CN1078508A - The high modulus polyester yarn that is used for cotton tyre cord and composite - Google Patents
The high modulus polyester yarn that is used for cotton tyre cord and composite Download PDFInfo
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- CN1078508A CN1078508A CN 93101268 CN93101268A CN1078508A CN 1078508 A CN1078508 A CN 1078508A CN 93101268 CN93101268 CN 93101268 CN 93101268 A CN93101268 A CN 93101268A CN 1078508 A CN1078508 A CN 1078508A
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- toughness
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- 229920000728 polyester Polymers 0.000 title claims abstract description 22
- 239000002131 composite material Substances 0.000 title description 3
- 229920000742 Cotton Polymers 0.000 title description 2
- 229920000642 polymer Polymers 0.000 claims abstract description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 17
- -1 dioctyl phthalate glycol ester Chemical class 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 11
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 10
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 9
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 9
- 238000007711 solidification Methods 0.000 claims description 9
- 230000008023 solidification Effects 0.000 claims description 9
- 239000004753 textile Substances 0.000 claims description 7
- 230000000630 rising effect Effects 0.000 claims description 4
- 230000004927 fusion Effects 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims 1
- 238000009987 spinning Methods 0.000 abstract description 22
- 238000002360 preparation method Methods 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 208000012886 Vertigo Diseases 0.000 description 19
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 8
- 229920000139 polyethylene terephthalate Polymers 0.000 description 8
- 239000005020 polyethylene terephthalate Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 239000000178 monomer Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 238000000113 differential scanning calorimetry Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-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
- OLRZCONQLKYQIB-UHFFFAOYSA-N C(C=1C(C(=O)OCCCCCCCC)=CC=CC1)(=O)OCCCCCCCC.C1(=CC=CC=C1)C=CC1=CC=CC=C1 Chemical compound C(C=1C(C(=O)OCCCCCCCC)=CC=CC1)(=O)OCCCCCCCC.C1(=CC=CC=C1)C=CC1=CC=CC=C1 OLRZCONQLKYQIB-UHFFFAOYSA-N 0.000 description 2
- 229920000305 Nylon 6,10 Polymers 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 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
- 240000004859 Gamochaeta purpurea Species 0.000 description 1
- 244000278243 Limnocharis flava Species 0.000 description 1
- 235000003403 Limnocharis flava Nutrition 0.000 description 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-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
- 239000002253 acid Substances 0.000 description 1
- 238000004458 analytical method Methods 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
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- GWZCCUDJHOGOSO-UHFFFAOYSA-N diphenic acid Chemical compound OC(=O)C1=CC=CC=C1C1=CC=CC=C1C(O)=O GWZCCUDJHOGOSO-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- UEVICWPULNDRTH-UHFFFAOYSA-N ethane-1,2-diol penta-1,3-diene Chemical compound C(CO)O.C=CC=CC UEVICWPULNDRTH-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010309 melting process Methods 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
- 238000005457 optimization Methods 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- URLKBWYHVLBVBO-UHFFFAOYSA-N p-dimethylbenzene Natural products CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 229960005137 succinic acid Drugs 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 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
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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)
- Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
- Tires In General (AREA)
Abstract
Yarn of the present invention is by spinning the preparation of PEN or other semicrystalline polyester polymer, this other polymer is to make when being aggregated to its best amorphous orientation and degree of crystallinity by similar rigidity monomeric compound, this is to be at least 0.030 not stretched polyester yarn by selection course parameter form dielectric grid rate to realize, this spun yam of hot-stretch reaches total drawing ratio 1.5/1 to 6.0/1 then, the Tg of stretching semicrystalline polyester yarn that makes gained is greater than 100 ℃, fusing point raises 8 ℃ at least, the toughness of preferred yarn is at least 6.5g/d, DIMENSIONAL STABILITY (EASL+ shrinkage factor) is less than 5%, and shrinkage factor is 4% or littler.Compare with existing document yarn, yarn of the present invention demonstrates surprising high-modulus and toughness, and low-shrinkage.
