DE643854C - Process for dyeing leather - Google Patents

Description

Process for dyeing leather through it has been found that it is possible to Leather, especially chrome leather, to be dyed largely or completely, if for this purpose salts of 4'-amino- or 4'-alkylamino-I, I'-azob: enzene-2'-sulfonic acids used, the still leine amino, alkylamino or acylamino group or several these groups alone or together with one or more nitro groups ior must contain one or more nitro groups alone and continue to do so Carboxyl groups, halogen and neutral or neutral substituents in the ring could be.

So far, those used for textile dyeing purposes have been acidic Azo dyes for dyeing leather, especially chrome leather, not to be used, since they only dye the outermost layers. This applies, for example, to the azo dyes Orange II from dianotated I-aminobenzene-4.sulfonic acid and 2-oxynaphthalene (Schultz, Dye tables, 6th edition, No. I45) or Metanil yellow extra from dianotized I-aminobenzene-3-sulfonic acid and diphenylamine (S c h u I t z, loc. Cit., No. I34.) Or for the nitrated azo dye azo yellow from dianotated I-aminobenzene-4-sulfonic acid and diphenylamine (Schultz, supra, No. I4I). Successful by adding alkali ges to drive the dyes further into the core of the chrome leather. The effect of the However, alkali on the leather is harmful because it has an adverse effect on its quality. In contrast, the new dyes penetrate deep into the leather without the addition of alkali one, most of the time they even dye it completely. Leather dyed in this way, especially chrome leather, have great advantages. They have solid-colored Interfaces and occurs in the event of damage to the surface or wear and tear due to use the unstained core is no longer exposed.

Dyes that penetrate deep into the dermis or chrome leather able to color completely, have only become known up to now in individual cases. z. B. color yellow monoazo dyes, which are made from diazotized 2-chloro-4-amino-I-methylb enz o1- 6 - sulfonic acid and 1,3-dioxyb; enzene, its substitution products round Homologues are obtained, chrome leather completely through. By finding a whole range of dyes that (without the addition of alkali inside the leather penetrate and largely color it through, the technique is significantly enriched.

The dyes can. can be used according to the following coloring methods: Dyeing instructions The neutralized pelts are placed in a barrel with 150 to 100% water stained at 65 ° C. The barrel is set in motion and the dye solution is passed through the hollow axis too. After 45 minutes, the fat liquor is moved around further 45 minutes. If the hides are very heavy, the dyeing time is appropriate to extend. In general, i to z% of the amount is sufficient Folding weight calculated dye in order to achieve strong staining.

The dyes are prepared by the usual method, to its Explanation in the following examples and in the table Production, Composition and coloring properties of some representatives of this group of dyes Aminoazobenzene series are given without a complete listing of all to want to give dyes to be considered.

Example I 138 parts by weight of 3-nitro-I-aminobenzene are, as usual, dianotiert. The diazo compound becomes a neutral solution of 2I4 at 0 ° C Parts by weight of 2-ethylamine, o-I-methylbenzene-4-sulfonic acid are added. By addition the Congo acid reaction is slowly blunted by sodium acetate solution. After this the coupling is complete, it is made weakly alkaline with sodium carbonate. then the dye is salted out and, as usual, isolated. It forms a crystalline one orange powder that dissolves very easily in water and chrome leather according to the above Dyeing instruction dyes through excellent.

Example 2 28 parts by weight of 4-nitro-2-aminobenzene-I-sulfonic acid become after customary dianotation at 0 to 5 ° C to a weakly lacquer acidic solution of 222.5 parts by weight of 4-chloro-3, 5-diaminobenzene-I-sulfonic acid added. The excess Acid is blunted with sodium acetate until it has a congoneutral reaction. After finished Coupling, the resulting dye is salted out while warm. He falls in crystalline Form and dry represents a yellowish-brown powder, which is very easy Dissolves in water and dyes chrome leather in strong brownish-orange tones.

Example 3 28 parts by weight of 5-nitro-2-aminobenzene-I-sulfonic acid Dianotiert, and the solution is at o ° C with a solution of the sodium salt of 229 parts by weight of 3-diethylaminobenzene-I-sulfonic acid combined. The dye formation is driven to an end by the addition of sodium acetate. Then it is salted out hot. The dye dissolves very easily in water with a burgundy color and stains Leather, especially chrome leather, deep burgundy through.

