US20070014989A1 - Polyester fibers, their production and their use - Google Patents
Polyester fibers, their production and their use Download PDFInfo
- Publication number
- US20070014989A1 US20070014989A1 US11/483,988 US48398806A US2007014989A1 US 20070014989 A1 US20070014989 A1 US 20070014989A1 US 48398806 A US48398806 A US 48398806A US 2007014989 A1 US2007014989 A1 US 2007014989A1
- Authority
- US
- United States
- Prior art keywords
- polyester
- shaped particles
- fiber according
- layered platelet
- fiber
- 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.)
- Abandoned
Links
- 229920000728 polyester Polymers 0.000 title claims abstract description 75
- 239000000835 fiber Substances 0.000 title claims abstract description 71
- 238000004519 manufacturing process Methods 0.000 title description 4
- 239000002245 particle Substances 0.000 claims abstract description 38
- 150000001247 metal acetylides Chemical class 0.000 claims abstract description 16
- 150000004767 nitrides Chemical class 0.000 claims abstract description 16
- 238000005299 abrasion Methods 0.000 claims abstract description 15
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims abstract description 14
- 150000004679 hydroxides Chemical class 0.000 claims abstract description 11
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims abstract description 10
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 10
- -1 polyethylene terephthalate repeat Polymers 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 150000002739 metals Chemical class 0.000 claims description 11
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 8
- 125000001931 aliphatic group Chemical group 0.000 claims description 7
- 239000008188 pellet Substances 0.000 claims description 7
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- 229910052733 gallium Inorganic materials 0.000 claims description 6
- 229910052732 germanium Inorganic materials 0.000 claims description 6
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 6
- 229910052738 indium Inorganic materials 0.000 claims description 6
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 5
- 150000002009 diols Chemical class 0.000 claims description 5
- 230000007062 hydrolysis Effects 0.000 claims description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- 238000006068 polycondensation reaction Methods 0.000 claims description 4
- 230000002040 relaxant effect Effects 0.000 claims description 4
- 239000003381 stabilizer Substances 0.000 claims description 4
- 229910052712 strontium Inorganic materials 0.000 claims description 4
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 4
- 150000001718 carbodiimides Chemical class 0.000 claims description 3
- 238000009833 condensation Methods 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229920000515 polycarbonate Polymers 0.000 claims description 3
- 239000004417 polycarbonate Substances 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000004593 Epoxy Substances 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 2
- 229910052735 hafnium Inorganic materials 0.000 claims description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 2
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052706 scandium Inorganic materials 0.000 claims description 2
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 230000000903 blocking effect Effects 0.000 claims 1
- 239000004744 fabric Substances 0.000 abstract description 5
- 238000005452 bending Methods 0.000 abstract description 4
- 239000000945 filler Substances 0.000 description 21
- 239000002994 raw material Substances 0.000 description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 11
- 230000000737 periodic effect Effects 0.000 description 10
- 239000000463 material Substances 0.000 description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 description 6
- 239000005020 polyethylene terephthalate Substances 0.000 description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- JXTHNDFMNIQAHM-UHFFFAOYSA-N dichloroacetic acid Chemical compound OC(=O)C(Cl)Cl JXTHNDFMNIQAHM-UHFFFAOYSA-N 0.000 description 4
- 239000004952 Polyamide Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000011017 operating method Methods 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- 238000009987 spinning Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000006057 Non-nutritive feed additive Substances 0.000 description 2
- 241000555745 Sciuridae Species 0.000 description 2
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 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
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- 229960005215 dichloroacetic acid Drugs 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052901 montmorillonite Inorganic materials 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 239000011112 polyethylene naphthalate Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- 229920002994 synthetic fiber 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
- 238000012360 testing method Methods 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 239000004034 viscosity adjusting agent Substances 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 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
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000003868 ammonium compounds Chemical class 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000013078 crystal 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
- 230000006866 deterioration Effects 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000007380 fibre production Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 238000009998 heat setting Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052863 mullite Inorganic materials 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
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 229910052615 phyllosilicate Inorganic materials 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000013306 transparent fiber Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000002759 woven fabric 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
- 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
- D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters
-
- 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
- D01F1/10—Other agents for modifying properties
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2933—Coated or with bond, impregnation or core
Definitions
- the present invention concerns polyester fibers having abrasion and high bending fatigue resistance, especially monofilaments useful in screens or conveyor belts for example.
- polyester fibers especially monofilaments for industrial applications, are in most cases subjected to high mechanical and/or thermal stressors in use.
- stressors due to chemical and other ambient influences, to which the material has to offer adequate resistance.
- adequate resistance to all these stressors the material has to possess good dimensional stability and constancy of its stress-strain properties over very long use periods.
- One example of industrial applications imposing the combination of high mechanical, thermal and chemical stresses is the use of monofilaments in filters, screens or as conveyor belts.
- This use requires a monofilament material possessing excellent mechanical properties, such as high initial modulus, breaking strength, knot strength and loop strength and also high abrasion resistance coupled with a high hydrolysis resistance in order that it may withstand high stresses encountered in its use and in order that the screens or conveyor belts may have an adequate use life.
- Polyesters are widely used materials for this purpose. It is also known to combine these polymers with other materials, for example in order to achieve a specific degree of abrasion resistance.
- Polyester-based manufactured fibers have a proven record of good performance in such environments, but when used in hot moist environments polyesters are vulnerable to mechanical abrasion as well as hydrolytic degradation.
- Abrasion can have a wide variety of causes in industrial uses.
- the sheet-forming wire screen in papermaking machines is in the process of dewatering the paper slurry pulled over suction boxes, and this results in enhanced wear of the wire screen.
- wire screen wear occurs as a consequence of speed differences between the paper web and the wire screen surface and between the wire screen surface and the surface of the drying drums.
- Fabric wear due to abrasion also occurs in other industrial fabrics, for instance in transportation belts due to dragging across stationary surfaces, in filter fabrics due to the mechanical cleaning and in screen printing fabrics due to the movement of a squeegee across the screen surface.
- GB-A-759,374 describes the production of artificial fibers and films having improved mechanical properties.