Description
The present invention relates to polyphenyl dioctyl phthalate glycol ester (PEN) multifilament textile and other yarn, other yarn is by having high modulus, and high tenacity and low-shrinkage are used in particular for the similar rigidity monomer composition that carcass fabric strengthens and make.Compare with the PEN yarn that makes with conventional method, PEN yarn of the present invention has shown higher modulus and DIMENSIONAL STABILITY, and the method for preparing the PEN multifilament is one aspect of the present invention.
At present, polyethylene terephthalate (PET) silk is everlasting and is used in the industry, comprises being used for the radial tyre carcass conveyer belt, safety belt, V band and rotary hose.Yet more high-modulus and DIMENSIONAL STABILITY are preferred in the high-performance tire carcass as uniqueness in the application of requirements at the higher level, and are necessary in the application that radially passenger tyre (radial passenger tire) is with.DIMENSIONAL STABILITY is defined as elongation and the shrinkage factor when 4.5g/d.U.S.Patent3,616,832 to Shima et al, the rubber that provides the PEN with good dimensional stability and toughness to strengthen, and U.S.Patent 3,929,180 to Kawase et al. provide the tire that strengthens as carcass with PEN.Yet these patents relate to the low birefringent PEN that do not stretch of conventional preparation, therefore can not fully obtain the potential character of these materials, and this purpose of the present invention just.Similarly, British Patent 1,445,464 to Hamana et al. have pointed out that the optimization of conventional spinning PEN stretches, U.S.Patent 4,000,239 to Hamana et al. provides the high melting-point of preparation as the electric insulation fabric, the method for stable on heating unstretched PEN.Because these materials are to make helping forming under the condition of high ground stress of high-crystallinity or high at least one-tenth nuclear structure, they lack drawability, can not reach to use desired high-modulus herein.The product that same application is arranged is at U.S.4,001,479 to Hamana et al., in description is arranged, it relate to highly stretch, the partially oriented yarn of low toughness.
Yarn of the present invention is the spinning preparation by PEN spinning or other semicrystalline polyester polymer, this polymer is made during to its best amorphous orientation and degree of crystallinity by similar rigidity monomer polymerization, the present invention is at least 0.030 not stretched polyester yarn by selection course parameter form dielectric grid rate to realize, to reach total drawing ratio be between 1.5/1 to 6.0/1 to the yarn that spins of hot-stretch then, the Tg of semicrystalline polyester yarn of drawn that makes gained is greater than 100 ℃, and fusing point raises 8 ℃ at least, the toughness of preferred yarn is at least 6.5g/d, DIMENSIONAL STABILITY (EASL+ shrinkage factor) is less than 5%, and shrinkage factor is 4% or littler.
Compare with the known references yarn, the yarn of gained demonstrates surprising high-modulus and toughness and low-shrinkage.
Fig. 1 is the contrast of PEN yarn modulus when toughness is 6.2g/d of embodiment 1 and 2.
Polyester mutifilament yarn of the present invention demonstrates high-modulus, high-dimensional stability and high tenacity, and this is that the utmost point was wished the characteristic that has when this material was added rubber composite such as tire as fiber reinforcement.PEN multifilament textile or other polyester polymers yarn can be with helping strengthening radially two parts of passenger tyre, and promptly the similar rigidity monomer composition of carcass and band makes.At present, the passenger tyre carcass mainly is to strengthen with polyethylene terephthalate.
Two characteristics of the tire of being controlled by the character of the carcass cord of dimensionally stable (modulus under given shrinkage factor) are sidewall impression and tire processing.The PEN yarn of relative PET and employing prior art, PEN of the present invention or other polyester yarn have high-modulus and DIMENSIONAL STABILITY, this tire that just means the carcass that strengthens with yarn of the present invention will demonstrate more shallow sidewall impression and better processability energy, compare with PET80 ℃ Tg, yarn of the present invention has and is higher than 100 ℃, it promptly is 120 ℃ high glass-transition temperature (Tg) to PEN, thereby yarn of the present invention equally also is desirable reinforcing material, high Tg will cause than the lower cord of PET tire in wide temperature range more heat taking place, and also cause longer tire operating period and total lower tire operating temperature.In addition, owing to be higher than modulus trend decline rapidly under the temperature of Tg, yarn of the present invention will keep modulus in the temperature range wideer than PET.When yarn of the present invention was used to strengthen high-performance tire, because low cord generation heat of this application requirements and high-modulus, this was the characteristic that should have when running at high speed the rising operating temperature especially, thereby above-mentioned these advantages all are very important.
