EP0250365A1 - Process for the after-treatment of dyed cellulosic fibrous material - Google Patents

Abstract

Process for the aftertreatment of dyed cellulose-containing fiber material to improve wet fastness using an aqueous liquor which contains a polyquaternary ammonium compound which, by the action of an epihalohydrin on a linear polymer, comprises the repeating units of the formula <IMAGE> in which R is C1-C6-alkyl, has is obtained.

Description

The present invention relates to a method for the aftertreatment of colored cellulose fiber material, in particular cellulose-containing textile material.

Dyeing and printing with substantive dyes often show inadequate wet fastness properties, especially washing and water fastness. The dye which is covalently bonded to the surface of the cellulose can be removed again by repeated washing operations and the bled-out dye can again be drawn onto undyed textile material which is washed in the same wash cycle.

Many attempts have been made to remedy this deficiency. For example, aftertreatment with a conventional cationic aftertreatment agent, e.g. of the Tinofix EWA type improve water fastness and there is also a slight improvement in wash fastness. However, the latter is not permanent. Repeated washing operations, especially under alkaline conditions and elevated temperatures, e.g. Above 50 ° C, the conventional cationic aftertreatment agent is removed from the textile material and this means that the dyeing loses its improved fastness to washing again.

With the use of reactive dyes one hoped to have solved the problem of wet fastness, because these dyes form a chemical bond with the cellulose. However, it turned out that this fiber / dye bond is not optimally resistant to acidic hydrolysis. This in turn has the consequence that such a hydrolyzed coloration is not resistant to a washing process, for example a hot wash. The dye component, which is no longer chemically fixed, is dissolved in the wash bath and can thus, for example, stain an undyed textile material that has been washed in the same wash cycle. Another disadvantage is the inadequate behavior of the fiber / dye bond against elevated temperatures in dry air, conditions such as those which occur in heat setting of, for example, cotton / polyester blended fabrics. This fiber / dye bond is partially destroyed again at temperatures of more than 180 ° C, which can also lead to loss of dye in a washing process. A major disadvantage of dyeing reactive dyes is the insufficient washability of the unfixed dye. Several very complex washing and rinsing processes are required to remove the unfixed dye from the fiber.

A new aftertreatment process has now been developed, which in particular significantly improves the wet fastness of cellulose dyeings which have been produced using substantive dyes. For example, fastness to washing can be improved under alkaline conditions at temperatures above 50 ° C and especially in today's usual 60 ° C washes with detergents containing sodium perborate (ISO 105 / C06 C2S). Likewise, the negative influence of acid hydrolysis and thermocraking in reactive dyeing can be largely suppressed by the aftertreatment process according to the invention.

worin R C₁-C₆-Alkyl bedeutet, aufweist, erhalten wird.The present invention therefore relates to a process for the aftertreatment of colored cellulose-containing fiber material, which is characterized in that this material is treated with an aqueous liquor which contains a polyquaternary ammonium compound which, by the action of an epihalohydrin on a linear polymer, comprises the repeating units of the formula

wherein R is C₁-C₆-alkyl, has, is obtained.

Suitable alkyl groups for R are methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-amyl, isoamyl, tert.amyl, hexyl, 2-ethylbutyl. Ethyl and especially methyl are preferred.

worin R die angegebene Bedeutung hat, vorzugsweise in Gegenwart eines Freiradikalkatalysators und anschliessendes Neutralisieren des Salzes z.B. mit wässeriger Natriumhydroxidlösung zu der polymeren freien Base hergestellt werden.Polymers with units of the formula (1) can be obtained by polymerizing the hydrohalide salt of a diallylamine of the formula

wherein R has the meaning given, preferably in the presence of a free radical catalyst and then neutralizing the salt, for example with aqueous sodium hydroxide solution to the polymeric free base.

Specific hydrohalide salts of diallylamines which can be polymerized to give polymers of the formula (1)
N-methyldiallylamine hydrochloride,
N-methyldiallylamine hydrobromide,
N-ethyldiallylamine hydrochloride,
N-ethyl diallylamine hydrobromide,
N-isopropyldiallylamine hydrochloride,
Nn-butyldiallylamine hydrobromide,
N-tert-butyldiallylamine hydrochloride,
Nn-hexyldiallylamine hydrochloride.

