CA2131581C - Process for the production of elastane fibers by inclusion of a combination of pdms and ethoxylated pdms in the spinning solution - Google Patents
Process for the production of elastane fibers by inclusion of a combination of pdms and ethoxylated pdms in the spinning solution Download PDFInfo
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- CA2131581C CA2131581C CA002131581A CA2131581A CA2131581C CA 2131581 C CA2131581 C CA 2131581C CA 002131581 A CA002131581 A CA 002131581A CA 2131581 A CA2131581 A CA 2131581A CA 2131581 C CA2131581 C CA 2131581C
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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
- 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
- Y10T428/2929—Bicomponent, conjugate, composite or collateral fibers or filaments [i.e., coextruded sheath-core or side-by-side type]
-
- 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
- Y10T428/2933—Coated or with bond, impregnation or core
- Y10T428/2964—Artificial fiber or filament
- Y10T428/2967—Synthetic resin or polymer
Abstract
The invention relates to a spinning process, more particularly a dry spinning process, for the production of elastane fibers in which 0.8 to 2% by weight of polydimethylsiloxane with a viscosity of 50 to 300 cSt and 0.2 to 0.6% by weight of ethoxylated polydimethyl-siloxane with a viscosity of 20 to 150 cSt are added to the elastane spinning solution before it is spun.
Description
~~.~a~8~.
A PROCESS FOR THE PRODUCTION OF ELASTANE FIBERS BY
INCLUSION OF A COMBINATION OF PDMS AND ETHOXYLATED PDMS
IN THE SPINNING SOLUTION
This invention relates to a spinning process, more particularly a dry spinning process, for the production of elastane fibers in which 0.8 to 2% by weight of polydimethylsiloxane with a viscosity of 50 to 300 cSt and 0.2 to 0.6% by weight of ethoxylated polydimethyl-siloxane with a viscosity of 20 to 150 cSt are added to the elastane spinning solution before it is spun.
Elastane fibers are fibers of which at least 85% by weight consist of segmented polyurethanes. The elastic and mechanical properties of elastane fibers are estab lished by the use of polyurea polyurethanes based on aromatic diisocyanates, for example, for the production of the elastane fibers. Elastanes of the type in ques-tion are typically produced by wet spinning or preferably dry spinning the solutions. Suitable solvents for both processes are polar solvents, for example dimethyl sulfoxide, N-methyl pyrrolidone, dimethyl formamide and preferably dimethyl acetamide.
Commercial yarns produced from such fibers have been known for many years. The most important application for fibers of the type in question is the elasticizing function for linen, corsetry and swimwear articles and their use in garter welts for socks and stockings and also elastic bands. By far the largest quantity of elastane filament yarns is processed in warp and raschel knitting machines for the major fields of fashion swim-wear and girdles. To this end, up to 1,500 filaments are wound adjacent one another onto a warp beam under con-stant, controlled elongation, for example in an expander-type warping frame. A warp consisting of several warp beams is then processed together with one or more warps Le A 29 767-FC 1 of non-elastic base yarns (fox example polyamide) to form a full-width fabric. Elastane-containing materials with elastane fiber contents of up to at most around 20~ are produced from these fabrics by dyeing and finishing, receiving not only their color and appearance, but also their final textile and mechanical (elastic) properties through these subsequent treatment steps.
At this stage of the production process, it has been found that, where they have been dyed in a single color, the textiles often show visible streaks so that they can only be used to a limited extent, if at all. This streakiness is assumed to be caused by irregularities in the thickness and elasticity of the elastane filaments used, although the exact cause is very difficult to pinpoint because the unwanted streakiness can only be detected after a plurality of process steps has been carried out.
The problem addressed by the present invention was to provide improved elastane fibers which, after proces sing on warp knitting machines, would produce distinctly less streakiness in dyed and finished textiles without any adverse effect on their processability in the inter-mediate steps required for the production of the tex-tiles.
It has now surprisingly been found that this problem can be solved by adding a mixture of polydimethylsiloxane (PDMS) with a viscosity of 50 to 300 cSt and ethoxylated polydimethylsiloxane to the polyurethane urea solution before it is spun and then carrying out the spinning process.
The present invention relates to a process for the production of elastane fibers from polyurea polyurethanes by dry spinning or wet spinning comprising the steps of spinning, removal of the spinning solvent, finishing, optionally twisting and winding of the spun fibers, Le A 29 7~7 2 zl~~~~~
characterized in that A) from 0.8 to 2~ by weight of polydimethylsiloxane with a viscosity of 50 to 300 cSt and B) from 0.2 to 0.6% by weight of ethoxylated polydi-methylsiloxane with a viscosity of 20 to 150 cSt (viscosities measured with a falling ball viscosimeter at 25°C) are added to the spinning solution before it is spun, the percentages shown being based on the siloxane content of the final fiber. The viscosity of the PDMS
used must not under any circumstances fall below 50 cSt because otherwise the desired effect would no longer .:
occur. The ethylene-oxide-modified polydimethylsiloxanes suitable for use in accordance with the invention prefer-ably correspond to general formula I:
( CH3 ) 3S 1~~ ( ( ~%H3 ) 2S l~ ) x- ( CH3- i 10 ) y-S 1 ( CH3 ) 3 ( I ) PE
in which PE is the single-bond unit CHZCHz-CHZO(Eo)mZ. In this formula, Eo stands for ethylene oxide and Z is either hydrogen or a C1_s alkyl radical and x, y and m are integers of or greater than 1 which are preferably selected so that formula (T) does not exceed a molecular weight of 4,000.
Products of this type are produced, for example, by Union Carbide under the trade name of Silwet~. Types caith a viscosity of 20 to 150 cSt and a molecular weight of around 600 to 4,000 are suitable far use in accordance with the invention. Unless otherwise specifically stated, all molecular weights are number average molecu lar weights (Mn) .
The inclusion of pure polydimethylsiloxane (PDMS) in x.e A 29 767 3 ~~J:~~~:~
the spinning solution is known in principle and is described, for example, in DE-A-3 912 510, according to which elastanes are produced by a special spinning process, namely a dry spinning process for the production of coarse-denier elastane fibers with introduction of superheated steam. This document refers to silicone oils as flow promoters among other possible additives. US
patent 4,973,647 also mentions the inclusion of silicone oil in the spinning solution. Neither document makes any reference to the effects of the oil after further proces-sing nor do they mention the inclusion of a special com-bination of oils with certain properties in the spinning solution.
The inclusion of amylsiloxane-modified polydimethyl siloxane oils in the spinning solution, which is not the subject of the present invention, is known from DE-AS 1 469 452.
It is not apparent from any of these documents whether the inclusion of pure or modified PDMS in the spinning solution is capable of influencing or improving the properties of the fibers, more particularly the optical uniformity of elastic warp-knitted fabrics of these elastane fibers.
The application of mixtures of polydimethylsiloxane and polyether-modified PDMS to the spun elastane fila ments by dipping or spraying or by roller is also known (see JP 57 128 276 or JP 03 146 774).
