EP2063003A1 - Hydrolysis resistant, equipped filaments, method for their manufacture and application thereof - Google Patents
Hydrolysis resistant, equipped filaments, method for their manufacture and application thereof Download PDFInfo
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- EP2063003A1 EP2063003A1 EP08018593A EP08018593A EP2063003A1 EP 2063003 A1 EP2063003 A1 EP 2063003A1 EP 08018593 A EP08018593 A EP 08018593A EP 08018593 A EP08018593 A EP 08018593A EP 2063003 A1 EP2063003 A1 EP 2063003A1
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- Prior art keywords
- thread
- carbodiimide
- mol
- threads
- molecular weight
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Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/92—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
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21F—PAPER-MAKING MACHINES; METHODS OF PRODUCING PAPER THEREON
- D21F1/00—Wet end of machines for making continuous webs of paper
- D21F1/0027—Screen-cloths
Definitions
- the present invention relates to elastic threads, in particular monofilaments, with excellent resistance to hydrolysis. These are excellently suited for the production of textile fabrics which are used in applications with aggressive environments, for example in screens for paper machines.
- Threads based on thermoplastic elastomeric polyesters are generally susceptible to hydrolysis. Such threads are therefore unsuitable for applications in which hydrolytic conditions prevail, for example for use as screens in the dryer section of paper machines.
- DE 198 34 008 A1 discloses core-shell monofilaments having very good abrasion resistance.
- the sheath of these monofilaments may be constructed of conventional polyesters, but preferably of elastomeric polyesters derived from dicarboxylic acids, short-chain diols and polyglycols. It is further disclosed that carbodiimides can be used to improve the hydrolytic stability in the sheath component of these threads.
- the core may consist of copolyesters and up to at least 70% of a thermoplastic polyester and from to be constructed to 30% of a thermoplastic elastomeric polyester.
- the jacket can also be constructed from a thermoplastic polyester and from a thermoplastic elastomeric polyester.
- the polyesters of the core and of the shell can be closed by reaction with mono-, bis- and / or polycarbodiimides. The use of monomeric and polymeric carbodiimides is described by way of example.
- polycarbodiimides are preferred for some applications. These compounds are more firmly anchored in the thread due to their molecular weight and are less susceptible to diffusion to the surface and thus less likely to be extracted from the thread.
- thermoplastic elastomeric polyesters which are characterized by a very low modulus of elasticity, one would therefore expect only a small stabilizing effect when using polycarbodiimides.
- the object of the present invention is therefore to provide elastic threads and textile fabrics derived therefrom which characterized by a high hydrolytic stability.
- the invention relates to a thread containing at least 80 wt.%, Based on the mass of the or the thread-forming polymers, one or more thermoplastic elastomeric polyester and a carbodiimide having a molecular weight of at least 2000 g / mol.
- threads are generally understood to mean fibers of finite length (staple fibers), fibers of infinite length (filaments) and multifilaments composed thereof or secondary-spun yarns of staple fibers. Preference is given to melt-spun threads in the form of monofilaments.
- thermoplastic elastomeric polyesters may be compounds known to those skilled in the art under the name TPE-E.
- thermoplastic and elastomeric polyesters can be composed of a wide variety of monomer combinations. As a rule, these are blocks of so-called hard and soft segments.
- the soft segments are typically derived from polyalkylene glycol ethers.
- the hard segments are typically derived from short chain diols. In addition to the diols, the hard and soft segments are usually built up from aliphatic, cycloaliphatic and / or aromatic dicarboxylic acids.
- thermoplastic, elastomeric polyesters are polyether esters. These are preferably block copolymers comprising blocks of polyethylene terephthalate and / or polybutylene terephthalate and blocks of polyalkylene glycol terephthalate.
- thermoplastic elastomeric polyesters are understood as meaning polyesters which, at room temperature, are comparable to the conventional elastomers, but can be plastically deformed under heat supply and thus exhibit a thermoplastic behavior.
