DE2308210C3 - Dyeing preparations, their manufacture and their use - Google Patents

Description

40

The invention relates to new dyeing preparations, their production and their use for dyeing or Printing of textile material.

There are already dye preparations known which contain a natural dye, a dispersant, an acid towie contain water and optionally an organic solvent. Such preparations lie on the one hand in homogeneous, dissolved form, on the other hand in the form of dispersions.

Such acidic dye preparations, especially those with high dye concentrations, can, however do not throw made of all basic dyes, since many basic dyes are not sufficiently soluble in an acidic medium to be highly concentrated To deliver dye preparations, and the dye preparations present in the form of dispersions in many cases are not sufficiently stable in storage.

New dye preparations have now been found which are free from these disadvantages and which are characterized by them are that they are out

a) one or more water-insoluble, basic dyes in the form of the dye base.

b) one or more nonionic or weakly cationic surfactants such as

c) optionally water and / or one with water Miscible organic, from carboxylic acid or cr Solvent free from sulfonic acid groups exist.

The production of the dyeing preparations according to the invention can be done so that the dye base at temperatures of 20 to 150 C, if appropriate with the addition of water and / or the water-miscible organic solvent in the surface-active Agent dissolves by stirring or kneading and then optionally granulated or sprayed.

The preparation can also be carried out in such a way that the inorganic or organic salt of a basic dye with the addition of an amount equivalent to the anion of an inorganic or organic Base with the surface-active agent and optionally with water and / or the organic Solvent melts.

As T-dye bases, which are used in the crlind according to Dye preparations are included, only those come into consideration that with an acid in Water is able to form sparingly or insoluble dye salt. The dye bases or anhydrobases can belong to a wide variety of dye classes, for example the di- and triaryl methanes Indophenol, indoldiary, methane, azine. Oxazine, thiazine, Acridine, quinoliri, xanthene, methine, azamethine or Diazamelhinreihc. preferably of the triary, methane or xanthene series.

Geciencte dyes are for example in the French Patents 20 45 397. 20 99 211, 21 21 198. 20 36 035, 20 30 08 I, 20 24 450, 15 60 192, 15 73 133. 15 33 149, Belgian patents 755 141.761 851.7 82681.5 61 613, German patents 11 61 370, 11 61 371, 9 49 649 and Swiss Patent specifications 5 19 552, 5 21418, 5 22 022 are described.

As non-ionic or weakly kaiionic surface-active Funds come into consideration, for example:

a) ethers of polyhydroxy compounds, such as polyoxyalkylated Fatty alcohols, polyoxyalkylicrle polyols, polyoxyalkylated mercaptans and aliphalic amines, polyoxyalkylated alkylphenols and -naphthols, polyoxyalkylated alkylarylmcreaptanes and alkylarylamines,

b) fatty acid esters of ethylene and polyethylene glycols and of propylene and butylene glycol. of glycerine or polyglycerine and pentaerythritol as well as sugar alcohols such as sorbitol, sorbitans and sucrose.

c) N-hydroxyalkyl-carbonamides. polyoxyalkylated Carbonamides and sulfonamides,

d) polyoxathylicrtc polypropylene and polybutylene glycols or

e) polyoxyethylene aliphatic amino-N-oxides.

Polyoxyalkylated hydroxy compounds, preferably addition products of 8 moles of ethylene oxide with 1 mole of p-tert-octylphenol, are particularly advantageous. from 15 Mo! Ethylene oxide on castor oil, from 20 moles of ethylene oxide on the alcohol C _Ih H ,, () H, ethylene oxide addition products on di- [<i-phrnylalh \ l] -phenols. Polyethylene tcrt.-dodecyl-thioether. Polyamine polyglycol ether. Addition products of

or 30 moles of ethylene oxide to 1 mole of amine

^or

H «NH> ^{or c} 18 ^H _{37N 2}

\ ls miscible "with" water organic Lösunus- "itel d" ^c negebenenfalls may be present in the dyeing preparations are, for example: PoIyalente alcohols, esters or ethers, such as glycol, w _et hyl- or butyl glycol diethylene glycol, Triäthylenolykol, Propandiolc. , butanediols, hexanediols, GIykolcarbonat, glycerol or Glyzerinmonoazetat, diacetone alcohol, ketones such as acetone, acetals, dioxane, further Dimelhylsulfoxyd, dimethylformamide, Dimethvlacetamid,. "- and /, '- tetra Hydroxyalkylnitrilc _m ethylensulfon N-methyl-pyrrolidone or tris-.. (dimethylamido (phosphate

Provide the color preparations according to the invention Liquids, doughs or waxy masses. If the dye bases are in high concentrations, for example up to 50 percent by weight, preferably fish 10 and 30 percent by weight and have a high storage stability.

