EP0154425B1 - Filage au fondu d'un mélange d'un polymère fibrogène avec un polymère non-miscible - Google Patents

Filage au fondu d'un mélange d'un polymère fibrogène avec un polymère non-miscible Download PDF

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Publication number
EP0154425B1
EP0154425B1 EP85300928A EP85300928A EP0154425B1 EP 0154425 B1 EP0154425 B1 EP 0154425B1 EP 85300928 A EP85300928 A EP 85300928A EP 85300928 A EP85300928 A EP 85300928A EP 0154425 B1 EP0154425 B1 EP 0154425B1
Authority
EP
European Patent Office
Prior art keywords
polymer
fibre
melt
nylon
forming polymer
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.)
Revoked
Application number
EP85300928A
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German (de)
English (en)
Other versions
EP0154425A3 (en
EP0154425A2 (fr
Inventor
Harry Brody
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Imperial Chemical Industries Ltd
Original Assignee
Imperial Chemical Industries Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
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First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=10557592&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0154425(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Imperial Chemical Industries Ltd filed Critical Imperial Chemical Industries Ltd
Publication of EP0154425A2 publication Critical patent/EP0154425A2/fr
Publication of EP0154425A3 publication Critical patent/EP0154425A3/en
Application granted granted Critical
Publication of EP0154425B1 publication Critical patent/EP0154425B1/fr
Anticipated expiration legal-status Critical
Revoked legal-status Critical Current

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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
    • D01F6/90—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
    • 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
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • 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

