EP2844788B1 - Thermoplastic fibres with reduced surface tension - Google Patents
Thermoplastic fibres with reduced surface tension Download PDFInfo
- Publication number
- EP2844788B1 EP2844788B1 EP13721664.4A EP13721664A EP2844788B1 EP 2844788 B1 EP2844788 B1 EP 2844788B1 EP 13721664 A EP13721664 A EP 13721664A EP 2844788 B1 EP2844788 B1 EP 2844788B1
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- EP
- European Patent Office
- Prior art keywords
- thermoplastic
- copolymer
- process according
- surface tension
- carbon atoms
- Prior art date
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Classifications
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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
- D01F6/84—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyesters
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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
- 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
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- 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
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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
- D01F6/02—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
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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
- D01F6/58—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
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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
- D01F6/88—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
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- 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
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- 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 products to be produced from these thermoplastic fibers with reduced surface tension by the melt spinning process, 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, preferably a 2-ethylhexanol is added.
- Products made from thermoplastic fibers from the group of polyamides or polyesters for the purposes of the present invention are nonwovens, nonwovens, woven fabrics, threads, yarns, ropes, felts, knitted fabrics, scrims or knitted fabrics.
- Preferred products for the purposes of the present invention are nonwovens or nonwovens.
- a fleece consists of loosely lying fibers that are not yet connected to one another. The strength of a fleece is based only on the fiber's own adhesion. However, this can be influenced by processing. In order to be able to process and use the fleece, it must be solidified, for which various methods can be used. Only a solidified fleece can be called a fleece. This distinction is not made in colloquial language.
- Nonwovens are essentially different from woven, knitted, laid and knitted fabrics, which are characterized by the laying of the individual fibers or threads determined by the manufacturing process.
- Nonwovens on the other hand, consist of fibers, the position of which can only be described using statistical methods.
- the fibers are tangled to each other in the nonwoven.
- the English term nonwoven clearly distinguishes it from woven, knitted, etc.
- Nonwovens are differentiated among other things according to the fiber material (e.g. the polymer in man-made fibers), the binding process, the type of fiber (staple or continuous fibers), the fiber fineness and the fiber orientation.
- the fibers can be laid down in a defined preferred direction or they can be oriented entirely stochastically, as in the case of random-layer nonwovens.
- the fibers have no preferred direction in their alignment (orientation), one speaks of an isotropic nonwoven fabric. If the fibers are arranged more frequently in one direction than in other directions, this is called anisotropy.
- Nonwovens are textile fabrics in which the formation of the surface does not take place by weaving, knitting, knitting or defined laying, but by laying down the fibers with subsequent fixation. Because of the many possible uses and the comparison Nonwovens still have high annual growth rates compared to knitted and woven fabrics that are comparatively low production costs.
- the surface tension plays a decisive role, for example, a reduction in the surface tension can lead to an increased water-repellent behavior, which can play an important role in particular for applications in the clothing industry, but also in filter fleeces in the automotive sector.
- Nonwovens according to the invention made from 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 process of melt spinning is used, for example, for polyester in EP 0 880 988 A1 or EP 1 473 070 A1 described.
- Polyester nonwovens are used in EP 2 090 682 A1 or EP 2 092 921 A1 described.
- the use of such nonwovens, manufactured using the meltblown process, as a filter medium is the subject of EP 0 466 381 B1 .
- thermoplastic fibers made from polyolefins such as polypropylene or polyethylene fibers
- more polar thermoplastics preferably polyamides and polyesters
- higher surface tensions are required, but on the other hand, higher-quality polymers such as polyamides or polyesters have to be used, for example because polyolefins are too low in temperature or chemical stability.
- more polar thermoplastics such as polyamides and Polyester, to be modified in such a way that, while retaining the known advantages such as temperature stability, mechanical strength and chemical resistance to fuels and oils, lower surface tensions are achieved.
- thermoplastic fibers to be spun by adding additives to the thermoplastic to be used for this purpose is illustrated using the example of polyesters in DE 19 937 729 A1 described in terms of tear strength. This is done there by adding a copolyester which contains, inter alia, acrylic acid esters or methacrylic acid esters as monomer units.
- a copolyester which contains, inter alia, acrylic acid esters or methacrylic acid esters as monomer units.
- Has a similar aim WO2005 / 040257 A1 where ethylene alkyl acrylate copolymers are used in films, tapes and melt spun polyester fibers in order to improve their mechanical properties such as tensile strength. Preference is given there to copolymer additions above 5%.
- Making polyester-based fabrics oil- and water-repellent is used in FR-OS 239 746 and U.S.
- WO 2009/152349 A1 describes, among other things, hygiene wipes that are equipped with fluorochemicals based on perfluorinated alkyl groups with up to four carbon atoms as repellent additives.
- fluorochemicals based on perfluorinated alkyl groups with up to four carbon atoms for example, copolymers of such perfluorinated substances with acrylate esters or methacrylate esters are listed.
- JP 2003 193331 A describes polyester monofilaments for reinforcing rubbers which, among other things, are equipped with copolymers of ethylene with glycidyl methacrylate.
- WO 2005/087868 A1 discloses ethylene copolymer modified polyamide products, these products being melt-spun fibers equipped with E / X / Y copolymers in which E stands for ethylene, X stands for alkyl acrylate and Y stands for glycidyl acrylate, glycidyl methacrylate or glycidyl vinyl ether, among others.
- WO 2008/083820 A1 finally discloses soft yarns based on polyamide or polyesters, which can be finished with plasticizer polymers made from ethylene-alkyl acrylates. Methyl acrylate, ethyl acrylate and butyl acrylate are listed.
- JP 2004 183196 and JP 2002 020931 Further information on the topics mentioned here can also be found in JP 2004 183196 and JP 2002 020931 .
- the object of the present invention was therefore to modify the polyamide or polyester beforehand in such a way that a reduction in surface tension is possible even without aftertreatment of the products made from the corresponding thermoplastic fiber, with a reduction in surface tension being achieved with as little use of material as possible target.
- the modification should manage without fluorine-containing chemicals, should be color-neutral and designed in such a way that the process of fiber production per se is not impaired in an unacceptable manner.
- the modification to reduce the surface tension should take place in such a way that added auxiliaries, due to their effectiveness, can be limited to an addition amount which does not influence the melt spinning process or does not influence it decisively.
- the fiber produced in this way should be able to be further processed in a variety of ways into products, in particular into nonwovens, nonwovens, woven, knitted, laid or knitted fabrics with reduced surface tension.
- the solution to the problem and the subject matter of the present invention is a method according to claim 1 for reducing the surface tension of thermoplastic fibers, characterized in that at least one E / X copolymer of an ⁇ -olefin and an acrylic acid ester or methacrylic acid ester of an unsubstituted aliphatic alcohol is added to the thermoplastic with 6 to 30 carbon atoms is added and spun by the melt spinning process, polyamide or polyester being used as thermoplastic and the content of ⁇ -olefin in the E / X copolymer being between 50 and 90% by weight.
- thermoplastics polyamide or polyester with the E / X copolymer to be used according to the invention reduces the surface tension of the corresponding thermoplastic fibers and their secondary products with high effectiveness and thus, for example, to a water-repellent finish of the thermoplastic-based fibers, preferably the polyamide or Polyester fibers and their derivatives.
- the effectiveness of the copolymer to be used according to the invention allows even at low concentrations strong reduction in surface tension, so that the melt spinning process is not or not decisively influenced.
- Thermoplastic fibers to be used with preference are fibers based on thermoplastic polymers from the group of polyamides or polyesters.
- thermoplastic fibers from the group of polyamides to be used are fibers based on aliphatic polyamides.
- Thermoplastic fibers from the group of polyesters to be used with particular preference are fibers based on polyalkylene terephthalates.
- thermoplastic polyamides to be spun according to the invention can be produced by various processes and synthesized from very different building blocks. In special applications, they are used alone or in combination with processing aids, stabilizers, polymeric alloy partners, in particular elastomers. Blends with proportions of other polymers are also suitable, preferably blends with polyethylene, polypropylene or ABS, it being possible to use one or more compatibilizers if necessary.
- the properties of the polyamides can be improved by adding elastomers, e.g. B. in terms of the tear strength of z. B. particularly low-viscosity polyamides. The multitude of possible combinations enables a very large number of products with a wide variety of properties.
- Preferred polyamides are semicrystalline polyamides which can be produced starting from diamines and dicarboxylic acids and / or lactams with at least 5 ring members or corresponding amino acids.
- 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, for example, tetramethylenediamine, hexamethylenediamine, 1,9 are used as starting materials -Nonanediamine, 2,2,4- and 2,4,4-trimethylhexamethylenediamine, the isomeric diamino-dicyclohexylmethanes, diaminodicyclohexylpropane, bis-aminomethyl-cyclohexane, phenylenediamines, xylylenediamines, aminocarboxylic acids such as aminocaproic acid, or the corresponding lactams. Copolyamides made from several of the monomers mentioned are included.
- Caprolactams are particularly preferred, and ⁇ -caprolactam is very particularly preferably used.
- polyamides produced according to the invention can also be used in a mixture with other polyamides and / or further polymers.
- thermoplastic polyesters to be spun according to the invention are particularly preferably partially aromatic polyesters.
- Polyesters to be spun with particular preference are selected from the group of derivatives of polyalkylene terephthalates.
- Polyesters to be spun are very particularly preferably selected from the group of polyethylene terephthalates, polytrimethylene terephthalates and polybutylene terephthalates, particularly particularly preferably polybutylene terephthalate and polyethylene terephthalate, particularly particularly preferably polybutylene terephthalate, or mixtures of these terephthalates.
- Partially aromatic polyesters are materials that contain not only aromatic parts of the molecule but also aliphatic parts of the molecule.
- polyalkylene terephthalates 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 with 2 to 10 carbon atoms by known methods ( Kunststoff-Handbuch, 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 1,4-butanediol residues.
- the preferred polyalkylene terephthalates can contain up to 20 mol% of residues of other aromatic dicarboxylic acids with 8 to 14 carbon atoms or residues of aliphatic dicarboxylic acids with 4 to 12 carbon atoms, in particular residues of phthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid , 4,4'-diphenyldicarboxylic acid, succinic, adipic, sebacic acid, azelaic acid, cyclohexanediacetic acid, cyclohexanedicarboxylic acid.
- the preferred polyalkylene terephthalates can contain, in addition to ethylene or 1,3-propanediol or 1,4-butanediol, up to 20 mol% of other aliphatic diols having 3 to 12 carbon atoms or cycloaliphatic diols having 6 to 21 carbon atoms included, in particular.
- Examples of preferred branching agents are trimesic acid, trimellitic acid, trimethylol ethane and propane and pentaerythritol.
- polyalkylene terephthalates which are produced solely from terephthalic acid and its reactive derivatives, in particular its 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 produced 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 / 1,4-butanediol) 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 phenol / o-dichlorobenzene (1: 1 parts by weight) at 25 ° C.
- thermoplastic polyesters to be spun with preference according to the invention can also be used in a mixture with other polyesters and / or further polymers.
- Polyethylene terephthalate (PET), polypropylene terephthalate or polybutylene terephthalate (PBT) or mixtures thereof are very particularly preferably used; in particular, polybutylene terephthalate is used.
- recycled polyesters from post or pre-consumer recyclates can also be used alone or in a mixture, 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.
- Poly (C 2-4 alkylene) terephthalates which contain up to 15 mol% of other dicarboxylic acids and / or diols, in particular isophthalic acid, adipic acid, diethylene glycol, polyethylene glycol, 1,4-cyclohexanedimethanol, or the polyesters to be used for the melt spinning process are particularly preferred each other C 2-4 alkylene glycols contain.
- IV intrinsic viscosity
- the thermoplastics to be spun according to the invention contain random E / X copolymers of E at least one ⁇ -olefin with X a methacrylic acid ester or acrylic acid ester of an unsubstituted aliphatic alcohol.
- Preferred ⁇ -olens as constituent E of the copolymers preferably have between 2 and 10 carbon atoms and can be unsubstituted or substituted by one or more aliphatic, cycloaliphatic or aromatic groups.
- Preferred ⁇ -olennes are selected from the group comprising ethene, propene, 1-butene, 1-pentene, 1-hexene, 1-octene, 3-methyl-1-pentene. Particularly preferred ⁇ -olennes are ethene and propene, and ethene is very particularly preferred. Mixtures of the ⁇ -olefins described are also suitable.
- the content of the ⁇ -olefin in the E / X copolymer is between 50 and 90% by weight, preferably between 55 and 75% by weight.
- the E / X copolymer is also defined by the second component in addition to the ⁇ -olefin.
- alkyl or arylalkyl esters of acrylic acid or methacrylic acid are suitable, the alkyl or arylalkyl group of which 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 can be linear or branched and contain cycloaliphatic or aromatic groups, and also be substituted by one or more ether or thioether functions.
- Suitable methacrylic or acrylic acid esters in this context are also those which have been synthesized from an alcohol component which are based on oligoethylene glycol or oligopropylene glycol with only one hydroxyl group and a maximum of 30 carbon atoms.
- the alkyl or arylalkyl group of the methacrylic acid or acrylic acid ester is preferably selected from the group comprising 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.
- Unsubstituted alkyl or arylalkyl groups with 6-20 carbon atoms, particularly preferably with 8-20 carbon atoms, are particularly preferred.
- branched alkyl groups which, compared to linear alkyl groups with the same number of carbon atoms, lead to a lower glass transition temperature T G.
- Particularly preferred according to the invention are copolymers in which the ⁇ -olefin is copolymerized with (2-ethyl) hexyl acrylate.
- 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 by the company. Arkema under the trade name Lotryl EH ® offered materials, which are also as hot melt adhesive use.