PEN multifilament textile of the present invention and other polyester yarn can be used for strengthening radially passenger tyre band and radially high-capacity tyre carcass equally.Because PET does not have enough intensity and modulus under given cord diameter, thereby the present normal used as said purpose of steel.PEN has higher modulus than PET, and the more high-modulus of PEN of the present invention will make PEN become the ideal material of steel substitute.
Polyphenyl dioctyl phthalate glycol ester yarn of the present invention contains 90%(mol at least) polyphenyl dioctyl phthalate glycol ester.In the preferred embodiment, polyester mainly is a polyphenyl dioctyl phthalate glycol ester, perhaps, can add in the polyester on a small quantity as copolymerization units from one or more except ethylene glycol and 2, the unit that obtains in the component of the formation ester of 6-naphthalenedicarboxylic acid or their derivatives.Can specifically comprise diol compound as 1, ammediol, 1 with other component that forms ester of polyphenyl dioctyl phthalate glycol ester unit copolymerization, the 4-butanediol, 1,6-hexylene glycol etc., with dicarboxylic acids such as terephthalic acid (TPA), M-phthalic acid, hexahydroterephthalic acid, Stilbene dioctyl phthalate, diphenic acid, adipic acid, decanedioic acid, azelaic acid etc.
Can make other polyester yarn of the present invention that contains polyester polymers, this polyester polymers is made by suitable rigidity and flexible monomer combination, thereby makes the polymer of gained be the melting spinning, and is hemicrystalline, and Tg is greater than 100 ℃.The rigidity monomer specifically comprises dicarboxylic acids as 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, diphenyl dioctyl phthalate, Stilbene dioctyl phthalate and terephthalic acid (TPA); Dihydroxy compounds such as quinhydrones, biphenol, paraxylene ethylene glycol, 1,4 cyclohexane dimethanol, new pentadiene ethylene glycol; With hydroxyl carboxylic acid such as P-hydroxybenzoic acid and 7-hydroxy-beta-naphthoic acid.Flexible monomer specifically comprises dihydroxy acid such as oxalic acid, butanedioic acid, adipic acid, decanedioic acid and dihydroxy compounds such as ethylene glycol, 1, ammediol, 1, the 4-butanediol, 1, the 6-hexylene glycol is being higher than under the temperature of its fusing point, the thermally-stabilised of polymer is gratifying, melting process can fully be carried out, and excessive degradation does not take place, this is very important.
Usually, every about 1 to 20 dawn of multifilament textile of the present invention (for example about 3 to 10 dawn), and contain about 6 to 600 continuous yarn (for example about 20 to 400 continuous yarn) usually.The number of every dawn and continuous yarn can change in wide range as the technology skilful person is conspicuous in the yarn.
Multifilament textile is specially adapted in the industry, wherein utilizes h in existing document, and fiber is specially adapted under the environment of high temperature (for example 100 ℃).Filamentary material not only can provide high-modulus, and the fibrous thermoplastic of high-modulus is also had very low shrinkage factor.
Birefringence is not at least 0.03 to stretch, be preferably 0.03 to 0.30 and be high amorphous orientation district's crystallization of feature, in spinning process, as if the unique form that forms brought beyond thought dimensionally stable advantage, the stress levels that this crystallization is depended in the spinning process and applied takes place in draw stage or in the spinning stage, if apply too much stress in fabrication processes, stretch yarn is not tending towards lacking drawability, and has the feature fusing point greater than 290 ℃ to PEN.
Relevant herein characteristic parameter can be measured by testing the multifilament textile that mainly contains parallel silk usually.
