EP1413653B1 - Conductive, soil-resistant core-sheath fibre with high resistance to chemicals, its production process and use - Google Patents
Conductive, soil-resistant core-sheath fibre with high resistance to chemicals, its production process and use Download PDFInfo
- Publication number
- EP1413653B1 EP1413653B1 EP03021088A EP03021088A EP1413653B1 EP 1413653 B1 EP1413653 B1 EP 1413653B1 EP 03021088 A EP03021088 A EP 03021088A EP 03021088 A EP03021088 A EP 03021088A EP 1413653 B1 EP1413653 B1 EP 1413653B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- melt
- core
- sheath
- polymer
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000835 fiber Substances 0.000 title claims abstract description 69
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 239000000126 substance Substances 0.000 title description 8
- 239000002689 soil Substances 0.000 title description 3
- 239000004811 fluoropolymer Substances 0.000 claims abstract description 38
- 229920002313 fluoropolymer Polymers 0.000 claims abstract description 37
- 229920000642 polymer Polymers 0.000 claims abstract description 35
- 229920000728 polyester Polymers 0.000 claims abstract description 33
- 238000002844 melting Methods 0.000 claims abstract description 21
- 230000008018 melting Effects 0.000 claims abstract description 21
- 239000002245 particle Substances 0.000 claims abstract description 18
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 18
- 238000009987 spinning Methods 0.000 claims abstract description 6
- -1 polyethylene terephthalate Polymers 0.000 claims description 24
- 239000004744 fabric Substances 0.000 claims description 22
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 17
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 15
- 239000002033 PVDF binder Substances 0.000 claims description 12
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 12
- 239000006229 carbon black Substances 0.000 claims description 8
- 239000004952 Polyamide Substances 0.000 claims description 7
- 229920002647 polyamide Polymers 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 4
- 239000005977 Ethylene Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 4
- 239000004711 α-olefin Substances 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- 229910001092 metal group alloy Inorganic materials 0.000 claims description 2
- 230000003014 reinforcing effect Effects 0.000 claims description 2
- 238000007650 screen-printing Methods 0.000 claims description 2
- 239000004020 conductor Substances 0.000 abstract description 6
- 239000007788 liquid Substances 0.000 abstract description 3
- 239000012943 hotmelt Substances 0.000 abstract 3
- 239000011162 core material Substances 0.000 description 22
- 239000000306 component Substances 0.000 description 12
- 125000003118 aryl group Chemical group 0.000 description 11
- 125000001931 aliphatic group Chemical group 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 229920003235 aromatic polyamide Polymers 0.000 description 5
- 238000005253 cladding Methods 0.000 description 5
- 239000011257 shell material Substances 0.000 description 5
- 239000004753 textile Substances 0.000 description 5
- 239000004677 Nylon Substances 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 239000004760 aramid Substances 0.000 description 4
- 150000001718 carbodiimides Chemical class 0.000 description 4
- JXTHNDFMNIQAHM-UHFFFAOYSA-N dichloroacetic acid Chemical compound OC(=O)C(Cl)Cl JXTHNDFMNIQAHM-UHFFFAOYSA-N 0.000 description 4
- 239000002657 fibrous material Substances 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229920001778 nylon Polymers 0.000 description 4
- 239000004417 polycarbonate Substances 0.000 description 4
- 229920000515 polycarbonate Polymers 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- 239000004416 thermosoftening plastic Substances 0.000 description 4
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000011258 core-shell material Substances 0.000 description 3
- 150000001991 dicarboxylic acids Chemical class 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000004745 nonwoven fabric Substances 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical group CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 2
- 239000004953 Aliphatic polyamide Substances 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000006057 Non-nutritive feed additive Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229920003231 aliphatic polyamide Polymers 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 229960005215 dichloroacetic acid Drugs 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 238000009998 heat setting Methods 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000006224 matting agent Substances 0.000 description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 2
- 229920001643 poly(ether ketone) Polymers 0.000 description 2
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 229920000767 polyaniline Polymers 0.000 description 2
- 229920000412 polyarylene Polymers 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 239000011112 polyethylene naphthalate Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000005871 repellent Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 229920001059 synthetic polymer Polymers 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 2
- 239000012815 thermoplastic material Substances 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- 239000004034 viscosity adjusting agent Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical group FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 description 1
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical group CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 description 1
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920001634 Copolyester Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- JUPQTSLXMOCDHR-UHFFFAOYSA-N benzene-1,4-diol;bis(4-fluorophenyl)methanone Chemical compound OC1=CC=C(O)C=C1.C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 JUPQTSLXMOCDHR-UHFFFAOYSA-N 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 1
- 238000007380 fibre production Methods 0.000 description 1
- 150000002221 fluorine Chemical class 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical group C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- 239000000615 nonconductor Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001652 poly(etherketoneketone) Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920006345 thermoplastic polyamide Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004634 thermosetting polymer Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/09—Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments
-
- 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
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/12—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyamide as constituent
-
- 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
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/14—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent
Definitions
- the present invention relates to conductive soil-repellent core-sheath fibers, in particular monofilaments, which can be used in particular in technical fabrics.
- melt-spinnable fluoropolymers have good thermal stability, good chemical resistance and dirt-repellent properties. It has already been attempted to process melt-spinnable fluoropolymers into fibers, multi- and monofilaments in order to produce textile surfaces for technical applications with the above-mentioned properties of fluoropolymers.
- a disadvantage of melt-spinnable fluoropolymers is the high creep behavior. Fibers and filaments of this material therefore have only low tensile strengths and are not dimensionally stable.
- fluoropolymers have good mechanical performance properties, e.g. with polyethylene terephthalate (hereinafter also referred to as "PET").
- PET polyethylene terephthalate
- fluoropolymers are often incompatible with other polymers and generally do not mix. Thus, a two-phase mixture often arises in which the fluoropolymers form spatial islands. The proportion by weight of fluoropolymer which can be metered in is thus frequently limited, since the boundary layers of the polymers adhere only poorly to one another. In fibers, this property is noticeable as a "splice tendency".
- the electrically conductive fibers may include electrically conductive particles such as carbon black or metal particles, metal coatings, or may be made of electrically conductive materials such as polyanilines. As fiber materials polyester and polyolefins are described.
- yarns are known for making spiral tapes coated with a layer of thermosetting polymers.
- This layer contains electrically conductive carbon.
- polymers for the cladding layer melamine resins, epoxies, phenolic resins or polyurethanes are exemplified.
- the DE-A-39 38 414 describes high-strength fabrics of synthetic fibers, which are woven in the form of electrically conductive fibers in warp and weft, and continue to contain electrically non-conductive fibers.
- the electrically conductive fibers consist of polyolefins and contain graphite or carbon black.
- the EP-A-160.320 describes core-shell monofilaments for use in hairbrushes of selected polymers.
- the core contains nylon or polyester comprising at least 60% by weight of polybutylene terephthalate units.
- the jacket contains special types of nylon or copolyetherester.
- Core sheath fibers are known, the core of thermoplastic material, preferably of polyamide, and their sheath of electrically conductive plastic, preferably of polyamide, which contains soot or metals embedded.
- the JP-A-07 / 278.956 describes electrically conductive copolyesters containing mainly polybutylene terephthalate units doped with carbon black. It also describes core-sheath fibers of this material in which the core is made of aromatic polyester.
- electrically conductive heterofilaments are known, which may be configured, for example, as core-sheath fibers.
- core and sheath polymers PET and other polyesters or PET / nylon are described.
- the WO-A-01 / 20.076 discloses nonwovens with high dielectric constant.
- fiber material mixtures of polyvinylidene fluoride and polypropylene are proposed.
- the resulting products are characterized by a prolonged half-life of electrostatic charges and can be used as electrostatic filters.
- the US-A-6,085,061 describes a brush for cleaning electrostatically charged surfaces.
- core-sheath fibers can be used, the core of which is electrically conductive and whose sheath consists of polyvinylidene fluoride.
- melt-spun undrawn, electrically nonconductive core-sheath fibers whose sheaths contain fluoropolymers are known.
- the core polymer used is polycarbonate.
- This fiber is used as an optical fiber and is not suitable because of the low strength for technical textiles, such as technical fabrics.
- high reflection at the boundary layer and the lowest possible attenuation of the electromagnetic wave are important. Both properties can only be achieved by using a high-purity coating.
- a semiconducting fiber of a carbon black-containing fluoropolymer will be described.
- This fiber has no core-shell structure and is used for the production of non-wovens, for example by the melt-blow process. The fiber is not stretched.
- the prioritized, not pre-published WO-A-03/004738 describes core-sheath fibers of high strength and good chemical resistance.
- the sheath of the fibers contains a fluoropolymer.
- Combinations of PET as core material and PVDF as cladding material are described.
- This document also discloses in a general way the possibility of adding additives in core or shell. Possible additives include electrically conductive materials.
- the present invention has the object to combine the performance advantages of the known materials for fiber production without having to accept the disadvantages associated with the use of the individual materials in purchasing.
- Another object of the present invention is thus to provide core-sheath fibers with good adhesion between the individual layers.
- the present invention thus provides fibers, in particular monofilaments, which combine antistatic properties with high chemical and chemical properties have thermal resistance and good mechanical dimensional stability and high tensile strength.