- the claimed process is characterized by the use of very finely divided metal oxides in the form of aerosols.
- the particle size shall be not more than 150 nm.
- Viscose, polyacrylonitrile and polyamides are mentioned as examples of polymers.
- EP-A-1,186,628 discloses a polyester raw material comprising finely dispersed silica gels.
- the individual particles have diameters of up to 60 nm and aggregates, if present, are not more than 5 ⁇ m in size.
- the filler is said to lead to polyester fibers having improved mechanical properties, improved color and improved handleability.
- the reference is unforthcoming about applications for these polyester fibers.
- U.S. Pat. No. 6,544,644 (which corresponds to WO-A-01/02,629) describes monofilaments useful, inter alia, in papermaking machines.
- the description part refers mainly to polyamide monofilaments; polyester raw materials are also mentioned in very general terms.
- the monofilaments described are characterized by the presence of nanoscale inorganic materials. These provide enhanced resistance to abrasion. Platelets are described as well as spherical particles.
- the non-spherical particles described are nanoclays, i.e., layered particles. These can be treated with swelling agents, such as phosphonium or ammonium compounds, so that the layered assemblies wholly or partly dissolve to form particles less than 10 nm thick in one dimension.
- nanoscale fillers can lead to fibers having improved mechanical properties.
- the addition of fillers leads not only to the desired improvement in some properties but at the same time also to a deterioration in others.
- polyester raw materials comprising certain nanoscale fillers possess distinctly improved abrasion resistance compared with unmodified polyester raw materials without their dynamic fatigue resistance, expressed by the bending fatigue resistance, being significantly reduced by the use of a filler; in fact, it may even be increased. This performance profile was observed on selected polyester raw materials.
- the present invention has for its object to provide filled polyester fibers which, as well as excellent abrasion resistance, possess dynamic fatigue resistances which are equivalent to or even superior than those of unfilled polyester fibers.
- the present invention further has for its object to provide transparent fibers having high abrasion resistance and excellent dynamic fatigue resistance.
- This invention provides fibers comprising aliphatic-aromatic polyester and non-layered platelet-shaped particles selected from the group of inorganic oxides, hydroxides, carbonates, bicarbonates, nitrides and carbides, having a thickness in the range from 20 nm to not more than 100 nm and an aspect ratio of not more than 20:1.
- Thickness refers to the smallest extension of the particle along one of its main axes of inertia.
- Aspect ratio is the quotient along the largest extension of the particle along one of the main axes of inertia to the smallest extension of the particle along one of the main axes of inertia; that is, the aspect ratio is the quotient formed from the largest length of the particle (along one of the main axes of inertia) to the thickness of the particle.
- polyester fibers having a free carboxyl group content of not more than 3 meq/kg.
- polyester fibers comprise an agent to cap free carboxyl groups, for example a carbodiimide and/or an epoxy compound.
- Polyester fibers thus endowed are stabilized to hydrolytic degradation and are particularly suitable for use in hot moist environments, especially in papermaking machines or as filters.
- Any fiber-forming polyester can be used as long as it comprises aliphatic and aromatic groups and is formable in the melt.
- Aliphatic groups are herein also to be understood as meaning cycloaliphatic groups.
- thermoplastic polyesters are known per se. Examples thereof are polybutylene terephthalate, polycyclohexanedimethyl terephthalate, polyethylene naphthalate or especially polyethylene terephthalate. Building blocks of fiber-forming polyesters are preferably diols and dicarboxylic acids or appropriately constructed oxyl carboxylic acids.
- the main acid constituent of polyesters is terephthalic acid or cyclohexanedicarboxylic acid, but other aromatic and/or aliphatic or cycloaliphatic dicarboxylic acids may be suitable as well, preferably para- or trans-disposed aromatic compounds, for example 2,6-naphthalenedicarboxylic acid or 4,4′-biphenyldicarboxylic acid, and also isophthalic acid.
- Aliphatic dicarboxylic acids such as adipic acid or sebacic acid for example, are preferably used in combination with aromatic dicarboxylic acids.
- Useful dihydric alcohols typically include aliphatic and/or cycloaliphatic diols, for example ethylene glycol, propanediol, 1,4-butanediol, 1,4-cyclohexanedimethanol or mixtures thereof. Preference is given to aliphatic diols which have two to four carbon atoms, especially ethylene glycol; preference is further given to cycloaliphatic diols, such as 1,4-cyclohexanedimethanol.
- polyesters comprising structural repeat units derived from an aromatic dicarboxylic acid and an aliphatic and/or cycloaliphatic diol.
- thermoplastic polyesters are especially selected from the group consisting of polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polypropylene terephthalate, polybutylene terephthalate, polycyclohexanedimethanol terephthalate, or a copolycondensate comprising polybutylene glycol, terephthalic acid and naphthalenedicarboxylic acid units.
- the polyesters used according to the present invention typically have solution viscosities (IV values) of not less than 0.60 dl/g, preferably of 0.60 to 1.05 dl/g and more preferably of 0.62-0.93 dl/g (measured at 25° C. in dichloroacetic acid (DCE)).
- IV values solution viscosities
- the nanoscale fillers used according to the present invention endow polyester fibers with excellent abrasion resistance without adversely affecting the dynamic properties, expressed by the bending fatigue resistance.
- the fillers used according to the present invention are specific non-layered platelet-shaped particles. These are selected from the group consisting of inorganic oxides, hydroxides, carbonates, bicarbonates, nitrides and carbides.
- a further characteristic property of these fillers is their shape.
- the particles are not spherical but platelet shaped. Their thickness is not more than 100 nm, preferably not more than 80 nm and in particular in the range from 20 to 60 nm.
- a further characteristic property of these fillers is their aspect ratio, i.e., the ratio of the largest extension of the particle on one of the main axes of inertia to the smallest extension of the particle along one of the main axes of inertia. The aspect ratio is not more than 20:1.
- Layered fillers such as phyllosilicates (so-called nanoclays), montmorillonites for example, are not wanted in this invention, since their use not only disrupts the processing of the fibers but also did not lead to any significant improvement in properties being observed.