- a method for reducing the surface tension of polyester-based fibers or polyamide-based fibers is particularly preferred, characterized in that an E / X copolymer of ethylene and an acrylic acid ester of an unsubstituted aliphatic alcohol having 6 to 30 carbon atoms, preferably of E and ethylene X an acrylic acid ester with 6 to 20 carbon atoms, particularly preferably composed of E ethylene and X 2-ethylhexyl acrylate, is added to the thermoplastic and the mixture is then spun by the melt spinning process.
- a method for reducing the surface tension of polyester-based fibers is particularly preferred, characterized in that an E / X copolymer of ethylene and an acrylic acid ester of an unsubstituted aliphatic alcohol with 6 to 30 carbon atoms, preferably E ethylene and X an acrylic acid ester with 6 up to 20 carbon atoms, particularly preferably from E ethylene and X 2-ethylhexyl acrylate, is added to the thermoplastic and the mixture is then spun by the melt spinning process.
- a method for reducing the surface tension of polyamide-based fibers is particularly preferred, characterized in that an E / X copolymer of ethylene and an acrylic acid ester of an unsubstituted aliphatic alcohol with 6 to 30 carbon atoms, preferably E ethylene and X an acrylic acid ester with 6 up to 20 carbon atoms, particularly preferably from E ethylene and X 2-ethylhexyl acrylate, is added to the thermoplastic and the mixture is then spun by the melt spinning process.
- the amount of the copolymer to be added to the polyamide or polyester mixture to be processed, for example by spinning, has already been specified above, with amounts of 6% by weight usually being sufficient.
- the concentration of the copolymer is preferably selected in the range from 0.75 to 6.0% by weight, depending on the desired take-off speed (> 700-1500 m / min), so that the birefringence of the fiber is ⁇ 3.5 ⁇ 10-3 is.
- Such birefringence in the fiber allow drawing 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 winding speeds of well over 3800 m / min.
- usage additives preferably dyes, further hydrophobizing agents, matting agents, stabilizers, antistatic agents, lubricants, branching agents, can add to the invention
- Thermoplastic copolymer mixtures can be added in amounts of 0.001 to 5.0% by weight without any disadvantage.
- Dyes to be used with preference are disperse dyes, in particular those based on azo dye or those based on very finely divided carbon blacks
- Matting agents to be used with preference are microcrystalline anatases with an average particle size [d50] of 0.25 to 0.35 ⁇ m, which can optionally also be provided with an organic or inorganic surface treatment.
- Stabilizers to be used with preference are, for example, aromatic polycarbodiimides such as Stabaxol P from Rheinchemie in Mannheim, Germany, but also heat stabilizers based on organically derivatized phosphites.
- Antistatic agents to be used with preference are, in particular, finely divided conductive blacks or carbon nanotubes.
- Lubricants to be used with preference are, in particular, long-chain fatty acids, preferably stearic acid or behenic acid, their salts, preferably Ca or Zn stearate, and their ester derivatives, and low molecular weight polyethylene or polypropylene waxes.
- montan waxes are mixtures of straight-chain, saturated carboxylic acids with 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 with 8 to 40 carbon atoms with aliphatic saturated amines or alcohols with 2 to 40 carbon atoms.
- Ethylene bis-stearylamide and pentaerythritol tetrastearate (PETS) are very particularly preferred according to the invention, pentaerythritol tetrastearate (PETS) is especially very particularly preferred.
- Preferred branching agents are meltable, modified bisphenol-A epichlorohydrin resins such as Araldite GY764CH or Araldite GT7071 from Huntsman in Everberg, Belgium.
- the melt can optionally be discharged into a strand, cooled and granulated.
- the mixing of the individual components can, however, also take place directly in the spinning or meltblow system, whereby the components can be physically premixed via a metering point or introduced separately via several metering points.
- the addition to a partial flow of the matrix polymer, which is then mixed into the main flow of the matrix polymer, is also practicable.
- a defined distribution is advantageously set there by specific selection of the mixer and the duration of the mixing process before the melt mixture is passed on through product distribution lines to the individual spinning stations and spinning nozzles.
- Mixers with a shear rate of 16 to 128 sec -1 have proven effective.
- the product of the shear rate (sec -1 ) and the 0.8th power of the residence time (in sec) should preferably be 250-2500, particularly preferably 350-1250. Values above 2500 are generally avoided in order to limit the pressure drop in the pipelines.
- thermoplastic is also circumscribed as polymer in the context of the present invention.
- Both the mixing of the polymers and the subsequent spinning of the polymer mixture take 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 preferably set for PET, and 225 to 300 ° C. for PA6 and PBT.
- thermoplastics to be used according to the invention takes place, for example, in a meltblown system.
- the components are heated in an extruder and brought to high pressure.
- the melt is then pressed through a suitable filter package in precise doses by means of the spinning pumps through a die, the so-called spinning bar.
- the polymer emerges from the nozzle plate as a fine fiber - also called filament in textile terminology - still in molten form. It is cooled by a stream of air and then stretched out of the melt.
- the air flow conveys the filaments onto, for example, a conveyor belt in the form of a sieve or onto a porous drum or onto an incoming substrate such as e.g. B. paper.
- This fiber structure is a random fleece that has to be consolidated.
- the solidification can take place, for example, with two heated rollers (calenders) or with a stream of steam.
- calenders heated rollers
- one of the two rollers is usually provided with an engraving, which consists of points, short rectangles or diamond-shaped points.
- the filaments fuse at the contact points and thus form the nonwoven fabric.
- 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, particularly preferably 750 to 1000 m / min, and drawing, heat setting and winding with a appropriate speed. This is done using spinning devices known per se.
- high-strength filaments made of polyamide or polyester are produced according to the melt spinning process in large direct melt spinning systems in which the melt is distributed over heated product lines to the individual spinning lines and within the lines to the individual spinning systems.
- a spinning line represents a string of at least one row of spinning systems and a spinning system is the smallest spinning unit with a spinning head that contains at least one spinneret package including spinneret plates.
- the melt is subject to high thermal stress with residence times of up to 35 minutes Surface tension even small amounts of the additive, eg ⁇ 2.0% and in many cases ⁇ 1.5% are sufficient despite high thermal loads.
- the nozzle block to be used according to the invention preferably has at least 20, preferably 150 to 1500 and particularly preferably 500 to 1000 nozzle holes per meter of nozzle width.
- diameters from 0.05 to 1 mm and particularly from 0.3 to 0.5 mm are preferred.
- the nozzle exit speed is preferably 1 to 20 m / min, but particularly preferably 3 to 10 m / min.
- the extruded threads are preferably stretched to 50 to 800 times their length after the nozzle outlet due to the hot current applied, which leads to 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 acid ester or methacrylic acid ester for reducing 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 with reduced surface tension obtainable by melt-spinning thermoplastic-based fibers or filaments which are additized with at least one copolymer of at least one ⁇ -olefin and at least one acrylic acid ester or methacrylic acid ester of an aliphatic alcohol.
- the present invention also relates to products, preferably nonwovens, nonwovens, woven, knitted fabrics, nonwovens or knitted fabrics, in particular nonwovens or nonwovens obtainable from thermoplastic-based fibers according to the invention with reduced surface tension, preferably polyester-based fibers or filaments or polyamide-based fibers or filaments, each with reduced surface tension, which have been added by at least one copolymer of at least one ⁇ -olefin and at least one acrylic acid ester or methacrylic acid ester.
- the surface tension of fibers can be determined based on their wettability with liquids of different polarity.
- Another possibility for determining the surface tension on fiber products produced according to the invention is to consider the absorption kinetics of a liquid medium (eg water or cyclohexane) absorbed by the fiber product with the aid of a suitable tensiometer.
- a liquid medium eg water or cyclohexane
- the lowering of the surface tension of the materials produced according to the invention is shown on the one hand quantitatively on injection molded plates, which serve as a model system for more precise determination of the surface surface tension, and on the other hand qualitatively on fleeces produced by the meltblown process.
- appropriate plastic molding compounds were first 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 granulability and granulated. After drying (usually 2-6 hours at 80 ° C. in a vacuum drying cabinet), the granulate was processed into test specimens.
- test specimens (rectangular plates of dimensions 60 ⁇ 40 ⁇ 4mm or 150 ⁇ 105 ⁇ 1.0mm) for the tests listed in Tables 1 and 2 were made on an Arburg 320-210-500 injection molding machine at a melt temperature of approx. 260 ° C and a mold temperature of approx. 80 ° C.
- the surface tension of the rectangular plates obtained from the materials produced according to the invention was determined simply and reproducibly in accordance with DIN ISO 8296 using test inks.
- the surface tensions according to DIN ISO 8296 cannot generally be compared with the values according to ASTM D 2587-84.
- the test method is based on the assessment of the wetting of inks with different surface tension on the polymer surface to be examined.
- the brush on the bottle cap is dipped into the test ink, wiped off at the edge of the bottle and the ink is immediately applied to the surface to be tested.
- the line length should be at least 100 mm.
- the behavior of the line edge is assessed over a length of about 90%, so that minor inhomogeneities are not taken into account. If the ink line contracts in less than two seconds, the measurement must be repeated with an ink with a lower surface tension until the edges remain there for two seconds. If the ink line stays longer remains unchanged for more than two seconds, the measurement must be repeated with inks with a higher surface tension until the two seconds have been reached.
- the value given on the bottle then corresponds to that of the surface energy of the test plate.
- the test is to be carried out in a standard climate of 23/50, ie at an air temperature of 23 ° C +/- 2 ° C and a relative humidity of 50% +/- 10%.
- test inks from Softal Electronic GmbH (see Softal Report No. 108), Hamburg, Germany, were used.
- nonwovens with a mass per unit area of approx. 55 g / m 2 were produced using a meltblown system.
- the melt temperature was approx. 275 ° C
- the hot air flow was approx. 360 ° C.
- the ratio of melt throughput and air volume flow was chosen so that with a nozzle diameter of 300 ⁇ m an average fiber thickness of approx. 1 ⁇ m was obtained.
- the webs described in the examples and comparative examples differ only in the polymer compositions used, while all other parameters and associated web parameters such as surface weight, pore size, fiber orientation and fiber thickness are kept constant for each example and comparative example.
- a drop of water was applied to the fleece for the qualitative assessment of the surface tension. Rapid wetting of the water droplet on the fleece indicates a high surface tension (hydrophilic behavior), while the retention of the droplet shape on the surface indicates a low surface tension. For further differentiation, the drop was exposed to a stream of air. If the drop leaves a trace of a water film, qualitatively a higher surface tension can be assumed; if 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 more and more hydrophobic as the number for the surface tension decreases.
- the examples show that the surface tension can only be reduced up to a limit value of 30 mN / m, the value 30 mN / m represents saturation. In the prior art (component B2 in comparative example 5), this limit value is only achieved with 6% by weight of a copolymer of ethylene and butyl acrylate. If only 3% by weight are used, the surface tension can only be reduced to 34 mN / m.
- a comparison of the surface tensions of component B1 and component B2 shows that with component B1, a copolymer of ethylene and 2-ethylhexyl acrylate, a very low surface tension of only 30 mN / m can be achieved even with a low dosage of, for example, 3% by weight.
- component B1 a copolymer of ethylene and 2-ethylhexyl acrylate
- a very low surface tension of only 30 mN / m can be achieved even with a low dosage of, for example, 3% by weight.
- the strongly decreasing adhesion of the water droplet with increasing concentration of component B1 is a measure of the strongly decreasing wettability of the fleece with water and thus shows the reduction in surface tension in the polyester fibers used for the fleece. Even 1% by weight of component B1 is sufficient to decisively increase the hydrophobicity.
Description
Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung von Thermoplastfasern mit reduzierter Oberflächenspannung sowie aus diesen Thermoplastfasern mit reduzierter Oberflächenspannung nach dem Schmelzspinnverfahren herzustellende Produkte, wobei der zu verwendende Thermoplast mit einem Copolymerisat aus mindestens einem α-Olefm und mindestens einem Acrylsäureester oder Methacrylsäureester eines aliphatischen Alkohols, bevorzugt eines 2-Ehtylhexanols versetzt wird.The present invention relates to a process for the production of thermoplastic fibers with reduced surface tension and products to be produced from these thermoplastic fibers with reduced surface tension by the melt spinning process, the thermoplastic to be used with a copolymer of at least one α-olefin and at least one acrylic acid ester or methacrylic acid ester of an aliphatic alcohol, preferably a 2-ethylhexanol is added.
Produkte aus Thermoplastfasern aus der Gruppe der Polyamide oder Polyester im Sinne der vorliegenden Erfindung sind Vliese, Vliesstoffe, Gewebe, Fäden, Garne, Seile, Filze, Gestricke, Gelege oder Gewirke. Bevorzugte Produkte im Sinne der vorliegenden Erfindung sind Vliese oder Vliesstoffe. Ein Vlies besteht aus lose zusammenliegenden Fasern, welche noch nicht miteinander verbunden sind. Die Festigkeit eines Vlieses beruht nur auf der fasereigenen Haftung. Diese kann aber durch Aufarbeitung beeinflusst werden. Damit man das Vlies verarbeiten und benutzen kann, muss es verfestigt werden, wofür verschiedene Methoden angewandt werden können. Erst ein verfestigtes Vlies ist als Vliesstoff zu bezeichnen. In der Umgangssprache wird dieser Unterschied nicht gemacht.Products made from thermoplastic fibers from the group of polyamides or polyesters for the purposes of the present invention are nonwovens, nonwovens, woven fabrics, threads, yarns, ropes, felts, knitted fabrics, scrims or knitted fabrics. Preferred products for the purposes of the present invention are nonwovens or nonwovens. A fleece consists of loosely lying fibers that are not yet connected to one another. The strength of a fleece is based only on the fiber's own adhesion. However, this can be influenced by processing. In order to be able to process and use the fleece, it must be solidified, for which various methods can be used. Only a solidified fleece can be called a fleece. This distinction is not made in colloquial language.