EXAMPLE 4 183 parts by weight of 2,4-dinitro-I-aminobenzene are dianotized with nitrosylsulfuric acid in a concentrated sulfuric acid solution, as usual. The solution of the diazo compound is allowed to flow into a weakly alkaline solution of 312 parts by weight of 2,6-diaminobenzene-1,4-disulfonic acid sodium. Sodium acetate is added until the reaction is weakly congo-acid, after the formation of the dye the mixture is made alkaline and the dye is isolated, as usual, by salting out. It dissolves easily in water with a reddish-violet color and dyes chrome leather through to the core in a strong red-violet. Leather dyeing dye on the surface I in the core a-Nitro-3'-methyl-4'-ethylam, ino-I, I'-azo- pale yellow dull yellow benzene-6'-sulfonic acid 3-nitro-3'-methy1-.4'-ethvlaniino-I, I'-azo-yellow strong yellow benzene-6'-sulfonic acid -4-Nitro-3'-tnetliyl 4'-ätlylainino-I, I'-azo- pale brown-red deep brown-orange benzene-6'-sulfonic acid 2, 4-Dinitro-3 = llletllvl-4'-iitlivlamino-I, I'-azo- pale chocolate brown purple brown benzene-6'-sulfonic acid -.- Nitro-3'-metllvl-.4 .'- iithvlamino-I, I-azo- pale claret red deep brown red benzene-2,6-disulfonic acid 3-nitro-3'-metllyl-4'-ethvlamino-I, I'-azo-pale yellow) deep brownish yellow benzene-6,6'-disulfonic acid 4-Nitro-3'-methvl-4'-äthylaniiilo-I, I'-azo- pale yellow-orange strong brownish- benzene-2,6'-disulfonic acid orange 2-Nitro-3'-metllyl-4'äthvlainino-i, i'-azo- pale yellow-brown strong brown-orange benzal-.l, 6'-disulfonic acid Leather dyeing dye on the surface in the core 3-nitro-6-methoxy-3 '-, methyl-4'-ethylamino- brownish yellow, b brownish yellow I, I'-azobenzene-6'-sulfonic acid 4-Nitro-2-methoxy-3 'methyl-4 -'-ethyla: mino- y, .t pale brown-orange deep brown-orange I, I'-azobenzene-6'-sulfonic acid 2-chloro-4-amino-3'-methyl-4'-ethylamino-yellow-brown yellow-brown I, I'-azobenzene-6'-sulfonic acid 2,4-Dinitro, -4'-diethylamino-I, I'-azobenzene- deep violet violet 6'-sulfonic acid i 4-chloro-2-nitro-4'-diethylamino-I, I'-azo-orange deep orange benzene-6'-sulfonic acid 2-nitro-4-methyl-4 '-, diethylamino-I, I'-azo- strong yellow-orange i -el-orange benzene-6'-sulfonic acid 2-nitro-4-amino-4'-diethylamino-I I'-azo-yellow-brown deep yellow-brown benzene-6'-sulfonic acid 4-acetylethylamino-4 '-. Diethylamino-I, I'-azo-yellow! strong yellow benzene-6'-sulfonic acid 3-chloro-4-acetylamino 4 .'- diethylamino- golden yellow, strong orange-yellow I, I'-azobenzene-6'-sulfonic acid 2-Nitro-4-acetylamino-4'-diethylamino orange deep orange I, I'-azobenzene-6'-sulfonic acid 4-methyl-3-acetylä, thylamino-4'-diethylamino- i strong olive yellow strong olive yellow I, I'-azobenzene-6'-sulfonic acid 2-nitro-3'-chloro-2 ', 4'-diamino-I, I'-azobenzene-orange strong orange 6'-sulfonic acid 2-nitro-4-methyl-3'-chloro-2 ', 4'-diamino- strong yellow-orange yellow-orange I, I'-azobenzene-6'-sulfonic acid 3-nitro-6-methoxy-3'-chloro-2 ', 4'-diamino-I yellow yellow I, I'-azobenzene-6'-sulfonic acid 4-Nitro-3'-chloro-2, q: -, diamino-I, I'-azobenzol- pale red dull red 2,6'-disulfonic acid 3-nitro-3'-chloro-2 ', 4'-diamino-1, I'-azobenzene pale yellow i yellow-orange 6, 6'-disulfonic acid 2,6-dichloro-4-amino-3'-chloro-2 ', 4'-diamino-yellow-orange orange-yellow I, I'-azobenzene-6'-sulfonic acid 4-methyl-3-acetylethylamino-3'-chloro-2 ', 4'-di-yellow yellow amino-I, I'-azobenzene-6'-sulfonic acid 2-methyl-5-acetylethylamino-3'-chloro-2 ', 4'-di- pure yellow pure yellow amino-I, I'-azobenzene-6'-sulfonic acid 2-nitro-4-amino-3'-chloro-2 ', 4'-diamino yellowish brown deep yellow brown I, I'-azobenzene-6'-sulfonic acid 2-nitro-4-chloro-3'-methyl-2 ', 4'-diamino- i brown orange deep brown orange I, I'-azobenzene-6'-sulfonic acid j 2-Nitro-4-methyl-3'-methyl-2 ', 4'-diamino- f brownish orange strong brown orange I, I'-azobenzene-6'-sulfonic acid 2-nitro-4-ethoxy-3'-methyl-2 ', 4'-diamino-light orange brown brown orange i, i'-azobenz, ol-6'-sulfonic acid 4-methyl-3'-methyl-2 ', 4' -. Diamino-i, i'-azo-! pale yellow yellow benzene-2, 6 '-. disulfonic acid Leather dyeing dye on the surface ! at the core I. 3, d.-Diclilor-3'-nietliVl-2 ', 4'-diamino-i. 1'-a 7, o- orange-yellow yellow-orange benzene-6,6'-disulfonic acid @r. 2 - Nitro-3'-inethv1-2 ', .f'-dianiino-i, i'-azo': @ @. brown-orange strong brown-orange benzene-d., 6'-disulfonic acid 3-nitro-3'-inethvl-2 ', 4'-clianiino-i. i'-azo-. @. dull yellow yellow-orange benzene-6. 6'-disulfonic acid 2-i '\'itro-d.-atnino-3'-inethvl-2'. d .'- diamino- dull brown brown i. i'-azolienzol-6'-sulfonic acid d.-lletlivl-3-acetvlätlivlaniino-3'-inetlicl- strong tan brown brown yellow 2 ', @' - diainino-i, i'-azobenzene-6'-sulfonic acid d-Nitro-2 ', d .'- dianiino-i, i'-azolietizol-3', 6'-di- deep red-brown red-brown sulfonic acid a, 4-Dinitro-2 ', a'-dianiino-i, i'-azobenzene - strong burgundy red deep red violet 3 ', 6'-disulfonic acid

Claims (1)

PATENT CLAIM Process for dyeing leather through, marked by using salts of 4'-amino- or 4'-alkylamino-I, I'-azobenzene-2'-sulfonic acids, which still has an amino, alkylamino or acylamino group or several of these groups alone or together with one or more nitro groups or one or must contain several nitro groups alone and also contain other core substituents can.