EP0623179B1 - Fil de polyester a module eleve pour cables de pneus et composites - Google Patents
Fil de polyester a module eleve pour cables de pneus et composites Download PDFInfo
- Publication number
- EP0623179B1 EP0623179B1 EP93901119A EP93901119A EP0623179B1 EP 0623179 B1 EP0623179 B1 EP 0623179B1 EP 93901119 A EP93901119 A EP 93901119A EP 93901119 A EP93901119 A EP 93901119A EP 0623179 B1 EP0623179 B1 EP 0623179B1
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- EP
- European Patent Office
- Prior art keywords
- yarn
- drawn
- undrawn
- tenacity
- melting point
- 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
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- 229920000728 polyester Polymers 0.000 title claims abstract description 24
- 239000002131 composite material Substances 0.000 title description 2
- 230000008018 melting Effects 0.000 claims abstract description 22
- 238000002844 melting Methods 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 14
- 230000008569 process Effects 0.000 claims abstract description 13
- 229920000642 polymer Polymers 0.000 claims abstract description 10
- 239000011112 polyethylene naphthalate Substances 0.000 claims description 32
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 claims description 31
- -1 polyethylene naphthalate Polymers 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 7
- 238000007711 solidification Methods 0.000 claims description 6
- 230000008023 solidification Effects 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 2
- 238000009987 spinning Methods 0.000 abstract description 11
- 239000000178 monomer Substances 0.000 abstract description 7
- 208000012886 Vertigo Diseases 0.000 description 10
- 229920000139 polyethylene terephthalate Polymers 0.000 description 9
- 239000005020 polyethylene terephthalate Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 238000010791 quenching Methods 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
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 230000002787 reinforcement Effects 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 150000001991 dicarboxylic acids Chemical class 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 2
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 229940035437 1,3-propanediol Drugs 0.000 description 2
- OONPLQJHBJXVBP-UHFFFAOYSA-N 3-(2-phenylethenyl)phthalic acid Chemical compound OC(=O)C1=CC=CC(C=CC=2C=CC=CC=2)=C1C(O)=O OONPLQJHBJXVBP-UHFFFAOYSA-N 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 230000020169 heat generation Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- 238000007373 indentation Methods 0.000 description 2
- 239000004615 ingredient Substances 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
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 1
- FSXKKRVQMPPAMQ-UHFFFAOYSA-N 7-hydroxynaphthalene-2-carboxylic acid Chemical compound C1=CC(O)=CC2=CC(C(=O)O)=CC=C21 FSXKKRVQMPPAMQ-UHFFFAOYSA-N 0.000 description 1
- 235000003403 Limnocharis flava Nutrition 0.000 description 1
- 244000278243 Limnocharis flava Species 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- BWVAOONFBYYRHY-UHFFFAOYSA-N [4-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=C(CO)C=C1 BWVAOONFBYYRHY-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000013213 extrapolation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004660 morphological change Effects 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
- WPUMVKJOWWJPRK-UHFFFAOYSA-N naphthalene-2,7-dicarboxylic acid Chemical compound C1=CC(C(O)=O)=CC2=CC(C(=O)O)=CC=C21 WPUMVKJOWWJPRK-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
Images
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
Definitions
- This invention relates to polyethylene naphthalate (PEN) multifilament yarn and other yarns made from similarly rigid monomer combinations with extremely high modulus, good tenacity, and low shrinkage particularly useful for the textile reinforcement of tires.
- the PEN yarn of this invention provides enhanced modulus and dimensional stability when compared to conventionally processed PEN yarns.
- a process for production of the multi-filament PEN yarn is an aspect of this invention.
- PET polyethylene terephthalate
- the yarns of this invention are prepared by spinning PEN or other semi-crystalline polyester polymers made from similarly rigid monomer combinations to a state of optimum amorphous orientation and crystallinity.
- the invention is accomplished by selection of process parameters to form an undrawn polyester yarn of birefringence at least 0.030.
- the spun yarn is then hot drawn to a total draw ratio of between 1.5/1 and 6.0/1 with the resulting drawn semicrystalline polyester yarn having Tg greater than 100°C and a melting point elevation at least 8°C.
