EP1838907B1 - Procede de realisation de fibres de polyoxymethylene et utilisation de ces fibres - Google Patents

Procede de realisation de fibres de polyoxymethylene et utilisation de ces fibres Download PDF

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Publication number
EP1838907B1
EP1838907B1 EP06700914.2A EP06700914A EP1838907B1 EP 1838907 B1 EP1838907 B1 EP 1838907B1 EP 06700914 A EP06700914 A EP 06700914A EP 1838907 B1 EP1838907 B1 EP 1838907B1
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EP
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Prior art keywords
fibres
brushes
temperature
copolymers
pom
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Not-in-force
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EP06700914.2A
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German (de)
English (en)
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EP1838907A1 (fr
Inventor
Dirk Zierer
Rainer Bernstein
Jörg Schweitzer
Klaus Kurz
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Ticona GmbH
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Ticona GmbH
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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
    • D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products

Definitions

  • the present invention relates to a process for the production of polyoxymethylene fibers with high Wiederaufraumsw, in particular monofilaments, which can be used in particular as bristles in brushes, brooms and brushes of all kinds.
  • Polyoxymethylene (hereinafter also referred to as "POM") is a high performance polymer with good mechanical properties and excellent chemical resistance. Moldings made of POM are characterized by high crystallinity and high moduli of elasticity.
  • a method of making high molecular weight linear POM filaments is known. This involves preparing a spinning solution of a certain viscosity and spinning this solution by the dry or wet spinning process into POM filaments, which are then subjected to drawing on a heating stirrup. Typical draw ratios are around 1:10.
  • the JP-A-01 / 172.821 describes the production of POM fibers by melt spinning.
  • the process comprises melting the raw material and spinning under defined conditions and carrying out at least a 1: 4 draw at defined input and output speeds.
  • the process is characterized by high productivity and high-strength POM filaments are produced.
  • EP-A-1,321,546 describes the production of high-strength and high-modulus POM split fibers.
  • a film is produced using selected POM copolymers with defined viscosities. By selecting the raw material, the crystallization rate can be controlled and stable film formation and controlled stretching of the film is possible.
  • EP-A-1,431,428 describes high-strength and high-modulus POM fibers. These are obtained by melt spinning using POM copolymers of selected crystallization rate. Again, by the selection of the raw material controlled stretching is possible, so that fibers are produced with very high tensile strengths.
  • Another object of the present invention is to provide bristles which are excellent for use in paintbrushes, brooms or brushes of all kinds and whose abrasion resistance is excellent in comparison with bristles of other materials.
  • Another object of the present invention is to provide a process for producing these POM fibers which is characterized by high productivity.
  • All polyoxymethylene copolymers are suitable for the production of the fibers according to the invention, provided that they have the mentioned melt indices.
  • polyoxymethylenes as used for example in the DE-A-29 47 490
  • POM polyoxymethylenes
  • they are straight-chain linear polymers which generally contain at least 80%, preferably at least 90%, oxymethylene units (-CH 2 -O-).
  • polyoxymethylene in this case comprises copolymers of formaldehyde or its cyclic oligomers, such as trioxane or tetroxane, with monomers copolymerizable therewith.
  • Copolymers are thus polymers derived from formaldehyde and / or its cyclic oligomers, in particular trioxane, and cyclic ethers, cyclic acetals and / or linear polyacetals.
  • the hydroxyl end groups of these copolymers are chemically stabilized against degradation in a conventional manner, for. B. by esterification or by etherification.
  • these polymers have at least 50 mole percent of recurring units -CH 2 -O- in the polymer backbone.
