EP1356143A1 - Method for spinning and winding pet filaments - Google Patents
Method for spinning and winding pet filamentsInfo
- Publication number
- EP1356143A1 EP1356143A1 EP01991856A EP01991856A EP1356143A1 EP 1356143 A1 EP1356143 A1 EP 1356143A1 EP 01991856 A EP01991856 A EP 01991856A EP 01991856 A EP01991856 A EP 01991856A EP 1356143 A1 EP1356143 A1 EP 1356143A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- thread
- filaments
- spinning
- dtex
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000009987 spinning Methods 0.000 title claims abstract description 60
- 238000004804 winding Methods 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims description 43
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- 239000000654 additive Substances 0.000 claims description 26
- 229920000642 polymer Polymers 0.000 claims description 26
- 230000000996 additive effect Effects 0.000 claims description 25
- 238000001816 cooling Methods 0.000 claims description 23
- 230000008569 process Effects 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 10
- 238000007711 solidification Methods 0.000 claims description 5
- 230000008023 solidification Effects 0.000 claims description 5
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 36
- 239000005020 polyethylene terephthalate Substances 0.000 description 36
- 229920001577 copolymer Polymers 0.000 description 23
- 239000000155 melt Substances 0.000 description 19
- -1 polyethylene terephthalate Polymers 0.000 description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 9
- 239000000178 monomer Substances 0.000 description 8
- 229920000728 polyester Polymers 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 150000003440 styrenes Chemical class 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 229920002959 polymer blend Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 150000005840 aryl radicals Chemical class 0.000 description 3
- 239000000112 cooling gas Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-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
- 125000000217 alkyl group Chemical group 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 230000002349 favourable 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
- 238000005259 measurement Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- MHCVCKDNQYMGEX-UHFFFAOYSA-N 1,1'-biphenyl;phenoxybenzene Chemical group C1=CC=CC=C1C1=CC=CC=C1.C=1C=CC=CC=1OC1=CC=CC=C1 MHCVCKDNQYMGEX-UHFFFAOYSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- FKTLISWEAOSVBS-UHFFFAOYSA-N 2-prop-1-en-2-yloxyprop-1-ene Chemical class CC(=C)OC(C)=C FKTLISWEAOSVBS-UHFFFAOYSA-N 0.000 description 1
- 241000945534 Hamana Species 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-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
- 150000007513 acids Chemical class 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000009795 derivation Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000002783 friction material Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000001261 hydroxy acids Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 239000012803 melt mixture Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 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
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of 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
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65H—HANDLING THIN OR FILAMENTARY MATERIAL, e.g. SHEETS, WEBS, CABLES
- B65H54/00—Winding, coiling, or depositing filamentary material
- B65H54/02—Winding and traversing material on to reels, bobbins, tubes, or like package cores or formers
- B65H54/40—Arrangements for rotating packages
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65H—HANDLING THIN OR FILAMENTARY MATERIAL, e.g. SHEETS, WEBS, CABLES
- B65H55/00—Wound packages of filamentary material
- B65H55/04—Wound packages of filamentary material characterised by method of winding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65H—HANDLING THIN OR FILAMENTARY MATERIAL, e.g. SHEETS, WEBS, CABLES
- B65H2701/00—Handled material; Storage means
- B65H2701/30—Handled filamentary material
- B65H2701/31—Textiles threads or artificial strands of filaments
Definitions
- the present invention relates to processes for spinning and winding up pre-oriented, non-crystalline filaments which consist of at least 90% by weight, based on the total weight of the filament, of polyethylene terephthalate (PET).
- PET polyethylene terephthalate
- pre-oriented, non-crystalline PET filaments which are also referred to as POY
- POY polycrystalline PET filaments
- Such filaments have elongation at break values of 90-165%, which have proven to be advantageous for further processing in a drawing or drawing texturing process.
- no crystallization is yet generated in the PET filaments, e.g. Fig. 2 from man-made fibers / textile industry, January 1980, page 27.
- WO 99/51799 discloses a method for spinning continuous filaments, in which the freshly spun filaments are cooled in a tube using an accelerated cooling gas. Such a procedure enables the spinning take-off speed to be increased to up to 4530 m / min without reducing the elongation at break of the filaments. Information regarding the fractions cannot be found in the publication.
- WO 99/07927 relates to a process for producing pre-oriented filaments from polymer mixtures based on polyester. In the presence of a certain amount of an additi copolymer, PET filaments with high elongation at break values are obtained even at high spinning take-off speeds of up to 6000 m / min. Information regarding the fractions cannot be found in this document either.
