CN1077925C - Process for processing polymer blends into filaments - Google Patents
Process for processing polymer blends into filaments Download PDFInfo
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- CN1077925C CN1077925C CN97125423A CN97125423A CN1077925C CN 1077925 C CN1077925 C CN 1077925C CN 97125423 A CN97125423 A CN 97125423A CN 97125423 A CN97125423 A CN 97125423A CN 1077925 C CN1077925 C CN 1077925C
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- 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
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- 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
- D01F6/90—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 polyamides
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Abstract
本发明涉及将聚酯或聚酰胺混合物，以≥1500米/分钟的拉出速度加工成断裂伸长≤180%的长丝的方法，其中添加的第二种非晶型聚合物量为0.05-5(重量)%，由至少两种下列单体单元组成：0-90(重量)%A(CH2＝C(R)-COOR1)的单体，式中R是-H或-CH3，R1是直链或支链C1-C10烷基或环己基；0-40(重量)%B(如马来酸)单体及5-85(重量)%C(如苯乙烯)单体，并通过高速拉伸方法或高速拉伸卷曲方法加工成长丝。The invention relates to a method for processing polyester or polyamide mixtures into filaments with elongation at break ≤ 180% at a pulling speed of ≥ 1500 m/min, wherein the amount of the second amorphous polymer added is 0.05-5 (weight) %, composed of at least two of the following monomer units: 0-90 (weight) % A (CH 2 =C (R)-COOR 1 ) monomer, where R is -H or -CH 3 , R 1 is linear or branched C 1 -C 10 alkyl or cyclohexyl; 0-40 (weight)% B (such as maleic acid) monomer and 5-85 (weight)% C (such as styrene) monomer body, and processed into filaments by a high-speed drawing method or a high-speed drawing and crimping method.
Description
The present invention relates to polymeric blends, be spun into the method for the long filament of extension at break≤180% with 〉=1500 meters/minute the speed of pulling out polyester or polyamide and amorphous second kind of polymer.
Can know the spining technology of polymeric blends from following document:
Japan Patent 56-85420A (Teijin) discloses a kind of polyamide (nylon) yarn that does not stretch, wherein added 0.5-10 (weight) thus the double phenol polycarbonate of % has improved productivity ratio.
European patent 35796A (Teijin) discloses and has comprised that those are by the polyester of the polysulfone polymer that contains 1-15 (weight) %, has high glass-transition temperature (Tg 〉=150 ℃) or the synthetic fiber of polyamide system.Add polymer and in matrix, keep spherical, thereby influenced the surface texture and the fibre frictoin performance of long filament.Spinning speed be 2000-5500 rice/minute.
European patent 41327B (ICI) discloses PET or the nylon 66 fiber that the another kind that contains 0.1-10 (weight) % has the polymer of anisotropy (LCP level), spinning speed be 1000-5000 rice/minute.Because the fiber that is spun into has higher extension at break, thereby reached winding speed inhibition (WUSS, Wind-Up Speed Suppression, so fiber has higher draw ratio and can increase substantially productivity ratio the winding speed that is improved when promptly the performance of the fiber that is spun under low winding speed of the fibre property that is spun into by polymeric blends and unmixing polymer is identical).
European patent 80274B (ICI) relates to PET, nylon 66 or the polypropylene fibre that contains the another kind of polymer of 0.1-10 (weight) %, and the average particle size particle size of another kind of polymer is the 0.5-3 micron in melt, and is deformed into fibrillation in the melt spinning process.Spinning speed be 2000-6000 rice/minute because the fiber that is spun into by (PET) has higher extension at break and lower birefringence, thereby winding speed suppresses (WUSS) and can reach 20% at least, therefore reached higher draw ratio and improved productivity ratio.Concerning PET, preferably add polymer and comprise polyethylene glycol or nylon 66, are polyolefin to nylon 66.Adding polymer is extremely sensitive to the effect such as output, spinning temperature, mixed type and extruder type manufacturing parameter.Because this method is very sensitive, it is difficult being diverted to this method in the equipment of different capabilities, type or the fiber number program.
Japan Patent 56-91013A (Teijin) discloses a kind of not stretched polyester yarn, has wherein added the styrene polymer of 0.5-10 (weight) % and has improved productivity ratio.The raising of productivity ratio be since improved 850-8000 rice/minute, be spun into the extension at break of fiber under meter/minute spinning speed of preferred 〉=2500.Therefore and reached higher draw ratio.
European patent 47464B (Teijin) discloses a kind of polyester yarn that does not stretch, wherein added 0.2-1.0 (weight) %-(CH
2CR
1R
2)
n-base polymer has improved productivity ratio as gathering (4-methyl-1-pentene) or polymethyl methacrylate.The raising of productivity ratio is owing to improved the extension at break that is spun into fiber under 2500-8000 rice/minute spinning speed.Therefore reached higher draw ratio.It is crucial making polymeric additive form a kind of meticulous homogeneous dispersion by mixing, wherein particle diameter necessary≤1 micron, to prevent to develop into fibrillation.The effect of polymeric additive is to be determined by the interaction between the compatibility of the chemical constitution of three kinds of performances-interpolation polymer (add polymer molecule almost can not extend), lower animal migration and polyester and interpolation polymer.
European patent 631638B (AKZO) discloses the PET fiber of the polyalkyl methacrylate of the 50-90% imino groupization that contains 0.1-5 (weight) %.Spinning speed be 500-10000 rice/minute and the fiber that makes that then stretches have higher initial modulus.Under the silk end breakage rate prerequisite that keeps routine, should be possible with very high spinning speed (as 8000 meters/minute) spinning.Up to 8000 meters/minute the time, can obtain partially oriented fiber at spinning speed, this fiber also is not stretched to final elongation, therefore, for example can be processed to textured yarn.With yarn, the influence of modulus is not easy repetition for process industry, the intensity that reaches is normally lower, and this is the critical defect of this product.Above-mentioned the drawn yarn to confession weaving usefulness is described.Extension at break≤65.3% of each undrawn yarn that under spinning speed surpasses 6000 meters/minute, is spun into, this silk since with the relevant high crystalline of boiling water shrinkage value (≤6.5%), be not suitable for doing further processing by crimping by stretching distortion or crimping by stretching method for processing.