- the invention relates to a melt spun fiber having a core-sheath structure and a tensile strength of at least 15 cN / tex, the core of which contains a melt-spinnable synthetic thermoplastic polymer having a first melting point which is not a fluoropolymer and whose sheath comprises at least one melt-spinnable fluoropolymer having a second melting point , which is at least 20 ° C below the first melting point, and contains particles of electrically conductive material, the amount of which is up to 50 wt.%, Based on the amount of the shell material.
- the core thermoplastic synthetic polymers can be of any nature as long as they are melt-spun and impart the fiber with the properties desired for the particular application. Fluoropolymers are not included in the synthetic thermoplastic polymers, although the core may also contain fluoropolymers as the blending component in addition to these polymers.
- thermoplastic materials are polyolefins such as polyethylene, polypropylene or copolymers containing ethylene and / or propylene units in conjunction with other alpha-olefin units copolymerized therewith, such as alpha-butylene, alpha-pentylene, alpha-hexylene or alpha-octylene; Polyesters such as polycarbonate, aliphatic / aromatic polyesters or wholly aromatic polyesters; Polyamides, such as aliphatic or aliphatic / aromatic polyamides (nylon types) or wholly aromatic polyamides (aramids); or polyether ketones, ie polymers which have at least ether and ketone groups and, as a rule, aromatic divalent radicals, such as phenylene, in the recurring chain, many combinations of these groups being possible, for example PEK, PEEK or PEKK; or polyarylene sulfides, preferably polyphenylene sulfide; or polyether esters, ie polyole
- the core of the core-sheath fibers according to the invention contains polyamides and in particular polyesters.
- thermoplastic polyamides which are preferably used in the compositions according to the invention are known per se.
- thread-forming polyamides such as aliphatic or aliphatic / aromatic polyamides, e.g. Polycaprolactam, poly (hexamethylene-1,6-diaminadipamide), poly (hexamethylene-1,6-diamine-sebacic acid diamide), poly (hexamethylene-1,6-diamine-terephthalic acid diamide) or poly (hexamethylene) -1,6-diamine isopthalklarediamid); or completely aromatic polyamides, such as poly (phenylene-1,4-diamine-terephthalic acid diamide) or poly (phenylene-1,4-diaminisophthalic acid diamide).
- polycaprolactam poly (hexamethylene-1,6-diaminadipamide), poly (hexamethylene-1,6-diamine-sebacic acid diamide), poly (hexamethylene-1,6-diamine-terephthalic acid diamide) or poly (hexamethylene) -1,6
- the polyamides used according to the invention usually have viscosity numbers according to DIN 53727 of 120 to 350, preferably 150 to 320 cm 3 / g (measured at 25 ° C in sulfuric acid).
- thermoplastic polyesters and / or aromatic liquid-crystalline polyesters which are particularly preferably used in the compositions according to the invention are known per se.
- polyesters such as polycarbonate or aliphatic / aromatic polyesters, such as polybutylene terephthalate, polycyclohexanedimethyl terephthalate, polyethylene naphthalate or especially polyethylene terephthalate, but also completely aromatic, liquid crystalline polyesters, such as Polyoxibenzonaphtoat.
- Building blocks of thread-forming polyesters are preferably diols and dicarboxylic acids, or appropriately constructed oxycarboxylic acids.
- the main acid constituent of the polyesters is terephthalic acid or cyclohexanedicarboxylic acid, but other aromatic and / or aliphatic or cycloaliphatic dicarboxylic acids may also be suitable, preferably para or trans aromatic compounds, for example 2,6-naphthalenedicarboxylic acid or 4,4'-biphenyldicarboxylic acid , but also p-hydroxy-benzoic acid.
- aliphatic Dicarboxylic acids such as adipic acid or sebacic acid are preferably used in combination with aromatic dicarboxylic acids.
- Typical suitable dihydric alcohols are aliphatic and / or cycloaliphatic and / or aromatic diols, for example ethylene glycol, propanediol, 1,4-butanediol, 1,4-cyclohexanedimethanol but also hydroquinone.
- thermoplastic polyesters are in particular selected from the group consisting of polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polypropylene terephthalate, polybutylene terephthalate, polycyclohexanedimethanol terephthalate, polycarbonate or a copolycondensate comprising polybutylene glycol, terephthalic acid and naphthalenedicarboxylic acid units.
- thermoplastic polyesters are aromatic, liquid-crystalline polyesters, in particular polyesters containing p-hydroxybenzoate units.
- polyesters which are to be used in moist-hot environments, as in the case of monofilaments used in paper machines, and which contain polyester as the core component, these polyesters are preferably stabilized against hydrolytic degradation by addition of polyester stabilizers.
- Such stabilized fibers show a significant reduction in the level of degradation of the polyester, so that life of monofilaments equivalent to monofilaments based on highly durable fiber materials such as polyarylene sulfides or oxides can be achieved.
- fibers comprising core-stabilized polyesters, more preferably carbodiimides.
- the polyesters used according to the invention usually have solution viscosities (IV values) of at least 0.60 dl / g, preferably from 0.60 to 1.05 dl / g, particularly preferably from 0.62 to 0.93 dl / g ( measured at 25 ° C in dichloroacetic acid (DCE)).
- IV values solution viscosities
- the mantle-forming fluoropolymers may also be of any nature as long as they are melt-spun and have a melting point that is at least 20 ° C below the melting point of the thermoplastic polymer of the core.
- the fluoropolymers used in the present invention are poly (fluoroolefin) homopolymers and / or copolymers derived from ethylenically-unsaturated fluorine-containing olefin monomers and other monomers copolymerizable therewith. Such polymers are also known per se.
- melt-spinnable copolymers of tetrafluoroethylene with other alpha-olefins such as ethylene, propylene, butylene, hexylene or octylene.
- homopolymers or copolymers derived from other fluorine-containing monomers for example from mono-, di- or trifluoroethylene, from vinyl fluoride or in particular from vinylidene fluoride.
- Particular preference is given to using melt-spinnable copolymers of tetrafluoroethylene with at least one alpha-olefin, preferably with ethylene.
- PVDF polyvinylidene fluoride
- the invention therefore also relates to a heterafilamentary fiber containing at least two components, wherein the first component is an electrical insulator and a thermoplastic polymer which is not a fluoropolymer and the second component comprises polyvinylidene fluoride.
- the particles of electrically conductive material present in the cladding of the melt-spun fiber according to the invention may be of any nature, as long as they impart increased electrical conductivity to the cladding.
- These may be particles of carbon, for example carbon fibers, carbon black or graphite; of metals, such as copper, silver, aluminum or iron; of metal alloys, for example of bronze; or of conductive plastics, for example polyanilines or polypyrrole.
- the particles may be in any form, for example in fibrous form or in the form of round or irregular particles.
- the content of the electrically conductive particles in the cladding should be chosen such that there is a significant increase in the electrical conductivity of the plastic material. Typical amounts are in the range of up to 50% by weight, preferably 2 to 15% by weight, based on the amount of shell material.
- melt-spun fibers in which the sheath contains between 2% by weight and 15% by weight, in particular between 4% by weight and 9% by weight, of electrically conductive particles.
- the core-sheath fibers according to the invention can be present in any desired form, for example as multifilaments, as staple fibers or in particular as monofilaments.
- the titer of the core-sheath fibers according to the invention can likewise vary within wide limits. Examples are 100 to 45,000 dtex, in particular 400 to 7,000 dtex.
- the staple lengths of staple fibers can also vary widely, for example between 30 to 70 mm.
- the core of the core-sheath fiber according to the invention forms the mechanical support of the fiber, while the sheath mainly determines the performance characteristics, such as antistatic behavior and sliding behavior.
- the core used may preferably be a commercially available PET raw material.
- a fluoropolymer based on PVDF is particularly preferably used which has been previously processed, in particular with carbon black, into a spinnable mixture.
- the two polymers or mixtures containing these polymers are preferably dried immediately before being fed into the extruder, melted in the extruder and filtered through a spin pack.
- the fluoropolymer is provided with the electroconductive particles. This is usually done before the delivery of the fluoropolymer to the extruder, but can also take place immediately before the spin pack. It is also possible to use masterbatches comprising the fluoropolymer and electrically conductive particles.
- the molten polymer filament is cooled in a spin bath, for example a water bath, and then wound or drawn off.
- the removal speed is greater than the injection rate of the polymer melt and thus causes a stretching of the formed thread.
- the heterofilament spun yarn produced in this way is then preferably subjected to a post-drawing, more preferably in several stages, in particular a two- or three-stage post-drawing, with a total draw ratio of 1: 3 to 1: 8, preferably 1: 4 to 1: 6.
- the spinning take-off speed is usually 10 to 40 m per minute.
- thermoplastic polymer of the core and the fluoropolymer of the shell When spinning the thermoplastic polymer of the core and the fluoropolymer of the shell to a bicomponent monofilament core-sheath structure surprisingly shows a very good core-shell adhesion.
- the conductivity of the jacket may be lost during stretching, but may be restored by a heat treatment and the shrinkage caused thereby, preferably above the melting point of the jacket material but below the melting temperature of the core.
- the conductively doped fluoropolymer mainly determines the surface properties.
- the fibers of the invention are characterized by very good dirt repellency, good chemical resistance and electrical conductivity.
- the combination with the fluoropolymer results in fibers with improved slip properties compared to pure thermoplastic polymer fibers. These fibers show increased soil repellency compared to pure thermoplastic polymer fibers.
- the fibers according to the invention may contain auxiliaries in addition to the components A) and B).