The object of applying finishing oils such as these is to improve the take-off properties of the elastane fibers in warping and knitting processes. The inclusion of the mixtures in the spinning solution is not mentioned in these documents, nor do they contain any reference to the fact that mixtures, especially those having the composition according to the invention, included in the elastane spinning solution produce an improvement in the he A 29 767 4 optical properties of warp-knitted fabrics obtained therefrom.
The polyurea polyurethanes are produced by methods known per se. A method which has proved to be particu-lariy successful for the synthesis of these fiber raw materials is the prepolymer process in which, in a first step, a long-chain dial is reacted with a diisocyanate in a solvent or in the melt to form a prepolymer in such a way that the reaction product is terminated by isocyanate l0 groups.
Preferred diols are, on the one hand, polyester diols and, on the other hand, polyether diols. Mixtures of polyester and polyether diols may also be used. The diols generally have a molecular weight of 1,000 to 6,000.
Suitable polyester diols are, for example, dicar-boxylic acid polyesters which may contain both several different alcohols and also several different carboxylic acids. Mixed polyesters of adipic acid, hexanediol and neopentyl glycol in a molar ratio of 1:0.7:0.43 are particularly suitable. Suitable polyesters preferably have a molecular weight of 1,000 to 4,000.
Suitable polyether diols are, for example, poly tetramethylene oxide diols, preferably having molecular weights of 1,000 to 2,000.
Polyester and/or polyether diols may also be used in combination with diols containing tertiary amino groups.
N-alkyl-N,N-bis-hydroxyalkylamines for example are particularly suitable. Suitable components are, for example, 4-tert.butyl-4-azaheptane-2,6-diol, 4-methyl-4-azaheptane-2,6-diol, 3-ethyl-3-azapentane-1,5-diol, 2-ethyl-2-dimethylaminomethyl propane-1,3-diol,4-tert.pen-tyl-4-azaheptane-2,6-diol, 3-cyclohexyl-3-azapentane-1,5-diol,3-methyl-3-azapentane-1,5-diol,3-tert.butylmethyl-3-azapentane-1,5-dioland3-tert.pentyl-3-azapentane-1,5-Le A 29 a67 5 ~1~~~,~3 diol.
In the synthesis of the elastane raw materials, the usual aromatic diisocyanates are optionally used in ad-mixture with small quantities of aliphatic diisocyanates.
Particularly useful results are obtained with the follow-ing diisocyanates: 2,4-tolylene diisocyanate and corre-sponding isomer mixtures: 4,4'-diphenylmethane diisocya-nate and corresponding isomer mixtures. Mixtures of aromatic diisocyanates may of course also be used.
In another embodiment of the synthesis of elastane raw materials according to the invention, polyester polyurethane and polyether polyurethane prepolymers are mixed and then reacted in known manner to form polyurea polyurethanes. The most favorable polyester diol/poly-ether diol mixing ratio for this purpose may readily be determined by preliminary tests.
In the synthesis of the polyurea polyurethanes, the required urea groups are introduced into the macromolecu-les by a chain-extending reaction. The macro diisocya-nates synthesized in the prepolymer stage are normally reacted in solution with diamines. Suitable diamines are, for example, ethylenediamine, tetramethylenediamine, 1,3-cyclohexandiamine, isophoronediamine.and.mixtures of these diamines. The required molecular weight can be adjusted by using a small quantity of monoamines, for example diethylamine or dibutylamine, during the chain-extending reaction. The chain-extending reaction itself may be carried out using COz as a retarding agent.
Polyester polyurethane and polyether polyurethane ureas may also be mixed on completion of the elastane synthesis.
The described reactions are normally carried out in an inert polar solvent, such as dimethyl acetamide, dimethyl formamide or the like.
In the process according to the invention, the he A 29 967 silicone oils are introduced ire c~onr:entratians of 0. ~3 to 24 by weight (for the palydimethylsiloxane) or 0.2 to 0.6% by weight (for the ethoxylated polydimethylsilox-ane). The ratio by weight of PnM~ to ethoxylated PDMS in the final phase is preferably ~.: ~. to 'S; ~.. The concentra-tion figures represent the content of oil in the spun e.lastane filament. The oils are introduced from a stock formulation in which the oils are dispersed in the solvent, for example dimethyl acetamide, together with other spinning aids, such as an antiblacking agent for example. The stock formu:lati.on is then added to and mixed with the spinning soluti.an ~..n a static mixer. or other mixer. The concentrat~.an of the two silicone ails together in the stack formulation is px°eferably from 15 to 2 2 % by we fight: .
The elastane filaments are then produced from the spinning solution obtained by wet slainraing or dry spin-ning, preferably by dry spinna.ng. Fi..bers produced by the process according to the invention preferably have an individual denier of 10 to 100 dtex. Multifilament yarns consisting of 3 to 5 coalesc~:ed individual capillaries are particularly preferred. They preferably have a denier of ° .
around 30 to 60 dtE~x, e.c~., 3at~ u.~:;~ ca~~~ dt~~x.
After leaving the spinning tube, the fibers may be provided with a typical external finish to fac~_litate their processing in the subsequent warping and knitting processes.
The present invention also relates to the elastane fibers obtainable by the process according to the inven tion.
The test described in the following was used to show that the elastane filaments produced irx accordance with the invention provide the fabrx.cs knitted from them with distinctly better uniformity than elastane filaments produced by a standard process.
A PROCESS FOR THE PRODUCTION OF ELASTANE FIBERS BY
INCLUSION OF A COMBINATION OF PDMS AND ETHOXYLATED PDMS
IN THE SPINNING SOLUTION
This invention relates to a spinning process, more particularly a dry spinning process, for the production of elastane fibers in which 0.8 to 2% by weight of polydimethylsiloxane with a viscosity of 50 to 300 cSt and 0.2 to 0.6% by weight of ethoxylated polydimethyl-siloxane with a viscosity of 20 to 150 cSt are added to the elastane spinning solution before it is spun.
Elastane fibers are fibers of which at least 85% by weight consist of segmented polyurethanes. The elastic and mechanical properties of elastane fibers are estab lished by the use of polyurea polyurethanes based on aromatic diisocyanates, for example, for the production of the elastane fibers. Elastanes of the type in ques-tion are typically produced by wet spinning or preferably dry spinning the solutions. Suitable solvents for both processes are polar solvents, for example dimethyl sulfoxide, N-methyl pyrrolidone, dimethyl formamide and preferably dimethyl acetamide.
Commercial yarns produced from such fibers have been known for many years. The most important application for fibers of the type in question is the elasticizing function for linen, corsetry and swimwear articles and their use in garter welts for socks and stockings and also elastic bands. By far the largest quantity of elastane filament yarns is processed in warp and raschel knitting machines for the major fields of fashion swim-wear and girdles. To this end, up to 1,500 filaments are wound adjacent one another onto a warp beam under con-stant, controlled elongation, for example in an expander-type warping frame. A warp consisting of several warp beams is then processed together with one or more warps Le A 29 767-FC 1 of non-elastic base yarns (fox example polyamide) to form a full-width fabric. Elastane-containing materials with elastane fiber contents of up to at most around 20~ are produced from these fabrics by dyeing and finishing, receiving not only their color and appearance, but also their final textile and mechanical (elastic) properties through these subsequent treatment steps.