1. birefringence-birefringence can use the petrographic microscope that the Berek compensator is housed to measure, if cannot see black master delustring band, then purple colour band and also can be used for this measurement.
2. density-density is to measure in normal heptane/carbon tetrachloride density gradient column in the time of 23 ℃, and gradient column is pressed ASTM D1505-68 preparation and calibration.
3. fusing point-fusing point is to use Perkin-Elmer differential scanning calorimetry (DSC) (DSC) to the velocity scanning of 10mg sample with 20 ℃/minute, measures from endothermic peak.Tg is under same experiment condition, obtains from the flex point that changes thermal capacitance and glass transition temperature, and the fusing point increment of stretch yarn (△ Tm) is defined as:
△Tm＝Tm′-Tm″
Wherein Tm ' is the fusing point of the stretch yarn paid close attention to, Tm " for before analyzing in DSC the premelt and the fusing point of the yarn of cooling rapidly.
4. the inherent viscosity of inherent viscosity-polymer and yarn (IV) is the easy tolerance of the degree of polymerization and molecular weight, the relative solution viscosity (η r) that is dissolved in the mixed liquor of tetrachloroethane solvent (60/40 weight ratio) by measurement phenol is measured IV, η r is the flowing time of PEN/ solvent solution and the neat solvent ratio by the flowing time of standard capillary, and IV is calculated when the relative solution viscosity data are extrapolated to zero-dose.
5. the tensile property of physical property-relevant herein is by using Instron tension test instrument, 10 inches sample lengths and 120%/minute rate of deformation under measure.All stretch and all at room temperature measure.The DIMENSIONAL STABILITY of relevant deformation extent is measured under given shrinkage factor, in tire industry, DIMENSIONAL STABILITY is defined as in given load and adds elongation under the amount of contraction, and in this case, available following formula obtains elongation under given load (EASL) from initial modulus data:
EASL=454/ modulus (g/d)
Known toughness and modulus increase with the increase of rate of extension.Almost can reach desirable high tenacity/silk, but high ratio of elongation be because yarn interrogation topic or excessive shrinkage can not reach usually, material of the present invention has high-modulus under given toughness.This available parameter L
TDetermine that it is as shown in the formula the ratio of L-5 with toughness:
L
T＝（（L-5）
4/T
5.16）1000
L-5 or LASE-5 give a definition in 5% elongation to be the modulus tolerance of the load of g/d.The L of material of the present invention
TBe at least 25.If owing to the elongation of yarn makes the L-5 immeasurability less than 5%, then before test, elevated temperature increases elongation makes it surpass at 5% o'clock, and yarn will take place pre-lax.
The shrinkage factor value is to record after 1 minute during in 177 ℃ under the power that is forced at 0.05g/ dawn by ASTM D885.
Be to form the detailed description that the present invention improves the process of yarn below, hereinafter desired yarn product is not subjected to the restriction of following procedure parameter.
When being lower than its degradation temperature the polyester of melting spinning is put into the extruding spinning head, keep the time of staying minimum in this stage and make temperature be no more than 350 ℃, be preferably 320 ℃ roughly being higher than melting point polymer.
The extruding silk impacts quench air on spun yam through conventional yarn solidification zone then, is frozen into required inner constructional form thus and prevents a mutual fusion.Preferred solidification zone comprises that (a) contains at least 150 ℃, be preferably the slow setting cooling zone that adds hot-air under 150 to 500 ℃ of temperature, (b) tightly adjacent with described slow setting cooling zone, and the cooling zone that makes described yarn in ventilating air, can cool off fast and solidify, the purpose of this process is to adjust processing conditions to be at least 0.03 to obtain birefringence, the rising fusing point is 1～25 ℃, the height that is preferably 3-23 ℃ is orientated not stretch yarn, for PEN, fusing point is necessary for 265 to 290 ℃, be preferably 268 to 288 ℃, the technology skilful person can obtain by regulating following condition: with the length and the temperature of the tight adjacent slow setting cooling zone of spinning head, the spinning head aperture, be blown into the method for quenching, the speed of quench air, minimizing with solidification zone, the speed that yarn moves from solidification zone is a significant effects parameter to the stress that is added on the spinning fibre, should be regulated to obtain desirable characteristic, use the conventional method stretch spinning then, obtain Tg greater than 100 ℃ through continuous or digital process, fusing point raises 8 ℃ at least, is preferably 8 to 15 ℃ stretch yarn, preferred stretch yarn has following character: toughness is at least 6.5g/d, preferably is at least 7.5g/d; DIMENSIONAL STABILITY (EASL+ shrinkage factor) is less than 5%; Shrinkage factor is 4% or littler.