- auxiliaries include processing aids, stabilizers, antioxidants, plasticizers, lubricants, pigments, matting agents, viscosity modifiers or crystallization accelerators.
- processing aids are siloxanes, waxes or longer-chain carboxylic acids or their salts, aliphatic, aromatic esters or ethers.
- stabilizers and antioxidants are the polyester stabilizers already mentioned above, phosphorus compounds such as phosphoric acid esters or carbodiimides.
- pigments or matting agents examples include organic dye pigments or titanium dioxide.
- viscosity modifiers are polybasic carboxylic acids and their esters or polyhydric alcohols.
- the fibers according to the invention are preferably used for the production of textile fabrics, such as fabrics, knitted fabrics, crocheted, laid and nonwovens.
- Textile fabrics comprising monofilaments according to the invention are particularly suitable for technical applications, such as for filters, as screen printing materials or in particular as paper machine screens.
- the monofilaments according to the invention have good textile-physical properties and can be easily interwoven.
- the fabrics have the usual dimensional stability of the core forming thermoplastic polymers.
- Fabrics made of these monofilaments are excellently suited for technical fabrics, in particular in the filtration of aggressive media, which are also at risk of electrostatic charge; i.e. especially in the solid-gaseous and solid-liquid filtration.
- the invention also relates to the use of the fibers for making fabrics used in environments of high chemical and / or physical stress, in particular as paper machine fabrics or as technical fabrics, e.g. used in filtration, for the production of conveyor belts or as reinforcing inserts.
- the fibers are used as monofilaments and in particular as weft threads in the fabric.
- the use of the monofilaments according to the invention as papermaking fabrics may take place in the forming section, the press section or, in particular, in the dryer section respectively.
- the monofilaments according to the invention are used in particular as spiral sieves.
- the fibers used according to the invention in particular in the form of monofilaments, usually have a titer range of 10 to 4500 tex, a modulus of elasticity of 2.0 to 8.0 N / tex, a tenacity of 15 to 50 cN / tex Elongation at break of 15 to 45% and hot air shrinkage at 180 ° C of 1.0 to 20.0%.
- PET polyethylene terephthalate
- PVDF polyvinylidene fluoride
- the core-sheath monofilament obtained had the following properties: titres 2890 dtex strength 24 cN / tex HLS (hot air shrink 10 'at 160 ° C) 2.5% loop strength > 20 cN / tex elongation 44% BZD (reference strain at 12 cN / tex): 8.5% BZD (reference strain at 15 cN / tex): 13% EGG. Resistance (10 mm clamping length): 8 * 10 5 (ohms) EGG. Resistance (150 mm clamping length): 9 * 10 6 (ohms)
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Abstract
Description
Die vorliegende Erfindung betrifft leitfähige schmutzabweisende Kern-Mantel-Fasern, insbesondere Monofilamente, die sich insbesondere in technischen Geweben einsetzen lassen.The present invention relates to conductive soil-repellent core-sheath fibers, in particular monofilaments, which can be used in particular in technical fabrics.
Es ist bekannt, dass Fluorpolymere eine gute thermische Stabilität, gute Chemikalienresistenz und schmutzabweisende Eigenschaften haben. Es ist bereits versucht worden, schmelzspinnbare Fluorpolymere zu Fasern, Multi- und Monofilamenten zu verarbeiten, um daraus textile Flächen für technische Anwendungen mit den oben genannten Eigenschaften von Fluorpolymeren herzustellen. Nachteilig bei schmelzspinnbaren Fluorpolymeren ist das hohe Kriechverhalten. Fasern und Filamente aus diesem Material haben deshalb nur geringe Zugfestigkeiten und sind nicht formstabil.It is known that fluoropolymers have good thermal stability, good chemical resistance and dirt-repellent properties. It has already been attempted to process melt-spinnable fluoropolymers into fibers, multi- and monofilaments in order to produce textile surfaces for technical applications with the above-mentioned properties of fluoropolymers. A disadvantage of melt-spinnable fluoropolymers is the high creep behavior. Fibers and filaments of this material therefore have only low tensile strengths and are not dimensionally stable.
Es ist auch bereits versucht worden, Fluorpolymere mit Polymeren mit guten mechanischen Gebrauchseigenschaften zu kombinieren, z.B. mit Polyethylenterephthalat (nachfolgend auch "PET" genannt). Dabei ist allerdings festzustellen, dass Fluorpolymere mit anderen Polymeren oft unverträglich sind und sich in der Regel nicht vermischen. Es entsteht also häufig ein Zweiphasengemisch, in dem die Fluorpolymeren räumliche Inseln bilden. Der Gewichtsanteil an Fluorpolymer, der zudosiert werde kann, ist somit häufig begrenzt, da die Grenzschichten der Polymere nur schlecht aneinander haften. In Fasern macht sich diese Eigenschaft als "Spleißneigung" bemerkbar.It has also been attempted to combine fluoropolymers with polymers having good mechanical performance properties, e.g. with polyethylene terephthalate (hereinafter also referred to as "PET"). However, it should be noted that fluoropolymers are often incompatible with other polymers and generally do not mix. Thus, a two-phase mixture often arises in which the fluoropolymers form spatial islands. The proportion by weight of fluoropolymer which can be metered in is thus frequently limited, since the boundary layers of the polymers adhere only poorly to one another. In fibers, this property is noticeable as a "splice tendency".
Monofilamente aus PET und statistischen Copolymeren aus Ethylen und Tetrafluorethylen ("ETFE") sind seit Jahren kommerziell erhältlich. Häufig weisen diese Fasern zur Hydrolysestabilisierung einen niedrigen Carboxylendgruppengehalt auf, und sind zum Verschluß der Carboxylendgruppen mit Carbodiimiden stabilisiert. Der Verschluß von Carboxylgruppen mittels Carbodiimiden ist z.B. in den
Technische Gewebe, die aus diesen Monofilamenten hergestellt werden, haben weitgehend die mechanischen Eigenschaften eines PET Monofilaments, jedoch mit erhöhter Hydrolyseresistenz und verbesserter Schmutzabweisung. Temperaturstabilität und Chemikalienbeständigkeit dieser Fasern entsprechen wegen des relativ geringen Anteils an Fluorpolymeren im wesentlichen den Werten des reinen PET. Die erhöhte Spleißneigung kann sich allerdings bei mechanischen Belastungen bemerkbar machen, z.B. beim Anschlag des Webriets.Technical fabrics made from these monofilaments have largely the mechanical properties of a PET monofilament, but with increased resistance to hydrolysis and improved soil repellency. Temperature stability and chemical resistance of these fibers correspond substantially to the values of pure PET due to the relatively low proportion of fluoropolymers. However, the increased splice tendency may be noticeable under mechanical loads, e.g. at the Webriets plot.
Fasern aus synthetischen Polymeren und daraus hergestellte Gewebe haben allerdings den Nachteil, dass sie sich durch Reibung mit statischer Elektrizität aufladen können. Leitfähige Fasern zur Herstellung von textilen Flächengebilden, wie Geweben für technischen Einsatz, oder für andere Einsatzzwecke, z.B. für Bürsten, waren von jeher Ziel zahlreicher Entwicklungen.However, synthetic polymer fibers and fabrics made therefrom have the disadvantage of being able to recharge with static electricity due to friction. Conductive fibers for the production of textile fabrics, such as fabrics for technical use, or for other purposes, e.g. for brushes, have always been the target of numerous developments.
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Ausgehend von diesem Stand der Technik lag der vorliegenden Erfindung die Aufgabe zugrunde, die anwendungstechnischen Vorteile der für die Faserherstellung bekannten Materialien zu kombinieren, ohne die mit dem Einsatz der einzelnen Materialen bekannten Nachteile in Kauf nehmen zu müssen.Based on this prior art, the present invention has the object to combine the performance advantages of the known materials for fiber production without having to accept the disadvantages associated with the use of the individual materials in purchasing.
Dem Fachmann ist bekannt, dass an der Grenzschicht zweier Polymere normalerweise Haftungsprobleme auftreten. Insbesondere gilt dies beim Einsatz von bekanntermaßen schlecht haftenden Fluorpolymeren mit anderen Polymeren. Überraschenderweise hat sich gezeigt, dass bei Einsatz eines mit elektrisch leitfähigen Teilchen dotierten Fluorpolymeren eine sehr gute Haftung mit dem Polymerkern zu erzielen ist.It is known to the person skilled in the art that adhesion problems usually occur at the boundary layer of two polymers. In particular, this applies to the use of known poorly adhering fluoropolymers with other polymers. Surprisingly, it has been shown that when using one with electric Conductive particles doped fluoropolymers to achieve a very good adhesion with the polymer core.
Eine weitere Aufgabe der vorliegenden Erfindung besteht somit in der Bereitstellung von Kern-Mantel-Fasern mit guter Haftung zwischen den einzelnen Schichten.Another object of the present invention is thus to provide core-sheath fibers with good adhesion between the individual layers.
Mit der vorliegenden Erfindung werden somit Fasern bereit gestellt, insbesondere Monofilamente, die antistatische Eigenschaften kombiniert mit hoher chemischer und thermischer Beständigkeit und guter mechanischer Formstabilität sowie hoher Zugfestigkeit aufweisen.The present invention thus provides fibers, in particular monofilaments, which combine antistatic properties with high chemical and chemical properties have thermal resistance and good mechanical dimensional stability and high tensile strength.
