DE3129990A1 - Process for pretreating cellulose-containing textile materials - Google Patents

Abstract

The invention concerns the use of reactive quaternary ammonium compounds for improving the dyeability of textile materials, in particular textile materials containing cotton fibres. The textile pretreatment process of the invention is based on modifying cellulose fibres with a quaternary ammonium compound prior to dyeing with anionic (anion-active) dyes. It is characterised in that the textile material is treated with an aqueous sodium hydroxide liquor having a concentration from 80 to 350 g/l and then with an aqueous liquor of a quaternary ammonium compound of the general formula <IMAGE> where Y is a group <IMAGE> or <IMAGE> , X is an anion of a strong inorganic or organic acid: n is 1, 2 or 3, and A is a group <IMAGE> or <IMAGE> where R1 and r3 are each C1-C3-alkyl or C1-C3-hydroxyalkyl, R2 is C1-C3-alkyl or C1-C3-hydroxyalkyl, phenyl or C7-C9-alkylaryl, R4 and R5 are each C1-C6-alkyl, and Z is -CH2- or -O-, and optionally neutralisation and/or subsequent washing with water. Owing to the use of the specific quaternary ammonium compounds, the pretreatment process of the invention makes it possible to achieve a significantly higher dyeability as compared with conventional processes; the subsequent dyeing gives complete coverage of dead and immature fibres.

Description

Process for the pretreatment of cellulose

containing textile materials The invention relates to the application reactive quaternary ammonium compounds in the pretreatment of cellulose fibers containing textile materials and in particular textile materials containing cotton fibers.

Cellulose fibers can be dyed very well per se, as this is the case for them The type of textile fiber that can be used is wide and different from the degree of utilization the coloring and the dye price dependent technologies can be applied. For a long time, there has been no improvement in the dyeability of cellulose fibers given special attention. Only after World War II were some Publications published in which the introduction of ammonium groups into the Cellulose macromolecule described with the aim of improving the dyeability became. Only in the last few years, however, have been under general pressure Energy and raw material shortages systematic attempts to develop and industrial Utilization of the cellulose fiber modification with the aim of increasing the dyeability undertaken.

Very good results have been obtained in this area by treating Cellulose fibers obtained with epoxyammonium compounds according to Rupin. In the publications this author is the use of N- (2. 3-epoxypropyl) -N.N.N-trimethylammonium chloride described that in an alkaline medium via its epoxy group with the hydroxyl groups of cellulose reacts. The quaternary ammonium group of the resulting cellulose ether is able to ionically bind anion-active dyes. This leads to a increased utilization of anion-active dyes in the dyeing process as well as an increase their authenticity values.

However, using this approach is the strong, uncomfortable one The smell of the above compound is extremely annoying.

Some preparations, which are flawless from an ecological point of view, are different Composition have already been patented, their effectiveness at least is comparable to that of N- (2,3-epoxypropyl) -N.N.N-trimethylammonium chloride.

All these reactive quaternary ammonium salts that are also general called cationizing preparations, can be used before the actual dyeing process, be applied simultaneously with the dye or after dyeing, the Modification with cationizing preparations before the dyeing process has the best effect in terms of the dye utilization and the increase in the fastness values results. In contrast the use of these preparations at the same time as the dye leads to one higher authenticity, but not too noticeable improvement in utilization the dyes. The treatment of the already colored goods ultimately only increases the authenticity values.

The actual modification before the dyeing process is best done under Use of the block process is feasible. When drying the applied liquor and with the heat treatment the preparations are best exploitable. Simultaneously Certain affinity irregularities are also compensated, which in practice means that, for example, knobs are covered by dead and immature fibers, the streakiness is suppressed by viscose fibers and the like.

The technique of the padding process and the deposition in the form of a coil however, it results in a lower utilization of the preparation, being dead and immature Fibers remain completely uncovered in the subsequent dyeing process. When modifying from long fleets the utilization of the preparations is also very low, since they have no substantivity.

The invention is based on the aforementioned disadvantages to avoid and a process for the pretreatment of fibers on cellulosic and in particular Specify cotton base, which means a much higher utilization of a cationizing preparation for modifying the fibers from a long liquor or a padding liquor without drying and allows savings in anionic dyes and a uniform and real coloring of the fibers, especially of dead and immature fibers, is allowed.

The problem is solved according to the claims.

