EP2660372A1 - Fibres thermoplastiques avec une tension de surface réduite - Google Patents

Fibres thermoplastiques avec une tension de surface réduite Download PDF

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Publication number
EP2660372A1
EP2660372A1 EP12166834.7A EP12166834A EP2660372A1 EP 2660372 A1 EP2660372 A1 EP 2660372A1 EP 12166834 A EP12166834 A EP 12166834A EP 2660372 A1 EP2660372 A1 EP 2660372A1
Authority
EP
European Patent Office
Prior art keywords
surface tension
thermoplastic
copolymer
fibers
filaments
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.)
Withdrawn
Application number
EP12166834.7A
Other languages
German (de)
English (en)
Inventor
Jochen Endtner
Wolfram Littek
Matthias Bienmüller
Wolfgang Wambach
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.)
Lanxess Deutschland GmbH
Original Assignee
Lanxess Deutschland GmbH
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 Lanxess Deutschland GmbH filed Critical Lanxess Deutschland GmbH
Priority to EP12166834.7A priority Critical patent/EP2660372A1/fr
Priority to PCT/EP2013/059259 priority patent/WO2013164452A1/fr
Priority to US14/398,319 priority patent/US20150084231A1/en
Priority to KR1020147033720A priority patent/KR101965471B1/ko
Priority to JP2015509449A priority patent/JP6290183B2/ja
Priority to EP13721664.4A priority patent/EP2844788B1/fr
Priority to HUE13721664A priority patent/HUE057122T2/hu
Priority to CN201380029189.0A priority patent/CN104350188A/zh
Publication of EP2660372A1 publication Critical patent/EP2660372A1/fr
Withdrawn legal-status Critical Current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
    • D01F6/78—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
    • 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
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/08—Melt spinning methods
    • 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
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/08—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of halogenated hydrocarbons
    • D01F6/10—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of halogenated hydrocarbons from polyvinyl chloride or polyvinylidene chloride
    • 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
    • D01F6/60—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from 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
    • 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
    • D01F6/88—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
    • 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
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
    • D10B2331/02—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyamides
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
    • D10B2331/04—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyesters, e.g. polyethylene terephthalate [PET]
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00—Physical properties
    • D10B2401/02—Moisture-responsive characteristics
    • D10B2401/021—Moisture-responsive characteristics hydrophobic

Definitions

  • the present invention relates to a process for the production of thermoplastic fibers with reduced surface tension and from these thermoplastic fibers with reduced surface tension produced by the melt spinning process products, wherein the thermoplastic to be used with a copolymer of at least one ⁇ -olefin and at least one acrylic acid ester or methacrylic acid ester of an aliphatic alcohol becomes.
  • thermoplastic fibers from the group of polyamides or polyesters in the context of the present invention are nonwovens, nonwovens, fabrics, threads, yarns, ropes, felts, knits, scrims or knitted fabrics.
  • Preferred products for the purposes of the present invention are nonwovens or nonwovens.
  • a fleece consists of loosely connected fibers, which are not yet connected to each other. The strength of a fleece is based only on the fiber's own liability. However, this can be influenced by workup. To be able to process and use the fleece, it must be solidified, for which various methods can be used. Only a solidified nonwoven is to be called a nonwoven fabric. In colloquial language, this difference is not made.
  • Nonwovens are substantially different from woven, knitted, laid and knitted fabrics, which are characterized by the production of certain laying of individual fibers or threads.
  • Nonwovens consist of fibers whose position can only be described by statistical methods.
  • Nonwovens are distinguished, inter alia, according to the fiber material (eg the polymer in man-made fibers), the bonding process, the type of fiber (staple or continuous fibers), the fiber fineness and the fiber orientation.
  • the fibers can be deposited defined in a preferred direction or be completely stochastically oriented as the random nonwoven fabric.
  • the fibers do not have a preferred direction of orientation, it is called an isotropic nonwoven fabric. If the fibers are arranged more frequently in one direction than in other directions, then this is called anisotropy.
  • Nonwovens are thus textile fabrics in which the surface formation does not take place by weaving, knitting, knitting or defined laying, but by depositing the fibers with subsequent fixation. Nonwovens still have high annual growth rates due to their versatility and comparatively low production costs compared to knitted and woven fabrics.