Die Erfindung betrifft eine schmelzgesponnene Faser mit Kern-Mantel Struktur und einer Zugfestigkeit von mindestens 15 cN/tex, deren Kern ein schmelzspinnbares synthetisches thermoplastisches Polymer mit einem ersten Schmelzpunkt enthält, das kein Fluorpolymer ist, und deren Mantel mindestens ein schmelzspinnbares Fluorpolymer mit einem zweiten Schmelzpunkt, der wenigstens 20°C unterhalb des ersten Schmelzpunktes liegt, und Teilchen aus elektrisch leitfähigem Material enthält, deren Menge bis zu 50 Gew. %, bezogen auf die Menge des Mantelmaterials, beträgt.The invention relates to a melt spun fiber having a core-sheath structure and a tensile strength of at least 15 cN / tex, the core of which contains a melt-spinnable synthetic thermoplastic polymer having a first melting point which is not a fluoropolymer and whose sheath comprises at least one melt-spinnable fluoropolymer having a second melting point , which is at least 20 ° C below the first melting point, and contains particles of electrically conductive material, the amount of which is up to 50 wt.%, Based on the amount of the shell material.
Die den Kern bildenden synthetischen thermoplastischen Polymere können beliebiger Natur sein, solange diese schmelzspinnbar sind und der Faser die für den jeweiligen Anwendungszweck gewünschten Eigenschaften verleihen. Fluorpolymere sind von den synthetischen thermoplastischen Polymeren nicht umfasst, obgleich der Kern neben diesen Polymeren auch Fluorpolymere als.Mischungskomponente enthalten kann.
Beispiele für synthetische thermoplastische Materialien sind Polyolefine, wie Polyethylen, Polypropylen oder Copolymere enthaltend Ethylen- und/oder Propyleneinheiten in Verbindung mit anderen damit copolymerisierten alpha-Olefin-Einheiten, wie alpha-Butylen, alpha-Pentylen, alpha-Hexylen oder alpha-Octylen; Polyester, wie Polycarbonat, aliphatisch / aromatische Polyester oder vollständig aromatische Polyester; Polyamide, wie aliphatische oder aliphatisch / aromatische Polyamide (Nylon-Typen) oder vollständig aromatische Polyamide (Aramide); oder Polyetherketone, also Polymere, die mindestens Ether- und Ketongruppen und in der Regel aromatische zweiwertige Reste, wie Phenylen, in der wiederkehrenden Kette aufweisen, wobei viele Kombinationen dieser Gruppen möglich sind, beispielsweise PEK, PEEK oder PEKK; oder Polyarylensulfide, vorzugsweise Polyphenylensulfid; oder Polyetherester, also Polymere, die mindestens Ether- und Estergruppen und in der Regel aromatische zweiwertige Reste, wie Phenylen, in der wiederkehrenden Kette aufweise, beispielsweise TPE-E; oder Polyacrylnitril oder Polyacrylnitril-Copolymere mit anderen ethylenisch-ungesättigten Comonomeren, wie Acryl- oder Methacrylsäure.The core thermoplastic synthetic polymers can be of any nature as long as they are melt-spun and impart the fiber with the properties desired for the particular application. Fluoropolymers are not included in the synthetic thermoplastic polymers, although the core may also contain fluoropolymers as the blending component in addition to these polymers.
Examples of synthetic thermoplastic materials are polyolefins such as polyethylene, polypropylene or copolymers containing ethylene and / or propylene units in conjunction with other alpha-olefin units copolymerized therewith, such as alpha-butylene, alpha-pentylene, alpha-hexylene or alpha-octylene; Polyesters such as polycarbonate, aliphatic / aromatic polyesters or wholly aromatic polyesters; Polyamides, such as aliphatic or aliphatic / aromatic polyamides (nylon types) or wholly aromatic polyamides (aramids); or polyether ketones, ie polymers which have at least ether and ketone groups and, as a rule, aromatic divalent radicals, such as phenylene, in the recurring chain, many combinations of these groups being possible, for example PEK, PEEK or PEKK; or polyarylene sulfides, preferably polyphenylene sulfide; or polyether esters, ie polymers which have at least ether and ester groups and, as a rule, aromatic divalent radicals, such as phenylene, in the recurring chain, for example TPE-E; or polyacrylonitrile or polyacrylonitrile copolymers with other ethylenically unsaturated comonomers such as acrylic or methacrylic acid.
Vorzugsweise enthält der Kern der erfindungsgemäßen Kern-Mantel-Fasern Polyamide und insbesondere Polyester.Preferably, the core of the core-sheath fibers according to the invention contains polyamides and in particular polyesters.
Die in den erfindungsgemäßen Zusammensetzungen bevorzugt zum Einsatz kommenden thermoplastischen Polyamide sind an sich bekannt.The thermoplastic polyamides which are preferably used in the compositions according to the invention are known per se.
Beispiele dafür sind fadenbildende Polyamide, wie aliphatische oder aliphatisch / aromatische Polyamide, wie z.B. Polycaprolactam, Poly-(hexamethylen-1,6-diaminadipinsäurediamid), Poly-(hexamethylen-1,6-diamin-sebacinsäure-diamid), Poly-(hexamethylen-1,6-diamin-terephthalsäure-diamid) oder Poly-(hexamethylen-1,6-diamin-isopthalsäurediamid); oder auch vollständig aromatische Polyamide, wie Poly-(phenylen-1,4-diamin-terephthalsäurediamid) oder Poly-(phenylen-1,4-diaminisophtalsäurediamid).Examples of these are thread-forming polyamides, such as aliphatic or aliphatic / aromatic polyamides, e.g. Polycaprolactam, poly (hexamethylene-1,6-diaminadipamide), poly (hexamethylene-1,6-diamine-sebacic acid diamide), poly (hexamethylene-1,6-diamine-terephthalic acid diamide) or poly (hexamethylene) -1,6-diamine isopthalsäurediamid); or completely aromatic polyamides, such as poly (phenylene-1,4-diamine-terephthalic acid diamide) or poly (phenylene-1,4-diaminisophthalic acid diamide).
Die erfindungsgemäß eingesetzten Polyamide weisen üblicherweise Viskositätszahlen nach DIN 53727 von 120 bis 350, vorzugsweise 150 bis 320 cm3/g auf (gemessen bei 25°C in Schwefelsäure).The polyamides used according to the invention usually have viscosity numbers according to DIN 53727 of 120 to 350, preferably 150 to 320 cm 3 / g (measured at 25 ° C in sulfuric acid).
Die in den erfindungsgemäßen Zusammensetzungen besonders bevorzugt zum Einsatz kommenden thermoplastischen Polyester und/oder aromatischen flüssigkristallinen Polyester sind an sich bekannt.The thermoplastic polyesters and / or aromatic liquid-crystalline polyesters which are particularly preferably used in the compositions according to the invention are known per se.
Beispiele dafür sind fadenbildende Polyester, wie Polycarbonat oder aliphatisch / aromatische Polyester, wie z.B. Polybutylenterephthalat, Polycyclohexandimethylterephthalat, Polyethylennaphthalat oder insbesondere Polyethylenterephthalat, aber auch vollständig aromatische, flüssig-kristalline Polyester, wie Polyoxibenzonaphtoat. Bausteine von fadenbildenden Polyestern sind vorzugsweise Diole und Dicarbonsäuren, bzw. entsprechend aufgebaute Oxycarbonsäuren. Hauptsäurebestandteil der Polyester ist Terephthalsäure oder Cyclohexandicarbonsäure, aber auch andere aromatische und/oder aliphatische bzw. cycloaliphatische Dicarbonsäuren können geeignet sein, vorzugsweise para- oder trans-ständige aromatische Verbindungen, wie z.B. 2,6-Naphthalin-dicarbonsäure oder 4,4'-Biphenyldicarbonsäure, aber auch p-Hydroxy-benzoesäure. Aliphatische Dicarbonsäuren, wie z.B. Adipinsäure oder Sebacinsäure werden vorzugsweise in Kombination mit aromatischen Dicarbonsäuren eingesetzt.Examples thereof are fiber-forming polyesters, such as polycarbonate or aliphatic / aromatic polyesters, such as polybutylene terephthalate, polycyclohexanedimethyl terephthalate, polyethylene naphthalate or especially polyethylene terephthalate, but also completely aromatic, liquid crystalline polyesters, such as Polyoxibenzonaphtoat. Building blocks of thread-forming polyesters are preferably diols and dicarboxylic acids, or appropriately constructed oxycarboxylic acids. The main acid constituent of the polyesters is terephthalic acid or cyclohexanedicarboxylic acid, but other aromatic and / or aliphatic or cycloaliphatic dicarboxylic acids may also be suitable, preferably para or trans aromatic compounds, for example 2,6-naphthalenedicarboxylic acid or 4,4'-biphenyldicarboxylic acid , but also p-hydroxy-benzoic acid. aliphatic Dicarboxylic acids such as adipic acid or sebacic acid are preferably used in combination with aromatic dicarboxylic acids.
Typische geeignete zweiwertige Alkohole sind aliphatische und/oder cycloaliphatische und/oder aromatische Diole, beispielsweise Ethylenglykol, Propandiol, 1,4-Butandiol, 1,4-Cyclohexandimethanol aber auch Hydrochinon. Bevorzugt sind aliphatische Diole, die zwei bis vier Kohlenstoffatome aufweisen, insbesondere Ethylenglykol; weiterhin bevorzugt sind cycloaliphatische Diole, wie 1,4-Cyclohexandimethanol.Typical suitable dihydric alcohols are aliphatic and / or cycloaliphatic and / or aromatic diols, for example ethylene glycol, propanediol, 1,4-butanediol, 1,4-cyclohexanedimethanol but also hydroquinone. Preference is given to aliphatic diols having from two to four carbon atoms, in particular ethylene glycol; furthermore preferred are cycloaliphatic diols, such as 1,4-cyclohexanedimethanol.