Suitable free radical-forming catalysts are symmetrical peroxide dicarbonates, peroxide dicarbamates, perbenzoates, perborates, persulfates or peroxide sulfates. The preferred catalyst is potassium persulfate and also azobis-isobutyronitrile or, above all, azo-bis (2-amidinopropane) hydrochloride.

These catalysts can be used in amounts of 0.05 to 5% by weight, advantageously 0.5 to 2% by weight, based on the N-alkyldiallylamine.

The epihalohydrin which is reacted with the N-alkyl-diallylamine polymer can be any epihalohydrin, e.g. Epibromohydrin, Epifluorhydrin, Epijodhydrin, ß-Methylepichlorhydrin or preferably epichlorohydrin.

The epihalohydrin is used in an amount of 0.5 to 1.5 mol, preferably 1 to 1.5 mol, per mol of the sum of tertiary amine in the polymer.

The reaction conditions for the preparation of the polyquaternary polymers are to be chosen such that there is no premature exchange of movable substituents either as a result of the pH of the reaction medium being too high or as a result of the temperature being too high. It is therefore preferred to work in a dilute, aqueous medium under as mild a temperature and pH conditions as possible, advantageously at a temperature of 30 to 85 ° C. and a pH of 6 to 8.5, preferably 7 to 8, in order to achieve the desired pH -Value and a hydrohalic acid, preferably hydrochloric acid is used to form the hydrohalide salt.

The aftertreatment according to the invention of the dyed cellulose-containing fiber material is as a rule carried out after dyeing, but preferably from a fresh bath.

Regenerated or in particular natural cellulose can be considered as fiber material, such as e.g. Cellulose, viscose silk, hemp, linen, jute or preferably cotton, as well as fiber blends with synthetic fibers e.g. those made of polyamide / cotton or in particular of polyester / cotton, where the polyester portion can be pre-colored with disperse dyes.

The textile can be used in any form, e.g. Flakes, yarns, packages, yarn strands, fabrics, knitted fabrics or felts that are made entirely or partially of native or regenerated cellulose.

The cellulose fiber material is generally dyed with reactive dyes or, preferably, with substantive dyes. You can use the pull-out procedure or two-stage processes such as the padding process or printing are produced, the padding process, in particular the so-called pad-steam process, thermofix process or the pad-cold dwelling process being considered.

The amount of dyes used depends on the desired depth of color. In general, amounts of 0.1 to 10% by weight, in particular 0.5 to 5% by weight, based on the material used, have proven successful.

The usual direct dyes are suitable as noun dyes, for example the "Direct Dyes" mentioned in Color Index, 3rd edition (1971) Volume 2 on pages 2005-2478.

Reactive dyes are understood to mean the usual dyes which form a chemical bond with the cellulose, for example those in Color Index, in volume 3 (3rd edition, 1971) on pages 3391-3560 and in volume 6 (revised 3rd edition, 1975 ) "Reactive Dyes" listed on pages 6268-6345.

The advantages of the method according to the invention are particularly evident in the aftertreatment of dyeings with noun dyes. Azo dyes and anthraquinone dyes and especially polyazo dyes with 2 to 6 sulfonic acid groups are particularly suitable.

The aftertreatment according to the invention is preferably carried out using the exhaust process.

The liquor ratio can be chosen within a wide range e.g. 1: 4 to 1: 100, preferably 1: 5 to 1:40.

Special devices are not required. For example, the usual dyeing machines, e.g. open baths, reel runners, jiggers, paddle, jet or circulation devices can be used.

It is convenient to work at a temperature of 20 to 70 ° C, preferably 30 to 50 ° C. The treatment time can be 20 to 60 minutes, but in most cases a treatment time of 30 to 40 minutes is sufficient. It expediently comprises 15 to 20 minutes of treatment with the cationic aftertreatment agent, then addition of the alkali and a further 15 to 20 minutes of treatment to fix the aftertreatment agent.

Regardless of the liquor ratio, the aftertreatment agent is advantageously used in an amount of 0.5 to 5% by weight, preferably 0.8 to 2% by weight active ingredient content, based on the weight of the cellulose material, to achieve the desired fastness standard.

In addition to the cationic aftertreatment agent, the liquors used according to the invention also contain alkaline compounds, such as sodium hydroxide or potassium hydroxide. A 30% aqueous sodium hydroxide solution is preferably added in an amount of 2 to 10 ml / l, preferably 4 to 6 ml / l liquor puts. The alkali can be added to the liquor at the beginning with the cationic aftertreatment agent or preferably only after 15 to 20 minutes with the aftertreatment agent.