- These thermoplastic and elastomeric polyesters have in physical areas physical crosslinking points (e.g., minor valence forces or crystallites) that dissolve on heat without the polymer molecules decomposing.
- the polymer component of the threads according to the invention consists mainly of thermoplastic, elastomeric polyesters.
- the thread according to the invention may also contain small amounts of other thread-forming polymers, for example on other polyesters or on polyolefins.
- the amount of thread-forming polymer or of thread-forming polymers in the thread according to the invention is usually at least 70% by weight.
- carbodiimides are used in the thread according to the invention. These are polymeric carbodiimides which have a molecular weight of at least 2,000 g / mol, preferably at least 3,000 g / mol to 20,000 g / mmol and most preferably from 3,500 to 15,000 g / mol. It is also possible to use mixtures of polymeric carbodiimides.
- Preferably used polymeric carbodiimides have a melting range of 60 to 210 ° C.
- the polymeric carbodiimides used according to the invention are commercially available. Examples are the products R Stabaxol P from Rhein Chemie GmbH, Mannheim or carbodiimides from Raschig GmbH, Ludwigshafen.
- the proportion of polymeric carbodiimides in the thread according to the invention is generally 0.05 to 5.0 wt.%, Preferably 0.1 to 3, 0 wt.%.
- the polymeric carbodiimide is added to the thermoplastic elastomeric polyester preferably in the form of a masterbatch in the preparation of the thread according to the invention.
- the masterbatch contains, in addition to the carbodiimide, a polymer component.
- the proportion of carbodiimide in the masterbatch is usually 10 to 50 wt.%.
- the melting point of the polymer used in the masterbatch may not be above the melting point of thermoplastic, elastomeric polyester.
- suitable polymers used in the masterbatch are polyolefins, such as polyethylene or polypropylene, or in particular polyesters, very preferably thermoplastic, elastomeric polyesters.
- the threads according to the invention may contain, in addition to the thread-forming polymers and the polymeric carbodiimide, further auxiliaries or additives.
- the total proportion of these auxiliaries and additives on the thread according to the invention may be up to 25% by weight, preferably up to 10% by weight.
- auxiliaries and additives are further hydrolysis stabilizers, processing aids, antioxidants, plasticizers, lubricants, pigments, matting agents, viscosity modifiers, crystallization accelerators, UV stabilizers, flame retardant additives and / or dyes.
- hydrolysis stabilizers examples include compounds containing epoxide groups.
- processing aids are siloxanes, waxes or longer-chain carboxylic acids or their salts, aliphatic, aromatic esters or ethers.
- antioxidants are phosphorus compounds, such as phosphoric acid esters or sterically hindered phenols.
- pigments or matting agents examples include organic dye pigments or titanium dioxide.
- viscosity modifiers are polybasic carboxylic acids and their esters or polyhydric alcohols.
- UV stabilizers examples include hindered amine light stabilizers (HALS).
- HALS hindered amine light stabilizers
- flame retardant additives are ammonium polyphosphates or melamine cyanurate.
- dyes are commercially available Renol R dyes (Clariant).
- the components required for producing the threads according to the invention are known per se, some are commercially available or can be prepared by methods known per se.
- the threads according to the invention can be in any desired form, for example as multifilaments, as staple fibers, as secondary spun yarns, also in the form of twisted yarns, or in particular as monofilaments.
- the threads according to the invention are present as single-component threads.
- the titer of the threads according to the invention can vary within wide limits. Examples are 1 to 45,000 dtex, in particular 100 to 7,000 dtex.
- the cross-sectional shape of the threads according to the invention may be arbitrary, for example round, oval or n-cornered, where n is greater than or equal to 3, or the threads have a point- or axis-symmetrical cross-section.
- the threads of the invention can be prepared by methods known per se.