  • non-woven materials lie in a high specific surface, the production methods allow a high variability in density, fiber strength, pore size or thickness and lead to a broad surface isotropy. From these advantageous properties, numerous uses in medicine for hygiene products, especially surgical drapes, sheets, wound dressings, gauze, etc., arise in the household as wipes of all kinds and as decorative nonwovens, especially tablecloths, napkins, in the clothing industry as a deposit nonwovens, for technical Applications, in particular insulating mats, covering mats or as filter fleeces in the engine / motor vehicle sector (eg oil filters) or as separators / separating fleeces in batteries ( WO 2009/103537 A1 ).
  • insulating mats covering mats or as filter fleeces in the engine / motor vehicle sector (eg oil filters) or as separators / separating fleeces in batteries ( WO 2009/103537 A1 ).
  • melt and dry spinning processes and wet spinning processes are suitable for nonwoven on the basis of continuous fibers.
  • Inventive nonwovens of continuous materials are produced from thermoplastic polymers from the group of polyamides or polyesters, for example by melt spinning as so-called meltblown nonwovens.
  • the method of melt spinning is used for example for polyester in EP 0 880 988 A1 or EP 1 473 070 A1 described.
  • Nonwoven polyester will be in EP 2 090 682 A1 or EP 2 092 921 A1 described.
  • the use of such nonwoven, produced by the meltblown process, as a filter medium is the subject of EP 0 466 381 B1 ,
  • thermoplastic fibers of polyolefins such as polypropylene or polyethylene fibers due to the intrinsic hydrophobic character of the polyolefins even without auxiliaries is a relatively low surface tension
  • it is in more polar thermoplastics, preferably in polyamides and polyesters, to do with higher surface tensions.
  • but - because of insufficient temperature or chemical stability of polyolefins - must resort to higher polymers such as polyamides or polyesters, to difficulties.
  • thermoplastic fibers to be spinned by the addition of the thermoplastic to be used is exemplified by polyesters in DE 19 937 729 A1 described in terms of tear strength. This is done there by addition of a copolyester which contains as monomer units, inter alia, acrylic acid ester or methacrylic acid ester.
  • Polyester-based fabrics are provided with oil and water repellency FR-OS 239 746 and US 3,378,609 described by applying to the finished fabric, an aqueous emulsion of a fluorine-containing polymer.
  • the individual polyester fiber will be water repellent EP 0 196 759 A1 in that the polyester fibers are subsequently provided with a polyoxyalkylene glycol and a water-based and oil-repellent fluorine-based agent which essentially do not react with the polyester.
  • the object of the present invention is a process for reducing the surface tension of thermoplastic-based fibers, which comprises reacting a copolymer of at least one ⁇ -olefin with at least one methacrylic acid ester or acrylic acid ester of an aliphatic alcohol, preferably an aliphatic alcohol. 30 carbon atoms added to the thermoplastic and the mixture is then spun, preferably by the melt spinning method.
  • thermoplastics preferably of thermoplastics based on polyamide or based on polyester
  • copolymer to be used according to the invention significantly reduces the surface tension of the thermoplastics then produced thermoplastic fibers and their derivatives and thus to a media repellent, in particular water-repellent finish of the thermoplastic-based fibers, preferably the polyamide fibers or polyester fibers, and their derivatives leads.
  • mixtures based on 99.9 to 10 parts by weight, preferably 99.5 to 40 parts by weight, particularly preferably 99.0 to 55 parts by weight of at least one thermoplastic are preferred 0.1 to 20 parts by weight, preferably 0.25 to 15 parts by weight, particularly preferably 0.5 to 10 parts by weight, very particularly preferably 0.75 to 6 parts by weight, in particular very particularly preferably 1 , 0 to 2.0 wt .-% of at least one of the above-mentioned copolymers used.
  • thermoplastic based fibers are fibers based on thermoplastic polymers from the group of polyamides or polyesters.
  • thermoplastic-based fibers from the group of polyamides to be used are fibers based on aliphatic polyamides.
  • thermoplastic based fibers from the group of polyesters are fibers based on the polyalkylene terephthalates.
  • thermoplastic polyamides to be spun according to the invention can be prepared by various processes and synthesized from very different building blocks. They are used in special applications alone or in combination with processing aids, stabilizers, polymeric alloying partners, in particular elastomers. Are suitable also blends with proportions of other polymers, preferably blends with polyethylene, polypropylene or ABS, wherein optionally one or more compatibilizers can be used.