- the nanoscale non-spherical oxides used according to the present invention are oxides of metals of group IIa of the periodic table, preferably oxides of magnesium, of calcium or of strontium, or oxides of metals of group IIIb of the periodic table, preferably oxides of aluminum, of gallium or of indium, or oxides of metals of group IVa of the periodic table, preferably oxides of titanium, of zirconium or of hafnium, or oxides of metals of group IIIa of the periodic table, preferably oxides of scandium or of yttrium or oxides of metals or semimetals of group IVb of the periodic table, preferably oxides of silicon, of germanium or of tin.
- the corresponding hydroxides can also be used, or else mixed crystals formed from different metal oxides, for example Al 2 O 3 *2SiO 2 (mullite).
- the nanoscale non-spherical carbonates used according to the present invention are carbonates of metals of group IIa of the periodic table, preferably carbonates of magnesium, of calcium or of strontium.
- the nanoscale non-spherical carbides used according to the present invention are carbides of metals of group IIIb of the periodic table, preferably carbides of aluminum, of gallium or of indium, or carbides of metals or semimetals of group IVb of the periodic table, preferably carbides of silicon, of germanium or of tin.
- the nanoscale non-spherical nitrides used according to the present invention are nitrides of metals of group IIIb of the periodic table, preferably nitrides of aluminum, of gallium or of indium, or nitrides of metals or semimetals of group IVb of the periodic table, preferably nitrides of silicon, of germanium or of tin.
- nanoscale non-spherical aluminum oxide aluminum nitride, silicon dioxide, zirconium dioxide, silicon carbide, silicon nitride, yttrium oxide or calcium carbonate.
- polyester raw materials filled and needed to produce the fibers of the present invention can be produced in various ways.
- polyester and filler, and also if appropriate further additives can be mixed in a mixing assembly, for example in an extruder, by melting the polyester, and the composition is then fed directly to the spinneret die or the composition is granulated and spun in a separate step.
- the pellet obtained may, if appropriate, also be spun as a masterbatch together with additional polyester. It is also possible to add the nanoscale fillers before or during the polycondensation of the polyester.
- Suitable nanoscale non-spherical fillers are commercially obtainable.
- the DP 6096 product (calcium carbonate in ethylene glycol) from Nano Technologies, Inc., Ashland, Mass., USA can be used.
- the level of nanoscale non-spherical filler in the fiber of the present invention can vary within wide limits, but is typically not more than 5% by weight, based on the mass of the fiber.
- the level of nanoscale spherical filler is preferably in the range from 0.1% to 2.5% by weight and in particular in the range from 0.5% to 2.0% by weight.
- the identities and amounts of the components a) and b) are preferably chosen so that transparent products are obtained.
- the polyesters used according to the present invention are notable for transparency. It has been determined that, surprisingly, the nanoscale non-spherical fillers have no adverse effect on transparency. By contrast, the addition of just about 0.3% by weight of non-nanoscale titanium dioxide (delusterant) causes the fiber to turn completely white.
- the abrasion resistance of the fibers according to the present invention can be still further enhanced by the addition of polycarbonate.
- the amount of polycarbonate is typically up to 5% by weight, preferably in the range from 0.1% to 5.0% by weight and more preferably in the range from 0.5% to 2.0% by weight, based on the total mass of the polymers.
- Fibers are in the context of this description to be understood as meaning any desired fibers.
- filaments or staple fibers which consist of a plurality of individual fibers, but are monofilaments in particular.
- polyester fibers of the present invention can be produced by conventional processes.
- the present invention also provides a process for producing the above-defined fibers, the process comprising the measures of:
- the polyester fibers of the present invention are subjected to single or multiple drawing in the course of their process of production.
- polyester fibers using a polyester produced by solid state condensation.
- polyester fibers of the present invention can be present in any desired form, for example as multifilaments, as staple fibers or especially as monofilaments.
- the linear density of the polyester fibers according to the present invention can likewise vary within wide limits. Examples thereof are 100 to 45 000 dtex and especially 400 to 7000 dtex.
- the polyester fibers according to the present invention can be produced using a commercially available polyester raw material.
- a commercially available polyester raw material will typically have a free carboxyl group content in the range from 15 to 50 meq/kg of polyester. Preference is given to using polyester raw materials produced by solid state condensation; their free carboxyl group content is typically in the range from 5 to 20 meq/kg and preferably less than 8 meq/kg of polyester.
- the polyester fibers of the present invention can also be produced using a polyester raw material which already comprises the nanoscale non-layered platelet-shaped filler.
- the polyester raw material is produced by adding the filler during the polycondensation and/or to at least one of the monomers.
- the hot strand of polymer is quenched, for example in a quench bath, preferably in a water bath, and subsequently wound up or taken off.
- the takeoff speed is greater than the ejection speed of the polymer melt.
- the polyester fiber thus produced is subsequently preferably subjected to an afterdrawing operation, more preferably in a plurality of stages, especially to a two- or three-stage afterdrawing operation, to an overall draw ratio in the range from 3:1 to 8:1 and preferably in the range from 4:1 to 6:1.
- Drawing is preferably followed by heat setting, for which temperatures in the range from 130 to 280° C. are employed; length is maintained constant, slight after-drawing is effected or shrinkage of up to 30% is allowed.
- polyester fibers of the present invention It has been determined to be particularly advantageous for the production of the polyester fibers of the present invention to operate at a melt temperature in the range from 285 to 315° C. and at a jet stretch ratio in the range from 2:1 to 6:1.
- the takeoff speed is customarily 10-80 m per minute.
- polyester fibers of the present invention may comprise further auxiliary materials.
- auxiliaries are processing aids, antioxidants, plasticizers, lubricants, pigments, delusterants, viscosity modifiers or crystallization accelerants.
- processing aids are siloxanes, waxes or long-chain carboxylic acids or their salts, aliphatic, aromatic esters or ethers.
- antioxidants are phosphorus compounds, such as phosphoric esters, or sterically hindered phenols.
- pigments or delusterants examples include organic dye pigments or titanium dioxide.
