EP1607499A1 - Chlorine resistant elastane fibres protected against color change - Google Patents

Abstract

Polyurethane urea fibers (A) (with decreased inclination to color change during a thermal treatment and high chlorine stability of at least 85% segmented polyurethane urea) comprises 0.30-10 wt.% of finely divided hydrotalcite (I), which is coated with 1-5 wt.%, related to the weight of the coated hydrotalcite, of dialkylsulfosuccinate (II). Polyurethane urea fibers (A) (with decreased inclination to color change during a thermal treatment and high chlorine stability of at least 85% segmented polyurethane urea) comprises 0.30-10 wt.% of finely divided hydrotalcite (I) of formula (M1-x2+>Alx(OH)2Ax/n-n->.mH2O), where the hydrotalcite is coated with 1-5 wt.%, related to the weight of the coated hydrotalcite, of dialkylsulfosuccinate (II). M2+>magnesium; A-n->anion with valence number n of OH-, CO32-> (preferred) or silicate; x : less than 0 or less than or equal to 0.5; and m : less than 0 or 1. Independent claims are also included for: (1) the preparation of (A); and (2) textile goods (preferably cord, knitwear or fabrics) prepared using (A) (preferably in mixture with synthetic fibers like polyamide, polyester or polyacryl fibers and/or with natural fibers like wool, silk or cotton).

Description

The invention relates to elastic polyurethane fibers, in particular polyurethane urea fibers, the have no discoloration due to required process steps for the production of textiles and in aqueous, chlorine-containing environments, such as swimming pools, for swimwear can be used. The invention relates to elastic polyurethane urea fibers, the coated hydrotalcites included.

The term "fiber" used in the context of the present invention comprises staple fibers and / or continuous filaments formed by spinning processes known in the Prmzip, e.g. the Dry spinning process or the wet spinning process, as well as the melt spinning can be produced can.

Elastic polyurethane urea fibers from long-chain synthetic polymers which are at least 85% of segmented polyurethane ureas based on e.g. Polyethers, polyesters and / or Polycarbonates are constructed, are well known. Elastic polyurethane fibers can be analogous to Polyurethane urea fibers are built. The main difference is that for the polymerization instead of Amine Diols. Yarns from the aforementioned fibers are made with hard fibers such as polyamide or polyester or other fibers such as cotton or viscose Manufacture of knitted fabrics used in their own right for textiles, including for Corsetry, stockings and sportswear, e.g. Swimsuits or swimwear, are suitable. to Production of knitted fabrics or fabrics or textiles pass through the fibers different Process steps and can during the heat-setting or molding high temperatures over 185 ° C or 100 ° C. Due to this thermal stress, a unwanted color change of polyurethane urea fibers take place, especially the Production of light textiles or those with high proportions by weight (> 10 wt .-%, based on the weight of the entire textile) of polyurethane urea fibers can complicate. Furthermore In swimming pools, the water is often so strongly chlorinated for reasons of hygiene that the active chlorine content is usually between 0.5 and 3.5 ppm (parts per million) or even higher. If polyurethane urea fibers are exposed to such an environment, this can lead to a Degradation of the physical properties, e.g. the strength, the fibers and thereby lead to premature textile wear.

In practical terms, in the manufacture of the textiles, a color change of the polyurethane urea fibers by thermal treatment, such as this in the course of heat setting or a molding process takes place, can not be accepted, as this particular textiles in bright shades can not be made safely. In the production of textiles with In addition, high levels of polyurethane urea fibers can be used, e.g. Shades not set correctly become. A certain degradation of the fiber by chlorine, however, can be tolerated without its effects are noticed by the user of the fabrics made from these fibers. Avoiding the color change by e.g. thermal treatment in textile production is therefore particularly required for the production of textiles with light shade, as well in the manufacture of textiles having a high content of polyurethane urea fibers, e.g. greater as 10% by weight. At the same time a good resistance of the fiber material to one through Be assured of chlorine-induced degradation.

To improve the chlorine water resistance of elastic polyurethaneurea yarns for the Field of application The polyurethane-ureas were often made of polyesters as swimwear produced low molecular weight mono-, di- or polyhydroxy-functional polymer. aliphatic However, polyesters show a high biological activity. That's why they have this Polymer-made polyurethane ureas have the disadvantage of being easily removed by microbes and fungi be reduced. Furthermore, it has been shown that the chlorine water resistance of Polyurethanhamstoffen based on polyesters is not satisfactory.

