DE1259832B - Process for dyeing and / or printing textile materials containing hydroxyl groups - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

Number: Case number:
Registration date:
Display day:

D 06 ρ

German AI .: 8 m-1/01

March 6, 1963
1st February 1968

It has been found that on textile materials containing hydroxyl groups in neutral to acidic medium, very real dyeings or prints are obtained if one is polycyclic from at least three Rings existing, keto groups-containing dyes that are not water-soluble and .the remainder of the general formula at least once

H
1 / R ₁

- CH ₂ - N (X® I

directly bound to the ring system in which the group ρ

Process for dyeing and / or printing
of textile materials containing hydroxyl groups

Applicant:

Aniline & Soda Factory in Baden

Aktiengesellschaft, 6700 Ludwigshafen

Named as inventor:
Dr. Arnold Tartter, 6715 Lambsheim;
Wilhelm Federkiel, 6711 Frankenthal;
Magnus Rosenkranz, 6700 Ludwigshafen

the remainder of the ammonia, a primary or secondary amine, Ri and R2 means members of a heterocyclic ring system and X is an inorganic or organic anion.

Among textile materials containing hydroxyl groups are, for. B. threads, yarns, fleeces and in particular To understand fabrics made of cotton, especially unheated cotton or rayon.

The dyes to be used according to the invention are derived from polycyclic dyes containing one or more keto groups, which are essentially free of anionic water-solubilizing groups, such as carboxylic acid, sulfonic acid groups and sulfuric acid ester groups, and which have at least three cyclic aromatic or quasi-aromatic, of which at least two are fused Have rings, of which at least one ring system must contain a keto group .. Essentially free of anionic water-solubilizing groups is intended to mean that the dyes can only contain these groups in an amount that does not make the dyes water-soluble. Particularly good dyeings and prints are obtained with group I dyes which contain at least four fused rings. Dyes of the type identified above are, for. B. the halomethylable vat dyes of the anthraquinone series, z. B. flavanthrene, pyranthrone, benzanthrone, anthraquinone acridone, perylenetetracarboximide dyes or halomethylatable anthraquinone derivatives, especially those which contain an optionally substituted aromatic radical of the benzene or naphthalene series bonded directly or via a nitrogen, oxygen or sulfur atom bridge. However, the dyes to be used according to the invention can also be based on dyes of an indigoid nature, pigment dyes, disperse dyes, which cannot be used as vat dyes. Further suitable base bodies are, for example, quinacridones, phthalo- or naphthaloperinones, phthalo- or naphthoylenebenzimidazoles, quino- or naphthophthalones.
In the remnants of the formula

- NC

, R ₁

means Ri z. B. a hydrogen atom or preferably an aliphatic or cycloaliphatic radical, R2 a hydrogen atom, an araliphatic one or aromatic and preferably an aliphatic or cycloaliphatic radical. The aliphatic Residues are in particular low molecular weight alkyl radicals, which optionally by nonionic groups, for example hydroxyl or cyano groups, can be substituted.

For the process according to the invention, those dyes are preferably used in which

- NC

, R ₁

means the remainder of a primary and especially a secondary amine. Of particular technical Of interest are dyes, where the rest

- NC

, R ₁

Part of a heterocyclic system is, for. B.

709 747/513

of the pyrrolidino, piperidino, hexamethyleneimino or morpholino ring.

The dyes to be used according to the invention are expediently chosen so that the total number of Carbon atoms in the remainder of the general formula. I does not exceed 15 because it is higher molecular residues reduce the solubility of the dyes.

