Classifications

• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F1/00—General methods for the manufacture of artificial filaments or the like
  • D01F1/02—Addition of substances to the spinning solution or to the melt
  • D01F1/04—Pigments
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
  • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
  • D01F6/70—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyurethanes
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
  • Y10T428/2913—Rod, strand, filament or fiber
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
  • Y10T428/2913—Rod, strand, filament or fiber
  • Y10T428/2927—Rod, strand, filament or fiber including structurally defined particulate matter

Definitions

• the invention relates to elastic polyurethane urea fibers containing a basic modified carbon black, so that the color of the fiber is significantly changed, and a process for their preparation and their use for the production of textile fabrics.
• fiber used in the present invention description includes staple fibers and continuous filaments which can be made by basically known spinning processes such as the dry spinning process, the wet spinning process or the melt spinning process.
• Polyurethane urea fibers show excellent elasticity and strong extensibility in combination with high restoring forces. Due to this excellent combination of properties, they find wide use in the clothing sector.
• dark polyurethane-urea fiber-elasticized textiles in the clothing area it is difficult to obtain a uniform coloring or visual appearance of the various yarns. The reason for this is that the different yarns used to make the textile have different shades of color. If, for example, the co-processed inelastic yarn is in a dark shade, a conventionally produced elastic polyurethaneurea fiber will be visible in the textile and smear through, thus disturbing the visual appearance of the textile.
• Another method for the production of dark polyurethaneurea fibers elasticized textiles in the clothing sector is staining with the desired dye.
• the coloring is a technically complex, additional and thus also cost-increasing process step in the production chain of the textile.
• the literature describes a method to produce a dark polyurethane urea fiber.
• a black polyurethane urea fiber can be obtained by the incorporation of graphite as an additive.
• the polyurethane urea fibers thus obtained are dyed and have a black color
• the incorporation of carbon black into polyurethane urea fibers rapidly forms agglomerates which interfere with the spinning process due to self-clogging filters.
• the distribution in the fiber may be disturbed so much that the uniformity in the thickness of the fiber is no longer present. This can lead to a non-homogeneous color of the fiber, as well as thread breaks in the processing to textiles.
• a dark polyurethane urea fiber can be obtained by the incorporation of dark spinel pigment based on iron oxide as an additive.
• the polyurethane urea fibers thus obtained are colored and have a dark color, they can not be processed sufficiently well in the production of the fibers.
• Dosing pumps, for example, may suffer damage due to abrasion when dosing the solutions containing hard spinel pigments.
• the incorporation of iron oxide-based dark spinel pigment as an additive into a polyurethaneurea composition can not be constant over a long period of time. Dosing fluctuations lead to different, generally ever decreasing, levels of spinel pigment in the polyurethaneurea fiber. This can result in increasingly bright appearing polyurethane urea fibers, which can then lead to undesirable color differences in further processing of the fibers into textiles.
• no disturbance of the spinning process due to, for example, the formation of agglomerates in the spinning solution should occur.
• the polyurethane urea fibers according to the invention are based on segmented polyurethane urea polymers.
• the polymers have segmental structure, i. they consist of "crystalline” and “amorphous” blocks (so-called hard segments or soft segments).
• the polyurethane urea fibers can in particular be produced from a linear homo- or copolymer having in each case one hydroxyl group at the end of the molecule and a molecular weight of 600 to 4000 g / mol, such as polyether diols, polyester diols, polyester amide diols, polycarbonate diols or a mixture or copolymers of this group , Particular preference is given to polyester diols and polyether diols, very particular preference to polyester diols, since polyester diols are stabilized without the addition of further stabilizers against degradation by chlorinated water.
• organic diisocyanates examples include 4,4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate and 4,4'-diphenylmethane diisocyanate.
• diamines are ethylenediamine, 1,2-propanediamine, 2-methyl-1,5-diaminopentane, isophoronediamine, 1,3-diaminocyclohexane, 1-methyl-2,4-diaminocyclohexane or 1,2-diaminocyclohexane.
• the polyurethane urea fibers can be prepared by generally known methods, such as those described in the documents US 3,553,290 and US Pat. No. 3,555,115 and in Scripture WO 9 3/09 174 are described.
• the basic modification of carbon black is carried out by adding a nitrogen-containing base to the carbon black before or during the incorporation into the polyurethaneurea composition and the subsequent spinning process for the production of the polyurethaneurea fiber.