- WO 93/19229 describes a method for spinning and cooling continuous filaments by means of a spinning device with spinnerets containing nozzle plates and cooling shafts with an air-permeable wall, through which an air stream is sucked into the interior of the cooling shafts.
- pre-oriented, non-crystalline PET filaments which consist of at least 90% by weight, based on the total weight of the filament, of PET, which enables the production and winding of pre-oriented, non-crystalline PET filaments at high spinning take-off speeds with a low number of defects.
- the pre-oriented, non-crystalline PET filaments should have elongation at break values in the range of 90% - 165% and a high degree of uniformity with regard to the filament characteristics and the preparation order.
- Another object of the present invention was to provide a method for spinning and winding up pre-oriented, non-crystalline PET filaments which can be carried out on an industrial scale and at low cost.
- the method according to the invention should be as high as possible
- Allow spinning take-off speeds preferably greater than 3800 m / min, in particular in the range from 4200 to 8000 m / min, with the lowest possible spinning error rate.
- a good bobbin build should be adjustable to enable high thread weights on the bobbin of more than 4 kg and good bobbin winding behavior in further processing.
- An object of the present invention was also to be seen in the fact that the POYs obtainable by the process according to the invention have a very high degree of good staining and processing level with the lowest possible material error rate stretching or stretch texturing.
- the spinning distortion is set in the range from 50 to 250
- the filaments pass through a cooling delay zone of 20 mm to 300 mm in length immediately after emerging from the spinneret, c) the filaments are cooled below the solidification temperature, d) the filaments in one Distance between 500 mm and 2500 mm from the underside of the nozzle, e) spinning preparation is metered in with at least one oiler pin per thread with a preparation order variation of the standard deviation of less than 90 digits, f) oiler pins, thread bundling and thread guiding elements with low-friction surfaces are used, g) the thread tension in front of the take-off godets is set between 0.07 cN / dtex and 0.5 cN / dtex, h) the thread with a thread tension between 0.05 cN / dtex and 0.20 cN / dtex and an air pressure between 1.0 swirled bar and 5.5 bar with a knot count of at least 10 n
- pre-oriented, non-crystalline PET filaments have elongation at break values in the range of 90% - 165% and a high degree of uniformity with regard to the filament characteristics and the preparation order.
- the method according to the invention has a number of further advantages. These include:
- the method according to the invention can be carried out in a simple manner, on an industrial scale and inexpensively.
- the method allows spinning and winding at high take-off speeds of greater than 3800 m / min, in particular between 4200 and 8000 m / min, and the production of high thread weights on the bobbin of more than 4 kg.
- the bobbins of pre-oriented, non-crystalline PET filaments obtainable by the process can thus be processed in a simple manner, with the least possible deficiencies, in a drawing or drawing texturing process.
- the present invention relates to a process for the production and winding of pre-oriented, non-crystalline filaments, which consist of at least 90% by weight, based on the total weight of the filament, of polyethylene terephthalate (PET), for example by polycondensation in a known manner and Way is available from terephthalic acid and ethylene glycol.
- PET polyethylene terephthalate
- the polyethylene terephthalate can be either a homo- or a copolymer.
- Suitable copolymers are, in particular, those which, in addition to the above-mentioned repeating units, also contain up to 15 mol%, based on all repeating units of the PET repeating units of conventional comonomers, such as, for. B. 1,3-propanediol, 1,4-butanediol, diethylene glycol, triethylene glycol, 1,4-cyclohexanedimethanol, polyethylene glycol, isophthalic acid and / or adipic acid.
- PET homopolymers are preferred in the context of the present invention.
- the PET can also have a small proportion, preferably up to 0.5% by weight, based on the total weight of the filament, of branching components.
- the branching components preferred according to the invention include, inter alia, polyfunctional acids, such as trimellitic acid, pyromellitic acid, or tri- to hexavalent alcohols, such as trimethylolpropane, pentaerythritol, dipentaerythritol, glycerol, or corresponding hydroxy acids.
- Additive polymers which are particularly suitable according to the invention include the polymers and / or copolymers mentioned below:
- B styrene or C 1 . 3- alkyl substituted styrenes
- R 1 , R 2 and R 3 are each an H atom or a C ,. 15 -alkyl radical or a C 1-4 aryl radical or a C 5 _ 12 -cycloalkyl radical, the copolymer being composed of 15 to 95% by weight of C and 2 to 80% by weight of D, preferably of 50 to 90% by weight C and 10 to 50 wt% D and particularly preferably consists of 70 to 85% of C and 15 to 30% by weight of D, the sum of C and D totaling 100% by weight.