  • the POM copolymers are generally prepared by copolymerization of formaldehyde or trioxane with suitable comonomers, preferably in the presence of suitable catalysts.
  • POM copolymers which, in addition to the repeating units -CH 2 -O-, also contain up to 50, preferably from 0.1 to 20 and in particular 0.5 to 10 mol% of recurring units wherein R 1 to R 4 are independently a hydrogen atom, a C 1 to C 4 alkyl group or a halogen-substituted alkyl group having 1 to 4 carbon atoms and R 5 is a -CH 2 -, -O-CH 2 -, a C 1 to C 4 alkyl or C 1 to C 4 haloalkyl substituted methylene group or a corresponding oxymethylene group and n has a value in the range of 0 to 3.
  • these groups can be introduced into the copolymers by ring opening of cyclic ethers.
  • Preferred cyclic ethers are those of the formula wherein R 1 to R 5 and n have the abovementioned meaning.
  • ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 1,3-butylene oxide, 1,3-dioxane, 1,3-dioxolane, 1,3-dioxepane and 1,3,6-trioxacyclo-octane as cyclic ethers and linear oligo- or polyformals, such as polydioxolane or polydioxepane, called comonomers.
  • Copolymers of 99.5-95 mol% of trioxane and 0.5 to 5 mol% of one of the abovementioned comonomers are particularly advantageously used.
  • the POM copolymers preferably used have melting points of at least 140 ° C and molecular weights (weight average) M w in the range of 5,000 to 200,000, preferably from 7,000 to 150,000.
  • End-group-stabilized POM copolymers which have C-C bonds or the methoxy end groups at the chain ends are particularly preferably used to prepare the fibers according to the invention.
  • the POM copolymers used to prepare the fibers according to the invention have a melt index (MVR value 190 / 2.16) of 0.3 to 30 ml / 10 min (ISO 1133), preferably an MVR value of 1 to 10 ml / 10 min and most preferably an MVR value of 1 to 3 ml / 10 min.
  • Preferred POM copolymers have in addition to recurring oxymethylene groups 0.5 to 10 mol%, preferably 1 to 5 mol% and in particular 1.5 to 4 mol%, of structural units derived from comonomers.
  • the latter are usually comonomers which are only bifunctional, that is, which can not form branches or crosslinks.
  • the POM copolymers used according to the invention are therefore in the essentially linear and are characterized by a high crystallization half-life.
  • Typical crystallization half-lives of the POM copolymers used according to the invention are at least 30 seconds, determined by cooling from 200 ° C to a temperature which is usually 10 ° C below the melting temperature of the respective POM copolymer, at a cooling rate of 80 ° C / minute and maintaining that temperature at that observation temperature. The determination of the time takes place from reaching the observation temperature.
  • Preferred POM copolymers have no or as few constituents as possible, which can accelerate the crystallization behavior. These include inorganic or organic nucleating agents, nucleating POM terpolymers or impurities resulting from the preparation of the POM copolymer. The latter can preferably be removed by reprecipitation, wherein the POM copolymer preferably in a water methanol mixture, which may contain other components such as trioxane, formaldehyde, amines, etc., under pressure, preferably between 1 bar and 50 bar, at temperatures of 100 ° C. to 250 ° C, preferably from 140 ° C, more preferably from 150 ° C to 200 ° C is dissolved. This process is also referred to as solution hydrolysis.
  • Particularly preferably used POM copolymers have, in addition to recurring oxymethylene groups of the formula I, 0.5 to 10 mol%, preferably 1 to 5 mol% and in particular 1.5 to 3 mol%, of oxyalkylene groups of the forms II, - [CH 2 -O] - (I), - [(CH 2 ) m -O] y - (II), wherein m is an integer from 2 to 4, preferably 2, and y is 1 or 2.
  • the determination of the MVR value of the polyoxymethylene copolymers used according to the invention is carried out according to ISO 1133: 190 ° C / 2.16 kg
  • Preferred polyoxymethylene copolymer fibers are derived from polyoxymethylene copolymers whose crystallization half-life is at least 100 seconds, most preferably at least 150 seconds.
  • Preferred polyoxymethylene copolymer fibers have a recovery capacity, measured by the double loop method in air and / or water, of at least 130 °.
  • the polyoxymethylene copolymer fibers typically have a tensile strength, determined according to DIN 53834-1 (tensile test on monofilaments), of up to 45 cN / tex, more preferably up to 40 cN / tex.