The pH of the treatment liquors can therefore generally be 8 to 13.5, preferably 10.5 to 13.

The liquors can also contain other common additives, e.g. Electrolytes, e.g. Contain sodium chloride or sodium sulfate, dispersing and wetting agents as well as defoamers and other cationic fixing agents, the latter also being fiber-reactive.

The aftertreatment of the cellulose-containing material is expediently carried out in such a way that the material, followed by dyeing but from a fresh bath, is treated with an aqueous liquor which contains the aftertreatment agent, alkali and optionally an electrolyte, preferably sodium sulfate. The dyed cellulose-containing materials are preferably added to a liquor which contains aftertreatment agents and sodium sulfate and has a temperature of 30 ° C., and the dyed material is treated at this temperature for 15 to 20 minutes, preferably 15 minutes. An alkali is added and the material is treated for a further 15 to 20 minutes at 30 ° C.

Following the aftertreatment according to the invention, the cellulose material is optionally rinsed with water, optionally neutralized with acetic acid and then dried in a customary manner.

The process according to the invention gives dyeings and prints on cellulose fiber material which have been produced using reactive and, in particular, substantive dyes and which show a considerable improvement in wet fastness properties, such as washing and water fastness.

The color yield, shade and light fastness of the dyeings are not adversely affected. In addition, the post-treated dyeings and prints show no stiffening.

In the following manufacturing instructions and examples, the percentages relate to the weight, unless stated otherwise. The amounts of the dyes relate to commercial, i.e. Coupé goods and with the auxiliaries on active substance.

Manufacturing examples

Example 1: 101.4 g of 30% hydrochloric acid are added dropwise to 92.5 g of N-methyldiallylamine at 20 ° C. in the course of 30 minutes and the mixture is stirred until a homogeneous solution has formed. The temperature is then increased to 60 ° C. and 13.5 g of a 10% strength aqueous potassium persulfate solution are added to the solution, whereupon the temperature rises to 80 ° C. in the course of 45 minutes. The mixture is subsequently polymerized at 70 ° C. for 5 hours and diluted with 696.75 g of water, the viscosity, measured in a Brookfield LV type viscometer, 25 ° C., being 850 mPas before dilution. The mixture is cooled to 40 ° C. and adjusted to a pH of 7.8 by adding 11 g of a 30% strength aqueous sodium hydroxide solution. Then 77 g of epichlorhyrin are added dropwise at 50 ° C. in 20 minutes and stirring is continued for one hour. Then 20 g of 37% hydrochloric acid are added and the mixture is stirred cold.
1012 g of a clear, low-viscosity solution are obtained, the active ingredient content of which is 16.7%.

Example 2: 98.64 g of 37% hydrochloric acid are added dropwise to 125 g of N-ethyldiallylamine over a period of 30 minutes at a maximum of 20 ° C., and the mixture is stirred until a homogeneous solution has formed. Thereupon the temperature is increased to 60 ° C. and the solution is mixed with 9.35 g of a 10% strength aqueous solution of 2,2′-azobis- (2-amidinopropane) dihydrochloride, whereupon the temperature in the course of Rises to 85 ° C for 60 minutes. Then 21.8 g of a 10% strength aqueous solution of 2,2′-azobis- (2-amidinopropane) dihydrochloride are added dropwise in the course of 30 minutes, the temperature rising to 92 ° C. The mixture is then stirred at 80 ° C for 6 hours and cooled to 45 ° C. The viscosity, measured in a Brookfield viscometer type LV, 25 ° C, is 910 mPas. The mixture is then diluted with 830 g of water and a pH of 6.5 is established by adding 10 g of a 30% strength aqueous sodium hydroxide solution. 92.5 g of epichlorohydrin are then added dropwise at 45 ° C. in 40 minutes, the temperature being kept at 50 ° C., and the mixture is subsequently stirred at 50 ° C. for 1 hour. A solution of 28 g of 37% hydrochloric acid in 48 g of water is then added and the mixture is stirred cold.
1263 g of a clear, low-viscosity solution are obtained, the active ingredient content of which is 20%.