The process according to the invention allows a high level of utilization of quaternary ammonium compounds in the modification in a liquor without drying and heat treatment in the pretreatment of textile materials containing cellulose fibers. According to the invention, a textile material is exposed to the action of an aqueous liquor containing 80 to 350 g sodium hydroxide / l for 1 to 240 minutes, whereupon the material is treated with an aqueous, quaternary ammonium compound of the general formula containing liquor is treated, in which mean: Y is a group or X is an anion of a strong inorganic or organic acid, n is 1, 2 or 3 and A is a group or with R1, R3 = C1- to C3-alkyl or C1- to C3-hydroxyalkyl, R2 = C1- to C3-alkyl or C1- to C3-hydroxyalkyl r phenyl or C7- to C9 -alkylaryl, R4, R5 = C1- to C6-alkyl and Z - - CH2 - or -0-, after which neutralization and / or a final washing with water are optionally carried out.

The effect of the aqueous sodium hydroxide liquor is that of mercerization or analogous leaching. The textile material is mixed with the aqueous sodium hydroxide liquor impregnated in a padder, a mercerizing system or a conventional causticizing system. Before treatment of the material with the aqueous liquor of the quaternary ammonium compound, the textile material can be deposited briefly. the Deposition time is between 1 to 20 minutes at concentrations of 200 to 350 g / l or at 20 to 240 min at concentrations of 80 to 200 g / l. Similar to The temperature of the aqueous sodium hydroxide liquor must be in the area of mercerization from 5 to 80 "C and preferably from 10 to 30 OC.

The treatment of the textile material with the aqueous, the quaternary The ammonium compound of the general formula (1) containing liquor is used for this To bind compound covalently to cellulose. The reaction between cellulose and the quaternary ammonium compound requires the textile material to be alkaline and a temperature of 15 to 70 OC. in this process step conventional Devices such as foulards, jiggers, reels, Rotowa winding systems, dyeing or Find nozzle dyeing machines use. The liquor ratio is in these devices between 1: 0.8 and 1:10.

The lower this ratio, the higher the percentage Utilization of the quaternary ammonium compound.

The duration of the treatment of the textile material with the aqueous, The liquor containing the compound of the general formula (1) depends on the species the devices used and the liquor temperature; usually are 30 up to 60 min at 50 OC sufficient. If there is a cold deposit in the form of a If a temperature of 20 to 25 OC is used, the deposition time must be 4 to 24 hours be. The reaction between the cellulose and the quaternary ammonium compound can can be accelerated by steaming with saturated steam for 20 to 60 seconds at 100 to 105 ° C.

The one with the aqueous one containing the quaternary ammonium compound Liquor-treated textile material can be introduced directly into a dye liquor or printed. If the dyeing process is not immediately followed by the pretreatment or the alkalinity would be disadvantageous when dyeing, it is advisable to use the material neutralize and wash beforehand to avoid yellowing or damage to the Avoid textile material by alkali.

For the pretreatment process according to the invention are suitable before especially those quaternary ammonium compounds of the general formula (1) in which X is an anion of an inorganic acid such as chloride, bromide, sulfate or phosphate or an anion of an organic acid such as an anion of aromatic as well as lower ones aliphatic acids such as a benzenesulfonate, p-toluenesulfonate, methanesulfonate or an ethanesulfonate and also an anion residue of an acidic alkyl ester such as one inorganic acid / about a methosulphate or an ethosulphate.

Typical compounds of the general formula (1) are: N- (2.3 -Epoxypropyl) -N .N-dimethyl-N-phenylammonium chloride, N- (3-chloro-2-hydroxypropyl) -N.N.N-trimethylammonium chloride, N- (3-chloro-2-hydroxypropyl) -N.N-dimethyl-N-benzylammonium chloride, N- (3-chloro-2-hydroxypropyl) -N .N .N-trimethylammonium methosulfate, N- (2. 3-epoxypropyl) -N-methylmorpholinium chloride and N- (3-chloro-2-hydroxypropyl) -N-methylpiperidinium methosulfate.

The pretreatment method according to the invention is for yarns, slivers as well as textile fabrics such as woven fabrics, knitted fabrics, knitted fabrics and nonwovens are suitable.

The only condition is that the textile material has hydroxyl groups such as must contain native cellulose fibers or fibers from regenerated cellulose, whereby it from mixtures of such fibers with polyester, polyacrylonitrile or triacetate fibers can exist.

The method is particularly suitable for textile materials containing cotton fibers, who tolerate the treatment with highly concentrated sodium hydroxide and with those covering affinity irregularities in subsequent dyeing, ie Covering the knobs of dead and immature fibers is required. With viscose fibers becomes a streak suppression and an improvement in dyeability as well as the color fastness achieved. The inventive method enables one to to three times the utilization of the quaternary ammonium compound of the formula (1) in comparison with the previously known methods.