  • the polyoxymethylene copolymer fibers typically have an elongation at break, determined according to DIN 53834-1 (tensile test on monofilaments), of up to 100%, particularly preferably 25 to 100% and very particularly preferably from 30 to 100%.
  • POM copolymer fibers are to be understood as meaning any POM copolymer-containing fibers.
  • filaments or staple fibers which consist of several individual fibers, but in particular monofilaments.
  • Important for achieving the property profile is the use of a certain POM raw material and a not too high draw ratio.
  • the filament formed is drawn several times.
  • the fibers can be present in any desired form, for example as multifilaments, as staple fibers or in particular as monofilaments.
  • the titer of the fibers can vary widely. Examples are 100 to 45,000 dtex, in particular 400 to 7,000 dtex.
  • a polyoxymethylene raw material stabilized against thermal degradation is used, which may optionally contain further additives customary for POM molding compounds.
  • stabilizers are antioxidants, acid scavengers, formaldehyde scavengers, and / or UV stabilizers.
  • adhesion promoters such as glass beads, calcium carbonate, talc, wollastonite or silica
  • Fillers such as glass beads, calcium carbonate, talc, wollastonite or silica
  • Reinforcing materials such as carbon fibers, aramid fibers or glass fibers, antistatic agents or additives, which give the molding composition a desired property, such as dyes and / or pigments and / or impact modifiers and / or electrical conductivity-imparting additives, e.g. Carbon black or metal particles, as well as mixtures of these additives, but without limiting the scope of the examples mentioned.
  • the proportion of these stabilizers and additives in the fibers according to the invention is usually 0.2 to 30 wt.%, Preferably 0.5 to 25 wt.%, Based on the mass of the fibers.
  • the hot polymer filament is cooled by introduction into a liquid bath.
  • the liquid bath has a temperature of less than 150 ° C; the temperature of the liquid bath can vary within wide ranges, for example from -80 ° C to 150 ° C, preferably 20 ° C to 90 ° C. It can be used different cooling liquids, preferably water or a mixture of water and alcohol. Instead of a cooling bath, the filament can also be passed through different cooling baths. The cooled filament is withdrawn from the cooling bath and optionally subsequently wound up. The removal speed is greater than the injection rate of the polymer melt.
  • the fiber thus produced is subsequently subjected to post-drawing, particularly preferably in several stages, in particular a two- or three-stage post-drawing, with a total draw ratio of up to 1: 6, in particular from 1: 2 to 1: 6, preferably from 1: 4 to 1 : 6, subjected.
  • Stretching can be done on heated godets, by passing over a heated iron and / or by passing the filament through an infrared tunnel or a heating bath.
  • the temperature during stretching is preferably 150 to 190 ° C, particularly preferably 170 to 180 ° C.
  • the polyoxymethylene fibers are used in particular in the form of monofilaments or bristles in a wide variety of applications.
  • Preferred applications include toothbrushes, hair brushes, artist and writing brushes, technical brushes, paintbrushes and painters brushes, paint rollers and ink pads, cosmetic brushes, cleaning brushes and brooms for street and household and brushes and brushes for body care.
  • Plastic granules (1) are melted in an extruder (2) and pressed through a melt pump (4) through the fine opening of a nozzle plate (5).
  • the extruded filament (8) is passed through a tempered water bath (7) and, before being wound between stretching units (10, 13, 16), drawn in heating furnaces (11, 14) in order to achieve the necessary parallel alignment of the molecules.
  • the furnace temperatures and the stretching ratios between the individual stretching units are of crucial importance for the property profile of the monofilament produced.
  • Crystallization half-life The crystallization of thin, melted at 200 ° C POM films (layer thickness 10-100 microns) was followed after rapid cooling to the respective observation temperature under the polarizing microscope with a photocell. The crystallization half-life resulted from the time between the optically detectable onset of crystallization and the achievement of half the maximum light intensity.
  • MVR value determined in accordance with ISO 1133 (MVR 190 ° C / 2.16 kg)

