CA2114281A1 - Non-tacky, highly elastic polyurethane elastomer monofilaments and multifilaments, process for their production, their use, and partially crosslinked thermoplastic polyurethanes for this purpose - Google Patents
Non-tacky, highly elastic polyurethane elastomer monofilaments and multifilaments, process for their production, their use, and partially crosslinked thermoplastic polyurethanes for this purposeInfo
- Publication number
- CA2114281A1 CA2114281A1 CA002114281A CA2114281A CA2114281A1 CA 2114281 A1 CA2114281 A1 CA 2114281A1 CA 002114281 A CA002114281 A CA 002114281A CA 2114281 A CA2114281 A CA 2114281A CA 2114281 A1 CA2114281 A1 CA 2114281A1
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- Canada
- Prior art keywords
- tacky
- molecular weight
- polyoxybutylene
- highly elastic
- multifilament
- Prior art date
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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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/6505—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6511—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38 compounds of group C08G18/3203
- C08G18/6517—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38 compounds of group C08G18/3203 having at least three hydroxy groups
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
- Artificial Filaments (AREA)
Abstract
The present invention relates to non-tacky, highly elastic polyurethane elastomer monofilaments and multifilaments, which are produced by spinning a melt of a partially crosslinked thermoplastic polyurethane, obtainable by reacting a) at least one organic diisocyanate with b) at least one dihydroxyl compound having a molecular weight of from 500 to 4,000, c) at least one difunctional hydroxyl-containing chain extender having a molecular weight of from 62 to 380, and d) at least one trifunctional hydroxyl-containing crosslinking agent, to a process for their production, to their use for the production of fibers andtextile sheet-like structures, and to the partially crosslinked, thermoplastic polyurethanes which can be used for this purpose.
Description
~A21 14281 Non-tackv,highly elastic Polyurethane elastomer monofilaments and multifilaments, process for their production, their use, and partiallv crosslinked thermoPlastic Polyurethanes for this Purpose The present invention relates to non-tacky, highly elastic polyurethane elastomer monofilaments and multifilaments, abbreviated to PU filaments below, which are produced by spinning a melt of a partially crosslinked thermoplastic polyurethane, abbreviated to TPU below, obtainable by reacting a) at least one organic diisocyanate with 10 b) at least one dihydroxyl compound having a molecular weight of from 500 to 4,000, c) at least one difunctional hydroxyl-containing chain extender having a molecular weight of from 62 to 380, and d) at least one at least trifunctional hydroxyl-containing crosslinking agent, to a process for their production by melt spinning, to their use for the production of fibers and textile sheet-like structures, and to the partially crosslinked, thermoplastic polyurethanes which can be used for this purpose.
It is known to produce PU filaments from PU elastomers based on organic diisocyanates, high-molecular-weight dihyroxyl compounds and low-molecular-weight chain extenders, for example alkanediols and/or diamines.
The elastomeric behavior of these polyurethanes is based on the entropy elasticity caused by the segment or block structure, ie by a certain arrangementof the hard and soft phases. The elastomeric behavior is affected by the starting materials used, the synthetic method, the spinning process and the aftertreatment.
Since urea structures formed from diamines do not melt without decomposing, spinning of these PU elastomers by melt spinning, which is economical and environmentally ~A 2 1 1 ~28 1 friendly, is impossible. The filament formation takes place, for example in the case of wet spinning, by coagulation of the dissolved polyurethane in non-dissolving, usually aqueous precipitation baths and in the case of reactive spinning, by carrying out the chain extension of an NCO prepolymer with a diamine and the filament formation simultaneously in the spinning bath.
Although PU elastomers containing no urea structures and based on relatively high- and low-molecular-weight dihydroxyl compounds can be melt-spun, they have, however, inadequate heat distortion resistance, which has a disadvantageous effect on the spinning, for example due to their high tack, and on textile processing, for example thermofixing, dyeing, washing and ironing.
Melt extrusion, the most economical spinning technique, is therefore unsuitable for TPUs (Kunststoff-Handbuch, Volume 7, Polyurethane, 2nd Edition, 1983, pages 611 to 627, edited by Dr. G. Oertel, Carl Hanser-Verlag, Munich, Vienna) .
In order to prevent tackiness, a special quenching process for the spun filaments, the use of abhesives and the use of tris(2-hydroxyethyl) isocyanurateduring spinning have, for example, been proposed. However, these measures have also been unable to solve the problem satisfactorily.
According to DE-A-22 04 470 (CA-A-999,394), polyimide groups have been incorporated into the polyurethane chain or polyimides have subsequently been introduced into the polyurethane melt in order to reduce the tack of extruded continuous PU filaments. However, the PU filaments produced using the resultant polyurethane compositions must be wound up very slowly and stretched in a second operation, which means that the productivity is unsatisfactory and the process is uneconomic. A further disadvantage is that the addition of additives reduces the molecular weight of the polymer, and thus reduces the melt viscosity, which in turn has an (~A 2 1 1 428 1 adverse effect on the elastic properties, the elongation at break and the strength of the resultant yarn.
DE-A-19 44 507 (GB-A-1,245,311) discloses a multistep process which reduces the tack of PU filaments during melt spinning. The first step involves 5 melt extrusion and solidification of the resultant filaments by quenching, andin the second step the filaments are drawn by at least 30 % and, in a further step, relaxed by at least 50 % before winding up. The process sequence suggests that the PU filaments are already in finished, fully cooled form on thetake-off godet. These filaments display the typical properties of a PU
10 elastomer, ie they can no longer be drawn in the true sense, but, due to their high elasticity, can be stretched greatly, but reversibly.
According to W0 88/04703, the tack of PU filaments to one another and of the fibrils to one another can be prevented and a high-modulus filament with better processing properties produced if the polyurethane and the stretching 15 conditions are selected so that irreversible stretching takes place, the relaxation is omitted, and the take-off rate is additionally increased. This process can beused to TPUs having a softening point of from 180 to 230C, a Shere A
hardness of from 80 to 95 and a density of from 1.1 to 1.25 g/cm2; the hardness of the TPU is particularly important for the tack of the PU filament.
20 This method has the disadvantage of low elasticity of the resultant PU filament and the complex spinning process.
According to DE-A-3 911 725, non-tacky PU filaments which can be produced by melt spinning can be obtained from plasticiser-containing TPU.
The only disadvantage of these PU filaments, which have high tear strength, 25 low plastic deformation and high elastic recovery, is their tendancy to exudethe plasticiser under certain reaction conditions during further processing.
Thermoplastic PU elastomers which can be converted into elastomer fibers by, inter alia, melt spinning can furthermore, according to DE-A-32 33 384 (US-A-4,442,281), be prepared by the polyaddition of essentially pure transcyclohexane 1,4-diisocyanate, diols having a molecular weight of from 800 to 4,000 and bisethoxylated bisphenol A, or mixtures of bisethoxylated bisphenol A and other short-chained diols as chain extenders.
This TPU has the disadvantages of relatively difficult and therefore expensive preparation of the starting component trans-cyclohexane 1 ,4-diisocyanate and the relatively low heat distortion resistance of the TPU, which makes textile aftertreatments of the fibers, for example dyeing, thermofixing, inter alia, at elevated temperature more difficult or even impossible.
It is an object of the present invention to overcome all or at least some of the abovementioned disadvantages and to provide a simplified, improved process for the production of non-tacky,highly elastic PU monofilaments and multifilaments by melt spinning of TPU. A TPU which can be used for this purpose should have high heat distortion resistance and high hydrolysis resistance, should be melt-spinnable, and should be based on industrially readily accessible and therefore inexpensive starting materials. The filaments produced from this TPU should be non-tacky and highly elastic and should be distinguished by good textile processing properties.