At this stage of the production process, it has been found that, where they have been dyed in a single color, the textiles often show visible streaks so that they can only be used to a limited extent, if at all. This streakiness is assumed to be caused by irregularities in the thickness and elasticity of the elastane filaments used, although the exact cause is very difficult to pinpoint because the unwanted streakiness can only be detected after a plurality of process steps has been carried out.
The problem addressed by the present invention was to provide improved elastane fibers which, after proces sing on warp knitting machines, would produce distinctly less streakiness in dyed and finished textiles without any adverse effect on their processability in the inter-mediate steps required for the production of the tex-tiles.
It has now surprisingly been found that this problem can be solved by adding a mixture of polydimethylsiloxane (PDMS) with a viscosity of 50 to 300 cSt and ethoxylated polydimethylsiloxane to the polyurethane urea solution before it is spun and then carrying out the spinning process.
The present invention relates to a process for the production of elastane fibers from polyurea polyurethanes by dry spinning or wet spinning comprising the steps of spinning, removal of the spinning solvent, finishing, optionally twisting and winding of the spun fibers, Le A 29 7~7 2 zl~~~~~
characterized in that A) from 0.8 to 2~ by weight of polydimethylsiloxane with a viscosity of 50 to 300 cSt and B) from 0.2 to 0.6% by weight of ethoxylated polydi-methylsiloxane with a viscosity of 20 to 150 cSt (viscosities measured with a falling ball viscosimeter at 25°C) are added to the spinning solution before it is spun, the percentages shown being based on the siloxane content of the final fiber. The viscosity of the PDMS
used must not under any circumstances fall below 50 cSt because otherwise the desired effect would no longer .:
occur. The ethylene-oxide-modified polydimethylsiloxanes suitable for use in accordance with the invention prefer-ably correspond to general formula I:
( CH3 ) 3S 1~~ ( ( ~%H3 ) 2S l~ ) x- ( CH3- i 10 ) y-S 1 ( CH3 ) 3 ( I ) PE
in which PE is the single-bond unit CHZCHz-CHZO(Eo)mZ. In this formula, Eo stands for ethylene oxide and Z is either hydrogen or a C1_s alkyl radical and x, y and m are integers of or greater than 1 which are preferably selected so that formula (T) does not exceed a molecular weight of 4,000.
Products of this type are produced, for example, by Union Carbide under the trade name of Silwet~. Types caith a viscosity of 20 to 150 cSt and a molecular weight of around 600 to 4,000 are suitable far use in accordance with the invention. Unless otherwise specifically stated, all molecular weights are number average molecu lar weights (Mn) .
The inclusion of pure polydimethylsiloxane (PDMS) in x.e A 29 767 3 ~~J:~~~:~
the spinning solution is known in principle and is described, for example, in DE-A-3 912 510, according to which elastanes are produced by a special spinning process, namely a dry spinning process for the production of coarse-denier elastane fibers with introduction of superheated steam. This document refers to silicone oils as flow promoters among other possible additives. US
patent 4,973,647 also mentions the inclusion of silicone oil in the spinning solution. Neither document makes any reference to the effects of the oil after further proces-sing nor do they mention the inclusion of a special com-bination of oils with certain properties in the spinning solution.
The inclusion of amylsiloxane-modified polydimethyl siloxane oils in the spinning solution, which is not the subject of the present invention, is known from DE-AS 1 469 452.
It is not apparent from any of these documents whether the inclusion of pure or modified PDMS in the spinning solution is capable of influencing or improving the properties of the fibers, more particularly the optical uniformity of elastic warp-knitted fabrics of these elastane fibers.
The application of mixtures of polydimethylsiloxane and polyether-modified PDMS to the spun elastane fila ments by dipping or spraying or by roller is also known (see JP 57 128 276 or JP 03 146 774).
The object of applying finishing oils such as these is to improve the take-off properties of the elastane fibers in warping and knitting processes. The inclusion of the mixtures in the spinning solution is not mentioned in these documents, nor do they contain any reference to the fact that mixtures, especially those having the composition according to the invention, included in the elastane spinning solution produce an improvement in the he A 29 767 4 optical properties of warp-knitted fabrics obtained therefrom.
The polyurea polyurethanes are produced by methods known per se. A method which has proved to be particu-lariy successful for the synthesis of these fiber raw materials is the prepolymer process in which, in a first step, a long-chain dial is reacted with a diisocyanate in a solvent or in the melt to form a prepolymer in such a way that the reaction product is terminated by isocyanate l0 groups.
Preferred diols are, on the one hand, polyester diols and, on the other hand, polyether diols. Mixtures of polyester and polyether diols may also be used. The diols generally have a molecular weight of 1,000 to 6,000.
Suitable polyester diols are, for example, dicar-boxylic acid polyesters which may contain both several different alcohols and also several different carboxylic acids. Mixed polyesters of adipic acid, hexanediol and neopentyl glycol in a molar ratio of 1:0.7:0.43 are particularly suitable. Suitable polyesters preferably have a molecular weight of 1,000 to 4,000.
Suitable polyether diols are, for example, poly tetramethylene oxide diols, preferably having molecular weights of 1,000 to 2,000.
Polyester and/or polyether diols may also be used in combination with diols containing tertiary amino groups.
N-alkyl-N,N-bis-hydroxyalkylamines for example are particularly suitable. Suitable components are, for example, 4-tert.butyl-4-azaheptane-2,6-diol, 4-methyl-4-azaheptane-2,6-diol, 3-ethyl-3-azapentane-1,5-diol, 2-ethyl-2-dimethylaminomethyl propane-1,3-diol,4-tert.pen-tyl-4-azaheptane-2,6-diol, 3-cyclohexyl-3-azapentane-1,5-diol,3-methyl-3-azapentane-1,5-diol,3-tert.butylmethyl-3-azapentane-1,5-dioland3-tert.pentyl-3-azapentane-1,5-Le A 29 a67 5 ~1~~~,~3 diol.
In the synthesis of the elastane raw materials, the usual aromatic diisocyanates are optionally used in ad-mixture with small quantities of aliphatic diisocyanates.
Particularly useful results are obtained with the follow-ing diisocyanates: 2,4-tolylene diisocyanate and corre-sponding isomer mixtures: 4,4'-diphenylmethane diisocya-nate and corresponding isomer mixtures. Mixtures of aromatic diisocyanates may of course also be used.
In another embodiment of the synthesis of elastane raw materials according to the invention, polyester polyurethane and polyether polyurethane prepolymers are mixed and then reacted in known manner to form polyurea polyurethanes. The most favorable polyester diol/poly-ether diol mixing ratio for this purpose may readily be determined by preliminary tests.
