DE271747C

DE271747C -

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Publication number: DE271747C
Application number: DENDAT271747D
Authority: DE
Also published as: FR439648A

Description

KAISERLICHESIMPERIAL

PATENTAMT.PATENT OFFICE.

PATENTSCHRIFTPATENT LETTERING

-M 271747-KLASSE 29*. GRUPPE -M 271747-CLASS 29 *. GROUP

Verfahren zur Herstellung von Nitrocellulose-Kunstseide. Patentiert im Deutschen Reiche vom 14. April 1912 ab.Process for the production of nitrocellulose rayon. Patented in the German Empire on April 14, 1912.

Bekanntlich ist die Nitrocellulose-Seide in trockenem und insbesondere in feuchtem Zustande weniger widerstandsfähig als Naturseide. Gegenstand der Erfindung ist nun ein Verfahren zur Herstellung von Nitrocellulose-Kunstseide von großer Haltbarkeit, aus der Gewebe hergestellt werden können, die in, kochendem Wasser gewaschen werden können. Das neue Verfahren besteht im wesentliehen darin, daß man der Kunstseide Metallresinate, z. B. Zinkresinat oder Magnesiumresinat oder ein Gemisch beider, zusetzt, die einen sehr hohen Schmelzpunkt besitzen, wobei, um ein schmiegsames Endprodukt zu erhalten, der Gehalt der Lösung an Resinaten zweckmäßig nicht über 20 Prozent beträgt. Man kann den Resinatzusatz aber auch über diesen Betrag hinaus steigern, wenn man dem Gemisch von Nitrocellulose mit den Resinaten stark oxydierte trocknende Öle, Stearin, Elaidin oder ein Gemisch dieser Körper zusetzt. Verwendet man Metallresinate im Überschuß, so erhält man ein hartes, celluloidartiges" Produkt. Es ist bekannt, noch schwefelsäurefeuchte Nitrocellulose mit trocknenden Ölen zu vermischen, die vorher mit Chlorschwefel behandelt worden sind, d. h. mit sogenanntem Faktis. Man hat auch vorgeschlagen, der Lösung eine Kautschuklösung zuzusetzen und das Gemenge mit Chlorschwefel zu vulkanisieren bzw. den aus dem Gemenge hergestellten Faden mit Albumin zu umhüllen, das durch den Chlorschwefel koaguliert wird. Auch unvulkanisierter Kautschuk, gemischt mit Zinnchlorür, ist als Zusatz verwendet worden, desgleichen mit Salpetersäure behandelte Metallresinate. Zur Herstellung bildsamer Massen nach Art des Celluloids hat man schließlich alkalische Natron- oder Kaliharzseifen mit Nitrocellulose gemischt.As is well known, the nitrocellulose silk is in when dry and especially when damp, it is less resistant than natural silk. The invention now relates to a process for the production of nitrocellulose rayon of great durability, from which fabrics can be made that are used in, Can be washed in boiling water. The new procedure consists essentially in that one of the rayon metal resinates, z. B. zinc resinate or magnesium resinate or a mixture of both, which have a very high melting point, where, In order to obtain a pliable end product, the resinate content of the solution is expediently not more than 20 percent. You can also increase the resin addition beyond this amount if you use the Mixture of nitrocellulose with the resinates, strongly oxidized drying oils, stearin, Elaidin or a mixture of these is added to the body. If metal resinates are used in excess, in this way a hard, celluloid-like "product is obtained. It is known that it is still moist with sulfuric acid Mix nitrocellulose with drying oils, previously mixed with chlorosulfur have been treated, d. H. with so-called factories. It has also been suggested add a rubber solution to the solution and vulcanize the mixture with chlorosulfur or the mixture from the mixture to encase manufactured thread with albumin, which is coagulated by the chlorosulfur. Uncured rubber mixed with tin chloride is also used as an additive as well as metal resinates treated with nitric acid. To make more sculptural After all, celluloid-type masses are alkaline soda or potash soaps mixed with nitrocellulose.

Alle diese Zusätze ergeben aber nicht eine brauchbare, in trockenem und feuchtem Zustande widerstandsfähige Seide.However, none of these additives result in a usable one in dry and moist condition resistant silk.

Gemäß der Erfindung erhält man eine solche Seide dagegen, wenn man der Nitrocelluloselösung Metallresinate zusetzt und dann aus dem Gemisch die Fäden herstellt. Hierdurch unterscheidet sich das neue Verfahren auch von dem bekannten Verfahren, fertige Fäden und Gewebe z. B. mit Tonerderesinat zu imprägnieren, wobei die Fäden nur eine ganz dünne Resinathülle erhalten, während, wenn die Resinate den Lösungen zugesetzt werden, der dann hergestellte Faden vollständig mit ihnen durchsetzt ist und infolgedessen gewissermaßen aus einem undurchlässigen Stoff besteht.According to the invention, on the other hand, such a silk is obtained by adding the nitrocellulose solution Metal resinate is added and then the threads are made from the mixture. This is also what makes the new process different from the known method, finished threads and fabrics z. B. to impregnate with alumina resin, the threads only get a very thin resin sheath, while if the resinate is added to the solutions, the then produced thread completely with is permeated with them and as a result, to a certain extent, made of an impermeable material consists.