One of target that polymeric blends is spun into synthetic fiber is under certain spinning speed condition, makes the fiber that is spun into have high extension at break without the fiber that the interpolation polymer modification is spun.This just can make the finished product yarn with higher draw ratio, and can improve the productivity ratio of spinning equipment.According to European patent 41327B, the increase in productivity of expection can by under establish an equation and calculate:
E/E ' is the extension at break of unmodified/modified fibre in the formula.Can find out that from this equation productivity ratio increases thereupon when the increment (E-E ') of elongation increases.Yet the reduction that excessive percentage elongation reaches the degree of orientation that is spun into fiber that causes thus all is unsuitable for carrying out the curling processes of high-speed stretch.
The method that another kind is boosted productivity be European patent 80274B propose make parameter WUSS 〉=20%.Promptly under the situation of spinning speed high at least 20%, the extension at break of its fiber and unmodified polymer are identical with the extension at break of the fiber that is spun into than low velocity.Yet, be not disclosed in spinning workshop in this patent or in any performance of the performance of further process equipment high speed operation or the finished product yarn made.
Boost productivity and tend to increase the profit of production technology.On the other hand, because production problem and expensive high-speed spinning equipment can reduce profit again to a certain extent.The surcharge of polymeric additive also has tangible influence to the raising of cost, so in fact profit exists a zero point as the function of addition.Can the interpolation polymer be buied also is a key factor.Therefore, the many kinds in the interpolation polymer of reporting in the document are not suitable for large-scale industrial production.
The producer or contractor must consider each link of whole production, and can not hinder the raising of next step (as at spinning workshop) production capacity, can not reduce the quality of following process.Specifically, one of main target of the present invention is not the further processing conditions that limits in each subsequent step, but these conditions of advantageous embodiment, although and under high spinning speed, still will realize this goal.
With regard to prior art, polymeric blends also reaches very high extension at break, can adapt to high speed spinning, and this high spinning speed greatly reduces relevant with orientation.As everyone knows, this fiber that spun is unsuitable for storing, and can not feed at a high speed in processing technology is curled in friction or with High-speed machining.On the other hand, the extension at break under the high speed spinning condition＜70% shows and has high-crystallinity.This high-crystallinity can be reduced in the intensity that can reach in the deformation processing.For the high orientation silk (HOY) that adopts utmost point high-speed spinning to be spun in the spinning technique, the increase of extension at break can make the mechanical stability generation problem of yarn when fabric processing (as weaving).Increase percentage elongation and can reduce the degree of orientation, the degree of orientation descends and can cause modulus to reduce again, and this point can be regarded the negatively influencing to quality as.
The purpose of this invention is to provide and a kind ofly produce extension at break≤180%, almost do not have or do not have fully a method of the long filament of above-mentioned shortcoming.This method comprises being that basis and the polymeric blends that contains second kind of polymer of amorphous state are processed and this mixture is carried out high speed spinning with 〉=1500 meters/minute the speed of pulling out with polyester or polyamide.Specifically, the second kind of polymeric additive that adds in polyester or the polyamide is should price not high, and spinning productivity ratio should be than the matrix polymer height of non-modified, and can carry out High-speed machining to the fiber that is spun into.
The present invention is by achieving the goal to polyester or a kind of copolymer of being made up of following at least two kinds of monomers of polyamide compound interpolation:
0-90 (weight) %A, A is chemical formula CH
2=C (R)-COOR
1Monomer, in the formula R be-H or-CH
3, R
1Be straight or branched C
1-C
10Alkyl or cyclohexyl.
0-40 (weight) %B, B is maleic acid or maleic anhydride monomer, and
5-85 (weight) %C, C is styrene or methyl substituted styrene monomer, allows ((weight) %A+ (weight) %B+ (weight) %C)=100, makes the gained mixture carry out high speed spinning with 〉=1500 meters/minute the speed of pulling out.Preferred R
1Be methyl, ethyl, n-pro-pyl, normal-butyl, isobutyl group, 2-ethyl-butyl, 2-ethylhexyl, n-hexyl, n-heptyl or cyclohexyl.Preferred C is α-Jia Jibenyixi, 3-methyl styrene or 4-methyl styrene.
Brief description of drawings
Figure 1A-B shows the fiber movement speed of embodiment 1 and the result that the deformation district measures.
Fig. 2 A-B and Fig. 3 A-B show the deformation district measurement result of embodiment 2
After Fig. 4 A-B shows that the polymeric matrix of experiment 5 and 6 leaves spinneret orifice, add the example of polymer particles Size Distribution in the polyester matrix.
Fig. 5 A-C and Fig. 6 A-C show the result that embodiment 3 deformation districts measure.
Fig. 7 A-B shows the result that distribution of additives is measured among the embodiment 4.
Detailed description of preferred embodiments
The invention provides improving one's methods of a kind of long filament of making extension at break≤180%, this method comprises that second kind of amorphous polymer with 0.05-5 (weight) % adds in polyester or the polyamide, and wherein second kind of polymer is by following at least two kinds of copolymers that monomeric unit is formed:
0-90 (weight) %A, A is chemical formula CH
2=C (R)-COOR
1Monomer, in the formula R be-H or-CH
3, R
1Be straight or branched C
1-C
10Alkyl or cyclohexyl.
0-40 (weight) %B, B is maleic acid or maleic anhydride monomer, and
5-85 (weight) %C, C is styrene or methyl substituted styrene monomer, allows ((weight) %A+ (weight) %B+ (weight) %C)=100, makes the gained mixture carry out high speed spinning with 〉=1500 meters/minute the speed of pulling out, preferred R
1Be methyl, ethyl, n-pro-pyl, normal-butyl, isobutyl group, 2-ethyl-butyl, 2-ethylhexyl, n-hexyl, n-heptyl or cyclohexyl.Preferred C is α-Jia Jibenyixi, 3-methyl styrene or 4-methyl styrene.