In the synthesis of the polyurea polyurethanes, the required urea groups are introduced into the macromolecu-les by a chain-extending reaction. The macro diisocya-nates synthesized in the prepolymer stage are normally reacted in solution with diamines. Suitable diamines are, for example, ethylenediamine, tetramethylenediamine, 1,3-cyclohexandiamine, isophoronediamine.and.mixtures of these diamines. The required molecular weight can be adjusted by using a small quantity of monoamines, for example diethylamine or dibutylamine, during the chain-extending reaction. The chain-extending reaction itself may be carried out using COz as a retarding agent.
Polyester polyurethane and polyether polyurethane ureas may also be mixed on completion of the elastane synthesis.
The described reactions are normally carried out in an inert polar solvent, such as dimethyl acetamide, dimethyl formamide or the like.
In the process according to the invention, the he A 29 967 silicone oils are introduced ire c~onr:entratians of 0. ~3 to 24 by weight (for the palydimethylsiloxane) or 0.2 to 0.6% by weight (for the ethoxylated polydimethylsilox-ane). The ratio by weight of PnM~ to ethoxylated PDMS in the final phase is preferably ~.: ~. to 'S; ~.. The concentra-tion figures represent the content of oil in the spun e.lastane filament. The oils are introduced from a stock formulation in which the oils are dispersed in the solvent, for example dimethyl acetamide, together with other spinning aids, such as an antiblacking agent for example. The stock formu:lati.on is then added to and mixed with the spinning soluti.an ~..n a static mixer. or other mixer. The concentrat~.an of the two silicone ails together in the stack formulation is px°eferably from 15 to 2 2 % by we fight: .
The elastane filaments are then produced from the spinning solution obtained by wet slainraing or dry spin-ning, preferably by dry spinna.ng. Fi..bers produced by the process according to the invention preferably have an individual denier of 10 to 100 dtex. Multifilament yarns consisting of 3 to 5 coalesc~:ed individual capillaries are particularly preferred. They preferably have a denier of ° .
around 30 to 60 dtE~x, e.c~., 3at~ u.~:;~ ca~~~ dt~~x.
After leaving the spinning tube, the fibers may be provided with a typical external finish to fac~_litate their processing in the subsequent warping and knitting processes.
The present invention also relates to the elastane fibers obtainable by the process according to the inven tion.
The test described in the following was used to show that the elastane filaments produced irx accordance with the invention provide the fabrx.cs knitted from them with distinctly better uniformity than elastane filaments produced by a standard process.
2:3189-7689 Description of the test In a first step, 1, 340 filaments with a denier of dtex of 45 are warped with a preliminary draft of 156 and a final draft of 40% onto two sectional warp beans (SWBs) of an ea.astane warping machine type GSE 50/30, Karl Mayer, Obe:rhausen).
In a second step, an elastic warp-knitted fabric is produced from these sectional warp beams together with two SWBs of polyamide dtex 44/10 (a product of SNIA). A
type HKS 2/E 32 warp loom rKarl Mayer, Oberhausen) is used as the warp knitting machine. The filament feed values are 59.0 cm for the elastane and 160.0 cm for. the polyamide.
The warp-knitted fabric thus produced is then relaxed on a steaming table with a vibration attachment, any differences in stitch density and fabric width largely being removed from the. raw ~'abx°ic.
The non-prewashed fabric is then fixed with hot air on a tenter frame for 40 seconds at 195aC with an over feed of 8~. The fixing width is 100 cr~i.
In a separate pass through the t:enter frame, the fixed fabric is wound cold onto per orated dyeing beams.
The fabric is dyed either white car blue in a beam dyeing system using the following st.anaard formulations:
A) For the color white:
TM
2.0 g/1 Blankit IN ~a product of BASF AG; techn.
sodium dithionite) ~~r~s 2.0°s Blankophor GbE fl. ~a product of Bayer AG;
optical brightener for polyamide, elas-tane) 0.3 m1/1 Acetic acid Before all the auxil~.ax°~.es are added, the 23.189-7689 closed system is first filled with water with no circulation of liquor (for thorough venting). The auxiliaries mentioned above are added after the cir-culation pump has been switched on and the required pressure of 2.2/2.0 bar has been established. The liquor is heated at ~. ° C per minute, the liquor being pumped from outside inwards up to 80nC and then from inside outwards beyond 80"C. After the required final temperature of 90°G has been reached,, the further treatment time aus 45 minutes. The fabric is then indirectly cooled to 70 ° ~C ~ c:.on~:inuously rinsed to room temperature by introduction of fresh cold water and, frinally, is rinsed once more with fresh water.
B) For the color blue:
The procedure in the beam dyeing system largely corresponds to that for the color white except for the following changes to the composition of thss dye:
TM
0.90% Telon Lichtblau RR. ~~2% (a product of Bayer AG; aci.d dye) 0.05% Telan MEchtarange AGT 200a (a product of B<~yex AG, ac:~.d dye) 2.00 g/1 Sodium aceta~:.e 1.500 Levegal~M FTS (a product of Bayer AG;
levelling agent, mixture of sulfonate and polyglycol ether derivative) 0.30 m1/1 Acetic acid Dyeing time 60 rnins. at 98"'C.
After dyeing, the dyeing ~aeams are delivered with the wet fabric to the padding machine where they are rinsed with water and uniformly squeE~zed dry.
~~~~J~~.
Subsequent intermediate drying takes place at 120°C in a screen drum dryer over which the fabric travels at a rate of approximately 7 m/minute. The fabric is folded flat on entering the screen drum dryer.
Finally, the intermediately dried fabric is tentered in a tenter frame at a temperature of 150 ° C
and at a speed of 10 m/minute for an overfeed of 50, resulting the formation of a smooth fabric with the prescribed width which is wound into roll form on leaving the tenter frame.
Optical uniformity is evaluated on a scale of 1 to 9 (test scores) by visual inspection of the dyed fabric both in transmitted light and in reflected light. This scale is applicable to all elastane deniers. Scores of 1 to 3 can only be achieved with relatively coarse den-iers (> dtex 80). For the denier of dtex 45 described herein, a score of 4 signifies an extremely uniform fabric, a score of 5 only corresponds to good uniformity while a score of 6 corresponds to a satisfactory uniform-ity which still corresponds to 1a fabric.
If fabric is given a score of 7, it can only be used for special purposes while fabrics with scores of 8 to 9 are unsaleable.
Examples The following Examples demonstrate the more favor-able optical uniformity of dyed knitted fabrics produced y~ith elastanes according to the invention.
The superiority of the elastane fibers according to the invention (see Examples 1, 3, 5 and 7 according to the invention) becomes clear by comparison with fibers which only differ in their composition in regard to inclusion of the mixtures of polydimethylsiloxane and Le A 29 767 10 ethoxylated polydimethylsiloxane in the spinning solution (Examples 2, 4, 6, 8 and 9).
In all the Examples, the fabrics were knitted from an elastane polymer which had been produced from a polyester diol, molecular weight 2,000, consisting of adipic acid, hexanediol and neopentyl glycol, capped with methylene-bis-(4-phenyl diisocyanate) ("MDI") and then chain-extended with a mixture of ethylenediamine (EDA) and diethylamine (DEA).
The elastane polymer for each of the Examples was produced by substantially the same method.