- viscosity modifiers are polybasic carboxylic acids and their esters or polyhydric alcohols.
- the fibers of the present invention can be used in all industrial fields. They are preferably employed for applications where increased wear due to mechanical stress is likely. Examples thereof are the use in screens or conveyor belts. These uses likewise form part of the subject matter of the present invention.
- polyester fibers of the present invention are preferably used for producing sheetlike structures, in particular woven fabrics used in screens.
- polyester fibers of the present invention in the form of monofilaments concerns their use as conveyor belts or as components of conveyor belts.
- the present invention further provides for the use of non-layered platelet-shaped particles selected from the group of inorganic oxides, hydroxides, carbonates, bicarbonates, nitrides and carbides, having a thickness not more than 100 nm and an aspect ratio of not more than 20:1, for producing fibers, especially monofilaments, having high abrasion resistance.
- PET Polyethylene terephthalate
- hydrolysis stabilizer if appropriate hydrolysis stabilizer were mixed in an extruder, melted and spun through a 20 hole spinneret die having a hole diameter of 1.0 mm at a feed rate of 488 g/min and a takeoff speed of 31 m/min to form monofilaments, triply drawn to draw ratios of 4.95:1, 1.13:1 and 0.79:1 and also heat-set in a hot air duct at 255° C. with shrinkage being allowed.
- the overall draw ratio was 4.52:1.
- Monofilaments having a diameter of 0.25 mm were obtained.
- the PET used was a type having an IV value of 0.72 dl/g, to which 0.04% by weight of nanoscale Al 2 O 3 of 50 nm had been added.
- the hydrolysis stabilizer used was a carbodiimide (Stabaxol® 1, from Rheinchemie).
- Monofilaments were produced as described in the operating method for Inventive Example 1. Different PET raw materials were used but no nanoscale fillers. A type having IV value of 0.72 dl/g was used in Comparative Example 1 and a type having IV value of 0.9 dl/g in Comparative Example 2.
- Fiber properties were determined as follows:
- Squirrel cage test conducted using a rotatable metallic abrader having metal bars mounted on a drum rotating at a constant speed of rotation. The monofil was mounted on this abrader using a constant pretension. The number of rotations to filament breakage is measured.
Abstract
Described are fibers comprising aliphatic-aromatic polyester and non-layered platelet-shaped particles selected from the group of inorganic oxides, hydroxides, carbonates, bicarbonates, nitrides and carbides, having a thickness in the range from 20 nm to not more than 100 nm and an aspect ratio of not more than 20:1. The polyester fibers possess excellent bending fatigue resistance, give distinctly reduced abrasion and are useful for producing screens or other industrial fabrics.
Description
- This application is based upon German Patent Application No. DE 10 2005 033 350.8, entitled “Polyesterfasern, Verfahren zu deren Herstellung und deren Verwendung”, filed Jul. 16, 2005. The priority of German Patent Application No. DE 10 2005 033 350.8 is hereby claimed and its disclosure incorporated herein by reference.
- The present invention concerns polyester fibers having abrasion and high bending fatigue resistance, especially monofilaments useful in screens or conveyor belts for example.
- It is known that polyester fibers, especially monofilaments for industrial applications, are in most cases subjected to high mechanical and/or thermal stressors in use. In addition, there are in many cases stressors due to chemical and other ambient influences, to which the material has to offer adequate resistance. As well as adequate resistance to all these stressors, the material has to possess good dimensional stability and constancy of its stress-strain properties over very long use periods.
- One example of industrial applications imposing the combination of high mechanical, thermal and chemical stresses is the use of monofilaments in filters, screens or as conveyor belts. This use requires a monofilament material possessing excellent mechanical properties, such as high initial modulus, breaking strength, knot strength and loop strength and also high abrasion resistance coupled with a high hydrolysis resistance in order that it may withstand high stresses encountered in its use and in order that the screens or conveyor belts may have an adequate use life.
- Molding compositions possessing high chemical and physical resistance and their use for fiber production are known. Polyesters are widely used materials for this purpose. It is also known to combine these polymers with other materials, for example in order to achieve a specific degree of abrasion resistance.
- Industrial manufacturers, such as paper makers or processors, utilize filters or conveyor belts in operations taking place at elevated temperatures and in hot moist environments. Polyester-based manufactured fibers have a proven record of good performance in such environments, but when used in hot moist environments polyesters are vulnerable to mechanical abrasion as well as hydrolytic degradation.
- Abrasion can have a wide variety of causes in industrial uses. For instance, the sheet-forming wire screen in papermaking machines is in the process of dewatering the paper slurry pulled over suction boxes, and this results in enhanced wear of the wire screen. At the dry end of the papermaking machine, wire screen wear occurs as a consequence of speed differences between the paper web and the wire screen surface and between the wire screen surface and the surface of the drying drums. Fabric wear due to abrasion also occurs in other industrial fabrics, for instance in transportation belts due to dragging across stationary surfaces, in filter fabrics due to the mechanical cleaning and in screen printing fabrics due to the movement of a squeegee across the screen surface.
- Adding fillers to improve the mechanical properties of fibers is known per se.
- GB-A-759,374 describes the production of artificial fibers and films having improved mechanical properties. The claimed process is characterized by the use of very finely divided metal oxides in the form of aerosols. The particle size shall be not more than 150 nm. Viscose, polyacrylonitrile and polyamides are mentioned as examples of polymers.
- EP-A-1,186,628 discloses a polyester raw material comprising finely dispersed silica gels. The individual particles have diameters of up to 60 nm and aggregates, if present, are not more than 5 μm in size. The filler is said to lead to polyester fibers having improved mechanical properties, improved color and improved handleability. The reference is unforthcoming about applications for these polyester fibers.