- F styrene or C ,. 3- alkyl substituted styrenes
- G one or more monomers of the formula I, II or III
- R 1 , R 2 and R 3 each represent an H atom or a C 5 alkyl radical or a C 5 . 12 -cycloalkyl radical or a C 6 . 14 aryl radical,
- H one or more ethylenically unsaturated monomers copolymerizable with E and / or with F and / or G from the group consisting of ⁇ -methylstyrene, vinyl acetate, acrylic acid esters, methacrylic acid esters other than E, vinyl chloride, vinylidene chloride, halogen-substituted styrenes, vinyl ethers , Isopropenyl ethers and dienes, the copolymer consisting of 30 to 99% by weight E, 0 to 50% by weight F,> 0 to 50% by weight G and 0 to 50% by weight H, preferably 45 to 97 %
- R 'and R 2 are substituents consisting of the optional atoms C, H, O, S, P and halogen atoms and the sum of the molecular weights of R 1 and R 2 is at least 40.
- additive polymers and / or copolymers are preferred which are amorphous and insoluble in the polyester matrix. They preferably have a glass transition temperature of 90 to 200 ° C., the glass transition temperature being determined in a known manner, preferably by differential scanning calorimetry. Further details can be found in the prior art, for example in publication WO 99/07927, the disclosure of which is hereby expressly incorporated by reference.
- the additive polymer and / or copolymer is selected such that the ratio of the melt viscosities of the additive polymer and / or copolymer and the matrix polymer is 0.8: 1 to 10: 1, preferably 1.5: 1 to 8: 1 ,
- the melt viscosity is measured in a known manner using an oscillation rheometer at an oscillation frequency of 2.4 Hz and a temperature which is equal to the melting temperature of the matrix polymer plus 34 ° C.
- the measuring temperature for the melt viscosity is 290 ° C. Further details can in turn be found in WO 99/07927.
- the melt viscosity of the additive polymer and / or copolymer is preferably higher than that of the matrix polymer, and it has been found that the choice of a specific viscosity range for the additive polymer and / or copolymer and the choice of the viscosity ratio to optimize the properties of the product Fadens contributes. With an optimized viscosity ratio, it is possible to minimize the amount of additive polymer and / or copolymer added, which among other things also improves the economics of the process.
- the polymer mixture to be spun preferably contains 0.05 to 2.5% by weight of additive polymer and / or copolymer.
- the favorable viscosity ratio By choosing the favorable viscosity ratio, a narrow distribution of the particle sizes of the additive polymer and / or copolymer in the polymer matrix is achieved with the desired fibril structure of the additive polymer and / or copolymer in the thread.
- the glass transition temperature of the additive polymer and / or copolymer which is high in comparison to the matrix polymer, ensures that this fibril structure is rapidly solidified in the filament.
- the maximum particle sizes of the additive polymer and / or copolymer are about 1000 nm immediately after emerging from the spinneret, while the average particle size is 400 nm or less.
- the favorable fibril structure is achieved in which the thread has at least 60% by weight of the additive polymer and / or copolymer in the form of fibrils with lengths in the range from 0.5 to 20 ⁇ m and diameters in the range from 0.01 to 0.5 ⁇ m.
- the polyethylene terephthalate according to the invention can contain customary amounts, preferably 0 to 5% by weight, preferably 0 to 1% by weight, in each case based on the total weight of the filament, of further additives, such as catalysts, stabilizers, antistatic agents, antioxidants, flame retardants, dyes, Dye uptake modifiers, light stabilizers, organic phosphites, optical brighteners and matting agents.
- further additives such as catalysts, stabilizers, antistatic agents, antioxidants, flame retardants, dyes, Dye uptake modifiers, light stabilizers, organic phosphites, optical brighteners and matting agents.
- the PET is spun to a pre-oriented, non-crystalline filament at a take-off speed greater than 3800 m / min, advantageously at least 4200 m / min, preferably greater than 4600 m / min, in particular at least 6000 m / min, particularly preferably greater than 6000 m / min wound.
- a particularly preferred range in the context of the present invention is between 4200 and 8000 m / min, in particular between 4600 and 6000 m / min.
- preoriented, non-crystalline filaments refer to those filaments which have an elongation at break of between 90 and 165%.
- the PET which can be used in the sense of the invention preferably has an intrinsic viscosity (intrinsic viscosity) in the range from 0.55 dl / g to 0.75 dl / g.
- a melt of the PET is spun at constant speed, the speed being set according to a known calculation formula so that the desired thread titer is obtained, pressed into nozzle packs and extruded through the nozzle holes of the nozzle plate of the pack to form molten filaments.