A variety of additives in elastane fibers has been described to improve the chlorine water resistance of elastic polyurethane urea fibers.

The specification US Pat. No. 6,406,788 teaches the incorporation of zinc oxide into filaments of segmented polyurethane ureas for chlorine stabilization described. However, zinc oxide has the serious Disadvantage that it during the dyeing process of the tissues, especially under acidic conditions (pH 3 to 4), is washed out of the filament. This will improve the chlorine water resistance the fiber greatly reduced. Furthermore, by the zinc-containing dye waste water bacterial cultures killed in biological wastewater treatment plants for the treatment of wastewater. In the episode can the operation of such treatment plants are significantly affected.

In the publication JP 59-133 248 is to improve the chlorine water resistance the Incorporation of hydrotalcite into filaments of segmented polyurethane ureas. In addition to the heavy metal-free stabilization is described that only small amounts of dispersed Hydrotalcite at dyeing conditions in the acidic range (pH 3 to 4) are washed out and thus a good chlorine water resistance is maintained. The disadvantage, however, shows that hydrotalcite in polar solvents such as dimethylacetamide or dimethylformamide and even in spinning solutions strongly agglomerated for polyurethane urea fibers. Agglomerates in spinning solutions for polyurethane urea fibers lead to clogging of the spinnerets during the spinning process, whereby the spinning process due to frequent breaking fibers and / or increasing pressure on the Spinnerets must be interrupted frequently. Spinning such PU compositions over a longer period with adequate operational safety is thus not according to this method possible. In addition, such filaments in the further processing into a textile, due to a heat-setting or a molding process, lead to an undesirable color change.

In the patent EP-A-558 758 a polyurethaneurea composition is described, which contains a water of crystallization containing hydrotalcite with attached fatty acid. disadvantage of this composition is that filaments made from the polyurethaneurea composition in the further processing into a textile, due to a heat-setting or a Molding process, ie a thermal treatment, lead to an undesirable color change can.

In the patent application EP-A-843 029 is a polyurethaneurea composition and specifically described from polyurethane urea elastic fibers, with polyorganosiloxane or a mixture of polyorganosiloxane and polyorganohydrogensiloxane coated Hydrotalcites and / or other basic metal-aluminum-hydroxy compounds. disadvantage This composition is that in the polyurethaneurea fibers described in a continuous spinning process over a longer period of time disturbances in the spinning process possible are and after a few days spinning time, the thread when winding on the bobbin demolish can start. Another disadvantage of this composition is that even from this Polyurethaneurea composition produced filaments in the further processing to a Textile, due to a heat-setting or a molding process, ie a thermal Treatment, can lead to an unwanted color change.

In the published patent application EP 1 200 518-A1 is a polyurethaneurea composition and specifically resulting Polyhamstofffasern described as an additive hydrotalcite and a Contain dialkylsulfosuccinate, which increases the strength of the fiber. As a disadvantage, however, shows even with this polyurethaneurea composition and filaments made from it, that it during further processing into a textile, due to a heat-setting or a molding process, So a thermal treatment, come to an undesirable color change can.

The invention is based on the object, a polyurethaneurea composition in particular to provide for polyurethane urea fibers (also called elastane fibers) opposite the prior art, no unwanted discoloration due to thermal stress of Polyurethane urea fibers, such as those during heat-setting or molding in the process chain for the production of knitted fabrics or fabrics or textiles may occur, and a has good chlorine water resistance.

The object is achieved in that the polyurethane urea fibers an effective Amount of finely divided, with dialkyl sulfosuccinate coated hydrotalcites is added.