- U.S. Pat. No. 6,544,644 (which corresponds to WO-A-01/02,629) describes monofilaments useful, inter alia, in papermaking machines. The description part refers mainly to polyamide monofilaments; polyester raw materials are also mentioned in very general terms. The monofilaments described are characterized by the presence of nanoscale inorganic materials. These provide enhanced resistance to abrasion. Platelets are described as well as spherical particles. The non-spherical particles described are nanoclays, i.e., layered particles. These can be treated with swelling agents, such as phosphonium or ammonium compounds, so that the layered assemblies wholly or partly dissolve to form particles less than 10 nm thick in one dimension. In the case of platelet-shaped particles, this reference thus mentions either the use of layered particles whose layered structure has only incompletely dissolved, if at all, so that aggregates below 100 nm in thickness are present, or whose layered structure has completely dissolved, in which case particles having thicknesses below 10 nm are present. Exfoliated montmorillonites are mentioned in this reference as one example of these platelets.
- The use of layer-shaped and platelet-shaped nanoparticles, so-called nanoclays, in polyester spinning dopes has shown that in general, there are problems with the spinning. Either the spinning dopes cannot be processed at all, or special measures have to be taken if a fiber is to be produced at all. If, on the other hand, nanoparticles lacking sufficient thickness are used, it has been determined that the fibers formed do not have satisfactory textile-technological properties. It is believed that the high fraction of interfaces due to these very small particles in the polymer has a disruptive effect on the drawing stage, so that polymer chains are insufficiently aligned after the drawing operation. This has an adverse effect on the mechanical properties, for example the strength, of the fiber.
- The use of nanoscale fillers can lead to fibers having improved mechanical properties. In general, however, the addition of fillers leads not only to the desired improvement in some properties but at the same time also to a deterioration in others.
- It has now been found that, surprisingly, selected polyester raw materials comprising certain nanoscale fillers possess distinctly improved abrasion resistance compared with unmodified polyester raw materials without their dynamic fatigue resistance, expressed by the bending fatigue resistance, being significantly reduced by the use of a filler; in fact, it may even be increased. This performance profile was observed on selected polyester raw materials.
- Proceeding from this prior art, the present invention has for its object to provide filled polyester fibers which, as well as excellent abrasion resistance, possess dynamic fatigue resistances which are equivalent to or even superior than those of unfilled polyester fibers.
- The present invention further has for its object to provide transparent fibers having high abrasion resistance and excellent dynamic fatigue resistance.
- This invention provides fibers comprising aliphatic-aromatic polyester and non-layered platelet-shaped particles selected from the group of inorganic oxides, hydroxides, carbonates, bicarbonates, nitrides and carbides, having a thickness in the range from 20 nm to not more than 100 nm and an aspect ratio of not more than 20:1.
- The invention is described in detail below with reference to several embodiments and numerous examples. Such discussion is for purposes of illustration only. Modifications to particular examples within the spirit and scope of the present invention, set forth in the appended claims, will be readily apparent to one of skill in the art. Terminology used herein is given its ordinary meaning consistent with the exemplary definitions set forth immediately below.
- Thickness, as used herein, refers to the smallest extension of the particle along one of its main axes of inertia.
- Aspect ratio, as used herein, is the quotient along the largest extension of the particle along one of the main axes of inertia to the smallest extension of the particle along one of the main axes of inertia; that is, the aspect ratio is the quotient formed from the largest length of the particle (along one of the main axes of inertia) to the thickness of the particle.
- Preference is given to polyester fibers having a free carboxyl group content of not more than 3 meq/kg.
- These polyester fibers comprise an agent to cap free carboxyl groups, for example a carbodiimide and/or an epoxy compound.
- Polyester fibers thus endowed are stabilized to hydrolytic degradation and are particularly suitable for use in hot moist environments, especially in papermaking machines or as filters.
- Any fiber-forming polyester can be used as long as it comprises aliphatic and aromatic groups and is formable in the melt. Aliphatic groups are herein also to be understood as meaning cycloaliphatic groups.
- These thermoplastic polyesters are known per se. Examples thereof are polybutylene terephthalate, polycyclohexanedimethyl terephthalate, polyethylene naphthalate or especially polyethylene terephthalate. Building blocks of fiber-forming polyesters are preferably diols and dicarboxylic acids or appropriately constructed oxyl carboxylic acids. The main acid constituent of polyesters is terephthalic acid or cyclohexanedicarboxylic acid, but other aromatic and/or aliphatic or cycloaliphatic dicarboxylic acids may be suitable as well, preferably para- or trans-disposed aromatic compounds, for example 2,6-naphthalenedicarboxylic acid or 4,4′-biphenyldicarboxylic acid, and also isophthalic acid. Aliphatic dicarboxylic acids, such as adipic acid or sebacic acid for example, are preferably used in combination with aromatic dicarboxylic acids.
- Useful dihydric alcohols typically include aliphatic and/or cycloaliphatic diols, for example ethylene glycol, propanediol, 1,4-butanediol, 1,4-cyclohexanedimethanol or mixtures thereof. Preference is given to aliphatic diols which have two to four carbon atoms, especially ethylene glycol; preference is further given to cycloaliphatic diols, such as 1,4-cyclohexanedimethanol.
- Preference is given to using polyesters comprising structural repeat units derived from an aromatic dicarboxylic acid and an aliphatic and/or cycloaliphatic diol.
- Preferred thermoplastic polyesters are especially selected from the group consisting of polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polypropylene terephthalate, polybutylene terephthalate, polycyclohexanedimethanol terephthalate, or a copolycondensate comprising polybutylene glycol, terephthalic acid and naphthalenedicarboxylic acid units.
- The polyesters used according to the present invention typically have solution viscosities (IV values) of not less than 0.60 dl/g, preferably of 0.60 to 1.05 dl/g and more preferably of 0.62-0.93 dl/g (measured at 25° C. in dichloroacetic acid (DCE)).
- The nanoscale fillers used according to the present invention endow polyester fibers with excellent abrasion resistance without adversely affecting the dynamic properties, expressed by the bending fatigue resistance.
- The fillers used according to the present invention are specific non-layered platelet-shaped particles. These are selected from the group consisting of inorganic oxides, hydroxides, carbonates, bicarbonates, nitrides and carbides.