- the melt can be produced from polymer chips in an extruder, for example, it being necessary to dry the chips beforehand to a water content ⁇ 100 ppm, in particular to a water content ⁇ 50 ppm.
- the direct feed of the PET melt from the end reactor of a polycondensation plant to the spinning mill is preferred.
- the temperature of the melt commonly referred to as the spinning temperature and measured in front of the spinning pump, depends on the melting point of the PET. It is preferably in the range given by Formula 1:
- T m melting point of PET, approx. 260 ° C
- T Sp spinning temperature [° C].
- the homogeneity of the melt has a direct influence on the material properties of the spun filaments.
- a static mixer with at least two elements, which is installed before and / or after the spinning pump, is therefore preferably used to homogenize the Melt.
- a Promix spinning pump from Barmag / D with an integrated mixer can be used.
- the temperature of the nozzle plate which is dependent on the spinning temperature, is regulated by its so-called trace heating.
- trace heating for example, a spinning beam heated with "diphyl” or additional convection, induction or radiant heaters are possible.
- the temperature of the nozzle plates is usually at the level of the spinning temperature.
- a temperature increase on the nozzle plate can be achieved through the pressure drop in the nozzle package.
- Known derivations such as, for example, K. Riggert "Advances in the Production of Polyester Tire Cord Yarn” Chemical fibers 21, page 379 (1971), describe a temperature increase of approximately 4 ° C. per 100 bar pressure drop.
- nozzle pressure by using loose filter media, in particular steel sand with an average grain size between 0.10 mm and 1.2 mm, preferably between 0.12 mm and 0.75 mm and / or filter discs made of metal mesh or nonwovens with a fineness of ⁇ 40 ⁇ m, preferably 5 to 20 ⁇ m, can be produced.
- loose filter media in particular steel sand with an average grain size between 0.10 mm and 1.2 mm, preferably between 0.12 mm and 0.75 mm and / or filter discs made of metal mesh or nonwovens with a fineness of ⁇ 40 ⁇ m, preferably 5 to 20 ⁇ m, can be produced.
- the pressure drop in the nozzle hole contributes to the total pressure.
- the nozzle pressure is preferably set between 80 bar and 450 bar, in particular between 100 bar and 250 bar, the latter corresponding to an increase in the melt temperature directly before the extrusion of 4-10 ° C.
- the spinning delay is between 50 and 250, preferably between 70 and 170.
- the length / diameter ratio of the nozzle hole is preferably chosen between 1.5 and 6, in particular between 1.5 and 4.
- the extruded filaments pass through a cooling delay zone. Directly below the nozzle package, this is designed as a recess zone, in which the filaments emerging from the nozzle holes are protected from the direct action of the cooling gas and are delayed in delay or cooling.
- An active part of the recess is designed as an offset of the nozzle package into the spinning beam, so that the filaments are surrounded by heated walls.
- a passive part is formed by insulation layers and unheated frames. The lengths of the active recess are between 0 and 300 mm, those of the passive part between 20 and 150 mm, with a total length of 20 - 300 mm being maintained.
- a reheater can be installed below the spinning beam.
- this zone with a cylindrical or rectangular cross section then has at least one heating independent of the spinning beam.
- the cooling delay can be achieved with the aid of cylindrical covers.
- the filaments are then cooled to temperatures below their solidification temperature.
- the solidification temperature denotes the temperature at which the melt changes to the solid state.
- Means for cooling the filaments are known to the person skilled in the art from the prior art.
- the use of cooling gases, in particular cooled air, has proven particularly useful according to the invention.
- the cooling air preferably has a temperature of 12 ° C. to 35 ° C., in particular 16 ° C. to 26 ° C.
- the speed of the cooling air is advantageously in the range from 0.20 m / sec to 0.55 m / sec.
- single thread systems can be used which consist of individual cooling tubes with a perforated wall.
- a cooling of each individual filament is achieved by active cooling air supply or also by utilizing the self-suction effect from the filaments and / or by extracting the cooling air.
- the known cross-flow blowing systems can also be used.
- a special embodiment of the cooling and warping area is to supply the filaments emerging from the delay zone in a zone of length in the range from 10 to 175 cm, preferably in a zone of length in the range of 10 to 80 cm, of cooling air.
- the filaments and the air accompanying them are passed together through a reduced-cross-section channel, the ratio of the air to the thread speed during the drawing off being 0.2 to 20: 1, preferably 0.4, by controlling the cross-sectional taper and the dimensioning in the thread running direction up to 5: 1.