M²⁺

für Magnesium steht,

A^n-

ein Anion mit der Valenzzahl n aus der Reihe OH^-, CO₃ ^2- oder Silikat, insbesondere CO₃ ^2- ist,

0 < x ≤ 0,5 und 0 < m < 1, dadurch gekennzeichnet, dass die Hydrotalcite mit 1 bis 15 Gew.-%, bezogen auf das Gewicht der beschichteten Hydrotalcite, eines Dialkylsulfosuccinats beschichtet sind.The invention relates to polyurethane urea fibers (elastane fibers) having a reduced tendency to change color during a thermal treatment and high chlorine resistance, comprising at least 85% segmented polyurethaneurea, wherein the polyurethaneurea fibers comprise from 0.30 to 10% by weight of finely divided hydrotalcite, in particular those of the general formula ( 1), M 1-x 2+ al x (OH) 2 A x / n n- · MH 2 O in which

M ²⁺

stands for magnesium,

^A-

an anion with the valence number n from the series OH ^- , CO ₃ ^2- or silicate, in particular CO ₃ ^2- is,

0 <x ≦ 0.5 and 0 <m <1, characterized in that the hydrotalcites are coated with from 1 to 15% by weight, based on the weight of the coated hydrotalcites, of a dialkyl sulphosuccinate.

The amount of dialkylsulfosuccinate-coated hydrotalcite incorporated into the polyurethaneurea is finely divided fibers is 0.30 wt .-% to 10 wt .-%, preferably 0.5 wt .-% to 8 wt .-%, particularly preferably 1.5 wt .-% to 7 wt .-% and most preferably 2 wt .-% to 6 wt .-%, based on the weight of the polyurethane urea fiber. In the elastane fibers can the amount of hydrotalcite is distributed within the elastane fibers and / or on the fiber surface.

The hydrotalcites are in particular preferably those as are shown, for example, in the formulas (2) and (3): mg 6 al 2 (OH) 16 (A 2 ) · WH 2 O mg 4 al 2 (OH) 12 (A 2 ) · WH 2 O

A ² has the meaning given above for formula (1) and 1 ≤ w ≤ 15.

Particularly preferred examples of the hydrotalcites are those having the formulas (4) and (5): mg 6 al 2 (OH) 16 CO 3 .5H 2 O mg 4 al 2 (OH) 12 CO 3 .4H 2 O

The dialkyl sulfosuccinates described are used to coat the hydrotalcites from 1 to 15 wt.% Based on the weight of the coated hydrotalcite used. Prefers Hydrotalcites are used, which are coated with 1.5 to 12 wt .-% dialkyl sulfosuccinate. In particular, preference is given to using hydrotalcites containing from 2 to 8% by weight of dialkylsulfosuccinate are coated.

in der

R₁ und R₂

unabhängig voneinander gleich oder verschieden für eine Alkylgruppe mit 5 bis 18 Kohlenstoffatomen, bevorzugt für eine Alkylgruppe mit 8 Kohlenstoffatomen stehen,

R₁ und R₂

besonders bevorzugt gleich sind und für Ethylhexyl-Reste: -CH₂-CH(CH₂-CH₃)-CH₂-CH₂-CH₂-CH₃ stehen, und

M⁺

Na⁺, K⁺ oder NH₄ ⁺ , bevorzugt Na⁺ ist.

The dialkyl sulfosuccinates used are preferably those corresponding to the general formula (6)

in the

R ₁ and R ₂

independently of one another are identical or different and represent an alkyl group having 5 to 18 carbon atoms, preferably an alkyl group having 8 carbon atoms,

R ₁ and R ₂

are particularly preferably the same and are ethylhexyl radicals: -CH ₂ -CH (CH ₂ -CH ₃ ) -CH ₂ -CH ₂ -CH ₂ -CH ₃ , and

M ⁺

Na ⁺ , K ⁺ or NH ₄ ⁺ , preferably Na ⁺ .

The preparation of the dialkylsulfosuccinates can according to known methods, such as in Literature C.R. Carly, Ind. Eng. Chem., Vol. 31, page 45, 1939 described.

Specific preferred dialkyl sulfosuccinates are sodium diisobutyl sulfosuccinate, sodium bis (n-octyl) sulfosuccinate, Sodium bis (2-ethylhexyl) sulfosuccinate, sodium dihexylsulfosuccinate, Sodium diamyl sulfosuccinate and sodium dicyclohexyl sulfosuccinate.

in der M⁺ für Na⁺, K⁺ oder NH₄ ⁺ , bevorzugt für Na⁺ steht.Particular advantages arise when a dialkylsulfosuccinate according to the formula (7) is used:

in which M ^{+ is} Na ⁺ , K ⁺ or NH ₄ ⁺ , preferably Na ⁺ .

Very particularly preferred dialkylsulfosuccinate is sodium bis (2-ethylhexyl) sulfosuccinate.