Embodiment 1
(comparison)
Under the flow of 23.2cc/min, with 32 be 0.042 inch from length, wide is to extrude in the spinning head of 0.021 inch spinneret orifice, makes not stretch yarn of PEN, silk solidifies in air quenched post and takes out with the speed of wrap of 305m/min.
With conventional warm-up mill at two stage stretch yarns, stretch yarn character not, stretch yarn character and stretching condition are summarized in the table I.
The modular ratio yarn of the present invention of the present embodiment yarn that makes from the not stretch yarn of △ n=0.004 with conventional method is low, and this can be from L
TBe confirmed less than 25.Equally, DIMENSIONAL STABILITY parameter (EASL+ shrinkage factor) is 8.3 to be higher than yarn of the present invention, and DIMENSIONAL STABILITY poorer (seeing the embodiment III) is described.
The table I
A. stretch yarn not
△n 0.004
Toughness (g/d) 0.6
Modulus (g/d) 18.6
Tm(℃) 268
B. stretch yarn
Draw ratio 6.3
Roller 1 (℃) 140
Roller 2 (℃) 157
Roller 3 (℃) RT
△n 0.426
Toughness (g/d) 6.2
Modulus (g/d) 176
Tm(℃) 272
Shrinkage factor (%) 5.7
EASL+ shrinkage factor (%) 8.3
△Tm(℃) 7
The embodiment II
Under the flow of 9.6cc/min, being 0.036 inch wide with 7 from length is to extrude the spinning head of 0.016 inch spinneret orifice, makes the PEN yarn, and silk solidifies in air quenched post and takes out with the speed of wrap of 770-5000m/min.Divide two stages, with heating plate these yarns that on second drawing zone, stretch, stretch yarn character not, stretch yarn character and stretching condition are summarized in to be shown in the II.
From then on as seen be drawn into the yarn of given toughness in the data of embodiment, its modulus increases with the increase of spinning speed and stretching, the fusing point that do not stretch, and shows parameter L
TIncrease with spinning speed increases, the birefringence that do not stretch is a unique parameter that does not influence yarn characteristic of the present invention, because this parameter is insensitive to the morphological change that takes place under high spinning stress, thereby fusing point and birefringence just are used for limiting scope of the present invention.Compare the data of present embodiment and the data of comparing embodiment 1, being pushed into toughness in the modulus value with the table II is 6.2g/d, and draws its figure to spinning speed (Fig. 1).This analysis has clearly shown the superiority of the existing relatively document yarn of yarn of the present invention.
The table II
A. stretch yarn not
Take-off speed (m/min)
770 2000 3000 4000 5000
△n 0.043 0.279 0.273 0.267 0.270
Toughness (g/d) 1.5 3.6 4.1 5.1 7.8
Modulus (g/d) 24 86 122 151 190
Tm(℃) 265 272 281 287 294
B. stretch yarn
Take-off speed (m/min)
770 2000 3000 4000
Draw ratio 3.0 3.6 1.4 1.5 1.2 1.3 1.3 1.3
Roller 1 (℃) 125 125 125 125 125 125 125 125
Roller 2 (℃) RT RT RT RT RT RT RT RT
Heating plate (℃) 230 230 235 230 240 230 240 230
△n 0.404 0.404 0.420 0.402 0.402 0.406 - 0.369
Toughness (g/d) 5.8 6.6 5.8 6.6 5.6 6.8 6.4 6.7
Modulus (g/d) 174 257 222 295 255 295 262 323
Tm(℃) 274 275 276 276 281 281 - 286
L-5(g/d) 3.2 5.0 4.8 5.9 4.8 5.9 6.2 5.4
L
T12 37 61 72 73 61 102 46
△Tm 9 10 11 11 16 16 - 21
The embodiment III
The not stretch yarn of embodiment II is stretched to their limiting length under 770m/min and 4000m/min.The 770m/min sample stretches a stage at drawing zone with baking oven, and the 4000m/min sample stretches in second stretching two stages of differentiation with heating plate, and the character of stretch yarn and stretching condition are summarized in the table III.This embodiment shows that yarn of the present invention has high modulus, and high tenacity and low-shrinkage make them obtain desirable application in rubber.