The dyes to be used according to the invention can be prepared by known processes, e.g. B. by reacting dyes containing halomethyl groups with primary or secondary amines, such as mono- or dimethyl-, -ethyl-, -propyl-, -butyl-, -hexyl- or -octylamine, which can be straight-chain or branched. Other suitable amines are, for example, diethanolamine, methyl, ethyl, butyl or phenylethanolamine, butylethylamine, cyclohexylamine, methyl, ethyl or ß-hydroxyethylcyclohexylamine, a-methylamino or a- (hydroxyethylamino) ethylbenzene, N-methyl or N-Ethyl-N - (/ S, y-dihydroxypropyl) -amine, methoxypropylamine, ethoxypropylamine, N-methyl- or N-ethyl-N-methoxypropylamine, N-methyl-N-cyanoethylamine, N - /? - hydroxyethyl - N - cyanomethylamine, bis - {ß - methylmercaptoethyl) amine and in particular pyrrolidine, piperidine, hexamethyleneimine or morpholine.

With the dyes to be used according to the invention one dyes from neutral to acidic bath, z. B. at pH 1 to 7. However, it is advantageous to im to stain acidic area. Acidic agents are therefore added to the dyebath to reduce the pH of the dyebath to a value less than 7, preferably between 3 and 4. The dye bath You can also use neutral salts such as sodium sulfate or sodium chloride, as well as the usual dyeing auxiliaries, e.g. B. Leveling aids and auxiliaries to improve the rub fastness.

Acidic agents which provide the anion X of the formula I, ¹ are above all inorganic and organic acids, such as hydrochloric acid, formic acid, acetic acid, oxalic acid, succinic acid, maleic acid, malonic acid, lactic acid, tartaric acid, citric acid, chloroacetic acid, sulfoacetic acid, methanesulfonic acid • or Toluenesulfonic acid. But acid salts, such as potassium oxalate, potassium tartrate or ammonium sulfate, can also be used.

The dyes to be used according to the invention must be suitable for dyeing from an aqueous bath have a certain minimum solubility in water. This is usually the case with low molecular weight dyes the case by the presence of a group of the formula I in the molecule. However, it is used to advantage those dyes which have two or more radicals of the formula, in particular dyes with hochkondensiertehi polycyclic ring system with several, z. B. two to four groups of formula I. On the other hand, the solubility of the color salts in water should not expediently be a certain level

O.

exceed, since otherwise the wet fastness of the dyeings or prints obtained is reduced.

The dyes to be used according to the invention can be applied to the textile material by various methods. They are particularly suitable for the exhaust process, for the pad steaming process and for the so-called cold dwell process or the ped-batch process.
• In the exhaust process, it is advisable to paste the dye with an inorganic or organic acid and then add the mixture to the dyebath adjusted to pH 3 to 4. The goods to be dyed are treated at about 30 ^° C., the temperature of the dyebath is increased to 90 to 95 ^° C. within 30 minutes and the dyeing is carried out at this temperature for about 1 hour. The goods are then thoroughly rinsed, soaped and dried.

For better exhaustion - of the dye bath, it can be an advantage to add buffer substances towards the end of the dyeing process. such as sodium acetate.

One embodiment of the pad steaming process is that the dye in an inorganic or organic acid dissolves and to the desired concentration and to a pH value sets from 3 to 4. The goods to be dyed are padded, expediently on a padder, with one squeezes off to about 70 to 100% liquor pick-up. After padding, it is dried . and steamed for about 5 to 10 minutes. In this way, dyeings which are very fast to the wet are obtained.

The cold pad or pad batch process is performed in a similar manner to the pad steaming process carried out. One solves z. B. the dye with an acid and adjusts to the desired Final concentration and to a pH of 3 to 4. The goods to be colored are then, for. B. on a padder, padded with the dye solution, taking up about 70 to 100% liquor uptake squeezes. After padding, the goods are rolled up and wrapped in a plastic cover so that As little air as possible can get to the goods, and with constant turning 3 to 24 hours stored. This is followed by rinsing and soaping. The wet fastness properties are often even with very short

"45 times excellent, so that the dyeings only need to be rinsed and dried and themselves If necessary, subsequent soaping is unnecessary.