  • the properties of the polyamides can be improved by adding elastomers, for. B. in view of the tensile strength of z. B. especially low-viscosity polyamides. The multitude of possible combinations enables a very large number of products with different properties.
  • Preferred polyamides are partially crystalline polyamides which can be prepared starting from diamines and dicarboxylic acids and / or lactams with at least 5 ring members or corresponding amino acids.
  • Suitable starting materials are aliphatic and / or aromatic dicarboxylic acids such as adipic acid, 2,2,4- and 2,4,4-trimethyladipic acid, azelaic acid, sebacic acid, isophthalic acid, terephthalic acid, aliphatic and / or aromatic diamines such as e.g.
  • Tetramethylenediamine Tetramethylenediamine, hexamethylenediamine, 1,9-nonanediamine, 2,2,4- and 2,4,4-trimethylhexamethylenediamine, the diamino-dicyclohexylmethane isomeric diamines, diaminodicyclohexylpropanes, bis-aminomethylcyclohexane, phenylenediamines, xylylenediamines, aminocarboxylic acids, e.g. Aminocaproic acid, or the corresponding lactams into consideration. Copolyamides of several of the monomers mentioned are included.
  • caprolactams most preferably ⁇ -caprolactam is used.
  • PA6 PA66
  • other aliphatic or / and aromatic polyamides or copolyamides in which 3 to 11 methylene groups are present on a polyamide group in the polymer chain.
  • the polyamides prepared according to the invention can also be used in a mixture with other polyamides and / or further polymers.
  • the polyamides may contain conventional additives such as e.g. Mold release agents, stabilizers and / or flow aids be admixed.
  • thermoplastic polyamides to be spun Thermoplastic polyesters are particularly preferably partially aromatic polyesters.
  • polyester to be spun are selected from the group of derivatives of the polyalkylene terephthalates.
  • polyesters to be spun selected from the group of polyethylene terephthalates, polytrimethylene terephthalates and polybutylene terephthalates, more preferably polybutylene terephthalate and polyethylene terephthalate, most preferably polybutylene terephthalate, or mixtures of these terephthalates.
  • Partly aromatic polyesters are understood as meaning materials which, in addition to aromatic moieties, also contain aliphatic moieties.
  • Polyalkylene terephthalates in the context of the invention are reaction products of aromatic dicarboxylic acids or their reactive derivatives, in particular dimethyl esters or anhydrides, and aliphatic, cycloaliphatic or araliphatic diols and mixtures of these reactants.
  • Preferred polyalkylene terephthalates can be prepared from terephthalic acid (or its reactive derivatives) and aliphatic or cycloaliphatic diols having 2 to 10 carbon atoms by known methods ( Plastics Handbook, Vol. VIII, p. 695 FF, Karl-Hanser-Verlag, Kunststoff 1973 ).
  • Preferred polyalkylene terephthalates contain at least 80 mol%, preferably 90 mol%, based on the dicarboxylic acid, terephthalic acid residues and at least 80 mol%, preferably at least 90 mol%, based on the diol component, ethylene glycol and / or 1,3-propanediol and / or butanediol-1,4-radicals.
  • the preferred polyalkylene terephthalates may contain up to 20 mol% of radicals of other aromatic dicarboxylic acids having 8 to 14 carbon atoms or radicals of aliphatic dicarboxylic acids having 4 to 12 carbon atoms, in particular radicals of phthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid , 4,4'-diphenyldicarboxylic acid, succinic, adipic, sebacic, azelaic, cyclohexanediacetic, cyclohexanedicarboxylic.
  • the preferred polyalkylene terephthalates may contain up to 20 mol% of other aliphatic diols having 3 to 12 C atoms or cycloaliphatic diols having 6 to 21 C atoms included, in particular.
  • preferred branching agents are trimesic acid, trimellitic acid, trimethylolethane and -propane and pentaerythritol.
  • polyalkylene terephthalates which are prepared solely from terephthalic acid and its reactive derivatives, in particular their dialkyl esters, and ethylene glycol and / or 1,3-propanediol and / or 1,4-butanediol, in particular polyethylene and polybutylene terephthalate, and mixtures of these polyalkylene terephthalates.
  • Preferred polyalkylene terephthalates are also copolyesters which are prepared from at least two of the abovementioned acid components and / or from at least two of the abovementioned alcohol components; particularly preferred copolyesters are poly (ethylene glycol / butanediol-1,4) terephthalates.