The coloring preparations can already be used during manufacture, especially if they have a doughy or waxy consistency mild, customary, water-soluble, kaiionic dye salts be mixed.

The color preparations are suitable after thinning with water and one of the dye bases at least equivalent amount of an inorganic or Omanic acid, for example sulfuric acid, phosphoric acid, formic acid, acetic acid. Lactic acid or their mixtures and, if necessary, with the addition of filing and / or printing auxiliaries to the Coloring or printing of acidic-group-containing textile material or the corresponding unstructured material Material such as B. Press cake.

Fibers are used as the textile material. Threads, flakes, woven and knitted fabrics made from polymers of acrylonitrile or from copolymers of acrylonitrile with other vinyl compounds, for example vinyl chloride. Vinyl fluoride, vinylidene chloride, vinyl acetate or vinyl propionate, vinyl pyridine, vinyl imidazole, vinyl pyrrolidone. Vinyl alcohol, acrylic or methacrylic acid esters or acrylamides, which contain acidic groups resulting from the production, can be considered. Acid-modified polyacrylonitrile materials are also used. as described, for example, in U.S. Patents 28 37 500 and 28 37 501, and acid-modified polyamide fibers, such as polycondensation products from 4 4-diamino-2,2'-diphynyldisulfonic acid or 4,4'-diamino-2, 2'-diphynylalkanedisulfonic acids with polyamide-forming starting materials, polycondensation products from monoaminocarboxylic acids or their amide-forming derivatives or dibasic carboxylic acids and diamines with aromatic dicarboxysulfonic acids, e.g. B. polycondensation products of caprolactam or Hexamcthylenendiammonium'adipat with potassium 3,5-dicarboxybenzenesulfonate, or acid modified polyester fibers, such as polycondensation products of aromatic polycarboxylic acids, z. B. terephthalic acid or isophthalic acid, with several alcohols, e.g. ethylene glycol and 1,2- or } 3-dihydroxy-3- (3-sodium sulfopropoxy) propane, ■> 2 - dimethylol - 1 - (3 - sodium - sulfopropoxy) - butane ~ > 2-bis- (3-sodium sulfopropoxyphenyl) propane or 3 S-dicarboxybenzenesulfonic acid or sulfonated terephthalic acid, sulfonated 4-methoxy-benzenecarboxylic acid or sulfonated diphenymium-dicarbon- The dye preparations according to the invention can also be used advantageously together with water-soluble cationic dyes in the form of powders. Solutions or dispersions can be used for dyeing and printing fibers containing acidic groups, since they are applied according to the usual dyeing or printing processes.

The following examples serve to illustrate the invention. The parts mean parts by weight that

ίο percentages percentages by weight.

example 1
10 parts of the dye of the formula

NH

are at 95 to 100 "C in 40 parts of a 100% action product of 25 moles of ethylene oxide Dissolved 1 mol of stcaryl alcohol and filtered hot to remove impurities. A shelf-stable one is obtained Dye preparation.

Example 2
15 parts of the dye of the formula

NH

NH

SO ₄

with 80 parts of an ICH) "/ nigen anti-effect product in 25 moles of ethylene oxide to 1 mole of stearyl alcohol and 5 parts of 33% sodium hydroxide solution at 80 C. melted together. A storage-stable dye sample is obtained.

Example 3
20 parts of the dye of the formula

C)

OH

are at 80 C in 80 parts of a 100% action product of 36 moles of ethylene oxide to 1 mole

Castor oil dissolved. A storage-resistant dye preparation is obtained.

If, in the above example, the dye of the formula is used instead of the dye mentioned there

If the dye of the formula is used instead of the dye given above

NH,

cn.,

N O

,1

i \

i OH
(, VCOOCH,

■ üh;

. ·· ■■ /

this also gives a shelf-stable CN FärWe prepared.

or the dye of the formula
OH

ci — ir ■>

'N'
1
Λ,

i- NH ~ ii

\ -OCH ₃

Example 5

10 parts of the dye of the formula

HO

■: - O

or the dye of the formula

OH

'^; r- NH -I.

CH,

Ä I-

are at KX) C in a melt of 70 parts of a 100% strength product of 25 mol Ethylene oxide dissolved in 1 mole of stearyl alcohol and 20 parts of dimethylformamide. A shelf-stable one is obtained Dye preparation.

Example 6

10 parts of the anhydrobase of the formula

this also gives a storage-stable dye preparation.