Add polymer (second kind of polymer) and must be armorphous, be insoluble to matrix polymer basically, promptly be mutual exclusive in essence, because of objectionable intermingling, so can form two-phase, this can be distinguished by microscopic examination.Preferably, add polymer and contain 50-85 (weight) %A, 5-20 (weight) %B and 5-30 (weight) %C (amounting to=100%), more preferably, 60-80 (weight) % methyl methacrylate units, 5-15 (weight) % maleic anhydride unit and 15-25 (weight) % styrene units (amounting to=100%).The commercially available prod that is suitable for is GHT120 (by Degussa AG, Frankfort, Germany provides) or HW55 (by Rohm GmbH, Darmstadt, Germany provides).STAPRON SZ26180 (by DSM N.V., Herleen, Holland provides) and be a kind of example of polymeric additive of the present invention, it is by two kinds of monomer components, promptly about 74 (weight) % styrene and about 26 (weight) % maleic anhydride are formed.Another kind of preferred polymeric additive contains 70-90 (weight) %A and 30-10 (weight) %C, and preferred polymeric additive contains 80-85 (weight) % methyl methacrylate units and 20-15 (weight) % styrene units.For many purposes, second kind of polymer addition≤2.5% is just enough, is very favourable like this to reducing cost.
Polyester (can be used as the matrix polymer that forms fiber as polyethylene terephthalate (PET) or polyamide (as nylon-6 or nylon-66).Homopolymers is preferred.Yet the copolymer that co-monomer content reaches about 15 (mole) % also can adopt.For example, for PET, comonomer can be diethylene glycol (DEG), 1,4 cyclohexane dimethanol, polyethylene glycol, isophthalic acid and/or adipic acid.In addition, polymer also can contain additive, as catalyst, stabilizing agent, fluorescent whitening agent and delustering agent.PET also can contain a spot of branching component, as polyfunctional acid (1,2,4-benzenetricarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid) or ternary or tetrahydroxylic alcohol (as trimethylolpropane, pentaerythrite, glycerol or corresponding carboxylic acid).
Polymeric additive (second kind of polymer) can solid-stately add in the extruder hopper of band chip blender or the heavy instrument of meter to mix mutually realizing with the matrix polymer section and mixes mutually with matrix polymer.Perhaps with another kind of method and matrix polymer mutually mixed melting add polymer and utilize in the melt-flow of gear pump with the melt feeding matrix polymer of metering.Distribute by in extruder, mixing or mixture being reached equably then by blender known method utilization static state or dynamic.
The design of spinneret assembly is very important, and its device has the fracture filtration medium (as steel ball) of filter unit and/or certain granules size.For polymeric additive being set up suitable shear action, determined specific spinning head pressure.Can estimate shear action in the spinneret assembly by the melt-flow spinning of adopting and do not adopt the built-in type spinneret assembly: under the identical condition of other pretreatment parameter, to the continuous yarn product sampling of discharging, count and measure adding polymer particles with electron microscope then.Because two kinds of polymer are inconsistent, polymeric additive has formed spherical particle in matrix polymer.As average grain diameter d
50≤ 400 nanometers, on the sample cross＞particle number of 1000 nanometers just reached best state less than 1% o'clock.Draw-spinning process can not detect by analytical method the influence of these particulates.
For polymeric additive of the present invention, the contradiction effect and the roller effect of the fibrillation effect described in the document do not appear again.We think that this is owing to can cause under the condition that reduces orientation and inhibition spinning induced crystallization, deformation has taken place in the boundary layer of matrix polymer between itself and second kind of polymer, and we also think also because every kind of polymer has all presented effect separately.Suitable evaluation criterion is to see the improvement effect that is spun into fiber and processing characteristics.
Adopt well-known spinning equipment to produce synthetic thread with 〉=1500 meters/minute high speed spinning methods of pulling out speed.
Melted polymer mixture is finished shearing and filtration treatment after pressurization is extruded from the hole of spinnerets in spinneret assembly.Cooling zone in the downstream, the melt fiber air-flow that is cooled is cooled to and is lower than softening point, to prevent that bonding or compacting phenomenon take place on the thread guide of back.If can guarantee that even air flow by strand is a uniform air flow, then the design of cooling zone is not very important just.Therefore, be right after below spinnerets, have the air quiescent centre with delay the cooling.Cooling blast can be by air handling system supply with laterally or radial air flow, or the air of drawing from environment through cooling tube by automatic inlet duct.
After the cooling, strand is through boundling and dewing oiling treatment.For this reason, spinning oil is supplied with the food tray of several grinding stone material systems with the emulsion form by measuring pump, and uses this food tray.The fiber that is spun into is preferably by the compactness of interlacing device with the raising yarn.Waste silk processing and protector also can be installed in fiber path before fiber arrival winding apparatus, and winding apparatus forms package with the winding filament that is spun on the cylindrical tube body.The peripheral speed of fiber package is self-adjusting and equates with wire winding speed.The speed of pulling out of fiber is because the reciprocating motion of reeling may be higher than wire winding speed 0.2-2.5%.
Optional is, before driven godet roller can be inserted in silk back or wrapping wire.The peripheral speed of the first draw-off godet system equals the speed of pulling out.Can adopt additional draw-off godet for the stretching of silk or lax.
The high-speed stretch processing or the high-speed tensile deformation processing that are spun into fiber can be undertaken by once step stretching or two-step stretch method.In the once step stretching method, the speed of pulling out is 〉=1500 meters/minute, and at least by a drawing zone, the linear velocity with 〉=4000 meters/minute is wound into stretcher strain processing bobbin silk to fiber after HEAT SETTING then by driven godet roller guiding.In the two-step stretch method, the fiber that is spun into is at first reeled with 〉=1500 meters/minute speed, supplies with stretching-machine then, and with at least 800 meters/minutes, preferably 〉=1000 meter/minute speed stretches in stretching-machine.
As being to spin with the fiber (being often referred to partially oriented yarn POY) that is spun into of rove with 〉=3600 meters/minute the speed of pulling out for the crimping by stretching deformation processing.Preferably the addition of polymeric additive will be enough to make these to be spun into the extension at break of fiber, reaches 60-180% concerning nylon, reaches 85-180% concerning PET, preferably reaches 95-145%.The crimping by stretching deformation processing is to carry out according to the type of filament linear-density, and concerning the long filament of common fiber number, the draw speed of employing 〉=750 meter/minute are preferably 〉=900 meters/minute.