• the amount of nitrogen-containing base added to the carbon black is 0.05 to 30%, in particular 0.1 to 20% and especially preferably 0.2 to 15%, with respect to percent by weight of carbon black.
• the carbon blacks used are those whose preparation is carried out by processes known per se, such as the FurnanceRuß process, the GasRuß process or the FlammRuß process, particularly preferably by the FurnanceRuß process or the GasRuß process, and more particularly preferably according to the GasRuß method.
• the FurnanceRuss process is a continuous process that uses liquid and gaseous hydrocarbons. The reaction takes place at high temperatures in a ceramic lined furnace. After soot formation, the process gas mixture is cooled abruptly by injecting water.
• a hydrogen-containing gas is passed over a heated oil, and the carrier gas saturated with oil vapor is supplied to a burner tube carrying a plurality of small burner caps.
• the nitrogen-containing bases used for the basic modification of the carbon black are aliphatic amines, in particular methylamine, ethylamine, propylamine, isopropylamine, butylamine, sec-butylamine, tert-butylamine, 3-methyl-1-butanamine, hexylamine, octylamine, 2-ethylhexylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, dihexylamine, di (2-ethylhexyl) amine, trimethylamine, triethylamine, tripropylamine, tributylamine, trihexylamine, tris (2-ethylhexyl) amine, N, N-dimethylethylamine, dimethylpropylamine, N, N-dimethylisopropylamine and N, N-dimethylbutylamine, alkoxyalkylamines, in particular 2-meth
• nitrogen-containing bases are aliphatic amines, especially those from the group propylamine, butylamine, sec-butylamine, tert-butylamine, 3-methyl-1-butanamine, hexylamine, 2-ethylhexylamine, diethylamine, dipropylamine, dibutylamine, dihexylamine and di (2-ethylhexyl) amine, alkoxyalkylamines, in particular from the group 2-methoxyethylamine, 3-methoxypropylamine and di (2-methoxyethyl) amine, cycloaliphatic amines, especially those from the group cyclohexylamine, polyamines, in particular ethylenediamine, 1,3-propanediamine, 1,2-propanediamine, neopentanediamine, 3- (methylamino) propylamine, 2- (diethylamino) ethylamine, 3- (diethylamin
• Very particularly preferred nitrogen-containing bases are aliphatic amines, in particular 3-methyl-1-butanamine, hexylamine, 2-ethylhexylamine, diethylamine, dibutylamine, dihexylamine and di (2-ethylhexyl) amine, polyamines, in particular ethylenediamine and 1,2-propanediamine and aminohydroxy compounds , in particular monoethanolamine, 3-amino-1-propanol, aminoethylethanolamine, N-ethylethanolamine, diethanolamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, N-methyldiethanolamine and N-butyldiethanolamine.
• the BET surface determination is a well-known method, named after Brunauer, Emmett and Teller and includes the outer and inner surface of the soot. It is thus a measure of the total surface area of the carbon black and also includes pores and gaps of the carbon black.
• Another object of the invention is the use of basic modified carbon black for the production of dark polyurethane urea fibers, wherein the basic modified carbon black from 0.05 to 8 wt .-%, in particular from 0.1 to 5 wt .-%, particularly preferably from 0, 2 to 3 wt .-% is evenly distributed in the fiber.
• the basic modified carbon black can be added to the polyurethane urea spinning solution in the production of polyurethane urea fibers at any point in the processing of the composition.
• the basic modified carbon black may be added as a powder or in the form of a dispersion to a solution, dispersion or slurry of other additives.
• the basic modified carbon black when processed into fibers, may then be mixed or injected upstream with the polymer spinning solution with respect to the fiber spinning nozzles.
• the base-modified carbon black may also be added separately to the polymer spinning solution as a powder or in the form of a dispersion in a suitable medium.
• the basic-modified carbon black may further be added in the above-mentioned formulations in the usual polyurethane-urea production.
• the polyurethaneurea fibers according to the invention may optionally contain as additives C) for various purposes substances such as flatting agents, fillers, antioxidants, dyes, release agents, antistatic agents, heat stabilizers, light, UV radiation, nitrogen oxides, chlorine-containing water and vapors.
• additives C for various purposes substances such as flatting agents, fillers, antioxidants, dyes, release agents, antistatic agents, heat stabilizers, light, UV radiation, nitrogen oxides, chlorine-containing water and vapors.
• antioxidants examples include stabilizers from the group of sterically hindered phenols, HALS stabilizers (h indered amine l ight s tabilizer), triazines, and benzotriazoles Benzophenpne.