Bevorzugte thermoplastische Polyester werden inbesondere ausgewählt aus der Gruppe bestehend aus Polyethylenterephthalat, Polyethylennaphthalat, Polybutylennaphthalat, Polypropylenterephthalat, Polybutylenterephthalat, Polycyclohexandimethanol-terephthalat, Polycarbonat oder einem Copolykondensat enthaltend Polybutylenglykol-, Terephthalsäure- und Naphthalindicarbonsäureeinheiten.Preferred thermoplastic polyesters are in particular selected from the group consisting of polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polypropylene terephthalate, polybutylene terephthalate, polycyclohexanedimethanol terephthalate, polycarbonate or a copolycondensate comprising polybutylene glycol, terephthalic acid and naphthalenedicarboxylic acid units.
Weitere bevorzugte thermoplastische Polyester aromatische, flüssigkristalline Polyester, inbesondere Polyester enthaltend p-Hydroxybenzoateinheiten.Further preferred thermoplastic polyesters are aromatic, liquid-crystalline polyesters, in particular polyesters containing p-hydroxybenzoate units.
Insbesondere bei Fasern die in feucht-heißen Umgebungen eingesetzt werden sollen, wie bei Monofilamenten beim Einsatz in Papiermaschinen, und die als Kernkomponente Polyester enthalten, werden diese Polyester vorzugsweise durch Zugabe von Polyesterstabilisatoren gegenüber hydrolytischem Abbau stabilisiert.In particular, in the case of fibers which are to be used in moist-hot environments, as in the case of monofilaments used in paper machines, and which contain polyester as the core component, these polyesters are preferably stabilized against hydrolytic degradation by addition of polyester stabilizers.
Derartige stabilisierte Fasern zeigen eine signifikante Verringerung der Abbauneigung des Polyesters, so dass Lebensdauern von Monofilamenten erzielt werden können, die denen von Monofilamenten auf der Basis von äußerst beständigen Fasermaterialien, wie Polyarylensulfiden oder -oxiden, gleichwertig sind.Such stabilized fibers show a significant reduction in the level of degradation of the polyester, so that life of monofilaments equivalent to monofilaments based on highly durable fiber materials such as polyarylene sulfides or oxides can be achieved.
Besonders bevorzugt werden Fasern enthaltend im Kern stabilisierte Polyester, besonders bevorzugt Carbodiimide.Particular preference is given to fibers comprising core-stabilized polyesters, more preferably carbodiimides.
Die erfindungsgemäß eingesetzten Polyester weisen üblicherweise Lösungsviskositäten (IV-Werte) von mindestens 0,60 dl/g, vorzugsweise von 0,60 bis 1,05 dl/g, besonders bevorzugt von 0,62 - 0,93 dl/g, auf (gemessen bei 25°C in Dichloressigsäure (DCE)).The polyesters used according to the invention usually have solution viscosities (IV values) of at least 0.60 dl / g, preferably from 0.60 to 1.05 dl / g, particularly preferably from 0.62 to 0.93 dl / g ( measured at 25 ° C in dichloroacetic acid (DCE)).
Die den Mantel bildendenden Fluorpolymere können ebenfalls beliebiger Natur sein, solange diese schmelzspinnbar sind und einen Schmelzpunkt aufweisen, der wenigstens 20°C unterhalb des Schmelzpunktes des thermoplastischen Polymeren des Kerns liegt.
Die erfindungsgemäß eingesetzten Fluorpolymeren sind Poly-(fluorolefin)-Homopolymere und/oder -Copolymere abgeleitet von ethylenisch-ungesätügten fluorhaltigen Olefin-Monomeren und anderen damit copolymerisierbaren Monomeren. Derartige Polymere sind ebenfalls an sich bekannt.The mantle-forming fluoropolymers may also be of any nature as long as they are melt-spun and have a melting point that is at least 20 ° C below the melting point of the thermoplastic polymer of the core.
The fluoropolymers used in the present invention are poly (fluoroolefin) homopolymers and / or copolymers derived from ethylenically-unsaturated fluorine-containing olefin monomers and other monomers copolymerizable therewith. Such polymers are also known per se.
Beispiele dafür sind schmelzspinnbare Copolymere von Tetrafluorethylen mit anderen alpha-Olefinen, wie Ethylen, Propylen, Butylen, Hexylen oder Octylen.Examples thereof are melt-spinnable copolymers of tetrafluoroethylene with other alpha-olefins such as ethylene, propylene, butylene, hexylene or octylene.
Es sind auch Homo- oder Copolymere einsetzbar, die sich von anderen fluorhaltigen Monomeren ableiten, beispielsweise von Mono-, Di- oder Trifluorethylen, von Vinylfluorid oder insbesondere von Vinylidenfluorid.
Besonders bevorzugt setzt man schmelzspinnbare Copolymere von Tetra-fluorethylen mit mindestens einem alpha-Olefin, vorzugsweise mit Ethylen, ein.It is also possible to use homopolymers or copolymers derived from other fluorine-containing monomers, for example from mono-, di- or trifluoroethylene, from vinyl fluoride or in particular from vinylidene fluoride.
Particular preference is given to using melt-spinnable copolymers of tetrafluoroethylene with at least one alpha-olefin, preferably with ethylene.
Ganz besonders bevorzugt wird als Mantelkomponente Polyvinylidenfluorid ("PVDF") eingesetzt.Very particular preference is given to using polyvinylidene fluoride ("PVDF") as the sheath component.
Beim Verspinnen von Polyestern, insbesondere von PET, mit PVDF zu einem Bikomponenten-Monofilament in Kern-Mantel Struktur zeigt sich überraschend eine sehr gute Kern-Mantel Haftung.When spinning polyesters, in particular PET, with PVDF to a bicomponent monofilament in core-sheath structure surprisingly shows a very good core-sheath adhesion.
Die Erfindung betrifft daher auch eine Heterafilamentfaser enthaltend mindestens zwei Komponenten, wobei die erste Komponente ein elektrischer Isolator ist und ein thermoplastisches Polymer umfasst, das kein Fluorpolymer ist, und die zweite Komponente Polyvinylidenfluorid umfasst.The invention therefore also relates to a heterafilamentary fiber containing at least two components, wherein the first component is an electrical insulator and a thermoplastic polymer which is not a fluoropolymer and the second component comprises polyvinylidene fluoride.
Die im Mantel der erfindungsgemäßen schmelzgesponnenen Faser vorhandenen Teilchen aus elektrisch leitfähigem Material können beliebiger Natur sein, solange diese dem Mantel eine erhöhte elektrische Leitfähigkeit verleihen.The particles of electrically conductive material present in the cladding of the melt-spun fiber according to the invention may be of any nature, as long as they impart increased electrical conductivity to the cladding.
Dabei kann es sich um Teilchen aus Kohlenstoff, beispielsweise um Kohlefasern, Ruß oder Graphit; aus Metallen, beispielsweise aus Kupfer, Silber, Aluminium oder Eisen; aus Metalllegierungen, beispielsweise aus Bronze; oder aus leitfähigen Kunststoffen, beispielsweise aus Polyanilinen oder aus Polypyrrol, handeln.These may be particles of carbon, for example carbon fibers, carbon black or graphite; of metals, such as copper, silver, aluminum or iron; of metal alloys, for example of bronze; or of conductive plastics, for example polyanilines or polypyrrole.
Die Teilchen können in beliebiger Form vorliegen, beispielsweise in Faserform oder in Form von runden oder irregulären Partikeln.The particles may be in any form, for example in fibrous form or in the form of round or irregular particles.
Der Gehalt der elektrisch leitfähigen Teilchen im Mantel ist so zu wählen, dass sich eine deutliche Erhöhung der elektrischen Leitfähigkeit des Kunststoffmaterials ergibt. Typische Mengen bewegen sich im Bereich von bis zu 50 Gew. %, vorzugsweise 2 bis 15 Gew. %, bezogen auf die Menge des Mantelmaterials.The content of the electrically conductive particles in the cladding should be chosen such that there is a significant increase in the electrical conductivity of the plastic material. Typical amounts are in the range of up to 50% by weight, preferably 2 to 15% by weight, based on the amount of shell material.
Besonders bevorzugt werden schmelzgesponnene Fasern, worin der Mantel zwischen 2 Gew. % und 15 Gew. %, insbesondere zwischen 4 Gew. % und 9 Gew. % elektrisch leitfähige Partikel enthält.Particular preference is given to melt-spun fibers in which the sheath contains between 2% by weight and 15% by weight, in particular between 4% by weight and 9% by weight, of electrically conductive particles.
Die erfindungsgemäßen Kern-Mantel-Fasern können in beliebiger Form vorliegen, beispielsweise als Multifilamente, als Stapelfasern oder insbesondere als Monofilamente.The core-sheath fibers according to the invention can be present in any desired form, for example as multifilaments, as staple fibers or in particular as monofilaments.