Bekanntlich wird der Schmelzpunkt von Harzen, Balsamen und Gummiharzen durch Zusatz von Zinkoxyd oder Magnesiumoxyd wesentlich erhöht. So bewirkt ein Zusatz von 4 Prozent Zinkoxyd zu Kolophonium eine Erhöhung des Schmelzpunktes von 70 ° auf ; 125 °, ein Zusatz von 8 Prozent eine solche auf 170°, d. h. auf eine Höhe, die das Harz gegen eine Temperatur von ioo° widerstandsfähig macht, so daß es nicht in einem für die Seide schädlichen Maße erweicht.,As is known, the melting point of resins, balms and gum resins is through Addition of zinc oxide or magnesium oxide significantly increased. So an addition of 4 percent zinc oxide to rosin increases the melting point by 70 °; 125 °, an addition of 8 percent to 170 °, i.e. H. to a height that the resin makes it resistant to a temperature of 100 °, so that it is not in a for the silk softens harmful dimensions.,

In der Kälte machen die Resinate die Seide wasserdicht und verleihen ihr eine große Festig-In the cold, the resinates make the silk waterproof and give it a great deal of strength.

Claims

speed; at the same time, they make them insensitive to washing with soap and alkali carbonates. If you increase the addition of resinates, especially when using aluminum resinate, without simultaneously adding emollients such as strongly oxidized drying oils or, what is even more useful, stearin or elaidic or a mixture of all of these bodies, ίο you get products that contain celluloid are similar and can replace it for many purposes. The resinate is represented as follows: Resin, balsam, gum resin are dissolved

1.5 or a mixture of these in ether. Then oxides or hydroxides of zinc,

, · 'Magnesium or a mixture thereof in the determined by the product to be achieved Ratio added and the whole shaken until completely dissolved.

One solves ζ. Β. ι kg of purified rosin in a liquid that is not miscible with water (ether, gasoline or the like). You get the solution A.

On the other hand, 300 g of pure zinc sulfate are dissolved in 600 g of distilled water. Man gets the solution B.

The two solutions A and B are in a closed container with Agitator, suitably a rotating cylinder with a hollow pivot pin and pebble stone or porcelain balls; they are let through the hollow pin while rotating the amount of caustic soda that is sufficient to fill the zinc sulphate to implement constantly:

Zn S O ₄ + 2 Na (OH) = Zn (O HJ ₂ + Na ₂ S O ₄ .

ι, By stirring the oxide hydrate with: the dissolved resin in intimate contact brought and combines with it with separation of water to form zinc resinate. Replaces the zinc sulfate by the sulfates of aluminum, magnesium, tungsten etc. or a mixture of these sulphates in the correct ratio, one obtains the corresponding, possibly complex resinates.

If that or the resinates have formed, what you can do with one that has been removed Sample finds the entire contents of the container in a closed decanter transferred and peeled off the upper layer consisting of the resinous solutions.

The aqueous solution containing sodium sulfate is poured off.

The addition of the metal resinate (s), dissolved in ether or benzene, to the nitrocellulose happens in the following way: If the collodion z. B. 600 g ether to 400 g alcohol and should contain 150 g nitrocellulose, the following amounts are used:

Nitrocellulose 150 g,

Resinate solution .... 120 ecm,

Ether 480 ecm,

Alcohol 400 ecm.

In such a mixture, the nitrocellulose dissolves easily and quickly.

If you add aluminum or magnesium to the zinc or magnesium resinates or their mixture Tungsten resinate is added, even if only in a small amount (0.5 percent), so the Flammability of the products obtained with nitrocellulose is reduced and consequently the Denitration made partially or entirely dispensable.

Since the thread always loses coherence due to denitration, the one after the silk that has not been denitrified at all or is incompletely denitrated despite its use, produced by new processes lower cellulose content but more resistant because the nitrocellulose, from the it exists, is tougher than the denitration product.

Sponsorship τ claims:

1. Process for the production of nitrocellulose rayon, characterized in that the rayon metal resinates, for. B. zinc resinate or magnesium resinate, which have a very high melting point, or a mixture of both is added for the purpose of adding a rayon obtained that withstands the action of boiling water while having reduced flammability.

2. The method according to claim 1, characterized in; that the content of the solution of resinate does not exceed 20 percent in order to ensure the suppleness of the end product not belittling.

3. The method according to claim 1, characterized in that the mixture Drying oils strongly oxidized by nitrocellulose and resinates, stearin, elaidin or a mixture of these bodies is added for the purpose of increasing the resin addition to enable and still get a pliable end product.

4. The method according to claim 1, characterized in that the nitrocellulose Metal resinate is added in excess, for the purpose of a hard celluloid-like product to obtain.