- A further characteristic property of these fillers is their shape. The particles are not spherical but platelet shaped. Their thickness is not more than 100 nm, preferably not more than 80 nm and in particular in the range from 20 to 60 nm. A further characteristic property of these fillers is their aspect ratio, i.e., the ratio of the largest extension of the particle on one of the main axes of inertia to the smallest extension of the particle along one of the main axes of inertia. The aspect ratio is not more than 20:1. Layered fillers, such as phyllosilicates (so-called nanoclays), montmorillonites for example, are not wanted in this invention, since their use not only disrupts the processing of the fibers but also did not lead to any significant improvement in properties being observed.
- Typically, the nanoscale non-spherical oxides used according to the present invention are oxides of metals of group IIa of the periodic table, preferably oxides of magnesium, of calcium or of strontium, or oxides of metals of group IIIb of the periodic table, preferably oxides of aluminum, of gallium or of indium, or oxides of metals of group IVa of the periodic table, preferably oxides of titanium, of zirconium or of hafnium, or oxides of metals of group IIIa of the periodic table, preferably oxides of scandium or of yttrium or oxides of metals or semimetals of group IVb of the periodic table, preferably oxides of silicon, of germanium or of tin.
- Instead of oxides, the corresponding hydroxides can also be used, or else mixed crystals formed from different metal oxides, for example Al2O3*2SiO2 (mullite).
- Typically, the nanoscale non-spherical carbonates used according to the present invention are carbonates of metals of group IIa of the periodic table, preferably carbonates of magnesium, of calcium or of strontium.
- Typically, the nanoscale non-spherical carbides used according to the present invention are carbides of metals of group IIIb of the periodic table, preferably carbides of aluminum, of gallium or of indium, or carbides of metals or semimetals of group IVb of the periodic table, preferably carbides of silicon, of germanium or of tin.
- Typically, the nanoscale non-spherical nitrides used according to the present invention are nitrides of metals of group IIIb of the periodic table, preferably nitrides of aluminum, of gallium or of indium, or nitrides of metals or semimetals of group IVb of the periodic table, preferably nitrides of silicon, of germanium or of tin.
- Particular preference is given to using nanoscale non-spherical aluminum oxide, aluminum nitride, silicon dioxide, zirconium dioxide, silicon carbide, silicon nitride, yttrium oxide or calcium carbonate.
- Very particular preference is given to using nanoscale non-spherical aluminum oxide or calcium carbonate.
- The polyester raw materials filled and needed to produce the fibers of the present invention can be produced in various ways. For instance, polyester and filler, and also if appropriate further additives, can be mixed in a mixing assembly, for example in an extruder, by melting the polyester, and the composition is then fed directly to the spinneret die or the composition is granulated and spun in a separate step. The pellet obtained may, if appropriate, also be spun as a masterbatch together with additional polyester. It is also possible to add the nanoscale fillers before or during the polycondensation of the polyester.
- Suitable nanoscale non-spherical fillers are commercially obtainable. For example, the DP 6096 product (calcium carbonate in ethylene glycol) from Nano Technologies, Inc., Ashland, Mass., USA can be used.
- The level of nanoscale non-spherical filler in the fiber of the present invention can vary within wide limits, but is typically not more than 5% by weight, based on the mass of the fiber. The level of nanoscale spherical filler is preferably in the range from 0.1% to 2.5% by weight and in particular in the range from 0.5% to 2.0% by weight.
- The identities and amounts of the components a) and b) are preferably chosen so that transparent products are obtained. Unlike polyamides, the polyesters used according to the present invention are notable for transparency. It has been determined that, surprisingly, the nanoscale non-spherical fillers have no adverse effect on transparency. By contrast, the addition of just about 0.3% by weight of non-nanoscale titanium dioxide (delusterant) causes the fiber to turn completely white.
- It has further been determined that, surprisingly, the abrasion resistance of the fibers according to the present invention can be still further enhanced by the addition of polycarbonate. The amount of polycarbonate is typically up to 5% by weight, preferably in the range from 0.1% to 5.0% by weight and more preferably in the range from 0.5% to 2.0% by weight, based on the total mass of the polymers.
- Fibers are in the context of this description to be understood as meaning any desired fibers.
- Examples thereof are filaments or staple fibers which consist of a plurality of individual fibers, but are monofilaments in particular.
- The polyester fibers of the present invention can be produced by conventional processes.
- The present invention also provides a process for producing the above-defined fibers, the process comprising the measures of:
-
- i) mixing polyester pellet with non-layered platelet-shaped particles selected from the group of inorganic oxides, hydroxides, carbonates, bicarbonates, nitrides and carbides having a thickness in the range from 20 nm to not more than 100 nm and an aspect ratio of not more than 20:1,
- ii) extruding the mixture comprising polyester and non-layered platelet-shaped particles through a spinneret die,
- iii) withdrawing the resulting filament, and
- iv) optionally drawing and/or relaxing the resulting filament.
The present invention also provides a process for producing the above-defined fibers, the process comprising the measures of: - i) feeding an extruder with polyester pellet mixed before or during the polycondensation with polyester pellet with non-layered platelet-shaped particles selected from the group of inorganic oxides, hydroxides, carbonates, bicarbonates, nitrides and carbides, having a thickness in the range from 20 nm to not more than 100 nm and an aspect ratio of not more than 20:1,
- ii) extruding the mixture comprising polyester and non-layered and platelet-shaped particles through a spinneret die,
- iii) withdrawing the resulting filament, and
- iv) optionally drawing and/or relaxing the resulting filament.
- Preferably, the polyester fibers of the present invention are subjected to single or multiple drawing in the course of their process of production.
- It is particularly preferable to produce the polyester fibers using a polyester produced by solid state condensation.
- The polyester fibers of the present invention can be present in any desired form, for example as multifilaments, as staple fibers or especially as monofilaments.
- The linear density of the polyester fibers according to the present invention can likewise vary within wide limits. Examples thereof are 100 to 45 000 dtex and especially 400 to 7000 dtex.
- Particular preference is given to monofilaments whose cross-sectional shape is round, oval or n-gonal, where n is not less than 3.