Der Titer der erfindungsgemäßen Kern-Mantel-Fasern kann ebenfalls in weiten Bereichen schwanken. Beispiele dafür sind 100 bis 45.000 dtex, insbesondere 400 bis 7.000 dtex.The titer of the core-sheath fibers according to the invention can likewise vary within wide limits. Examples are 100 to 45,000 dtex, in particular 400 to 7,000 dtex.
Besonders bevorzugt sind Monofilamente.Particularly preferred are monofilaments.
Besonders bevorzugt werden Monofilamente, deren Querschnittsform rund, oval oder n-eckig ist, wobei n größer gleich 3 ist.Particular preference is given to monofilaments whose cross-sectional shape is round, oval or n-shaped, where n is greater than or equal to 3.
Die Stapellängen bei Stapelfasern können ebenfalls in weiten Bereichen schwanken, beispielsweise zwischen 30 bis 70 mm.The staple lengths of staple fibers can also vary widely, for example between 30 to 70 mm.
Der Kern der erfindungsgemäßen Kern-Mantel-Faser bildet den mechanischen Träger der Faser, während der Mantel hauptsächlich die Gebrauchseigenschaften, wie antistatisches Verhalten und Gleitverhalten, bestimmt.The core of the core-sheath fiber according to the invention forms the mechanical support of the fiber, while the sheath mainly determines the performance characteristics, such as antistatic behavior and sliding behavior.
Als Kern kann vorzugsweise ein handelsüblicher PET-Rohstoff verwendet werden.The core used may preferably be a commercially available PET raw material.
Für den Mantel wird besonders bevorzugt ein Fluorpolymer auf Basis von PVDF verwendet, das zuvor insbesondere mit Ruß zu einem verspinnbaren Gemisch verarbeitet wurde.
Gewichtsanteil der den Kern bildenden Komponente A) zur den Mantel bildenden Komponente B) beträgt, bezogen auf die Gesamtmenge dieser Komponenten, für Komponente A) 50 bis 95 Gew. %, vorzugsweise 60 bis 80 Gew. %, und für Komponente B) 50 bis 5 Gew. %, vorzugsweise 40 bis 20 Gew. %.For the jacket, a fluoropolymer based on PVDF is particularly preferably used which has been previously processed, in particular with carbon black, into a spinnable mixture.
Weight fraction of the core-forming component A) to the shell-forming component B), based on the total amount of these components, for component A) 50 to 95 wt.%, Preferably 60 to 80 wt.%, And for component B) 50 bis 5% by weight, preferably 40 to 20% by weight.
Die Herstellung der erfindungsgemäßen Kern-Mantel-Fasern kann nach an sich bekannten Verfahren erfolgen.
Diese Verfahren umfassen die Maßnahmen:
- i) Auswahl eines ersten Polymeren, das ein schmelzspinnbares synthetisches thermoplastisches Polymer und kein Fluorpolymer ist und das einen ersten Schmelzpunkt aufweist,
- ii) Auswahl eines zweiten Polymeren, das ein schmelzspinnbares Fluorpolymer ist, das einen zweiten Schmelzpunkt aufweist, der wenigstens 20°C unterhalb des ersten Schmelzpunktes liegt, und das Teilchen aus elektrisch leitfähigem Material enthält,
- iii) Koextrusion des ersten Polymeren und des zweiten Polymeren durch eine Heterofilament-Spinndüse bei einer Spinntemperatur oberhalb des ersten Schmelzpunktes, so dass sich eine Bikomponentenfaser mit einem Kern aus dem ersten Polymeren und einem Mantel aus dem zweiten Polymeren ausbildet, und
- iv) Verstrecken des gebildeten Kern-Mantel Filaments zur Vergrößerung der Zugfestigkeit.
These procedures include the measures:
- i) selecting a first polymer which is a melt spinnable synthetic thermoplastic polymer and not a fluoropolymer and which has a first melting point,
- ii) selecting a second polymer which is a melt-spinnable fluoropolymer having a second melting point at least 20 ° C below the first melting point and containing particles of electrically conductive material,
- iii) coextrusion of the first polymer and the second polymer through a heterofilament spinneret at a spin temperature above the first Melting point, so that a bicomponent fiber is formed with a core of the first polymer and a shell of the second polymer, and
- iv) stretching the formed core-sheath filament to increase the tensile strength.
Die beiden Polymeren bzw. Mischungen enthaltend diese Polymeren werden vorzugsweise unmittelbar vor der Zuführung in den Extruder getrocknet, in dem Extruder aufgeschmolzen und durch ein Spinnpack filtriert. Das Fluorpolymere wird mit den elektrisch leitfähigen Teilchen versehen. Dieses erfolgt üblicherweise vor der Zuführung des Fluorpolymeren zum Extruder, kann aber auch unmittelbar vor dem Spinnpack erfolgen. Es können auch Masterbatches enthaltend das Fluorpolymer und elektrisch leitfähige Teilchen zum Einsatz kommen.The two polymers or mixtures containing these polymers are preferably dried immediately before being fed into the extruder, melted in the extruder and filtered through a spin pack. The fluoropolymer is provided with the electroconductive particles. This is usually done before the delivery of the fluoropolymer to the extruder, but can also take place immediately before the spin pack. It is also possible to use masterbatches comprising the fluoropolymer and electrically conductive particles.
Nach dem Verpressen der Polymerschmelzen durch eine Heterofilament-Spinndüse wird der geschmolzene Polymerfaden in einem Spinnbad, beispielsweise einem Wasserbad, abgekühlt und anschließend aufgewickelt oder abgezogen. Die Abziehgeschwindigkeit ist dabei größer als die Spritzgeschwindigkeit der Polymerschmelze und bewirkt somit ein Verstrecken des gebildeten Fadens.After compressing the polymer melts through a heterofilament spinneret, the molten polymer filament is cooled in a spin bath, for example a water bath, and then wound or drawn off. The removal speed is greater than the injection rate of the polymer melt and thus causes a stretching of the formed thread.
Der so hergestellte Heterofilament-Spinnfaden wird anschließend vorzugsweise einer Nachverstreckung, besonders bevorzugt in mehreren Stufen, insbesondere einer zwei- oder dreistufigen Nachverstreckung, mit einem Gesamtverstreckungsverhältnis von 1 : 3 bis 1 : 8, vorzugsweise 1 : 4 bis 1 : 6, unterzogen.The heterofilament spun yarn produced in this way is then preferably subjected to a post-drawing, more preferably in several stages, in particular a two- or three-stage post-drawing, with a total draw ratio of 1: 3 to 1: 8, preferably 1: 4 to 1: 6.
Nach der Verstreckung schließt sich vorzugsweise eine Thermofixierung an, wobei Temperaturen von 130 bis 280°C zum Einsatz kommen; dabei wird bei konstanter Länge gearbeitet oder es wird ein Schrumpf von bis zu 30 % zugelassen.After stretching preferably followed by a heat-setting, with temperatures of 130 to 280 ° C are used; while working at a constant length or a shrinkage of up to 30% is allowed.
Als besonders vorteilhaft für die erfindungsgemäßen Monofilamente hat es sich erwiesen, wenn bei einer Schmelzetemperatur im Bereich von 285 bis 315°C und bei einem Spinnverzug von 1 : 2 bis 1 : 6 gearbeitet wird.It has proved to be particularly advantageous for the monofilaments according to the invention when working at a melt temperature in the range from 285 to 315 ° C. and at a spinning draw of from 1: 2 to 1: 6.
Die Spinnabzugsgeschwindigkeit beträgt üblicherweise 10 - 40 m pro Minute.The spinning take-off speed is usually 10 to 40 m per minute.
Beim Verspinnen des thermoplastischen Polymeren des Kern und des Fluorpolymers des Mantels zu einem Bikomponenten-Monofilament in Kern-Mantel Struktur zeigt sich überraschend eine sehr gute Kern-Mantel Haftung.When spinning the thermoplastic polymer of the core and the fluoropolymer of the shell to a bicomponent monofilament core-sheath structure surprisingly shows a very good core-shell adhesion.
Die Leitfähigkeit des Mantels kann beim Verstrecken verloren gehen, kann aber durch eine Wärmebehandlung und den dadurch ausgelösten Schrumpf, vorzugsweise oberhalb des Schmelzpunktes des Mantelmaterials, aber unterhalb der Schmelztemperatur des Kerns, wieder hergestellt werden.The conductivity of the jacket may be lost during stretching, but may be restored by a heat treatment and the shrinkage caused thereby, preferably above the melting point of the jacket material but below the melting temperature of the core.
Durch das leitfähig dotierte Fluorpolymer werden die Oberflächeneigenschaften hauptsächlich bestimmt. Die erfindungsgemäßen Fasern zeichnen sich durch sehr gute Schmutzabweisung, gute Chemikalienbeständigkeit und elektrische Leitfähigkeit aus.The conductively doped fluoropolymer mainly determines the surface properties. The fibers of the invention are characterized by very good dirt repellency, good chemical resistance and electrical conductivity.
Die Kombination mit dem Fluorpolymeren führt zu Fasern mit verbesserten Gleiteigenschaften verglichen mit Fasern aus reinem thermoplastischem Polymer. Diese Fasern zeigen im Vergleich zu Fasern aus reinem thermoplastischem Polymer eine erhöhte Schmutzabweisung.The combination with the fluoropolymer results in fibers with improved slip properties compared to pure thermoplastic polymer fibers. These fibers show increased soil repellency compared to pure thermoplastic polymer fibers.