Definitions

  • This invention relates to the manufacture of synthetic fibres by melt spinning and drawing a high molecular weight, high viscosity, fibre-forming polymer, more particularly polyethylene terephthalate or nylon 66, containing another polymer which is immiscible in a melt of the fibre-forming polymer.
  • Japanese Patent No. 56-118912 (Teijin KK) is concerned with the manufacture of a high strength fibre by melt spinning polyethylene terephthalate containing between 1 and 7 parts by weight % of a bisphenol type polycarbonate.
  • the melt spun fibre is wound up at a speed of 1500 m/minute or less.
  • the limiting viscosity of the polyethylene terephthalate used must fall between 0.55 and 0.70. If it falls below 0.55, satisfactory strength and modulus cannot be developed in the fibre. On the other hand, when the limiting viscosity is in excess of 0.70, recognisable improvement in strength becomes insignificant or disappears and there is a tendency for the modulus value to decline as well.
  • DE-A-3113717 is concerned with a bristle for brushes consisting of polyethylene terephthalate incorporating between 2 and 25% by weight of a polyolefine, which may be polyethylene or polypropylene or polymer mixture of ethylene and propylene.
  • DE-A-2328917 is concerned with a process for producing a composite filament which comprises melt-extruding a mixture of a polyethylene having a melt index of at least 27 and a fibre-forming polyester and withdrawing the extruded filaments from the spinneret at a speed above 2,500 metres per minute.
  • An advantage of the process described in European Patent Application No. 80274 is that it allows significant productivity gains to be achieved.
  • the effect of blending the immiscible polymer with the fibre-forming polymer is that of wind up speed suppression, i.e. the properties of the spun fibre are those that would be obtained from a fibre which had been spun at a lower wind up speed.
  • the present invention therefore, we provide a process of melt spinning a fibre-forming polymer selected from the group consisting of polyethylene terephthalate and nylon 66 in which before melt spinning, there is added to the fibre-forming polymer between 0.1% and 10% by weight of another polymer, but excluding a liquid crystal polymer, which is immiscible in a melt of the fibre-forming polymer, such other polymer having an average particle size less than 3 micrometres in the melt immediately prior to spinning, said immiscible polymer being selected from the group consisting of polyethylene, polypropylene, polyethylene glycol and nylon 66 when the fibre-forming polymer is polyethylene terephthalate and said immiscible polymer being selected from the group consisting of polyethylene, polypropylene, polyethylene terephthalate and polyethylene glycol, when the fibre-forming polymer is nylon 66 characterised in that the polyethylene terephthalate fibre-forming polymer has an intrinsic viscosity greater than 0.70, the nylon fibre-forming polymer has
  • the additive polymer has an average particle size in the melt of substantially less than 3 micrometres and more preferably of the order of 1 micrometre.
  • the intrinsic viscosity of polyethylene terephthalate is measured in ortho-chloro-phenol.
  • the relative viscosity of nylon 66 is measured on a 8.4% w/w solution in 90% formic acid compared with the viscosity of 90% formic acid itself.
  • an “immiscible polymer” we mean that at the spinning temperature such a polymer forms a two phase melt with the fibre-forming thermoplastic polymer. Microscopic examination and optical photographs of such a melt show a two phase system in which the immiscible polymer is in the form of circles (indicating spherical particles) dispersed in the continuous, fibre-forming, polymer matrix.
  • an immiscible polymer to exclude a liquid crystal polymer, i.e. the additive polymers used in the invention do not form an anisotropic melt in the temperature range at which the thermoplastic polymer may be melt spun.
  • This anisotropic condition may form when a liquid crystal polymer is heated or by the application of shear to the polymer, although in the latter case it must persist for a few seconds.
  • the immiscible polymer is selected from the group consisting of polyethylene, polypropylene, polyethylene terephthalate and polyethylene glycol.
  • the immiscible polymer is selected from the group consisting of polyethylene, polypropylene, polyethylene glycol and nylon 66.
  • a preferred immiscible polymer is nylon 66.
  • the extensional viscosity of nylon 66 is such that the molten spheres of the polymer immediately prior to spinning, deform into microfibrils along the spinning threadline.
  • melt spun fibres of polyethylene terephthalate made from polymer having an intrinsic viscosity greater than 0.70 containing between 0.1% and 10% by weight of nylon 66 which is present in the melt spun fibres as microfibrils.
  • These microfibrils have an aspect ratio i.e. length/diameter ratio which is very high e.g. typically greater than 50 and such microfibrils will have diameters of about 0.5 micron. It is believed that it is the conversion of the spheres of nylon 66 into microfibrils and the extent of this deformation that produces the change of rheology which is responsible for the orientation suppression and in turn wind up speed suppression which is referred to below.
  • a major advantage of the process of the invention is that it allows significant productivity gains to be achieved.
  • the effect of blending the immiscible polymer with the fibre-forming polymer is that of orientation suppression which manifests itself as wind up speed suppression i.e. the properties of the spun fibre are those that would be obtained from fibre which has been spun at a lower wind up speed.
  • the properties of the drawn yarn decrease. Accordingly by lowering the effective wind up speed by the addition of an immiscible polymer (while keeping the actual wind up speed the same) it is possible to achieve improved properties such as a higher modulus which is quite surprising in view of the teaching of Japanese Patent No. 56-118912.
  • a particularly useful property of a sewing thread is its modulus, since it has been found that a higher modulus allows faster sewing speeds and gives less puckering of sewn seams.
  • a higher modulus can, of course, be obtained in the normal drawing process by using a higher draw ratio but this is not very desirable since it can lead to a high break level.
  • the present invention achieves this object in a much more convenient and efficient manner.
  • the particle size of the additive, i.e. immiscible, polymer was of the order of 1 micrometer.
  • Polyethylene terephthalate having an intrinsic viscosity (IV) (measured in ortho-chloro-phenol) of 0.73 was dried at 165°C for 4 hours and blended with 3% by weight of Imperial Chemical Industries PLC.
  • the barrel temperature was 290°C and the screw was rotated at 50 rpm.
  • a lace of 2.54 mm (0.1 inch) diameter was extruded into a water bath and then passed to a lace cutter. The average output rate was 100 grams per minute.
  • polyethylene terephthalate alone was extruded in a similar manner.
  • the chips from the lace cutter were then dried at 165°C for 4 hours and made into candles at 240°C for 8 mins.
  • the candles were then spun on a rod spinner.
  • the spinning temperature was 293°C and the throughput per hole was 96 gm/hr/hole into ambient air with no deliberate quenching apparatus, using 35 thou spinneret holes.
  • the filaments so formed were wound up at a wind up speed (WUS) of 200 mpm to 1000 mpm without adjustment of spinning rate so that higher speeds yielded finer filaments.
  • the intrinsic viscosity of the control fibre after spinning was 0.70.
  • the wind up speed suppression produced a potential increase in productivity that can be calculated from the extensibility of the spun filaments as determined on an Instron.
  • the gauge length used was 10 cms and the strain rate was 200% per minute.
  • a spun filament has a percent extension-to-break of E, then the maximum draw ratio to which it can subsequently be subjected is roughly (1+E/100). If a second spun filament has a larger extension-to-break E' then it can be subjected to a larger draw ratio, roughly (1+E'/100). To make drawn filaments of equal decitex d at these maximum draw ratios the spun filaments must therefore have decitexes of d(1+E/100) and d(1+E'/100) respectively. If both filaments are spun at the same speed their production rates are proportional to these decitexes and the percentage increase in productivity of the second filament is
  • Example 2 gives results for other concentrations of nylon and demonstrates that even very small amounts of nylon are very effective in producing orientation suppression.
  • the same blending and spinning conditions were used as in Example 1 except that the spinneret hole used was 15 thou.
  • This example demonstrates that better tensile properties are obtained at the same WUS by the use of a nylon blend.
  • the improvement shown is in the initial modulus after drawing.
  • the polymers were blended and spun as in Example 1 at 96 g/hr/hole and 800 mpm. They were then drawn to a range of final extensions, using a hot pin at 85°C, a hot plate at 170°C and a draw speed of 20 mpm.
  • a special technique was used on the Instron to measure the initial modulus very precisely. The gauge length was 50 cm, the cross head speed was 5 cm per minute and the chart speed was 100 cm per minute. This gave a load-strain curve which was linear up to 2% strain and from which the initial modulus could be very accurately measured. For a given final extension there was a small scatter of a few percent, and all the results obtained are given in Table 3.
  • the modulus of the 1 % and 3% nylon blends is about 20% higher than the control at 10% drawn extension.
  • the draw ratio of the control for 10% extension was 3.9, while that of the 1% blend was 4.9, giving a productivity increase of 26%.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Artificial Filaments (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Claims (4)