We have found that, surprisingly, this object is achieved by using a specific partially crosslinked TPU.
The present invention accordingly provides non-tacky, highly elastic polyurethane elastomer monofilaments and multifilaments, produced by spinning a melt of a partially crosslinked TPU obtainable by reacting a) at least one organic, preferably aromatic, diisocyanate with b) at least one dihydroxyl compound having a molecular weight of from 500 to 4,000.
~A21 1 ~281 c) at least one difunctional hydroxyl-containing chain extender having a molecular weight of from 62 to 380, and d) at least one at least trifunctional hydroxyl-containing crosslinking agent.
The present invention furthermore provides a process for the production of non-tacky, highly elastic PU monofilaments and multifilaments by melt-spinning the partially crosslinked TPU as claimed in claim 11, the partially crosslinked TPUs, which are preferably prepared by the one-shot process, as claimed in claim 15, and the use of non-tacky, highly elastic PU monofilaments and multifilaments according to the invention for the production of textile fibers, textile sheet-like structures and industrial fibers as claimed in claim 14.
The addition of at least trif unctional, preferably trif unctional hydroxyl-containing crosslinking agents allows the heat distortion resistance of the TPU to be increased without any adverse effect on the spinning properties of the TPU
melt. The use of, preferably, polyoxyalkylene glycols and polyether polycarbonate diols asthe relatively high-molecular-weight dihydroxyl compound(s) (b) guarantees high hydrolysis resistance of the PU filaments. It was furthermore surprising that the PU filaments produced can be wound up without sticking, are highly elastic and have good textile processing properties.
The following details apply to the preparation of the TPUs which can be used according to the invention, to the starting components therefor, and to the production of the non-tacky, highly elastic PU monofilaments and multifilaments:a) The organic diisocyanates (a) used are, for example, aliphatic, cycloaliphatic and preferably aromatic diisocyanates. Specific examples which may be mentioned are: aliphatic diisocyanates having up to a maximum of 12 carbon atoms in the alkylene radical, ~A21 14281 for example hexamethylene diisocyanate, cycloaliphatic diisocyanates, for example isophorone diisocyanate, 1-methyl-2,4- and 2,6-cyclohexane diisocyanate and the corresponding isomer mixtures, 4,4'-, 2,4'- and 2,2'-dicyclohexylmethane diisocyanate and the corresponding isomer mixtures, and preferably aromatic diisocyanates, for example 2,4-tolylene diisocyanate, mixtures of 2,4- and 2,6- tolylene diisocyanate, 4,4'-, 2,4'-and 2,2'- diphenylmethane diisocyanate, mixtures of 2,4'- and 4,4'-diphenylmethane diisocyanate and 4,4'-diisocyanate-1,2-diphenylethane.
Preference is given to 1,6-hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate isomer mixtures having a 4,4'-diphenylmethane diisocyanate content of greater than 96 % by weight, and in particular 4,4'-diphenylmethane diisocyanate.
b) The dihydroxyl compounds (b) having a molecular weight of from 500 to 4,000, preferably from 600 to 3,000, in particular from 800 to 2,200, are preferably polyether polycarbonate diols and polyoxyalkylene glycols, expediently those selected from the group consisting of polyoxybutylene glycols, polyoxybutylene-polyoxyethylene glycols, polyoxybutylene-polyoxypropylene glycols and polyoxybutylene-polyoxypropylene-polyoxyethylene glycols. Particular preference is given to polyoxybutylene glycols. Suitable polyether polycarbonate diols are described, for example, in US-A-5,137,935 (DE-A-40 04 882), which is incorporated into this patent description by way of reference. Preferred polyether polycarbonate diols are polyoxybutylene polycarbonate diols. However, other suitable dihydroxyl compounds are hydroxyl-containing polymers, for example polyacetals, such as polyoxymethylenes, and in particular water-insoluble formals, for example polybutanediol formal and polyhexanediol ~A21 14281 formal, and polycarbonates, in particular those made from diphenyl carbonate and 1,6-hexanediol or 1,4-butanediol, or mixtures thereof, prepared by esterification. The dihydroxyl compounds mentioned by way of example can be used as individual components or in the form of mixtures of at least two dihydroxyl compounds.
c) The difunctional hydroxyl-containing chain extenders having a molecular weight from 62 to 380, preferably from 62 to 210, are preferably alkanediols having 2 to 12 carbon atoms, preferably 4 and/or 6 carbon atoms, for example ethanediol, 1,3-propanediol, 1,4-butanediol, 1,5-1 0 pentanediol, 1 ,6-hexanediol, 1 ,7-heptanediol, 1 ,8-octanediol, 1 ,10-decanediol and 1,1 2-dodecanediol, and dialkylene glycols, for example diethylene glycol, dipropylene glycol and dibutylene glycol.
However, other suitable chain extenders are, for example, diesters of terephthalic acid with glycols having 2 to 4 carbon atoms, for example bisethylene 1 5 glycol terephthalate or bis- 1 ,4-buta nediol terephthalate, and hydroxyal kylene ethers of hydroquinone, for example 1,4-i(,B-hydroxyethyl)hydroquinone.
Chain extenders which have proven highly successful and are therefore preferred are 1,6-hexanediol and in particular 1 ,4-butanediol, or mixtures of 1,6-hexanediol and 1,4-butanediol.
d) The essential prerequisite for the preparation of the partially crosslinkedTPUs which can be used according to the invention is the use of at least one, at least trifunctional, preferably trifunctional to octafunctional, in particular trifunctional, hydroxyl-containing crosslinking agent (d).
Crosslinking agents of this type advantageously have a molecular weight of from 90 to 400, preferably from 90 to 138. Specific examples of suitable crosslinking agents are: glycerol, trimethylolpropane, ~A2 I 1 4281 glycerol which has been alkoxylated with up to 3 mol of alkylene oxide, for example ethylene oxide, and/or trimethylopropane, pentaerythritol, sorbitol and sucrose, particular preference being given to glycerol or trimethylolpropane or mixtures of glycerol and trimethylolpropane.
In order to adjust the hardness of melting point of the TPU, the starting components (b) to (d) can be varied in relatively broad molar ratios.
Success has been achieved, for example, using molar dihydroxyl compound (b):
chain extender (c) ratios of from 1:0.5 to 1:20, preferably from 1:1 to 1:10, inparticular from 1:1 to 1:5, and addition of crosslinking agent (d) in an amount of from 0.01 to 10 mol %, preferably from 0.2 to 5 mol %, in particular from 0.3 to3.5 mol %, based on the molecular weight of the dihydroxyl compounds (b).