Claims (16)

  1. Procédé de réalisation de fibres contenant des copolymères de polyoxyméthylène avec un indice de fusion MVR, déterminé selon ISO 1133 à 190°C et sous une contrainte de 2,16 kg, de 0,3 à 30 ml/10 mn, qui présentent une aptitude de redressement, mesurée selon la méthode à double boucle dans l'air et/ou dans l'eau, d'au moins 125°, comprenant les mesures :
    i) extrusion d'une masse en fusion contenant des copolymères de polyoxyméthylène avec un indice de fusion MVR, déterminé selon ISO 1133 à 190°C et sous une contrainte de 2,16 kg, de 0,3 à 30 ml/10 m, par une buse de filage,
    ii) introduction du filament formé dans un bain de liquide qui présente une température de moins de 150°C,
    iii) retrait du filament formé,
    iv) étirement simple ou multiple avec un rapport d'étirement total de pas plus de 1:6, et
    v) éventuellement, chauffage du filament étiré en autorisant un rétrécissement.
  2. Procédé de fabrication de fibres selon la revendication 1, comprenant la précipitation du copolymère de polyoxyméthylène sous pression à une température de 150°C à 200°C.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce que les fibres contiennent des copolymères de polyoxyméthylène qui présentent des points de fusion d'au moins 140°C et des poids moléculaires (valeur moyenne de poids) Mw de l'ordre de 5 000 à 200 000.
  4. Procédé selon au moins l'une des revendications 1 à 3, caractérisé en ce que les fibres contiennent des copolymères de polyoxyméthylène qui présentent un indice de fusion (valeur MVR 190/2,16) de 1 à 10 ml/mn.
  5. Procédé selon au moins l'une des revendications 1 à 4, caractérisé en ce que les fibres contiennent des copolymères de polyoxyméthylène qui, en plus de groupes d'oxyméthyle récurrents, contiennent 0,5 à 10 % mol. d'unités de structure qui sont dérivées de comonomères.
  6. Procédé selon au moins l'une des revendications 1 à 5, caractérisé en ce que les fibres contiennent des copolymères de polyoxyméthylène qui présentent des demi-vies de cristallisation d'au moins 30 secondes, déterminées par refroidissement de 200°C à une température qui se situe 10°C sous la température de fusion du copolymère POM respectif, compte tenu d'une vitesse de refroidissement de 80°C/minute et du maintien de cette température à cette température d'observation.
  7. Procédé selon au moins l'une des revendications 1 à 6, caractérisé en ce que les fibres ne contiennent pas de moyens de nucléisation.
  8. Procédé selon au moins l'une des revendications 1 à 7, caractérisé en ce que les fibres contiennent des copolymères de polyoxyméthylène hydrolisés en solution.
  9. Procédé selon au moins l'une des revendications 1 à 8, caractérisé en ce que les fibres contiennent des copolymères de polyoxyméthylène qui, en plus de groupes d'oxyméthylène récurrents de formule I, présentent 0,5 à 10 % mol. de groupes d'oxyalkyle de formule II

