EP0267984B1 - Verfahren zur Herstellung von Fasern aus aromatischem Polyester - Google Patents

Verfahren zur Herstellung von Fasern aus aromatischem Polyester Download PDF

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Publication number
EP0267984B1
EP0267984B1 EP86116011A EP86116011A EP0267984B1 EP 0267984 B1 EP0267984 B1 EP 0267984B1 EP 86116011 A EP86116011 A EP 86116011A EP 86116011 A EP86116011 A EP 86116011A EP 0267984 B1 EP0267984 B1 EP 0267984B1
Authority
EP
European Patent Office
Prior art keywords
oxygen
fiber
containing atmosphere
aromatic polyester
heat
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.)
Expired
Application number
EP86116011A
Other languages
English (en)
French (fr)
Other versions
EP0267984A1 (de
Inventor
Hiroaki Sugimoto
Kazuo Hayatsu
Toshiyuki Kobashi
Seiji Takao
Jun Takagi
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.)
Japan Exlan Co Ltd
Sumitomo Chemical Co Ltd
Original Assignee
Japan Exlan Co Ltd
Sumitomo Chemical Co 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
Application filed by Japan Exlan Co Ltd, Sumitomo Chemical Co Ltd filed Critical Japan Exlan Co Ltd
Priority to DE8686116011T priority Critical patent/DE3677516D1/de
Publication of EP0267984A1 publication Critical patent/EP0267984A1/de
Application granted granted Critical
Publication of EP0267984B1 publication Critical patent/EP0267984B1/de
Expired legal-status Critical Current

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Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
    • D01D10/02—Heat treatment
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters
    • 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
    • D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
    • D01F6/84—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyesters

Definitions

  • This invention relates to a process for producing an aromatic polyester fiber having high strength and high modulus of elasticity.
  • fibers of high strength and high modulus of elasticity can be produced by melt-spinning an aromatic polyester that exhibits anisotropy in its molten state.
  • This process has various advantages in that no solvent is used and conventional spinning apparatuses can be used in the process.
  • such a polyester forms a highly oriented and highly crystalline structure and exhibits excellent properties merely by melt-spinning, both the strength and the modulus of elasticity of the fiber can be further improved when the fiber is heat-treated in the vicinity of its softening temperature.
  • Japanese Patent Publication No. 20008/80 describes the method of carrying out a similar heat-treatment in an atmosphere of inert gas such as nitrogen.
  • inert gas such as nitrogen.
  • this heat-treatment may consume a long time and the use of such inert gas cannot be economically desirable.
  • the above object of the invention can be achieved by using a dehumidified oxygen-containing atmosphere for the heat-treatment of melt-spun fibers of an aromatic polyester exhibiting anisotropy in the molten state.
  • the polyester which exhibits anisotropy in its molten state referred to in this invention means one which has a property of allowing the transmission of light at a temperature region in which it is flowable when the powder sample of the polyester is placed on a heating sample stage positioned between two polarizing plates crossed at an angle of 90° and the temperature of the sample is increased.
  • Such polyesters are those formed of aromatic dicarboxylic acids, aromatic diols and/or aromatic hydroxycarboxylic acid, and the derivatives thereof, disclosed in Japanese Patent Application Kokoku (Post-Exam. Publn.) Nos. 18016/81 and 20008/80, and optionally include copolymers of these with alicyclic dicarboxylic acids, alicyclic diols, aliphatic diols, and the derivatives thereof.
  • melt-processable aromatic polyesters capable of forming an anisotropic melt phase at elevated temperature which after their processing are subjected to a thermal treatment in an oxygen-containing atmosphere.
  • aromatic dicarboxylic acids examples include terephthalic acid, isophthalic acid, 4, 4 ⁇ -dicarboxydiphenyl, 2, 6-dicarboxynaphthalene, 1, 2-bis(4-carboxyphenoxy)ethane, and the nuclear-substituted products thereof with an alkyl, aryl, alkoxy, or halogen group.
  • aromatic diols examples include hydroquinone, resorcin, 4, 4 ⁇ -dihydroxydiphenyl, 4, 4 ⁇ -dihydroxybenzophenone, 4, 4 ⁇ -dihydroxydiphenylmethane, 4, 4 ⁇ -dihydroxydiphenylethane, 2, 2-bis(4-hydroxyphenyl)-propane, 4, 4 ⁇ -dihydroxydiphenyl ether, 4, 4 ⁇ -dihydroxydiphenyl sulfone, 4, 4 ⁇ -dihydroxydiphenyl sulfide, 2, 6-dihydroxynaphthalene, 1, 5-dihydroxynaphthalene, and the nuclear-substituted products thereof with an alkyl, aryl, alkoxy, and halogen group.
  • aromatic hydroxycarboxylic acids examples include p-hydroxybenzoic acid, m-hydroxybenzoic acid, 2-hydroxynaphthalene-6-carboxylic acid, 1-hydroxynaphthalene-5-carboxylic acid, and the nuclear-substituted products thereof with an alkyl, aryl, alkoxy, and halogen group.
  • alicyclic dicarboxylic acids include trans-1, 4-dicarboxycyclohexane, cis-1, 4-dicarboxycyclohexane and the substituted products thereof with an alkyl, aryl, and halogen group.
  • Examples of the alicyclic and aliphatic diols include trans-1, 4-dihydroxycyclohexane, cis-1, 4-dihydroxycyclohexane, ethylene glycol, 1, 4-butanediol, and xylylene diol.
  • polyesters to be used in this invention are subjected to polycondensation as they are or after being esterified by an aliphatic or aromatic monocarboxylic acid or the derivative thereof, or an aliphatic alcohol, a phenol, or the derivative thereof.
  • the polycondensation can be carried out by using a known method including mass polymerization, solution polymerization and suspension polymerization. It may be conducted at a temperature of 150 to 360°C under normal pressure or a reduced pressure of 1330 to 13,3 Pa (10 to 0.1 Torr)optionally in the presence of polymerization catalyst such as a Sb, Ti and Ge compound, a stabilizer such as a phosphorus compound, and fillers such as TiO2, CaCO3, and talc, added thereto.
  • polymerization catalyst such as a Sb, Ti and Ge compound, a stabilizer such as a phosphorus compound, and fillers such as TiO2, CaCO3, and talc, added thereto.
  • the polymer thus obtained is heat-treated, as it is or in a pulverized form, in an inert gas or under reduced pressure to give a sample material for spinning. It is also be used after once granulated through an extruder.
  • the melt spinning apparatus to be used for the aromatic polyester according to this invention may be of any desired type so long as it is provided with a melting section comprising a screw or a plunger equipped with a heat control device, a metering section such as a gear pump, and a spinning head including a spinneret.
  • Suitable temperature for spinning in this invention is 280 to 420°C, more preferably 300 to 400°C. Temperatures lower than the above-mentioned temperature region will result in too large load on the apparatus or insufficiency of uniform melting of the sample, whereas temperatures higher than the region will cause fiber breakage due to decomposition and foaming.
  • preferable spinneret include those having a hole diameter (d) of 0.3 mm or less and the ratio (l/d) of the hole length (l) to the hole diameter of 0.8 or more. Further, the breakage of single filaments and spiral extrusion can be prevented and effects of promoting orientation and suppressing foam generation in fibers can be exhibited by controlling the spinning pressure at the spinneret section at 294,312 PG (3 kg/cm2G) or more.
  • the fibers obtained by melt spinning as mentioned above are then taken up or drawn down as they are or after adhering a textile oil thereto.
