DE173011C

DE173011C -

Info

Publication number: DE173011C
Application number: DENDAT173011D
Authority: DE

Description

KAISERLICHESIMPERIAL

PATENTAMT.PATENT OFFICE.

PATENTSCHRIFPATENT DOCUMENT

KLASSEGREAT

in BASEL.in Basel.

Patentiert im Deutschen Reiche vom 7. Januar 1905 ab.Patented in the German Empire on January 7, 1905.

Durch Kupplung der i-Diazo-2-naphtol-4-sulfosäure bezw. ihres Anhydrides mit ß-Naphtol (Französisches Patent 350055) wird ein Farbstoff erhalten, dessen Färbung auf Wolle mit Chromsalzen nachbehandelt ein Blauschwarz von hervorragenden Echtheitseigenschaften ergibt. Wegen seiner etwas geringen Löslichkeit in essigsaurem Bade ist jedoch seine Anwendung in der Apparatenfärberei mit einigen Schwierigkeiten verbunden. Um diese gänzlich zu heben und den betreffenden Farbstoff in eine löslichere Form überzuführen, wurde versucht, denselben durch Einwirkung von konzentrierter Schwefelsäure weiter zu sulfidieren. Es hat sich nun gezeigt, daß bei Vermeidung von hohen Temperaturen, die eine Zersetzung des Farbstoffes bewirken, durch Einwirkung von konzentrierter Schwefelsäure, vorzugsweise durch solche mit einem gewissen Zusatz.von Schwefelsäureanhydrid, die Sulfuration sich leicht bewerkstelligen läßt. Die Befürchtung, der auf diese Weise erhaltene neue, ungemein leicht lösliche Farbstoff könnte vielleicht auf der Faser nachchromiert nicht mehr die nämliche ausgezeichnete Walk- und Pottingechtheit aufweisen wie der ursprüngliche, erwies sich vollkommen unbegründet. Der Farbstoff besitzt außer dem Vorteil viel größerer Löslichkeit im übrigen noch all die guten Echtheitseigenschaften des Ausgangsmaterials. By coupling the i-diazo-2-naphthol-4-sulfonic acid respectively your anhydride with ß-naphtol (French patent 350055) obtained a dye, the dyeing of which on wool after-treated with chromium salts Gives blue-black of excellent fastness properties. Because of his something However, its low solubility in acetic acid bath is its application in apparatus dyeing associated with some difficulties. In order to lift this completely and turn the dye in question into a more soluble one An attempt was made to transform it into a more concentrated form by the action of Sulfuric acid to sulfide further. It has now been shown that when avoiding high temperatures, which cause the dye to decompose, due to the action of concentrated sulfuric acid, preferably by those with a certain addition of Sulfuric anhydride, the sulfuration can be easily accomplished. The fear the new, extremely easily soluble dye obtained in this way could perhaps appear the fiber no longer has the same excellent mill and potting fastness after chroming exhibit like the original, turned out to be completely unfounded. The dye has a lot besides the advantage Incidentally, greater solubility still has all the good fastness properties of the starting material.

Er unterscheidet sich von den ähnlich zusammengesetzten, auch zwei Sulfogruppen enthaltenden Farbstoffen, erhalten nach dem Verfahren der Patentschrift 156440 aus Naphtylamintrisulfosäuren, dadurch wesentlich, daß die beiden Sulfogruppen nicht, wie dort, in einem Kern sich befinden, sondern verteilt in beiden Kernen, so daß ihm wahrscheinlich eine der folgenden Konstitutionen zukommt:It differs from the similarly composed, also two sulfo-containing dyes obtained after Process of patent specification 156440 from naphthylamine trisulfonic acids, thereby essential that the two sulfo groups are not, as there, in one nucleus, but rather distributed in both nuclei, giving it probably one of the following constitutions comes to:

oderor

SO_SHSO _S H

UJUJ

N-N-OH OH-N-N-OH OH-

r—UtI Uli—! ιr — UtI Uli—! ι

SOoH.SOoH.

Was das Verfahren selbst betrifft, das zu diesem neuartigen Farbstoff führt, so bedeutet dasselbe gegenüber dem Verfahren der Patentschrift 156440 einen bedeutenden gewerblichen Fortschritt, und zwar aus folgenden Gründen. Der hier als Ausgangsmaterial gewählte Farbstoff ist leichtAs for the process itself that leads to this novel dye, so the same means an important one compared to the method of patent specification 156440 commercial progress for the following reasons. The one here as the starting material chosen dye is light

Claims

accessible and can be specifically according to the method of patent 171024 and the French patent 350055 in excellent yield and in excellent purity obtain; due to a sulfuration which goes against all expectations smoothly, it becomes in the new dye transferred from the desired solubility. In the case of the Patent specification 156440, on the other hand, is difficult to find in sufficient yield and purity Naphthylamine trisulfonic acids to be represented are assumed, the disulfurized oxyazo dye is obtained in hardly satisfactory yields, since the combination of the intermediate Diazonaphthol disulfonic acids produced by no means run smoothly under the circumstances prevailing there.

■ '-. . · ■■ Example.

For sulfuration, the dye obtained by coupling the i-diazo-2-naphthol-4-sulfonic acid with β-naphthol is used, preferably in the form in which it is obtained when it is precipitated from its alkaline solution by dilute acids, washed out and then dried and pulverized. Of the same part 1 is then slowly added to 3 parts concentrated sulfuric acid at about 30 to 40 ⁰ with stirring. Here, the dye partially dissolves with a blue color, and sometimes it turns into metallic, green, shiny needles.

1 part of fuming sulfuric acid (with about 25 percent anhydride content) is allowed to run slowly into the resulting pulp, with vigorous stirring, the mixture becoming thinner under heating, which is allowed to rise to 65 °, possibly 70 °. Stirring is continued at this temperature until a sample taken is readily soluble in cold water with sufficient dilution. After the sulfuration has ended, the mixture is poured into ice water, salted out with salt, the precipitate is filtered off, washed out with moderately concentrated salt solution, dried and ground. The dye obtained in this way is a metallic, green, glossy dark powder that dissolves easily with a raspberry-red color even in cold water. When ammonia is added, the color changes to pure blue, while concentrated hydrochloric acid causes a precipitate in the form of violet-brown flakes. In concentrated sulfuric acid, the dye dissolves _s with dark blue color. On wool it gives a brownish-red shade from an acetic acid bath, which after copper-plating turns into a dark violet and chrome-plated into a blue-black.

The proportions and amounts given in this example for the sulfuration can can of course be changed within certain limits without the result materially to influence.

Pat ε ν τ - A ν 3 ρ ε υ c η:

Process for the preparation of a particularly suitable one for apparatus dyeing o-Oxyazo dye, characterized in that the dye obtained from the i-diazo-2-naphthol-4-sulfonic acid respectively. their anhydride and ß-naphtol Sulfurization by means of concentrated sulfuric acid, the subsequent smoking Sulfuric acid is added, converted into a readily soluble form.