  • the polyalkylene terephthalates generally have an intrinsic viscosity of about 0.3 dl / g to 1.5 cm 3 / g, preferably 0.4 dl / g to 1.3 dl / g, particularly preferably 0.5 dl / g 1.0 dl / g each measured in phenovo-dichlorobenzene (1: 1 parts by weight) at 25 ° C.
  • thermoplastic polyesters preferably to be spun according to the invention can also be used in a mixture with other polyesters and / or further polymers.
  • very particular preference is given to using polyethylene terephthalate (PET), polypropylene terephthalate or polybutylene terephthalate (PBT) or mixtures thereof, in particular polybutylene terephthalate.
  • recycled polyester from post or pre-consumer recycled materials can be used alone or in the mixture, with polyester recyclates from beverage bottles, so-called PET copolyesters, being preferred.
  • PET copolyesters An example is the PET Plus80 ® from. PET plastic recycling GmbH, Beselich-Obertiefenbach, Germany.
  • polyesters are poly (C 2-4 -alkylene) terephthalates containing up to 15 mol% of other dicarboxylic acids and / or diols, especially isophthalic acid, adipic acid, diethylene glycol, polyethylene glycol, 1,4-cyclohexanedimethanol, or the each other C 2-4 alkylene glycols.
  • IV intrinsic viscosity
  • the thermoplastics to be spun according to the invention contain random copolymers of at least one ⁇ -olefin with at least one methacrylic ester or acrylic acid ester of an aliphatic alcohol.
  • Preferred ⁇ -olefins as a constituent of the copolymer preferably have between 2 and 10 carbon atoms and can be unsubstituted or substituted with substituted one or more aliphatic, cycloaliphatic or aromatic groups.
  • Preferred ⁇ -olefins are selected from the group comprising ethene, propene, 1-butene, 1-pentene, 1-hexene, 1-octene, 3-methyl-1-pentene.
  • Particularly preferred ⁇ -olefins are ethene and propene, most preferably ethene. Also suitable are mixtures of the described ⁇ -olefins.
  • the content of the ⁇ -olefin in the copolymer is between 50 and 90% by weight, preferably between 55 and 75% by weight.
  • the copolymer is further defined by the second component besides the ⁇ -olefin.
  • alkyl or arylalkyl esters of acrylic acid or methacrylic acid are suitable whose alkyl or arylalkyl group is formed from 5-30 carbon atoms and no or only a low concentration of reactive functions selected from the group comprising epoxides, oxetanes, anhydrides, imides, aziridines , Furans, acids, amines.
  • the alkyl or arylalkyl group may be linear or branched and may contain cycloaliphatic or aromatic groups, but may also be substituted by one or more ether or thioether functions.
  • Suitable methacrylic or acrylic esters in this context are also those synthesized from an alcohol component based on oligoethylene glycol or oligopropylene glycol having only one hydroxyl group and at most 30 carbon atoms.
  • the alkyl or arylalkyl group of the methacrylic or acrylic ester is preferably selected from the group comprising methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, 1-pentyl, 1-hexyl, 2 Hexyl, 3-hexyl, 1-heptyl, 3-heptyl, 1-octyl, 1- (2-ethyl) hexyl, 1-nonyl, 1-decyl, 1-dodecyl, 1-lauryl or 1-octadecyl.
  • Particularly preferred are alkyl or arylalkyl groups having 6-20 carbon atoms. Branched alkyl groups are particularly preferred which lead to a lower glass transition temperature T G compared to linear alkyl groups of the same number of carbon atoms.
  • the content of acrylic acid esters or methacrylic acid esters in the copolymer is between 10 and 50% by weight, preferably between 25 and 45% by weight.
  • Particularly suitable copolymers are selected from the group of materials supplied by Messrs. Arkema under the trade name Lotryl EH ® or Lotryl ® BA, which are in part also as a hot melt adhesive use.
  • the e.g. amount of the copolymer to be added by spinning to be processed polyamide or polyester mixture has already been stated above, with usually addition amounts of ⁇ 6% by weight being sufficient.
  • concentration of the copolymer in the range 0.75 to 6.0 wt .-%, depending on the desired take-off speed (> 700-1500 m / min) is chosen so that the birefringence of the fiber ⁇ 3.5 ⁇ 10-3 is.