- the preferred yarn has a tenacity at least 6.5 g/d (57.4 mN/dtex), dimensional stability (EASL + Shrinkage) of less than 5%, and shrinkage 4% or less.
- the resulting yarn exhibits surprisingly high modulus and tenacity together with low shrinkage when compared to prior art yarns.
- the invention also provides a drawn semicrystalline polyester multifilament yarn having Tg greater than 100°C and a melting point elevation of at least 9°C, which is obtained by drawing a polyester yarn having an undrawn birefringence of at least 0.030.
- Fig. 1 represents a comparison of modulus at a tenacity of 6.2 g/d (54.7 mN/dtex) for the PEN yarns of Examples 1 and 2.
- the polyester multifilament yarn of the present invention provides high modulus, high dimensional stability and good tenacity, characteristics which are extremely desirable when this material is incorporated as fibrous reinforcement into rubber composites such as tires.
- PEN multifilament yarns or other yarns of polyester polymers made from similarly rigid monomer combinations can be used advantageously to reinforce two parts of a radial passenger tire, the carcass and the belt.
- passenger tire carcasses are reinforced primarily by polyethylene terephthalate.
- Two tire characteristics which are controlled by the carcass cord property of dimensional stability (modulus at a given shrinkage) are sidewall indentations and tire handling.
- the high modulus and dimensional stability of the PEN or other polyester yarns of this invention relative to PET and prior art PEN yarns means that tires with carcasses reinforced with the yarns of this invention will exhibit lower sidewall indentation and better handling behavior.
- the yarns of this invention are also a desirable reinforcement material because of their high glass transition temperature (Tg) greater than 100°C, i.e. 120°C for PEN, compared to a Tg of 80°C for PET.
- Tg glass transition temperature
- the high Tg will result in lower cord heat generation over a wider temperature range relative to PET tires, resulting in longer tire lifetimes and overall cooler tire operating temperatures.
- modulus tends to drop precipitously at temperatures above Tg, the yarns of this invention will maintain modulus over a wider temperature range than PET. All of the above mentioned advantages will be of critical importance when yarns of this invention are used to reinforce high performance tires since this application requires low cord heat generation and high modulus, especially at elevated operating temperatures characteristic of high speed performance driving.
- PEN multifilament yarns and other polyester yarns of this invention can also be used to reinforce the belts of radial passenger tires and the carcasses of radial truck tires.
- steel is used for these applications since PET prossesses insufficient strength and modulus for a given cord diameter.
- the high modulus of PEN relative to PET, and the additional modulus advantages of the PEN of this invention will make PEN an ideal material to be used as a steel substitute.
- the polyethylene naphthalate yarn of the invention contains at least 90 mol percent polyethylene naphthalate.
- the polyester is substantially all polyethylene naphthalate.
- the polyester may incorporate as copolymer units minor amounts of units derived from one or more ester-forming ingredients other than ethylene glycol and 2,6 naphthylene dicarboxylic acid or their derivatives.
- ester forming ingredients which may be copolymerized with the polyethylene naphthalate units include glycols such as 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, etc., and dicarboxylic acids such as terephthalic acid, isophthalic acid, hexahydroterephthalic acid, stilbene dicarboxylic acid, bibenzoic acid, adipic acid, sebacic acid, azelaic acid, etc.
- glycols such as 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, etc.
- dicarboxylic acids such as terephthalic acid, isophthalic acid, hexahydroterephthalic acid, stilbene dicarboxylic acid, bibenzoic acid, adipic acid, sebacic acid, azelaic acid, etc.
- polyester yarns of the invention can be prepared to contain polyester polymer made from suitable combinations of rigid and flexible monomers providing the resulting polymer is melt-spinnable, is semi-crystalline, and has a Tg greater than 100°.
- rigid monomers include dicarboxylic acids such as 2,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, diphenyl dicarboxylic acid, stilbene dicarboxylic acid and terephthalic acid; dihydroxy compounds such as hydroquinone, biphenol, p-xylene glycol, 1,4 cyclohexanedimethanol, neopentylene glycol; and hydroxycarboxylic acid such as P-hydroxybenzoic acid and 7-hydroxy- ⁇ -naphthoic acid.