1. Procédé de filage à état fondu d'un polymère apte à la formation de fibres, choisi dans le groupe comprenant le téréphtalate de polyéthylène et le Nylon 66, dans lequel, avant filage à l'état fondu, il est ajouté au polymère apte à la formation de fibres 0,1% à 10% en poids d'un autre polymère, mais à l'exclusion d'un polymère à cristallinité liquide, qui est non miscible à une masse fondue du polymère apte à la formation de fibres, cet autre polymère ayant un diamètre moyen des particules inférieur à 3 micromètres dans la masse fondue immédiatement avant filage, ledit polymère non miscible étant choisi dans le groupe comprenant le polyéthylène, le polypropylène, le polyéthylèneglycol et le Nylon 66 lorsque le polymère apte à la formation de fibres est le téréphtalate de polyéthylène, et ledit polymère non miscible étant choisi dans le groupe comprenant le polyéthylène, le polypropylène, le téréphtalate de polyéthylène et le polyéthylèneglycol lorsque le polymère apte à la formation de fibres est le Nylon 66, caractérisé en ce que le téréphtalate de polyéthylène constituant le polymère apte à la formation de fibres possède une viscosité intrinsèque supérieure à 0,70, le Nylon consituant le polymère apte à la formation de fibres possède une viscosité relative supérieure à 55 et la fibre filée est enroulée à une vitesse de bobinage inférieure à 1 kilomètre/minute.
2. Fibres de téréphtalate de polyéthylène filées à l'état fondu, produites suivant la revendication 1.
3. Fibres de téréphtalate de polyéthylène filées à l'état fondu produites suivant la revendication 1, dans lesquelles le polymère non miscible est le Nylon 66, qui est présent dans les fibres filées à l'état fondu sous forme de microfibrilles ayant un rapport d'aspect supérieur à 50 et des diamètres d'environ 0,5 micromètre.
4. Fibres de Nylon 66 filées à l'état fondu, produites suivant la revendication 1.
EP85300928A 1984-03-05 1985-02-12 Filage au fondu d'un mélange d'un polymère fibrogène avec un polymère non-miscible Revoked EP0154425B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB848405694A GB8405694D0 (en) 1984-03-05 1984-03-05 Melt spinning of blend of fibre forming polymer
GB8405694 1984-03-05