  • Such birefringence in the fiber allow draw ratios of 1: 5 and ensure the desired high thread strengths regardless of the spinning take-off speed of up to 1500 m / min at Aufspul yorken of well over 3800 m / min.
  • thermoplastic-copolymer mixtures preferably dyes, other hydrophobizing agents, matting agents, stabilizers, antistatic agents, lubricants, branching agents, can be added to the thermoplastic-copolymer mixtures according to the invention in amounts of from 0.001 to 5.0% by weight without any disadvantage.
  • Preferred dyes to be used are disperse dyes, in particular those based on azo dye or those based on very finely divided carbon blacks
  • Preferably used matting agents are microcrystalline anatase having an average particle size [d50] of 0.25 to 0.35 ⁇ m, which may optionally also be provided with an organic or inorganic surface treatment.
  • preferred stabilizers are aromatic polycarbodiimides such as Stabaxol P from Rheinchemie in Mannheim, Germany, but also heat stabilizers based on organically derivatized phosphites.
  • antistatic agents are in particular finely divided conductive carbon blacks or carbon nanotubes.
  • Lubricating agents which are preferably to be used are, in particular, long-chain fatty acids, preferably stearic acid or behenic acid, their salts, preferably Ca or Zn stearate, and also their ester derivatives, and low molecular weight polyethylene or polypropylene waxes.
  • montan waxes are mixtures of straight-chain, saturated carboxylic acids having chain lengths of 28 to 32 carbon atoms.
  • Preferred lubricants and / or mold release agents are compounds from the group of low molecular weight polyethylene waxes and from the group of amides or esters of saturated or unsaturated aliphatic carboxylic acids having 8 to 40 carbon atoms with aliphatic saturated amines or alcohols having 2 to 40 carbon atoms.
  • Ethylene bisstearylamide and pentaerythritol tetrastearate (PETS) are very particularly preferred according to the invention, pentaerythritol tetrastearate (PETS) is particularly particularly preferred.
  • Preferred branching agents are fusible modified bisphenol-A epichlorohydrin resins, such as e.g. Araldite GY764CH or Araldite GT7071 from Huntsman in Everberg, Belgium.
  • the melt can optionally be discharged into a strand, cooled and granulated.
  • Both the mixing of the polymers and the subsequent spinning of the polymer mixture takes place at temperatures, depending on the matrix polymer, preferably in the range from 5 to 85 ° C., particularly preferably from 30 to 70 ° C., in each case above the melting temperature of the matrix polymer.
  • temperatures of 265 to 340 ° C are set, for PA6 and PBT preferably 225 to 300 ° C.
  • thermoplastics to be used according to the invention takes place, for example, in a meltblown plant.
  • the components are heated in an extruder and brought to a high pressure.
  • the melt is then pressed after optional pre-filtration through a suitable filter package in exact dosage by means of the spinning pumps through a die, the so-called spin bar (Spinerette).
  • the polymer exits the die plate as a fine fiber - also called filament in textile terminology - in molten form. It is cooled by a stream of air and still stretched out of the melt.
  • the air flow conveys the filaments to, for example, a conveyor belt, which is designed as a sieve or on a porous drum or on an incoming substrate such. Eg paper.
  • This fiber fabric is a random nonwoven that must be consolidated.
  • the solidification can be done for example by two heated rollers (calender) or by a vapor stream. When solidified by a calender, one of the two rolls is usually provided with an engraving consisting of points, short rectangles or diamond-shaped points. At the contact points, the filaments merge to form the nonwoven fabric. Lighter nonwovens can be produced exclusively in this way (thermobonded), heavier nonwovens are produced with a second incorporated low-melting polymer, which is melted in a passage through a so-called fixing oven, the hot melt adhesive and the matrix fibers are usually glued together at their crossing points and thus ensures the desired nonwoven strengths become.
  • a further possibility of solidification is hydroentanglement, in which water jets impinge on the still unconsolidated web with water pressures of up to 400 bar.
  • thermoplastic-based mixtures to be used according to the invention preferably the polyamide or polyester mixtures
  • the production of high-strength filaments from the thermoplastic-based mixtures to be used according to the invention is preferably carried out by spinning at take-off speeds of> 700 m / min, more preferably 750 to 1000 m / min, and stretching, thermofixing and winding with a appropriate speed. This is done using known spinning devices.