- the distance of the bundling from the underside of the nozzle which is suitable according to the invention can be determined by methods known to the person skilled in the art for online measurement of the thread speed and / or thread temperature, for example using a laser Doppler anemometer from TSI / D or an infrared camera from Goratec / D Type IRRIS 160. It is 500 to 2500 mm. Individual filaments with a spinning titer ⁇ 4.5 dtex are preferably bundled at a smaller distance ⁇ 1500 mm, thicker filaments preferably at a larger distance.
- the filaments are bundled in an oil pen, which feeds the desired amount of spin finish evenly to the thread.
- a particularly suitable oil pen is characterized by an inlet part, the thread channel with an oil inlet opening and the outlet part.
- the inlet part is widened in a funnel shape, so that contact through the still dry filaments is avoided becomes.
- the point of impact of the filaments takes place within the thread channel after the inflow of the preparation.
- the width of the thread channel and oil inlet opening is adapted to the thread titer and the number of filaments. Openings and widths in the range from 1.0 mm to 4.0 mm have proven particularly successful.
- the outlet part of the oiler pen is designed as a smoothing section, which preferably has oil reservoirs.
- Suitable oiling pens can be obtained, for example, from Ceramtec / D, type TriboFil, from Goulston / USA, type LuroJet, from Kyocera / J, type SF, and from Rauschert / D, type PN.
- the uniformity of the oil application is of great importance according to the invention. It can be determined, for example, with a Rossa measuring device in accordance with the method described in chemical fibers / textile industry, 42J94, Nov. 1992 on page 896.
- the amount of oil applied and its fluctuation is given in relative units, so-called digits.
- values for the standard deviation of the oil application of less than 90 digits, in particular less than 60 digits are obtained with such a procedure.
- values for the standard deviation of the oil application of less than 45 digits, in particular of less than 30 digits are particularly preferred.
- a value for the standard deviation of 45 digits corresponds to approximately 3.1% of the coefficient of variation.
- a preparation pump of the Profin type from Barmag / D is used.
- the filaments are swirled before winding.
- Conventional systems have proven to be of little use, because due to the high speed and thus the increased air pressure, considerable formation of loops and fluff can be observed. In addition, they require high winding tensions, which have a negative impact on the bobbin build-up and lead to saddle formation, slipping in and thread chipping on the bobbin.
- nozzles with closed yarn channels since in such systems the thread is prevented from getting caught in the insertion slot even when the thread tension is low and the air pressure is high.
- the entangling nozzles are preferably arranged between godets, the exit thread tension being regulated by means of different speeds of the inlet and outlet godets. It should not exceed 0.20 cN / dtex and primarily the thread tension should have values between 0.05 cN / dtex and 0.18 cN / dtex.
- the air pressure of the entangling air is between 1.0 and 5.5 bar.
- Node numbers of at least 10 n / m are set. Maximum opening lengths of less than 100 cm and values for the coefficient of variation of the number of nodes below 100% are of particular interest. When using air pressures> 3.0 bar, node numbers> 15 n / m are advantageously achieved, which are characterized by a high degree of uniformity, the coefficient of variation being less than or equal to 70% and the maximum opening length being 50 cm.
- the peripheral speed of the first godet unit is referred to as the take-off speed.
- Further godet systems can be used before the thread is wound into bobbins (bobbins) on tubes in the winder unit.
- Stable, error-free bobbins are a basic requirement for error-free removal of the thread and for error-free further processing. Therefore, a winding tension in the range of 0.03 cN / dtex - 0.20 cN / dtex, preferably in the range of 0.0 5 cN / dtex - 0.15 cN / dtex, is used in the context of the present method.
- the winder is preferably provided with a vane wheel traversing for thread laying and a driven feeler roller for controlling the speed of the winding mandrel, which in turn is driven, and onto which the winding tube is attached.
- a vane wheel traversing for thread laying and a driven feeler roller for controlling the speed of the winding mandrel, which in turn is driven, and onto which the winding tube is attached.
- a mirror interference method to vary the laying angle in steps by at least 1 ° in order to prevent thread layers from slipping in, especially in mirror areas.
- a variation of the laying angle over the coil travel between 3.5 ° and 7.5 ° is particularly preferred according to the invention for stabilizing the coil structure.
- the angle between the is considered perpendicular to the coil tube Thread running direction on the bobbin and the perpendicular to the bobbin tube referred to as the laying angle.
- an important parameter of the method according to the invention is the setting of the thread tension before the take-off godets.
- this tension essentially consists of the actual orientation tension according to Hamana, the friction tension on the thread guides and the oiler pin and the thread-air friction tension.