The dialkylsulfosuccinates used for coating hydrotalcites can be described as Single substances or as mixtures of several Dialkylsulfosuccinate be used.

The coating of the hydrotalcites can be achieved by spraying and / or mixing in the dialkylsulfosuccinate preferably in front of and / or together or separately in any order during a final grinding of the hydrotalcite. It does not matter if that Dialkylsulfosuccinat in the preparation of the hydrotalcite resulting moist filter cake, Pastes or slurries is mixed before drying or if it is the dry good immediately before the final grinding in a suitable manner, for example by spraying, added or, in the case of steam jet drying, the steam immediately at the Feed is added to the jet mill. The dialkylsulfosuccinate may be optionally before the addition is converted into an emulsion.

The preparation of the hydrotalcites as such is carried out, for example, by basically known methods. Such methods are e.g. described in the published patent EP 129 805-A1.

The preparation of the hydrotalcites coated with dialkylsulfosuccinate preferably takes place from their starting compounds, for example from MgCO ₃ , Al ₂ O ₃ and water in the presence of dialkylsulfosuccinate and a solvent such as, for example, B. water or a C ₁ -C ₈ alcohol with subsequent drying by z. B. spray drying and optionally subsequent grinding by, for example, a bead mill. When using the hydrotalcites coated with dialkylsulfosuccinate as a fiber additive, preference is given to using coated hydrotalcites having a mean diameter (number average) of at most 5 μm, particularly preferably those having at most 3 μm, very particularly preferably those having at most 2 μm and especially very preferably those having at most 1 μm mean Diameter.

The dialkyl sulfosuccinate-coated hydrotalcites may be the polyurethane urea composition added at any point in the production of polyurethane urea fibers become. For example, the dialkylsulfosuccinate-coated hydrotalcites may be in the form a solution or slurry to a solution or dispersion of other fiber additives and then mixed upstream with the polymer solution with respect to the fiber spinning nozzles or be injected into it. Of course, those coated with dialkyl sulfosuccinate Hydrotalcites also separated to the polymer dope solution as dry powders or as a slurry be added in a suitable medium. The with dialkyl sulfosuccinate In principle, coated hydrotalcites may also be used as mixtures with uncoated ones or with known coating agents (e.g., metal fatty acids or polyorganosiloxane or a mixture of polyorganosiloxane and polyorganohydrogensiloxane) Hydrotalcites for the production of polyurethane urea fibers according to the above described procedure be used when the above-described disadvantages of known coated hydrotalcites are tolerable in the mixture.

Preferably, the addition of hydrotalcites coated with dialkylsulfosuccinates takes place in Polyurethaneurea compositions according to the procedure described below. A 20% dispersion of dialkyl sulfosuccinate-coated hydrotalcites becomes by mixing in a suitable solvent, e.g. Dimethylacetamide, prepared. The Dispersion may optionally by means of a bead mill, z. B. Fryma mill, type MSZ 12, Fryma-Maschinenbau GmbH, ground. The dispersion is treated with a polyurethaneurea spinning solution adjusted so that in the resulting dispersion, a 12 to 16% iger Content (wt .-%) of dialkylsulfosuccinate-coated hydrotalcites results. This dispersion ensures that the dialkyl sulfosuccinate-coated hydrotalcites do not sediment and also finely distributed after storage. The mean diameter (number average) of hydrotalcites coated with dialkyl sulfosuccinates in this dispersion is preferred at most 3 microns, more preferably at most 2 microns and most preferably at most 1 micron.

The polyurethane urea fibers of the present invention may be a variety of different others Additives for various purposes, for example matting agents, fillers, antioxidants, Dyes, stains, stabilizers against heat, light, UV radiation and Fumes.

Examples of antioxidants, stabilizers against heat, light or UV radiation are stabilizers from the group of sterically hindered phenols, HALS stabilizers (h indered a mine l ight s tabilizer), triazines, benzophenones and benzotriazoles. Examples of pigments and matting agents are titanium dioxide, zinc oxide and barium sulfate. Examples of dyes are acid dyes, disperse and pigment dyes and optical brighteners. The stabilizers mentioned can also be used in mixtures and contain an organic or inorganic coating agent. The said additives should preferably be metered in such amounts that they do not show any effects opposite to the dialkyl sulfosuccinate-coated hydrotalcites.