  • high-strength filaments made of polyamide or polyester are produced by the melt spinning process in large direct melt spinning plants, in which the melt is distributed over heated product lines on the individual spin lines and within the lines on the individual spinning systems.
  • a spinning line represents a juxtaposition of at least one row of spinning systems
  • a spinning system represents the smallest spinning unit with a spinning head containing at least one spinneret pack including spinneret plates.
  • the melt in such systems is subject to high thermal stress Residence times up to 35 min.
  • the effectiveness of the copolymer to be used according to the invention for reducing the surface tension does not lead to any appreciable limitations of its action, so that, depending on the desired reduction of the surface tension, small addition amounts of the additive, for example ⁇ 2.0% and in many cases even ⁇ 1.5% despite high thermal load.
  • the nozzle block to be used according to the invention preferably has at least 20, preferably 150 to 1500 and more preferably 500 to 1000 nozzle holes per meter of nozzle width.
  • diameters of 0.05 to 1 mm and especially of 0.3 to 0.5 mm are preferred.
  • the nozzle exit velocity is preferably 1 to 20 m / min, but more preferably 3 to 10 m / min. Due to the applied hot flow, the extruded filaments are preferably drawn to 50 to 800 times their length after the nozzle exit, resulting in spinning speeds of up to 10,000 m / min.
  • the present invention also relates to the use of at least one copolymer of at least one ⁇ -olefin and at least one acrylic ester or methacrylic acid ester to reduce the surface tension of thermoplastic-based fibers or filaments, preferably polyester-based fibers or filaments or polyamide-based fibers or filaments, particularly preferably polyester-based fibers or filaments.
  • the present invention further relates to fibers or filaments having reduced surface tension obtainable by melt-spinning thermoplastic-based fibers or filaments whose thermoplastic before processing to the fiber or filament, preferably before spinning with at least one copolymer of at least one ⁇ -olefin and at least one acrylic acid ester or methacrylic acid ester aliphatic alcohol was added.
  • the present invention furthermore relates to products, preferably nonwovens, nonwovens, woven fabrics, knitted fabrics, fabrics or knitted fabrics, in particular nonwovens or nonwovens obtainable from inventive thermoplastic fibers or filaments with reduced surface tension, preferably polyester-based fibers or filaments or polyamide-based fibers or filaments each with reduced Surface tension, the underlying thermoplastic before spinning by at least one copolymer of at least one ⁇ -olefin and at least one acrylic acid ester or methacrylic acid ester was additivated.
  • the surface tension of fibers can be determined by their wettability with liquids of different polarity.
  • a further possibility for determining the surface tension of fiber products produced according to the invention is the consideration of the absorption kinetics of a liquid medium absorbed by the fiber product (for example water or cyclohexane) with the aid of a suitable tensiometer.
  • the lowering of the surface tension of the materials according to the invention is shown quantitatively on injection-molded plates, which serve as a model system for more accurate determination of the surface surface tension, and on the other hand qualitatively produced by the meltblown process webs.
  • plastic molding compounds For exemplifying the reduction of the surface tension described according to the invention, first of all corresponding plastic molding compounds were prepared by compounding.
  • the individual components were mixed in a twin-screw extruder (ZSK 26 Mega Compounder from Coperion Werner & Pfleiderer (Stuttgart, Germany)) at temperatures between 250 and 285 ° C., discharged as a strand, cooled to granulation capability and granulated. After drying (usually 2-6 h at 80 ° C in a vacuum oven), the processing of the granules to test specimens.
  • test specimens (rectangular plates measuring 60 ⁇ 40 ⁇ 4 mm or 150 ⁇ 105 ⁇ 1.0 mm) for the tests listed in Tables 1 and 2 were cast on an Arburg 320-210-500 injection molding machine at a melt temperature of about 260 ° C and a mold temperature of about 80 ° C sprayed.
  • the surface tension of the rectangular plates obtained from the materials produced according to the invention was determined in a simple and reproducible manner according to DIN ISO 8296 with test inks.
  • the surface tensions according to DIN ISO 8296 can generally not be compared with the values according to ASTM D 2587-84.
  • the test method is based on the evaluation of the wetting of inks with different surface tension on the polymer surface to be examined.
  • the brush located on the bottle cap is dipped into the test ink, stripped off the edge of the bottle and the ink is immediately applied to the surface to be tested.
  • the stroke length should be at least 100 mm.
