EP0059876A1 - Process for colouring mixed polyester and keratinous fibre materials - Google Patents

Abstract

1. Process for coloring textile materials made from mixtures of linear polyester and keratinous fibers simultaneously with disperse and reactive dyestuffs, produced by padding or printing with aqueous dyeing or printing preparations which contain glycerol and/or urea in addition to usual thickeners and combinations of the both dyestuff types, and subsequently high temperature fixation of the applied dyestuffs assisted by an alkali metal salt of formic acid, characterised in that the fixation is caused in the presence of 0.2 to 1% of sodium formiate in conjunction with 0.5 to 5% of glycerol and/or urea, each time referring to the weight of padding liquor or printing paste.

Description

Mixed materials made of polyester and keratin fibers, especially wool, have become very important for outerwear in dyeing. In the print shop, however, they only play a subordinate role, since the transfer of the previously known printing processes to these materials is not yet satisfactory.

From DE-OS 28 00 600 a method for printing keratin-polyester fiber structures is known, in which the material is printed with a mixture of a disperse dye and a reactive dye, the printing pastes may contain glycerol and / or urea. Fixing the prints requires a two-stage process in which the printed material is first treated with low-temperature steam and then with high-temperature steam at essentially atmospheric pressure.

It has now been found that the two-stage fixation treatment can be replaced by a conventional high-temperature fixation if the preparations contain a salt of formic acid as an auxiliary.

The invention therefore relates to a process for coloring mixed materials made of polyester and keratin fibers by padding or printing with preparations which contain disperse and reactive dyes and glycerol and / or urea and a subsequent high-temperature fixation, which is characterized in that the fixation in the presence of a Alkaline salt of formic acid takes place.

• Die erfindungsgemäß zu kolorierenden Mischmaterialien enthalten zwischen etwa 90 und 50 Gew.-% synthetische lineare Polyester und im übrigen Keratinfasern wie Schaf-, Angora-, Mohair-, Lama- oder Alpakawolle . Andere Fasern können in untergeordnetem Ausmaß enthalten sein.

Preferred embodiments of the method according to the invention are explained in more detail below:

• The mixed materials to be colored according to the invention contain between about 90 and 50% by weight of synthetic linear polyester and, moreover, keratin fibers such as sheep, angora, mohair, llama or alpaca wool. Other fibers may be included to a minor extent.

Dispersion dyes which come into consideration are the products which are well known for dyeing fiber materials made from linear polyesters, for example those from the series of azo or anthraquinone dyes. The disperse dyes are preferably used as preparations with non-ionic surfactants, as are known for example from EP-OS 13 576. These low-electrolyte settings are particularly advantageous when using synthetic thickeners.

Suitable reactive dyes are those organic dyes which contain at least one group which is reactive with the keratin fiber, a precursor therefor or a substituent which is reactive with the keratin fiber. Particularly suitable as the basic body of these organic dyes are those from the series of anthraquinone, azo and phthalocyanine dyes. the azo and phthalocyanine dyes can be metal-free or metal-containing.

The usual alginate, starch ether or locust bean gum ether thickeners and heavy gasoline emulsions can be used as thickeners for the padding liquors and printing pastes. However, the wash-out of the block colorations and prints is improved if polymerization products containing carboxy groups are used as the thickener. Such connections are known for example from DE-AS 25 51 432. Of these synthetic thickeners, 0.5-5% by weight, preferably 1 to 2% by weight, are generally used in printing inks. The addition of conventional thickeners or binders is possible, but not necessary.

When working with conventional thickeners or emulsion thickeners, the salts of formic acid can be added to the padding liquor or printing ink. When printing with synthetic thickeners, it is advisable to add only the dyes and glycerin or urea to the printing pastes and to block and dry the goods with 2 to 10 g / 1 salt of formic acid. This procedure works with small amounts of thickeners because the viscosity of the printing paste is not reduced by the salt of formic acid. If you want to avoid this two-stage procedure, the amount of thickener weighed in is expediently increased by about 20-40% by weight. In this case, the salt of formic acid is expediently used as an aqueous solution, for example in a weight ratio of 1: 9, diluted with water. Sodium formate is preferred as the alkali salt of formic acid.

From DE-PS 24 05 057 it is known to use alkali salts of formic acid as an aid in padding or printing mixed materials made of cellulose and polyester fibers. However, relatively large amounts of formate are required for this (2 or 3% by weight in the examples of this PS). In the process according to the invention, smaller amounts in the range from about 0.2 to 1% by weight are sufficient.

Glycerin and / or urea are added to the padding liquors or printing pastes in the usual amounts of about 0.5 to 5% by weight.