- the production of the threads according to the invention can be carried out by conventional melt spinning processes, combined with single or multiple stretching and optionally fixing the threads obtained.
- the threads of the invention are characterized by a particularly good combination of elasticity and hydrolysis resistance.
- the threads of the invention are preferably used for the production of textile fabrics, in particular of woven, laid, knitted, braided or knitted fabrics.
- the fabrics are preferably used in areas where resistance to hydrolytic degradation of the polyester is required.
- the fibers of the invention can be used in all industrial fields. They are preferably used in applications in which increased wear due to mechanical stress and hydrolytic degradation of the polyester is to be expected. Examples include the use in screens, filters or in conveyor belts.
- the threads according to the invention are preferably used for the production of fabrics, in particular fabrics, which are used in screens.
- filaments of the invention in the form of monofilaments relates to their use as conveyor belts or as components of conveyor belts.
- thermoplastic, elastomeric polyetherester (Heraflex E-type, Radici / Chignolo d'Isola, Italy) and a different carbodiimide and TPE-E containing Materbatch (Rhein Chemie, Mannheim, Germany) were used.
- the masterbatch was added to the TPE-E in such an amount that the carbodiimide was introduced into the dope in the amount described below.
- the polymeric masterbatch was gravimetrically metered into the TPE-E Schnitzelstrom in the feed tube of the extruder, melted in the extruder and mixed, fed via a spinning pump to a spin pack and pressed through fine hole nozzles. Subsequently, the resulting filaments were quenched in a water bath, stretched several times under the action of temperature and wound on disc coils by means of a winding machine.
- the process conditions were chosen in all cases to achieve monofilaments of about 0.40 mm in diameter with approximately the same textile values.
- the carbodiimides used are shown in Table 1 and the process data and the resulting textile values of the monofilaments are listed in Table 2.
- Table 1 Carbodiimides used Example no. carbodiimide 1 (comparison) - 2 (comparison) Bis-carbodiimide, molecular weight 362, Stabaxol R 1 3 (according to the invention) Polym. Carbodiimide, molecular weight about 3,500, Stabaxol R KE 9514 4 (according to the invention) Polym.
- Carbodiimide molecular weight about 10,000, Stabaxol R KE 9464 example 1 Example 2 1 )
- Example 3 Example 4 Content of carbodiimide (% by weight) 0.0 1.0 1.6 1.2 Titre (dtex) 1595 - 1611 1572 Strength 2) (cN / tex) 36.9 - 34.6 37.3 rel. Elongation at 15 cN / tex 3) (%) 37.0 - 37.7 35.8 rel. Elongation at 20 cN / tex 3) (%) 3) 40.2 - 41.4 39.4 rel. Elongation at 27 cN / tex 3) (%) 44.4 - 46.6 43.9 free shrink 160 ° C / 30 min.
Abstract
Description
Die vorliegende Erfindung betrifft elastische Fäden, insbesondere Monofilamente, mit ausgezeichneter Hydrolysebeständigkeit. Diese eignen sich vorzüglich zur Herstellung textiler Flächengebilde, die in Einsatzgebieten mit aggressiver Umgebung zur Anwendung kommen, beispielsweise in Sieben für Papiermaschinen.The present invention relates to elastic threads, in particular monofilaments, with excellent resistance to hydrolysis. These are excellently suited for the production of textile fabrics which are used in applications with aggressive environments, for example in screens for paper machines.
Fäden auf der Basis von thermoplastisch-elastomeren Polyestern sind im allgemeinen hydrolyseanfällig. Solche Fäden sind daher für Anwendungen ungeeignet, in denen hydrolytische Bedingungen herrschen, beispielsweise für Anwendung als Siebe in der Trocknerpartie von Papiermaschinen.Threads based on thermoplastic elastomeric polyesters are generally susceptible to hydrolysis. Such threads are therefore unsuitable for applications in which hydrolytic conditions prevail, for example for use as screens in the dryer section of paper machines.