The table III
The A stretch yarn
Take-off speed (m/min)
770 4000
Draw ratio 5.9 2.0
Roller 1 (℃) 120 95
Baking oven (℃) 170-
Roller 2 (℃) RT RT
Heating plate (℃)-240
Roller 3 (℃)-RT
Toughness (g/d) 10.3 7.6
Modulus (g/d) 362 417
Shrinkage factor (%) 3.5＜1
EASL+ shrinkage factor (%) 4.8＜2.1
L-5(g/d) 8.3 7.5
L
T28 90
The embodiment IV
Present embodiment shows and can make high birefringence rate under the spinning speed that is lower than the embodiment II, modulus, not stretch yarn with fusing point, obtain to can be used for the method that is more suitable for industrial application that to carry out at a high speed thus, under the flow of 9.6cc/min, with 7 from length be 0.069 inch, wide be to extrude the spinning head of 0.030 inch spinneret orifice, make the PEN yarn, silk solidifies in air quenched post and takes out to the speed of wrap of 2500m/min with 410m/min.The character of this yarn is summarized in the table IV.
The table IV
Take-off speed (M/MIN)
410 770 1200 1600 2000 2500
△n 0.178 0.154 0.192 0.232 0.233 0.226
Toughness (g/d) 2.1 2.0 2.6 3.8 4.0 4.5
Modulus (g/d) 64 58 63 114 143 158
Tm(℃) 269 267 268 279 291 292
Claims (10)
1, a kind of method that is used to prepare high-modulus and high tenacity stretched polyester yarn, it comprises:
(a) with Tg greater than 100 ℃, inherent viscosity be 0.6 or bigger molten state crystallizable polyester polymer from the moulding extruding spinneret orifice that many holes are arranged, extrude, form the spun yam of fusion;
(b) spun yam makes it to solidify through solidification zone;
(c) yarn is solidified in taking-up under enough not stretching take-off speeds, and the form dielectric grid rate is at least 0.030 partially oriented yarn; With
(d) this yarn of hot-stretch reaches total drawing ratio and is at least 1.5/1, forms stretch yarn.
2, the method for claim 1, it is characterized in that, spun yam is solidified through solidification zone, this solidification zone comprises that (a) contains the slow setting cooling zone that adds hot-air of at least 150 ℃ of temperature, (b) tightly adjacent with described slow setting cooling zone, and the described yarn cooling zone that in ventilating air, can cool off fast and solidify.
3, method as claimed in claim 1 or 2 is characterized in that, the take-off speed that do not stretch is 400 to 4500m/min, and the birefringence that do not stretch is 0.030 to 0.30.
4, the method that is used to prepare stretching polyphenyl dioctyl phthalate glycol ester yarn as claimed in claim 1, it is characterized in that, the molten polyester polymer of extruding in step (a) for polyphenyl dioctyl phthalate glycol ester and in step (c) the partially oriented not position for 1-25 ℃ of fusing point rising stretch yarn.
5, method as claimed in claim 4, it is characterized in that, spun yam is solidified through solidification zone, this solidification zone comprises that (a) contains the slow setting cooling zone that adds hot-air of at least 150 ℃ of temperature, (b) tightly adjacent with described slow setting cooling zone, and the described yarn cooling zone that in ventilating air, can cool off fast and solidify.