- the thread tension in front of the take-off godets is in the range from 0.07 cN / dtex to 0.50 cN / dtex, preferably between 0.07 cN / dtex and 0.20 cN / dtex.
- the tension is regulated by the spinning take-off speed, the lubricator pin distance from the nozzle, the friction surfaces and the length of the distance between the oil pin and the take-off godet.
- This line length is advantageously not more than 6.0 m, preferably less than 2.5 m, the spinning mill and the take-off machine being arranged in a parallel manner in such a way that a straight thread run is ensured.
- the winding speed of the POY is advantageously 0-2% below the take-off speed.
- a winding speed that is 0-1% below the spinning take-off speed is preferably selected.
- a temperature ⁇ 35 ° C., in particular between 12 and 28 ° C., and a relative humidity between 40-90% is set in the environment of the on dishwasher in the implementation of the method.
- the characteristics of the intermingling are determined with an ITEMAT node counter from Enka-Technica / D at a speed of 100 m / min and a set level No. 1.
- a Fraytec device from ENKA-Tecnica / D is used for online fluff detection during spinning.
- the fluff detection sensor has to trigger a video camera directly downstream, the image of which is saved, thus making possible errors evaluable and classifiable. Incorrect measurements, e.g. Oil droplets or vibrations can be avoided by such a procedure.
- the evaluation allows in particular to determine texturing-relevant errors. These defects, which look like filament tufts and are caused by postponing breaks, could be reduced to 0 per hour at a spinning take-off speed of 5000 m / min by using the method according to the invention.
- a melt of polyethylene terephthalate was discharged from a reactor with an intrinsic viscosity of 0.64 dl / g corresponding to a melt viscosity at 290 ° C of 250 Pas and a temperature of 282 ° C and by means of a booster pump with a pressure of 205 bar and an amount of 302.4 kg / h required by the melt line.
- the melt flowed through a filter with a fineness of 20 ⁇ m and a heat exchanger that cooled the melt temperature from 292 ° C to the spinning temperature of 290 ° C.
- This filtered partial stream 1 of the amount 302.4 kg / h was in the second partial stream of the amount 13.98 kg / h, corresponding to 4.62 wt .-% of the first stream, and the third partial stream of the amount 288.42 kg / h split and branched.
- a 6-speed planetary gear pump from Mahr GmbH, Göttingen / DE, operated in a counterclockwise direction, was used. It is a 6-fold spinning pump which combines the same volume flows from 6 input channels in one output channel by reversing the direction of rotation and thus the direction of flow.
- the second partial flow was fed in equal parts to 5 of 6 inputs of a 6-speed planetary gear pump from Mahr GmbH, Göttingen / DE, operated in a left-turning manner.
- a copolymeric additive from the 3rd group of substances containing 9% by weight of styrene, 89% by weight of methyl methacrylate and 2% by weight of N-cyclohexylmaleimide, was selected with a viscosity ratio of 5.8.
- the additive dried to a residual moisture content of ⁇ 0.1% by weight was melted in an extruder and at a melt temperature of 265 ° C. at a rate of 2.33 kg / h, corresponding to 0.77% by weight of the first Partial flow, the remaining input channel of the 6-fold planetary pump.
- This additive flow was combined in the outlet channel of the planetary gear pump with the polyester flow from one of the 5 input channels fed with polyester and by means of a static premixer of the type SMXS DN 12 from Sulzer AG, Zurich / CH, with an inner diameter of 12.9 mm and 3 times Length of the inner diameter premixed before the polyester streams of the 4 remaining input channels were fed to this premix in the outlet of the planetary gear pump.
- the residence time of the additive melt until it was brought together with the other polymers was approximately 70 seconds.
- the subsequent preparation of the first polymer mixture with an additive content of 16.7% by weight was carried out in a first static main mixer of the type SMXS DN 17 from Sulzer AG, Zurich / CH, with an inside diameter of 17.8 mm and 9 times the length of the Inside diameter.
- This first mixture was introduced into the third partial flow and, after a flow section L of 4 times the inside diameter of the first main mixer, was fed to a second SMX main mixer from Sulzer AG with an inside diameter of 52.5 mm and a length of 10 times the diameter, there homogenized and dispersed.
- the residence time of the additive melt until it came into contact with the third partial stream was approximately 100 seconds.
- the polymer mixture was distributed to 12 spinning positions, each containing 6 spinneret packs, using product lines.
- Each spin pack contained a round nozzle with 34 holes with a diameter of 0.25 mm and the length of the 2- times the diameter.