Es ist bekannt, die Hydrolysebeständigkeit von Polyestern durch Verwendung von Carbodiimiden erheblich verbessert werden kann.It is known that the hydrolysis resistance of polyesters can be significantly improved by using carbodiimides.
Die Verwendung von Polycarbodiimiden ist für manche Anwendungen bevorzugt. Diese Verbindungen sind aus Gründen ihres Molekulargewichts fester im Faden verankert und neigen weniger zur Diffusion an die Oberfläche und somit weniger zur Extraktion aus dem Faden.The use of polycarbodiimides is preferred for some applications. These compounds are more firmly anchored in the thread due to their molecular weight and are less susceptible to diffusion to the surface and thus less likely to be extracted from the thread.
Bei der Ausrüstung von Polyesterfäden mit Polycarbodiimiden hat sich gezeigt, dass der Effekt der Hydrolysestabilisierung bei Fäden mit vergleichsweise geringem Elastizitätsmodul, wie z.B. bei Fäden aus Polybutylenterephthalat oder aus Polypropylenterephthalat, nur gering ausgeprägt ist.In finishing polyester yarns with polycarbodiimides, it has been found that the effect of hydrolysis stabilization on relatively low modulus yarns, e.g. in threads of polybutylene terephthalate or polypropylene terephthalate, is only slightly pronounced.
Bei Fäden enthaltend einen überwiegenden Anteil an thermoplastischen elastomeren Polyestern, die durch einen sehr geringen Elastizitätsmodul gekennzeichnet sind, würde man also beim Einsatz von Polycarbodiimiden nur einen geringen stabilisierenden Effekt erwarten.For threads containing a predominant proportion of thermoplastic elastomeric polyesters, which are characterized by a very low modulus of elasticity, one would therefore expect only a small stabilizing effect when using polycarbodiimides.
Überraschenderweise wurde gefunden, dass Fäden aus einem überwiegenden Anteil aus thermoplastischem elastomeren Polyester mit Polycarbodiimid verschlossen werden können und eine ausgezeichnete Hydrolysestabilität aufweisen. Dieser Effekt nimmt mit ansteigendem Molekulargewicht der polymeren Carbodiimide überraschenderweise sogar noch zu.Surprisingly, it has been found that threads made from a predominant proportion of thermoplastic elastomeric polyester with polycarbodiimide can be closed and have excellent stability to hydrolysis. This effect surprisingly even increases with increasing molecular weight of the polymeric carbodiimides.
Aufgabe der vorliegenden Erfindung ist daher die Bereitstellung von elastischen Fäden und davon abgeleiteten textilen Flächengebilden, welche sich durch eine hohe hydrolytische Stabilität auszeichnen.The object of the present invention is therefore to provide elastic threads and textile fabrics derived therefrom which characterized by a high hydrolytic stability.
Die Erfindung betrifft einen Faden enthaltend mindestens 80 Gew. %, bezogen auf die Masse des oder der fadenbildenden Polymeren, einen oder mehrere thermoplastische, elastomere Polyester und ein Carbodiimid mit einem Molekulargewicht von mindestens 2.000 g/mol.The invention relates to a thread containing at least 80 wt.%, Based on the mass of the or the thread-forming polymers, one or more thermoplastic elastomeric polyester and a carbodiimide having a molecular weight of at least 2000 g / mol.
Unter Fäden werden im Rahmen dieser Beschreibung ganz allgemein Fasern endlicher Länge (Stapelfasern), Fasern unendlicher Länge (Filamente) sowie daraus zusammengesetzte Multifilamente oder aus Stapelfasern sekundär gesponnene Garne verstanden. Bevorzugt sind schmelzgesponnene Fäden in Form von Monofilamenten.In the context of this description, threads are generally understood to mean fibers of finite length (staple fibers), fibers of infinite length (filaments) and multifilaments composed thereof or secondary-spun yarns of staple fibers. Preference is given to melt-spun threads in the form of monofilaments.