You can use the invention to be ver ^:

turning dyes also produce printing pastes, z. B. using an oil-in-water emulsion, and thus textiles of the 'type mentioned in the usual way and after drying the dyes z. B. fix with hot air at 16O ^{0 C.} ,

■■ "■ _" - ■ - ''"" ■ '',

■ Example 1

100 g of cotton fabric "are in a dye bath that in 3 l of water 2 g of the dye of the formula

CH ₂ ■ CH2

CHa-Nv _- .

and oil is adjusted with acetic acid "aiif -pH ^; 3 to '4'," 60 mummies. · Treated at 90 to '95 ° C ".

Conveniently, you go with the goods at 3O ⁰ C and the temperature is raised within 30 minutes to 90 to 95 ⁰ C. After dyeing is rinsed and soaped. A violet dyeing is obtained which, in addition to good lightfastness, shows very good wetfastness properties.

The dye of the formula given was obtained by reacting from the USA 2,645,646 known 2,11 - bis (chloromethyl) - dinaphtho - [1,2,3 - cd -l ', 2', 3 '- Im] - perylene - 9,18 - dione obtained with hexamethyleneimine in a conventional manner.

Example 2

Dissolve 20 g of a dye, whose preparation is described below, with the same amount of acetic acid at 80 to 9O ⁰ C in a little water and made up to 11 with an acidified aqueous solution. The solution obtained in this way is used to pad a cotton fabric on the padder, squeeze it off, dry and steam for about 6 minutes at 100.degree. It is then rinsed and soaped. A strong, red-orange color is obtained.

To prepare the dye, 100 parts of paraformaldehyde are gradually introduced into a mixture of 400 parts of chlorosulfonic acid and 200 parts of 98% strength sulfuric acid. When everything has gone into solution, the mixture is cooled to about 5 ^° C. and, at this temperature, 50 parts of the dye of the formula are stirred in small portions

35

a. Then the mixture is stirred about 10 hours at 25 to 3O ⁰ C, the mixture onto ice, the resulting chloromethyl compound is filtered off and washed neutral with water.

The still moist filter material is made into a paste in 100 parts of ethanol and gradually cooled with cooling 80 parts of pyrrolidine are added. After standing for several hours at room temperature the mixture is refluxed until a sample is in dilute acetic acid or hydrochloric acid is clearly soluble. Then one wears in cold water, sucks off and dries. You get about 70 parts of a dye which is soluble in dilute acids with a red-orange color.

Similar dyes are obtained if, instead of pyrrolidine, piperidine, hexamethyleneimine, Morpholine, 2,6-dimethylmorpholine or diethylamine are used. These dyes also color Cotton in red-orange tones.

Example 3

100 g of cotton fabric are placed in a bath which contains 3 g of the dye described below in 3 l of water and is adjusted to pH 3 to 4 with acetic acid. Heating the bath within 30 minutes at 9O ⁰ C and stained for a further 30 minutes at this temperature. After adding 10 g / l sodium acetate, the bath is ^{kept at 90 °} C. for 20 minutes and, after adding 3 g / l soda, the fabric is ^{aftertreated at 100 °} C. for 20 minutes. Then it is rinsed and soaped. A gray color is obtained.

The dye is obtained as follows: To a solution of 50 parts of paraformaldehyde, 200 parts of chlorosulfonic acid and 100 parts of 98% sulfuric acid are at 5 to 1O ⁰ C, 25 parts of the compound of formula

registered. The solution is gradually heated to 8O ⁰ C and held for 3 hours at 80 to 85 ⁰ C and 1 to 2 hours at 90 to 95 ⁰ C. The mixture is poured into ice water, the chloromethyl compound is filtered off with suction and washed neutral. The filtered material to wear in the cold in a solution of 80 parts of hexamethyleneimine in 40 parts of water and stirred for about 20 hours at 25 to 31 ⁰ C. Then it is heated for several hours at 6O ⁰ C, diluted with water and separated from the dye.