- The polyester fibers according to the present invention can be produced using a commercially available polyester raw material. A commercially available polyester raw material will typically have a free carboxyl group content in the range from 15 to 50 meq/kg of polyester. Preference is given to using polyester raw materials produced by solid state condensation; their free carboxyl group content is typically in the range from 5 to 20 meq/kg and preferably less than 8 meq/kg of polyester.
- However, the polyester fibers of the present invention can also be produced using a polyester raw material which already comprises the nanoscale non-layered platelet-shaped filler. The polyester raw material is produced by adding the filler during the polycondensation and/or to at least one of the monomers.
- After the polyester melt has been forced through a spinneret die, the hot strand of polymer is quenched, for example in a quench bath, preferably in a water bath, and subsequently wound up or taken off. The takeoff speed is greater than the ejection speed of the polymer melt.
- The polyester fiber thus produced is subsequently preferably subjected to an afterdrawing operation, more preferably in a plurality of stages, especially to a two- or three-stage afterdrawing operation, to an overall draw ratio in the range from 3:1 to 8:1 and preferably in the range from 4:1 to 6:1.
- Drawing is preferably followed by heat setting, for which temperatures in the range from 130 to 280° C. are employed; length is maintained constant, slight after-drawing is effected or shrinkage of up to 30% is allowed.
- It has been determined to be particularly advantageous for the production of the polyester fibers of the present invention to operate at a melt temperature in the range from 285 to 315° C. and at a jet stretch ratio in the range from 2:1 to 6:1.
- The takeoff speed is customarily 10-80 m per minute.
- The polyester fibers of the present invention, as well as nanoscale non-layered platelet-shaped filler, may comprise further auxiliary materials.
- Besides the hydrolysis stabilizer already mentioned, examples of further auxiliaries are processing aids, antioxidants, plasticizers, lubricants, pigments, delusterants, viscosity modifiers or crystallization accelerants.
- Examples of processing aids are siloxanes, waxes or long-chain carboxylic acids or their salts, aliphatic, aromatic esters or ethers.
- Examples of antioxidants are phosphorus compounds, such as phosphoric esters, or sterically hindered phenols.
- Examples of pigments or delusterants are organic dye pigments or titanium dioxide.
- Examples of viscosity modifiers are polybasic carboxylic acids and their esters or polyhydric alcohols.
- The fibers of the present invention can be used in all industrial fields. They are preferably employed for applications where increased wear due to mechanical stress is likely. Examples thereof are the use in screens or conveyor belts. These uses likewise form part of the subject matter of the present invention.
- The polyester fibers of the present invention are preferably used for producing sheetlike structures, in particular woven fabrics used in screens.
- A further use for the polyester fibers of the present invention in the form of monofilaments concerns their use as conveyor belts or as components of conveyor belts.
- Particular preference is given to uses for the fibers of the present invention in screens which are wire screens and intended for use in the dry end of papermaking machines.
- These uses likewise form part of the subject matter of the present invention.
- The present invention further provides for the use of non-layered platelet-shaped particles selected from the group of inorganic oxides, hydroxides, carbonates, bicarbonates, nitrides and carbides, having a thickness not more than 100 nm and an aspect ratio of not more than 20:1, for producing fibers, especially monofilaments, having high abrasion resistance.
- The examples which follow illustrate the invention without limiting the invention in any way.
- Polyethylene terephthalate (PET) and if appropriate hydrolysis stabilizer were mixed in an extruder, melted and spun through a 20 hole spinneret die having a hole diameter of 1.0 mm at a feed rate of 488 g/min and a takeoff speed of 31 m/min to form monofilaments, triply drawn to draw ratios of 4.95:1, 1.13:1 and 0.79:1 and also heat-set in a hot air duct at 255° C. with shrinkage being allowed. The overall draw ratio was 4.52:1. Monofilaments having a diameter of 0.25 mm were obtained.
- The PET used was a type having an IV value of 0.72 dl/g, to which 0.04% by weight of nanoscale Al2O3 of 50 nm had been added.
- The hydrolysis stabilizer used was a carbodiimide (Stabaxol® 1, from Rheinchemie).
- Monofilaments were produced as described in the operating method for Inventive Example 1. Different PET raw materials were used but no nanoscale fillers. A type having IV value of 0.72 dl/g was used in Comparative Example 1 and a type having IV value of 0.9 dl/g in Comparative Example 2.
- Fiber properties were determined as follows:
-
- Tensile strength to DIN EN/ISO 2062
- Breaking extension to DIN EN/ISO 2062
- Hot air shrinkage to DIN 53843
- Squirrel cage test: conducted using a rotatable metallic abrader having metal bars mounted on a drum rotating at a constant speed of rotation. The monofil was mounted on this abrader using a constant pretension. The number of rotations to filament breakage is measured.
- The table which follows summarizes the properties of the monofilaments.
Hot air Fiber Tensile Breaking shrinkage Squirrel Example diameter strength extension at 200° C. cage test No. [mm] [cN/tex] (%) (%) (cycles) Inv. 1 0.25 31.5 37.8 10.8 7503 Comp. 1 0.254 31.2 37.2 11.0 1249 Comp. 2 0.25 33.3 41.0 4.4 7342 - While the invention has been described in detail, modifications within the spirit and scope of the invention will be readily apparent to those of skill in the art. In view of the foregoing discussion, relevant knowledge in the art and references including co-pending applications discussed above in connection with the Background and Detailed Description, the disclosures of which are all incorporated herein by reference, further description is deemed unnecessary.
Claims (22)
1. A fiber comprising aliphatic-aromatic polyester and non-layered platelet-shaped particles selected from the group of inorganic oxides, hydroxides, carbonates, bicarbonates, nitrides and carbides, having a thickness in the range from 20 nm to not more than 100 nm and an aspect ratio of not more than 20:1.
2. The fiber according to claim 1 wherein the polyester comprises structural repeat units derived from an aromatic dicarboxylic acid and an aliphatic and/or cycloaliphatic diol, especially polyethylene terephthalate repeat units alone or combined with other structural repeat units derived from alkylene glycols and aliphatic dicarboxylic acids.