In every case, 49.88 parts by weight of polyester diol, molecular weight 2,000, were mixed at 25°C with 1.00 part by weight of 4-methyl-4-azaheptane-2,6-diol and 36.06 parts by weight of dimethyl acetamide (DMAC) and 13.06 parts by weight of MDI, heated to 50°C and kept at that temperature fox 110 minutes to obtain an isocyanate-capped polymer with an NCO content of 2.65%.
In Examples 1 and 2, after the cooling step, 100 parts of the capped polymer were cooled to 25°C and rapidly mixed with a solution of 1.32 parts by weight of EDA and 0.03 part by weight of DEA in 189.05 parts of DMAC, so that a spinning solution of the polyurethane urea in DMAC with a solids content of 22.5% was formed.
By addition of hexamethylene diisocyanate (HDI), the molecular weight of the polymer was adjusted in such a way that a viscosity of 70 Pa.s/25°C and an intrinsic viscosity ~llnh. of 1.4 dl/g were obtained.
For the remaining Examples, chain extension was harried out as follows:
100 Parts of the capped polymer were cooled to 20°C, after which the solution was diluted with 59.85 parts by weight of DMAC. The solution was then intensively mixed with a mixture of 1.23 parts by weight of EDA, 0.08 part by weight of DEA and 60.72 parts by weight of DMAC in a Le A 29 767 11 continuous reactor, so that a spinning solution of polyurethane urea in DMAC with a solids content of approximately 30%, a viscosity of 50 Pa.s/50°C and an intrinsic viscosity ninh. of 1.4 dl/g was formed.
After the production of the polymers as described in the foregoing, a stock formulation of additives was introduced. This stock formulation consisted of 58.72 parts by weight of DMAC, 10.32 parts by weight of Cyanox~
1790 (a product of American Cyanamid: stabilizer), 5.16 parts by weight of Tinuvin~ 622 (a product of Ciba Geigy stabilizer), 25.80 parts by weight of a 30% spinning solution and 0.009 part by weight of the dye Makrolex-violett~ B (a product of Bayer AG). This stock formula-tion was added to the spinning solution in such a way that the final filaments contained 1% by weight of Cyanox~ 1790 and 0.5% by weight of Tinuvin~ 622, based on the solids content of the fiber polymer.
A second stock formulation consisting of 30.94 parts by weight of titanium dioxide (RKB 2, a product of Bayer AG), 44.52 parts by weight of dimethyl acetamide and 24.53 parts by weight of a 22% spinning solution was then added to the spinning solution in such a quantity that the final filaments contained 0.05% by weight of titanium dioxide, based on the polyurethane urea polymer.
Further stock formulations were then added to the spinning solution. They consisted of 4.4 parts by weight of magnesium stearate, 32.3 parts by weight of DMAC, 41.2 parts by weight of 30% spinning solution and quantities of polydimethylsiloxane and ethoxylated polydimethyl-siloxane which had been selected so that the percentage contents shown in Examples 1 to 9 were obtained in the final fibers.
Ex~nple l:
Additive content in the final fiber Iae A 29 767 12 ~~.~.i~u~.
0.3% by weight magnesium stearate 0.3% by weight Silwet~ L 7607 (a product of 'Union Carbides ethoxylated PDMS) 1.0% by weight Baysilonol~ M 100 (a product of Bayer AG) with a viscosity of 100 cSt Example 2 (comparis~n):
Additive content in the final fiber 0.3% by weight magnesium stearate without polydi-methylsiloxane 0.3% by weight Silwet~ L 7607 In Examples 1 and 2, the spinning solution was dry spun through spinnerets in a typical spinning machine 5 meters in length to form filaments with a denier of 11 dtex, four individual filaments being combined to form coalesced filament yarns with a denier of 44 dtex which were wound at 330 m/minute.
As can be seen from Table 1, a distinct improvement in optical uniformity, as reflected in a score improve ment of 0.76 points, is obtained by the inclusion in the spinning solution of a mixture of polydimethylsiloxane and ethoxylated polydimethylsiloxane in accordance with the present invention.
Table 1:
Improvement of optical uniformity in accordance to the invention Example Number Test score Remarks I of (average) tests 1 12 5.04 According to the invention, viscosity of the PDMS: 100 cSt 2 10 5.80 Comparison, no PDMS
included in the spinning solution L~ ?r 29 767 13 EXa:nple 3:
Additive content in the final fiber 0.3% by weight magnesium stearate 0.3% by weight Silwet~ L 7607 (Union Carbide) 1.0% by weight Baysiloriol~ M 100 (Bayer AG), vis-cosity 100 cSt Example 4 (comparison):
Additive content in the final fiber 0.3% by weight magnesium stearate 0.3% by weight Silwet~ L 7607 (Union Carbide) In Examples 3 and 4, the spinning solution was dry-spun in a spinning machine 10 meters in length to form filaments with an indi~ridual denier of 11 dtex, four individual filaments being combined to form coalesced filament yarns with a denier of 44 dtex which were wound at 500 m/minute.
As can be seen from Table 2, a distinct improvement in optical uniformity of 0.56 points is achieved by the process according to the invention, even in this modified spinning process.
Table 2:
Improvement of optical uniformity in accordance with the invention - modified spinning process:
Example Nufmber Test score Remarks of (average) tests 3 64 5.50 According to the invention, viscosity of the PDMS: 100 cSt 4 25 6.06 Comparison, no PDMS
included in the spinning solution Le A 29 767 14 ~~~~~i Exaatple 5:
Additive content in the final fiber 0.3% by weight magnesium stearate 0.3% by weight Silwet~ L 7607 1.0% by weight Baysilonol~ M 100, viscosity 300 cSt Example t (comparison):
Additive content in the final fiber 0.3% by weight magnesium stearate 0.3% by weight Silwet~ L 7607 0.75% by weight Baysilonol~ M 100, viscosity 100 cSt Example 7:
Additive content in the final fiber 0.3% by weight magnesium stearate 0.3% by weight Silwet~ L 7607 1.5% by weight Baysilonol~ M 100, viscosity 100 cSt Example 8 (comparison):
Additive content in the final fiber 0.3% by weight magnesium stearate 0.3% by weight Silwet~ L 7607 1.0% by weight Amylsiloxane-containing PDMS
Example 9 (comparison):
Additive content in the final fiber q.3% by weight magnesium stearate without ethoxy-lated polydimethylsiloxane 1.0% by weight, Baysilon~1~ M 100, viscosity 100 cSt In the series of tests for Examples 5 to 9, the spinning solution was again dry spun through spinnerets Le A 29 7fi7 15 in a spinning machine 10 meters in length to form fila-ments with a denier of 11 dtex, 4 individual filaments being combined to form coalesced filament yarns with a denier of 44 dtex which were wound at 500 m/minute.
The results are set out in Table 3.