Unter Monofilamenten werden im Rahmen dieser Beschreibung einzelne Fäden verstanden. Diese weisen typischerweise Durchmesser von 55 bis 5000 µm, vorzugsweise von 100 bis 1000 µm, auf.Under monofilaments are understood in the context of this description individual threads. These typically have diameters of 55 to 5000 .mu.m, preferably from 100 to 1000 .mu.m.
Bei den thermoplastischen elastomeren Polyestern kann es sich um Verbindungen handeln, die dem Fachmann unter der Bezeichnung TPE-E bekannt sind.The thermoplastic elastomeric polyesters may be compounds known to those skilled in the art under the name TPE-E.
Die thermoplastischen und elastomeren Polyester können aus unterschiedlichsten Monomerkombinationen aufgebaut sein. In der Regel handelt es sich um Blöcke aus sogenannten Hart- und Weichsegmenten. Die Weichsegmente leiten sich typischerweise von Polyalkylenglykolethern ab. Die Hartsegmente leiten sich typischerweise von kurzkettigen Diolen ab. Neben den Diolen werden die Hart- und Weichsegmente üblicherweise von aliphatischen, cycloaliphatischen und/oder aromatischen Dicarbonsäuren aufgebaut.The thermoplastic and elastomeric polyesters can be composed of a wide variety of monomer combinations. As a rule, these are blocks of so-called hard and soft segments. The soft segments are typically derived from polyalkylene glycol ethers. The hard segments are typically derived from short chain diols. In addition to the diols, the hard and soft segments are usually built up from aliphatic, cycloaliphatic and / or aromatic dicarboxylic acids.
Besonders bevorzugte thermoplastische, elastomere Polyester sind Polyetherester. Dabei handelt es sich bevorzugt um Block-Copolymere, die Blöcke aus Polyethylenterephthalat und/oder aus Polybutylenterephthalat sowie Blöcke aus Polyalkylenglykolterephthalat aufweisen.Particularly preferred thermoplastic, elastomeric polyesters are polyether esters. These are preferably block copolymers comprising blocks of polyethylene terephthalate and / or polybutylene terephthalate and blocks of polyalkylene glycol terephthalate.
Unter thermoplastischen, elastomeren Polyestern sind im Rahmen dieser Beschreibung Polyester zu verstehen, der sich bei Raumtemperatur vergleichbar den klassischen Elastomeren verhalten, sich jedoch unter Wärmezufuhr plastisch verformen lassen und somit ein thermoplastisches Verhalten zeigen. Diese thermoplastischen und elastomeren Polyester haben in Teilbereichen physikalische Vernetzungspunkte (z.B. Nebenvalenzkräfte oder Kristallite), die sich bei Wärme auflösen, ohne dass sich die Polymermoleküle zersetzen.In the context of this description, thermoplastic elastomeric polyesters are understood as meaning polyesters which, at room temperature, are comparable to the conventional elastomers, but can be plastically deformed under heat supply and thus exhibit a thermoplastic behavior. These thermoplastic and elastomeric polyesters have in physical areas physical crosslinking points (e.g., minor valence forces or crystallites) that dissolve on heat without the polymer molecules decomposing.
Die Polymerkomponente der erfindungsgemäßen Fäden besteht hauptsächlich aus thermoplastischen, elastomeren Polyestern. Dieses bedeutet im Rahmen dieser Beschreibung, dass mindestens 80 Gew. % der fadenbildenden Polymerkomponente, vorzugsweise mindestens 90 Gew. % und ganz besonders bevorzugt mindestens 95 Gew. % aus thermoplastischem, elastomeren Polyester oder aus Gemischen von thermoplastischen, elastomeren Polyestern bestehen. Neben den thermoplastischem, elastomeren Polyester kann der erfindungsgemäßen Faden auch noch geringe Anteile an anderen fadenbildenden Polymeren enthalten, beispielsweise an anderen Polyestern oder an Polyolefinen.The polymer component of the threads according to the invention consists mainly of thermoplastic, elastomeric polyesters. In the context of this description, this means that at least 80% by weight of the filament-forming polymer component, preferably at least 90% by weight and very particularly preferably at least 95% by weight consist of thermoplastic, elastomeric polyester or of mixtures of thermoplastic, elastomeric polyesters. In addition to the thermoplastic, elastomeric polyester, the thread according to the invention may also contain small amounts of other thread-forming polymers, for example on other polyesters or on polyolefins.