In order to prepare the TPUs which can be used according to the invention, the starting components (a) to (d) are advantageously reacted in suchamounts that the ratio between the number of equivalents of NC0 groups of the diisocyanates (a) and the total number of hydroxyl compounds (b) to (d) is from 0.9 to 1.1:1, preferably from 0.95 to 1.05:1, in particular from 0.98 to 1.03:1.The polyhydroxyl compounds (b) to (d) are advantageously reacted with the diisocyanate in the form of a mixture.
a) The TPUs which can be used according to the invention are preferably prepared in the absence of catalysts (a). However, it may be expedient, depending on the type of starting components (a) to (d) used and in particular on their reactivity, to accelerate the reaction between the NC0 groups of the diisocyanate (a) and the hydroxyl groups of the starting components (b) to (d) by using catalysts. Examples of suitable catalysts are the tertiary amines known from the prior art, for example triethylamine, N,N-dimethylcyclohexylamine, N-methylmorpholine, N,N'-dimethyl- and -diethylpiperizine, (~A21 14281 tris (dimethylaminoethyl)-(s)-triazine, pentamethyl-diethylenetriamine, N,N,N',N'-tetramethylbutylenediamine, N,N,N',N'-tetramethyl-4,4'-diaminodicyclohexylmethane, 2-(dimethylaminoethoxy)ethanol and diazabicyclo[2. 2. 2.]octane, and in particular organo-metallic compounds, for example titanic esters, iron compounds, tin compounds, for example tin diacetate, tin dioctanoate, tin dilaurate or the dialkyltin salts of aliphatic carboxylic acid, for example dibutyltin diacetate, and dibutyltin dilaurate, and mixtures of tertiary amines and organometallic compounds. The catalysts are usually employed in amounts of from 0.001 to 0.1 parts by weight per 100 parts by weight of the polyhydroxyl compounds (b) to (d).
f) In addition to catalysts, auxiliaries and/or additives (f) can, if desired, be incorporated into the starting components. Examples which may be mentioned are lubricants, inhibitors, hydrolysis, light, heat and discoloration stabilizers, for example caused by chlorine attack, flameproofing agents, 1 5 dyes and pigments.
Further details on the above auxiliaries and additives (f) are given in the specialist literature, for example the monograph by J.H. Saunders and K.C.
Frisch, "High Polymers", Volume XVI, Polyurethane, Parts 1 and 2, Interscience Publishers, 1 962 and 1 964 respectively, and DE-A 29 01 774.
The partially crosslinked TPUs which can be used according to the invention are preferably prepared by the one-shot process. The TPUs can be obtained by the extruder or preferably by the belt method by batchwise or continuous mixing of the starting components (a) to (d) and, if used, (e) and/or (f), allowing the reaction mixture to react to completion in the extruder or on a support belt at from 40 to 230C, preferably at 70 to 1 80C, and subsequently granulating the resultant TPUs.
~A 2 1 1 428 1 In the belt method, which is preferred, the starting components (a) to (d) and, if used, (e) and/or (f) are mixed continuously at above the melting point of the starting components (a) to (d) with the aid of a mixer head. The reactionmixture is applied to a support, preferably a conveyor belt, for example made ofmetal, and passed through a temperature-controlled zone with a length of from 1 to 20 meters, preferably from 3 to 10 meters, at a rate of from 1 to 20 m/min, preferably from 4 to 10 m/min. The reaction temperature in this zone is from 60 to 300C, preferably from 100 to 1 80C. The partially crosslinked TPUs obtainedcan be granulated after cooling and stored if desired.
The non-tacky, highly elastic PU monofilaments and multifilaments according to the invention can be produced by the melt spinning process, which is known per se. Particularly suitable for the production, and therefore preferred, are extruder melt-spinning units, which can optionally, in addition to the air cooling usually used, for example by means of a cooling air shaft, be fitted with a water-cooling device for cooling the freshly spun PU filaments.
In a preferred variant of the process for the production of the PU
filaments according to the invention, the TPUs which are suitable according to the invention are melted in a extruder at from 150 to 250C, preferably at from 170 to 230C, depending on the partially crosslinked TPU employed in each case, the melt is shaped to give filaments with the aid of a gear spinning pump and a single-hole or multi-hole spinneret with melt filtration, and the resultant filaments are cooled by water or air, depending on the take-off rate used, and wound up on conventional reeling units.
The reeling up of the PU filaments produced according to the invention is advantageously carried out with additional application of a spin finish based on, for example, silicone or silicic acid dispersions, which (~A21 14281 additionally improve the reeling and winding up, which are essentially already tack-free, of the spinning reel and the further processing of the PU monofilaments and multifilaments.
Spin finishes of this type of known commercial products. Suitable spin finishes based on polysiloxane elastomers or mixtures of polysiloxanes and a silicon compound, for example, are commercially available from BASF
Aktiengesellschaft under the tradenames Siligen SIP, Siligen NSI, and Silign LSI, and one based on silicates under the tradename Siligen E.
The melt spinning can be carried out using dies of conventional capillary geometry. However, it is advantageous for melt spinning to use dies having a special capillary geometry, expediently those having a length of from 1 D
to 5D and a capillary diameter of from 0.05 to 2 mm, capillary diameters of from0.1 to 0.5 mm being particularly preferred in the case of multifilaments and capillary diameters of from 0.5 to 2 mm being particularly preferred in the case of monofilaments, since these measures additionally permanently improve the mechanical properties of the PU filaments according to the invention, and in particular PU filaments having very good elastic recovery and elongation at break can be obtained.
The PU filaments according to the invention or produced by the process according to the invention do not stick to one another, and in the case of multifilaments the individual capillaries do not stick to one another, and have a high tear strength with an elongation at break, measured in accordance with DIN 53 815, of greater than 300 %, preferably from 320 to 800 %, and low plastic deformation and high elastic recovery (measured in accordance with DIN 53 835).
The elongation ratio, defined as the quotient of the elastic elongation EB and the total elongation EW8~ measured in accordance with DIN 53 835, is greater than 0.8, preferably from 0.85 to 0.95.
(~A21 14281 The textile properties of the PU filaments according to the invention can, if desired, be further improved with respect to their elastic recovery, tear strength and elongation at break by thermal aftertreatment, for example by conditioning at from 50 to 170C, preferably at from 75 to 130C, in air or in awater-vapor atmosphere or, for example, by hot post-drawing, for example at a filament tension of, expediently, from 0.05 to 0.2 cN/dtex.
The high heat distortion resistance of the TPUs which can be used according to the invention and the non-tacky winding up and unwinding from the spinning reel mean that the PU filaments according to the invention can advantageously be subjected to textile conversion, for example dyeing and thermof ixing .
The non-tacky, highly elastic PU monofilaments and multifilaments according to the invention are used for the production of industrial fibers and textile fibers and sheet-like structures made from industrial fibers and textile fibers.
EXAMPLES
The TPU preparation is carried out by the one-shot process.
To this end, a mixture of 1,500 9 (1.49 mol) of polyoxybutylene glycol and 1.25 9 (0.009 mol) of trimethylolpropane was degassed for 1 hour at 110C and 5 mbar. 187.5 9 (2.08 mol) of 1,4-butanediol were stirred into the mixture, the resultant clear solution was warmed to 70C, and 909.3 9 (3.63 mol)of 4,4'-diphenylmethane diisocyanate at 65C were then added with vigorous stirring (1,000 revolutions/minute).
When a reaction temperature of 120C had been reached, the homogeneous reaction mixture was poured onto a hotplate measuring 550 x 380 mm held at 125 C and covered with teflon-treated glass fiber fabric.
After a reaction time of approximately 2 minutes, the hot TPU obtained was coarsely comminuted and conditioned at 100C for 15 hours in a drying cabinet. After cooling to room temperature, TPU granules having a particle size in the range from 4 to 6 mm were produced with the aid of a cutting mill and were stored in the interim or immediately spun by melt spinning.
Production of PU multifilaments The TPU prepared as described in Example 1 was spun using an extruder spinning unit which had the following technical data:
Extruder screw diameter: 25 mm, Extruder screw length: 25 D, Spinneret: 30 hole/0.3 mm capillary diameter and 0.6 mm capillary length and Throughput: 1.2 kg/h, at a melt temperature of 220C and a spinning rate of 450 m/min, with application of a polysiloxane-based spin finish (Siligen MBI from BASF Aktiengesellschaft) and with air cooling of the freshly spun PU filaments.
The PU filaments, which can be wound up without sticking, were subsequently treated for 10 minutes with air at 100C.
The PU filaments obtained in this way had the mechanical properties shown in Table ll.