Die erfindungsgemäßen Fasern können neben den Komponenten A) und B) Hilfsstoffe enthalten. Beispiele dafür sind Verarbeitungshilfsmittel, Stabilisatoren, Antioxidantien, Weichmacher, Gleitmittel, Pigmente, Mattierungsmittel, Viskositätsmodifizierer oder Kristallisationbeschleuniger.The fibers according to the invention may contain auxiliaries in addition to the components A) and B). Examples include processing aids, stabilizers, antioxidants, plasticizers, lubricants, pigments, matting agents, viscosity modifiers or crystallization accelerators.
Beispiele für Verarbeitungshilfsmittel sind Siloxane, Wachse oder längerkettige Carbonsäuren oder deren Salze, aliphatische, aromatische Ester oder Ether.Examples of processing aids are siloxanes, waxes or longer-chain carboxylic acids or their salts, aliphatic, aromatic esters or ethers.
Beispiele für Stabilisatoren und Antioxidantien sind die bereits oben erwähnten Polyesterstabilisatoren, Phosphorverbindungen, wie Phosphorsäureester oder Carbodiimide.Examples of stabilizers and antioxidants are the polyester stabilizers already mentioned above, phosphorus compounds such as phosphoric acid esters or carbodiimides.
Beispiele für Pigmente oder Mattierungsmittel sind organische Farbstoffpigmente oder Titandioxid.Examples of pigments or matting agents are organic dye pigments or titanium dioxide.
Bespiele für Viskositätsmodifizierer sind mehrwertige Carbonsäuren und deren Ester oder mehrwertige Alkohole.Examples of viscosity modifiers are polybasic carboxylic acids and their esters or polyhydric alcohols.
Die erfindungsgemäßen Fasern, insbesondere die Monofilamente, werden vorzugsweise zur Herstellung von textilen Flächengebilden, wie Geweben, Gewirken, Gestricken, Gelegen und Nonwovens eingesetzt.The fibers according to the invention, in particular the monofilaments, are preferably used for the production of textile fabrics, such as fabrics, knitted fabrics, crocheted, laid and nonwovens.
Textile Flächengebilde enthaltend erfindungsgemäße Monofilamente eignen sich insbesondere für technische Einsatzzwecke, wie für Filter, als Siebdruckmaterialien oder insbesondere als Papiermaschinensiebe.Textile fabrics comprising monofilaments according to the invention are particularly suitable for technical applications, such as for filters, as screen printing materials or in particular as paper machine screens.
Die erfindungsgemäßen Monofilamente haben gute textilphysikalische Eigenschaften und lassen sich leicht verweben. Die Gewebe haben die übliche Formstabilität der den Kern bildenden thermoplastischen Polymeren.The monofilaments according to the invention have good textile-physical properties and can be easily interwoven. The fabrics have the usual dimensional stability of the core forming thermoplastic polymers.
Gewebe aus diesen Monofilamenten eigenen sich hervorragend für technische Gewebe, insbesondere in der Filtration aggressiver Medien, bei denen auch die Gefahr elektrostatischer Aufladung besteht; d.h. insbesondere in der fest-gasförmig und fest-flüssig Filtration.Fabrics made of these monofilaments are excellently suited for technical fabrics, in particular in the filtration of aggressive media, which are also at risk of electrostatic charge; i.e. especially in the solid-gaseous and solid-liquid filtration.
Die Erfindung betrifft auch die Verwendung der Fasern zur Herstellung von textilen Flächengebilden, die in Umgebungen mit starker chemischer und/oder physikalischer Beanspruchung eingesetzt werden, insbesondere als Papiermaschinensiebe oder als technische Gewebe, wie sie z.B. in der Filtration, zur Herstellung von Förderbändern oder als Verstärkungseinlagen eingesetzt werden. Hier kommen die Fasern als Monofilamente und insbesondere als Schussfäden im Gewebe zum Einsatz.The invention also relates to the use of the fibers for making fabrics used in environments of high chemical and / or physical stress, in particular as paper machine fabrics or as technical fabrics, e.g. used in filtration, for the production of conveyor belts or as reinforcing inserts. Here the fibers are used as monofilaments and in particular as weft threads in the fabric.
Der Einsatz der erfindungsgemäßen Monofilamente als Papiermaschinensiebe kann in der Forming-Partie, der Preßpartie oder insbesondere in der Trockenpartie erfolgen. In der Trockenpartie kommen die erfindungsgemäßen Monofilamente insbesondere als Spiralsiebe zum Einsatz.The use of the monofilaments according to the invention as papermaking fabrics may take place in the forming section, the press section or, in particular, in the dryer section respectively. In the dryer section, the monofilaments according to the invention are used in particular as spiral sieves.
Für diese Anwendungen haben die erfindungsgemäß eingesetzten Fasern, insbesondere in Form von Monofilamenten, üblicherweise einen Titerbereich von 10 bis 4500 tex, einen Elastizitätsmodul von 2,0 bis 8,0 N/tex, eine feinheitsbezogene Festigkeit von 15 bis 50 cN/tex, eine Bruchdehnung von 15 bis 45 % und einen Heißluftschrumpf bei 180°C von 1,0 bis 20,0 %.For these applications, the fibers used according to the invention, in particular in the form of monofilaments, usually have a titer range of 10 to 4500 tex, a modulus of elasticity of 2.0 to 8.0 N / tex, a tenacity of 15 to 50 cN / tex Elongation at break of 15 to 45% and hot air shrinkage at 180 ° C of 1.0 to 20.0%.
Das nachfolgende Beispiel erläutert die Erfindung ohne diese zu begrenzen.The following example illustrates the invention without limiting it.
Die Komponenten Polyethylenterephthalat ("PET") (70 Gew. %) und Polyvinylidenfluorid (als Masterbatch enthaltend 9 Gew.% Leitfähigkeitsruß; Palmarole EXP 184/14; 30 Gew. %) wurden in zwei Extrudern mit getrennter Temperaturführung aufgeschmolzen (PET bei 282°C Schmelztemperatur (Kernmaterial) bzw. PVDF bei 240°C Schmelztemperatur (Mantelmaterial) und durch eine 20 Loch Spinndüse mit einem Lochdurchmesser von 1,40 mm und einer Abzugsgeschwindigkeit von 15 m/min zu einem Kern-Mantel-Monofilament versponnen, zweifach verstreckt (erste Verstreckung im Wasserbad bei 80°C; zweite Verstreckung im Heißluftkanal bei 150°C), sowie im Heißluftkanal bei 205°C thermofixiert. Die Gesamtverstreckung betrug 4,1 : 1. Der Enddurchmesser des Kern-Mantel Monofilaments betrug 0,500 mm.The components polyethylene terephthalate ("PET") (70% by weight) and polyvinylidene fluoride (as masterbatch containing 9% by weight of conductive carbon black; Palmarole EXP 184/14; 30% by weight) were melted in two extruders with separate temperature control (PET at 282 ° C.) C melting temperature (core material) or PVDF at 240 ° C melting temperature (sheath material) and spun through a 20-hole spinneret with a hole diameter of 1.40 mm and a take-off speed of 15 m / min to a core-sheath monofilament, stretched twice ( first drawing in a water bath at 80 ° C., second drawing in the hot air channel at 150 ° C.) and heat-setting in the hot-air channel at 205 ° C. The total drawing was 4.1: 1. The final diameter of the core-sheath monofilament was 0.500 mm.
Das erhaltene Kern-Mantel-Monofilament wies folgende Eigenschaften auf:
Claims (13)
- A melt-spun fiber having a core-sheath structure and a tensile strength of at least 15 cN/tex whose core contains a melt-spinnable synthetic thermoplastic polymer having a first melting point which is not a fluoropolymer and whose sheath contains at least one melt-spinnable fluoropolymer having a second melting point at least 20°C below the first melting point and particles composed of electroconductive material whose amount is up to 50% by weight, based on the amount of the sheath material, and where the core is 50 to 95% by weight and the sheath is 50 to 5% by weight, based on the total amount of core and sheath.
- The melt-spun fiber of claim 1, wherein the synthetic thermoplastic polymer of the core is a polyamide and especially a polyester.
- The melt-spun fiber of claim 2, wherein the polyester is a polyethylene terephthalate.
- The melt-spun fiber of claim 2, wherein the polyester is a liquid-crystalline polyester.
- The melt-spun fiber of claim 1, wherein the melt-spinnable fluoropolymer is a copolymer of tetrafluoroethylene with at least one alpha-olefin, preferably ethylene.
- The melt-spun fiber of claim 1, wherein the melt-spinnable fluoropolymer is a polyvinylidene fluoride.
- The melt-spun fiber of claim 1, wherein the sheath contains 2 to 15% by weight of electroconductive particles.
- The melt-spun fiber of claim 6, wherein the sheath contains between 2% by weight and 15% by weight and especially between 4% by weight and 9% by weight of electroconductive particles.
- The melt-spun fiber of claim 1, wherein the particles composed of electroconductive material consist of carbon, metals or metal alloys and are especially carbon black or graphite.
- The melt-spun fiber of claim 1 which is a filament, especially a monofilament.