Die Menge an fadenbildendem Polymer oder an fadenbildenden Polymeren im erfindungsgemäßen Faden beträgt üblicherweise mindestens 70 Gew. %.
Als weitere Komponente kommen im erfindungsgemäßen Faden ausgewählte Carbodiimide zum Einsatz. Dabei handelt es sich um polymere Carbodiimide, die ein Molekulargewicht von mindestens 2.000 g/mol, vorzugsweise mindestens 3.000 g/mol bis 20.000 g/mmol und ganz besonders bevorzugt von 3.500 bis 15.000 g/mol aufweisen. Es können auch Gemische von polymeren Carbodiimiden eingesetzt werden.The amount of thread-forming polymer or of thread-forming polymers in the thread according to the invention is usually at least 70% by weight.
As a further component selected carbodiimides are used in the thread according to the invention. These are polymeric carbodiimides which have a molecular weight of at least 2,000 g / mol, preferably at least 3,000 g / mol to 20,000 g / mmol and most preferably from 3,500 to 15,000 g / mol. It is also possible to use mixtures of polymeric carbodiimides.
Bevorzugt eingesetzte polymere Carbodiimide weisen einen Schmelzbereich von 60 bis 210°c auf.Preferably used polymeric carbodiimides have a melting range of 60 to 210 ° C.
Die erfindungsgemäß eingesetzten polymeren Carbodiimide sind kommerziell erhältlich. Beispiele sind die Produkte RStabaxol P von Rhein Chemie GmbH, Mannheim oder Carbodiimide von Raschig GmbH, Ludwigshafen.The polymeric carbodiimides used according to the invention are commercially available. Examples are the products R Stabaxol P from Rhein Chemie GmbH, Mannheim or carbodiimides from Raschig GmbH, Ludwigshafen.
Der Anteil der polymeren Carbodiimide in dem erfindungsgemäßen Faden beträgt allgemein 0,05 bis 5,0 Gew. %, vorzugsweise 0,1 bis 3, 0 Gew. %.The proportion of polymeric carbodiimides in the thread according to the invention is generally 0.05 to 5.0 wt.%, Preferably 0.1 to 3, 0 wt.%.
Das polymere Carbodiimid wird bei der Herstellung des erfindungsgemäßen Fadens vorzugsweise in Form eines Masterbatches dem thermoplastischen, elastomeren Polyester zugemischt. Der Masterbatch enthält neben dem Carbodiimid eine Polymerkomponente. Der Anteil an Carbodiimid im Masterbatch beträgt üblicherweise 10 bis 50 Gew. %. Um eine ausreichende Verspinnbarkeit und Vermischbarkeit im Extruder zu gewährleisten, darf der Schmelzpunkt des im Masterbatch eingesetzten Polymeren nicht oberhalb des Schmelzpunktes thermoplastischen, elastomeren Polyesters liegen.The polymeric carbodiimide is added to the thermoplastic elastomeric polyester preferably in the form of a masterbatch in the preparation of the thread according to the invention. The masterbatch contains, in addition to the carbodiimide, a polymer component. The proportion of carbodiimide in the masterbatch is usually 10 to 50 wt.%. In order to ensure sufficient spinnability and miscibility in the extruder, the melting point of the polymer used in the masterbatch may not be above the melting point of thermoplastic, elastomeric polyester.