Publications (3)

Publication Number Publication Date
EP0154425A2 EP0154425A2 (fr) 1985-09-11
EP0154425A3 EP0154425A3 (en) 1988-07-27
EP0154425B1 true EP0154425B1 (fr) 1990-10-03

Family

ID=10557592

Family Applications (1)

Application Number Title Priority Date Filing Date
EP85300928A Revoked EP0154425B1 (fr) 1984-03-05 1985-02-12 Filage au fondu d'un mélange d'un polymère fibrogène avec un polymère non-miscible

Country Status (5)

Country Link
EP (1) EP0154425B1 (fr)
JP (1) JPS60209015A (fr)
DE (1) DE3579926D1 (fr)
GB (1) GB8405694D0 (fr)
ZA (1) ZA851261B (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6923925B2 (en) 2002-06-27 2005-08-02 E. I. Du Pont De Nemours And Company Process of making poly (trimethylene dicarboxylate) fibers

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2029475T3 (es) * 1986-05-16 1992-08-16 Imperial Chemical Industries Plc Fibras y tubos fibrosos huecos.
JPH02500176A (ja) * 1987-04-20 1990-01-25 アライド・コーポレーション 改良されたファイバーおよびこれらのファイバーを含むフィルター
JPH03163799A (ja) * 1989-11-20 1991-07-15 Nippon Sheet Glass Co Ltd 平板型蛍光灯のインバータの出力制御方法
ITMI20021373A1 (it) 2002-06-21 2003-12-22 Effeci Engineering S A S Di Fo Mescole polimeriche e loro uso
US6921803B2 (en) 2002-07-11 2005-07-26 E.I. Du Pont De Nemours And Company Poly(trimethylene terephthalate) fibers, their manufacture and use
KR101812237B1 (ko) * 2011-09-27 2017-12-27 코오롱인더스트리 주식회사 폴리에틸렌테레프탈레이트 연신사의 제조방법, 폴리에틸렌테레프탈레이트 연신사 및 타이어 코오드
CN102618946B (zh) * 2012-04-24 2015-10-21 可隆（南京）特种纺织品有限公司 聚对苯二甲酸乙二酯拉伸丝的制造方法、聚对苯二甲酸乙二酯拉伸丝及轮胎帘子布

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4913428A (fr) * 1972-06-06 1974-02-05
FR2226438B1 (fr) * 1973-04-20 1977-02-18 Kleber Colombes
JPS5691013A (en) * 1979-12-20 1981-07-23 Teijin Ltd Undrawn polyester yarn and its production
DE3113717A1 (de) * 1980-04-07 1982-02-11 Hoechst Ag, 6000 Frankfurt "borste fuer pinsel und buersten"
EP0080273A3 (fr) * 1981-11-23 1984-03-28 Imperial Chemical Industries Plc Fibres frisées en polyester
DE3271192D1 (en) * 1981-11-23 1986-06-19 Ici Plc Process of melt spinning of a blend of a fibre-forming polymer and an immiscible polymer and melt spun fibres produced by such process

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6923925B2 (en) 2002-06-27 2005-08-02 E. I. Du Pont De Nemours And Company Process of making poly (trimethylene dicarboxylate) fibers

Also Published As

Publication number Publication date
DE3579926D1 (de) 1990-11-08
JPS60209015A (ja) 1985-10-21
EP0154425A3 (en) 1988-07-27
ZA851261B (en) 1985-10-30
EP0154425A2 (fr) 1985-09-11
JPS6360128B2 (fr) 1988-11-22
GB8405694D0 (en) 1984-04-11

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