The procedure was similar to that of Example 1, but the starting components and amounts shown in Table I were used, with the abbreviations as follows:
MDI: 4,4'-diphenylmethane diisocyanate BuOH: 1,4-butanediol TMP: Trimethylolpropane TMP-EO: Product of the reaction of 1 mol of ethylene oxide and 1 mol of TMP (tradename Lupranol 3900, MW:
178246) PTHF 1000 (1): Polyoxytetramethyleneglycol, molecular weight: 1010 PTHP 1000 (2): Polyoxytetramethyleneglycol, molecular ~ A 2 1 1 428 1 weight: 1003 PTHF 1000 (3): Polyoxytetramethylene glycol, molecular weight: 993 PTHF-CD 1 250: Polyoxybutylenepolycarbonate diol, molecular weight:
PTHF-CD 2000: Polyoxybutylenepolycarbonate diol, molecular weight:
The PU filaments obtained had the mechanical properties shown in Table ll.
TABLE I
TPU prepared by the one-shot process Example Diisocyanate Dihydroxyl Compound Chain extender Crosslinking agent TypeAmount Type Amount TypeAmount TypeAmount MDI909.3 gPTHF 1000 (1) 1500 9 BuOH187.5 9 TMP1.25 9 (3.63 mol) (1.49 mol) (2.08 mol) (0.009 mol) 2 MDI917.9 9PTHF 1000 (2) 1500 9 BuOH187.5 9Glycerol 2.25 9 (3.67 mol) (1.50 mol) (2.08 mol)(0.024 mol) 3 MDI918.2 9PTHF 1000 (1) 1500 g BuOH187.5 9Glycerol 3.00 g (3.67 mol) (1.49 mol) (2.08 mol)(0.033 mol) 4 MDI718.9 9PTHF-CD 2000 (1)1500 9 BuOH187.5 g TMP1.50 9 (2.87 mol) (0.73 mol) (2.08 mol) (0.011 mol) MDI834.4 gPTHF-CD 1250 1500 9 BuOH187.5 9 TMP2.5 9 (3.33 mol) (1.18 mol) (2.08 mol) (0.019 mol) 6 MDI916.4 9PTHF 1000 (3) 1500 9 BuOH187.5 9TMP-H0 2.00 9(3.66 mol) (1.51 mol) (2.08 mol)(0.011 mol) Comparative MDI905.8 9PTHF 1000 (1) 1500 9 BuOH187.5 9 Example (3.62 mol) (1.49 mol) (2.08 mol) TABLE ll Mechanical properties of PU filaments produced by melt spinning of the TPUs fromExamples 1 to 6 and the comparative example PU Filament Linear Tear strengthElongation at break Elastic recovery Tack from Example density in accordancein accordance in accordance temperature with DIN 53with DIN 53 815 with DIN 53 835 [C]
600/30 dtex 1.0 cN/dtex 500 % 0.90 170 2 483/30 dtex 0.8 cN/dtex 568 % 0.87 170 3 637/30 dtex 0.75 cN/dtex 338 % 0.84 170 4 492/30 dtex 0.9 cN/dtex 465 % 0.9 170 532/30 dtex 0.9 cN/dtex 465 % 0.89 170 6-6 557/30 dtex 0.8 cN/dtex 419 % 0.85 165 Comparative 470/30 dtex 0.8 cN/dtex 440 % 0.75 160 Example Stretching ratio r~
r~
~o
It is known to produce PU filaments from PU elastomers based on organic diisocyanates, high-molecular-weight dihyroxyl compounds and low-molecular-weight chain extenders, for example alkanediols and/or diamines.
The elastomeric behavior of these polyurethanes is based on the entropy elasticity caused by the segment or block structure, ie by a certain arrangementof the hard and soft phases. The elastomeric behavior is affected by the starting materials used, the synthetic method, the spinning process and the aftertreatment.
Since urea structures formed from diamines do not melt without decomposing, spinning of these PU elastomers by melt spinning, which is economical and environmentally ~A 2 1 1 ~28 1 friendly, is impossible. The filament formation takes place, for example in the case of wet spinning, by coagulation of the dissolved polyurethane in non-dissolving, usually aqueous precipitation baths and in the case of reactive spinning, by carrying out the chain extension of an NCO prepolymer with a diamine and the filament formation simultaneously in the spinning bath.
Although PU elastomers containing no urea structures and based on relatively high- and low-molecular-weight dihydroxyl compounds can be melt-spun, they have, however, inadequate heat distortion resistance, which has a disadvantageous effect on the spinning, for example due to their high tack, and on textile processing, for example thermofixing, dyeing, washing and ironing.
Melt extrusion, the most economical spinning technique, is therefore unsuitable for TPUs (Kunststoff-Handbuch, Volume 7, Polyurethane, 2nd Edition, 1983, pages 611 to 627, edited by Dr. G. Oertel, Carl Hanser-Verlag, Munich, Vienna) .
In order to prevent tackiness, a special quenching process for the spun filaments, the use of abhesives and the use of tris(2-hydroxyethyl) isocyanurateduring spinning have, for example, been proposed. However, these measures have also been unable to solve the problem satisfactorily.
According to DE-A-22 04 470 (CA-A-999,394), polyimide groups have been incorporated into the polyurethane chain or polyimides have subsequently been introduced into the polyurethane melt in order to reduce the tack of extruded continuous PU filaments. However, the PU filaments produced using the resultant polyurethane compositions must be wound up very slowly and stretched in a second operation, which means that the productivity is unsatisfactory and the process is uneconomic. A further disadvantage is that the addition of additives reduces the molecular weight of the polymer, and thus reduces the melt viscosity, which in turn has an (~A 2 1 1 428 1 adverse effect on the elastic properties, the elongation at break and the strength of the resultant yarn.
DE-A-19 44 507 (GB-A-1,245,311) discloses a multistep process which reduces the tack of PU filaments during melt spinning. The first step involves 5 melt extrusion and solidification of the resultant filaments by quenching, andin the second step the filaments are drawn by at least 30 % and, in a further step, relaxed by at least 50 % before winding up. The process sequence suggests that the PU filaments are already in finished, fully cooled form on thetake-off godet. These filaments display the typical properties of a PU
10 elastomer, ie they can no longer be drawn in the true sense, but, due to their high elasticity, can be stretched greatly, but reversibly.
According to W0 88/04703, the tack of PU filaments to one another and of the fibrils to one another can be prevented and a high-modulus filament with better processing properties produced if the polyurethane and the stretching 15 conditions are selected so that irreversible stretching takes place, the relaxation is omitted, and the take-off rate is additionally increased. This process can beused to TPUs having a softening point of from 180 to 230C, a Shere A
hardness of from 80 to 95 and a density of from 1.1 to 1.25 g/cm2; the hardness of the TPU is particularly important for the tack of the PU filament.
20 This method has the disadvantage of low elasticity of the resultant PU filament and the complex spinning process.
According to DE-A-3 911 725, non-tacky PU filaments which can be produced by melt spinning can be obtained from plasticiser-containing TPU.
The only disadvantage of these PU filaments, which have high tear strength, 25 low plastic deformation and high elastic recovery, is their tendancy to exudethe plasticiser under certain reaction conditions during further processing.
Thermoplastic PU elastomers which can be converted into elastomer fibers by, inter alia, melt spinning can furthermore, according to DE-A-32 33 384 (US-A-4,442,281), be prepared by the polyaddition of essentially pure transcyclohexane 1,4-diisocyanate, diols having a molecular weight of from 800 to 4,000 and bisethoxylated bisphenol A, or mixtures of bisethoxylated bisphenol A and other short-chained diols as chain extenders.