Hydrotalcites may agglomerate as described in the beginning under certain circumstances in polar solvents such as. Dimethylacetamide, dimethylformamide or dimethyl sulfoxide, in the dry or Wet spinning process commonly used to make polyurethaneurea fibers become. For this reason, spinning solutions with incorporated hydrotalcites can be used during the spinning process difficulties due to blockages of the spinnerets occur, resulting in a greatly increasing nozzle pressure results and / or tearing off the freshly formed fibers comes before or during winding on a bobbin. When incorporated with dialkylsulfosuccinate coated hydrotalcites in polyurethane urea spinning solutions according to the invention no agglomeration occurs in the spinning solution and the mean grain size of dialkylsulfosuccinate coated hydrotalcite remains essentially unchanged. This ensures the service life of the spinnerets and, associated with this, the operational safety and economic efficiency in the dry or wet-spinning process of the polyurethane urea fibers according to the invention.

The invention also provides a process for the production of polyurethane urea fibers, in which a long-chain synthetic polymer with at least 85% segmented polyurethane in an organic solvent, e.g. Dimethylacetamide, dimethylformamide or dimethyl sulfoxide, in a proportion of 20 to 50% by weight with respect to the polyurethaneurea composition, preferably at a level of from 25 to 40% by weight with respect to the polyurethaneurea composition dissolved, and this solution then through spinnerets after the dry or wet spinning process is spun into filaments, characterized in that with a dialkylsulfosuccinate coated hydrotalcite in an amount of 0.30 wt .-% to 10 wt .-%, preferably from 0.5% to 8% by weight, more preferably from 1.5% to 7% by weight Wt .-%, and most preferably an amount of 2 wt .-% to 6 wt .-%, based on the Weight of the polyurethane urea fiber added to the spinning solution and within the filaments and optionally additionally distributed on the filament surface.

Be less than 0.30 wt .-% of dialkylsulfosuccinate coated hydrotalcites within of the filament and optionally also distributed on the filament surface, is the effectiveness may be less satisfactory against the degradation of the polymer by chlorine.

The dispersion of substantially more than 10 wt .-% of the dialkylsulfosuccinate coated Hydrotalcites within the filament and optionally also on the filament surface can lead to adverse physical properties of the fibers and is therefore less recommended.

The improved polyurethane urea fibers according to the invention consist of segmented polyurethanes, for example, those based on polyethers, polyesters, polyether esters, polycarbonates and the like. Such fibers can be prepared by basically known methods are prepared, for example, according to those methods which are described in the documents WO 94/23100-A1 or WO 98/25986-A1. Furthermore, the polyurethane urea fibers from thermoplastic polyurethanes, their preparation for example in the published patent application EP 1 379 591-A1.

The segmented polyurethanes are in principle in particular a linear homo- or Copolymer with one hydroxyl group at the end of the molecule and a molecular weight of 600 up to 4000, e.g. from the group of polyester diols, polyether diols, polyester amidodiols, polycarbonate diols, Polyacryldiols, Polythioesterdiole, Polythioetherdiole, Polyhydrocarbonsäurediole or a Mixture or copolymers of compounds of this group, prepared. Furthermore, this is based segmented polyurethane in particular on organic diisocyanates and chain extenders with several active hydrogen atoms, such as. As di- and polyols, di- and polyamines, hydroxylamines, Hydrazines, polyhydrazides, polysemicarbazides, water or a mixture of these Components.

Some of these polymers are more sensitive to chlorine-induced degradation than other. Accordingly, polyurethane urea fibers are polyether-based polyurethane urea much more sensitive than polyurethane urea fibers from one on polyester based polyurethaneurea. For this reason, polyurethane urea fibers are particularly preferably comprising polyether-based polyurethane ureas.

The dialkyl sulfosuccinate-coated hydrotalcites are non-dialcohol additives Contain heavy metal and harmless from a toxicological point of view and are therefore preferred. This can ensure that in the further processing of polyurethane urea fibers such as. the coloring does not produce effluents, which is the functioning of a biological reduce or destroy the working sewage treatment plant.