• release agents examples include magnesium stearate, calcium stearate and aluminum stearate.
• antistatic agents are alkali metal salts of sulfosuccinic or ethylene oxide or propylene oxide-modified silicones.
• pigments and matting agents examples of titanium dioxide, zinc oxide and barium sulfate.
• dyes examples include acid dyes, disperse and pigment dyes and optical brighteners.
• stabilizers against degradation of the fibers by chlorine or chlorine-containing water are zinc oxide, magnesium oxide, magnesium calcium or magnesium aluminum hydroxycarbonates.
• the stabilizers mentioned can also be used in mixtures.
• the additives mentioned should preferably be metered in such amounts that they show no effects which are contrary to the basic modified carbon black.
• carbon blacks may be present in polar solvents, e.g. Dimethylacetamide, dimethylformamide or dimethyl sulfoxide, which are commonly used in the dry or wet spinning process for the production of polyurethane urea fibers, in the form of agglomerates.
• polar solvents e.g. Dimethylacetamide, dimethylformamide or dimethyl sulfoxide
• the invention further provides a process for the preparation of spun-dyed polyurethane urea fibers by the dry spinning or wet spinning process, preferably by the dry spinning process, by preparing the spinning solution, spinning the spinning solution with a spinneret, threading below the spinneret by removing the spinning solvent by drying or in a coagulation bath , Preparing and winding the threads, characterized in that the polyurethaneurea spinning solution prior to spinning the solution to the polyurethane urea fiber 0.05 to 8 wt .-%, in particular 0.1 to 5 wt .-%, particularly preferably 0.2 to 3 wt. - Mixed% basic modified carbon black and evenly distributed in the fiber.
• Another object of the invention is the use of the polyurethaneurea fibers according to the invention for the production of elastic fabrics, knitted fabrics, knitted fabrics and other textile goods.
• the use of the polyurethaneurea fibers according to the invention takes place preferred in the manufacture of blended fabrics together with other synthetic based dark stains, eg polyamide, polyester or polyacrylonitrile or non-synthetic fibers, eg cotton, wool, linen or silk.
• the polyurethaneurea spinning solution used for the following examples and the comparative examples was prepared by the following procedure:
• a polyurethane urea spinning solution was prepared from a polyester diol having an average molecular weight of 2000 g / mol, which consists of adipic acid, hexanediol and neopentyl glycol, capped with methylene bis (4-phenyl diisocyanate) (MDI) and then with a mixture of ethylenediamine (EDA) and Diethylamine (DEA) was chain extended.
• MDI methylene bis (4-phenyl diisocyanate
• EDA ethylenediamine
• DEA Diethylamine
• polyester diol having a molecular weight of 2000 g / mol was added with 1.00 parts by weight of 4-methyl-4-azaheptanediol-2,6 and 36.06 parts by weight of dimethylacetamide (DMAc) and 13.06 parts by weight of MDI 25 ° C, heated to 50 ° C, held for 110 minutes at this temperature and then cooled to 25 ° C to obtain an isocyanate-capped polymer having an NCO content of 2.65% NCO.
• DMAc dimethylacetamide
• Chain extension was accomplished by rapidly mixing 100 parts by weight of the isocyanate-capped polymer into a solution consisting of 1.32 parts by weight EDA and 0.03 parts by weight DEA in 189.05 parts by weight DMAc.
• the solids content of the resulting polyurethane urea spinning solution was 22%.
• the molecular weight of the polyurethane urea spinning solution was adjusted so that a viscosity of 70 Pa * s at a measurement temperature of 25 ° C resulted.
• the polyurethaneurea spinning solution was then admixed with a stock of additives.
• This stock mixture consisted of 66.6% 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), 5.7% by weight of Tinuvin® 622 (polymer consisting of succinic acid and Hydroxy-2,2,6,6-tetramethyl-1-piperidinethanol, Ciba), 16.6 wt .-% 22% polyurethaneurea spinning solution and 0.001 wt .-% of the dye Makrolex® violet (Bayer AG).
• This stock is added to the polyurethaneurea spinning solution such that the content of Cyanox® 1790 is 1.0% by weight, based on the total solids content.
• This polyurethane urea spinning solution was then mixed with a second stock solution.
• This consists of 5.5% by weight 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% by weight DMAC and 44.0% by weight of a 30% spinning solution and was added so as to have a magnesium stearate content of 0.30% by weight, based on the solid the polyurethane-urea polymers resulted.