Example 4

With a liquor containing per liter 20 g contains the below 'the dye solution and 50 g of 30% acetic acid, cotton fabric is padded, squeezed, dried, and steamed for 8 minutes at 100 ⁰ C. This is followed by rinsing and soaping. A strong, olive-green dyeing which has good light and wet fastness is obtained.

Lightfast and wetfast dyeings are also obtained after the cold piling process. To do this, one solves 30 g of the dye described below with 30 g of tartaric acid or 50 g of 30% acetic acid Warm in a little water and make up to 11 with an acidified aqueous solution. With a cotton fabric is impregnated with this solution, squeezed and the goods are rolled up. Man then wrap it airtight with a plastic wrap and store it under constant pressure for 16 or 40 hours Turn. This is followed by rinsing and soaping.

The dye to be used in the preceding paragraphs is produced in the following way obtain:

In a solution of 45 parts of paraformaldehyde in 170 parts of chlorosulfonic acid, 25 parts of the compound of the formula ^{are added at 0 ° C.}

stirred in and the mixture is heated for 6 hours at 6O ⁰ C. The cooled mixture is poured onto ice, the precipitate is filtered off and washed with water. The filter material obtained is then treated with 150 parts of diethylamine for 10 hours at ordinary

Stirred temperature and then heated to reflux until a sample in dilute Acetic acid is soluble. Water is then added and the dye is separated off.

5 Example 5

Cotton fabric is padded with a liquor containing 20 g per liter of the dye obtained by chloromethylation of perylenetetracarboxylic acid di-p-methylphenylimide and reaction with hexamethyleneimine and 50 g of 30% acetic acid on the padder, squeezed off, dried and 8 minutes at 100 ⁰ C steamed. Then it is rinsed and soaped. A lightfast and waterfast red coloration is obtained.

Example 6

100 g of cotton fabric are placed in a bath containing 3 g of the dye described below and 25 g of acetic acid (30%) in 31 water, the bath is heated to 90 ° C. within 30 minutes and dyed at this temperature for 30 minutes. After adding 30 g of sodium acetate, the bath is kept at 90 ^° C. for a further 20 minutes, 3 g / l of soda are added and treated at a temperature of up to 100 ^° C. for 20 minutes. After rinsing and soaking, a strong, lightfast and wetfast blue coloration is obtained.

Of the preceding paragraph to be used after the dye is obtained when chloromethylated Dihydroxydibenzanthron 15 hours at ambient temperature and for 6 hours at 6O ⁰ C in sulfuric acid solution and then with hexamethyleneimine.

If, instead of hexamethyleneimine, dimethylamine, diethylamine, ethylbutylamine, methylethanolamine, Diethanolamine, N- (methoxypropyl) -N-methylamine or N-methyl-N-cyclohexylamine and dyes with the dyes thus obtained in a corresponding manner or according to the dyeing process of Example 5, real blue cotton dyeings are also obtained.

Claims (4)

Patent claims: 1. Process for dyeing and / or printing hydroxyl-containing textile materials in neutral to acidic medium, characterized in that polycyclic, Dyes containing at least three rings and containing keto groups are used are not water-soluble and which at least once the remainder of the general formula I.
CH ₂ - N X® wear directly bound to the ring system in which the group / R ₁
-n ( \ R ₂ the remainder of the ammonia, a primary or secondary amine, Ri and R2 means members of a heterocyclic ring system and X can be an inorganic or organic anion means. 2. The method according to claim 1, characterized in that one after the exhaust process colors. 3. The method according to claim 1, characterized in, that one dyes by the pad-steaming or pad-hot air process. 4. The method according to claim 1, characterized in that one after the cold padding process colors. Considered publications:
British Patent No. 633 160. When the application was announced, a coloring table was displayed. 709 747/513 1.68 © Bundesdruckerei Berlin