Does it come in the processing of polyurethane urea fibers to a fabric to discoloration due to an undesirable color change of the polyurethane urea fiber, for example In dyeing processes the color tones of the textile goods are not hit. Such unwanted Discolouration complicates in particular the production of textile goods in light Shades of color, or make them impossible. When incorporated with dialkylsulfosuccinate coated hydrotalcites in polyurethane urea spinning solutions according to the invention For example, as shown in Examples 1 and 2, the discoloration of the polyurethaneurea composition may occur or the resulting polyurethane urea fibers are prevented. The service life of the spinnerets and the associated reliability in the dry spinning process and the resistance to chlorine water-induced degradation of the polyurethane urea fibers remain at a high level.

Another object of the invention are textile goods, in particular knitted, knitted or woven goods, prepared using the polyurethane urea fibers according to the invention, preferably in Mixture with synthetic hard fibers such as polyamide, polyester or polyacrylic fibers and / or with Natural fibers such as wool, silk or cotton.

The invention will be further described by way of examples, which are not limitative where all percentages refer to the total weight of the fiber, if nothing is specified otherwise.

Examples:

In the examples, the color change or yellowing is suitable for making fibers Polyurethaneurea compositions and the resulting polyurethaneurea fibers shown containing hydrotalcite coated with various agents. The polyurethaneurea compositions are made on the basis of polyether diols and contain those with different Agents coated hydrotalcites as an internal additive.

In Examples 1 and 2, polyurethane urea spinning solutions were prepared from a polyether diol, consisting of polytetrahydrofuran (PTHF) with an average molecular weight of 2000 g / mol produced. The diol was treated with methylene bis (4-phenyl diisocyanate) (MDI) with a capped molar ratio of 1 to 1.65, diluted in dimethylacetamide and then with a Mixture of ethylenediamine (EDA) and diethylamine (DEA) chain-extended in dimethylacetamide. The molecular weight of the polyether is based on the number average. The content of Polymer in the produced polyurethaneurea spinning solution is 30% by weight.

Example 1:

Hydrotalcites coated with various coating agents were 20% in dimethylacetamide dispersed as solvent by means of an Ultra-Turrax and then in the above-described Polyurethane urea spinning solution incorporated in the manner that the content of coated Hydrotalcite based on the polymer in the polyurethane urea spinning solution 10 wt .-% is.

From the coated polyurethane according to Table 1 hydrotalcite polyurethaneurea spinning solution a film was drawn with a squeegee. The solvent was in a convection oven evaporated at a temperature of 70 ° C over a period of 10 hours. The finished one Film had a layer thickness of 1 mm.

In order to be able to examine and assess the yellowing of the material for elastane fibers more precisely used the gerakelten from the elastane solution films.

The examination of yellowing was made by passing the films through a tenter with a Speed of 5 m / min at a temperature of 195 ° C were performed. This pass by a tenter corresponds to the processing step of the hot air fixing during manufacture of textiles. The throughput time of the films through the tenter was 50 seconds.

The results of yellowing are listed in Table 1. It turns out that only the polyurethaneurea composition film shows no yellowing containing the sodium dioctylsulfosuccinate-coated hydrotalcite. All other films showed a strong yellowing. sample stabilizer Coating (wt% with respect to stabilizer) yellowing 1-1-V Mg ₆ Al ₂ (OH) ₁₆ CO ₃ x 5 H ₂ O 5% stearic acid strongly 1-2-V Mg ₆ Al ₂ (OH) ₁₆ CO ₃ x 5 H ₂ O 5% Baysilone oil GPW 2233 strongly 1-3 V Mg ₆ Al ₂ (OH) ₁₆ CO ₃ x 5 H ₂ O Without strongly 1-4 Mg ₆ Al ₂ (OH) ₁₆ CO ₃ .5H ₂ O 5% sodium dioctylsulfosuccinate None

Example 2 :

The polyurethaneurea spinning solution described above was added to the following stock of the following stock solutions:
The first stock mixture consisted of 55.3% by weight of dimethylacetamide (DMAC), 11.1% by weight of Cyanox® 1790 ((1,3,5-tris (4-tert-butyl-3-hydroxy-2, 5-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, from Cytec), 7.6% by weight of Aerosol OT® 100 (sodium bis- (2-ethylhexyl) sulfosuccinate, Cytec), 26.0 wt .-% 30% spinning solution and 0.001 wt .-% of the dye Makrolex® violet (Bayer AG) .This stock was added to the spinning solution so that in the finished fiber, the content of Cyanox® 1790 was 1% by weight, based on the solids of the fiber polymer.

