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
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
  • Y10T428/2913—Rod, strand, filament or fiber
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
  • Y10T428/2913—Rod, strand, filament or fiber
  • Y10T428/2933—Coated or with bond, impregnation or core
  • Y10T428/2964—Artificial fiber or filament
  • Y10T428/2967—Synthetic resin or polymer
  • Y10T428/2969—Polyamide, polyimide or polyester

Definitions

• the invention relates to polyester staple fibers and a method for Production of these staple fibers.
• the aim is the highest possible spinning factor, preferably in Range from 2.9 to 10.0.
• the hole density LD is due to the available spinning system given and can not be arbitrary for geometric reasons increase.
• the spinning take-off speed is through the cable storage system the filaments and their further processing into staple fibers Speeds below 2500 m / min limited.
• the draw ratio depends in a first approximation on the elongation at break of the filament in one linear relationship, wherein the elongation at break for a given Polymer, the lower the higher the spin-off speed is.
• low titers, especially microfilaments ⁇ 1 dpf or one intensive cooling reduces the elongation at break and thus the Draw ratio and the spin factor: Capacity losses are the Episode.
• the spin factor For a given spinning take-off speed can therefore be the spin factor by choosing a polymer with higher elongation at break Lift.
• the polymer is characteristic of the quality the staple fibers and therefore can not or only minimally changed become.
• the process is but produced at take-off speeds of less than 2500 m / min Spun threads are not transferable, since these, in contrast to POY fibers little crystalline ( ⁇ 12%) and a high boiling shrinkage (> 40%) and a have high elongation at break (> 225%).
• EP 0 631 638 B subsequently describes end-drawn threads Polyethylene terephthalate containing imidized poly (methacrylic acid alkyl ester) contains.
• the industrial yarns spun at 510 m / min Although they have an increased elongation at break, but the stretching is not improved, and the yarns have otherwise worse Properties as threads without additive.
• the object of the present invention is the maximization of the spinning factor in the production of polyester staple fibers, wherein the staple fibers have the same or better quality values than after Staple fibers produced by known methods.
• Polyesters here are poly (C 2-4 -alkylene) terephthalates which contain up to 15 mol% of other dicarboxylic acids and / or diols, such as.
• isophthalic acid, adipic acid, diethylene glycol, polyethylene glycol, 1,4-cyclohexanedimethanol, or the other C 2-4 alkylene glycols may contain to understand.
• polyethylene terephthalate having an intrinsic viscosity (IV) in the range of 0.5 to 0.7 dl / g
• polypropylene terephthalate having an IV of 0.6 to 1.2 dl / g
• polybutylene terephthalate having an IV of 0.6 to 1 , 2 dl / g.
• Conventional additives such as dyes, matting agents, stabilizers, antistatic agents, lubricants, branching agents, can be added to the polyester or the polyester / additive mixture in amounts of 0 to 5.0 wt .-% without any disadvantage.
• the polyester is a copolymer in an amount of 0.1 added to 2.0 wt .-%, wherein the copolymer is amorphous and in the Polyester matrix must be largely insoluble. They are essentially the two polymers incompatible with each other and form two Phases that can be distinguished microscopically. Furthermore must the copolymer has a glass transition temperature (determined by DSC with 10 ° C / min heating rate) from 90 to 170 ° C and thermoplastic be processable.
• the melt viscosity of the copolymer is to be chosen so that the Ratio of its extrapolated to the zero measurement time Melt viscosity, measured at an oscillation rate of 2.4 Hz and a temperature equal to the melting temperature of the polyester plus 34.0 ° C (for polyethylene terephthalate 290 ° C) relative to that of the polyester, measured under the same conditions, between 1: 1 and 10: 1 lies.
• Ie. is the melt viscosity of the copolymer at least equal to or preferably higher than that of the polyester.
• Optimized viscosity ratio is a minimization of the amount of Additive additive possible, reducing the cost of the process becomes particularly high and particularly favorable processing properties be achieved.
• this is according to the invention as ideally determined viscosity ratio for the use of Polymer blends for the production of staple fibers above the Range, which in the literature for the mixing of two polymers is shown as cheap.
• Polymer blends with high molecular weight copolymers to spin Surprisingly, it was found that among the inventive Conditions, the melt viscosity of the mixture does not appreciably increase becomes. This results in a positive avoidance of Pressure loss increases in the melt lines.
• the maximum particle sizes of the additive polymer are immediate After exiting the spinneret at about 1000 nm, while the middle Particle size is 400 nm or less. After warping below The spinneret produces fibrils with a mean diameter ⁇ 80 nm.
• the ratio of the melt viscosity of the copolymer is too that of the polyester under the above conditions between 1.5: 1 and 7: 1.