Table 3:
Tmprovement of optical uniformity in accordance with the invention in relation to comparison inclusions in the spinning solution:
Example Number Test score Remarks of tests (average) I
IS 1 4.83 According to the invention, viscosity of the PDMS: 300 cSt 6 3 5.25 According to the invention, viscosity of the PDMS: 100 cst, but concentration reduced to 0.750 7 1 4.50 According to the invention, viscosity of the PDMS: 100 cSt, but concentration increased to 1.50 8 3 5.58 Comparison, PDMS
replaced by amyl-siloxane-containing PDMS
9 * * Comparison, with PDMS
included in the spinning solution, viscosity 100 cSt, but without ethoxy-lated PDMS
* Irk these tests, it was not possible to produce a sheet-form textile because the warping process was constantly hampered by entanglements which in turn resulted in filament breakages.
a A 29 ?G7 16 This series again reflects the distinct improvement in optical uniformity by 0.42 to 1.0~ points where the spinning additives according to the invention are used.
Le A a 9 'sa 17
In a second step, an elastic warp-knitted fabric is produced from these sectional warp beams together with two SWBs of polyamide dtex 44/10 (a product of SNIA). A
type HKS 2/E 32 warp loom rKarl Mayer, Oberhausen) is used as the warp knitting machine. The filament feed values are 59.0 cm for the elastane and 160.0 cm for. the polyamide.
The warp-knitted fabric thus produced is then relaxed on a steaming table with a vibration attachment, any differences in stitch density and fabric width largely being removed from the. raw ~'abx°ic.
The non-prewashed fabric is then fixed with hot air on a tenter frame for 40 seconds at 195aC with an over feed of 8~. The fixing width is 100 cr~i.
In a separate pass through the t:enter frame, the fixed fabric is wound cold onto per orated dyeing beams.
The fabric is dyed either white car blue in a beam dyeing system using the following st.anaard formulations:
A) For the color white:
TM
2.0 g/1 Blankit IN ~a product of BASF AG; techn.
sodium dithionite) ~~r~s 2.0°s Blankophor GbE fl. ~a product of Bayer AG;
optical brightener for polyamide, elas-tane) 0.3 m1/1 Acetic acid Before all the auxil~.ax°~.es are added, the 23.189-7689 closed system is first filled with water with no circulation of liquor (for thorough venting). The auxiliaries mentioned above are added after the cir-culation pump has been switched on and the required pressure of 2.2/2.0 bar has been established. The liquor is heated at ~. ° C per minute, the liquor being pumped from outside inwards up to 80nC and then from inside outwards beyond 80"C. After the required final temperature of 90°G has been reached,, the further treatment time aus 45 minutes. The fabric is then indirectly cooled to 70 ° ~C ~ c:.on~:inuously rinsed to room temperature by introduction of fresh cold water and, frinally, is rinsed once more with fresh water.
B) For the color blue:
The procedure in the beam dyeing system largely corresponds to that for the color white except for the following changes to the composition of thss dye:
TM
0.90% Telon Lichtblau RR. ~~2% (a product of Bayer AG; aci.d dye) 0.05% Telan MEchtarange AGT 200a (a product of B<~yex AG, ac:~.d dye) 2.00 g/1 Sodium aceta~:.e 1.500 Levegal~M FTS (a product of Bayer AG;
levelling agent, mixture of sulfonate and polyglycol ether derivative) 0.30 m1/1 Acetic acid Dyeing time 60 rnins. at 98"'C.
After dyeing, the dyeing ~aeams are delivered with the wet fabric to the padding machine where they are rinsed with water and uniformly squeE~zed dry.
~~~~J~~.
Subsequent intermediate drying takes place at 120°C in a screen drum dryer over which the fabric travels at a rate of approximately 7 m/minute. The fabric is folded flat on entering the screen drum dryer.
Finally, the intermediately dried fabric is tentered in a tenter frame at a temperature of 150 ° C
and at a speed of 10 m/minute for an overfeed of 50, resulting the formation of a smooth fabric with the prescribed width which is wound into roll form on leaving the tenter frame.
Optical uniformity is evaluated on a scale of 1 to 9 (test scores) by visual inspection of the dyed fabric both in transmitted light and in reflected light. This scale is applicable to all elastane deniers. Scores of 1 to 3 can only be achieved with relatively coarse den-iers (> dtex 80). For the denier of dtex 45 described herein, a score of 4 signifies an extremely uniform fabric, a score of 5 only corresponds to good uniformity while a score of 6 corresponds to a satisfactory uniform-ity which still corresponds to 1a fabric.
If fabric is given a score of 7, it can only be used for special purposes while fabrics with scores of 8 to 9 are unsaleable.
Examples The following Examples demonstrate the more favor-able optical uniformity of dyed knitted fabrics produced y~ith elastanes according to the invention.
The superiority of the elastane fibers according to the invention (see Examples 1, 3, 5 and 7 according to the invention) becomes clear by comparison with fibers which only differ in their composition in regard to inclusion of the mixtures of polydimethylsiloxane and Le A 29 767 10 ethoxylated polydimethylsiloxane in the spinning solution (Examples 2, 4, 6, 8 and 9).
In all the Examples, the fabrics were knitted from an elastane polymer which had been produced from a polyester diol, molecular weight 2,000, consisting of adipic acid, hexanediol and neopentyl glycol, capped with methylene-bis-(4-phenyl diisocyanate) ("MDI") and then chain-extended with a mixture of ethylenediamine (EDA) and diethylamine (DEA).
The elastane polymer for each of the Examples was produced by substantially the same method.
In every case, 49.88 parts by weight of polyester diol, molecular weight 2,000, were mixed at 25°C with 1.00 part by weight of 4-methyl-4-azaheptane-2,6-diol and 36.06 parts by weight of dimethyl acetamide (DMAC) and 13.06 parts by weight of MDI, heated to 50°C and kept at that temperature fox 110 minutes to obtain an isocyanate-capped polymer with an NCO content of 2.65%.
In Examples 1 and 2, after the cooling step, 100 parts of the capped polymer were cooled to 25°C and rapidly mixed with a solution of 1.32 parts by weight of EDA and 0.03 part by weight of DEA in 189.05 parts of DMAC, so that a spinning solution of the polyurethane urea in DMAC with a solids content of 22.5% was formed.
By addition of hexamethylene diisocyanate (HDI), the molecular weight of the polymer was adjusted in such a way that a viscosity of 70 Pa.s/25°C and an intrinsic viscosity ~llnh. of 1.4 dl/g were obtained.
For the remaining Examples, chain extension was harried out as follows:
100 Parts of the capped polymer were cooled to 20°C, after which the solution was diluted with 59.85 parts by weight of DMAC. The solution was then intensively mixed with a mixture of 1.23 parts by weight of EDA, 0.08 part by weight of DEA and 60.72 parts by weight of DMAC in a Le A 29 767 11 continuous reactor, so that a spinning solution of polyurethane urea in DMAC with a solids content of approximately 30%, a viscosity of 50 Pa.s/50°C and an intrinsic viscosity ninh. of 1.4 dl/g was formed.