Vliesstoffe sind wesentlich verschieden von Geweben, Gestricken, Gelegen und Gewirken, die sich durch vom Herstellverfahren bestimmte Legung der einzelnen Fasern oder Fäden auszeichnen. Vliesstoffe bestehen dagegen aus Fasern, deren Lage sich nur mit den Methoden der Statistik beschreiben lässt.Nonwovens are essentially different from woven, knitted, laid and knitted fabrics, which are characterized by the laying of the individual fibers or threads determined by the manufacturing process. Nonwovens, on the other hand, consist of fibers, the position of which can only be described using statistical methods.
Die Fasern liegen wirr im Vliesstoff zueinander. Die englische Bezeichnung nonwoven (nicht gewebt) grenzt sie eindeutig von Geweben, Gestricken etc. ab. Vliesstoffe werden unter anderem nach dem Fasermaterial (z.B. das Polymer bei Chemiefasern), dem Bindungsverfahren, der Faserart (Stapel- oder Endlosfasern), der Faserfeinheit und der Faserorientierung unterschieden. Die Fasern können dabei definiert in einer Vorzugsrichtung abgelegt werden oder gänzlich stochastisch orientiert sein wie beim Wirrlagen-Vliesstoff.The fibers are tangled to each other in the nonwoven. The English term nonwoven clearly distinguishes it from woven, knitted, etc. Nonwovens are differentiated among other things according to the fiber material (e.g. the polymer in man-made fibers), the binding process, the type of fiber (staple or continuous fibers), the fiber fineness and the fiber orientation. The fibers can be laid down in a defined preferred direction or they can be oriented entirely stochastically, as in the case of random-layer nonwovens.
Wenn die Fasern keine Vorzugsrichtung in ihrer Ausrichtung (Orientierung) haben, spricht man von einem isotropen Vliesstoff. Sind die Fasern in einer Richtung häufiger angeordnet als in anderen Richtungen, dann spricht man von Anisotropie.If the fibers have no preferred direction in their alignment (orientation), one speaks of an isotropic nonwoven fabric. If the fibers are arranged more frequently in one direction than in other directions, this is called anisotropy.
Nonwovens sind also textile Flächengebilde, bei denen die Flächenbildung nicht durch Weben, Wirken, Stricken oder definiertes Legen erfolgt, sondern durch Ablegen der Fasern mit anschließender Fixierung. Wegen der vielseitigen Verwendungsmöglichkeiten und der im Vergleich zu gestrickten und gewebten Flächengebilden vergleichsweise niedrigen Produktionskosten weisen Nonwovens nach wie vor hohe jährliche Wachstumsraten auf.Nonwovens are textile fabrics in which the formation of the surface does not take place by weaving, knitting, knitting or defined laying, but by laying down the fibers with subsequent fixation. Because of the many possible uses and the comparison Nonwovens still have high annual growth rates compared to knitted and woven fabrics that are comparatively low production costs.
Die Vorteile dieser Vliesmaterialien bzw. Nonwovens liegen in einer hohen spezifischen Oberfläche, die Herstellungsverfahren erlauben eine hohe Variabilität in Dichte, Faserstärke, Porengröße oder Dicke und führen zu einer weitgehenden Flächenisotropie. Aus diesen vorteilhaften Eigenschaften ergeben sich zahlreiche Verwendungsmöglichkeiten in der Medizin für Hygieneprodukte, insbesondere Operations-Abdecktücher, Betttücher, Wundabdeckungen, Gaze usw., im Haushalt als Wischtücher aller Art und als Dekorationsvliesstoffe, insbesondere Tischdecken, Servietten, in der Bekleidungsindustrie als Einlagevliese, für technische Anwendungen, insbesondere Isoliermatten, Abdeckmatten oder als Filtervliese im Motoren- / Kraftfahrzeugbereich (z.B. Ölfilter) oder als Separatoren/Trennvliese in Batterien (
Für viele dieser Anwendungen spielt die Oberflächenspannung eine maßgebliche Rolle, so kann eine Reduzierung der Oberflächenspannung z.B. zu einem verstärkt wasserabweisenden Verhalten führen, was insbesondere für Anwendungen in der Bekleidungsindustrie, aber auch in Filtervliesen im Kraftfahrzeugbereich eine wichtige Rolle spielen kann.For many of these applications, the surface tension plays a decisive role, for example, a reduction in the surface tension can lead to an increased water-repellent behavior, which can play an important role in particular for applications in the clothing industry, but also in filter fleeces in the automotive sector.
Bei der Herstellung von Spinnvliesstoffen erfolgt die direkte Verknüpfung von Spinn- und Vliesbildungsprozess. Sowohl Schmelz- und Trockenspinnverfahren als auch Nassspinnverfahren sind für die Vliesbildung auf Basis von Endlosfasern geeignet. Als Ausgangsmaterial für die Vliesstoffe ist eine Vielzahl von faserbildenden Polymeren bekannt. Erfindungsgemäße Vliesstoffe aus Endlosmaterialien werden aus thermoplastischen Polymeren aus der Gruppe der Polyamide oder Polyestern z.B. durch Schmelzspinnen als sogenannte Meltblown-Nonwovens hergestellt. Das Verfahren des Schmelzspinnens wird beispielsweise für Polyester in
Während in Thermoplastfasern aus Polyolefinen wie z.B. bei Polypropylen- oder Polyethylenfasern aufgrund des intrinsisch hydrophoben Charakters der Polyolefine auch ohne Hilfsstoffe eine relativ niedrige Oberflächenspannung vorliegt, hat man es bei polareren Thermoplasten, bevorzugt bei Polyamiden und Polyestern, mit höheren Oberflächenspannungen zu tun. Dies führt bei zahlreichen Anwendungen, bei denen man einerseits auf niedrige Oberflächenspannungen angewiesen ist, andererseits aber - etwa wegen zu geringer Temperatur- oder Chemikalienstabilität von Polyolefinen - auf höherwertige Polymere wie Polyamide oder Polyester zurückgreifen muss, zu Schwierigkeiten. Daraus ergibt sich vielfach der Wunsch, auch polarere Thermoplaste, wie z.B. Polyamide und Polyester, dahingehend zu modifizieren, dass man bei Erhalt der bekannten Vorteile wie z.B. Temperaturstabilität, mechanische Belastbarkeit und chemische Beständigkeit gegenüber Kraftstoffen und Ölen dennoch niedrigere Oberflächenspannungen erreicht.While thermoplastic fibers made from polyolefins, such as polypropylene or polyethylene fibers, have a relatively low surface tension due to the intrinsically hydrophobic character of polyolefins, even without auxiliaries, more polar thermoplastics, preferably polyamides and polyesters, have higher surface tensions. This leads to difficulties in numerous applications in which, on the one hand, low surface tensions are required, but on the other hand, higher-quality polymers such as polyamides or polyesters have to be used, for example because polyolefins are too low in temperature or chemical stability. This often results in the desire to also use more polar thermoplastics, such as polyamides and Polyester, to be modified in such a way that, while retaining the known advantages such as temperature stability, mechanical strength and chemical resistance to fuels and oils, lower surface tensions are achieved.
Die Eigenschaften von zu verspinnenden Thermoplastfasern durch Additivierung des dazu zu verwendenden Thermoplasten zu beeinflussen wird am Beispiel von Polyestern in
Weitere Informationen zu den hier genannten Themen finden sich auch in
Nachteil all dieser Lösungen des Standes der Technik ist, dass die in dem öl- und wasserabweisenden Verhalten resultierende Veränderung der Oberflächenspannung jeweils erst nachträglich in einem zusätzlichen Verfahrensschritt durch Applikation von Hilfsstoffen auf das Gewebe realisiert werden.The disadvantage of all these prior art solutions is that the change in surface tension resulting in the oil- and water-repellent behavior is only implemented subsequently in an additional process step by applying auxiliary substances to the tissue.
Die nachträgliche Applikation auf die Oberfläche birgt abgesehen von der erhöhten Verfahrenskomplexität auch ein erhöhtes Risiko von Desorption oder Auswaschungen des Hilfsstoffes, was zum einen den gewünschten Oberflächeneffekt abschwächt, zum anderen aber auch mit einer problematischen Kontamination der Umgebung verbunden sein kann, beispielsweise einer Verunreinigung des Filtrats bei nachbehandelten Filtervliesen. Außerdem muss häufig auf fluorierte Chemikalien zurückgegriffen werden, die nicht nur sehr teuer sind, sondern auch hinsichtlich ihrer toxischen Potentiale z.B. bei der Verwertung durch Verbrennung gesondert betrachtet werden müssen.Subsequent application to the surface, apart from the increased process complexity, also entails an increased risk of desorption or leaching of the auxiliary substance, which on the one hand weakens the desired surface effect, but on the other hand can also be associated with problematic contamination of the environment, for example contamination of the filtrate with post-treated filter fleeces. In addition, fluorinated chemicals often have to be used, which are not only very expensive, but also have to be considered separately with regard to their toxic potential, e.g. when recycling by incineration.
Aufgabe der vorliegenden Erfindung war es deshalb, bereits das Polyamid- bzw. den Polyester vorab derartig zu modifizieren, dass eine Verringerung der Oberflächenspannung auch ohne Nachbehandlung der aus der entsprechenden Thermoplastfaser hergestellten Produkte möglich ist, wobei eine Reduktion der Oberflächenspannung mit möglichst wenig Materialeinsatz erzielt werden soll. Ferner sollte die Modifizierung ohne fluorhaltige Chemikalien auskommen, farbneutral und derartig ausgestaltet sein, dass der Prozess der Faserherstellung an sich nicht in inakzeptabler Weise beeinträchtigt wird. Des weiteren sollte die Modifizierung zur Verringerung der Oberflächenspannung derartig erfolgen, dass zugegebene Hilfsstoffe aufgrund ihrer Effektivität auf eine Zugabemenge begrenzt werden können, die das Schmelzespinnverfahren nicht oder nicht entscheidend beeinflussen. Die so hergestellte Faser sollte so in vielfältiger Weise zu Produkten, insbesondere zu Vliesen, Vliesstoffen, Geweben, Gestricken, Gelegen oder Gewirken mit verringerter Oberflächenspannung weiterverarbeitet werden können.The object of the present invention was therefore to modify the polyamide or polyester beforehand in such a way that a reduction in surface tension is possible even without aftertreatment of the products made from the corresponding thermoplastic fiber, with a reduction in surface tension being achieved with as little use of material as possible target. Furthermore, the modification should manage without fluorine-containing chemicals, should be color-neutral and designed in such a way that the process of fiber production per se is not impaired in an unacceptable manner. Furthermore, the modification to reduce the surface tension should take place in such a way that added auxiliaries, due to their effectiveness, can be limited to an addition amount which does not influence the melt spinning process or does not influence it decisively. The fiber produced in this way should be able to be further processed in a variety of ways into products, in particular into nonwovens, nonwovens, woven, knitted, laid or knitted fabrics with reduced surface tension.
Die Lösung der Aufgabe und Gegenstand der vorliegenden Erfindung ist ein Verfahren nach Anspruch 1 zur Reduktion der Oberflächenspannung von thermoplastbasierten Fasern, dadurch gekennzeichnet, dass man dem Thermoplasten wenigstens ein E/X Copolymerisat aus einem a-Olefin und einem Acrylsäureester oder Methacrylsäureester eines unsubstituierten aliphatischen Alkohols mit 6 bis 30 Kohlenstoffatomen zugibt und diesen nach dem Schmelzspinnverfahren verspinnt, wobei als Thermoplast Polyamid oder Polyester eingesetzt wird und der Gehalt des a-Olefins am E/X Copolymerisat zwischen 50 bis 90 Gew.% liegt.The solution to the problem and the subject matter of the present invention is a method according to claim 1 for reducing the surface tension of thermoplastic fibers, characterized in that at least one E / X copolymer of an α-olefin and an acrylic acid ester or methacrylic acid ester of an unsubstituted aliphatic alcohol is added to the thermoplastic with 6 to 30 carbon atoms is added and spun by the melt spinning process, polyamide or polyester being used as thermoplastic and the content of α-olefin in the E / X copolymer being between 50 and 90% by weight.
Es wurde überraschend gefunden, dass die Additivierung der Thermoplaste Polyamid oder Polyester mit dem erfindungsgemäß einzusetzenden E/X Copolymerisat die Oberflächenspannung der entsprechenden Thermoplastfasern und deren Folgeprodukte mit hoher Effektivität reduziert und somit beispielsweise zu einer wasserabweisenden Ausrüstung der thermoplastbasierten Fasern, bevorzugt der Polyamid- bzw. Polyesterfasern, und deren Folgeprodukte führt. Die Effektivität des erfindungsgemäß einzusetzenden Copolymerisates erlaubt bereits bei geringen Konzentrationen eine starke Absenkung der Oberflächenspannung, so dass der Schmelzespinnprozess nicht oder nicht entscheidend beeinflusst wird.It was surprisingly found that the addition of additives to the thermoplastics polyamide or polyester with the E / X copolymer to be used according to the invention reduces the surface tension of the corresponding thermoplastic fibers and their secondary products with high effectiveness and thus, for example, to a water-repellent finish of the thermoplastic-based fibers, preferably the polyamide or Polyester fibers and their derivatives. The effectiveness of the copolymer to be used according to the invention allows even at low concentrations strong reduction in surface tension, so that the melt spinning process is not or not decisively influenced.