Concerning stretcher strain processing with the bobbin silk, under sufficiently high spinning speed, can by or not under the situation by the stretching between two online draw-off godets, the extension at break of nylon can reach 10-70%, PET can reach 10-45%, preferred 20-45%.The full stretcher strain processing of producing with high speed spin drawing with bobbin silk (HOY) pull out speed and winding speed is 〉=6000 meters/minute.
As everyone knows, the structure that is spun into fiber is that the deformation district below spinning head forms to a great extent, and promptly in the deformation district, the stress that solidifies because of fiber causes fiber deformation, and the speed of service of fiber is improved.Have found that the length in deformation district can be used as the quantitative measure of fibrous physics structure, equally also can influence the processing characteristics that is spun into fiber.Therefore, this parameter does not belong to intrinsic conventional parameter, but an independence parameter.For unmodified polymer, the deformation section length can speed is different to be changed because of fiber is pulled out.Be at least 2500 meters/minute rove for the routine speed of pulling out, about 300 millimeters of the deformation section length of POY, preferred 〉=250 millimeters to≤700 millimeters; ≤ 200 millimeters approximately of the deformation section length of the finished fiber of stretching spinning, preferred≤100 millimeters.
Have found that, compare with conventional method, the speed of pulling out during the polymeric blends spinning that improves the appropriate amount polymeric additive, for become to stretch with High-speed machining or the stretcher strain long filament, can make the fiber that is spun into premium properties.
When pulling out rapid change, the addition of second kind of polymer also should be adjusted thereupon, so that make asynchronous region length consistent with the deformation district of unmodified matrix polymer.Have been found that concerning the rove that is used for crimping by stretching distortion when the speed υ of pulling out was about 8000 meters/minute of 2500-, for reaching optimum, second kind of polymer addition M at the most must meet the numerical value that following formula provides:
And preferred to being on a small quantity:
Also find, for only adopt draw-spinning process, concerning height-oriented fullly drawn yarn (FDY) (HOY), during in winding speed 〉=6000 meter/minute, second kind of polymer addition P at the most must meet the numerical value that following formula provides:
Concerning the rove that is used for the crimping by stretching deformation processing, the P value is lower than the M value.
Embodiment
The assay method of the performance number that provides in the following example is as follows:
The distribution of polymeric additive particulate: with will be in the liquid nitrogen freezing melt bar of sharp keen chisel or extrude sample and blend.Utilize the plane of disruption of scanning electronic microscope test sample and then carry out graphical analysis.Four scanning electrons by each section show emblem mirror image, and three sections of each sample are assessed.Because the low contrast between matrix and polymeric additive, in graphical analysis to each polymeric additive particulate mark in addition one by one.This analysis is based on is used as ellipse (ellipsoid) to particulate, calculates the average diameter of particulate from the length and width value of ellipse.
Fiber movement speed is fixed with laser-Doppler anemometry instrumentation.In the method, laser beam is divided into two bundles, and two-beam is intersected on testee.In the back reflection scope, measure interference frequencies and can calculate object of which movement speed by the displacement of interference frequencies.For the present invention, adopting power is the diode laser (LS50M type, by TSIGmbH, Aachen, Germany's distribution) of 10 milliwatts.Below spinnerets, measure the fiber movement speed and the mapping at several different distance place.The variation that spinning deformation district is increased to by fiber movement speed on the speed of pulling off device regulation characterizes.Promptly in fiber movement speed be 1000 meters/minute locate to reach final speed 90% between length (with millimeter) be defined as standard of measurement.This deformation section length is generally the hundreds of millimeter.For the extreme case of high speed spinning, the deformation section length can foreshorten to about 100 millimeters.If the necking phenomenon that everybody knows takes place, the fiber movement velocity variations almost occurred in some when then spinning speed was higher than about 1750 meters/minute.
Inherent viscosity is to restrain polyester in 100 milliliters of phenol and 1 with 0.5 under 25 ℃, measures in the solution of 2-dichloro-benzenes (3: 2 (weight portion)) mixture.
The strength character and the boiling water shrinkage that are spun into fiber are measured by United States Patent (USP) 4446299 described methods, and Wu Site (Uster) value is pressed the described method of European patent 346641B and measured, and birefringence is pressed the described method of Deutsche Bundespatent 19519898A and measured.
The curl characteristics of modified continuous filament (the nominal fiber number reaches 500 dtexs) is measured according to part 1 among the DIN53840.
Dye uptake during dyeing be according to DIN54001 with fabric tube with the dark blue GRL-C200% of Terasil (Ciba-Geigy, Basel, Switzerland) dyeing, the reflectivity that dyes with the reflectance photometer measurement of comparison is measured.
Contrast
Inherent viscosity η
Intr=0.64 deciliter/gram, residual moisture be the polyethylene terephthalate of 32ppm in single screw extrusion machine fusion and by gear wheel metering pump through nine static mixer (SMX types, by Sulzer AG, Zurich, Switzerland) to deliver to temperature be in 296 ℃ the spinneret assembly.
From the direction of melt flows as seen, spinneret assembly comprises can produce the medium of certain shear action and filtration by following design: the volume high 30 millimeters (steel ball particle size 177-250 micron) that holds steel ball, 40 microns ultra-fine cloth filters, gripper shoe, 40 micron second ultra-fine cloth filter, 34 hole spinneretss, bore dia is 0.25 millimeter, L=2D, spinnerets diameter are 80 millimeters, and corresponding filter area is 40 centimetres
2, because polymer throughputs is different, the spinning pressure that polymer is subjected to is 90 * 10
5-200 * 10
5Between the handkerchief (90-200 crust).
Cool off through crossflow at conventional quench duct from the melt fiber of spinneret orifice ejection, air velocity is set in 0.45 meter per second.
1200 millimeters places below spinnerets utilize upper oil-pan oil supply boundling through cooled fibers.Upper oil-pan provides the emulsion of spinning oil in water, and wherein the consumption of emulsion is 0.4% of a fiber.