Anion-active dyes are used for dyeing textile materials, those under the designation direct dyes, reactive dyes and acid dyes are known. Such dyes are described in Color Index, 3rd Edition (1971).

For dyeing, known discontinuous, semi-continuous or continuous processes and devices suitable for the given textile material can be used. The utilization of the dyes is very high, with those according to the most criteria correspond to the highly reactive, indigosol or vat dyes Authenticity values are achievable.

The pretreatment method of the present invention is due to the degradation the consumption of anionic dyes and because of the savings in expensive highly beneficial dyes. Besides the lowering of the Dye consumption decreases the consumption of water as well as its salt content, thereby in turn, the environmental impact in the vicinity of dye works is reduced. That Pretreatment processes can also be used in the usual mercerising or causticising processes Devices are applied. To ensure the necessary modification however, these are the conditions for full exposure to the sodium hydroxide and the quaternary ammonium compound.

In this regard, it should be noted that the resulting effect of the pretreatment process according to the invention not just the sum of the individual Effects of the separate mercerization and modification processes represents but is much higher.

So far, the use of cationizing preparations has only allowed by drying and hot air fixation of the preparation a coverage of dead and immature fibers can be achieved. In contrast, enabled the inventive method the complete coverage of dead and immature fibers in the subsequent dyeing with anion-active dyes also in those cases in which the cationizing preparation from a long liquor according to the block type with large lap deposits was applied. The coverage of dead and immature fibers is also with the dyes perfect, which according to the information of dye works as for dyeing dead and unripe ones Textile materials containing fibers are unsuitable.

The method according to the invention is illustrated by the following exemplary embodiments explained in more detail.

Example 1 A cotton orchestra was made in a vacuum poulard with an aqueous, 15 ° C warm and 200 g sodium hydroxide / l containing liquor 100% liquor pick-up soaked. After 30 minutes of deposition in roll form, the Tissue on a jigger without washing with a liquor with N- (3-chloro-2-hydroxypropyl) -N.N-dimethyl-N-benzylammonium chloride at a concentration of 20 g / l.

Fleet ratio: 1: 3 Duration of treatment: 45 min at 50 ° C.

This was followed by 20 min staining with 2 W direct blue (C.I. 71) at 50 ° C., then 20 min at 70 oC and then 20 min at 95 oC.

The resulting coloration had very good fastness values, in particular Wet fastness, on. The dye utilization was almost 100 tons. Dead and immature fibers were completely colored so that the coloring was very even. The effect of the sodium hydroxide ensured a high gloss of the stained Manchester.

Similar results were obtained using either of the following Quaternary ammonium compounds of the general formula (1) obtained: N- (2.3-EpOxypropyl) -N.N-dimethyl-N-phenylammonium chloride, N- (3-chloro-2-hydroxypropyl) -N.N.N-trimethylammonium chloride and N- (3-chloro-2-hydroxypropyl) -N.N.N-trimethylammonium methosulfate.

Example 2, a terry cloth made of a cotton / polyamide mixture (60/40) was on a padder (85% liquor pick-up) with an aqueous, 25 OC warm and 100 g sodium hydroxide / l containing liquor impregnated on the perforated Tree of a plant Rotowa NW 41 wound up and without deposit with a fleet with N- (3-chloro-2-hydroxypropyl) -N.N.N-trimethylammonium chloride in one concentration of 25 g / l treated.

Treatment temperature: 50 OC Treatment time: 50 min.

This was followed by washing, neutralizing to pH 6-7 and dyeing with 1.5 reactive yellow (C.I. 3) at pH 4 of the liquor.

The temperature was increased from 30 to 95 ° C. in the course of 40 minutes; at this temperature was stained for 20 min.

After washing with 60 OC warm and then with cold water it was the coloring is finished. The coloring had high fastness values; the dye has been fully used.

Similar results are obtained using other quaternary ammonium compounds of formula (1), for example the compounds listed in Example 1, achieved.

Example 3 A cotton twill fabric for workwear was made on a Foulard (65% liquor pick-up) with an aqueous, 20 OC warm and 150 g sodium hydroxide / l impregnated containing liquor. Impregnation followed in a second foulard with an aqueous solution of N- (2. 3-epoxypropyl) -N.N-dimethyl-N-phenylammonium chloride in a concentration of 50 g / l at 20 OC and 95% liquor uptake. The mesh was left to stand for 4 h at 20 to 25 ° C. and then dyed as in Example 1.

The resulting coloration had very good fastness values, in particular Wet fastness, on. The dye utilization was almost 100%. Dead and immature fibers were completely stained so that the coloration was very uniform.