  • the velocity of taking up or drawing down is 10 to 10,000 m/minute, 100 to 2,000 m/minute being preferable from the viewpoint of productivity and stable spinning.
  • the diameter and the cross sectional shape of the fiber to be obtained can be selected as desired according to intended uses. A diameter of 0,055 to 1,11 tex (0.5 to 10 deniers) is preferable from the viewpoint of physical properties.
  • the thus obtained fiber is heat-treated in an atmosphere.
  • This atmosphere contains oxygen and has been dehumidified.
  • the oxygen-containing atmosphere has an oxidizing action or the like, which will result in slight crosslinkage between main chains of the polymer to increase its molecular weight and will decompose and remove the remaining monomer and oligomer which hinder the heat-treated fiber from exhibiting improved properties. If the atmosphere contains much water vapor, no suf­ficient improvement of the fiber in strength and in elastic modulus will be achieved conceivably because of the main-chain scission resulting from hydrolysis.
  • the content of water vapor in the dehumidified oxygen-containing atmosphere is generally up to 0.3%, preferably up to 0.1%, particularly preferably up to 0.05%, by volume.
  • Higher brightness and lower satu­rations intensities of color, in addition to the improved strength and elastic modulus, are given to the fiber when the atmosphere is dehumidified than when it is not dehumidified as in the prior art heat-treatment.
  • the dehumidification of oxygen-containing atmospheric gas can be accomplished by; the contact thereof with a moisture absorbent or drying agent such as a molecular sieve, calcium chloride, silica gel, phosphorus pentoxide, or sulfuric acid; cooling the gas with a refrigerant such as liquid nitrogen, liquid ammonia, or LPG; adiabatic compression of the gas; or combination of these means.
  • a moisture absorbent or drying agent such as a molecular sieve, calcium chloride, silica gel, phosphorus pentoxide, or sulfuric acid
  • a refrigerant such as liquid nitrogen, liquid ammonia, or LPG
  • adiabatic compression of the gas or combination of these means.
  • the fiber is heat-treated at a temperature of 220 to 440°C, preferably 280 to 360°C, for a period of several minutes to scores of hours.
  • the oxygen-containing atmosphere may comprise any of nitrogen, argon, helium, and the like, besides oxygen. Suitable oxygen concentrations in the atmosphere are from 1 to 100% by volume.
  • the fiber obtained by melt-spinning of an aromatic polyester exhibiting anisotropy in the molten state can be brought into contact with the oxygen-containing atmosphere, for example, in the following way:
  • the fiber wound up around a bobbin is brought as such into contact with the atmosphere or the fiber is continuously moved in a stream of the atmospheric gas.
  • tension may be applied to the fiber so far as it does not break the fiber; however, it is unnecessary to apply such high tension as to stretch the fiber.
  • the fiber thus obtained shows no phenomenon of fusion and can be used in a wide field of applications including tire cords, ropes, cables, the tension member of FRP (fiber reinforced plastic), FRTP (fiber reinforced thermoplastic), FRC (fiber reinforced concrete) and FRM (fiber reinforced metal), speaker cones, ballistic applications, space suits, and submarine working clothes.
  • FRP fiber reinforced plastic
  • FRTP fiber reinforced thermoplastic
  • FRC fiber reinforced concrete
  • FRM fiber reinforced metal
  • the yield of polymer was 10.88 kg, 97.8% of theoretical yield.
  • the polymer was pulverized in a hammer mill to give particles of 2.5 mm or less.
  • the polymer powder was then treated in a rotary kiln in nitrogen atmosphere at 280°C for 5 hours.
  • the resulting product gave a "flowing temperature" of 326°C and showed optical anisotropy at a temperature of 350°C or higher.
  • the polymer obtained above was melt-spun by using a 30 mm extruder.
  • the spinneret used had a hole diameter of 0.07 mm, a hole length of 0.14 mm and a number of holes of 300.
  • the spinning temperature at the spinneret was 355°C.
  • a 200 g portion of the multifilaments prepared in Referential Example was rewound around a hollow cylindrical aluminum bobbin of 15 mm outer diameter having a large number of 5-mm diametric perforations. These rewound multifilaments were placed each in a 280°C oven, then its temperature was raised over 4 hours upto 320°C, and after 3-hour heating at this temperature, the multifilaments were taken out.
  • the atmospheric gas used for this heat-treatment was prepared by mixing air with nitrogen gas and passing the mixture through a metal pipe of 2 m length and 3 cm inner diameter packed with a molecular sieve 4A.
  • the content of water vapor in this gas mixture was 450 ppm, as measured at 27°C with a dew-point hygrometer (water content analyzer).
  • Table 1 shows tensile strengths, elastic moduli, and color properties of heat-treated fiber as stated above, where the oxygen concentration in the atmospheric gas mixture was varied.
  • Example 1 The procedure of Example 1 was followed but using a nitrogen gas of 99.9 vol% purity in which the water vapor content was 6 ppm at 27°C, in place of the gas mixture. Results are shown in Table 1. This heat-treated fiber, as compared with those of Example 1, exhibits low elastic modulus and low brightness.
  • Example 1 The procedure of Example 1 was followed except that the gas mixture of Example 1 was replaced with air (oxygen concentration 21.1 vol%, water vapor content 2.3 vol% at 27°C) and with dehumidified air (water vapor content 0.88 vol% at 27°C) prepared by passing the above air through a pipe of 25 cm length and 3 cm inner diameter packed with silica gel. As shown in Table 1, these heat-treated multifilaments are inferior to those of Example 1 in tensile strength as well as in colorlessness.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Artificial Filaments (AREA)
  • Treatment Of Fiber Materials (AREA)
  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)