  • the behavior of the line edge is evaluated at a length of about 90%, so that slight inhomogeneities are not taken into account. If the ink stroke contracts in less than two seconds, repeat the measurement with a lower surface tension ink until the edges stop for two seconds. If the ink stroke remains unchanged for more than two seconds, the measurement is with Repeat higher surface tension inks until the two seconds are reached.
  • the value indicated on the bottle then corresponds to the surface energy of the test plate.
  • the test shall be carried out in standard climate 23/50, ie at an air temperature of 23 ° C +/- 2 ° C and a relative humidity of 50% +/- 10%.
  • test inks of the company Softal Electronic GmbH (see Softal Report No. 108), Hamburg, Germany, were used.
  • nonwovens having a basis weight of about 55 g / m 2 were produced by means of a meltblown system.
  • the melt temperature was about 275 ° C
  • the hot air flow about 360 ° C.
  • the ratio of melt throughput and air flow was chosen so that at a nozzle diameter of 300 .mu.m, an average fiber thickness of about 1 .mu.m was obtained.
  • the nonwovens described in the examples and comparative examples differ only in the polymer compositions used in each case, while all other parameters and associated nonwoven characteristics such as basis weight, pore size, fiber orientation and fiber thickness are kept constant for each example and comparative example.
  • the nonwoven fabric was subjected to a water drop.
  • a rapid wetting of the water droplet on the nonwoven indicates a high surface tension (hydrophilic behavior), while the retention of the droplet shape on the surface indicates a low surface tension.
  • the drop was exposed to an air stream. If the drop leaves a trace of a water film, it can be assumed qualitatively of a higher surface tension, the drop moves over the fleece without leaving a visible trace of water, then a lower surface tension can be assumed (see Table 3).
  • a high value stands for a high surface tension and thus for a hydrophilic behavior, while the material becomes increasingly more hydrophobic with decreasing surface tension.
  • Drops wet the surface so much that it can not practically be blown off Drops can be blown away, but leaves a highly visible trace of water. Drops can be blown away without leaving any visible water residue on the fleece surface.
  • the strongly decreasing adhesion of the water drop with increasing concentration of component B1 is a measure of the strongly decreasing wettability of the nonwoven with water and thus indicates the reduction of the surface tension in the polyester fibers used for the nonwoven.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Artificial Filaments (AREA)
  • Nonwoven Fabrics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
EP12166834.7A 2012-05-04 2012-05-04 Fibres thermoplastiques avec une tension de surface réduite Withdrawn EP2660372A1 (fr)

Priority Applications (8)

Application Number Priority Date Filing Date Title
EP12166834.7A EP2660372A1 (fr) 2012-05-04 2012-05-04 Fibres thermoplastiques avec une tension de surface réduite
PCT/EP2013/059259 WO2013164452A1 (fr) 2012-05-04 2013-05-03 Fibres thermoplastiques possédant une tension superficielle réduite
US14/398,319 US20150084231A1 (en) 2012-05-04 2013-05-03 Thermoplastic fibres with reduced surface tension
KR1020147033720A KR101965471B1 (ko) 2012-05-04 2013-05-03 감소된 표면 장력을 갖는 열가소성 섬유
JP2015509449A JP6290183B2 (ja) 2012-05-04 2013-05-03 表面張力を低減した熱可塑性繊維
EP13721664.4A EP2844788B1 (fr) 2012-05-04 2013-05-03 Fibres thermoplastiques avec une tension de surface réduite
HUE13721664A HUE057122T2 (hu) 2012-05-04 2013-05-03 Csökkentett felületi feszültségû hõre lágyuló mûanyag szálak
CN201380029189.0A CN104350188A (zh) 2012-05-04 2013-05-03 具有降低的表面张力的热塑性塑料纤维

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CN113789004B (zh) * 2021-07-28 2023-07-07 广东金发科技有限公司 一种热塑性合金材料及其在塑料模具制备中的应用和制备的手模

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KR20150003392A (ko) 2015-01-08
WO2013164452A1 (fr) 2013-11-07
US20150084231A1 (en) 2015-03-26
EP2844788A1 (fr) 2015-03-11
JP2015520806A (ja) 2015-07-23
KR101965471B1 (ko) 2019-04-03
CN104350188A (zh) 2015-02-11
HUE057122T2 (hu) 2022-04-28
EP2844788B1 (fr) 2021-10-27
JP6290183B2 (ja) 2018-03-07

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