Similar results are obtained using other quaternary ammonium compounds of formula (1), for example the compounds according to Example 1, achieved.

Example 4 A pretreated cotton shirt fabric was made on a Foulard (70% liquor pick-up) with an aqueous, 10 OC warm and 200 g sodium hydroxide / l containing liquor soaked. After 30 minutes of deposition in roll form, the fabric became on a jigger without intermediate washing stage with an aqueous liquor with N- (2. 3-epoxypropyl) -N-methylmorpholinium chloride treated at a concentration of 30 g / l.

Liquor ratio: 1: 3 treatment time: 45 min treatment temperature: 55 oC.

The fabric was then washed and neutralized with acetic acid. This was followed by a washing process again carried out on a jigger, whereupon the fabric 40 min at 80 ° C. with 2.5 * reactive blue (C.I. 4). The finished coloring had very good fastness values, in particular light and wet fastness. The dye was drawn up from the fleet whole, and dead as well as immature fibers were completely covered. Instead of the usual soaping, there was a single cold water wash step sufficient.

Similar results are obtained using other quaternary ammonium compounds of formula (1), for example the compounds according to Example 1, achieved.

Example 5 A pretreated cotton terry toweling fabric was made on a padder (65% liquor pick-up) with an aqueous, 25 OC warm and 180 g sodium hydroxide / l containing liquor impregnated.

On a second padder (110% liquor pick-up) was on this Fabric N- (3-chloro-2-hydroxypropyl) -N-methylpiperidinium methosulfate (liquor concentration 70 g / l) applied.

The fabric was then deposited for 6 hours at 25 OC in the form of a roll, whereupon it was washed out and neutralized at a jigger.

This was followed by dyeing on the jigger with 3% direct red (C.I. 80) for 40 minutes 90 OC. After this time the dye was completely exhausted, so that it was sufficient Finally, wash the fabric in a single pass with cold water.

The resulting deep brilliant red color was in all parameters comparable to the coloration with naphthols. Similar results are using other quaternary ammonium compounds, e.g. the compounds of Example 1, achieved.

Example 6 An elastic Manchester made of a cotton / polyamide / polyurethane mixture (76.5 / 12 / 1.5) was soaked on padding with aqueous liquors as in Example 5. Instead of the deposit, however, the fabric was steamed with saturated steam at 102 ° C. for 1 min. This was followed by washing and neutralization as in Example 5. The same coloration resulted as achieved in Example 5.

Claims (7)

Claims 1. A process for the pretreatment of textile materials predominantly containing cellulose fibers before dyeing with anionic dyes by modifying the cotton fibers with a quaternary ammonium compound in an alkaline medium, characterized by (a) treating the textile material with an aqueous liquor containing 80 to 350 g sodium hydroxide / l and then (b) treatment with an aqueous liquor containing a quaternary ammonium compound of the general formula contains, in which mean: Y is a group or X is an anion of a strong inorganic or organic acid, n is 1, 2 or 3 and A is a group or with R1, R3 = C1- to C3-alkyl or Ci to C3-hydroxyalkyl, R2 = C1- to C3-alkyl or C1- to C3-hydroxyalkyl, phenyl or C7- to C9-alkylaryl, R4, R5 = C1- to C6-alkyl and Z = - CH2 - or -0-, and optionally (c) neutralization and / or final washing with water. 2. The method according to claim 1, characterized in that the textile material in step (a) with an aqueous sodium hydroxide liquor having a concentration of 200 to 350 g / l is treated for 1 to 20 min at 10 to 30 ° C. 3. The method according to claim 1, characterized in that the textile material in step (a) with an aqueous sodium hydroxide liquor one Concentration of 100 to 200 g / l is treated for 20 to 240 min at 10 to 30 ° C. 4. The method according to claim 1, characterized in that the textile material in step (b) with an aqueous liquor of the quaternary ammonium compound Concentration of 60 g / l is treated for 30 to 60 min at 40 to 70 OC. 5. The method according to claim 1, characterized in that the textile material in step (b) with an aqueous liquor of the quaternary ammonium compound Concentration of 30 to 80 g / l impregnated and then 2 to 24 h at 15 to 30 OC is deposited. 6. The method according to claim 1, characterized in that the textile material in step (b) with an aqueous liquor of the quaternary ammonium compound Concentration of 30 to 80 g / l impregnated and steamed for 20 to 60 s at 100 to 110 OC will. 7. Application of the method according to one of claims 1 to 6 on the Pretreatment of cotton fibers and textile materials predominantly containing cotton fibers.