• the mean particle size is of the additive polymer immediately after exit from the spinneret 120 - 300 nm, resulting in fibrils with a mean diameter of about 40 nm.
• Component H is an optional component. Although the advantages to be achieved according to the invention already by Copolymers comprising components from groups E to G, can be achieved, the present invention to achieve Advantages also when used in the structure of the invention Copolymer other monomers from the group H are involved.
• the component H is preferably selected so that they have no Adverse effect on the properties of the invention too having used copolymer.
• the component H can u. a. therefore be used to the properties of the copolymer to desired Way to modify, for example, by increases or Improvements in flow properties when the copolymer is applied to the Melting temperature is heated, or to reduce a residual color in Copolymer or by using a polyfunctional monomer to in this way a certain degree of crosslinking in the copolymer introduce.
• H can also be chosen so that a copolymerization of Components E to G is possible or supported in the first place, such as in the case of MSA and MMA, which do not copolymerize per se, however Addition of a third component such as styrene copolymerize easily.
• monomers suitable for this purpose are u. a.
• Vinylester Esters of acrylic acid, for example methyl and ethyl acrylate, esters of methacrylic acid other than methyl methacrylate, for example, butyl methacrylate and ethylhexyl methacrylate, Vinyl chloride, vinylidene chloride, styrene, ⁇ -methylstyrene and the various halogen-substituted styrenes, vinyl and Isopropenyl ethers, dienes such as 1,3-butadiene and Divinylbenzene.
• the color reduction of the copolymer may be, for example particularly preferably by using an electron-rich monomer, such as a vinyl ether, vinyl acetate, styrene or ⁇ -methylstyrene can be achieved.
• an electron-rich monomer such as a vinyl ether, vinyl acetate, styrene or ⁇ -methylstyrene
• Particularly preferred among the Compounds of component H are vinyl aromatic monomers, such as for example, styrene or ⁇ -methylstyrene.
• copolymers to be used according to the invention are on known. They can be in substance, solution, suspension or Emulsion polymerization are prepared. Find helpful hints with regard to the bulk polymerization in Houben-Weyl, Volume E20, Part 2 (1987), page 1145ff. Notes on solution polymerization finds one just described there on page 1149ff, while the Emulsion polymerization just run there on page 1150ff and is explained.
• the present invention for example, by mixing in the melt of the fiber polymers to be used copolymers in the form of Particles with a mean diameter of 0.1 to 1.0 mm. It but are also larger or smaller beads or granules can be used, but smaller beads have special requirements for Logistics, such as conveying and drying.
• the imidized copolymer types 2 and 3 can be made from both the monomers be prepared using a monomeric imide as well by subsequent complete or preferably partial imidization a copolymer containing the corresponding maleic acid derivative.
• These additive polymers are obtained for example by complete or preferably partial reaction of the corresponding copolymer in the Melting phase with ammonia or a primary alkyl or arylamine, For example, aniline (Encyclopedia of Polymer Science and Engineering Vol 16 [1989], Wiley-Verlag, page 78). All inventive Copolymers and, as far as given, their non-imidized Starting copolymers are commercially available or according to one of the Produce expert familiar process.
• the amount of the copolymer to be added to the polyester is from 0.1 to 2.0% by weight, with addition amounts of less than 1.0% usually being sufficient.
• R d the desired elongation at break of the spun yarn with additive additive here is ⁇ 370%, if R do ⁇ 354%.
• a is selected according to the desired staple fiber quality, with a low VV high elongation staple fibers and a high VV low elongation staple fibers with the same elongation at break R d of the filament.
• Z is preferably selected between 66 and 146 and an increase in the draw ratios of (VV-VV 0 ) ⁇ 0.45 is realized.
• the invention makes it possible, with variation of at least one of Influences on the spin factor a thereby occurring Reduction of the draw ratio by adding the additive compensate so that SF remains at least constant.
• the hole density LD are increased, resulting in a smaller VV results, with the result that a desired lower titer, in particular microtiter, can no longer be produced.
• the addition of additive increases the VV and smaller titers can at the same SF to be produced.
• the titer or the Spinning speed changed, so can lower VV by the Additive compensated, and SF and accordingly throughput
• the spinning system can be increased proportionally.
• the mixing of the additive polymer (copolymer) with the matrix polymer takes place by adding as a solid to the matrix polymer chips in Extruder inlet with chip mixer or gravimetric dosing or alternatively by melting the additive polymer, dosage by means of Gear pump and feed into the melt stream of the matrix polymer. Also so-called masterbatch techniques are possible, with the additive as a concentrate in polyester chips, later in solid or molten state are added to the matrix polyester is present. Also, the addition of a partial stream of the matrix polymer, which then the Mainstream of the matrix polymer is mixed, is practicable.
• a defined particle distribution is set by specific choice of the mixer and the duration of the mixing process, before the melt mixture is passed through product distribution lines to the individual spinning stations and spinnerets.