Bevorzugt werden für das Verfahren zum Verspinnen Mischungen basierend auf 99,9 bis 10 Gew.-Teile, bevorzugt 99,5 bis 40 Gew.-Teile, besonders bevorzugt 99,0 bis 55 Gew.-Teile mindestens eines Thermoplasten und
0,1 bis 20 Gew.-Teile, vorzugsweise 0,25 bis 15 Gew.-Teile, besonders bevorzugt 0,5 bis 10 Gew.-Teile ganz besonders bevorzugt 0,75 bis 6 Gew.-Teile, insbesondere ganz besonders bevorzugt 1,0 bis 2,0 Gew.-% des oben bezeichneten E/X Copolymerisates eingesetzt.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, are preferred for the spinning process
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, particularly very particularly preferably 1 , 0 to 2.0 wt .-% of the above-mentioned E / X copolymer is used.
Bevorzugt einzusetzende thermoplastbasierte Fasern sind Fasern auf Basis thermoplastischer Polymere aus der Gruppe der Polyamide oder der Polyester.Thermoplastic fibers to be used with preference are fibers based on thermoplastic polymers from the group of polyamides or polyesters.
Besonders bevorzugt einzusetzende thermoplastbasierte Fasern aus der Gruppe der Polyamide sind Fasern auf Basis aliphatischer Polyamide.Particularly preferred thermoplastic fibers from the group of polyamides to be used are fibers based on aliphatic polyamides.
Besonders bevorzugt einzusetzende thermoplastbasierte Fasern aus der Gruppe der Polyester sind Fasern auf Basis der Polyalkylenterephthalate.Thermoplastic fibers from the group of polyesters to be used with particular preference are fibers based on polyalkylene terephthalates.
Die erfindungsgemäß zu verspinnenden thermoplastischen Polyamide können nach verschiedenen Verfahren hergestellt und aus sehr unterschiedlichen Bausteinen synthetisiert worden sein. Sie werden im speziellen Anwendungsfall allein oder in Kombination mit Verarbeitungshilfsmitteln, Stabilisatoren, polymeren Legierungspartnern, insbesondere Elastomeren, eingesetzt. Geeignet sind auch Blends mit Anteilen von anderen Polymeren, bevorzugt Blends mit Polyethylen, Polypropylen oder ABS, wobei ggf. ein oder mehrere Kompatibilisatoren eingesetzt werden können. Die Eigenschaften der Polyamide lassen sich durch Zusatz von Elastomeren verbessern, z. B. im Hinblick auf die Reißfestigkeit von z. B. besonders niederviskosen Polyamiden. Die Vielzahl der Kombinationsmöglichkeiten ermöglicht eine sehr große Zahl von Produkten mit unterschiedlichsten Eigenschaften.The thermoplastic polyamides to be spun according to the invention can be produced by various processes and synthesized from very different building blocks. In special applications, they are used alone or in combination with processing aids, stabilizers, polymeric alloy partners, in particular elastomers. Blends with proportions of other polymers are also suitable, preferably blends with polyethylene, polypropylene or ABS, it being possible to use one or more compatibilizers if necessary. The properties of the polyamides can be improved by adding elastomers, e.g. B. in terms of the tear strength of z. B. particularly low-viscosity polyamides. The multitude of possible combinations enables a very large number of products with a wide variety of properties.
Zur Herstellung von Polyamiden sind eine Vielzahl von Verfahrensweisen bekannt geworden, wobei je nach gewünschtem Endprodukt unterschiedliche Monomerbausteine, verschiedene Kettenregler zur Einstellung eines angestrebten Molekulargewichtes oder auch Monomere mit reaktiven Gruppen für später beabsichtigte Nachbehandlungen eingesetzt werden.A large number of procedures have become known for the production of polyamides, different monomer units, different chain regulators for setting a desired molecular weight or monomers with reactive groups for subsequent treatments being used depending on the desired end product.
Die technisch relevanten Verfahren zur Herstellung von Polyamiden laufen meist über die Polykondensation in der Schmelze. In diesem Rahmen wird auch die hydrolytische Polymerisation von Lactamen als Polykondensation verstanden.The technically relevant processes for the production of polyamides usually run through polycondensation in the melt. In this context, the hydrolytic polymerization of lactams is also understood as polycondensation.
Bevorzugte Polyamide (PA) sind teilkristalline Polyamide, die ausgehend von Diaminen und Dicarbonsäuren und/oder Lactamen mit wenigstens 5 Ringgliedern oder entsprechenden Aminosäuren hergestellt werden können.Preferred polyamides (PA) are semicrystalline polyamides which can be produced starting from diamines and dicarboxylic acids and / or lactams with at least 5 ring members or corresponding amino acids.
Als Edukte kommen aliphatische und/oder aromatische Dicarbonsäuren wie Adipinsäure, 2,2,4- und 2,4,4-Trimethyladipinsäure, Azelainsäure, Sebazinsäure, Isophthalsäure, Terephthalsäure, aliphatische und/oder aromatische Diamine wie z.B. Tetramethylendiamin, Hexamethylendiamin, 1,9-Nonandiamin, 2,2,4- und 2,4,4-Trimethylhexamethylendiamin, die isomeren Diamino-dicyclohexylmethane, Diaminodicyclohexylpropane, Bis-aminomethyl-cyclohexan, Phenylendiamine, Xylylendiamine, Aminocarbonsäuren wie z.B. Aminocapronsäure, bzw. die entsprechenden Lactame in Betracht. Copolyamide aus mehreren der genannten Monomeren sind eingeschlossen.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, for example, tetramethylenediamine, hexamethylenediamine, 1,9 are used as starting materials -Nonanediamine, 2,2,4- and 2,4,4-trimethylhexamethylenediamine, the isomeric diamino-dicyclohexylmethanes, diaminodicyclohexylpropane, bis-aminomethyl-cyclohexane, phenylenediamines, xylylenediamines, aminocarboxylic acids such as aminocaproic acid, or the corresponding lactams. Copolyamides made from several of the monomers mentioned are included.
Besonders bevorzugt werden Caprolactame, ganz besonders bevorzugt wird ε-Caprolactam eingesetzt.Caprolactams are particularly preferred, and ε-caprolactam is very particularly preferably used.
Besonders geeignet sind weiterhin die meisten auf PA6, PA66 und anderen aliphatischen oder/und aromatischen Polyamiden bzw. Copolyamiden basierenden Compounds, bei denen auf eine Polyamidgruppe in der Polymerkette 3 bis 11 Methylengruppen kommen.Most of the compounds based on PA6, PA66 and other aliphatic and / or aromatic polyamides or copolyamides in which there are 3 to 11 methylene groups for each polyamide group in the polymer chain are particularly suitable.
Die erfindungsgemäß hergestellten Polyamide können auch im Gemisch mit anderen Polyamiden und/oder weiteren Polymeren eingesetzt werden.The polyamides produced according to the invention can also be used in a mixture with other polyamides and / or further polymers.
Den Polyamiden können übliche Additive wie z.B. Entformungsmittel, Stabilisatoren und/oder Fließhilfsmittel zugemischt sein.Conventional additives such as mold release agents, stabilizers and / or flow aids can be mixed with the polyamides.
Die erfindungsgemäß zu verspinnenden thermoplastischen Polyester sind besonders bevorzugt teilaromatische Polyester.The thermoplastic polyesters to be spun according to the invention are particularly preferably partially aromatic polyesters.
Besonders bevorzugt zu verspinnende Polyester sind ausgewählt aus der Gruppe der Derivate der Polyalkylenterephthalate. Ganz besonders bevorzugt zu verspinnende Polyester sind ausgewählt aus der Gruppe der Polyethylenterephthalate, der Polytrimethylenterephthalate und der Polybutylenterephthalate, insbesondere besonders bevorzugt Polybutylenterephthalat und Polyethylenterephthalat, insbesondere ganz besonders bevorzugt Polybutylenterephthalat, oder Mischungen dieser Terephthalate.Polyesters to be spun with particular preference are selected from the group of derivatives of polyalkylene terephthalates. Polyesters to be spun are very particularly preferably selected from the group of polyethylene terephthalates, polytrimethylene terephthalates and polybutylene terephthalates, particularly particularly preferably polybutylene terephthalate and polyethylene terephthalate, particularly particularly preferably polybutylene terephthalate, or mixtures of these terephthalates.
Unter teilaromatischen Polyestern versteht man Materialien, die neben aromatischen Molekülteilen auch aliphatische Molekülteile enthalten.Partially aromatic polyesters are materials that contain not only aromatic parts of the molecule but also aliphatic parts of the molecule.
Polyalkylenterephthalate im Sinne der Erfindung sind Reaktionsprodukte aus aromatischen Dicarbonsäuren oder ihren reaktionsfähigen Derivaten, insbesondere Dimethylestern oder Anhydriden, und aliphatischen, cycloaliphatischen oder araliphatischen Diolen und Mischungen dieser Reaktanden.For the purposes of the invention, polyalkylene terephthalates 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.
Bevorzugte Polyalkylenterephthalate lassen sich aus Terephthalsäure (oder ihren reaktionsfähigen Derivaten) und aliphatischen oder cycloaliphatischen Diolen mit 2 bis 10 C-Atomen nach bekannten Methoden herstellen (
Bevorzugte Polyalkylenterephthalate enthalten mindestens 80 Mol-%, vorzugsweise 90 Mol-%, bezogen auf die Dicarbonsäure, Terephthalsäurereste und mindestens 80 Mol-%, vorzugsweise mindestens 90 Mol-%, bezogen auf die Diolkomponente, Ethylenglykol- und/oder Propandiol-1,3- und/oder Butandiol-1,4-reste.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 1,4-butanediol residues.
Die bevorzugten Polyalkylenterephthalate können neben Terephthalsäureestern bis zu 20 Mol-% Reste anderer aromatischer Dicarbonsäuren mit 8 bis 14 C-Atomen oder Reste aliphatischer Dicarbonsäuren mit 4 bis 12 C-Atomen enthalten, insbesondere Reste von Phthalsäure, Isophthalsäure, Naphthalin-2,6-dicarbonsäure, 4,4'-Diphenyldicarbonsäure, Bernstein-, Adipin-, Sebacinsäure, Azelainsäure, Cyclohexandiessigsäure, Cyclohexandicarbonsäure.In addition to terephthalic acid esters, the preferred polyalkylene terephthalates can contain up to 20 mol% of residues of other aromatic dicarboxylic acids with 8 to 14 carbon atoms or residues of aliphatic dicarboxylic acids with 4 to 12 carbon atoms, in particular residues of phthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid , 4,4'-diphenyldicarboxylic acid, succinic, adipic, sebacic acid, azelaic acid, cyclohexanediacetic acid, cyclohexanedicarboxylic acid.
Die bevorzugten Polyalkylenterephthalate können neben Ethylen- bzw. Propandiol-1,3- bzw. Butandiol-1,4-glykolresten bis zu 20 Mol-% anderer aliphatischer Diole mit 3 bis 12 C-Atomen oder cycloaliphatischer Diole mit 6 bis 21 C-Atomen enthalten, insbesondere. Reste von Propandiol-1,3, 2-Ethylpropandiol-1,3, Neopentylglykol, Pentan-diol-1,5, Hexandiol-1.6, Cyclohexan-dimethanol-1,4, 3-Methylpentandiol-2,4, 2-Methylpentandiol-2,4, 2,2,4-Trimethylpentandiol-1,3 und -1,6,2-Ethylhexandiol-1,3 2,2-Diethylpropandiol-1,3, Hexandiol-2,5, 1,4-Di-(ß-hydroxyethoxy)-benzol, 2,2-Bis-(4-hydroxycyclohexyl)-propan, 2,4-Dihydroxy-1,1,3,3-tetramethyl-cyclobutan, 2,2-bis-(3-ß-hydroxyethoxyphenyl)-propan oder 2,2-bis-(4-hydroxypropoxyphenyl)-propan (
Die Polyalkylenterephthalate können durch Einbau relativ kleiner Mengen 3- oder 4-wertiger Alkohole oder 3- oder 4-basischer Carbonsäuren, wie sie z.B. in der
Es ist ratsam, nicht mehr als 1 Mol-% des Verzweigungsmittels, bezogen auf die Säurekomponente, zu verwenden.It is advisable not to use more than 1 mole percent of the branching agent based on the acid component.
Besonders bevorzugt sind Polyalkylenterephthalate, die allein aus Terephthalsäure und deren reaktionsfähigen Derivaten, insbesondere deren Dialkylestern, und Ethylenglykol und/oder Propandiol-1,3 und/oder Butandiol-1,4 hergestellt werden, insbesondere Polyethylen- und Polybutylenterephthalat, und Mischungen dieser Polyalkylenterephthalate.Particularly preferred are polyalkylene terephthalates which are produced solely from terephthalic acid and its reactive derivatives, in particular its 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.
Bevorzugte Polyalkylenterephthalate sind auch Copolyester, die aus mindestens zwei der obengenannten Säurekomponenten und/oder aus mindestens zwei der obengenannten Alkoholkomponenten hergestellt werden, besonders bevorzugte Copolyester sind Poly-(ethylenglykol/butandiol-1,4)-terephthalate.Preferred polyalkylene terephthalates are also copolyesters which are produced 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 / 1,4-butanediol) terephthalates.
Die Polyalkylenterephthalate besitzen im allgemeinen eine intrinsische Viskosität von ca. 0,3 dl/g bis 1,5 cm3/g, vorzugsweise 0,4 dl/g bis 1,3 dl/g, besonders bevorzugt 0,5 dl/g bis 1,0 dl/g jeweils gemessen in Phenol/o-Dichlorbenzol (1:1 Gew.-Teile) bei 25°C.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 phenol / o-dichlorobenzene (1: 1 parts by weight) at 25 ° C.