This spinning solution was admixed with a second stock mixture consisting of 30.9% by weight titanium dioxide Type RKB 3 (Kerr-McGee Pigments GmbH & Co. KG), 44.5 wt .-% DMAC and 24.6 % By weight 30% spinning solution, such that in the finished fiber a titanium dioxide content of 0.20 Wt .-% based on the polyurethane-urea polymers resulted.

This polyurethaneurea spinning solution is now mixed with a third stock solution. This consists of 5.5% by weight of Silwet® L 7607 (polyalkoxy-modified polydimethylsiloxane; Viscosity: 50 mPas (at 25 ° C.), molecular weight 1000 g / mol, from OSI Specialties), 5.5% by weight Magnesium stearate, 45.0 wt .-% DMAC and 44.0 wt .-% of a 30% spinning solution and is added so that a magnesium stearate content of 0.27 wt .-%, based on the solids of Polyurethane-urea polymers resulted.

This spinning solution was admixed with a fourth stock mixture consisting of 13.8% by weight of the Coated hydrotalcites indicated in Table 2, 55.2% by weight of dimethylacetamide and 31.0 % By weight 30% spinning solution, in such a way that in the finished elastane fiber 3.0 wt .-% of in Table 2 reported coated hydrotalcites based on the polyurethane-urea polymers resulted.

The finished spinning solutions became filaments through spinnerets in a typical spinning apparatus spun dry with a titer of 15 dtex, each with three individual filaments to coalescing filament yarns having a total titer of 44 dtex. The Fiber preparation consisting of polydimethylsiloxane having a viscosity of 5 cSt / 25 ° C was about a spin finish, with about 4.0 wt .-% based on the weight of the fiber were applied. The fiber was then wound at a speed of 900 m / min.

The examination of yellowing was made by the filaments by means of a knitting machine to a Knitted hose and this then by a tenter at a speed of 5 m / min at a temperature of 195 ° C was performed. The lead time of the knitted tubes through the clamping frame was 50 seconds.

The results of yellowing are listed in Table 2. It turns out that only the filament with the polyurethaneurea composition shows no yellowing which contains the sodium dioctylsulfosuccinate-coated hydrotalcite. All other filaments showed a strong yellowing or yellowing. sample stabilizer Coating (wt% with respect to stabilizer) yellowing 2-1 V Mg ₆ Al ₂ (OH) ₁₆ CO ₃ x 5 H ₂ O 5% stearic acid yellowing 2-2 V Mg ₆ Al ₂ (OH) ₁₆ CO ₃ x 5 H ₂ O 5% Baysilone oil GPW 2233 yellowing 2-3-V Mg ₆ Al ₂ (OH) ₁₆ CO ₃ x 5 H ₂ O Without yellowing 2-4 Mg ₆ Al ₂ (OH) ₁₆ CO ₃ .5H ₂ O 5% sodium dioctylsulfosuccinate No discoloration

The good service life of the spinnerets and the associated reliability in the dry spinning process was shown in a 14-day spinning trial. During this time, 5.0% by weight of the dialkyl sulfosuccinate-coated hydrotalcite with respect to the finished elastane fiber. There was no disturbance of the spinning process by e.g. an agglomeration of the with dialkyl sulfosuccinate coated hydrotalcites with the potential consequences of a build-up of pressure upstream of the filter in the spinneret or thread breaks in the spinning process. The durability the polyurethaneurea fibers thus produced against a chlorine water induced Degradation remained at a high level.

Claims (11)

Polyurethane urea fiber having a reduced tendency to color change during a thermal treatment and high chlorine resistance of at least 85% segmented polyurethaneurea, the polyurethane urea fiber containing from 0.30 to 10% by weight of finely divided hydrotalcite, especially that of the general formula (1), M 1-x 2+ al x (OH) 2 A x / n n- · MH 2 O in which

M ²⁺

stands for magnesium,

^A-

an anion with the valence number n from the series OH ^- , CO ₃ ^2- or silicate, in particular CO ₃ ^2- is,