            -[CH2-O]-     (I),

            -1(CH2)m-O]y-     (II),

    où m est un nombre entier de 2 à 4, de préférence 2, et y représente 1 ou 2.
  10. Procédé selon au moins l'une des revendications 1 à 9, caractérisé en ce que les fibres présentent une aptitude de redressement, mesurée selon la méthode à double boucle dans l'air et/ou dans l'eau, d'au moins 130°.
  11. Procédé selon au moins l'une des revendications 1 à 10, caractérisé en ce que les fibres présentent une résistance à la traction, déterminée selon DIN 53834-1, de jusqu'à 45 cN/tex.
  12. Procédé selon au moins l'une des revendications 1 à 11, caractérisé en ce que les fibres présentent un allongement à la rupture, déterminé selon DIN 53834-1, de jusqu'à 100 %.
  13. Procédé selon au moins l'une des revendications 1 à 12, caractérisé en ce que les fibres sont des monofilaments.
  14. Procédé selon au moins l'une des revendications 1 à 13, caractérisé en ce que les fibres présentent un titre de 100 à 45 000 dtex.
  15. Utilisation de fibres contenant des copolymères de polyoxyméthylène avec un indice de fusion MVR (déterminé selon ISO 1133 à 190°C et sous une contrainte de 2,16 kg) de 0,3 à 30 ml/10 mn, qui présentent une aptitude de redressement, mesurée selon la méthode à double boucle dans l'air et/ou dans l'eau, d'au moins 125°, dans des pinceaux et des brosses.
  16. Utilisation selon la revendication 15, caractérisée en ce que les fibres sont utilisées sous la forme de monofilaments dans des brosses à dents, brosses à cheveux, pinceaux d'artiste et d'écriture, brosses techniques, pinceaux de peintre et brosses de peintre, rouleaux à peinture et tampons à peinture, pinceaux cosmétiques, brosses de nettoyage pour la rue et le ménage ainsi que dans des brosses et pinceaux pour soins corporels.
EP06700914.2A 2005-01-12 2006-01-10 Procede de realisation de fibres de polyoxymethylene et utilisation de ces fibres Not-in-force EP1838907B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE200510001373 DE102005001373A1 (de) 2005-01-12 2005-01-12 Polyoxymethylenfasern, Verfahren zu deren Herstellung und deren Verwendung
PCT/EP2006/000118 WO2006074889A1 (fr) 2005-01-12 2006-01-10 Fibres de polyoxymethylene, procede de realisation et leur utilisation

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EP1838907A1 EP1838907A1 (fr) 2007-10-03
EP1838907B1 true EP1838907B1 (fr) 2013-07-31

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EP (1) EP1838907B1 (fr)
JP (1) JP2008527192A (fr)
CN (1) CN101103148B (fr)
DE (1) DE102005001373A1 (fr)
WO (1) WO2006074889A1 (fr)

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JPWO2009123064A1 (ja) 2008-03-31 2011-07-28 三菱瓦斯化学株式会社 ポリアセタール含有ブラシ
JP5648477B2 (ja) * 2008-07-02 2015-01-07 三菱瓦斯化学株式会社 低フィッシュアイ・ポリアセタール樹脂
CN102011201B (zh) * 2010-12-15 2012-10-10 四川省纺织科学研究院 一种聚甲醛纤维的熔融纺丝方法
CN102677217B (zh) * 2012-05-18 2014-06-18 东华大学 一种改性pom纤维及其制备方法
JP2014201838A (ja) * 2013-04-01 2014-10-27 三菱瓦斯化学株式会社 先端テーパー状を有するポリアセタール樹脂モノフィラメント及びブラシ用ブリッスル
CN104499087B (zh) * 2014-12-23 2016-06-01 江苏苏博特新材料股份有限公司 一种聚氧亚甲基纤维的制备方法
CN109837627B (zh) * 2019-02-15 2021-11-12 南通纺织丝绸产业技术研究院 一步法纳米纤维纱增强方法及一种亲水化纤织物
CN110129921B (zh) * 2019-03-27 2022-02-08 中国水产科学研究院东海水产研究所 一种渔用聚甲醛单丝及其制备方法与应用

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GB1095750A (en) * 1965-12-06 1967-12-20 Montedison Spa Process for the spinning of crystalline polyoxymethylene polymers
DE2947490A1 (de) 1979-11-24 1981-06-04 Hoechst Ag, 6000 Frankfurt Polyoxymethylenfibride und verfahren zu ihrer herstellung
JP4907023B2 (ja) * 2001-09-18 2012-03-28 ポリプラスチックス株式会社 ポリオキシメチレン繊維の製造方法
JP4260392B2 (ja) 2001-12-14 2009-04-30 ポリプラスチックス株式会社 ポリオキシメチレン樹脂製フラットヤーン、その製造方法及び用途
JP2004360146A (ja) * 2003-06-09 2004-12-24 Polyplastics Co ポリオキシメチレン樹脂製不織布及びその製造方法

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CN101103148A (zh) 2008-01-09
CN101103148B (zh) 2013-01-02
DE102005001373A1 (de) 2006-07-27
JP2008527192A (ja) 2008-07-24
EP1838907A1 (fr) 2007-10-03
WO2006074889A1 (fr) 2006-07-20

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