This TPU has the disadvantages of relatively difficult and therefore expensive preparation of the starting component trans-cyclohexane 1 ,4-diisocyanate and the relatively low heat distortion resistance of the TPU, which makes textile aftertreatments of the fibers, for example dyeing, thermofixing, inter alia, at elevated temperature more difficult or even impossible.
It is an object of the present invention to overcome all or at least some of the abovementioned disadvantages and to provide a simplified, improved process for the production of non-tacky,highly elastic PU monofilaments and multifilaments by melt spinning of TPU. A TPU which can be used for this purpose should have high heat distortion resistance and high hydrolysis resistance, should be melt-spinnable, and should be based on industrially readily accessible and therefore inexpensive starting materials. The filaments produced from this TPU should be non-tacky and highly elastic and should be distinguished by good textile processing properties.
We have found that, surprisingly, this object is achieved by using a specific partially crosslinked TPU.
The present invention accordingly provides non-tacky, highly elastic polyurethane elastomer monofilaments and multifilaments, produced by spinning a melt of a partially crosslinked TPU obtainable by reacting a) at least one organic, preferably aromatic, diisocyanate with b) at least one dihydroxyl compound having a molecular weight of from 500 to 4,000.
~A21 1 ~281 c) at least one difunctional hydroxyl-containing chain extender having a molecular weight of from 62 to 380, and d) at least one at least trifunctional hydroxyl-containing crosslinking agent.
The present invention furthermore provides a process for the production of non-tacky, highly elastic PU monofilaments and multifilaments by melt-spinning the partially crosslinked TPU as claimed in claim 11, the partially crosslinked TPUs, which are preferably prepared by the one-shot process, as claimed in claim 15, and the use of non-tacky, highly elastic PU monofilaments and multifilaments according to the invention for the production of textile fibers, textile sheet-like structures and industrial fibers as claimed in claim 14.
The addition of at least trif unctional, preferably trif unctional hydroxyl-containing crosslinking agents allows the heat distortion resistance of the TPU to be increased without any adverse effect on the spinning properties of the TPU
melt. The use of, preferably, polyoxyalkylene glycols and polyether polycarbonate diols asthe relatively high-molecular-weight dihydroxyl compound(s) (b) guarantees high hydrolysis resistance of the PU filaments. It was furthermore surprising that the PU filaments produced can be wound up without sticking, are highly elastic and have good textile processing properties.
The following details apply to the preparation of the TPUs which can be used according to the invention, to the starting components therefor, and to the production of the non-tacky, highly elastic PU monofilaments and multifilaments:a) The organic diisocyanates (a) used are, for example, aliphatic, cycloaliphatic and preferably aromatic diisocyanates. Specific examples which may be mentioned are: aliphatic diisocyanates having up to a maximum of 12 carbon atoms in the alkylene radical, ~A21 14281 for example hexamethylene diisocyanate, cycloaliphatic diisocyanates, for example isophorone diisocyanate, 1-methyl-2,4- and 2,6-cyclohexane diisocyanate and the corresponding isomer mixtures, 4,4'-, 2,4'- and 2,2'-dicyclohexylmethane diisocyanate and the corresponding isomer mixtures, and preferably aromatic diisocyanates, for example 2,4-tolylene diisocyanate, mixtures of 2,4- and 2,6- tolylene diisocyanate, 4,4'-, 2,4'-and 2,2'- diphenylmethane diisocyanate, mixtures of 2,4'- and 4,4'-diphenylmethane diisocyanate and 4,4'-diisocyanate-1,2-diphenylethane.
Preference is given to 1,6-hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate isomer mixtures having a 4,4'-diphenylmethane diisocyanate content of greater than 96 % by weight, and in particular 4,4'-diphenylmethane diisocyanate.
b) The dihydroxyl compounds (b) having a molecular weight of from 500 to 4,000, preferably from 600 to 3,000, in particular from 800 to 2,200, are preferably polyether polycarbonate diols and polyoxyalkylene glycols, expediently those selected from the group consisting of polyoxybutylene glycols, polyoxybutylene-polyoxyethylene glycols, polyoxybutylene-polyoxypropylene glycols and polyoxybutylene-polyoxypropylene-polyoxyethylene glycols. Particular preference is given to polyoxybutylene glycols. Suitable polyether polycarbonate diols are described, for example, in US-A-5,137,935 (DE-A-40 04 882), which is incorporated into this patent description by way of reference. Preferred polyether polycarbonate diols are polyoxybutylene polycarbonate diols. However, other suitable dihydroxyl compounds are hydroxyl-containing polymers, for example polyacetals, such as polyoxymethylenes, and in particular water-insoluble formals, for example polybutanediol formal and polyhexanediol ~A21 14281 formal, and polycarbonates, in particular those made from diphenyl carbonate and 1,6-hexanediol or 1,4-butanediol, or mixtures thereof, prepared by esterification. The dihydroxyl compounds mentioned by way of example can be used as individual components or in the form of mixtures of at least two dihydroxyl compounds.
c) The difunctional hydroxyl-containing chain extenders having a molecular weight from 62 to 380, preferably from 62 to 210, are preferably alkanediols having 2 to 12 carbon atoms, preferably 4 and/or 6 carbon atoms, for example ethanediol, 1,3-propanediol, 1,4-butanediol, 1,5-1 0 pentanediol, 1 ,6-hexanediol, 1 ,7-heptanediol, 1 ,8-octanediol, 1 ,10-decanediol and 1,1 2-dodecanediol, and dialkylene glycols, for example diethylene glycol, dipropylene glycol and dibutylene glycol.
However, other suitable chain extenders are, for example, diesters of terephthalic acid with glycols having 2 to 4 carbon atoms, for example bisethylene 1 5 glycol terephthalate or bis- 1 ,4-buta nediol terephthalate, and hydroxyal kylene ethers of hydroquinone, for example 1,4-i(,B-hydroxyethyl)hydroquinone.
Chain extenders which have proven highly successful and are therefore preferred are 1,6-hexanediol and in particular 1 ,4-butanediol, or mixtures of 1,6-hexanediol and 1,4-butanediol.
d) The essential prerequisite for the preparation of the partially crosslinkedTPUs which can be used according to the invention is the use of at least one, at least trifunctional, preferably trifunctional to octafunctional, in particular trifunctional, hydroxyl-containing crosslinking agent (d).
Crosslinking agents of this type advantageously have a molecular weight of from 90 to 400, preferably from 90 to 138. Specific examples of suitable crosslinking agents are: glycerol, trimethylolpropane, ~A2 I 1 4281 glycerol which has been alkoxylated with up to 3 mol of alkylene oxide, for example ethylene oxide, and/or trimethylopropane, pentaerythritol, sorbitol and sucrose, particular preference being given to glycerol or trimethylolpropane or mixtures of glycerol and trimethylolpropane.
In order to adjust the hardness of melting point of the TPU, the starting components (b) to (d) can be varied in relatively broad molar ratios.
Success has been achieved, for example, using molar dihydroxyl compound (b):
chain extender (c) ratios of from 1:0.5 to 1:20, preferably from 1:1 to 1:10, inparticular from 1:1 to 1:5, and addition of crosslinking agent (d) in an amount of from 0.01 to 10 mol %, preferably from 0.2 to 5 mol %, in particular from 0.3 to3.5 mol %, based on the molecular weight of the dihydroxyl compounds (b).