- Examples of flexible monomers include dicarboxylic acids such as oxalic acid, succinic acid, adipic acid, sebacic acid, and dihydroxy compounds such as ethylene glycol, 1,3 propanediol, 1,4 butanediol, 1,6 hexanediol. It is important that the thermal stability of the polymer above its melting point be sufficient to allow melt processing without excessive degradation.
- the multi-filament yarn of the present invention commonly possesses a denier per filament of about 1 to 20 (e.g. about 3 to 10), and commonly consists of about 6 to 600 continuous filaments (e.g. about 20 to 400 continuous filaments).
- the denier per filament and the number of continuous filaments present in the yarn may be varied widely as will be apparent to those skilled in the art.
- the multi-filament yarn is particularly suited for use in industrial applications wherein high strength polyester fibers have been utilized in the prior art.
- the fibers are particularly suited for use in environments where elevated temperatures (e.g. 100°C) are encountered. Not only does the filamentary material provide enhanced modulus but it undergoes a very low degree of shrinkage for a high modulus fibrous thermoplastic.
- the unexpected dimensional stability advantage seems to originate from the formation of a unique morphology during spinning which arises from the crystallization of highly oriented amorphous regions characterized by an undrawn birefringence of at least 0.03, preferably 0.03 to 0.30. This crystallization occurs in either the drawing stage or the spinning stage depending on the level of stress imposed during spinning. If too much stress is applied during spinning, the undrawn yarns tend to lack drawability and characteristically exhibit melting points greater than 290°C for PEN.
- the characterization parameters referred to herein may conveniently be determined by testing the multifilament yarn which consists of substantially parallel filaments.
- BIREFRINGENCE - Birefringence was determined using a polarizing light microscope equipped with a Berek compensator. If the black primary extinction band is not visible the purple colored band should be used for this measurement.
- DENSITY - Densities were determined in a n-heptane/carbon tetrachloride density gradient column at 23°C. The gradient column was prepared and calibrated according to ASTM D1505-68.
- MELTING POINT - Melting points were determined with a Perkin-Elmer Differential Scanning Calorimeter (DSC) from the maxima of the endotherm resulting from scanning a 10 mg sample at 20°C per minute. Tg is to be taken under the same experimental conditions as the inflection point in the change heat capacity associated with the glass transition temperature.
- IV Intrinsic viscosity of the polymer and yarn is a convenient measure of the degree of polymerization and molecular weight. IV is determined by measurement of relative solution viscosity ( ⁇ r ) in a mixture of phenol and tetrachloroethane (60/40 by weight) solvents. ⁇ r is the ratio of the flow time of a PEN/solvent solution to the flow time of pure solvent through a standard capillary. IV is calculated by extrapolation of relative solution viscosity data to a concentration of zero.
- L T ((L-5) 4 /T 5.16 ) 1000 L-5 or LASE-5 is a measure of modulus defined as load in g/d at 5% elongation.
- the materials of this invention have L T at least 25. If L-5 is not measurable because of yarn elongations less than 5% the yarns will be pre-relaxed at elevated temperatures before testing to increase elongation beyond 5%.
- Shrinkage values were determined in accordance with ASTM D885 after one minute at 177°C employing a constraining force of 0.05 g/denier (0.44 mN/dtex).
- the melt-spinnable polyester is supplied to an extrusion spinnerette at a temperature above its melting point and below the temperature at which the polymer degrades substantially.
- the residence time at this stage is kept to a minimum and the temperature should not rise above 350°C, preferably 320°C.
- the extruded filaments then traverse a conventional yarn solidification zone where quench air impinges on the spun yarn thereby freezing in desirable internal structural features and preventing the filaments from fusing to one another.
- the solidification zone preferably comprises (a) a retarded cooling zone comprising a gaseous atmosphere heated at a temperature to at least 150°C, preferably 150 to 500°C, and (b) a cooling zone adjacent to said retarded cooling zone wherein said yarn is rapidly cooled and solidified in a blown air atmosphere.
- the key to the current process is to adjust processing conditions to achieve a highly oriented undrawn yarn of birefringence at least 0.03 and an elevated melting point of 1-25°C, preferably 3-23°C.
- PEN a melting point of 265 to 290°C, preferably 268 to 288°C must be achieved.