• Silwet® L 7607 polyalkoxy-modified polydimethylsiloxane, viscosity: 50 mPas (at 25 ° C.), molecular weight 1000 g / mol, from OSI Specialties
• Magnesium stearate 45.0% by weight DMAC and 44.0% by weight of
• This polyurethane urea spinning solution was delivered to the spinnerets. Before the spinnerets, a further stock batch was admixed to this polyurethaneurea spinning solution, which contained the following quantities of the additive for staining the polyurethaneurea spinning solution:
• Example 1 (according to the invention):
• Heucodur® Black 9-100 copper chromite spinel pigment Cu (Fe, Cr) 2 O 4 , Pigment Black 28, manufactured by Heubach GmbH
• 10% strength Dispersion in dimethylacetamide (wt .-%) and 50 wt .-% of a 22% polyurethaneurea spinning solution 1.0% by weight (based on the solids content of the polyurethaneurea spinning solution) of Heucodur® Black 9-100 (copper chromite spinel pigment Cu (Fe, Cr) 2 O 4 , Pigment Black 28, manufactured by Heubach GmbH) as 10% strength Dispersion in dimethylacetamide (wt .-%) and 50 wt .-% of a 22% polyurethaneurea spinning solution.
• Makrolex® Black 1 mixture consisting of 57.0% by weight of Makrolex® Red EG Gran and 43.0% by weight of Makrolex® Green 5B Gran , Manufacturer Fa. Bayer AG
• 50 wt .-% of a 22% polyurethaneurea spinning solution 0.2% by weight (based on the solids content of the polyurethaneurea spinning solution) of Makrolex® Black 1 (mixture consisting of 57.0% by weight of Makrolex® Red EG Gran and 43.0% by weight of Makrolex® Green 5B Gran , Manufacturer Fa. Bayer AG) and 50 wt .-% of a 22% polyurethaneurea spinning solution.
• Makrolex® Black 2 (mixture consisting of 15.0% by weight of Makrolex® Yellow G Gran, 65.5% by weight of Makrolex® Violet 3R Gran and 19.5% by weight of Makrolex® Green 5B Gran, manufactured by Bayer AG) and 50% by weight of a 22% spinning solution.
• the finished spinning solution was spun dry by spinnerets in a spinning apparatus typical for a dry spinning process into filaments having a denier of 11 dtex, wherein four individual filaments were combined to coalescing filament yarns.
• the fiber preparation (Baysilone® oil M20, GE Bayer Silicones) was applied via a preparation roller, wherein 4 wt .-% based on the weight of the polyurethane urea fiber were applied.
• the take-off speed of the thread winders was 550 m / min.
• Table 1 shows the observations that occurred during the five-day spinning process. ⁇ b> ⁇ u> Table 1: ⁇ / u> ⁇ /b> Tabular comparison of observations during the spinning process: example number Assessment of spinning process 1 No abnormality 2 No abnormality 3 No abnormality 4 No abnormality V 1 Dope already contains agglomerates; Strong construction of nozzle pressure; Termination of the spinning process according to Id; inhomogeneous distribution of the carbon black in the filament and light color nuances V 2 Change in color shade (lightening) over spin time V 3 No abnormality V 4 No abnormality
• nonbasically modified carbon black (Comparative Example C1)
• agglomerates already form in the spinning solution.
• the distribution of the carbon black in the fiber is not homogeneous and there is a bright color nuance.
• non-base-modified carbon black is not suitable for producing dark polyurethane urea fibers.
• Umwindungsgarne produced using the polyurethane urea fibers according to the invention even after the above treatment methods no visible color differences in comparison to the Beigarns used in the production of the yarn based on natural fibers or synthetic fibers.

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• Engineering & Computer Science (AREA)
• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Textile Engineering (AREA)
• Manufacturing & Machinery (AREA)
• Artificial Filaments (AREA)

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• 2005
  • 2005-03-19 DE DE102005012797A patent/DE102005012797A1/de not_active Withdrawn
• 2006
  • 2006-03-07 EP EP06004545A patent/EP1703003A1/fr not_active Withdrawn
  • 2006-03-09 US US11/371,401 patent/US7364792B2/en not_active Expired - Fee Related
  • 2006-03-14 MX MXPA06002881A patent/MXPA06002881A/es unknown
  • 2006-03-16 CA CA002539859A patent/CA2539859A1/fr not_active Abandoned

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