In order to prepare the TPUs which can be used according to the invention, the starting components (a) to (d) are advantageously reacted in suchamounts that the ratio between the number of equivalents of NC0 groups of the diisocyanates (a) and the total number of hydroxyl compounds (b) to (d) is from 0.9 to 1.1:1, preferably from 0.95 to 1.05:1, in particular from 0.98 to 1.03:1.The polyhydroxyl compounds (b) to (d) are advantageously reacted with the diisocyanate in the form of a mixture.
a) The TPUs which can be used according to the invention are preferably prepared in the absence of catalysts (a). However, it may be expedient, depending on the type of starting components (a) to (d) used and in particular on their reactivity, to accelerate the reaction between the NC0 groups of the diisocyanate (a) and the hydroxyl groups of the starting components (b) to (d) by using catalysts. Examples of suitable catalysts are the tertiary amines known from the prior art, for example triethylamine, N,N-dimethylcyclohexylamine, N-methylmorpholine, N,N'-dimethyl- and -diethylpiperizine, (~A21 14281 tris (dimethylaminoethyl)-(s)-triazine, pentamethyl-diethylenetriamine, N,N,N',N'-tetramethylbutylenediamine, N,N,N',N'-tetramethyl-4,4'-diaminodicyclohexylmethane, 2-(dimethylaminoethoxy)ethanol and diazabicyclo[2. 2. 2.]octane, and in particular organo-metallic compounds, for example titanic esters, iron compounds, tin compounds, for example tin diacetate, tin dioctanoate, tin dilaurate or the dialkyltin salts of aliphatic carboxylic acid, for example dibutyltin diacetate, and dibutyltin dilaurate, and mixtures of tertiary amines and organometallic compounds. The catalysts are usually employed in amounts of from 0.001 to 0.1 parts by weight per 100 parts by weight of the polyhydroxyl compounds (b) to (d).
f) In addition to catalysts, auxiliaries and/or additives (f) can, if desired, be incorporated into the starting components. Examples which may be mentioned are lubricants, inhibitors, hydrolysis, light, heat and discoloration stabilizers, for example caused by chlorine attack, flameproofing agents, 1 5 dyes and pigments.
Further details on the above auxiliaries and additives (f) are given in the specialist literature, for example the monograph by J.H. Saunders and K.C.
Frisch, "High Polymers", Volume XVI, Polyurethane, Parts 1 and 2, Interscience Publishers, 1 962 and 1 964 respectively, and DE-A 29 01 774.
The partially crosslinked TPUs which can be used according to the invention are preferably prepared by the one-shot process. The TPUs can be obtained by the extruder or preferably by the belt method by batchwise or continuous mixing of the starting components (a) to (d) and, if used, (e) and/or (f), allowing the reaction mixture to react to completion in the extruder or on a support belt at from 40 to 230C, preferably at 70 to 1 80C, and subsequently granulating the resultant TPUs.
~A 2 1 1 428 1 In the belt method, which is preferred, the starting components (a) to (d) and, if used, (e) and/or (f) are mixed continuously at above the melting point of the starting components (a) to (d) with the aid of a mixer head. The reactionmixture is applied to a support, preferably a conveyor belt, for example made ofmetal, and passed through a temperature-controlled zone with a length of from 1 to 20 meters, preferably from 3 to 10 meters, at a rate of from 1 to 20 m/min, preferably from 4 to 10 m/min. The reaction temperature in this zone is from 60 to 300C, preferably from 100 to 1 80C. The partially crosslinked TPUs obtainedcan be granulated after cooling and stored if desired.
The non-tacky, highly elastic PU monofilaments and multifilaments according to the invention can be produced by the melt spinning process, which is known per se. Particularly suitable for the production, and therefore preferred, are extruder melt-spinning units, which can optionally, in addition to the air cooling usually used, for example by means of a cooling air shaft, be fitted with a water-cooling device for cooling the freshly spun PU filaments.
In a preferred variant of the process for the production of the PU
filaments according to the invention, the TPUs which are suitable according to the invention are melted in a extruder at from 150 to 250C, preferably at from 170 to 230C, depending on the partially crosslinked TPU employed in each case, the melt is shaped to give filaments with the aid of a gear spinning pump and a single-hole or multi-hole spinneret with melt filtration, and the resultant filaments are cooled by water or air, depending on the take-off rate used, and wound up on conventional reeling units.
The reeling up of the PU filaments produced according to the invention is advantageously carried out with additional application of a spin finish based on, for example, silicone or silicic acid dispersions, which (~A21 14281 additionally improve the reeling and winding up, which are essentially already tack-free, of the spinning reel and the further processing of the PU monofilaments and multifilaments.
Spin finishes of this type of known commercial products. Suitable spin finishes based on polysiloxane elastomers or mixtures of polysiloxanes and a silicon compound, for example, are commercially available from BASF
Aktiengesellschaft under the tradenames Siligen SIP, Siligen NSI, and Silign LSI, and one based on silicates under the tradename Siligen E.
The melt spinning can be carried out using dies of conventional capillary geometry. However, it is advantageous for melt spinning to use dies having a special capillary geometry, expediently those having a length of from 1 D
to 5D and a capillary diameter of from 0.05 to 2 mm, capillary diameters of from0.1 to 0.5 mm being particularly preferred in the case of multifilaments and capillary diameters of from 0.5 to 2 mm being particularly preferred in the case of monofilaments, since these measures additionally permanently improve the mechanical properties of the PU filaments according to the invention, and in particular PU filaments having very good elastic recovery and elongation at break can be obtained.
The PU filaments according to the invention or produced by the process according to the invention do not stick to one another, and in the case of multifilaments the individual capillaries do not stick to one another, and have a high tear strength with an elongation at break, measured in accordance with DIN 53 815, of greater than 300 %, preferably from 320 to 800 %, and low plastic deformation and high elastic recovery (measured in accordance with DIN 53 835).
The elongation ratio, defined as the quotient of the elastic elongation EB and the total elongation EW8~ measured in accordance with DIN 53 835, is greater than 0.8, preferably from 0.85 to 0.95.
(~A21 14281 The textile properties of the PU filaments according to the invention can, if desired, be further improved with respect to their elastic recovery, tear strength and elongation at break by thermal aftertreatment, for example by conditioning at from 50 to 170C, preferably at from 75 to 130C, in air or in awater-vapor atmosphere or, for example, by hot post-drawing, for example at a filament tension of, expediently, from 0.05 to 0.2 cN/dtex.
The high heat distortion resistance of the TPUs which can be used according to the invention and the non-tacky winding up and unwinding from the spinning reel mean that the PU filaments according to the invention can advantageously be subjected to textile conversion, for example dyeing and thermof ixing .
The non-tacky, highly elastic PU monofilaments and multifilaments according to the invention are used for the production of industrial fibers and textile fibers and sheet-like structures made from industrial fibers and textile fibers.
EXAMPLES
The TPU preparation is carried out by the one-shot process.
To this end, a mixture of 1,500 9 (1.49 mol) of polyoxybutylene glycol and 1.25 9 (0.009 mol) of trimethylolpropane was degassed for 1 hour at 110C and 5 mbar. 187.5 9 (2.08 mol) of 1,4-butanediol were stirred into the mixture, the resultant clear solution was warmed to 70C, and 909.3 9 (3.63 mol)of 4,4'-diphenylmethane diisocyanate at 65C were then added with vigorous stirring (1,000 revolutions/minute).
When a reaction temperature of 120C had been reached, the homogeneous reaction mixture was poured onto a hotplate measuring 550 x 380 mm held at 125 C and covered with teflon-treated glass fiber fabric.
After a reaction time of approximately 2 minutes, the hot TPU obtained was coarsely comminuted and conditioned at 100C for 15 hours in a drying cabinet. After cooling to room temperature, TPU granules having a particle size in the range from 4 to 6 mm were produced with the aid of a cutting mill and were stored in the interim or immediately spun by melt spinning.