- One skilled in the art can achieve this by adjusting the following conditions: length and temperature of the retarded cooling zone adjacent to the spinnerette, diameter of the spinnerette holes, method of blowing the quench, quench air velocity, and drawdown in the solidification zone.
- the speed of withdrawal of the yarn from the solidification zone is an important parameter affecting the stress on the spun fiber, and should be adjusted to yield the desired characteristics.
- the spun yarn is then drawn by conventional means in either a continuous or non-continuous process to yield a drawn yarn with Tg greater than 100°C and a melting point elevation at least 8°C, preferably 8 to 15°C.
- tenacity at least 6.5 g/d (57.4 mN/dtex), preferably at least 7.5 g/d (66.2 mN/dtex); dimensional stability (EASL + shrinkage) of less than 5%; and shrinkage of 4% or less.
- a PEN undrawn yarn was produced by extruding 32 filaments through a spinnerette with orifices of length 0.042 inches (0.107cm) and of width 0.021 inches (0.053 cm) at a thruput of 23.2 cc/min.
- the filaments were solidified in an air quenching column and taken up at winder speeds of 305 m/min.
- EASL + shrinkage the dimensional stability parameter of 8.3 is higher than that of yarns of this invention, indicating poorer dimensional stability (see Example III).
- PEN yarns were produced by extruding seven filaments through a spinnerette with orifices of length 0.036 inches (0.091 cm) and width of 0.016 inches (0.041 cm) at a thruput of 9.6 cm 3 /min.
- the filaments were solidified in an air quenching column and taken up at winder speeds ranging from 770-5000 m/min. These yarns were drawn in two stages using a heating plate in draw zone two.
- the undrawn yarn properties, drawn yarn properties, and drawing conditions are summarized in Table II.
- Example II The undrawn yarns of Example II spun at 770 m/min and 4000 m/min were drawn to their ultimate limit.
- the 770 m/min sample was drawn in one stage using an oven in the draw zone and the 4000 m/min sample was drawn in two stages using a heated plate in the second draw zone.
- PEN yarns were produced by extruding seven filaments through a spinnerette with orifices of length 0.069 inches and width 0.030 inches at a thruput of 9.6 cc/min. The filaments were solidified in an air quenching column and taken up at winder speeds ranging from 410 m/min to 2500 m/min. The properties of these yarns are summarized in Table IV.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Artificial Filaments (AREA)
- Tires In General (AREA)
- Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
Abstract
Claims (9)
- Procédé de production d'un fil de polyester étiré de module amélioré et de bonne ténacité, comprenant les étapes consistant à:(a) extruder un polymère polyester cristallisable en fusion, ayant une Tg supérieure à 100°C et ayant une viscosité intrinsèque de 0,6 ou plus, à travers un orifice d'extrusion possédant une forme, présentant une pluralité d'ouvertures, pour former un fil filé en fusion,(b) solidifier le fil filé en le faisant passer dans une zone de solidification,(c) soutirer le fil solidifié à une vitesse de bobinage sans étirage suffisante pour former un fil partiellement orienté ayant une biréfringence d'au moins 0,030, et(d) étirer le fil à chaud, jusqu'à un taux d'étirage total d'au moins 1,5/1, pour former un fil étiré.
- Procédé selon la revendication 1, dans lequel le fil filé est solidifié en passant dans une zone de solidification qui comprend (a) une zone de refroidissement retardé comprenant une atmosphère gazeuse chauffée à une température d'au moins 150°C, et (b) une zone de refroidissement adjacente à ladite zone de refroidissement retardé, dans laquelle ledit fil est rapidement refroidi et solidifié dans une atmosphère d'air soufflé.
- Procédé selon la revendication 1 ou la revendication 2, dans lequel la vitesse de bobinage sans étirage est de 400 à 4 500 m/min et la biréfringence sans étirage est de 0,030 à 0,30.
- Procédé selon la revendication 1 ou 2, pour la production d'un fil de poly(éthylène-naphtalate) étiré dans lequel le polymère polyester fondu extrudé dans l'étape (a) est un poly(éthylène-naphtalate) et, dans l'étape (c), le fil non étiré, partiellement orienté, présente une élévation du point de fusion de 1-25°C.