3. The fiber according to claim 1 wherein the aliphatic-aromatic polyester has a free carboxyl group content of not more than 3 meq/kg.
4. The fiber according to claim 3 comprising a hydrolysis stabilizer for blocking free carboxyl groups, preferably at least one carbodiimide and/or at least one epoxy compound.
5. The fiber according to claim 1 wherein the non-layered platelet-shaped particles are not more than 80 nm and in particular from 20 to 60 nm in thickness.
6. The fiber according to claim 1 wherein the non-layered platelet-shaped particles are oxides of magnesium, of calcium, of strontium, of aluminum, of gallium, of indium, of titanium, of zirconium, of hafnium, of scandium, of yttrium, of silicon, of germanium, of tin or mixed oxides of these metals or semimetals.
7. The fiber according to claim 1 wherein the non-layered platelet-shaped particles are carbonates of magnesium, of calcium or of strontium.
8. The fiber according to claim 1 wherein the non-layered platelet-shaped particles are carbides of aluminum, of gallium, of indium, of silicon, of germanium or of tin.
9. The fiber according to claim 1 wherein the non-layered platelet-shaped particles are nitrides of aluminum, of gallium, of indium, of silicon, of germanium or of tin.
10. The fiber according to claim 1 wherein the non-layered platelet-shaped particles are selected from the group consisting of aluminum oxide, aluminum nitride, silicon dioxide, zirconium dioxide, silicon carbide, silicon nitride, yttrium oxide or calcium carbonate.
11. The fiber according to claim 10 wherein the non-layered platelet-shaped particles are selected from the group consisting of aluminum oxide or calcium carbonate.
12. The fiber according to claim 1 whose content of non-layered platelet-shaped particles is in the range from 0.1% to 5% by weight and preferably in the range from 1% to 2% by weight, based on the mass of the fiber.
13. The fiber according to claim 1 which, as well as the aliphatic-aromatic polyester, comprises from 0.1% to 5% by weight and preferably from 0.5% to 2% by weight, based on the total mass of the polymers, of polycarbonate.
14. The fiber according to claim 1 which is transparent.
15. The fiber according to claim 1 which is a monofilament.
16. The fiber according to claim 1 incorporated into a screen or conveyor belt.
17. The fiber according to claim 1 incorporated into a wire screen intended for use in the dry end of papermaking machines.
18. A process for producing the fibers according to claim 1 , the process comprising the steps of:
i) mixing polyester pellet with non-layered platelet-shaped particles selected from the group of inorganic oxides, hydroxides, carbonates, bicarbonates, nitrides and carbides having a thickness in the range from 20 nm to not more than 100 nm and an aspect ratio of not more than 20:1,
ii) extruding the mixture comprising polyester and non-layered platelet-shaped particles through a spinneret die,
iii) withdrawing the resulting filament, and
iv) optionally drawing and/or relaxing the resulting filament.
19. The process according to claim 18 wherein the polyester fiber is subjected to single or multiple drawing.
20. The process according to claim 18 wherein the polyester fiber is produced using a polyester produced by solid state condensation.
21. A process for producing the fibers according to claim 1 , the process comprising the steps of:
i) feeding an extruder with polyester pellet mixed before or during the polycondensation with polyester pellet with non-layered platelet-shaped particles selected from the group of inorganic oxides, hydroxides, carbonates, bicarbonates, nitrides and carbides, having a thickness in the range from 20 nm to not more than 100 nm and an aspect ratio of not more than 20:1,
ii) extruding the mixture comprising polyester and non-layered platelet-shaped particles through a spinneret die,
iii) withdrawing the resulting filament, and
iv) optionally drawing and/or relaxing the resulting filament.
22. In a process for making polyester monofilament, the improvement comprising providing high abrasion resistance by incorporating a non-layered platelet-shaped particles selected from the group of inorganic oxides, hydroxides, carbonates, bicarbonates, nitrides and carbides, having a thickness in the range from 20 nm to not more than 100 nm and an aspect ratio of not more than 20:1.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEDE102005033350.8 | 2005-07-16 | ||
DE102005033350A DE102005033350A1 (en) | 2005-07-16 | 2005-07-16 | Polyester fibers, process for their preparation and their use |
Publications (1)
Publication Number | Publication Date |
---|---|
US20070014989A1 true US20070014989A1 (en) | 2007-01-18 |
Family
ID=37192480
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US11/483,988 Abandoned US20070014989A1 (en) | 2005-07-16 | 2006-07-10 | Polyester fibers, their production and their use |
Country Status (4)
Country | Link |
---|---|
US (1) | US20070014989A1 (en) |
EP (1) | EP1743963A1 (en) |
JP (1) | JP2007023474A (en) |
DE (1) | DE102005033350A1 (en) |
Cited By (3)
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US20060058441A1 (en) * | 2004-08-28 | 2006-03-16 | Teijin Monofilament Germany Gmbh | Polyester fibers, their production and their use |
US20100107508A1 (en) * | 2008-09-18 | 2010-05-06 | E.I. Du Pont De Nemours And Company Dupont Xingda Filaments Company Limited | Acid-resistant filaments for industrial application and brush with same |
US11333657B2 (en) | 2013-07-01 | 2022-05-17 | Albert DONNAY | Interpretation of gas levels measured via breath, blood and skin after different breath-holding times |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
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DE102009053588A1 (en) | 2009-11-17 | 2011-05-19 | Teijin Monofilament Germany Gmbh | Abrasion resistant monofilaments |
DE202012001985U1 (en) | 2012-02-25 | 2012-03-30 | Nextrusion Gmbh | Abrasion resistant monofilaments for paper machine clothing |
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Also Published As
Publication number | Publication date |
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EP1743963A1 (en) | 2007-01-17 |
DE102005033350A1 (en) | 2007-01-18 |
JP2007023474A (en) | 2007-02-01 |
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Owner name: TEIJIN MONOFILAMENT GERMANY GMBH, GERMANY Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:BRUNING, HANS-JOACHIM;DELKER,REX;REEL/FRAME:018182/0548 Effective date: 20060802 |
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STCB | Information on status: application discontinuation |
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