Die erfindungsgemäß bevorzugt zu verspinnenden thermoplastischen Polyester können auch im Gemisch mit anderen Polyestern und/oder weiteren Polymeren eingesetzt werden. Ganz besonders bevorzugt werden Polyethylenterephthalat (PET), Polypropylenterephthalat oder Polybutylenterephthalat (PBT) oder deren Mischungen eingesetzt, insbesondere wird Polybutylenterephthalat eingesetzt.The thermoplastic polyesters to be spun with preference according to the invention can also be used in a mixture with other polyesters and / or further polymers. Polyethylene terephthalate (PET), polypropylene terephthalate or polybutylene terephthalate (PBT) or mixtures thereof are very particularly preferably used; in particular, polybutylene terephthalate is used.
Des weiteren können auch recycelte Polyester aus Post- oder Pre-Consumer Rezyklaten alleine oder in der Mischung eingesetzt werden, wobei Polyester-Rezyklate aus Getränkeflaschen, sogenannte PET-Copolyester, bevorzugt sind. Ein Beispiel hierfür wäre das PET Plus80® der Fa. PET Kunststoffrecycling GmbH, Beselich-Obertiefenbach, Deutschland.Furthermore, recycled polyesters from post or pre-consumer recyclates can also be used alone or in a mixture, polyester recyclates from beverage bottles, so-called PET copolyesters, being preferred. An example is the PET Plus80 ® from. PET plastic recycling GmbH, Beselich-Obertiefenbach, Germany.
Insbesondere bevorzugt für das Schmelzspinnverfahren einzusetzende Polyester sind Poly(C2-4-alkylen)terephthalate, welche bis zu 15 Mol-% andere Dicarbonsäuren und/oder Diole, insbesondere Isophthalsäure, Adipinsäure, Diethylenglykol, Polyethylenglykol, 1,4-Cycloehexandimethanol, oder die jeweils anderen C2-4-Alkylenglykole, enthalten. Bevorzugt ist Polyethylenterephthalat mit einer Intrinsic Viskosität (I.V.) im Bereich von 0,5 bis 1,4 dl/g, Polypropylenterephthalat mit einer I.V. von 0,7 bis 1,6 dl/g oder Polybutylenterephthalat mit einer I.V. von 0,5 bis 1,8 dl/g, wobei Polyethylenterephthalat mit einer Intrinsic Viskosität (I.V.) im Bereich von 0,6 bis 1,0 dl/g oder Polybutylenterephthalat mit einer I.V. von 0,6 bis 0,9 dl/g besonders bevorzugt ist. Poly (C 2-4 alkylene) terephthalates, which contain up to 15 mol% of other dicarboxylic acids and / or diols, in particular isophthalic acid, adipic acid, diethylene glycol, polyethylene glycol, 1,4-cyclohexanedimethanol, or the polyesters to be used for the melt spinning process are particularly preferred each other C 2-4 alkylene glycols contain. Polyethylene terephthalate with an intrinsic viscosity (IV) in the range from 0.5 to 1.4 dl / g, polypropylene terephthalate with an IV of 0.7 to 1.6 dl / g or polybutylene terephthalate with an IV of 0.5 to 1 is preferred , 8 dl / g, with polyethylene terephthalate with an intrinsic viscosity (IV) in the range from 0.6 to 1.0 dl / g or polybutylene terephthalate with an IV of 0.6 to 0.9 dl / g being particularly preferred.
Zur Reduktion der Oberflächenspannung enthalten die erfindungsgemäß zu verspinnenden Thermoplaste statistische E/X Copolymerisate aus E mindestens einem α-Olefm mit X einem Methacrylsäureester oder Acrylsäureester eines unsubstituierten aliphatischen Alkohols Bevorzugte α-Olenne als Bestandteil E der Copolymerisate weisen bevorzugt zwischen 2 und 10 Kohlenstoff-Atomen auf und können unsubstituiert oder mit einer oder mehreren aliphatischen, cycloaliphatischen oder aromatischen Gruppen substituiert sein. Bevorzugte α-Olenne sind ausgewählt aus der Gruppe umfassend Ethen, Propen, 1-Buten, 1-Penten, 1-Hexen, 1-Octen, 3-Methyl-1-penten. Besonders bevorzugte α-Olenne sind Ethen und Propen, ganz besonders bevorzugt ist Ethen. Ebenfalls geeignet sind Mischungen der beschriebenen α-Olefine.To reduce the surface tension, the thermoplastics to be spun according to the invention contain random E / X copolymers of E at least one α-olefin with X a methacrylic acid ester or acrylic acid ester of an unsubstituted aliphatic alcohol. Preferred α-olens as constituent E of the copolymers preferably have between 2 and 10 carbon atoms and can be unsubstituted or substituted by one or more aliphatic, cycloaliphatic or aromatic groups. Preferred α-olennes are selected from the group comprising ethene, propene, 1-butene, 1-pentene, 1-hexene, 1-octene, 3-methyl-1-pentene. Particularly preferred α-olennes are ethene and propene, and ethene is very particularly preferred. Mixtures of the α-olefins described are also suitable.
Der Gehalt des a-Olefins am E/X Copolymerisat liegt zwischen 50 bis 90 Gew.-%, bevorzugt zwischen 55 und 75 Gew.-%.The content of the α-olefin in the E / X copolymer is between 50 and 90% by weight, preferably between 55 and 75% by weight.
Das E/X Copolymerisat wird weiterhin definiert durch den zweiten Bestandteil neben dem α-Olefin. Als zweiter Bestandteil sind Alkyl- oder Arylalkylester der Acrylsäure oder Methacrylsäure geeignet, deren Alkyl- oder Arylalkylgruppe aus 5-30 Kohlenstoffatomen gebildet wird und keine oder nur eine geringe Konzentration an reaktiven Funktionen ausgewählt aus der Gruppe umfassend Epoxide, Oxetane, Anhydride, Imide, Aziridine, Furane, Säuren, Amine enthält. Die Alkyl- oder Arylalkylgruppe kann dabei linear oder verzweigt sein sowie cycloaliphatische oder aromatische Gruppen enthalten, daneben auch durch eine oder mehrere Ether- oder Thioetherfunktionen substituiert sein. Geeignete Methacrylsäure- oder Acrylsäureester in diesem Zusammenhang sind auch solche, die aus einer Alkoholkomponente synthetisiert wurden, die auf Oligoethylenglycol oder Oligopropylenglycol mit nur einer Hydroxylgruppe und maximal 30 C-Atomen basieren.The E / X copolymer is also defined by the second component in addition to the α-olefin. As a second component, alkyl or arylalkyl esters of acrylic acid or methacrylic acid are suitable, the alkyl or arylalkyl group of which 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 can be linear or branched and contain cycloaliphatic or aromatic groups, and also be substituted by one or more ether or thioether functions. Suitable methacrylic or acrylic acid esters in this context are also those which have been synthesized from an alcohol component which are based on oligoethylene glycol or oligopropylene glycol with only one hydroxyl group and a maximum of 30 carbon atoms.
Bevorzugt wird die Alkyl- oder Arylalkylgruppe des Methacrylsäure- oder Acrylsäureesters ausgewählt aus der Gruppe umfassend, 1-Hexyl, 2-Hexyl, 3-Hexyl, 1-Heptyl, 3-Heptyl, 1-Octyl, 1-(2-Ethyl)-hexyl, 1-Nonyl, 1-Decyl, 1-Dodecyl, 1-Lauryl oder 1-Octadecyl. Besonders bevorzugt sind unsubstituierte Alkyl- oder Arylalkylgruppen mit 6-20 Kohlenstoffatomen, insbesondere bevorzugt mit 8-20 Kohlenstoffatomen. Bevorzugt sind insbesondere auch verzweigte Alkylgruppen, die im Vergleich zu linearen Alkylgruppen gleicher Anzahl an Kohlenstoffatomen zu einer niedrigeren Glasübergangs-Temperatur TG führen.The alkyl or arylalkyl group of the methacrylic acid or acrylic acid ester is preferably selected from the group comprising 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. Unsubstituted alkyl or arylalkyl groups with 6-20 carbon atoms, particularly preferably with 8-20 carbon atoms, are particularly preferred. Also preferred are branched alkyl groups which, compared to linear alkyl groups with the same number of carbon atoms, lead to a lower glass transition temperature T G.
Erfindungsgemäß besonders bevorzugt sind Copolymerisate bei denen das α-Olefm mit Acrylsäure-(2-ethyl)-hexylester copolymerisiert wird.Particularly preferred according to the invention are copolymers in which the α-olefin is copolymerized with (2-ethyl) hexyl acrylate.
Ebenfalls geeignet sind Mischungen der beschriebenen Acrylsäureester oder Methacrylsäurester.Mixtures of the acrylic acid esters or methacrylic acid esters described are also suitable.
Der Gehalt der Acrylsäureester oder Methacrylsäureester am Copolymerisat liegt zwischen 10 bis 50 Gew.-%, bevorzugt zwischen 25 und 45 Gew.-%.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.
Insbesondere geeignete Copolymerisate werden ausgewählt aus der Gruppe der von der Fa. Arkema unter dem Markennamen Lotryl® EH angebotenen Materialien, die teilweise auch als Schmelzkleber Verwendung finden.Particularly suitable copolymers are selected from the group of by the company. Arkema under the trade name Lotryl EH ® offered materials, which are also as hot melt adhesive use.
Erfindungsgemäß insbesondere bevorzugt ist deshalb ein Verfahren zur Reduktion der Oberflächenspannung Polyester-basierter Fasern oder Polyamid-basierter Fasern, dadurch gekennzeichnet, dass ein E/X Copolymerisat aus Ethylen und einem Acrylsäureester eines unsubstituierten aliphatischen Alkohols mit 6 bis 30 Kohlenstoffatomen, bevorzugt aus E Ethylen und X einem Acrylsäureester mit 6 bis 20 Kohlenstoffatomen, besonders bevorzugt aus E Ethylen und X 2-Ethylhexylacrylat dem Thermoplasten zugesetzt wird und man die Mischung anschließend nach dem Schmelzspinnverfahren verspinnt.According to the invention, therefore, a method for reducing the surface tension of polyester-based fibers or polyamide-based fibers is particularly preferred, characterized in that an E / X copolymer of ethylene and an acrylic acid ester of an unsubstituted aliphatic alcohol having 6 to 30 carbon atoms, preferably of E and ethylene X an acrylic acid ester with 6 to 20 carbon atoms, particularly preferably composed of E ethylene and X 2-ethylhexyl acrylate, is added to the thermoplastic and the mixture is then spun by the melt spinning process.
Erfindungsgemäß insbesondere bevorzugt ist deshalb ein Verfahren zur Reduktion der Oberflächenspannung Polyester-basierter Fasern, dadurch gekennzeichnet, dass ein E/X Copolymerisat aus Ethylen und einem Acrylsäureester eines unsubstituierten aliphatischen Alkohols mit 6 bis 30 Kohlenstoffatomen, bevorzugt aus E Ethylen und X einem Acrylsäureester mit 6 bis 20 Kohlenstoffatomen, besonders bevorzugt aus E Ethylen und X 2-Ethylhexylacrylat dem Thermoplasten zugesetzt wird und man die Mischung anschließend nach dem Schmelzspinnverfahren verspinnt.According to the invention, therefore, a method for reducing the surface tension of polyester-based fibers is particularly preferred, characterized in that an E / X copolymer of ethylene and an acrylic acid ester of an unsubstituted aliphatic alcohol with 6 to 30 carbon atoms, preferably E ethylene and X an acrylic acid ester with 6 up to 20 carbon atoms, particularly preferably from E ethylene and X 2-ethylhexyl acrylate, is added to the thermoplastic and the mixture is then spun by the melt spinning process.
Erfindungsgemäß insbesondere bevorzugt ist deshalb ein Verfahren zur Reduktion der Oberflächenspannung Polyamid-basierter Fasern, dadurch gekennzeichnet, dass ein E/X Copolymerisat aus Ethylen und einem Acrylsäureester eines unsubstitutierten aliphatischen Alkohols mit 6 bis 30 Kohlenstoffatomen, bevorzugt aus E Ethylen und X einem Acrylsäureester mit 6 bis 20 Kohlenstoffatomen, besonders bevorzugt aus E Ethylen und X 2-Ethylhexylacrylat dem Thermoplasten zugesetzt wird und man die Mischung anschließend nach dem Schmelzspinnverfahren verspinnt. Die der z.B durch Verspinnen zu verarbeitenden Polyamid- bzw. Polyestermischung zuzusetzende Menge des Copolymerisats wurde bereits oben angegeben, wobei meist Zugabemengen von ≤ 6 Gew.-% genügen. Bevorzugt wird die Konzentration des Copolymerisats im Bereich 0,75 bis 6,0 Gew.-% in Abhängigkeit von der gewünschten Abzugsgeschwindigkeit (> 700-1500 m/min) so gewählt, dass die Doppelbrechung der Faser < 3,5·10-3 ist. Solche Doppelbrechungen in der Faser erlauben Verstreckverhältnisse von 1:5 und sichern die gewünschten hohen Fadenfestigkeiten unabhängig von der Spinnabzugsgeschwindigkeit von bis zu 1500 m/min bei Aufspulgeschwindigkeiten von deutlich über 3800 m/min.According to the invention, therefore, a method for reducing the surface tension of polyamide-based fibers is particularly preferred, characterized in that an E / X copolymer of ethylene and an acrylic acid ester of an unsubstituted aliphatic alcohol with 6 to 30 carbon atoms, preferably E ethylene and X an acrylic acid ester with 6 up to 20 carbon atoms, particularly preferably from E ethylene and X 2-ethylhexyl acrylate, is added to the thermoplastic and the mixture is then spun by the melt spinning process. The amount of the copolymer to be added to the polyamide or polyester mixture to be processed, for example by spinning, has already been specified above, with amounts of 6% by weight usually being sufficient. The concentration of the copolymer is preferably selected in the range from 0.75 to 6.0% by weight, depending on the desired take-off speed (> 700-1500 m / min), so that the birefringence of the fiber is <3.5 · 10-3 is. Such birefringence in the fiber allow drawing 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 winding speeds of well over 3800 m / min.