Example 3: 88.8 g of 37% hydrochloric acid are added dropwise over a period of 30 minutes at a maximum of 20 ° C. to 125 g of N-isopropyldiallylamine and the mixture is stirred until a homogeneous solution has formed. The temperature is then increased to 60 ° C. and the solution is mixed with 9.38 g of a 10% strength aqueous solution of 2,2′-azobis- (2-amidinopropane) dihydrochloride, whereupon the temperature is raised to 71 ° in the course of 50 minutes C increases. Then, over the course of 50 minutes, 21.9 g of a 10% strength aqueous solution of 2,2ʹ-azobis- (2-amidinopropane) dihydrochloride are added dropwise, the temperature rising to 95 ° C. The mixture is then stirred at 80 ° C for 7 hours and then cooled to 45 ° C. The viscosity, measured in a Brookfield viscometer type LV, 25 ° C, is 750 mPas. The mixture is then diluted with 793 g of water and a pH of 6.8 is established by adding 8.5 g of a 30% strength aqueous sodium hydroxide solution. Thereafter, 83.25 g of epichlorohydrin are added dropwise at 45 ° C. in the course of 30 minutes, the temperature being kept at 50 ° C., and the mixture is subsequently stirred at 50 ° C. for 1 hour. A solution of 28 g of 37% hydrochloric acid in 48 g of water is then added and the mixture is stirred cold.
This gives 1205.5 g of a clear, low-viscosity solution, the active ingredient content of which is 20%.

Examples of use

• 1) 1,9 % eines Farbstoffes der Formel
  
• 2) 1,5 % eines Farbstoffes der Formel
  
  bzw.
• 3) 1,2 % eines Farbstoffes der Formel
  

gefärbt und anschliessend 5 Minuten in kaltem Wasser gespült, worauf eine gelbe, rote bzw. blaue Färbung erhalten wird. Example 1: 20 g of cotton tricot, bleached and mercerized, are separated using a conventional pull-out method

• 1) 1.9% of a dye of the formula
  
• 2) 1.5% of a dye of the formula
  
  respectively.
• 3) 1.2% of a dye of the formula
  

dyed and then rinsed in cold water for 5 minutes, whereupon a yellow, red or blue color is obtained.

These three dyeings (20 g each) are treated for 15 minutes at 30 ° C. and a liquor ratio of 1:20 with an aqueous liquor which
1.6% of the reaction product according to Preparation Example 1 and 5 g / l sodium sulfate calc.
contains. Then 5 ml / l of a 30% sodium hydroxide solution are added, whereupon the dyeings are treated again at 30 ° C. for 15 minutes.

The following fastness properties are tested from these post-treated dyeings
- Laundry 3 (SN ISO 105 / CO3)
- ISO C2S wash (ISO 105 / CO6 C2S)
- Xenon light (SN ISO 105 / B02)
appropriate colorings, each of which is treated with 3% Tinofix EWA, are also checked.

The authenticity ratings are listed in Table 1.

Example 2:

• (A) 20 g of cotton cretonne bleached, not mercerized according to a cold residence process with an aqueous dyeing liquor
  30 g / l of a dye of the formula
  
  10 g / l sodium carbonate calc.
  5 ml / l aqueous sodium hydroxide solution (30%)
  contains, padded (liquor absorption 80%), stored for 6 hours and freed of the non-fixed dye by repeated rinsing and washing.
• (B) 20 g of this dyed cotton are treated at 30 ° C. for 15 minutes with an aqueous liquor which contains 1.5% of the reaction product according to Preparation Example 1. Then add 5 ml / l of 30% sodium hydroxide solution and treat the material for a further 15 minutes at 30 ° C.

A red color is obtained which has excellent acid fastness to hydrolysis.

und behandelt die resultierende Färbung gemäss (B), so erhält man ebenfalls eine gegen saure Hydrolyse echte Reaktivfärbung. Die Ergebnisse der Prüfungen auf die saure Hydrolyse sind in Tabelle 2 aufgeführt.

If in (A) 30 g / l of a dye of the formula are used instead of the dye of the formula (104)

and if the resulting coloration is treated in accordance with (B), a reactive coloration which is true against acid hydrolysis is likewise obtained. The results of the acid hydrolysis tests are shown in Table 2.