Example 4 10 parts of the dye of the formula

CH ₁ ON

'YX X),

H ₁ NON

are at KK) C in 90 parts of a 100% one 65 Effective product of 25 mol of ethylene oxide dissolved in 1 mol of stearyl alcohol. A shelf-stable one is obtained I iirhenrarat.

rr.il 90 parts of an action product of 25 moles of ethylene oxide melted to 1 mole of oleyl alcohol. 1 part of this preparation is used in Dissolved 20 parts of a 1% strength aqueous hydrochloric acid. After diluting this stock solution, one obtains after the usual dyeing process on polyacrylonitrile fibers a reddish-yellow dyeing with good NaIv authenticity.

H e i s ρ i e I 7

5 parts of the F; irbsloffbasc tier formula
O

HO

OH

OH

are with 80 parts of an action product of 23 moles of ethylene oxide to 1 mole of nonylphenol and melted with 15 parts of water. 1 part of this preparation is divided into 20 parts of a 1 "/" igen dissolved aqueous sulfuric acid. After diluting this slurry solution, polyacrylonitrile fibers are obtained a greenish tinge with good wet smudges.

Staining example

1 g of a dye preparation that I5 "i> Dye of the formula

()H

-NH-

CH,

CH.,

CW,

and 85 "- i. of a 100,000 product of the action of

Contains 25 moles of ethylene oxide to 1 mole of stearyl alcohol, is dissolved in 50 ml of a l'Oigen acetic acid while warming to 50 to 60 ° C. 5 ml of this solution are diluted to 200 ml with water. In this dye bath 5 g of polyacrylonitrile fabric is dyed by entered the dye bath at 60 C, heated to 95 to KX) C within 30 minutes and 60 minutes is treated at this temperature; then it is rinsed and dried. You get a lightfast, bright blue coloring.

Fabrics made from acid-modified polyester fibers can also be dyed in the same way.

Print sample

20 g dye preparation according to Example 2.

30 g of 30% acetic acid,
450 g of a thickening made from corn meal ether and

Carboxymethyl cellulose 1: 1.
5 g citric acid and

495 g of water are converted into a printing paste

is working.

Colors offb ;: se

1000 g

The printing paste obtained in this way is used to print polyacrylonitrile fabric using one of the customary methods, dried at 100 to 1 IOC and steamed for 20 minutes at 0.2 to 0.4 atm. After that, as usual washed and dried. A bright blue print of good lightfastness is obtained.

In the above examples, the dye component and the surface-active agent are replaced by corresponding amounts of the dye bases and surface-active agents indicated in the table below Medium and proceed as indicated, this also gives storage-stable dye preparations.

Surface means

> -N (CH ₃ ),

(CH ₃ I ₂ N-:, - Ν - =, 'V --- O

Product of the action of 25 moles of ethylene oxide on 1 mole of stearyl alcohol

desul.

NH, N

CH., CH OH NH ■ / y-c- C. Ii N cn,

NH,

CU,

^c "V

dessil.

OC ₂ H ₁ effect product of 23 mo

Ethylene oxide to 1 mole nom phenol

Continuation

10

V-HN-

H ₃ C-

NH

OH

V-NH- <

■ V / NI
CH ₃

OH

^N c- / A

j> - NH- i

tiiichciiiiklives min

Product of action of 25 mol Ethylene oxide to 1 mole of oleic alcohol

dcsiil.

C \ - / ~ \

NH

NH OH

-CH ₃

NH- / ■

\ j

NH-V desül.

Claims (6)

23 03 210 Patent claims: I. Dye preparations, consisting of a) one or more water-insoluble basic dyes in the form of the dye base, b) one or more nonionic or weakly cationic surfactants as well as ίο c) optionally water and / or a water-miscible organic, carboxylic acid or sulfonic acid group-free solvent. 15th 2. dyeing preparations according to claim 1, characterized in that the FarbstoßkomponenSe is a triarylmethane dye. 3. dyeing preparations according to claim 1, characterized in that the dye component is a Is xanthene dye. 4. dyeing preparations according to claims 1 to 3, characterized in that the surface-active Agent is a polyoxyalkylated hydroxy compound. 5. Process for the production of dye preparations according to Claims 1 to 4, characterized in that that the dye base at 20 to 150 C, optionally with the addition of water and / or the water-miscible organic solvent in the surfactant dissolves or fuses with the surface-active agent and then optionally granulates or sprayed. 6. Use of the dyeing preparations according to An-Proverbs 1 to 4 for dyeing fiber material acidic group-containing polymers.