Übliche Zusatzstoffe, bevorzugt Farbstoffe, weitere Hydrophobisierungsmittel, Mattierungsmittel, Stabilisatoren, Antistatika, Gleitmittel, Verzweigungsmittel, können den erfindungsgemäßen Thermoplast-Copolymerisat-Gemischen in Mengen von 0,001 bis 5,0 Gew.-% ohne Nachteil zugesetzt werden.Usual additives, preferably dyes, further hydrophobizing agents, matting agents, stabilizers, antistatic agents, lubricants, branching agents, can add to the invention Thermoplastic copolymer mixtures can be added in amounts of 0.001 to 5.0% by weight without any disadvantage.
Bevorzugt einzusetzende Farbstoffe sind Dispersionsfarbstoffe, insbesondere solche auf Azofarbstoff-Basis oder solche auf Basis sehr feinteiliger RußeDyes to be used with preference are disperse dyes, in particular those based on azo dye or those based on very finely divided carbon blacks
Bevorzugt einzusetzende Mattierungsmittel sind mikrokristalline Anatase mit einer durchschnittlichen Partikelgröße [d50] von 0,25 bis 0,35µm, die wahlweise auch mit einer organischen oder anorganischen Oberflächenbehandlung ausgestattet sein können.Matting agents to be used with preference are microcrystalline anatases with an average particle size [d50] of 0.25 to 0.35 μm, which can optionally also be provided with an organic or inorganic surface treatment.
Bevorzugt einzusetzende Stabilisatoren sind z.B. aromatische Polycarbodiimide wie z.B. Stabaxol P der Fa. Rheinchemie in Mannheim, Deutschland aber auch Hitzestabilisatoren auf Basis organisch derivatisierter Phosphite.Stabilizers to be used with preference are, for example, aromatic polycarbodiimides such as Stabaxol P from Rheinchemie in Mannheim, Germany, but also heat stabilizers based on organically derivatized phosphites.
Bevorzugt einzusetzende Antistatika sind insbesondere feinteilige Leitruße oder Kohlenstoffnanoröhren (engl. "carbon nanotubes").Antistatic agents to be used with preference are, in particular, finely divided conductive blacks or carbon nanotubes.
Bevorzugt einzusetzende Gleitmittel sind insbesondere langkettige Fettsäuren, bevorzugt Stearinsäure oder Behensäure, deren Salze, bevorzugt Ca- oder Zn-Stearat, sowie deren Esterderivate, sowie niedermolekulare Polyethylen- bzw. Polypropylenwachse. Erfindungsgemäß werden als Montanwachse Mischungen geradkettiger, gesättigter Carbonsäuren mit Kettenlängen von 28 bis 32 C-Atomen verstanden. Bevorzugte Gleit- und/oder Entformungsmittel sind Verbindungen aus der Gruppe der niedermolekularen Polyethylenwachse sowie aus der Gruppe der Amide oder Ester gesättigter oder ungesättigter aliphatischer Carbonsäuren mit 8 bis 40 C-Atomen mit aliphatischen gesättigten Aminen oder Alkoholen mit 2 bis 40 C-Atomen. Ethylen-bis-stearylamid und Pentaerythrit-tetrastearat (PETS) sind erfindungsgemäß ganz besonders bevorzugt, Pentaerythrit-tetrastearat (PETS) ist insbesondere ganz besonders bevorzugt.Lubricants to be used with preference are, in particular, long-chain fatty acids, preferably stearic acid or behenic acid, their salts, preferably Ca or Zn stearate, and their ester derivatives, and low molecular weight polyethylene or polypropylene waxes. According to the invention, montan waxes are mixtures of straight-chain, saturated carboxylic acids with 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 with 8 to 40 carbon atoms with aliphatic saturated amines or alcohols with 2 to 40 carbon atoms. Ethylene bis-stearylamide and pentaerythritol tetrastearate (PETS) are very particularly preferred according to the invention, pentaerythritol tetrastearate (PETS) is especially very particularly preferred.
Bevorzugt einzusetzende Verzweigungsmittel sind aufschmelzbare modifizierte Bisphenol-A Epichlorhydrinharze wie z.B. Araldite GY764CH oder Araldite GT7071 der Fa. Huntsman in Everberg, Belgien.Preferred branching agents are meltable, modified bisphenol-A epichlorohydrin resins such as Araldite GY764CH or Araldite GT7071 from Huntsman in Everberg, Belgium.
Das Vermischen des erfindungsgemäß einzusetzenden Copolymerisats mit dem Polyamid bzw. mit dem Polyester (=Matrixpolymer) erfolgt durch Compoundierung, bevorzugt mittels Mischelementen in einem Extruder, unter Verwendung statischer Mischer oder mittels anderer geeigneter Vorrichtungen, welche die zwei oder mehr Komponenten miteinander mischen können. Die Schmelze kann optional zu einem Strang ausgetragen, abgekühlt und granuliert werden.The copolymer to be used according to the invention is mixed with the polyamide or with the polyester (= matrix polymer) by compounding, preferably by means of mixing elements in an extruder, using static mixers or by means of other suitable devices which can mix the two or more components with one another. The melt can optionally be discharged into a strand, cooled and granulated.
Auch sogenannte Masterbatch-Techniken sind möglich, wobei das Copolymerisat als Konzentrat oder reine Substanz mit den Polyestergranulat gemischt wird.So-called masterbatch techniques are also possible, in which the copolymer is mixed with the polyester granulate as a concentrate or pure substance.
Die Vermischung der Einzelkomponenten kann aber auch direkt in der Spinn- oder Meltblow-Anlage erfolgen, wobei die Komponenten physikalisch vorgemischt über eine Dosierstelle oder aber separat über mehrere Dosierstellen eingebracht werden können. Auch der Zusatz zu einem Teilstrom des Matrix-Polymers, der dann dem Hauptstrom des Matrix-Polymers zugemischt wird, ist praktikabel. Vorteilhafterweise wird dort durch spezifische Wahl des Mischers und der Dauer des Mischvorgangs eine definierte Verteilung eingestellt, bevor die Schmelzemischung durch Produktverteilungsleitungen zu den einzelnen Spinnstellen und Spinndüsen weitergeleitet wird. Mischer mit einer Scherrate von 16 bis 128 sec-1 haben sich bewährt. Dabei soll das Produkt aus Scherrate (sec-1) und der 0,8ten Potenz der Verweilzeit (in sec) vorzugsweise 250 - 2500, besonders bevorzugt 350 bis 1250 betragen. Werte über 2500 werden im Allgemeinen vermieden, um den Druckabfall in den Rohrleitungen limitiert zu halten. Zur Klarstellung sei angemerkt, dass der Begriff Thermoplast im Rahmen der vorliegenden Erfindung auch mit Polymer umschrieben wird.The mixing of the individual components can, however, also take place directly in the spinning or meltblow system, whereby the components can be physically premixed via a metering point or introduced separately via several metering points. The addition to a partial flow of the matrix polymer, which is then mixed into the main flow of the matrix polymer, is also practicable. A defined distribution is advantageously set there by specific selection of the mixer and the duration of the mixing process before the melt mixture is passed on through product distribution lines to the individual spinning stations and spinning nozzles. Mixers with a shear rate of 16 to 128 sec -1 have proven effective. The product of the shear rate (sec -1 ) and the 0.8th power of the residence time (in sec) should preferably be 250-2500, particularly preferably 350-1250. Values above 2500 are generally avoided in order to limit the pressure drop in the pipelines. For clarification, it should be noted that the term thermoplastic is also circumscribed as polymer in the context of the present invention.
Hierbei ist die Scherrate definiert durch die Scherrate im Leerrohr (sec-1) mal dem Mischerfaktor, wobei der Mischerfaktor eine charakteristische Kenngröße des Mischertyps ist. Für Sulzer-SMX-Typen beispielsweise beträgt dieser Faktor etwa 7-8. Die Scherrate γ im Leerrohr berechnet sich gemäß
- F =
- Fördermenge des Polymeren (g/min)
- V2 =
- Innenvolumen des Leerrohres (cm3)
- R =
- Leerrohrradius (mm)
- ε =
- Leervolumenanteil (bei Sulzer-SMX-Typen 0,84 bis 0,88)
- δ =
- Nenndichte der Polymermischung in der Schmelze (etwa 1,2 g/cm3).
- F =
- Polymer flow rate (g / min)
- V2 =
- Internal volume of the empty pipe (cm 3 )
- R =
- Conduit radius (mm)
- ε =
- Empty volume percentage (for Sulzer SMX types 0.84 to 0.88)
- δ =
- Nominal density of the polymer mixture in the melt (about 1.2 g / cm 3 ).
Sowohl das Vermischen der Polymere als auch das nachfolgende Verspinnen der Polymermischung erfolgt bei Temperaturen, je nach Matrix-Polymer, bevorzugt im Bereich von 5 bis 85°C, besonders bevorzugt von 30 bis 70°C jeweils oberhalb der Schmelztemperatur des Matrix-Polymers. Für PET werden vorzugsweise Temperaturen von 265 bis 340°C eingestellt, für PA6 und PBT vorzugsweise 225 bis 300°C.Both the mixing of the polymers and the subsequent spinning of the polymer mixture take 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 preferably set for PET, and 225 to 300 ° C. for PA6 and PBT.
Die Herstellung von Vliesen aus den erfindungsgemäß einzusetzenden Thermoplasten erfolgt z.B. in einer Meltblown-Anlage. Dort werden die Komponenten in einem Extruder erhitzt und auf einen hohen Druck gebracht. Die Schmelze wird dann nach optionaler Vorfiltration durch ein geeignetes Filterpaket in genauer Dosierung mittels der Spinnpumpen durch eine Matrize, den so genannten Spinnbalken (Spinerette) gepresst. Das Polymer tritt aus der Düsenplatte als feine Faser - in der textilen Terminologie auch Filament genannt - noch in geschmolzener Form aus. Durch einen Luftstrom wird es abgekühlt und noch aus der Schmelze gestreckt. Der Luftstrom befördert die Filamente auf z.B. ein Förderband, das als Sieb ausgebildet ist oder auf eine poröse Trommel oder auf ein einlaufendes Substrat wie z. B. Papier. Durch eine Absaugung unter dem Siebband werden die Fäden fixiert. Dieses Fasergelege ist ein Wirrlagen-Vlies, das verfestigt werden muss. Die Verfestigung kann z.B. durch zwei beheizte Walzen (Kalander) oder durch einen Dampfstrom erfolgen. Bei der Verfestigung durch einen Kalander ist meist eine der beiden Walzen mit einer Gravur versehen, die aus Punkten, kurzen Rechtecken oder rautenförmigen Punkten besteht. An den Kontaktpunkten verschmelzen die Filamente und bilden so den Vliesstoff. Leichtere Vliesstoffe können ausschließlich auf diesem Wege (thermobondiert) hergestellt werden, schwerere Vliesstoffe werden mit einem zweiten eingearbeiteten niedrigschmelzenden Polymer hergestellt, wobei bei einem Durchgang durch einen sogenannten Fixierofen der Schmelzkleber aufgeschmolzen wird und die Matrixfasern meist an ihren Kreuzungspunkten zusammengeklebt und die gewünschten Vliesfestigkeiten somit gewährleistet werden. Eine weitere Möglichkeit der Verfestigung ist die Wasserstrahlverfestigung, bei der Wasserstrahlen mit Wasserdrücken bis zu 400 bar auf das noch unverfestigte Vlies auftreffen.The manufacture of nonwovens from the thermoplastics to be used according to the invention takes place, for example, in a meltblown system. There the components are heated in an extruder and brought to high pressure. After optional pre-filtration, the melt is then pressed through a suitable filter package in precise doses by means of the spinning pumps through a die, the so-called spinning bar. The polymer emerges from the nozzle plate as a fine fiber - also called filament in textile terminology - still in molten form. It is cooled by a stream of air and then stretched out of the melt. The air flow conveys the filaments onto, for example, a conveyor belt in the form of a sieve or onto a porous drum or onto an incoming substrate such as e.g. B. paper. The threads are fixed by suction under the sieve belt. This fiber structure is a random fleece that has to be consolidated. The solidification can take place, for example, with two heated rollers (calenders) or with a stream of steam. When solidifying by means of a calender, one of the two rollers is usually provided with an engraving, which consists of points, short rectangles or diamond-shaped points. The filaments fuse at the contact points and thus form the nonwoven fabric. Lighter nonwovens can only be produced in this way (thermobonded), heavier nonwovens are produced with a second incorporated low-melting polymer, whereby the hot-melt adhesive is melted when passing through a so-called fixing oven and the matrix fibers are usually glued together at their intersection points, thus ensuring the desired strength of the nonwoven will. Another possibility of consolidation is hydroentanglement, in which water jets with water pressures of up to 400 bar strike the non-woven fabric that has not yet been consolidated.