As claim 4 or 5 described methods, it is characterized in that 6, the take-off speed that do not stretch is 400 to 4500m/min, the birefringence that do not stretch is 0.030 to 0.30,3-23 ℃ of the fusing point rising of partially oriented yarn.
7, a kind of stretching semicrystalline polyester multifilament textile, the Tg that it is characterized in that it is greater than 100 ℃, and fusing point raises 8 ℃ at least.
8, stretch yarn as claimed in claim 7 is characterized in that, its toughness is at least 6.5g/d, and DIMENSIONAL STABILITY (EASL+ shrinkage factor) is less than 5%, and shrinkage factor is 4% or littler.
9, stretch yarn as claimed in claim 8 is characterized in that, it is a polyphenyl dioctyl phthalate glycol ester.
10, stretching polyphenyl dioctyl phthalate glycol ester as claimed in claim 9 is characterized in that, its fusing point raises 8 to 15 ℃, and modulus is at least 280g/d, and toughness is at least 7.5g/d.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US82279992A | 1992-01-21 | 1992-01-21 | |
| US07/822,799 | 1992-01-21 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1078508A true CN1078508A (en) | 1993-11-17 |
| CN1051586C CN1051586C (en) | 2000-04-19 |
Family
ID=25237011
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN93101268A Expired - Fee Related CN1051586C (en) | 1992-01-21 | 1993-01-21 | High modulus polyester yarn for tire cords and composites |
Country Status (12)
| Country | Link |
|---|---|
| EP (1) | EP0623179B2 (en) |
| JP (1) | JP2629075B2 (en) |
| CN (1) | CN1051586C (en) |
| AU (1) | AU3331293A (en) |
| BR (1) | BR9207038A (en) |
| CA (1) | CA2126328C (en) |
| DE (1) | DE69213474T3 (en) |
| ES (1) | ES2091589T5 (en) |
| MX (1) | MX9300142A (en) |
| TR (1) | TR28032A (en) |
| TW (1) | TW224960B (en) |
| WO (1) | WO1993014252A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101622385B (en) * | 2007-02-28 | 2012-03-21 | 帝人纤维株式会社 | Polyethylene naphthalate fiber and method for production thereof |
| CN107949668A (en) * | 2015-09-08 | 2018-04-20 | 株式会社普利司通 | Manufacture method, PEF raw yarns line and the tire of PEF raw yarn lines |
| CN112281272A (en) * | 2020-10-15 | 2021-01-29 | 联新（开平）高性能纤维有限公司 | Polyester cord fabric warp with ultrahigh strength and dimensional stability as well as preparation method and application thereof |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4320593A1 (en) * | 1993-06-22 | 1995-01-05 | Akzo Nobel Nv | Multifilament yarn made of polyethylene naphthalate and process for its manufacture |
| KR100402839B1 (en) * | 2001-05-10 | 2003-10-22 | 주식회사 효성 | Polyethylene naphtalate fiber of high strength |
| DE10140774B4 (en) * | 2001-08-20 | 2004-08-12 | Metzeler Automotive Profile Systems Gmbh | molded hose |
| CA2450158C (en) * | 2003-08-22 | 2007-10-30 | Hyosung Corporation | High tenacity polyethylene-2, 6-naphthalate fibers |
| JP4616658B2 (en) * | 2005-01-31 | 2011-01-19 | 帝人ファイバー株式会社 | Non-woven |
| JP5480807B2 (en) * | 2007-07-03 | 2014-04-23 | ザ ゲイツ コーポレイション | Power transmission belt |
| US9005754B2 (en) | 2008-03-31 | 2015-04-14 | Kolon Industries, Inc. | Undrawn polyethylene terephthalate (PET) fiber, drawn PET fiber, and tire-cord comprising the same |