Beispiele für geeignete im Masterbatch eingesetzte Polymere sind Polyolefine, wie Polyethylen oder Polypropylen, oder insbesondere Polyester, ganz bevorzugt thermoplastische, elastomere Polyester.Examples of suitable polymers used in the masterbatch are polyolefins, such as polyethylene or polypropylene, or in particular polyesters, very preferably thermoplastic, elastomeric polyesters.
Die erfindungsgemäßen Fäden können neben den fadenbildenden Polymeren und dem polymeren Carbodiimid noch weitere Hilfs- oder Zusatzstoffe enthalten.The threads according to the invention may contain, in addition to the thread-forming polymers and the polymeric carbodiimide, further auxiliaries or additives.
Der Gesamtanteil dieser Hilfs- und Zusatzstoffe am erfindungsgemäßen Faden kann bis zu 25 Gew. % betragen, vorzugsweise bis zu 10 Gew. %.The total proportion of these auxiliaries and additives on the thread according to the invention may be up to 25% by weight, preferably up to 10% by weight.
Beispiele für Hilfs- und Zusatzstoffe sind weitere Hydrolysestabilisatoren, Verarbeitungshilfsmittel, Antioxidantien, Weichmacher, Gleitmittel, Pigmente, Mattierungsmittel, Viskositätsmodifizierer, Kristallisationbeschleuniger, UV-Stabilisatoren, flammhemmende Zusätze und/oder Farbstoffe.Examples of auxiliaries and additives are further hydrolysis stabilizers, processing aids, antioxidants, plasticizers, lubricants, pigments, matting agents, viscosity modifiers, crystallization accelerators, UV stabilizers, flame retardant additives and / or dyes.
Beispiele für weitere Hydrolysestabilisatoren sind Epoxidgruppen enthaltende Verbindungen.Examples of further hydrolysis stabilizers are compounds containing epoxide groups.
Beispiele für Verarbeitungshilfsmittel sind Siloxane, Wachse oder längerkettige Carbonsäuren oder deren Salze, aliphatische, aromatische Ester oder Ether.Examples of processing aids are siloxanes, waxes or longer-chain carboxylic acids or their salts, aliphatic, aromatic esters or ethers.
Beispiele für Antioxidantien sind Phosphorverbindungen, wie Phosphorsäureester oder sterisch gehinderte Phenole.Examples of antioxidants are phosphorus compounds, such as phosphoric acid esters or sterically hindered phenols.
Beispiele für Pigmente oder Mattierungsmittel sind organische Farbstoffpigmente oder Titandioxid.Examples of pigments or matting agents are organic dye pigments or titanium dioxide.
Beispiele für Viskositätsmodifizierer sind mehrwertige Carbonsäuren und deren Ester oder mehrwertige Alkohole.Examples of viscosity modifiers are polybasic carboxylic acids and their esters or polyhydric alcohols.
Beispiele für UV-Stabilisatoren sind "hindered amine light stabilizers (HALS)".Examples of UV stabilizers are hindered amine light stabilizers (HALS).
Beispiele für flammhemmende Zusätze sind Ammonium-Polyphosphate oder Melamin-cyanurat.Examples of flame retardant additives are ammonium polyphosphates or melamine cyanurate.
Beispiele für Farbstoffe sind handelsübliche RenolR Farbstoffe (Clariant).Examples of dyes are commercially available Renol R dyes (Clariant).
Die zur Herstellung der erfindungsgemäßen Fäden benötigten Komponenten sind an sich bekannt, teilweise kommerziell erhältlich oder können nach an sich bekannten Verfahren hergestellt werden.The components required for producing the threads according to the invention are known per se, some are commercially available or can be prepared by methods known per se.