Fibre bundle is by two godets-stretchings, the bundle coiled S type between two draw-off godets that stretches, and on the bobbin of birotor horizontal wraparound machine (SW7 type, by Barmag AG, Remscheid, Germany provides) the coiling wrapping wire.The spinning speed of pulling out is by the decision of the peripheral speed of draw-off godet.Winding speed be set in reduce about 1% so that make the fiber tension that forms 10 lis of oxen between draw-off godet and the up-coiler.The nominal fiber number of the fiber that is spun into by this method is the 84f34 dtex.
Pull out speed setting at 3200 meters/minute, the speed of polymer feeding spinnerets is 41.4 gram/minute.In second experiment, the speed of pulling out bring up to 5000m/minute, simultaneously the feeding rate setting of polymer is in 63 gram/minute.These performances that are spun into fiber are compiled in table 1.
Table 1
| Control experiment NO. | 1 2 |
| Pull out speed (m/min) fiber number (dtex) tensile strength (li ox/spy) fracture load CV (%) extension at break (%) extension at break CV (%) Wu Site-half slow method (U%) Wu Site-natural law (U%) boiling water shrinkage (%) birefringence (10-3) drawing zone (millimeter) speed CV (%) | 3200 5000 130 128 25.3 35.6 2.6 1.9 117.3 59.7 2.3 2.8 0.23 0.24 0.66 0.46 64 6.6 48.4 70.9 288 89 3.2 29 |
(the CV=coefficient of variation)
Fiber movement speed and deformation district measurement result are as shown in Figure 1.When the speed of pulling out be 5000m/minute the time, necking phenomenon (cross-sectional area decline) obviously appears.The velocity perturbation at constriction place (CV%) is also very irregular.
The fiber that is spun into by two experiments is equipped with Barmag disc assembly (7 type CO.85 ceramic disk at one, configuration 1-5-1, D/Y=2.2), and the temperature repacking Barmag draw texturizing machine (FK6-S-900) that is respectively the heater 1 of 195 ℃ and 160 ℃ and heater 2 go up and make further processed with 800 meters/minute speed.Draw ratio is to be adapted to this characteristic that is spun into fiber, and the characteristic of draw ratio and textured yarn is compiled in the table 2.
Table 2
The result of experiment 1 and 2 crimping by stretching deformation processing
| Control experiment no. | 1 2 |
| Pull out speed (m/min) the curling shrinkage of draw ratio (1 :) tension force F1/F2 (li ox) fiber number (dtex) tensile strength (li ox/dtex) extension at break (%) (%) crimp retention (%) dye-uptake (%) processability | 3200 5000 1.68 1.17 28/37 35/39 80 116 42.0 34.4 23.3 26.0 20 21 85 82 100 - + - |
(+=just,-=negative)
Though the No.1 yarn according to DESCRIPTION OF THE PRIOR ART can successfully be processed, when spinning speed bring up to 5000m/minute the time, can break end and the problem of strand tension force defective, thereby draw ratio must reduce widely.Therefore, the fibre strength that can reach has also reduced.Its reason is that the degree of crystallinity that POY is spun into fiber has improved, and shows low extension at break and the necking phenomenon in draw-spinning process to occur.
According to the spinning system of embodiment 1 and under identical spinning condition, in the polyethylene terephthalate section, add the particulate additives for polymers of different amounts respectively.Add polymer for being purchased product (HW55 type, Rohm GmbH, Darmstadt, Germany), be equivalent to the random copolymer of methyl methacrylate of the present invention, styrene and maleic anhydride.
Yet, the spinning speed of pulling out be fixed on 5000m/minute.The flux of polymer melt is 63 gram/minute.Spinning head pressure is 135 * 10
5Handkerchief to 185 * 10
5Between the handkerchief (135-185 crust).Table 3 has been listed the characteristic that is spun into fiber.
Table 3
| Experiment No. | 3 4 5 6 |
| Add polymer concentration (weight) % fiber number (dtex) tensile strength (li ox/spy) fracture load CV (%) extension at break (%) extension at break CV (%) Wu Site-half slow method (U%) Wu Site-natural law (U%) boiling water shrinkage (%) birefringence (10-3) drawing zone (millimeter) speed CV (%) | 0.3 0.6 1.0 1.65 129 128 129 129 30.8 27.0 24.0 18.7 2.6 2.5 2.2 3.2 71.6 85.5 112.8 144.5 3.7 3.1 1.9 2.4 0.17 0.31 0.24 0.36 0.44 0.62 0.51 0 59 11 0 16.4 35.1 43 6 64.5 57.9 43.4 26.5 119 285 378 326 53 6.1 3.2 3.7 |
The measurement result in deformation district shows among Fig. 2 and Fig. 3, in experiment 4 (contain 0.6% and add polymer) experiment afterwards necking phenomenon just takes place no longer, and in experiment 5 (contain 1.0% and add polymer) experiment afterwards, deformation district velocity variations is permissible.
Fig. 4 shows, in experiment 5 and 6, adds the particle size distribution situation of polymer in polyester matrix after polymer melt leaves spinneret orifice.The average diameter of measuring is that 235 nanometers note is made d
50Dispersion is CV=25-26%.Maximum particle size is 680 nanometers in the sample.
Temperature higher except deformation velocity, primary heater is brought up to 220 ℃, is spun into fiber and carries out crimping by stretching processing by embodiment 1.Process velocity is increased to 1000 meters/minute and any problem do not take place in experiment 5 and 6.The textile property of yarn is compiled in table 4.
For experiment 3 and 4, because tension force is too high, so draw ratio can not be set to sufficiently high degree.(experiment No.1) compares with unmodified polymer, significantly improves.
Table 4
The result of experiment 3-6 crimping by stretching deformation processing
| Experiment No. | 3 4 5 6 |
| The curling shrinkage of polymeric additive concentration (%) draw ratio (1 :) tension force F1/F2 (li ox) fiber number (dtex) tensile strength (li ox/spy) extension at break (%) (%) crimp retention (%) dye-uptake (%) processability | 0.3 0.6 1.0 1.65 1.25 1.38 1.58 1.85 40/49 41/52 37/46 31/39 105.6 95.9 83.7 72.1 37.6 39.0 40.1 37.3 28.1 27.5 25.4 22.0 32.3 31 2 27.7 22.0 89 2 88.5 86.2 85.9 172 173 160 146 - - + + |
According to the spinning system of embodiment 2 and identical spinning condition, under the situation of polymeric additive concentration maintenance certain (1.2 (weight) %), change spinning and pull out speed.To be spun into fiber and to reach certain fiber number in order to make, polymer throughputs will be adapted to the speed of pulling out.
