper etchings (so-called etching paper), the paper is then drawn off after about one minute and pressed immediately upon the copper plate or copper-cylinder intended to receive the etching. On the copper the picture is developed as usual with water of a temperature of 40 C. and then, after drying, etched with ferric chloride.

Instead of 4-diazo-3-meth l--dimcthylanilinsulfate there may be use the cadmium salt of l-diazol-monoethylnaphthylamine or the diazo compound of para-aminodi'phenylamine.

3. So-called Alberts autotypy-paper is placed in a bath prepared from a solution of 4 parts of the diazo compound from 1-amino-2-oxy-acetylamino-5-benzenesulfonic acid in 100 parts of water, dried on a glass plate, then exposed. to light under a negative decomposed through a dotted screen, placed in a bath prepared from a' 2% solution of potassium bichromate and finally thoroughly watered. On the picture when dry is applied by a roller a photolithographic re-printing color giving a uniformly grey tone and then placed in water. When the paper has become sufliciently moist, the picture can be developed by means of a wet small piece of wedding; after drying the developed picture it is fur ther re-printed by the usual method on a lithographic stone, zinc or aluminium and further treated.

4. A photo-print film, produced from suitable .de ree of hardness, such' as the known Ag a film, is placed in a bath prepared from 4 parts of thediazo'compound from v1-amino-2-oxy-3-naphthalenecarboxylic acid in 100 parts of water and a small quantity of ammonia, then drawn through acetic acid and by drying it at 2829 C. a' wrinkled grain is produced thereon. Upon the film so prepared a negative is copied, the film exposed to light and then placed for 2 minutes in a bath prepared from a 2% solution of potassium bichromate, whereupon it is thoroughly watered and dried. The further treatment and printing are operated in the usual manner.

5. 10 parts of gelatine, 2 parts of colcothar red iron oxide, 2 parts of sugar and 60 parts of water are made up into an emulsion and there is then added a solution, acidified with diluted hydrochloric acid, of 0.5 parts of a diazo compound obtained by diazotizing 1- aminoA-phenlyaminobenzene in a hydrochloric solution and 1.5 parts of sodium 1.3.6-naphthalenetrisulfonate in 20 parts of water; the emulsion thus obtained is poured onpaper in the usual manner and the latter dried, exposed to light and further treated as indicated in Example 2. y

In the following claims by the term tanning action is to be understood that action by which the solubility and the swelling up of colloids are diminished under the influence of light.

By the term tanning agent are to be understood ammonium hypobromite, etc., and likewise diazo compounds of great coupling capacity,

\Ve claim:

1. The process of "preparing pictures to be produced by tanning action consisting in applying a mixture of a diazo compound and an organic colloid on a base placing the object to be copied on the layer sensitive to light, exposing it to light, treating it with a tanning agent and developing it with water.

2. The process of preparing pictures to be produced by tanning action consisting in applying a mixture of a diazo compound, an organic colloid and a pigment on a base placingthe object to be copied on the layer sensitive to light, exposing it to light, treating it with a tanning agent and developing it with water.

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agent and developing it 'with water.-

' posin in applying a mixture '0 4. The process of preparing pictures to be produced by tanning action consisting and an organic .colloid on a basf' pl'a'cing the object to be copied on the layer sensitive to light, exposing it to light, treating it' with a solution of a chromate and developing it with water.

5. The process of preparing pictures to be produced by tanning action consisting in applying a mixture of a. diazo compound, an organic colloid and a pigment on a base placing the object to be copied on the layer sensitive to light, exposing it to light, treating it witha solution of a chromate and developing it with water.

6. The process of preparing pictures to be produced by tannin action consisting in applying a mixture 0 a diazo compound, an organic colloid, a pigment and asta-' bilizer on a base placing the object to be copied on the layer sensitive to light, ex-

it to light, treating it with a solutionof .a c romate and developing it with water.

7. The process of preparing pictures to be produced by tanning action consisting in applying a mixture of a diazo compound containin besides the diazo group a basic group an an organic colloid on a base placing the object to be copied on the layer sensitive to light, exposing it to light, treating it with a tanning agent and eveloping'it with water.

8. The process of preparing pictures to be produced by tanning action consisting in applying a mixture of a diazo compound containing besides the diazo group a basic group, an organic colloid and a pigment on a base placing the object to be copied on the layer sensitive to light, exposing it to light,

treating it with a tanning agent and developingrit with water.

9. he process of preparing pictures to be produced by tanning action consisting in applying a mixture of a diazo compound containing besides the diazo group a basic group,-an organic colloid, a pigment and a stabilizer on a base, placing the object to be copied on the, layer sensitive to light, exposing it to li ht, treating it with a tanning agent and eveloping it with water.

10. The process of preparing pictures to be produced by tanning action consisting in applying a mixture of a diazo compound contaimn besides the diazo group abasic group an an organic colloid on a base placing t e object to be copied on the layer sendiazo compound,

a diazo compound pressing it the layer sensitive to light, exposing it to light, treating it with a, solution of a chromate and developing it with water.

12. The process of preparing pictures to be produced by tanning action consisting in applying a mixture of a diazo compound containing besides the diazogroup a basic group, an organic colloid, a igment and a stabilizer on a base placing t e object to be copied-on the layer sensitive to light, exposing it to light, treating it with' a solution of a chromate and developing it with water.

13. The process of preparing pictures to be produced by tanning action consisting in applying a mixture of the diazo compound of the 1A-amino-monoethyl-naphthylamine, an organic colloid, a pigment and a stabilizer on a base placing the object to be copied on the layer sensitive to light, exposing-it to light, treating it with a solution of a chromate and developing it with water. I

14. The process of preparing pictures to be produced by tanning action consisting in applying a diazo compound on a base placing the object to be copied on the layer sensitive to light, exposing it to light, pressing it on a layer of an organic colloid, having been treated with a solution of a chromate and developing it with water.

15. The process of preparing pictures to be produced by tanning action consisting in applying a mixture of a diazo compound and a pigment on a base placing the object to be copied on the layer sensitive to light. exposing it to light, pressing it on a layer of an organic colloid, having been treated with a solution of a chromate and developing it with water.

16. The process of preparing pictures to be produced by tanning action consisting in applying a diazo compound containing besides the diazo group a basic group on a base placing the object to be copied on the layer sensitive to light, exposing it to light, on a layer of an organic colloid,

aving been treated with a solution of a chromate and developing it with water.

17. The rocess of preparing pictures to be produced by tanningaction consisting in applying a mixture of a diazo compound containing besides the diazo group a basic group and a pigment on a base plac ng'tho object to be copied. on the layer sensitive to layer of an organic colloid, having been treated with a solution of a chromate and developing it with water.

18. The process of preparing pictures to be produced by tanning action consisting in applying a 'mixture of the diazo compound CERTIFICATE OF CORRECTION.

Patent No. 1, 762,033.

Granted June 3, 1930, to

MAXIMILIAN PAUL SCHMIDT ET AL.

reb certified that the name of assignee in the above numbered patent was zrl dniiduslj written and printed as "Halie & Co. Aktiengesellscicaft, whereas said .name should have been written. and printed as Kalle 8: Go. Aktiengeseilschatt,

. as shown by the records of assignments in this office; and that the said Letters Patents should be read with this correction therein that the same may conform to the record of the case in the Patent Office.

Signed andsealed this 2nd day of September, A. 1930.

' M. J. Moore, Acting Commissioner of Patents.