| FR2971187B1 (en) * | 2011-02-03 | 2013-03-08 | Michelin Soc Tech | SOLDER COMPOSITE REINFORCEMENT OF A SELF-ADHERING RUBBER POLYMER LAYER |
| FR2971188B1 (en) | 2011-02-03 | 2013-03-08 | Michelin Soc Tech | SOLDER COMPOSITE REINFORCEMENT OF A SELF-ADHERING RUBBER POLYMER LAYER |
| CN102851782B (en) * | 2011-06-30 | 2016-05-04 | 上海杰事杰新材料(集团)股份有限公司 | A kind of polyamide industrial yarn and manufacture method thereof for tyre framework material |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3616832A (en) * | 1968-12-24 | 1971-11-02 | Teijin Ltd | Rubber articles reinforced with filaments |
| 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 (en) * | 1973-09-20 | 1981-04-09 | ||
| FR2271315B1 (en) * | 1973-10-19 | 1976-10-01 | Teijin Ltd | |
| JPS62156312A (en) † | 1985-12-26 | 1987-07-11 | Teijin Ltd | Polyester fiber |
| WO1990000638A1 (en) * | 1988-07-05 | 1990-01-25 | Allied-Signal Inc. | Dimensionally stable polyester yarn for high tenacity treated cords |
| JP2861335B2 (en) * | 1990-08-31 | 1999-02-24 | 東洋紡績株式会社 | Method for producing naphthalate polyester fiber |
| JP2954391B2 (en) * | 1991-05-22 | 1999-09-27 | 帝人株式会社 | Polyethylene naphthalate fiber and method for producing the same |
-
1992
- 1992-12-22 ES ES93901119T patent/ES2091589T5/en not_active Expired - Lifetime
- 1992-12-22 BR BR9207038A patent/BR9207038A/en not_active IP Right Cessation
- 1992-12-22 EP EP93901119A patent/EP0623179B2/en not_active Expired - Lifetime
- 1992-12-22 WO PCT/US1992/011063 patent/WO1993014252A1/en active IP Right Grant
- 1992-12-22 CA CA002126328A patent/CA2126328C/en not_active Expired - Fee Related
- 1992-12-22 JP JP5512461A patent/JP2629075B2/en not_active Expired - Fee Related
- 1992-12-22 DE DE69213474T patent/DE69213474T3/en 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/en not_active IP Right Cessation
- 1993-01-19 TW TW082100327A patent/TW224960B/zh active
- 1993-01-20 TR TR00065/93A patent/TR28032A/en unknown
- 1993-01-21 CN CN93101268A patent/CN1051586C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101622385B (en) * | 2007-02-28 | 2012-03-21 | 帝人纤维株式会社 | Polyethylene naphthalate fiber and method for production thereof |
| CN107949668A (en) * | 2015-09-08 | 2018-04-20 | 株式会社普利司通 | Manufacture method, PEF raw yarns line and the tire of PEF raw yarn lines |
| CN112281272A (en) * | 2020-10-15 | 2021-01-29 | 联新（开平）高性能纤维有限公司 | Polyester cord fabric warp with ultrahigh strength and dimensional stability as well as preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| AU3331293A (en) | 1993-08-03 |
| MX9300142A (en) | 1994-07-29 |
| EP0623179B2 (en) | 2001-02-14 |
| EP0623179B1 (en) | 1996-09-04 |
| ES2091589T3 (en) | 1996-11-01 |
| EP0623179A1 (en) | 1994-11-09 |
| DE69213474T2 (en) | 1997-02-06 |
| WO1993014252A1 (en) | 1993-07-22 |
| TR28032A (en) | 1995-12-11 |
| BR9207038A (en) | 1995-12-05 |
| JP2629075B2 (en) | 1997-07-09 |
| JPH06511293A (en) | 1994-12-15 |
| CA2126328A1 (en) | 1993-07-22 |
| TW224960B (en) | 1994-06-11 |
| CA2126328C (en) | 2002-05-21 |
| ES2091589T5 (en) | 2001-05-16 |
| DE69213474D1 (en) | 1996-10-10 |
| DE69213474T3 (en) | 2001-08-23 |
| CN1051586C (en) | 2000-04-19 |
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