The characteristic that is spun into fiber is compiled in table 5, and the measurement result in deformation district is plotted among Fig. 5 and Fig. 6.
Table 5
| Experiment No. | 7 8 9 10 11 |
| Spinning pull out speed (m/min) flux (gram/minute) spinning head pressure (bar) fiber number (dtex) tensile strength (li ox/spy) breaking load CV (%) extension at break (%) extension at break CV (%) Wu Site-half slow method (U%) Wu Site-natural law (U%) boiling water shrinkage (%) birefringence (10-3) drawing zone (millimeter) speed CV (%) | 3200 4000 5000 6000 650 44.0 53.0 63.0 75.6 81.9 113 136 159 185 203 138 133 128 124 130 18.4 20.8 22.4 23.4 22.9 2.7 3.1 2.3 3.3 2.4 177.6 144 8 118.4 86 4 84.1 2.0 2.1 2.4 3.3 3.1 0.2 0.34 0.34 0.26 0.44 0.55 0 63 0.52 0.57 0.76 56.8 62 33.8 9 7 8.0 22.1 34 5 37.7 53.7 55.5 248 313 337 219 189 2.3 2.5 2.6 3.1 9 |
Being spun into fiber further processes on as embodiment 2 described draw texturizing machines.The textile performance of textured yarn is compiled in table 6.
Table 6
The result of experiment 7-11 crimping by stretching deformation processing
| Experiment No. | 7 8 9 10 11 |
| Spinning pull out speed (m/min) the curling shrinkage of draw ratio (1 :) tension force F1/F2 (li ox) fiber number (dtex) tensile strength (li ox/spy) extension at break (%) (%) crimp retention (%) dye-uptake (%) processability | 3200 4000 5000 6000 6500 2.17 1.88 1.64 1.43 - 29/39 30/38 35/44 46/55 65.6 73.00 80.4 92.1 38.6 41.2 41.0 35.5 16.4 23.5 23.9 25.2 20.0 24.1 25.3 27 2 84.0 85.8 85.7 84.8 89 104 129 182 - * + * + - - |
* deformation velocity=800 meter/minute
Runnability is a positive sign.The textile performance and the draw ratio of every kind of situation are listed in table 7
Table 7
| Experiment No. | 10 11 |
| Draw ratio (1 :) fiber number (dtex) tensile strength (li ox/spy) extension at break (%) processability | 1.364 1.324 94.9 99.3 32.3 32.9 32.7 31.7 + + |
Be applicable to fully with high draw speed and make drawn yarn by experiment 10 and 11 fibers that make.
According to embodiment 2 spinning systems, remaining spinning condition is done test and is adjusted its concentration as requested as polymeric additive with 2: two kinds of additional polymer of embodiment except following change.Experiment 12 in the same old way, as polymeric additive, being equipped with particle size in spinneret assembly is the coarse steel ball of 250-350 micron to adopt nylon 66 (AS2503 type, by BASFAG, Ludwigshafen, Germany provides).Spinning head pressure was set in 113 * 10 when the polymer melt flux was 63 gram/minute
5Handkerchief (113 crust).Yet the experiment 12 that the assembly of above-mentioned steel ball is housed has produced 164 * 10
5The spinning head pressure of handkerchief (164 crust).In experiment 13, added interpolation polymer GHT120 of the present invention (by Degussa AG, Frankfort, Germany provides).
Table 8 has been listed the performance data that is spun into fiber, and Fig. 7 shows the measurement result of polymeric additive particle size distribution.The result of control experiment 12 clearly illustrates that the polymeric additive particle size distribution is relatively poor, average grain diameter d in the experiment 12
50=600 nanometers, CV=50%, the average grain diameter of Dui Zhao experiment 13 is 220 nanometers with it, CV=28%, adding the polymer maximum particle diameter in the experiment 12 is 1740 nanometers, is 500 nanometers and test 13.
The POY extension at break of these two experiments is all within normal ranges.
Table 8
| Experiment No. | 12 13 (contrast) (the present invention) |
| Polymeric additive type polymer additive concentration (%) fiber number (dtex) tensile strength (li ox/spy) breaking load CV (%) extension at break (%) extension at break CV (%) Wu Site-half slow method (U%) Wu Site-natural law (U%) boiling water shrinkage (%) birefringence (10-3) drawing zone (millimeter) speed CV (%) | Nylon 66 * GHT120 **4.1 1.2 126 129 20.4 22.2 2.7 2.6 112.3 116.8 2.1 2.5 0.9 0.4 1.39 0.77 36.0 47.0 42.0 38.2 290 328 is very high by 2.4 |
* polymer nylon 66, and the AS2503 type is by BASF AG, Ludwigshafen, Germany provides, and * * contains the copolymer of about 70-75% methyl methacrylate units, about 15-20% styrene units and about 10% maleic anhydride unit, by Degussa AG, Frankfort, Germany provides.
Be spun into fiber and on as embodiment 2 described draw texturizing machines, do further processing.The textile property of textured yarn is compiled in table 9.
Table 9
The result of experiment 12 and 13 crimping by stretching deformation processing
* deformation velocity=800 meter/minute
| Experiment No. | 12 13 (contrast) (the present invention) |
| The curling shrinkage of polymeric additive draw ratio (1 :) tension force F1/F2 (li ox) fiber number (dtex) tensile strength (li ox/spy) extension at break (%) (%) crimp retention (%) processability | Nylon 66 GHT120 1.44 1.44 36,/45 91.5 41.0 24.8 28.3 87.9-* + |
The crimping by stretching performance of control experiment 12 is unsettled, and deformation velocity can not improve.We think that the two synergy causes owing to bulky grain in polymeric additive type and the polymeric additive distributes too much for this.