After the production of the polymers as described in the foregoing, a stock formulation of additives was introduced. This stock formulation consisted of 58.72 parts by weight of DMAC, 10.32 parts by weight of Cyanox~
1790 (a product of American Cyanamid: stabilizer), 5.16 parts by weight of Tinuvin~ 622 (a product of Ciba Geigy stabilizer), 25.80 parts by weight of a 30% spinning solution and 0.009 part by weight of the dye Makrolex-violett~ B (a product of Bayer AG). This stock formula-tion was added to the spinning solution in such a way that the final filaments contained 1% by weight of Cyanox~ 1790 and 0.5% by weight of Tinuvin~ 622, based on the solids content of the fiber polymer.
A second stock formulation consisting of 30.94 parts by weight of titanium dioxide (RKB 2, a product of Bayer AG), 44.52 parts by weight of dimethyl acetamide and 24.53 parts by weight of a 22% spinning solution was then added to the spinning solution in such a quantity that the final filaments contained 0.05% by weight of titanium dioxide, based on the polyurethane urea polymer.
Further stock formulations were then added to the spinning solution. They consisted of 4.4 parts by weight of magnesium stearate, 32.3 parts by weight of DMAC, 41.2 parts by weight of 30% spinning solution and quantities of polydimethylsiloxane and ethoxylated polydimethyl-siloxane which had been selected so that the percentage contents shown in Examples 1 to 9 were obtained in the final fibers.
Ex~nple l:
Additive content in the final fiber Iae A 29 767 12 ~~.~.i~u~.
0.3% by weight magnesium stearate 0.3% by weight Silwet~ L 7607 (a product of 'Union Carbides ethoxylated PDMS) 1.0% by weight Baysilonol~ M 100 (a product of Bayer AG) with a viscosity of 100 cSt Example 2 (comparis~n):
Additive content in the final fiber 0.3% by weight magnesium stearate without polydi-methylsiloxane 0.3% by weight Silwet~ L 7607 In Examples 1 and 2, the spinning solution was dry spun through spinnerets in a typical spinning machine 5 meters in length to form filaments with a denier of 11 dtex, four individual filaments being combined to form coalesced filament yarns with a denier of 44 dtex which were wound at 330 m/minute.
As can be seen from Table 1, a distinct improvement in optical uniformity, as reflected in a score improve ment of 0.76 points, is obtained by the inclusion in the spinning solution of a mixture of polydimethylsiloxane and ethoxylated polydimethylsiloxane in accordance with the present invention.
Table 1:
Improvement of optical uniformity in accordance to the invention Example Number Test score Remarks I of (average) tests 1 12 5.04 According to the invention, viscosity of the PDMS: 100 cSt 2 10 5.80 Comparison, no PDMS
included in the spinning solution L~ ?r 29 767 13 EXa:nple 3:
Additive content in the final fiber 0.3% by weight magnesium stearate 0.3% by weight Silwet~ L 7607 (Union Carbide) 1.0% by weight Baysiloriol~ M 100 (Bayer AG), vis-cosity 100 cSt Example 4 (comparison):
Additive content in the final fiber 0.3% by weight magnesium stearate 0.3% by weight Silwet~ L 7607 (Union Carbide) In Examples 3 and 4, the spinning solution was dry-spun in a spinning machine 10 meters in length to form filaments with an indi~ridual denier of 11 dtex, four individual filaments being combined to form coalesced filament yarns with a denier of 44 dtex which were wound at 500 m/minute.
As can be seen from Table 2, a distinct improvement in optical uniformity of 0.56 points is achieved by the process according to the invention, even in this modified spinning process.
Table 2:
Improvement of optical uniformity in accordance with the invention - modified spinning process:
Example Nufmber Test score Remarks of (average) tests 3 64 5.50 According to the invention, viscosity of the PDMS: 100 cSt 4 25 6.06 Comparison, no PDMS
included in the spinning solution Le A 29 767 14 ~~~~~i Exaatple 5:
Additive content in the final fiber 0.3% by weight magnesium stearate 0.3% by weight Silwet~ L 7607 1.0% by weight Baysilonol~ M 100, viscosity 300 cSt Example t (comparison):
Additive content in the final fiber 0.3% by weight magnesium stearate 0.3% by weight Silwet~ L 7607 0.75% by weight Baysilonol~ M 100, viscosity 100 cSt Example 7:
Additive content in the final fiber 0.3% by weight magnesium stearate 0.3% by weight Silwet~ L 7607 1.5% by weight Baysilonol~ M 100, viscosity 100 cSt Example 8 (comparison):
Additive content in the final fiber 0.3% by weight magnesium stearate 0.3% by weight Silwet~ L 7607 1.0% by weight Amylsiloxane-containing PDMS
Example 9 (comparison):
Additive content in the final fiber q.3% by weight magnesium stearate without ethoxy-lated polydimethylsiloxane 1.0% by weight, Baysilon~1~ M 100, viscosity 100 cSt In the series of tests for Examples 5 to 9, the spinning solution was again dry spun through spinnerets Le A 29 7fi7 15 in a spinning machine 10 meters in length to form fila-ments with a denier of 11 dtex, 4 individual filaments being combined to form coalesced filament yarns with a denier of 44 dtex which were wound at 500 m/minute.
The results are set out in Table 3.
Table 3:
Tmprovement of optical uniformity in accordance with the invention in relation to comparison inclusions in the spinning solution:
Example Number Test score Remarks of tests (average) I
IS 1 4.83 According to the invention, viscosity of the PDMS: 300 cSt 6 3 5.25 According to the invention, viscosity of the PDMS: 100 cst, but concentration reduced to 0.750 7 1 4.50 According to the invention, viscosity of the PDMS: 100 cSt, but concentration increased to 1.50 8 3 5.58 Comparison, PDMS
replaced by amyl-siloxane-containing PDMS
9 * * Comparison, with PDMS
included in the spinning solution, viscosity 100 cSt, but without ethoxy-lated PDMS
* Irk these tests, it was not possible to produce a sheet-form textile because the warping process was constantly hampered by entanglements which in turn resulted in filament breakages.
a A 29 ?G7 16 This series again reflects the distinct improvement in optical uniformity by 0.42 to 1.0~ points where the spinning additives according to the invention are used.
Le A a 9 'sa 17
Claims (10)
1. A process for the production of elastane fibers from polyurea polyurethanes by dry spinning or wet spinning, comprising the steps of spinning, removal of a spinning solvent, and finishing, wherein:
A) from 0.8 to 2% by weight of a polydimethylsiolxane with a viscosity of 50 to 300 cSt, and B) from 0.2 to 0.6% by weight of an ethoxylated polydimethylsiloxane with a viscosity of 20 to 150 cSt, viscosities being measured with a falling ball viscosimeter at 25°C, are added to the spinning solution before spinning, the percentages being based on the siloxane content of the final fiber.
A) from 0.8 to 2% by weight of a polydimethylsiolxane with a viscosity of 50 to 300 cSt, and B) from 0.2 to 0.6% by weight of an ethoxylated polydimethylsiloxane with a viscosity of 20 to 150 cSt, viscosities being measured with a falling ball viscosimeter at 25°C, are added to the spinning solution before spinning, the percentages being based on the siloxane content of the final fiber.
2. A process as claimed in claim 1, wherein the elastane fibers are produced by dry spinning.
3. A process as claimed in claims 1 or 2, wherein the ratio by weight of polydimethylsiloxane to ethoxylated polydimethylsiloxane in the final fiber is 1:1 to 5:1.