- Procédé selon la revendication 4, dans lequel la vitesse de bobinage sans étirage est de 400 à 4 500 m/min, la biréfringence sans étirage est de 0,030 à 0,30, et l'élévation du point de fusion du fil partiellement orienté est de 3-23°C.
- Fil multifilament en polyester semicristallin étiré, ayant une Tg supérieure à 100°C et une élévation du point de fusion d'au moins 9°C, qui est obtenu par étirage d'un fil en polyester ayant une biréfringence sans étirage d'au moins 0,030.
- Fil étiré selon la revendication 6, possédant une ténacité d'au moins 6,5 g/d (57,4 mN/dtex), une stabilité dimensionnelle (allongement sous une charge spécifique + rétrécissement) inférieure à 5%, et un rétrécissement de 4% ou moins.
- Fil étiré selon la revendication 7, qui est du poly(éthylène-naphtalate).
- Fil étiré de poly(éthylène-naphtalate) selon la revendication 8, dans lequel l'élévation du point de fusion est de 9 à 15°C, le module est d'au moins 280 g/d (2 470 mN/dtex) et la ténacité est d'au moins 7,5 g/d (66,2 mN/dtex).
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US82279992A | 1992-01-21 | 1992-01-21 | |
US822799 | 1992-01-21 | ||
PCT/US1992/011063 WO1993014252A1 (fr) | 1992-01-21 | 1992-12-22 | Fil de polyester a module eleve pour cables de pneus et composites |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0623179A1 EP0623179A1 (fr) | 1994-11-09 |
EP0623179B1 true EP0623179B1 (fr) | 1996-09-04 |
EP0623179B2 EP0623179B2 (fr) | 2001-02-14 |
Family
ID=25237011
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP93901119A Expired - Lifetime EP0623179B2 (fr) | 1992-01-21 | 1992-12-22 | Fil de polyester a module eleve pour cables de pneus et composites |
Country Status (12)
Country | Link |
---|---|
EP (1) | EP0623179B2 (fr) |
JP (1) | JP2629075B2 (fr) |
CN (1) | CN1051586C (fr) |
AU (1) | AU3331293A (fr) |
BR (1) | BR9207038A (fr) |
CA (1) | CA2126328C (fr) |
DE (1) | DE69213474T3 (fr) |
ES (1) | ES2091589T5 (fr) |
MX (1) | MX9300142A (fr) |
TR (1) | TR28032A (fr) |
TW (1) | TW224960B (fr) |
WO (1) | WO1993014252A1 (fr) |
Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4320593A1 (de) * | 1993-06-22 | 1995-01-05 | Akzo Nobel Nv | Multifilament-Garn aus Polyäthylennaphthalat und Verfahren zu seiner Herstellung |
KR100402839B1 (ko) * | 2001-05-10 | 2003-10-22 | 주식회사 효성 | 고강력 폴리에틸렌 나프탈레이트 섬유 |
DE10140774B4 (de) * | 2001-08-20 | 2004-08-12 | Metzeler Automotive Profile Systems Gmbh | Formschlauch |
AU2003272123A1 (en) * | 2003-08-22 | 2005-03-10 | Hyosung Corporation | High tenacity polyethylene-2,6-naphthalate fibers |
JP4616658B2 (ja) * | 2005-01-31 | 2011-01-19 | 帝人ファイバー株式会社 | 不織布 |
JP4928308B2 (ja) * | 2007-02-28 | 2012-05-09 | 帝人ファイバー株式会社 | 産業資材用ポリエチレンナフタレート繊維とその製造方法 |
CN101688586A (zh) * | 2007-07-03 | 2010-03-31 | 盖茨公司 | 动力传输带 |
WO2009123414A2 (fr) | 2008-03-31 | 2009-10-08 | Kolon Industries, Inc. | Fibre de poly(téréphtalate d'éthylène) (pet) non étirée, fibre de pet étirée et câble pour pneu la comprenant |