0 <x ≦ 0.5 and 0 <m <1, characterized in that the hydrotalcites are coated with from 1 to 15% by weight, based on the weight of the coated hydrotalcites, of a dialkyl sulphosuccinate. Polyurethane urea fibers according to claim 1, characterized in that the amount of dialkylsulfosuccinate-coated hydrotalcite, which is finely divided in the polyurethane urea fibers, 0.5 wt .-% to 8 wt .-%, preferably 1.5 wt .-% to 7 Wt .-% and particularly preferably 2 wt .-% to 6 wt .-%, based on the weight of the fiber. Polyurethaneurea fiber according to claim 1 or 2, characterized in that the hydrotalcites are those of the formulas (2) or (3): mg 6 al 2 (OH) 16 (A 2 ) · WH 2 O mg 4 al 2 (OH) 12 (A 2 ) · WH 2 O in which A ^{2 has} the meaning given above for formula (1) and 1 ≤ w ≤ 15. Polyurethane urea fiber according to claim 3, characterized in that the hydrotalcites are those of the formula (4) or (5): mg 6 al 2 (OH) 16 CO 3 .5H 2 O mg 4 al 2 (OH) 12 CO 3 .4H 2 O Polyurethaneurea fiber according to Claims 1 to 4, characterized in that the dialkylsulphosuccinate is used to coat the hydrotalcites at a content of 1 to 15% by weight, based on the weight of the coated hydrotalcite, preferably from 1.5 to 12% by weight. , more preferably from 2 to 8 wt .-%. Polyurethaneurea fiber according to Claims 1 to 5, characterized in that the dialkylsulphosuccinate is one corresponding to the general formula (6)

in which R ₁ and R _2, independently of one another, are identical or different and represent an alkyl group having 5 to 18 carbon atoms, preferably an alkyl group having 8 carbon atoms,
and R ₁ and R _{2 are} particularly preferably the same and for ethylhexyl radicals:
-CH ₂ -CH (CH ₂ -CH ₃ ) -CH ₂ -CH ₂ -CH ₂ -CH ₃ , and
M ⁺ Na ⁺ , K ⁺ or NH ₄ ⁺ , preferably Na ⁺ . Polyurethaneurea fiber according to claim 6, characterized in that as dialkylsulphosuccinate for coating Natriumdiisobutylsulfosuccinat, sodium bis (n-octyl) sulfosuccinate, sodium bis (2-ethylhexyl) sulfosuccinate, Natriumdihexylsulfosuccinat, Natriumdiamylsulfosuccinat or Natriumdicyclohexylsulfosuccinat is included. Polyurethane urea fiber according to claim 7, characterized in that as dialkylsulfosuccinate

in which M ^{+ is} Na ⁺ , K ⁺ or NH ₄ ⁺ , preferably Na ⁺ and
preferably sodium bis (2-ethylhexyl) sulfosuccinate. Polyurethaneurea fiber according to claims 1 to 8, characterized in that the hydrotalcite coated with dialkylsulphosuccinate has a mean diameter (number average) of at most 5 μm, particularly preferably of at most 3 μm, very particularly preferably of at most 2 μm and especially very preferably of at most 1 μm. A process for the preparation of polyurethane urea fibers, in particular a polyurethane urea fiber according to any one of claims 1 to 9, wherein a long-chain synthetic polymer having at least 85% segmented polyurethane in an organic solvent, for example dimethylacetamide, dimethylformamide or dimethyl sulfoxide, in a proportion of 20 to 50 wt. % with respect to the polyurethaneurea composition, preferably in a proportion of 25 to 45% by weight with respect to the polyurethaneurea composition, and this solution is then spun into spun-bonded filaments by the dry or wet-spinning process, characterized in that Dialkyl sulfosuccinate-coated hydrotalcite in an amount of 0.30 wt .-% to 10 wt .-%, preferably in an amount of 0.5 wt .-% to 8 wt .-%, particularly preferably in an amount of 1.5 wt. % to 7 wt .-%, and most preferably an amount of 2 wt .-% to 6 wt .-%, based on the weight of the polyurethane urea fiber, which is added to the spinning solution and distributed within the filaments and optionally additionally on the filament surface. Textile goods, in particular knitted, knitted or woven goods, manufactured using The polyurethane urea fibers according to any one of claims 1 to 9, preferably in admixture with synthetic hard fibers such as polyamide, polyester or polyacrylic fibers and / or with Natural fibers such as wool, silk or cotton.