DE290562C - - Google Patents

Description

IMPERIAL

PATENT OFFICE.

PATENT LETTERING

- JVl 290562 CLASS 22 «. GROUP

in BASEL, Switzerland.

It has been found that valuable post-chromable o-oxydisazo dyes are obtained, if you have the coupling of sulfated o-diazophenols or o-diazonaphtholes or their derivatives are further diazotized with m-aminophenols available in concentrated alkaline solution monoazo dyes and then coupled with the usual azo components. Through the patents

ίο 143892 and 157786 and the French patent specification 350055 is the use of o-diazophenol sulfonic acids and o-diazonaphthol sulfonic acids for the representation of o-oxymonoazo dyes known. The surprising observation has now been made that the diazo compounds mentioned are also suitable for the preparation of technically very valuable secondary disazo dyes, namely using m-aminophenols as an intermediate component. Through this new process are the by coupling of o-Diazophenolsulfosäüreh or o-Diazonaphtolsulfoäuren with m-aminophenols obtainable, in and of themselves not very valuable monoazo dyes used for the first time in the production of post-chromable disazo dyes. By inserting the m-aminophenol or 3-amino-4-methyl-i-oxybenzene in In addition, the middle positions become very special and technically very valuable effects triggered. While z. B. the combination i-amino - 2 - oxynaphthalene - 4 - sulf osäureresorcin in direct color it gives burgundy red coloration, when chroming gives violet colorations the corresponding combination with m-aminophenol or 3-amino-4-methyl-i-oxybenzene in Middle position i-amino-2-oxynaphthalene-4-sulfonic acid-m-aminophenol or m-aminocresolresorcinol, dyes that directly produce deep blue colorations which turn to black-green when chromium plating, which nuances with post-chromable o-oxymono dyes not at all and not even with such authenticity with the o-oxydisazo fabrics the patent specification 201377 can be generated. Differ from the latter the new dyes thanks to their better milled and potting fastness as well as through better solubility, better leveling power and less sensitivity to limescale. For the technical use of the dyes, especially for the production Walk, light and wearable cloths, namely military cloths, as self-color like also especially for greening in a mixture with other chromating dyes, for production which recently served so valuable field gray and field green nuances is the improvement the properties mentioned, as they are with the dyes of the present process is achieved is important. The situation is similar with other combinations that are made according to the new process can be represented. While the combination i-amino-2-oxynaphthalene-4-sulfonic acid-naphthol directly a bordeaux red, chromed represents a distinct violet blue, provides the appropriate combination

with m-aminophenol or 3-amino-4-methyli-oxybenzene in middle position, ζ. B. the combination i-Amino ^ -oxynaphthalene ^ -sulfonic acid-3-amino-4-methyl-i-oxybenzene-ß-naphtol, directly violet-blue, chrome-plated greenish blue-black nuances of excellent fulled, Light and potting fastness. The same phenomenon can be found in all possible Track combinations according to the present method; always causes the middle class m-aminophenol or m-aminocresol component a strong shift in the shade towards the green part of the spectrum and mostly hand in hand with it a favorable influence on the authenticity properties. Furthermore, in the new method is the following, with regard to the previously known surprising fact to note: while in the azo combinations described so far Resorcinol as a component always produced significantly redder dyes than ß-naphtol, gives with the new re-chromable disazo dyes of the present process Resorcinol always the greener products.

However, the insertion of the m-aminophenol or m-aminocresol in the middle position provides The valuable dyes described only when the coupling of the diazotized Aminonaphthol or aminophenol sulfonic acids with m-aminophenol or m-aminocresol in concentrated alkaline solution takes place. Namely, this combination is used in the usual In an acetic acid or diluted soda-alkaline solution, so be made in the subsequent further diazotization of the monoazo dye and combination with Azo dye components received only weak, worthless, violet coloring azo dyes. The azo group probably enters the m-aminophenol molecule or m-aminocresol in the p-position to the amino group when working in concentrated alkaline solution, while when coupling in soda-alkaline or acetic acid solution the substitution not or only to a minor extent in the p-position to the amino group will. The success of the new process is therefore due to a very specific way of working bound, which was by no means given in advance.

Example 1.

24 parts of i-amino-2-oxynaphthalene-4-sulfonic acid are concentrated in a known manner and as much as possible diazotized, whereupon the diazo compound, with stirring, in a solution of 10.9 parts of m-aminophenol mixed with 60 parts of ice is allowed to run in 50 parts of 3% sodium hydroxide solution. The resulting monoazo dye is acidified with hydrochloric acid, filtered and then in as little as possible Water dissolved again with the addition of 13 parts of sodium hydroxide solution (3%). One adds then add 7 parts of sodium nitrite and acidify in the cold by means of 30 parts more concentrated Hydrochloric acid. After the end of the diazotization, the deposited diazoazo compound is left in a 40 parts of soda solution of 11 parts of resorcinol in 250 parts of water come in. From the reaction mass, the dye is after partial neutralization of the Alkalis deposited by salting out. He dyes wool from an acid bath blue-black Tones that change to black green after treatment with bichromate. the Post-chromed dyeings have excellent fullness, potting and lightfastness.