The prints or dyeings are fixed with superheated steam or hot air at temperatures of around 160 to 210 ° C. The steam treatment takes about 5 to 15 minutes and the hot air treatment takes about 40 to 180 seconds.

The fixed prints or dyeings are finished in the usual way by rinsing, soapy with a non-ionic auxiliaries, for example a fatty acid polyglycol ester in a neutral medium, repeated rinsing and drying.

In the following examples, parts and percentages are by weight.

If the dyes used are not defined by the Color Index No. (according to the 3rd edition), they were identified by a letter that describes the formula shown in the table.

example 1

• Eine Mischung aus
• 40 Teilendes gemäß Beispiel 1 der EP-OS 13 576 nicht-ionisch formierten roten Dispersionsfarbstoffs der Formel A und
• 40 Teilen der flüssigen Handelsform von C.I.17757 (_Reactive Orange 16) wird mit
• 420 Teilen kaltem Wasser verdünnt. Diese Lösung wird in
• 500 Teile einer Stammverdickung eingerührt, die
• 657 Teile Wasser,
• 5 Teile eines handelsüblichen Sequestrierungsmittels,
• 18 Teile eines hochviskosen Natriumalginats,
• 15 Teile eines Stärkeethers,
• 10 Teile Natrium-m-nitrobenzolsulfonat
• 5 Teile eines Kondensationsproduktes von Polyethylenglykol mit dem mittleren Molgewicht 2000 und Stearinsäure,
• 80 Teile Glycerin,
• 60 Teile einer 10%igen Lösung von Natriumformiat und
• 150 Teile Schwerbenzin (Siedebereich 160 bis 220°C) enthält.

A chlorinated blended fabric made of 85% polyester fibers and 15% wool in rouleaux printing is printed with a printing paste which is produced as follows:

• A mix of
• 40 parts of the red disperse dye of the formula A and nonionically formed according to Example 1 of EP-OS 13 576
• 40 parts of the liquid commercial form of CI17757 _(R eactive Orange 16) with
• Diluted 420 parts of cold water. This solution is in
• 500 parts of a thickened stem, which
• 657 parts of water,
• 5 parts of a commercially available sequestering agent,
• 18 parts of a highly viscous sodium alginate,
• 15 parts of a starch ether,
• 10 parts of sodium m-nitrobenzenesulfonate
• 5 parts of a condensation product of polyethylene glycol with an average molecular weight of 2000 and stearic acid,
• 80 parts glycerin,
• 60 parts of a 10% solution of sodium formate and
• Contains 150 parts of heavy gasoline (boiling range 160 to 220 ° C).

The goods are dried and fixed for 7 minutes at 175 ° C with superheated steam. It is then rinsed cold and aftertreated with 1 g / 1 of an auxiliary agent based on fatty acid polyglycol esters at 40, 60 and 80 ° C., rinsed and dried. You get a brilliant scarlet fever with good water, wash and sweat fastness.

Example 2

• 50 Teile des gemäß Beispiel 1 der EP-OS 13 576 nicht-ionisch formierten blauen Dispersionsfarbstoffs B und
• 25 Teile des pulverförmigen blauen Reaktivfarbstoffs F werden mit
• 425 Teilen Wasser von 30 bis 40°C verdünnt bzw. gelöst.. Diese Mischung wird in
• 500 Teile einer Stammverdickung eingerührt, die wie in Beispiel 1 angegeben hergestellt wird, mit der Abweichung, daß jedoch anstelle der 150 Teile Schwerbenzin eine Mischung aus 120 Teilen eines Umsetzungsprodukts aus 1 Mol n-Butanol mit 35 Mol 1,2-Propylenoxid (gemäß DE-OS 29 12 497) eingesetzt wird.

A chlorinated knitted fabric made of 70% polyester fibers and 30% wool is printed with a printing paste which is produced as follows:

• 50 parts of the blue disperse dye B and non-ionically formed according to Example 1 of EP-OS 13 576
• 25 parts of the powdery blue reactive dye F are with
• 425 parts of water from 30 to 40 ° C diluted or dissolved. This mixture is in
• 500 parts of a stock thickening stirred in, which is prepared as described in Example 1, with the difference that, however, instead of the 150 parts of heavy gasoline, a mixture of 120 parts of a reaction product of 1 mol of n-butanol with 35 mol of 1,2-propylene oxide (according to DE -OS 29 12 497) is used.

After drying, the mixture is fixed at 170 ° C. for 10 minutes and treated as described in Example 1.

A blue print is obtained with good fastness to water, washing and sweat.