Claims (5)

1. Verfahren zur Herstellung von Fasern eines aromatischen Polyesters mit Anisotropie im Schmelzezustand durch Wärmebehandeln der durch Schmelzspinnen erhaltenen Fasern des aromatischen Polyesters in einer sauerstoff­haltigen Atmosphäre, dadurch gekennzeichnet, daß die sauerstoffhaltige Atmosphäre entfeuchtet ist.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß als sauerstoffhaltige Atmosphäre Luft benutzt wird.
3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß der Gehalt an Wasserdampf in der entfeuchteten sauer­stoffhaltigen Atmosphäre bis zu 0,3 Vol.-% beträgt.
4. Verfahren nach Anspruch 3, dadurch gekennzeichnet, daß der Gehalt an Wasserdampf in der entfeuchteten sauer­stoffhaltigen Atmosphäre bis zu 0,1 Vol.-% beträgt und daß die Faser bei einer Temperatur von 220 - 440°C wärmebehandelt wird.
5. Verfahren nach Anspruch 4, dadurch gekennzeichnet, daß als sauerstoffhaltige Atmosphäre Luft benutzt wird und daß es sich bei dem aromatischen Polyester um einen Mischpolyester aus 40-70 Mol-% p-Hydroxybenzoesäure­resten, 15-30 Mol-% an aromatischen Dicarbonsäureresten und 15 - 30 Mol-% an aromatischen Diolresten handelt.
EP86116011A 1985-09-21 1986-11-18 Verfahren zur Herstellung von Fasern aus aromatischem Polyester Expired EP0267984B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DE8686116011T DE3677516D1 (de) 1986-11-18 1986-11-18 Verfahren zur herstellung von fasern aus aromatischem polyester.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP60209314A JPH06104930B2 (ja) 1985-09-21 1985-09-21 芳香族ポリエステル繊維の製造法
JP60294927A JPS62156313A (ja) 1985-09-21 1985-12-25 芳香族ポリエステル繊維の製造法

Publications (2)

Publication Number Publication Date
EP0267984A1 EP0267984A1 (de) 1988-05-25
EP0267984B1 true EP0267984B1 (de) 1991-02-06

Family

ID=39642887

Family Applications (1)

Application Number Title Priority Date Filing Date
EP86116011A Expired EP0267984B1 (de) 1985-09-21 1986-11-18 Verfahren zur Herstellung von Fasern aus aromatischem Polyester

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EP (1) EP0267984B1 (de)
JP (2) JPH06104930B2 (de)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2503023B2 (ja) * 1987-08-12 1996-06-05 株式会社クラレ 全芳香族ポリエステル紡績糸の製造方法
US5025082A (en) * 1988-08-24 1991-06-18 Mitsubishi Kasei Corporation Aromatic polyester, aromatic polyester-amide and processes for producing the same
US5397527A (en) * 1991-12-30 1995-03-14 Alliedsignal Inc. High modulus polyester yarn for tire cords and composites
JP6741654B2 (ja) * 2015-07-31 2020-08-19 Ｋｂセーレン株式会社 タイヤ用ビード繊維

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3975487A (en) * 1973-08-20 1976-08-17 The Carborundum Company Process for spinning high modulus oxybenzoyl copolyester fibers
SE416814B (sv) * 1974-05-10 1981-02-09 Du Pont Nya syntetiska polyestrar och sett for deras framstellning
GB1499513A (en) * 1975-01-25 1978-02-01 Carborundum Co High modulus oxybenzoyl copolyester fibres
US4183895A (en) * 1975-04-29 1980-01-15 E. I. Du Pont De Nemours And Company Process for treating anisotropic melt-forming polymeric products
JPS5741937A (en) * 1980-08-26 1982-03-09 Yokohama Rubber Co Ltd:The Molding method of reinforced tube for tire type fender
JPS57199815A (en) * 1981-05-28 1982-12-07 Asahi Chem Ind Co Ltd Fiber consisting of liquid crystal polyester
US4374228A (en) * 1981-08-03 1983-02-15 Fiber Industries, Inc. Wholly aromatic polyester capable of forming an anisotropic melt phase consisting essentially of para-oxybenzoyl moiety, bromo-substituted-para-oxybenzoyl moiety, and meta-oxybenzoyl moiety
JPS5884821A (ja) * 1981-11-16 1983-05-21 Asahi Chem Ind Co Ltd コポリエステル繊維またはフイルムおよびそれらの製法
JPS58191219A (ja) * 1982-04-28 1983-11-08 Sumitomo Chem Co Ltd 芳香族ポリエステル繊維の製造方法
CA1228957A (en) * 1982-06-21 1987-11-10 Norman S. Anderson Yarn which exhibits high tenacity comprised of thermotropic liquid crystalline polymer fibers, a reinforcing cord comprised thereof and a process of production thereof

Also Published As

Publication number Publication date
EP0267984A1 (de) 1988-05-25
JPS6269821A (ja) 1987-03-31
JPH06104930B2 (ja) 1994-12-21
JPS62156313A (ja) 1987-07-11

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