4. A process as claimed in any one of claims 1 to 3, wherein the number average molecular weight of the ethoxylated polydimethylsiolxane is 600 to 4,000.
5. A process as claimed in any one of claims 1 to 4, wherein the ethoxylated polydimethylsiloxane corresponds to general formula (I):
wherein PE is a single-bond unit CH2CH2-CH2O(Eo)m Z, where Z
is hydrogen or a C1-6 alkyl radical, Eo is an ethylene oxide unit, and x, y and m independently of one another are integers of or greater than 1.
wherein PE is a single-bond unit CH2CH2-CH2O(Eo)m Z, where Z
is hydrogen or a C1-6 alkyl radical, Eo is an ethylene oxide unit, and x, y and m independently of one another are integers of or greater than 1.
6. A process as claimed in claim 5, wherein x, y and m are selected so that the molecular weight of the ethoxylated polydimethylsiloxane of general formula (I) does not exceed 4,000.
7. A process as claimed in any one of claims 1 to 6, wherein the polydimethylsiloxanes A) and B) are added in the form of a 15 to 22% by weight stock solution in tree spinning solvent, based on the percentage contends of A) +B) in the spinning solution.
8. A process as claimed in any one of claims 1 to 7, wherein the spun filaments have are individual denier of 10 to 160 dtex.
9. A process as claimed in any one of claims 1 to 8, wherein the spun fibers are multifilament fibers with 3 to 5 capillaries and have an overall denier 30 to 60 dtex.
10. A process as claimed in any one of claims 1 to 9, wherein after the finishing step, the fibers are twisted and wound.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4330725A DE4330725A1 (en) | 1993-09-10 | 1993-09-10 | Process for the production of elastane fibers by spinning a combination of PDMS and ethoxylated PDMS |
| DEP4330725.6 | 1993-09-10 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2131581A1 CA2131581A1 (en) | 1995-03-11 |
| CA2131581C true CA2131581C (en) | 2004-07-06 |
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ID=6497381
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002131581A Expired - Fee Related CA2131581C (en) | 1993-09-10 | 1994-09-07 | Process for the production of elastane fibers by inclusion of a combination of pdms and ethoxylated pdms in the spinning solution |
Country Status (5)
| Country | Link |
|---|---|
| US (2) | US6123885A (en) |
| EP (1) | EP0643159B1 (en) |
| JP (1) | JP3507907B2 (en) |
| CA (1) | CA2131581C (en) |
| DE (2) | DE4330725A1 (en) |
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| DE19805153A1 (en) * | 1998-02-09 | 1999-08-12 | Bayer Ag | Biodegradable coating agents |
| DE19829164A1 (en) * | 1998-06-30 | 2000-03-30 | Bayer Faser Gmbh | Elastane threads and process for their manufacture |
| DE10258587A1 (en) * | 2002-12-16 | 2004-06-24 | Bayer Faser Gmbh | Process for the production of polyurethane urea fibers by spinning a combination of polydimethylsiloxane, alkoxylated polydimethylsiloxane and fatty acid salt |
| JP4595775B2 (en) * | 2005-10-05 | 2010-12-08 | 東レ・オペロンテックス株式会社 | Polyurethane elastic fiber and method for producing the same |
| JP4575266B2 (en) * | 2005-10-05 | 2010-11-04 | 東レ・オペロンテックス株式会社 | Modifier for elastic fiber production |
| US20070174972A1 (en) * | 2005-11-14 | 2007-08-02 | Invista North America S.A R.I. | Spandex having enhanced whiteness, and fabrics and garments comprising the same |
| DE102007016291A1 (en) | 2007-04-04 | 2008-10-09 | Wacker Chemie Ag | Organopolysiloxane-containing fiber |
| JP4834858B2 (en) * | 2007-12-13 | 2011-12-14 | 東レ・オペロンテックス株式会社 | Polyurethane yarn and method for producing the same |
| JP6931040B2 (en) * | 2016-07-29 | 2021-09-01 | エイアンドエイティー ユーケー リミテッド | Removal of silicone oil from spandex spinning solution |
| JP7162195B1 (en) * | 2022-02-25 | 2022-10-28 | 東レ・オペロンテックス株式会社 | polyurethane elastic fiber |
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| US4296174A (en) * | 1980-08-08 | 1981-10-20 | E. I. Du Pont De Nemours And Company | Spandex filaments containing certain metallic soaps |
| DE3239900A1 (en) * | 1982-10-28 | 1984-05-03 | Bayer Ag, 5090 Leverkusen | LEVELING POLYURETHANE HIGH SOLID REACTIVE COATING SYSTEMS AND THEIR USE FOR REACTIVE COATING |
| DE3338663C1 (en) * | 1983-10-25 | 1985-05-23 | Th. Goldschmidt Ag, 4300 Essen | Organosilicon compounds and textile fiber preparations containing them |
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| US5045387A (en) * | 1989-07-28 | 1991-09-03 | Hercules Incorporated | Rewettable polyolefin fiber and corresponding nonwovens |
| US4999120A (en) * | 1990-02-26 | 1991-03-12 | E. I. Du Pont De Nemours And Company | Aqueous emulsion finish for spandex fiber treatment comprising a polydimethyl siloxane and an ethoxylated long-chained alkanol |
| DE4222772A1 (en) * | 1992-07-10 | 1994-01-13 | Bayer Ag | Process for the preparation of viscosity-stable, gel-poor highly concentrated elastane spinning solutions |
| US5288516A (en) * | 1993-02-11 | 1994-02-22 | E. I. Du Pont De Nemours And Company | Process of producing bioabsorbable filaments |
| US5723080A (en) * | 1995-07-27 | 1998-03-03 | Bayer Faser Gmbh | Process for producing splittable elastane yarns |
-
1993
- 1993-09-10 DE DE4330725A patent/DE4330725A1/en not_active Withdrawn
-
1994
- 1994-08-29 EP EP94113440A patent/EP0643159B1/en not_active Expired - Lifetime
- 1994-08-29 DE DE59407269T patent/DE59407269D1/en not_active Expired - Fee Related
- 1994-09-02 US US08/300,669 patent/US6123885A/en not_active Expired - Fee Related
- 1994-09-07 CA CA002131581A patent/CA2131581C/en not_active Expired - Fee Related
- 1994-09-08 JP JP23964794A patent/JP3507907B2/en not_active Expired - Fee Related
-
2000
- 2000-06-30 US US09/608,866 patent/US6284371B1/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07150416A (en) | 1995-06-13 |
| EP0643159A1 (en) | 1995-03-15 |
| DE59407269D1 (en) | 1998-12-17 |
| CA2131581A1 (en) | 1995-03-11 |
| DE4330725A1 (en) | 1995-03-16 |
| US6123885A (en) | 2000-09-26 |
| US6284371B1 (en) | 2001-09-04 |
| JP3507907B2 (en) | 2004-03-15 |
| EP0643159B1 (en) | 1998-11-11 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKLA | Lapsed |