- the spin pack above the nozzle plate contained a spin filter pack consisting of a steel sand pack of 30 mm high and a grain size of 0.35 to 0.50 mm as well as a finest mesh fabric of 40 ⁇ m and a steel fleece filter of 20 ⁇ m pore diameter.
- the cross-sectional area of the spinning filter packet was 45 cm 2 .
- a nozzle pressure of 150 bar was established during the throughput of the melt mixture.
- the residence time of the melt in the Filte ⁇ aket was about 1.5 minutes.
- the surface of the spinneret was 30 mm above the lower edge of the heating box (active recess). The total recess was 110 mm.
- the heating of the spin pack was set to 290 ° C using HTM heat transfer oil.
- the molten filaments extruded from the nozzle holes were cooled by means of blown air, which flowed in horizontally to the thread run over a length of 1500 mm at a speed of 0.5 m / sec and had a temperature of 19 ° C., and at a distance of 1400 mm from the nozzle plate was bundled into a thread in a TriboFil-type oil pen from CeramTec, the diameter of the oil channel being 1 mm, and coated with spin finish from Goulston, an order of 0.35% having been set. The standard deviation of the order was 38 digits.
- Preoriented (POY) threads were obtained which were characterized by a titer of 141 dtex, a tensile strength of 25 cN / tex and an elongation at break of 11%.
- the POY coils were stretch-textured in a Barmag FK6 texturing machine at a speed of 900 m / min. 1.70 was selected as the draw ratio.
- the first heater had a temperature of 210 ° C, the second of 170 ° C.
- the textured yarn had a titer of 88 dtex, a tensile strength of 42 cN / tex and an elongation at break of 22% and was characterized by good dyeing uniformity.
- the method according to the invention was also distinguished here in particular by a small number of thread breaks both during spinning and during texturing.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
- Artificial Filaments (AREA)
- Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10063286A DE10063286A1 (en) | 2000-12-19 | 2000-12-19 | Process for spinning and winding PET filaments |
DE10063286 | 2000-12-19 | ||
PCT/EP2001/014876 WO2002050348A1 (en) | 2000-12-19 | 2001-12-17 | Method for spinning and winding pet filaments |
Publications (2)
Publication Number | Publication Date |
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EP1356143A1 true EP1356143A1 (en) | 2003-10-29 |
EP1356143B1 EP1356143B1 (en) | 2005-06-22 |
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Application Number | Title | Priority Date | Filing Date |
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EP01991856A Expired - Lifetime EP1356143B1 (en) | 2000-12-19 | 2001-12-17 | Method for spinning and winding pet filaments |
Country Status (11)
Country | Link |
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US (1) | US20040026818A1 (en) |
EP (1) | EP1356143B1 (en) |
KR (1) | KR100820098B1 (en) |
CN (1) | CN1298899C (en) |
AT (1) | ATE298376T1 (en) |
AU (1) | AU2002231712A1 (en) |
DE (2) | DE10063286A1 (en) |
MY (1) | MY124905A (en) |
PL (1) | PL365326A1 (en) |
TW (1) | TW554096B (en) |
WO (1) | WO2002050348A1 (en) |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
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DE10134073C1 (en) | 2001-07-13 | 2003-02-06 | Zimmer Ag | Filament winding process |
US20130045346A1 (en) * | 2011-08-15 | 2013-02-21 | Greif Flexibles Trading Holding B.V. | Oriented Tape For The Production Of Woven Fabrics And Products Produced Therefrom |
CN107003646B (en) * | 2014-11-13 | 2020-01-10 | 西门子公司 | Production module for performing a production function at a product |
DE102015120437A1 (en) | 2015-11-25 | 2017-06-01 | Maschinenfabrik Rieter Ag | Air-jet spinning machine and method for operating the same |
CN106381527A (en) * | 2016-08-31 | 2017-02-08 | 常州欣战江特种纤维有限公司 | Production method for spun dyeing anti-flaming DTY fiber for motor car |
CN108396402B (en) * | 2018-03-15 | 2020-12-15 | 江苏垶恒复合材料有限公司 | High-toughness polyester staple fiber and preparation method thereof |