Example 3

• Eine Mischung aus
  • 40 Teilen des gemäß Beispiel 1 der EP-OS 13 576 nicht-ionisch formierten roten Dispersionsfarbstoffs C und
  • 40 Teilen der flüssigen Handelsform von C.I.17 757 (Reactive Orange 16) werden mit
  • 150 Teilen kaltem Wasser verdünnt. Diese Lösung wird in
  • 700 Teile einer Verdickung, bestehend aus einer Mischung aus 60 % einer 3%igen Lösung eines Ammoniumpolyacrylats vom Molgewicht 600 000 und 40 % einer 2%igen Lösung eines Copolymerisats aus Propylen und Maleinsäureanhydrid (Molverhältnis 1:1) vom Molgewicht 1 500 000 eingerührt. Anschließend gibt man noch
  • 40 Teile Glycerin und
  • 30 Teile einer 10%igen Lösung von Natriumformiat zu.

A mixed fabric of 90% polyester fibers and 10% wool is printed in rouleaux with a printing paste which is produced as follows:

• A mix of
  • 40 parts of the red disperse dye C and nonionically formed according to Example 1 of EP-OS 13 576
  • 40 parts of the liquid commercial form of CI17 757 (Reactive Orange 16) are with
  • Diluted 150 parts of cold water. This solution is in
  • 700 parts of a thickening consisting of a mixture of 60% of a 3% solution of an ammonium polyacrylate with a molecular weight of 600,000 and 40% of a 2% solution of a copolymer of propylene and maleic anhydride (molver Ratio 1: 1) with a molecular weight of 1,500,000. Then you give
  • 40 parts of glycerin and
  • Add 30 parts of a 10% solution of sodium formate.

After drying, the mixture is fixed at 180 ° C. for 8 minutes and treated as described in Example 1.

An orange is obtained with good fastness to water, washing and perspiration.

Example 4

• Eine Mischung aus
  • 45 Teilen des gemäß Beispiel 1 der EP-OS 13 576 nicht-ionisch formierten Farbstoffs der Formel D,
  • 15 Teilen des ebenso nicht-ionisch formierten Farbstoffs C.I. Disperse Blue 56 (C.I. 63 285) und
  • 25 Teilen der flüssigen Handelsform des blauen Reaktivfarbstoffs F (22,4 % Farbstoffgehalt) werden mit
  • 365 Teilen kaltem Wasser verdünnt. Diese Lösung wird in
  • 500 Teile einer 3%igen Lösung eines Natrium- oder Ammoniumpolyacrylats vom Molgewicht 3 000 000 eingetragen.Anschließend gibt man noch
  • . 50 Teile. Glycerin zu.

A chlorinated mixed fabric of 80% polyester fibers and 20% wool with a 0.5% solution of sodium formate is padded with a liquor absorption of 90% and dried. Then you print in rouleaux with a printing paste, which is produced as follows:

• A mix of
  • 45 parts of the dye of the formula D formed according to Example 1 of EP-OS 13 576 non-ionically,
  • 15 parts of the likewise non-ionically formed dye CI Disperse Blue 56 (CI 63 285) and
  • 25 parts of the liquid commercial form of the blue reactive dye F (22.4% dye content) are with
  • Diluted 365 parts of cold water. This solution is in
  • 500 parts of a 3% solution of a sodium or ammonium polyacrylate with a molecular weight of 3,000,000 are entered
  • . 50 parts. Glycerin too.

The printed goods are dried and finished as indicated in Example 1. You get a deep navy blue with good water, wash and sweat fastness.

Example 5

• 70 Teilen des gemäß Beispiel 1 der EP-OS 13 576 nicht-ionisch formierten roten Dispersionsfarbstoffs E und
• 40 Teilen einer.flüssigen Einstellung des roten Reaktivfarbstoffs G (Farbstoffgehalt: 17 %), verdünnt mit
• 390 Teilen Wasser.

_M an proceeds as described in Example 2, but uses a mixture of

• 70 parts of the red disperse dye E and non-ionically formed according to Example 1 of EP-OS 13 576
• 40 parts of a liquid setting of the red reactive dye G (dye content: 17%), diluted with
• 390 parts of water.

A brilliant red is obtained with good fastness to water, washing and sweat.

Disperse dyes A to E used in the examples:

C) Mixture of equal parts of the dyes

Reactive dyes F and G used in the examples

Claims (4)

1. Process for coloring mixed materials made of polyester and keratin fibers by padding or printing with preparations which contain disperse and reactive dyes and glycerol and / or urea and a subsequent high-temperature fixation, characterized in that the fixation takes place in the presence of an alkali salt of formic acid. 2. The method according to claim 1, characterized in that the salt is sodium formate. 3. The method according to claim 1 and 2, characterized in that padding liquors or printing pastes are used which contain 2 to 10 g of the salt per kilogram or liter. 4. The method according to claim 1 and 2, characterized in that a solution of the salt is padded onto the goods and then printed on the goods.