Containing the particle diameter identical with embodiment 1 in the spinneret assembly is the steel ball of 170-250 micron, but adopts 10 microns non-woven materials as ultrafilter in the assembly.Spinnerets has 24 spinneret orifices as embodiment 1 illustration.Spinning head pressure corresponding to the polymer melt flux is 183 * 10
5Handkerchief (183 crust) or 188 * 10
5Handkerchief (188 crust).After polymer melt leaves spinneret orifice, add the d of polymer in polyester matrix
50Be 240 nanometers.
Melt fiber in antipriming pipe by automatically from environment inhaled air cool off.1450 millimeters places oil to fiber by finish consumption 0.53% with the oil-in-water spinning oil below spinning head.Then, this strand is 5.5 * 10 with air pressure
5The injection apparatus interlacing of handkerchief (5.5 crust) and with various speed drawings, be wound on the up-coiler (Remscheid, Germany provides for CW8T type, Bar-mag AG).
The nominal fiber number that makes is that the fiber of 75f24 dtex is height-oriented, need not carry out stretch process again.The textile performance of fiber is listed in table 10.Runnability is a positive sign.
Table 10
* pull out speed=speed (meter/minute) 1.0046
| Experiment No. | 14 15 |
| Speed (rice/minute *) polymer throughputs (gram/minute) fiber number (dtex) tensile strength (li ox/spy) breaking load CV (%) extension at break (%) extension at break CV (%) Wu Site-half slow method (U%) Wu Site-natural law (U%) interlacing tubercle (individual/rice) drawing zone (millimeter) | 6500 7000 46.6 50.2 73.2 74.0 41.4 42.8 2.6 3.0 40.9 36.7 5.9 6.3 0.23 0.37 0.61 0.78 11 9 106 73 |
According to the spinning system of embodiment 2, except following change, other spinning condition is with embodiment 2, and the copolymer of being made up of about 83 (weight) % methyl methacrylate and about 17 (weight) % styrene is tested with variable concentrations as polymeric additive.Be set at 170 * 10 with the corresponding spinning head pressure of polymer melt flux 63 Grams Per Minutes
5Handkerchief.
Table 11 has been listed the performance data that is spun into fiber.The extension at break of POY is in normal ranges in this two experiment.
Table 11
| Experiment No. | 16 17 |
| Polymeric additive concentration (%) fiber number (dtex) tensile strength (li ox/spy) breaking load CV (%) extension at break (%) extension at break CV (%) Wu Site-half slow method (U%) Wu Site-natural law (U%) boiling water shrinkage (%) birefringence (10-3) | 0.65 0.72 129 129 23.4 22.3 2.8 2.7 115.4 122.9 2.9 2.5 0.45 0.48 0.90 0.98 - 61.3 - 50.8 |
Being spun into fiber is further processing by embodiment 2 described draw texturizing machine work.The textile performance of textured yarn is compiled in table 12.
Table 12
The result of experiment 16 and 17 crimping by stretching deformation processing
| Experiment No. | 16 17 |
| Draw ratio (1 :) tension force F1/F2 (li ox) fiber number (dtex) tensile strength (li ox/spy) extension at break (%) processability | 1.72 1.81 30/40 33/43 85.8 73.4 36.7 40.8 18.6 17.5 + + |
Claims (15)
1. make the method for extension at break≤180% long filament, comprise the polymeric blends that is main component with polyester or polyamide, is added with second kind of armorphous polymer of 0.05-5 (weight) % is processed, wherein, second kind of copolymer that polymer is made up of at least two kinds of following monomer units:
0-90 (weight) %A, A is chemical formula CH
2=C (R)-COOR
1Monomer, in the formula R be-H or-CH
3, R
1Be straight or branched C
1-C
10Alkyl or cyclohexyl;
0-40 (weight) %B, B is maleic acid or maleic anhydride monomer; And
5-85 (weight) %C, C is styrene or methyl substituted styrene, allows ((weight) %A+ (weight) %B+ (weight) %C)=100%, and makes the gained mixture carry out high speed spinning with 〉=1500 meters/minute the speed v of pulling out.
2. handle melt blend under the shearing condition according to the process of claim 1 wherein that described method is included in, so that make melt blend after leaving spinning head, the average grain diameter (d of second kind of polymer
50) be at most 400 nanometers.
3. according to the process of claim 1 wherein when strand is used rove as the crimping by stretching deformation processing, pull out speed v 2500-8000 rice/minute between, the addition of second kind of polymer is at most M, wherein M is stipulated by following formula:
4. according to the method for claim 3, wherein the minimum addition M of second kind of polymer is:
5. according to the method for claim 3, wherein the speed of pulling out is at least 2500 meters/minute, and the addition of second kind of polymer is adjusted to and makes the deformation section length between the 250-700 millimeter.
6. according to the method for claim 3, wherein strand is wound on earlier on the bobbin, delivers to the draw texturizing machine that process velocity is at least 750 meters/minute then and processes.
7. according to the process of claim 1 wherein that strand is wound on earlier on the bobbin, deliver to the draw texturizing machine that process velocity is at least 800 meters/minute then and process.
8. according to the process of claim 1 wherein through spray silk and after pulling out, and then strand is directed between two draw-off godets through mechanical stretching, and HEAT SETTING also is wound on the bobbin as the winding speed with 〉=4000 meters/minute of stretch yarn fully.
9. according to the method for claim 1, it is characterized in that the height-oriented yarn of stretching fully (HOY) that made by the spin-drawing method makes under winding speed 〉=6000 meter/minute.
10. according to the method for claim 9, wherein second kind of polymer addition P is at most:
11. according to the process of claim 1 wherein that second kind of polymer is made up of 50-85 (weight) %A, 5-20 (weight) %B and 5-30 (weight) %C.
12. method according to claim 11, wherein second kind of polymer is by 60-80 (weight) % methyl methacrylate units, 5-15 (weight) % maleic anhydride unit and 5-25 (weight) % styrene units are formed, wherein (weight) % methyl methacrylate units+(weight) % maleic anhydride unit+(weight) % styrene units=100%.