MX2021004939A (en) * | 2018-10-29 | 2021-11-12 | Dror Selivansky | Concrete curing blankets and anti-bacterial textile fibers. |
US10668664B1 (en) * | 2018-11-09 | 2020-06-02 | Thermwood Corporation | Systems and methods for printing components using additive manufacturing |
CN113166977B (en) | 2018-11-22 | 2023-08-29 | Bb工程公司 | Method and device for melt spinning filaments |
CN111060418B (en) * | 2019-12-16 | 2022-08-02 | 广东溢达纺织有限公司 | Yarn dryness judging method |
BR102021025568B1 (en) * | 2021-12-17 | 2023-01-17 | Senai/Cetiqt - Serviço Nacional De Aprendizagem Industrial-Centro De Tecnologia Da Indústria Química E Têxtil | PROCESS OF REUSE OF SYNTHETIC TEXTILE WASTE TO OBTAIN CONTINUOUS YARN |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
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NL270846A (en) * | 1960-12-07 | |||
US3638872A (en) * | 1968-03-28 | 1972-02-01 | Du Pont | Process for winding a yarn package |
US3563021A (en) * | 1969-12-09 | 1971-02-16 | Du Pont | Interlaced yarn and method of making same |
FR2540894B1 (en) * | 1983-02-16 | 1985-11-08 | Rhone Poulenc Fibres | SIMPLIFIED PROCESS FOR OBTAINING HIGH SPEED POLYESTER YARNS |
IT1170088B (en) * | 1983-12-30 | 1987-06-03 | Snia Fibre | SINGLE STAGE PROCESS FOR HIGH SPEED PRODUCTION OF CONTINUOUS POLYESTER BASED WIRES AND RELATED PRODUCTS |
US4687610A (en) * | 1986-04-30 | 1987-08-18 | E. I. Du Pont De Neumours And Company | Low crystallinity polyester yarn produced at ultra high spinning speeds |
DE3819913A1 (en) * | 1988-06-11 | 1989-12-21 | Davy Mckee Ag | METHOD FOR PRODUCING UNIFORM POY FILAMENTS |
US5976431A (en) * | 1993-12-03 | 1999-11-02 | Ronald Mears | Melt spinning process to produce filaments |
CN1060827C (en) * | 1996-03-18 | 2001-01-17 | 中国纺织大学 | High speed single step spining art for polyester full stretchable filament, equipment and the schics heat-pipe thereof |
DE59804443D1 (en) * | 1997-08-05 | 2002-07-18 | Roehm Gmbh | METHOD FOR PROCESSING POLYMER BLENDS INTO FILAMENTS |
US6667003B2 (en) * | 2000-05-25 | 2003-12-23 | Zimmer A.G. | Method for the manufacture of synthetic fibers from a melt mixture based on fiber forming polymers |
DE10022889B4 (en) * | 2000-05-25 | 2007-12-20 | Lurgi Zimmer Gmbh | Process for producing synthetic threads from a polyester-based polymer blend |
-
2000
- 2000-12-19 DE DE10063286A patent/DE10063286A1/en not_active Withdrawn
-
2001
- 2001-11-21 TW TW090128873A patent/TW554096B/en active
- 2001-12-06 MY MYPI20015568A patent/MY124905A/en unknown
- 2001-12-17 WO PCT/EP2001/014876 patent/WO2002050348A1/en not_active Application Discontinuation
- 2001-12-17 US US10/433,255 patent/US20040026818A1/en not_active Abandoned
- 2001-12-17 AT AT01991856T patent/ATE298376T1/en not_active IP Right Cessation
- 2001-12-17 KR KR1020037005767A patent/KR100820098B1/en not_active IP Right Cessation
- 2001-12-17 AU AU2002231712A patent/AU2002231712A1/en not_active Abandoned
- 2001-12-17 DE DE50106599T patent/DE50106599D1/en not_active Expired - Fee Related
- 2001-12-17 EP EP01991856A patent/EP1356143B1/en not_active Expired - Lifetime
- 2001-12-17 PL PL01365326A patent/PL365326A1/en unknown
- 2001-12-17 CN CNB018195962A patent/CN1298899C/en not_active Expired - Fee Related
Non-Patent Citations (1)
Title |
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See references of WO0250348A1 * |
Also Published As
Publication number | Publication date |
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CN1633528A (en) | 2005-06-29 |
WO2002050348A1 (en) | 2002-06-27 |
PL365326A1 (en) | 2004-12-27 |
DE10063286A1 (en) | 2002-06-20 |
MY124905A (en) | 2006-07-31 |
EP1356143B1 (en) | 2005-06-22 |
CN1298899C (en) | 2007-02-07 |
AU2002231712A1 (en) | 2002-07-01 |
TW554096B (en) | 2003-09-21 |
KR100820098B1 (en) | 2008-04-10 |
DE50106599D1 (en) | 2005-07-28 |
US20040026818A1 (en) | 2004-02-12 |
KR20030061826A (en) | 2003-07-22 |
ATE298376T1 (en) | 2005-07-15 |
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