Im Meltblown-Verfahren werden typischerweise folgende Parameter eingesetzt:
- Faserdurchmesser 0,1 µm bis 20 µm, bevorzugt 1 bis 10µm
- Vliesbreite bis zu 5000 - 6000 mm
- Lufttemperatur 230 bis 400 °C, bevorzugt 290° bis 370°C
- Luftgeschwindigkeit 0,5 - 0,8 -fache Schallgeschwindigkeit
- Flächengewicht 8 bis 350 g/m2, typischerweise 20 bis 200 g/m2
- Bohrungen im Düsenbalken (Spinnerette) ∅ 100 to 500 µm mit 1 bis 6 Bohrungen / mm
- Fiber diameter 0.1 µm to 20 µm, preferably 1 to 10 µm
- Fleece width up to 5000 - 6000 mm
- Air temperature 230 to 400 ° C, preferably 290 ° to 370 ° C
- Air speed 0.5 - 0.8 times the speed of sound
- Basis weight 8 to 350 g / m 2 , typically 20 to 200 g / m 2
- Bores in the nozzle bar (spinnerette) ∅ 100 to 500 µm with 1 to 6 bores / mm
Die Herstellung von hochfesten Filamenten aus den erfindungsgemäß einzusetzenden thermoplastbasierten Mischungen, bevorzugt den Polyamid- bzw. Polyestermischungen, erfolgt bevorzugt durch Spinnen mit Abzugsgeschwindigkeiten von > 700 m/min, besonders bevorzugt 750 bis 1000 m/min, und Verstrecken, Thermofixieren und Aufwickeln mit einer entsprechenden Geschwindigkeit. Dies geschieht unter Verwendung an sich bekannter Spinneinrichtungen.The production of high-strength filaments from the thermoplastic-based mixtures to be used according to the invention, preferably the polyamide or polyester mixtures, is preferably carried out by spinning at take-off speeds of> 700 m / min, particularly preferably 750 to 1000 m / min, and drawing, heat setting and winding with a appropriate speed. This is done using spinning devices known per se.
Typisch für hochfeste Filamente aus Polyamid bzw. Polyester ist es, dass sie nach dem Schmelzspinnverfahren in großen Direktschmelze-Spinnanlagen hergestellt werden, in denen die Schmelze über beheizte Produktleitungen auf die einzelnen Spinnlinien und innerhalb der Linien auf die einzelnen Spinnsysteme verteilt wird. Hierbei stellt eine Spinnlinie eine Aneinanderreihung von mindestens einer Reihe von Spinnsystemen dar und ein Spinnsystem die kleinste Spinneinheit mit einem Spinnkopf, der mindestens ein Spinndüsenpaket einschließlich Spinndüsenplatten enthält. Die Schmelze unterliegt in derartigen Systemen einer hohen thermischen Belastung bei Verweilzeiten bis 35 min. Die Effektivität des erfindungsgemäß zur Reduktion der Oberflächenspannung einzusetzenden Copolymerisats führt dabei infolge der hohen thermischen Stabilität des Copolymerisats zu keinen nennenswerten Einschränkungen seiner Wirkung, so dass abhängig von der gewünschten Reduktion der Oberflächenspannung auch geringe Zugabemengen des Additives z.B. ≤ 2,0 % und in vielen Fällen auch ≤ 1,5 % trotz hoher thermischer Belastung ausreichen.It is typical for high-strength filaments made of polyamide or polyester that they are produced according to the melt spinning process in large direct melt spinning systems in which the melt is distributed over heated product lines to the individual spinning lines and within the lines to the individual spinning systems. Here, a spinning line represents a string of at least one row of spinning systems and a spinning system is the smallest spinning unit with a spinning head that contains at least one spinneret package including spinneret plates. In systems of this type, the melt is subject to high thermal stress with residence times of up to 35 minutes Surface tension even small amounts of the additive, eg ≤ 2.0% and in many cases ≤ 1.5% are sufficient despite high thermal loads.
Der erfindungsgemäß einzusetzende Düsenblock weist vorzugsweise mindestens 20, bevorzugt 150 bis 1500 und besonders bevorzugt 500 bis 1000 Düsenlöcher pro Meter Düsenbreite auf. Hinsichtlich des Durchmessers der Düsenlöcher sind dabei Durchmesser von 0,05 bis 1 mm und besonders von 0,3 bis 0,5 mm bevorzugt.The nozzle block to be used according to the invention preferably has at least 20, preferably 150 to 1500 and particularly preferably 500 to 1000 nozzle holes per meter of nozzle width. With regard to the diameter of the nozzle holes, diameters from 0.05 to 1 mm and particularly from 0.3 to 0.5 mm are preferred.
Die Düsenaustrittsgeschwindigkeit beträgt bevorzugt 1 bis 20 m/min, besonders bevorzugt jedoch 3 bis 10 m/min. Durch den anliegenden Heißstrom werden die extrudierten Fäden vorzugsweise auf das 50- bis 800-fache ihrer Länge nach dem Düsenaustritt verstreckt, was zu Spinngeschwindigkeiten von bis zu 10 000 m/min führt.The nozzle exit speed is preferably 1 to 20 m / min, but particularly preferably 3 to 10 m / min. The extruded threads are preferably stretched to 50 to 800 times their length after the nozzle outlet due to the hot current applied, which leads to spinning speeds of up to 10,000 m / min.
Die vorliegende Erfindung betrifft auch die Verwendung wenigstens eines Copolymerisats aus mindestens einem α-Olefm und mindestens einem Acrylsäureester oder Methacrylsäureester zur Reduktion der Oberflächenspannung thermoplastbasierter Fasern oder Filamente, bevorzugt Polyester basierter Fasern oder Filamente oder Polyamid basierter Fasern oder Filamente, insbesondere bevorzugt Polyester basierter Fasern oder Filamente.The present invention also relates to the use of at least one copolymer of at least one α-olefin and at least one acrylic acid ester or methacrylic acid ester for reducing 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.
Die vorliegende Erfindung betrifft ferner Fasern oder Filamente mit reduzierter Oberflächenspannung erhältlich durch Schmelzspinnen thermoplastbasierter Fasern oder Filamente die mit wenigstens einem Copolymerisat aus mindestens einem α-Olefm und mindestens einem Acrylsäsureester oder Methacrylsäureester eines aliphatischen Alkohols additiviert sind.The present invention further relates to fibers or filaments with reduced surface tension obtainable by melt-spinning thermoplastic-based fibers or filaments which are additized with at least one copolymer of at least one α-olefin and at least one acrylic acid ester or methacrylic acid ester of an aliphatic alcohol.
Die vorliegende Erfindung betrifft zudem Produkte, bevorzugt Vliese, Vliesstoffe, Gewebe, Gestricke, Gelege oder Gewirke, insbesondere Vliese oder Vliesstoffe erhältlich aus erfindungsgemäßen thermoplastbasierten Fasern mit reduzierter Oberflächenspannung, bevorzugt Polyester basierter Fasern oder Filamente beziehungsweise Polyamid basierter Fasern oder Filamente jeweils mit reduzierter Oberflächenspannung, die wenigstens durch ein Copolymerisat aus mindestens einem α-Olefin und mindestens einem Acrylsäsureester oder Methacrylsäureester additiviert wurden.The present invention also relates to products, preferably nonwovens, nonwovens, woven, knitted fabrics, nonwovens or knitted fabrics, in particular nonwovens or nonwovens obtainable from thermoplastic-based fibers according to the invention with reduced surface tension, preferably polyester-based fibers or filaments or polyamide-based fibers or filaments, each with reduced surface tension, which have been added by at least one copolymer of at least one α-olefin and at least one acrylic acid ester or methacrylic acid ester.
Zur Klarstellung sei angemerkt, dass im Rahmen der vorliegenden Erfindung alle vorstehend aufgeführten allgemeinen oder in Vorzugsbereichen genannten Definitionen und Parameter in beliebigen Kombinationen umfasst sind.For clarification, it should be noted that within the scope of the present invention, all definitions and parameters listed above, general or in areas of preference, are included in any combination.
Generell lässt sich die Oberflächenspannung von Fasern anhand ihrer Benetzbarkeit mit Flüssigkeiten unterschiedlicher Polarität bestimmen. Eine weitere Möglichkeit zur Bestimmung der Oberflächenspannung an erfindungsgemäß hergestellten Faserprodukten ist die Betrachtung der Absorptionskinetik eines vom Faserprodukt absorbierten flüssigen Mediums (z.B. Wasser oder Cyclohexan) mit Hilfe eines geeigneten Tensiometers.In general, the surface tension of fibers can be determined based on their wettability with liquids of different polarity. Another possibility for determining the surface tension on fiber products produced according to the invention is to consider the absorption kinetics of a liquid medium (eg water or cyclohexane) absorbed by the fiber product with the aid of a suitable tensiometer.
Die Absenkung der Oberflächenspannung der erfindungsgemäß hergestellten Materialien wird zum einen quantitativ an spritzgegossenen Platten, die als Modellsystem zur genaueren Bestimmung der Oberflächenflächenspannung dienen, und zum anderen qualitativ an nach dem Meltblown-Verfahren hergestellten Vliesen gezeigt.The lowering of the surface tension of the materials produced according to the invention is shown on the one hand quantitatively on injection molded plates, which serve as a model system for more precise determination of the surface surface tension, and on the other hand qualitatively on fleeces produced by the meltblown process.
Zum exemplarischen Nachweis der erfindungemäß beschriebenen Verringerung der Oberflächenspannung wurden zunächst durch Compoundierung entsprechende Kunststoff-Formmassen angefertigt. Die einzelnen Komponenten wurden hierzu in einem Zweiwellenextruder (ZSK 26 Mega Compounder der Fa. Coperion Werner & Pfleiderer (Stuttgart, Deutschland)) bei Temperaturen zwischen 250 und 285°C gemischt, als Strang ausgetragen, bis zur Granulierfähigkeit abgekühlt und granuliert. Nach dem Trocknen (in der Regel 2-6h bei 80°C im Vakuumtrockenschrank) erfolgte die Verarbeitung des Granulates zu Prüfkörpern.As an example of the reduction in surface tension described according to the invention, appropriate plastic molding compounds were first prepared by compounding. For this purpose, 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 granulability and granulated. After drying (usually 2-6 hours at 80 ° C. in a vacuum drying cabinet), the granulate was processed into test specimens.
Die Prüfkörper (Rechteckplatten der Abmessung 60∗40∗4mm bzw. 150∗105∗1,0mm) für die in den Tabelle 1 und 2 aufgeführten Untersuchungen wurden auf einer Spritzgießmaschine des Typs Arburg 320-210-500 bei einer Massetemperatur von ca. 260°C und einer Werkzeugtemperatur von ca. 80°C verspritzt.The test specimens (rectangular plates of dimensions 60 ∗ 40 ∗ 4mm or 150 ∗ 105 ∗ 1.0mm) for the tests listed in Tables 1 and 2 were made on an Arburg 320-210-500 injection molding machine at a melt temperature of approx. 260 ° C and a mold temperature of approx. 80 ° C.
Die Oberflächenspannung der aus dem erfindungsgemäß hergestellten Materialien erhaltenen Rechteckplatten wurde nach DIN ISO 8296 mit Testtinten einfach und reproduzierbar bestimmt.The surface tension of the rectangular plates obtained from the materials produced according to the invention was determined simply and reproducibly in accordance with DIN ISO 8296 using test inks.
Die Oberflächenspannungen nach DIN ISO 8296 lassen sich im Allgemeinen nicht mit den Werten nach ASTM D 2587-84 vergleichen. Die Werte der Oberflächenspannung werden in nN/m (= dyn/cm) angegeben.The surface tensions according to DIN ISO 8296 cannot generally be compared with the values according to ASTM D 2587-84. The surface tension values are given in nN / m (= dynes / cm).
Die Testmethode basiert auf der Beurteilung der Benetzung von Tinten mit unterschiedlicher Oberflächenspannung auf der zu untersuchenden Polymeroberfläche. Der an dem Flaschenverschluss befindliche Pinsel wird in die Testtinte getaucht, am Flaschenrand abgestreift und die Tinte unverzüglich auf die zu prüfende Oberfläche aufgetragen. Die Strichlänge sollte mindestens 100 mm betragen. Beurteilt wird das Verhalten des Strichrandes auf einer Länge von etwa 90 %, so dass geringfügige Inhomogenitäten nicht berücksichtigt werden. Zieht sich der Tintenstrich in weniger als zwei Sekunden zusammen, ist die Messung mit einer Tinte mit niedrigerer Oberflächenspannung so lange zu wiederholen, bis die Ränder zwei Sekunden stehen bleiben. Bleibt der Tintenstrich länger als zwei Sekunden unverändert, so ist die Messung mit Tinten höherer Oberflächenspannung zu wiederholen, bis die zwei Sekunden erreicht sind. Der auf der Flasche angegebene Wert entspricht dann dem der Oberflächenenergie der Testplatte. Die Prüfung ist im Normklima 23/50 durchzuführen, d.h. bei einer Lufttemperatur von 23°C +/-2°C und relativer Luftfeuchte von 50 % +/- 10 %.The test method is based on the assessment of the wetting of inks with different surface tension on the polymer surface to be examined. The brush on the bottle cap is dipped into the test ink, wiped off at the edge of the bottle and the ink is immediately applied to the surface to be tested. The line length should be at least 100 mm. The behavior of the line edge is assessed over a length of about 90%, so that minor inhomogeneities are not taken into account. If the ink line contracts in less than two seconds, the measurement must be repeated with an ink with a lower surface tension until the edges remain there for two seconds. If the ink line stays longer remains unchanged for more than two seconds, the measurement must be repeated with inks with a higher surface tension until the two seconds have been reached. The value given on the bottle then corresponds to that of the surface energy of the test plate. The test is to be carried out in a standard climate of 23/50, ie at an air temperature of 23 ° C +/- 2 ° C and a relative humidity of 50% +/- 10%.