Production of PU multifilaments The TPU prepared as described in Example 1 was spun using an extruder spinning unit which had the following technical data:
Extruder screw diameter: 25 mm, Extruder screw length: 25 D, Spinneret: 30 hole/0.3 mm capillary diameter and 0.6 mm capillary length and Throughput: 1.2 kg/h, at a melt temperature of 220C and a spinning rate of 450 m/min, with application of a polysiloxane-based spin finish (Siligen MBI from BASF Aktiengesellschaft) and with air cooling of the freshly spun PU filaments.
The PU filaments, which can be wound up without sticking, were subsequently treated for 10 minutes with air at 100C.
The PU filaments obtained in this way had the mechanical properties shown in Table ll.
The procedure was similar to that of Example 1, but the starting components and amounts shown in Table I were used, with the abbreviations as follows:
MDI: 4,4'-diphenylmethane diisocyanate BuOH: 1,4-butanediol TMP: Trimethylolpropane TMP-EO: Product of the reaction of 1 mol of ethylene oxide and 1 mol of TMP (tradename Lupranol 3900, MW:
178246) PTHF 1000 (1): Polyoxytetramethyleneglycol, molecular weight: 1010 PTHP 1000 (2): Polyoxytetramethyleneglycol, molecular ~ A 2 1 1 428 1 weight: 1003 PTHF 1000 (3): Polyoxytetramethylene glycol, molecular weight: 993 PTHF-CD 1 250: Polyoxybutylenepolycarbonate diol, molecular weight:
PTHF-CD 2000: Polyoxybutylenepolycarbonate diol, molecular weight:
The PU filaments obtained had the mechanical properties shown in Table ll.
TABLE I
TPU prepared by the one-shot process Example Diisocyanate Dihydroxyl Compound Chain extender Crosslinking agent TypeAmount Type Amount TypeAmount TypeAmount MDI909.3 gPTHF 1000 (1) 1500 9 BuOH187.5 9 TMP1.25 9 (3.63 mol) (1.49 mol) (2.08 mol) (0.009 mol) 2 MDI917.9 9PTHF 1000 (2) 1500 9 BuOH187.5 9Glycerol 2.25 9 (3.67 mol) (1.50 mol) (2.08 mol)(0.024 mol) 3 MDI918.2 9PTHF 1000 (1) 1500 g BuOH187.5 9Glycerol 3.00 g (3.67 mol) (1.49 mol) (2.08 mol)(0.033 mol) 4 MDI718.9 9PTHF-CD 2000 (1)1500 9 BuOH187.5 g TMP1.50 9 (2.87 mol) (0.73 mol) (2.08 mol) (0.011 mol) MDI834.4 gPTHF-CD 1250 1500 9 BuOH187.5 9 TMP2.5 9 (3.33 mol) (1.18 mol) (2.08 mol) (0.019 mol) 6 MDI916.4 9PTHF 1000 (3) 1500 9 BuOH187.5 9TMP-H0 2.00 9(3.66 mol) (1.51 mol) (2.08 mol)(0.011 mol) Comparative MDI905.8 9PTHF 1000 (1) 1500 9 BuOH187.5 9 Example (3.62 mol) (1.49 mol) (2.08 mol) TABLE ll Mechanical properties of PU filaments produced by melt spinning of the TPUs fromExamples 1 to 6 and the comparative example PU Filament Linear Tear strengthElongation at break Elastic recovery Tack from Example density in accordancein accordance in accordance temperature with DIN 53with DIN 53 815 with DIN 53 835 [C]
600/30 dtex 1.0 cN/dtex 500 % 0.90 170 2 483/30 dtex 0.8 cN/dtex 568 % 0.87 170 3 637/30 dtex 0.75 cN/dtex 338 % 0.84 170 4 492/30 dtex 0.9 cN/dtex 465 % 0.9 170 532/30 dtex 0.9 cN/dtex 465 % 0.89 170 6-6 557/30 dtex 0.8 cN/dtex 419 % 0.85 165 Comparative 470/30 dtex 0.8 cN/dtex 440 % 0.75 160 Example Stretching ratio r~
r~
~o
Claims (15)
1. A non-tacky, highly elastic polyurethane elastomer monofilament or multifilament, produced by spinning a melt of a partially crosslinked thermoplastic polyurethane obtainable by reacting a) at least one organic diisocyanate with b) at least one dihydroxyl compound having a molecular weight of from 500 to 4,000, c) at least one difunctional hydroxyl-containing chain extender having a molecular weight of from 62 to 380, and d) at least one at least trifunctional hydroxyl-containing crosslinking agent.
2. A non-tacky, high elastic polyurethane elastomer monofilament or multifilament, produced by spinning a melt of a partially crosslinked thermoplastic polyurethane obtainable by reacting a) at least one organic diisocyanate with a mixture of polyhydroxyl compounds which comprises b) at least one dihydroxyl compound having a molecular weight of from 500 to 4,000, selected from the group consisting of polyoxybutylene glycols, polyoxybutylene-polyoxyethylene glycols, polyoxybutylene-polyoxypropylene glycols, polyoxybutylene-polyoxypropylene-polyoxyethylene glycols and polyether polycarbonate diols, c) at least one difunctional hydroxyl-containing chain extender having a molecular weight of from 62 to 380, and d) at least one at least trifunctional hydroxyl-containing crosslinking agent having a molecular weight of from 90 to 400.
3. A non-tacky, highly elastic polyurethane elastomer monofilament or multifilament as claimed in claim 1 or 2, wherein the thermoplastic polyurethane is prepared using, as organic diisocyanate (a) 4,4'-diphenyl-methane diisocyanate or a mixture of diphenylmethane diisocyanate isomers containing at least 96 % by weight of 4,4'-diphenylmethane diisocyanate.
4. A non-tacky, highly elastic polyurethane elastomer monofilament or multifilament as claimed in claim 1 or 2, wherein the thermoplastic polyurethane is prepared using, as difunctional chain extender (c), 1,4-butanediol, 1,6-hexanediol or a mixture thereof.
5. A non-tacky, highly elastic polyurethane elastomer monofilament or multifilament as claimed in claim 1 or 2, wherein the thermoplastic polyurethane is prepared using, as trifunctional crosslinking agent (d), glycerol, trimethylol propane or a mixture thereof.
6. A non-tacky, highly elastic polyurethane elastomer monofilament or multifilament as claimed in claim 1 or 2, wherein the thermoplastic polyurethane is prepared using the dihydroxyl compound(s) (b) and the chain extender(s) (c) in a molar ratio of from 1:0.5 to 1:20.
7. A non-tacky, highly elastic polyurethane elastomer monofilament or multifilament as claimed in claim 1 or 2, wherein the thermoplastic polyurethane is prepared using the crosslinking agent(s) (d) in an amount of from 0.01 to 10 mol %, based on the dihydroxyl compound(s) (b).
8. A non-tacky, highly elastic polyurethane elastomer monofilament or multifilament as claimed in claim 1 or 2, wherein the thermoplastic polyurethane is prepared using components (a) to (d) in such amounts that the NCO:OH group ratio is in the range of from 0.9:1 to 1.1:1.
9. A non-tacky, highly elastic polyurethane elastomer monofilament or multifilament as claimed in claim 1 or 2, wherein the thermoplastic polyurethane is prepared by reacting components (a) to (d) by the one-shot process.
10. A non-tacky, highly elastic polyurethane elastomer monofilament or multifilament as claimed in claim 1 or 2, produced by melt-spinning with subsequent continuous thermal aftertreatment at from 50 to 170°C and at a filament tension of from 0.05 to 0.2 cN/dtex.