Example 3: The dyeings according to Example 2 (A) with subsequent aftertreatment (B) are repeated, the impregnated goods being exposed to dry heat on a hot air fixer for 2 minutes at 210 ° C. after the padding. After the aftertreatment, the water fastness test is carried out strictly (SN ISO 105 / E01) with multi-fiber tape as accompanying fabric. The results of these tests are shown in Table 3.

EXAMPLE 4 The procedure is as described in Example 1, but 2.4% of the reaction product according to Preparation Example 2 is used for the aftertreatment instead of the reaction product according to Preparation Example 1.

The ISO C2S wash is tested on these post-treated dyeings. The results are shown in Table 4.

Example 5:

• (A) A cheese bobbin of 500 g of bleached cotton yarn is dyed with an aqueous dye liquor containing 1.5% of a dye of the formula at a liquor ratio of 1:20
  
  1.5% of a dye of the formula
  
  5% of a dye of the formula
  
  and contains 80 g / l sodium sulfate, the coloring being carried out at 50 ° C. for 60 minutes. Then 5 g / l sodium carbonate calc. and 1 ml / l of 30% sodium hydroxide solution are added, after which the goods are treated for a further 60 minutes at 50 ° C.
  The color obtained is then
  10 minutes in cold water
  10 minutes in water at 80 ° C
  Soaped and boiled for 10 minutes
  10 minutes in water at 40 ° C
  rinsed.
• (B) The cotton dyed black according to (A) is treated at 20 ° C. with an aqueous preparation which, at a liquor ratio of 1:20, contains 1.2% of the reaction product according to Preparation Example 1 and 5 g / l sodium sulfate. The temperature is then increased to 50 ° C. in 20 minutes. 4 ml / l of 30% sodium hydroxide solution are added and the material is treated at 50 ° C. for a further 30 minutes. The goods are then rinsed twice in 10 minutes in cold water and finally dried. You get a real black color.
• (C) In (A), instead of the specified dye mixture, 5% of a dye of the formula (104), 0.5% of a dye of the formula are used
  
  and if the resulting violet coloration is treated in accordance with (B), a real reactive coloration is also obtained.

The results of the tests on the hot laundry (laundry 4, SNV 195814/1962) are listed in table 5. Corresponding colorations, each of which has been post-treated with Tinofix EWA, are also compared.

Example 6:

(A) A cheese bobbin of 500 g of bleached cotton yarn is dyed at a liquor ratio of 1:20 with an aqueous dye liquor which contains 2% of a dye of the formula (102). It starts at 40 ° C and increases the temperature in the course of 30 minutes at 98 ° C. Then 3 portions of 6.5 g / l sodium sulfate are added at intervals of 5 minutes each, followed by further dyeing at 98 ° C. for 45 minutes. The dyeing is then rinsed with water at 40 ° C. for 10 minutes and with cold water for 10 minutes, then treated with 1.2% of the reaction product according to Preparation Example 1 as described in Example 5 (B). The ISO C2S wash is checked from this post-treated dyeing, and a corresponding dyeing, which is post-treated with 3% Tinofix EWA, is also checked.

Table 6 shows the results of the tests.

Claims (8)

1. A process for the aftertreatment of colored cellulose-containing fiber material, characterized in that this material is treated with an aqueous liquor which contains a polyquaternary ammonium compound which, by the action of an epihalohydrin on a linear polymer, contains the repeating units of the formula

wherein R is C₁-C₆-alkyl, has, is obtained. 2. The method according to claim 1, characterized in that a polyquaternary ammonium compound is used which is obtained by the action of epichlorohydrin on a linear polymer which has recurring units of the formula (1). 3. The method according to any one of claims 1 and 2, characterized in that in formula (1) R is ethyl or especially methyl. 4. The method according to any one of claims 1 to 3, characterized in that the aftertreatment takes place after the exhaust process. 5. The method according to any one of claims 1 to 4, characterized in that the aftertreatment is carried out at a temperature of 20 to 70 ° C, preferably 30 to 50 ° C. 6. The method according to any one of claims 1 to 5, characterized in that the aftertreatment is carried out from an alkaline medium. 7. The method according to any one of claims 1 to 6, characterized in that the aqueous liquor additionally contains 2 to 10 ml / l of a 30% aqueous sodium hydroxide solution. 8. The method according to any one of claims 1 to 7, characterized in that cellulose fiber material dyed with reactive dyes or preferably with substantive dyes is used.