13. according to the process of claim 1 wherein R
1Be methyl, ethyl, n-pro-pyl, normal-butyl, isobutyl group, 2-ethyl-butyl, 2-ethylhexyl, n-hexyl, n-heptyl or cyclohexyl, C is α-Jia Jibenyixi, 3-methyl styrene, 4-methyl styrene or styrene.
14. according to the process of claim 1 wherein that second kind of polymer is made up of 70-90 (weight) %A and 30-10 (weight) %C.
15. according to the method for claim 14, wherein second kind of polymer is made up of 80-85 (weight) % methyl methacrylate units and 20-15 (weight) % styrene units.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19707447.2 | 1997-02-25 | ||
| DE19707447A DE19707447A1 (en) | 1997-02-25 | 1997-02-25 | Process for processing polymer mixtures into filaments |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1191906A CN1191906A (en) | 1998-09-02 |
| CN1077925C true CN1077925C (en) | 2002-01-16 |
Family
ID=7821377
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97125423A Expired - Fee Related CN1077925C (en) | 1997-02-25 | 1997-12-09 | Process for processing polymer blends into filaments |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0860524B1 (en) |
| CN (1) | CN1077925C (en) |
| DE (2) | DE19707447A1 (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| PT1002146E (en) * | 1997-08-05 | 2002-11-29 | Zimmer Ag | PROCESS FOR THE PROCESSING OF POLYMERIC MIXTURES TO OBTAIN FILAMENTS |
| DE19747867B4 (en) * | 1997-10-30 | 2008-04-10 | Lurgi Zimmer Gmbh | Process for the production of filaments from polymer blends |
| JP3769379B2 (en) * | 1998-03-19 | 2006-04-26 | 帝人ファイバー株式会社 | Highly stretched polyester filament yarn with improved tearability and method for producing the same |
| KR20020000640A (en) * | 1999-05-10 | 2002-01-05 | 아코르디스 인두스트리알 피베르스 게엠베하 | Thread-forming polyesters and copolyesters and method for producing the same |
| DE19922240A1 (en) * | 1999-05-14 | 2000-11-16 | Lurgi Zimmer Ag | Manufacture of synthetic continuous polyester or polyamide yarn, by melt spinning at high drawing speeds, achieves ultra-fine dimensions and low breakage rate, in light of mathematical understanding of process and materials variables |
| DE19924838A1 (en) | 1999-05-29 | 2000-11-30 | Lurgi Zimmer Ag | Spinning device for spinning molten polymers and method for heating the spinning device |
| DE19937727A1 (en) | 1999-08-10 | 2001-02-15 | Lurgi Zimmer Ag | Polyester staple fibers and process for their manufacture |
| DE10022889B4 (en) * | 2000-05-25 | 2007-12-20 | Lurgi Zimmer Gmbh | Process for producing synthetic threads from a polyester-based polymer blend |
| DE10054758A1 (en) * | 2000-11-04 | 2002-05-08 | Zimmer Ag | Process for the production of synthetic threads from polymer blends |
| ITMI20021373A1 (en) | 2002-06-21 | 2003-12-22 | Effeci Engineering S A S Di Fo | POLYMERIC COMPOUNDS AND THEIR USE |
| DE10303491A1 (en) * | 2003-01-30 | 2004-08-12 | Röhm GmbH & Co. KG | Process for the production of synthetic threads with improved dyeing properties, synthetic threads with improved dyeing properties and their use |
| CN102493016B (en) * | 2011-12-21 | 2014-08-20 | 苏州大学 | Porous superfine polyamide 6 fully-drawn yarn, preparation method thereof, and equipment thereof |
| CN102517680B (en) * | 2011-12-21 | 2014-09-17 | 苏州大学 | Multi-hole superfine denier polyamide 6 POY/FDY interlacing composite fiber, its preparation method and its device |
| CN102517679B (en) * | 2011-12-21 | 2016-01-20 | 苏州大学 | The fine denier polyamide fiber 6 pre-oriented yarn of a kind of porous, preparation method and equipment thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5691013A (en) * | 1979-12-20 | 1981-07-23 | Teijin Ltd | Undrawn polyester yarn and its production |
| EP0047464B1 (en) * | 1980-09-03 | 1985-01-23 | Teijin Limited | Undrawn polyester yarn and process for manufacturing the same |
| JPS6221817A (en) * | 1985-05-30 | 1987-01-30 | Teijin Ltd | Ultra-high speed spinning of polyester fiber |
| WO1993019231A1 (en) * | 1992-03-20 | 1993-09-30 | Akzo Nobel N.V. | Polyester fibres and process for producing the same |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS491657B1 (en) * | 1970-12-23 | 1974-01-16 | ||
| JPH07173720A (en) * | 1993-12-21 | 1995-07-11 | Teijin Ltd | Method for producing polyester filament |
-
1997
- 1997-02-25 DE DE19707447A patent/DE19707447A1/en not_active Withdrawn
- 1997-12-09 CN CN97125423A patent/CN1077925C/en not_active Expired - Fee Related
-
1998
- 1998-02-02 DE DE59809989T patent/DE59809989D1/en not_active Expired - Fee Related
- 1998-02-02 EP EP98101697A patent/EP0860524B1/en not_active Expired - Lifetime
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5691013A (en) * | 1979-12-20 | 1981-07-23 | Teijin Ltd | Undrawn polyester yarn and its production |
| EP0047464B1 (en) * | 1980-09-03 | 1985-01-23 | Teijin Limited | Undrawn polyester yarn and process for manufacturing the same |
| JPS6221817A (en) * | 1985-05-30 | 1987-01-30 | Teijin Ltd | Ultra-high speed spinning of polyester fiber |
| WO1993019231A1 (en) * | 1992-03-20 | 1993-09-30 | Akzo Nobel N.V. | Polyester fibres and process for producing the same |
| CN1078274A (en) * | 1992-03-20 | 1993-11-10 | 阿克佐公司 | Polyester fiber and manufacture method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| DE19707447A1 (en) | 1998-08-27 |
| DE59809989D1 (en) | 2003-12-04 |
| EP0860524B1 (en) | 2003-10-29 |
| CN1191906A (en) | 1998-09-02 |
| EP0860524A3 (en) | 1999-02-03 |
| EP0860524A2 (en) | 1998-08-26 |
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