• Mixers with a shear rate of 12 to 128 sec -1 have proven themselves.
• the product of shear rate (s -1 ) and the power of 0.8th of the residence time (in sec) should be at least 250, preferably 350 to 1250. Values over 2500 are generally avoided in order to limit the pressure drop in the pipelines.
• Both the mixing of the two polymers and the subsequent Spinning the polymer blend occurs at temperatures, as appropriate Matrix polymer, in the range of 220 to 320 ° C, preferably at (Melting temperature of the matrix polymer + 34) ⁇ 15 ° C.
• Matrix polymer in the range of 220 to 320 ° C, preferably at (Melting temperature of the matrix polymer + 34) ⁇ 15 ° C.
• PET preferably temperatures of 275 to 305 ° C set.
• the molten polymer mixture is after shearing and Filtration treatment in the nozzle package through the holes of the nozzle plate pressed.
• the melt strands become Cooled by cooling air below its solidification temperature, so that a Glueing or upsetting on the following thread guide avoided becomes.
• the cooling air can by transverse or radial blowing of a Be supplied to the air conditioning system or by means of a cooling pipe from the Environment can be removed by self-priming.
• Typical of staple fibers made of polyester is that they are in large Direct melt spinning plants are manufactured, in which the melt over long heated product lines on the individual spinning lines and distributed within the lines on the individual spinning systems.
• a spinning line represents a juxtaposition of at least a series of spinning systems whose filaments are in one Cable storage system summarized and stored, and a Spinning system the smallest spinning unit with a spinning head, the one Spinneret package including a spinneret plate contains.
• the melt is subject to a high thermal in such systems Load at residence times up to 35 min.
• the effectiveness of Polymer additive according to the invention leads due to the high thermal stability of the additive to no appreciable Limitations of strain increase in the spun yarn, so that a small Addition amount of the additive ⁇ 2% and in many cases ⁇ 1% despite high sufficient thermal load. Under the conditions mentioned creates a uniform polymer mixture, which surprisingly by a finely dispersed additive distribution with a middle Particle size of maximum 400 nm is characterized and thereby a good drawability.
• the polyester / additive mixture according to the invention preferably allows the setting of an equal throughput per unit time on the spinning pump, if lower fiber titer to be produced, based on the possible throughput during polymer spinning without polymeric additive.
• the throughput or the rotational speed of the spinning pump by the factor f set higher than during spinning without addition.
• LD is the hole density (n / cm 2 ) of the spinneret plate
• z is a constant in the range of 39 to 153, preferably 66 or 146
• C is the concentration of the polymer additive in wt .-%
• VV is the Automatverstrecktex
• v is the spin-off speed in m / min, where the indices 1 and 0 refer to the spinning of the matrix polymer without additive polymer at the take-off speeds v 1 and v 0 .
• an improvement of the stretchability characterized by a higher draw ratio achieved.
• the Total draw ratio VV by at least 0.45 units, in particular to values ⁇ 2.9, and more preferably to ⁇ 3.5.
• the ratio of the outlet to inlet velocity in the subsequent fiber length increases, preferably to at least 2.9. At the same inlet speed is thus a higher Production speed of the fiber route possible.
• the properties of the additive polymer and the blending technique cause the additive polymer to form globule-like or elongated particles in the matrix polymer immediately upon exit of the polymer blend from the spinneret. Best conditions were obtained when the average particle size (arithmetic mean) d 50 ⁇ 400 nm, and the proportion of particles> 1000 nm in a sample cross-section was less than 1%.
• the additives according to this invention is a Glass transition temperature of 90 to 170 ° C and preferably a Flow activation energy of the copolymers of at least 80 kJ / mol, ie a higher flow activation energy than that of the polyester matrix required. Under this condition, it is possible that the Solidify additive fibrils in front of the polyester matrix and one record a significant proportion of the applied spinning tension.
• the preferred to apply additives are also characterized by a high Thermostability off. Thus, in the case of a large residence time and / or High temperature operated direct spinning the strain losses minimized by additive decomposition.
• the staple fibers of the invention have at least the same Quality values, such as analog staple fibers without polymeric Additive.
• Additive fibrils The study of microtome-made Thin sections were made by transmission electron microscopy and subsequent image analytical evaluation, wherein the diameter of the Fibrils were evaluated, and the length from the on samples immediately was estimated after the spinneret particle diameter.
• Intrinsic viscosity was measured on a solution of 0.5 g of polyester in 100 ml of a mixture of phenol and 1,2-dichlorobenzene (3: 2 parts by weight) at 25 ° C.
• the measurement temperature was 290 ° C for polyethylene terephthalate and additive polymers, which are added to polyethylene terephthalate, or was equal to the melting temperature of the polyester concerned plus 34.0 ° C.
