DE109161C - - Google Patents

Description

IMPERIAL

PATENT OFFICE.

PATENT LETTERING

CLASS 22: dyes, varnishes, lacquers.

Patented in the German Empire on June 16, 1896.

Of the simple azo dyes from diazonaphtolsulfonic acids, only those are so far which as a component m-diamido respectively. m-amidooxy- respectively. m - dioxybenzene derivatives or Q ₁ a ₄ -dioxynaphthalene derivatives have been used to prepare trisazo dyes (see patents 84546, 91036, 91894 and French patent 243735). It has been proven that this results in trisazo dyes, which contain the component that can be coupled twice in the single azo dye in the middle position, while the amidonaphthol sulfonic acid in the end position has the general formula:

ρ - diamine <

m - diamine

respectively
o. _x a ₄ -Dioxynaphthalene

- amidonaphthol sulfonic acid.

If, on the other hand, one uses the simple azo dyes from diazonaphtholsulphonic acids and the component α-naphthylamine, which only couples once, then when a tetrazo compound acts as a naphthol the same interferes with the residue of the originally used diazonaphtholsulphonic acid, and one arrives at intermediate products with amidonaphtholsulphonic acid in middle and azoic acid -Naphthylamine in end position. The representatives of this group suitable for further coupling are obtained after subsequent experiments using the azo dye formed in acidic solution from diazotized β _t a ₄ - amidonaphthol - β, β ₃ - disulfonic acid (patent 53023) and α-naphthylamine; by coupling them further with a molecule of an amidonaphthol sulfonic acid one arrives at valuable mixed trisazo dyes of the general formula:

ρ - diamine

'P ₁ a ₄ - amidonaphthol - ß ₂ ß ₃ - disulfonic acid - a - naphthylamine,. Amidonapthol sulfonic acid,

which unheated cotton in intense violet to blue-black nuances, dye and according to the two terminal, in turn diazotizable residues of a-naphthylamine and an amidonaphthol are most suitable as developing dyes. Those with them on the fiber by re-diazotizing and coupling with β-naphtol or Dark blue and deep black colors that can be achieved with m-diamines are absolute Washfastness and the analog development colors from the best known diamine black colors equal.

While you now these mixed Trisazo dyes by the method described with quantitative yield as completely uniform and always uniformly pure receives coloring products, carries out the usual

Process of the step-by-step construction of the same by further diazotization of the intermediate product from a molecule of tetrazo compound and a molecule of β, _{α 4} -amidonaphthol-β ₂ β ₃ -disulfonic acid (according to patent 80003) and successive coupling of the unsymmetrical tetrazo compound thus obtained with α-naphthylamine and one Amidonaphthol sulfonic acid is unavoidable in dye mixtures, the composition and shade of which changes depending on the choice of reaction conditions, and which in some cases cannot be salted out at all from an alkaline solution, so that the yield of direct coloring end products is considerably reduced.

The new process thus shows great technical advances compared to the old one.

Nor can the process be used to build up the present trisazo pits of the 75762 patent, as the mixed disazo dye to be used here one p-diamine and two molecules of amidonaphthol sulfonic acids in diazotization Tetrazo compounds must provide and therefore impossible to convert them into a trisazo dye can be.

Examples:

i. 34.2 kg of the acidic sodium _{salt of, S 1} a ₄ -Amidonaphtol-ß. ₂ ß ₃ -disulfosäure (iooprocentig) are diazotirt with 6.9 kg nitrite and 300 1 Amount suspension of Diazonaphtolsulfosäure with the cooled solution of 14.3 kg A-naphthylamine in 12.5 kg of hydrochloric acid 21 ⁰ B. and 400 l of water combined. Most of the dye separates out as a brown-violet powder and, after 24 hours, is brought into solution by adding 8 kg of sodium bicarbonate, then a solution of 30 kg of soda is added, and the tetrazodiphenyl solution corresponding to 18.4 kg of benzidine is quickly introduced at 10 °. The solution of 23.9 kg of amidonaphthol sulfonic acid γ is now added to the intermediate product which separates out immediately as a black-violet, gelatinous precipitate. Add 4 kg of baking soda and 500 liters of water. If the stirring is continued, the combination will end after 24 hours. It is filtered directly, without the addition of salt, cold and dried. The trisazo dye obtained in this way dyes unheated cotton from neutral or soda-alkaline salty baths intensely purple-black.

It dissolves easily with a violet-black color in hot water, from which it becomes an additive of mineral acid precipitated as a blue powder, while caustic alkalis, in small quantities Red-violet coloring, producing a black-blue precipitate in excess. The solution in concentrated Sulfuric acid is blue.

2. The tetrazo solution obtained from 2 1.2 kg of tolidine is coupled in a soda-alkaline solution with the simple azo dyes obtained according to Example 1 from 34.2 kg of S ₁ & ₄ amidonaphtholβ ₂ βg-disulfonic acid and 14.3 kg. α-naphthylamine and add to this intermediate product the solution of 34.1 kg of Ci ₁ a ₄ -arnidonaphtolß ₂ ß _g -disulphonic acid (acid sodium salt, iooprocentig) in 4 kg of soda and 500 liters of water, then this also occurs here as a gelatinous precipitate Intermediate product rapidly changes into a trisazo dye which partly dissolves in a blue-black color. After 12 hours, it is boiled and salted out. The dye produces strong blue-black nuances from salty baths, which in light tones come very close to the colors produced with indoin blue.

Claims (2)

Patent Claims: ι. Process for the preparation of mixed trisazo dyes with β, a ₄ -amidonaphthol-β ₂ β-disulfonic acid in the middle position, characterized in that a molecule of the simple azo dye obtained in acidic solution is obtained from diazotized P ₁ a ₄ -amidonaphthol-β ₂ β-disulfonic acid and a Naphthylamine is combined in a soda-alkaline solution with a molecule of the tetrazo compound of a p-diamine to form an intermediate product and the same is then coupled further with a molecule of an amidonaphthol sulfonic acid. 2. The special embodiments of the ^ method characterized in claim 1 using benzidine, tolidine and dianisidine as p-diamine and of amidonaphthol sulfonic acid γ and Ct ₁ ct ₄ amidonaphthol-ß, ß ₃ -disulfonic acid as the second component.