Im Rahmen der vorliegenden Versuche wurde mit Testtinten der Firma Softal Electronic GmbH, (siehe Softal Report Nr. 108), Hamburg, Deutschland, gearbeitet.In the context of the present tests, test inks from Softal Electronic GmbH, (see Softal Report No. 108), Hamburg, Germany, were used.
Zur erfindungsgemäßen Reduzierung der Oberflächenspannung auf Thermoplastfasern wurden mit einer Meltblownanlage Vliese mit einer Flächenmasse von ca. 55g/m2 hergestellt. In den Versuchen betrug die Schmelzetemperatur ca. 275°C, der Heißluftstrom ca. 360°C. Das Verhältnis von Schmelzedurchsatz und Luftvolumenstrom wurde so gewählt, dass bei einem Düsendurchmesser von 300µm eine mittlere Faserdicke von ca. 1µm erhalten wurde. Die in den Beispielen und Vergleichsbeispielen beschriebenen Vliese unterscheiden sich nur in den jeweils eingesetzten Polymerzusammensetzungen, während sämtliche anderen Parameter und damit einhergehend Vlieskenngrößen wie Flächenmasse, Porengröße, Faserorientierung und Faserdicke jeweils für Beispiel und Vergleichsbeispiel konstant gehalten werden.In order to reduce the surface tension on thermoplastic fibers according to the invention, nonwovens with a mass per unit area of approx. 55 g / m 2 were produced using a meltblown system. In the tests, the melt temperature was approx. 275 ° C, the hot air flow was approx. 360 ° C. The ratio of melt throughput and air volume flow was chosen so that with a nozzle diameter of 300 µm an average fiber thickness of approx. 1 µm was obtained. The webs described in the examples and comparative examples differ only in the polymer compositions used, while all other parameters and associated web parameters such as surface weight, pore size, fiber orientation and fiber thickness are kept constant for each example and comparative example.
Zur qualitativen Bewertung der Oberflächenspannung wurde das Vlies mit einem Wassertropfen beaufschlagt. Eine rasche Benetzung des Wassertropfen auf dem Vlies deutet auf eine hohe Oberflächenspannung hin (hydrophiles Verhalten), während der Erhalt der Tropfenform auf der Oberfläche auf eine geringe Oberflächenspannung schließen lässt. Zur weiteren Differenzierung wurde der Tropfen mit einem Luftstrom beaufschlagt. Hinterlässt der Tropfen eine Spur aus einem Wasserfilm kann qualitativ von einer höheren Oberflächenspannung ausgegangen werden, bewegt sich der Tropfen über das Vlies, ohne eine sichtbare Spur aus Wasser zu hinterlassen, so kann von einer geringeren Oberflächenspannung ausgegangen werden (s. Tabelle 3).A drop of water was applied to the fleece for the qualitative assessment of the surface tension. Rapid wetting of the water droplet on the fleece indicates a high surface tension (hydrophilic behavior), while the retention of the droplet shape on the surface indicates a low surface tension. For further differentiation, the drop was exposed to a stream of air. If the drop leaves a trace of a water film, qualitatively a higher surface tension can be assumed; if the drop moves over the fleece without leaving a visible trace of water, then a lower surface tension can be assumed (see Table 3).
In den Versuchen wurde verwendet:
- Komponente A1: Lineares Polybutylenterephthalat (Pocan® B600, der Fa. Lanxess Deutschland GmbH, Leverkusen, Deutschland) mit einer intrinsischen Viskosität von ca. 69 cm3/g (gemessen in Phenol: 1,2-Dichlorbenzol = 1:1 bei 25°C)
- Komponente A2: Lineares Polybutylenterephthalat (Pocan® B1300, der Fa. Lanxess Deutschland GmbH, Leverkusen, Deutschland) mit einer intrinsischen Viskosität von ca. 94 cm3/g (gemessen in Phenol: 1,2-Dichlorbenzol = 1:1 bei 25°C)
- Komponente A3: PET Copolymerisat mit einer intrinsichen Viskosität von ca. 80cm3/g (PETplus 80 der PET Kunststoffrecycling GmbH, Beselich-Obertiefenbach, Deutschland)
- Komponente A4: Polyamid 6 (Durethan® B40F, Fa. Lanxess Deutschland GmbH, Leverkusen, Deutschland)
- Komponente B1: Copolymerisat aus Ethen und Acrylsäure-2-ethylhexylester mit einem Ethen-Anteil von 63 Gew.-% und einem MFI von 550 (Lotryl® 37 EH 550 der Arkema, Puteaux, Frankreich) [
CAS-Nr. 26984-27-0 - Komponente B2: Lotryl® 35 BA 320: Copolymerisat aus Ethen und Acrylsäsure-n-butylester mit einem Ethen-Anteil von 65 Gew.-% und einem MFI von 320 (Lotryl® 35 BA 320 der Arkema, Puteaux, Frankreich) [
CAS-Nr. 25750-84-9
- Component A1: Linear polybutylene terephthalate (Pocan ® B600, the company Lanxess Germany GmbH, Leverkusen, Germany.) Having an intrinsic viscosity of about 69 cm 3 / g (measured in phenol: 1,2-dichlorobenzene = 1: 1 at 25 ° C)
- Component A2: Linear polybutylene terephthalate (Pocan B1300 ®, the company Lanxess Germany GmbH, Leverkusen, Germany.) Having an intrinsic viscosity of about 94 cm 3 / g (measured in phenol: 1,2-dichlorobenzene = 1: 1 at 25 ° C)
- Component A3: PET copolymer with an intrinsic viscosity of approx. 80 cm 3 / g (PETplus 80 from PET Kunststoffrecycling GmbH, Beselich-Obertiefenbach, Germany)
- Component A4: Polyamide 6 (Durethan ® B40F, Lanxess Deutschland GmbH, Leverkusen, Germany)
- Component B1: copolymer of ethene and acrylic acid 2-ethylhexyl ester having an ethylene content of 63 wt .-% and an MFI of 550 (37 Lotryl ® EH 550 of Arkema, Puteaux, France) [
CAS no. 26984-27-0 - Component B2: ® Lotryl 35 BA 320: copolymer of ethene and Acrylsäsure-n-butyl ester with an ethene content of 65 wt .-% and an MFI of 320 (® Lotryl 35 BA 320 of Arkema, Puteaux, France) [
CAS no. 25750-84-9
Ein hoher Wert steht für eine hohe Oberflächenspannung und damit für ein hydrophiles Verhalten, während das Material mit abnehmender Zahl für die Oberflächenspannung zunehmend hydrophober wird. Die Beispiele zeigen, dass sich die Oberflächenspannung nur bis zu einem Grenzwert von 30mN/m reduzieren läßt, der Wert 30 mN/m eine Sättigung darstellt. Im Stand der Technik (Komponente B2 in Vergleichsbeispiel 5) wird dieser Grenzwert erst mit 6 Gew.-% Copolymerisat aus Ethylen und Butylacrylat erzielt. Bei Einsatz von nur 3 Gew.-% läßt sich die Oberflächenspannung nur auf 34 mN/m reduzieren. Ein Vergleich der Oberflächenspannnungen von Komponente B1 und Komponenten B2 zeigt, dass mit Komponente B1, einem Copolymerisat aus Ethylen und 2-Ethylhexylacrylat, schon bei geringer Dosierung von z.B. 3 Gew.-% eine sehr geringe Oberflächenspannung von nur 30mN/m erreicht werden kann.
Die mit zunehmender Konzentration an Komponente B1 stark abnehmende Anhaftung des Wassertropfens ist ein Maß für die stark abnehmende Benetzbarkeit des Vlieses mit Wasser und zeigt so die Reduzierung der Oberflächenspannung in den für das Vlies verwendeten Polyesterfasern an. Schon 1 Gew.-% der Komponente B1 sind ausreichend, um die Hydrophobie entscheidend zu erhöhen.The strongly decreasing adhesion of the water droplet with increasing concentration of component B1 is a measure of the strongly decreasing wettability of the fleece with water and thus shows the reduction in surface tension in the polyester fibers used for the fleece. Even 1% by weight of component B1 is sufficient to decisively increase the hydrophobicity.
Claims (10)
- Process for reducing the surface tension of thermoplastic-based fibres or filaments, characterized in that the thermoplastic is additized with at least one E/X copolymer of an α-olefin and an acrylic or methacrylic ester of an unsubstituted aliphatic alcohol having 6 to 30 carbon atoms and spun by the melt-spinning process, wherein the thermoplastic used is polyamide or polyester and the α-olefin content of the E/X copolymer is between 50 and 90 wt%.
- Process according to Claim 1, characterized in that the polyesters used are polyalkylene terephthalates, preferably polyethylene terephthalates, polytrimethylene terephthalates or polybutylene terephthalates, more preferably polybutylene terephthalate and polyethylene terephthalate, in particular most preferably polybutylene terephthalate, or mixtures of these terephthalates.
- Process according to Claim 1, characterized in that the polyamides used are aliphatic polyamides.
- Process according to any of Claims 1 to 3, characterized in that mixtures are used for spinning which are based on 99.9 to 10 parts by weight of at least one thermoplastic and 0.1 to 20 parts by weight of copolymer.
- Process according to any of Claims 1 to 4, characterized in that the α-olefins have between 2 and 10 carbon atoms and may be unsubstituted or substituted with one or more aliphatic, cycloaliphatic or aromatic groups.
- Process according to Claim 5, characterized in that α-olefins are selected from the group comprising ethene, propene, 1-butene, 1-pentene, 1-hexene, 1-octene, 3-methyl-1-pentene, preferred α-olefins are ethene and propene, ethene is very particularly preferable, and also mixtures of these α-olefins.
- Process according to either of Claims 5 and 6, characterized in that the α-olefin content of the copolymer is between 50 and 90 wt%, preferably between 55 and 75 wt%.
- Process according to any of Claims 1 to 7, characterized in that customary added substances, preferably dyes, further hydrophobicizing agents, delustrants, stabilizers, antistats, lubricants, branching agents, are added to the thermoplastic-copolymer mixture in amounts of 0.001 to 5.0 wt%.
- Process according to any of Claims 1 to 8, characterized in that the thermoplastic is additized with an E/X copolymer of ethylene and an acrylic ester of an unsubstituted aliphatic alcohol having 6 to 30 carbon atoms, preferably of E ethylene and X an acrylic ester having 6 to 20 carbon atoms, more preferably of E ethylene and X 2-ethylhexyl acrylate.
- Process according to any of claims 1 to 9, characterized in that copolymers are employed where the α-olefin is copolymerized with 2-ethylhexyl acrylate.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP13721664.4A EP2844788B1 (en) | 2012-05-04 | 2013-05-03 | Thermoplastic fibres with reduced surface tension |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP12166834.7A EP2660372A1 (en) | 2012-05-04 | 2012-05-04 | Thermoplastic fibres with reduced surface tension |
PCT/EP2013/059259 WO2013164452A1 (en) | 2012-05-04 | 2013-05-03 | Thermoplastic fibres with reduced surface tension |
EP13721664.4A EP2844788B1 (en) | 2012-05-04 | 2013-05-03 | Thermoplastic fibres with reduced surface tension |
Publications (2)
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EP2844788A1 EP2844788A1 (en) | 2015-03-11 |
EP2844788B1 true EP2844788B1 (en) | 2021-10-27 |
Family
ID=48407487
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
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EP12166834.7A Withdrawn EP2660372A1 (en) | 2012-05-04 | 2012-05-04 | Thermoplastic fibres with reduced surface tension |
EP13721664.4A Active EP2844788B1 (en) | 2012-05-04 | 2013-05-03 | Thermoplastic fibres with reduced surface tension |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
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EP12166834.7A Withdrawn EP2660372A1 (en) | 2012-05-04 | 2012-05-04 | Thermoplastic fibres with reduced surface tension |
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US (1) | US20150084231A1 (en) |
EP (2) | EP2660372A1 (en) |
JP (1) | JP6290183B2 (en) |
KR (1) | KR101965471B1 (en) |
CN (1) | CN104350188A (en) |
HU (1) | HUE057122T2 (en) |
WO (1) | WO2013164452A1 (en) |
Families Citing this family (2)
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TWI707905B (en) * | 2019-08-21 | 2020-10-21 | 南亞塑膠工業股份有限公司 | Dark infrared reflective fiber without metal composition, manufacturing method thereof, and dark infrared reflective fiber textile |
CN113789004B (en) * | 2021-07-28 | 2023-07-07 | 广东金发科技有限公司 | Thermoplastic alloy material, application thereof in preparation of plastic mold and prepared hand mold |
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2012
- 2012-05-04 EP EP12166834.7A patent/EP2660372A1/en not_active Withdrawn
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2013
- 2013-05-03 US US14/398,319 patent/US20150084231A1/en not_active Abandoned
- 2013-05-03 EP EP13721664.4A patent/EP2844788B1/en active Active
- 2013-05-03 WO PCT/EP2013/059259 patent/WO2013164452A1/en active Application Filing
- 2013-05-03 HU HUE13721664A patent/HUE057122T2/en unknown
- 2013-05-03 CN CN201380029189.0A patent/CN104350188A/en active Pending
- 2013-05-03 KR KR1020147033720A patent/KR101965471B1/en active IP Right Grant
- 2013-05-03 JP JP2015509449A patent/JP6290183B2/en active Active
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HUE057122T2 (en) | 2022-04-28 |
JP6290183B2 (en) | 2018-03-07 |
US20150084231A1 (en) | 2015-03-26 |
KR101965471B1 (en) | 2019-04-03 |
CN104350188A (en) | 2015-02-11 |
KR20150003392A (en) | 2015-01-08 |
EP2844788A1 (en) | 2015-03-11 |
WO2013164452A1 (en) | 2013-11-07 |
EP2660372A1 (en) | 2013-11-06 |
JP2015520806A (en) | 2015-07-23 |
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