• the measuring temperature thus determined corresponds to the typical processing or spinning temperature of the respective polyester.
• the amount of sample was chosen so that the rheometer gap was completely filled.
• the measurement was carried out in oscillation with the frequency 2.4 Hz (corresponding to a shear rate of 15 sec -1 ) and a deformation amplitude of 0.3, and determines the amount of the complex viscosity as a function of the measuring time. Thereafter, the initial viscosity was converted to the zero measurement time by linear regression.
• the polyester sample was initially at Melted 310 ° C for 1 min and immediately afterwards Room temperature quenched. Subsequently, the Glass transition temperature and melting temperature by DSC measurement (Differential scanning calorimetry) at a heating rate of 10 ° C / min determined. Pretreatment and measurement were carried out under Nitrogen flow.
• the flow activation energy (E) is a measure of the rate of change of Zero viscosity as a function of the change in the measuring temperature, where the zero viscosity extrapolated to the shear rate 0 Viscosity is.
• the measurement of the zero viscosity took place at Temperatures in the range of 240 to 280 ° C with a high pressure capillary rheometer, Type Rheograph 2002, Göttfert GmbH, Buchen / DE, and the evaluation according to the three-parameter approach of Carreau-Winter. After that was the flow activation energy by Arrhenius approach from the Zero viscosity according to M. Pahl et al., Practical Rheology of Plastics and Elastomers, VDI-Verlag, Düsseldorf (1995), Pages 256 ff., Determined.
• the tearing properties of the filaments were confirmed by a tensile tester a clamping length of 200 mm, a preload force of 0.05 cN / dtex and a test speed of 2000 mm / min determined.
• PET Polyethylene terephthalate
• the melt threads emerging from the die plate were cooled by means of cooling air fed radially inwards from the inside to a quantity of 1400 m 3 / h and applied at a distance of 850 mm from the nozzle plate to a ring oiler and charged with a water / oil mixture so that a very stable thread condition resulted.
• the spinning take-off speed was 1350 m / min and the resulting strand tension 380%.
• the spin factor is 3.7.
• Execution and polyethylene terephthalate correspond to Example 1.
• a side stream melting system consisting of a Extruder, a dosing pump and an injector.
• the injection of Additive melt took place directly in front of the polymer line installed mixer.
• the additive used was a copolymer of 91.2% by weight.
• Methyl methacrylate with 8.8 wt .-% styrene selected which is a Glass transition temperature of 119 ° C and a Melt viscosity ratio based on PET of 4.2: 1 had.
• the concentration C (wt.%) was determined by suitable choice of the speed the metering pump, based on the polymer throughput set.
• the polymer throughput was 1750 g / min.
• the mixing conditions and the Spinning corresponded to those of Comparative Example 2.
• the additive concentration and draw ratio were based on the in value specified in the table. Accordingly, the Throughput raised so that the same final titer was obtained. SF increased according to the table with the additive quantity. The boiling shrinkage of the filament decreased from 54 to 51%. By the increase the draw ratio according to the table became a better one Stretchiness allows. Also, the stretching problems of the Comparative Example 2 not on.
• the mean diameter of the fibrils in the fibers was below 80 nm.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Artificial Filaments (AREA)
• Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
• Preliminary Treatment Of Fibers (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

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• 1999
  • 1999-08-10 DE DE19937727A patent/DE19937727A1/de not_active Withdrawn
• 2000
  • 2000-07-25 AT AT00954560T patent/ATE262059T1/de not_active IP Right Cessation
  • 2000-07-25 AU AU66975/00A patent/AU6697500A/en not_active Abandoned
  • 2000-07-25 ES ES00954560T patent/ES2214302T3/es not_active Expired - Lifetime
  • 2000-07-25 MX MXPA02001289A patent/MXPA02001289A/es not_active Application Discontinuation
  • 2000-07-25 EA EA200200174A patent/EA004442B1/ru not_active IP Right Cessation
  • 2000-07-25 EP EP00954560A patent/EP1208254B1/de not_active Expired - Lifetime
  • 2000-07-25 CN CNB008116512A patent/CN1168857C/zh not_active Expired - Fee Related
  • 2000-07-25 DE DE50005713T patent/DE50005713D1/de not_active Expired - Fee Related
  • 2000-07-25 US US10/049,013 patent/US6576339B1/en not_active Expired - Fee Related
  • 2000-07-25 KR KR1020027001701A patent/KR20020036842A/ko not_active Application Discontinuation
  • 2000-07-25 PT PT00954560T patent/PT1208254E/pt unknown
  • 2000-07-25 WO PCT/EP2000/007087 patent/WO2001011117A2/de active IP Right Grant
  • 2000-07-25 JP JP2001515360A patent/JP2003506586A/ja active Pending

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