- A process for preparing the melt-spun core-sheath fiber of claim 1, comprising the measures of:i) selecting a first polymer which is a melt-spinnable synthetic thermoplastic polymer and not a fluoropolymer and which has a first melting point,ii) selecting a second polymer which contains particles composed of electroconductive material whose amount is up to 50% by weight, based on the amount of the sheath material, and which is a melt-spinnable fluoropolymer which has a second melting point at least 20°C below the first melting point,iii) coextruding the first polymer and the second polymer through a heterofilament spinneret at a spinning temperature above the first melting point to form a bicomponent fiber having a core composed of the first polymer and a sheath composed of the second polymer andiv) drawing the produced core-sheath filament to increase the tensile strength.
- The use of melt-spun core-sheath fibers of claim 1 for producing industrial wovens.
- The use of claim 12, wherein the industrial woven is a paper machine wire, a filter cloth, a screen printing cloth, a conveyor belt or a reinforcing ply.
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DE10249585A DE10249585B4 (en) | 2002-10-24 | 2002-10-24 | Conductive, stain resistant core-sheath fiber with high chemical resistance, process for its preparation and use |
DE10249585 | 2002-10-24 |
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US20070098984A1 (en) * | 2005-11-01 | 2007-05-03 | Peterson James F Ii | Fiber with release-material sheath for papermaking belts |
US20070248823A1 (en) * | 2006-04-24 | 2007-10-25 | Daikin Industries, Ltd. | Fluorine containing copolymer fiber and fabric |
AT503675B1 (en) * | 2006-05-15 | 2008-09-15 | Lenzing Plastics Gmbh | CHEMICALLY RESISTANT AND FORM-RESISTANT MONOFILAMENTS, A METHOD FOR THE PRODUCTION THEREOF, AND THEIR USE |
DE102006042635A1 (en) * | 2006-08-31 | 2008-03-06 | Twd Fibres Gmbh | Textile product and process for its preparation |
JP4773920B2 (en) * | 2006-10-18 | 2011-09-14 | 帝人ファイバー株式会社 | Screen filament monofilament |
JP4773919B2 (en) * | 2006-10-18 | 2011-09-14 | 帝人ファイバー株式会社 | Polyester monofilament for screens with excellent anti-static properties |
CA2708804C (en) * | 2007-12-14 | 2016-01-12 | 3M Innovative Properties Company | Fiber aggregate |
WO2010108285A1 (en) | 2009-03-26 | 2010-09-30 | Asteia Technology Inc. | Non-braided reinforced hollow fibre membrane |
US9061250B2 (en) | 2009-06-26 | 2015-06-23 | Bl Technologies, Inc. | Non-braided, textile-reinforced hollow fiber membrane |
AU2011302393B2 (en) | 2010-09-15 | 2016-09-08 | Bl Technologies, Inc. | Method to make a yarn-reinforced hollow fibre membranes around a soluble core |
US8529814B2 (en) | 2010-12-15 | 2013-09-10 | General Electric Company | Supported hollow fiber membrane |
US9321014B2 (en) | 2011-12-16 | 2016-04-26 | Bl Technologies, Inc. | Hollow fiber membrane with compatible reinforcements |
US9643129B2 (en) | 2011-12-22 | 2017-05-09 | Bl Technologies, Inc. | Non-braided, textile-reinforced hollow fiber membrane |
US9022229B2 (en) | 2012-03-09 | 2015-05-05 | General Electric Company | Composite membrane with compatible support filaments |
US8999454B2 (en) | 2012-03-22 | 2015-04-07 | General Electric Company | Device and process for producing a reinforced hollow fibre membrane |
DE102012103301A1 (en) * | 2012-04-17 | 2013-10-17 | Elringklinger Ag | Fiber produced by melt spinning |
US9227362B2 (en) | 2012-08-23 | 2016-01-05 | General Electric Company | Braid welding |
MX2015007503A (en) * | 2012-12-14 | 2016-04-04 | Polysteel Atlantic Ltd | Filaments and fibers and method for making filaments and fibers. |
DE102013101201A1 (en) | 2013-02-07 | 2014-08-07 | Contitech Elastomer-Beschichtungen Gmbh | Multilayer article, in particular bellows, containing at least one textile fabric |
CN103911685A (en) * | 2014-04-29 | 2014-07-09 | 厦门怡龙谷新材料科技有限公司 | Novel composite monofilament with skin core structure and large diameter, as well as manufacturing method and application thereof |
DE102015101449A1 (en) * | 2015-02-02 | 2016-08-04 | AstenJohnson PGmbH | Industrial fabric, process for producing a nonwoven fabric and use of an industrial fabric |
EP3286263B1 (en) * | 2015-04-22 | 2020-05-06 | University of Limerick | Heating of polymeric materials |
US20220316099A1 (en) * | 2019-06-03 | 2022-10-06 | Kent State University | Liquid crystal clad fibers |
TWI718819B (en) * | 2019-12-19 | 2021-02-11 | 財團法人工業技術研究院 | Conductive fiber and method for fabricating the same |
CN112481736A (en) * | 2020-12-28 | 2021-03-12 | 南通新帝克单丝科技股份有限公司 | Polyvinylidene fluoride polyester composite monofilament and preparation method thereof |
TWI830258B (en) * | 2022-06-17 | 2024-01-21 | 立綺實業有限公司 | A core-sheath fiber and fabric thereof |
Family Cites Families (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3803453A (en) * | 1972-07-21 | 1974-04-09 | Du Pont | Synthetic filament having antistatic properties |
US4185137A (en) * | 1976-01-12 | 1980-01-22 | Fiber Industries, Inc. | Conductive sheath/core heterofilament |
DE2700436A1 (en) * | 1976-01-12 | 1977-07-14 | Fiber Industries Inc | CONDUCTIVE CORE-COAT FEDES AND THEIR USE |
US4255487A (en) * | 1977-05-10 | 1981-03-10 | Badische Corporation | Electrically conductive textile fiber |
DE3276379D1 (en) * | 1981-08-25 | 1987-06-25 | Teijin Ltd | Dyed polyester fiber composite structure |
DE8606334U1 (en) * | 1986-03-07 | 1986-05-07 | Carl Veit GmbH, 7320 Göppingen | Drying felt, in particular for paper machines |
US5288554A (en) * | 1987-03-06 | 1994-02-22 | Kureha Kagaku Kogyo K.K. | Abrasive filaments and production process thereof |
US4891263A (en) * | 1987-12-17 | 1990-01-02 | Allied-Signal Inc. | Polycarbonate random copolymer-based fiber compositions and method of melt-spinning same and device |
US5130342A (en) * | 1988-10-14 | 1992-07-14 | Mcallister Jerome W | Particle-filled microporous materials |
DE3938414C2 (en) * | 1989-08-19 | 1994-04-14 | Eurea Verpackung | Bulk goods container made of a woven carrier bag and carrier devices attached to it |
DE3930845A1 (en) * | 1989-09-15 | 1991-03-28 | Hoechst Ag | POLYESTER FIBERS MODIFIED WITH CARBODIIMIDES AND METHOD FOR THEIR PRODUCTION |
DE4412396A1 (en) * | 1993-04-12 | 1994-10-13 | Furukawa Electric Co Ltd | Plastic optical fibre, and process for the production thereof |
JP2000144533A (en) * | 1998-11-10 | 2000-05-26 | Toray Ind Inc | Polyester yarn for canvas and canvas |
US6085061A (en) * | 1998-12-22 | 2000-07-04 | Xerox Corporation | Active electrostatic cleaning brush |
JP3967039B2 (en) * | 1999-05-12 | 2007-08-29 | 株式会社クレハ | Semiconductive polyvinylidene fluoride resin composition |
JP2001271218A (en) * | 2000-03-22 | 2001-10-02 | Gunze Ltd | Semiconductive fiber and its use |
JP3656732B2 (en) * | 2000-04-21 | 2005-06-08 | 日産自動車株式会社 | Energy conversion fiber and sound absorbing material |
KR20040015770A (en) * | 2001-07-03 | 2004-02-19 | 허니웰 인터내셔날 인코포레이티드 | High-strength chemically resistant thin sheath fibers and methods of manufacture |
-
2002
- 2002-10-24 DE DE10249585A patent/DE10249585B4/en not_active Expired - Fee Related
-
2003
- 2003-09-18 DK DK03021088T patent/DK1413653T3/en active
- 2003-09-18 AT AT03021088T patent/ATE422570T1/en active
- 2003-09-18 PT PT03021088T patent/PT1413653E/en unknown
- 2003-09-18 EP EP03021088A patent/EP1413653B1/en not_active Expired - Lifetime
- 2003-09-18 DE DE50311164T patent/DE50311164D1/en not_active Expired - Lifetime
- 2003-09-18 ES ES03021088T patent/ES2321389T3/en not_active Expired - Lifetime
- 2003-10-07 US US10/680,284 patent/US20040078903A1/en not_active Abandoned
- 2003-10-22 PL PL03363021A patent/PL363021A1/en not_active Application Discontinuation
- 2003-10-24 JP JP2003364329A patent/JP2004143659A/en active Pending
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DE10249585A1 (en) | 2004-05-13 |
PT1413653E (en) | 2009-04-29 |
JP2004143659A (en) | 2004-05-20 |
EP1413653A3 (en) | 2004-10-06 |
DK1413653T3 (en) | 2009-05-11 |
EP1413653A2 (en) | 2004-04-28 |
DE10249585B4 (en) | 2007-10-04 |
PL363021A1 (en) | 2004-05-04 |
US20040078903A1 (en) | 2004-04-29 |
ATE422570T1 (en) | 2009-02-15 |
DE50311164D1 (en) | 2009-03-26 |
ES2321389T3 (en) | 2009-06-05 |
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