11. A process for the production of non-tacky, highly elastic polyurethane elastomer monofilaments or multifilaments by melt spinning, which comprises spinning a partially crosslinked thermoplastic polyurethane obtainable by reacting a) at least one organic diisocyanate with b) at least one dihydroxyl compound having a molecular weight of from 500 to 4,000, selected from the group consisting of polyoxybutylene glycols, polyoxybutylene-polyoxyethylene glycols, polyoxybutylene-polyoxypropylene glycols, polyoxybutylene-polyoxypropylene-polyoxyethylene glycols and polyether polycarbonate diols, c) at least one difunctional hydroxyl-containing chain extender having a molecular weight of from 62 to 380, and d) at least one at least trifunctional hydroxyl-containing crosslinking agent having a molecular weight of from 90 to 400, from the melt in the presence or absence of a spin finish.
12. A process as claimed in claim 11, wherein the elastomer monofilaments or multifilaments are subjected to continuous thermal aftertreatment at from 50 to 170°C and a filament tension of from 0.05 to0.02 cN/dtex.
13. A process as claimed in claim 11 , wherein the thermoplastic polyurethane is prepared using - the dihydroxyl compound(s) (b) and the chain extender(s) (c) in a molar ratio of from 1:0.5 to 1:20, - the crosslinking agent(s) (d) in an amount of from 0.01 to 10 mol %, based on the dihydroxyl compound(s) (b), and - components (a) to (d) in such amounts that the NCO:OM group ratio is in the range from 0.9:1 to 1.1:1.
14. The use of a non-tacky, highly elastic polyurethane elastomer monofilament or multifilament as claimed in claim 1 or 2 for the production of industrial fibers, textile fibers and textile sheet-like structures.
15. A partially crosslinked thermoplastic polyurethane obtainable by reacting a) at least one organic diisocyanate with b) at least one dihydroxyl compound having a molecular weight of from 500 to 4,000, selected from the group consisting of polyoxybutylene glycols, polyoxybutylene-polyoxyethylene glycols, polyoxybutylene-polyoxypropylene glycols, polyoxybutylene-polyoxypropylene-polyoxyethylene glycols and polyether polycarbonate diols, c) at least one difunctional hydroxyl-containing chain extender having a molecular weight of from 62 to 380,and d) at least one at least trifunctional hydroxyl-containing crosslinking agent having a molecular weight of from 90 to 400 by the one-shot process at from 40 to 230°C, with the proviso that the reaction uses - the dihydroxyl compound(s) (b) and the chain extender(s) (c) in a molar ratio of from 1:0.5 to 1:20, - the crosslinking agent(s) (d) in an amount of from 0.01 to 10 mol %, based on the dihydroxyl compound(s) (b), and - components (a) to (d) in such amounts that the NCO:OH group ratio is in the range from 0.9:1 to 1.1.:1.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4301355A DE4301355A1 (en) | 1993-01-20 | 1993-01-20 | Non-tacky, highly elastic mono- and multifilament polyurethane elastomer threads, processes for their production and their use as well as partially cross-linked thermoplastic polyurethanes therefor |
| EP94100083A EP0607794A1 (en) | 1993-01-20 | 1994-01-05 | Non-tacky, high elastic mono- and multifilament polyurethane yarns, process for their production, their uses and partially cross-linked thermoplastic polyurethane therefor |
| JP6003578A JPH06294012A (en) | 1993-01-20 | 1994-01-18 | Nonsticky and high elasticity polyurethane elastomer monofilament and multifilament, preparation thereof, application thereof and partially crosslinked thermoplastic polyurethane for this purpose |
| CA002114281A CA2114281A1 (en) | 1993-01-20 | 1994-01-26 | Non-tacky, highly elastic polyurethane elastomer monofilaments and multifilaments, process for their production, their use, and partially crosslinked thermoplastic polyurethanes for this purpose |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4301355A DE4301355A1 (en) | 1993-01-20 | 1993-01-20 | Non-tacky, highly elastic mono- and multifilament polyurethane elastomer threads, processes for their production and their use as well as partially cross-linked thermoplastic polyurethanes therefor |
| CA002114281A CA2114281A1 (en) | 1993-01-20 | 1994-01-26 | Non-tacky, highly elastic polyurethane elastomer monofilaments and multifilaments, process for their production, their use, and partially crosslinked thermoplastic polyurethanes for this purpose |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2114281A1 true CA2114281A1 (en) | 1995-07-27 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002114281A Abandoned CA2114281A1 (en) | 1993-01-20 | 1994-01-26 | Non-tacky, highly elastic polyurethane elastomer monofilaments and multifilaments, process for their production, their use, and partially crosslinked thermoplastic polyurethanes for this purpose |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0607794A1 (en) |
| JP (1) | JPH06294012A (en) |
| CA (1) | CA2114281A1 (en) |
| DE (1) | DE4301355A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018046699A1 (en) * | 2016-09-09 | 2018-03-15 | Covestro Deutschland Ag | Melt spun multifilaments based on thermoplastic polyurethane, their production and use |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006199719A (en) * | 2003-05-02 | 2006-08-03 | Bridgestone Corp | Crosslinked polyurethane composition |
| WO2009085929A1 (en) * | 2007-12-20 | 2009-07-09 | The Polymer Technology Group, Inc. | Hybrid polyurethane block copolymers with thermoplastic processability and thermoset properties |
| JP5832400B2 (en) * | 2012-09-12 | 2015-12-16 | 三井化学株式会社 | Rigid thermoplastic polyurethane resin, method for producing the same, and molded product |
| KR20240076116A (en) * | 2022-11-23 | 2024-05-30 | 효성티앤씨 주식회사 | Method for preparing polyurethanurea elastic yarn with improved heat resistance and elasticity recovery |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1368153A (en) * | 1963-05-07 | 1964-07-31 | Rhone Poulenc Sa | Elastic thermoplastic polyesterurethanes |
| GB1093519A (en) * | 1965-06-10 | 1967-12-06 | Firestone Tire & Rubber Co | Method of producing polyurethane elastomer |
| JPS5844764B2 (en) * | 1980-02-06 | 1983-10-05 | カネボウ株式会社 | Manufacturing method of polyurethane elastic yarn |
| CA1174577A (en) * | 1980-04-30 | 1984-09-18 | Vernon G. Ammons | Polyurethane composition for safety glass interlayer |
-
1993
- 1993-01-20 DE DE4301355A patent/DE4301355A1/en not_active Withdrawn
-
1994
- 1994-01-05 EP EP94100083A patent/EP0607794A1/en not_active Withdrawn
- 1994-01-18 JP JP6003578A patent/JPH06294012A/en not_active Withdrawn
- 1994-01-26 CA CA002114281A patent/CA2114281A1/en not_active Abandoned
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018046699A1 (en) * | 2016-09-09 | 2018-03-15 | Covestro Deutschland Ag | Melt spun multifilaments based on thermoplastic polyurethane, their production and use |
| CN109642348A (en) * | 2016-09-09 | 2019-04-16 | 科思创德国股份有限公司 | Melt-spun multifilament, its preparation and use based on thermoplastic polyurethane |
| US11346021B2 (en) | 2016-09-09 | 2022-05-31 | Covestro Deutschland Ag | Melt spun multifilaments based on thermoplastic polyurethane, their production and use |
| CN109642348B (en) * | 2016-09-09 | 2022-07-05 | 科思创德国股份有限公司 | Melt-spun multifilament yarns based on thermoplastic polyurethane, production and use thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| DE4301355A1 (en) | 1994-07-21 |
| EP0607794A1 (en) | 1994-07-27 |
| JPH06294012A (en) | 1994-10-21 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Discontinued |