Example 2.

The diazo compound prepared from 24 parts of i-amino-2-oxynaphthalene-4-sulfonic acid is dissolved in a solution of 12.3 parts of m-aminop-cresol (OH: NH ₂ : CH ₃ = 1: 3: 4) in 50 parts of 3% strength Sodium hydroxide solution and 60 parts of ice entered. When the formation of the monoazo dye has ended, it is acidified with hydrochloric acid, the dye acid is filtered off and, for further diazotization, dissolved in as little water as possible with the addition of 13 parts of sodium hydroxide solution (3%). 7 parts of sodium nitrite are then added and the mixture is acidified with 30 parts of concentrated hydrochloric acid at a temperature not exceeding ^{10 ° C., with thorough stirring.} When the diazotization is complete, the diazotization composition is allowed to run into a cooled solution of 14 parts of β-naphthol, -13 parts of sodium hydroxide solution (3%) and 40 parts of soda in 250 parts of water. After coupling has taken place, the deposited dye is filtered off, pressed and dried. It dyes wool from an acid bath in violet tones, which, when chromium-plated, turn into a deep blue-black, of good fullness, light and potting fastness.

In the above examples, the i-amino-2-oxynaphthalene-4-sulfonic acid can be replaced by other o-aminonaphthol sulfonic acids or by o-aminophenol sulfonic acids or by their substitution products; Instead of β-naphthol or resorcinol, dioxynaphthalenes, m-aminophenols or other suitable azo components can be used as the end component. Furthermore, instead of m-aminophenol or m-aminop-cresol, any other m-aminophenol derivatives which contain a free o-position to the hydroxyl, which must at the same time be a free p-position to the NH ₂ group, can be used as the intermediate component.

In the table below are the dyeing properties of some of the following Processes of representable dyes compared:

Diazo connection
5 middle
component End
component Coloring on wool chromed o-aminophenol-p-sulfonic acid m-amino
p-cresol ß-naphtol angry blue ¹⁰ i-amino-2-oxynaphthalene
4-sulfonic acid m-amino
p-cresol ß-naphtol bordeaux blue black Nitro-i-amino-2-oxynaphthalene-
4-sulfonic acid m-amino
p-cresol ß-naphtol violet blue black i-amino-2-oxynaphthalene
4-sulfonic acid m-amino
p-cresol Resorcinol violet black green Nitro- i-amino-2-oxynaphthalene-
²⁰ 4-sulfonic acid m-amino
p-cresol Resorcinol blue black black green i-amino-2-oxynaphthalene
4-sulfonic acid m-amino
p-cresol ι: 6-Dioxy-
naphthalene purple black blue black ²⁵ i-amino-2-oxynaphthalene
4-sulfonic acid m-amino
p-cresol 2: 7 dioxy
naphthalene blue blue black o-aminophenol-p-sulfonic acid m-amino
phenol ß-naphtol blue purple black i-amino-2-oxynaphtarine-
4-sulfonic acid m-amino
phenol ß-naphtol bordeaux blue black Nitro-i-amino-2-oxynaphthalene-
³⁵ 4-sulfonic acid m-amino
phenol ß-naphtol violet blue black i-amino-2-oxynaphthalene
4-sulfonic acid m-amino
phenol Resorcinol violet black green ⁴⁰ i-amino-2-oxynaphthalene
4-sulfonic acid m-amino
phenol ι: 5-dioxy
naphthalene blue black purple black i-amino-2-oxynaphthalene
4-sulfonic acid
45. ^. m-amino
phenol ι: 6-Dioxy-
naphthalene violet purple black i-amino-2-oxynaphthalene
4-sulfonic acid m-amino
phenol 2: 7 dioxy
naphthalene violet purple black i-amino-2-oxynaphthalene
⁵⁰ 4-sulfonic acid m-amino
phenol m-amino
phenol violet black green
■ black purple

Claims (1)

Patent claim: Process for the preparation of post-chromable o-oxydisazo dyes, consisting of that the coupling of sulfated o-diazophenols, diazonaphtols or their derivatives are further diazotized with monoazo dyes obtained in strongly alkaline solution with m-aminophenols ¹¹⁰ and the resulting diazoazo compounds are combined with the usual azo components.