FR2971187B1 (fr) * | 2011-02-03 | 2013-03-08 | Michelin Soc Tech | Renfort composite gaine d'une couche de polymere auto-adherente au caoutchouc |
FR2971188B1 (fr) | 2011-02-03 | 2013-03-08 | Michelin Soc Tech | Renfort composite gaine d'une couche de polymere auto-adherente au caoutchouc |
CN102851782B (zh) * | 2011-06-30 | 2016-05-04 | 上海杰事杰新材料(集团)股份有限公司 | 一种用于轮胎骨架材料的聚酰胺工业丝及其制造方法 |
JP2017053060A (ja) * | 2015-09-08 | 2017-03-16 | 株式会社ブリヂストン | Pef原糸の製造方法、pef原糸及びタイヤ |
CN112281272A (zh) * | 2020-10-15 | 2021-01-29 | 联新(开平)高性能纤维有限公司 | 一种超高强度尺寸稳定性聚酯帘子布经纱及其制备方法和应用 |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1295450A (fr) * | 1968-12-24 | 1972-11-08 | ||
US3564835A (en) † | 1969-03-12 | 1971-02-23 | Du Pont | High tenacity tire yarn |
US4026973A (en) † | 1973-08-31 | 1977-05-31 | Teijin Limited | Process for preparing heat-resistant aromatic polyester filaments |
JPS5615321B2 (fr) * | 1973-09-20 | 1981-04-09 | ||
GB1445464A (en) * | 1973-10-19 | 1976-08-11 | Teijin Ltd | Method of producing a polyethylene-2,6-naphthalate yarn |
JPS62156312A (ja) † | 1985-12-26 | 1987-07-11 | Teijin Ltd | ポリエステル系繊維 |
WO1990000638A1 (fr) * | 1988-07-05 | 1990-01-25 | Allied-Signal Inc. | Fil polyester dimensionnellement stable pour cables traites de haute tenacite |
JP2861335B2 (ja) * | 1990-08-31 | 1999-02-24 | 東洋紡績株式会社 | ナフタレートポリエステル繊維の製造方法 |
JP2954391B2 (ja) * | 1991-05-22 | 1999-09-27 | 帝人株式会社 | ポリエチレンナフタレート繊維およびその製造方法 |
-
1992
- 1992-12-22 JP JP5512461A patent/JP2629075B2/ja not_active Expired - Fee Related
- 1992-12-22 EP EP93901119A patent/EP0623179B2/fr not_active Expired - Lifetime
- 1992-12-22 BR BR9207038A patent/BR9207038A/pt not_active IP Right Cessation
- 1992-12-22 ES ES93901119T patent/ES2091589T5/es not_active Expired - Lifetime
- 1992-12-22 CA CA002126328A patent/CA2126328C/fr not_active Expired - Fee Related
- 1992-12-22 WO PCT/US1992/011063 patent/WO1993014252A1/fr active IP Right Grant
- 1992-12-22 DE DE69213474T patent/DE69213474T3/de not_active Expired - Fee Related
- 1992-12-22 AU AU33312/93A patent/AU3331293A/en not_active Abandoned
-
1993
- 1993-01-13 MX MX9300142A patent/MX9300142A/es not_active IP Right Cessation
- 1993-01-19 TW TW082100327A patent/TW224960B/zh active
- 1993-01-20 TR TR00065/93A patent/TR28032A/xx unknown
- 1993-01-21 CN CN93101268A patent/CN1051586C/zh not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
DE69213474D1 (de) | 1996-10-10 |
EP0623179B2 (fr) | 2001-02-14 |
MX9300142A (es) | 1994-07-29 |
TW224960B (fr) | 1994-06-11 |
CN1078508A (zh) | 1993-11-17 |
JPH06511293A (ja) | 1994-12-15 |
WO1993014252A1 (fr) | 1993-07-22 |
ES2091589T3 (es) | 1996-11-01 |
EP0623179A1 (fr) | 1994-11-09 |
DE69213474T3 (de) | 2001-08-23 |
CA2126328A1 (fr) | 1993-07-22 |
ES2091589T5 (es) | 2001-05-16 |
CN1051586C (zh) | 2000-04-19 |
AU3331293A (en) | 1993-08-03 |
DE69213474T2 (de) | 1997-02-06 |
CA2126328C (fr) | 2002-05-21 |
BR9207038A (pt) | 1995-12-05 |
JP2629075B2 (ja) | 1997-07-09 |
TR28032A (tr) | 1995-12-11 |
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