Die erfindungsgemäßen Fäden können in beliebiger Form vorliegen, beispielsweise als Multifilamente, als Stapelfasern, als sekundär gesponnene Garne, auch in der Form von Zwirnen, oder insbesondere als Monofilamente.The threads according to the invention can be in any desired form, for example as multifilaments, as staple fibers, as secondary spun yarns, also in the form of twisted yarns, or in particular as monofilaments.
In einer besonders bevorzugten Ausführungsform liegen die erfindungsgemäßen Fäden als Einkomponentenfäden vor.In a particularly preferred embodiment, the threads according to the invention are present as single-component threads.
Der Titer der erfindungsgemäßen Fäden kann in weiten Bereichen schwanken. Beispiele dafür sind 1 bis 45.000 dtex, insbesondere 100 bis 7.000 dtex.The titer of the threads according to the invention can vary within wide limits. Examples are 1 to 45,000 dtex, in particular 100 to 7,000 dtex.
Die Querschnittsform der erfindungsgemäßen Fäden kann beliebig sein, beispielsweise rund, oval oder n-eckig, wobei n größer gleich 3 ist oder die Fäden weisen einen punkt- oder achsensymmetrischen Querschnitt auf.The cross-sectional shape of the threads according to the invention may be arbitrary, for example round, oval or n-cornered, where n is greater than or equal to 3, or the threads have a point- or axis-symmetrical cross-section.
Die erfindungsgemäßen Fäden können nach an sich bekannten Verfahren hergestellt werden.The threads of the invention can be prepared by methods known per se.
Ein typisches Herstellverfahren umfasst die Maßnahmen:
- i) Vermischen von thermoplastischem, elastomeren Polyester mit einem Masterbatch enthaltend ein faden bildendes Monomer und ein polymeres Carbodiimid mit einem Molekulargewicht von mindestens 2.000 g/mol in einem Extruder,
- ii) Extrudieren des Gemisches durch eine Spinndüse,
- iii) Abziehen des gebildeten Filaments,
- iv) gegebenenfalls Verstrecken und/oder Relaxieren des gebildeten Filaments, und
- v) Aufspulen des gebildeten Filaments.
- i) blending a thermoplastic elastomeric polyester with a masterbatch containing a fiber-forming monomer and a polymeric carbodiimide having a molecular weight of at least 2,000 g / mol in an extruder,
- ii) extruding the mixture through a spinneret,
- iii) stripping off the formed filament,
- iv) optionally stretching and / or relaxing the formed filament, and
- v) winding the formed filament.
Die Herstellung der erfindungsgemäßen Fäden kann durch herkömmliche Schmelzspinnverfahren erfolgen, kombiniert mit ein- oder mehrfachem Verstrecken und gegebenenfalls Fixieren der erhaltenen Fäden.The production of the threads according to the invention can be carried out by conventional melt spinning processes, combined with single or multiple stretching and optionally fixing the threads obtained.
Die erfindungsgemäßen Fäden zeichnen sich durch eine besonders gute Kombination von Elastizität und Hydrolysebeständigkeit aus.The threads of the invention are characterized by a particularly good combination of elasticity and hydrolysis resistance.
Bevorzugt werden die erfindungsgemäßen Fäden zur Herstellung von textilen Flächengebilden, insbesondere von Geweben, Gelegen, Gewirken, Geflechten oder Gestricken, eingesetzt.The threads of the invention are preferably used for the production of textile fabrics, in particular of woven, laid, knitted, braided or knitted fabrics.
Die textilen Flächengebilde werden vorzugsweise in Gebieten eingesetzt, in denen die Beständigkeit gegenüber hydrolytischem Abbau des Polyesters gefragt sind.The fabrics are preferably used in areas where resistance to hydrolytic degradation of the polyester is required.
Die erfindungsgemäßen Fasern lassen sich auf allen industriellen Gebieten einsetzen. Bevorzugt kommen sie bei Anwendungen zum Einsatz, in denen mit einem erhöhten Verschleiß durch mechanische Belastung sowie mit einem hydrolytischen Abbau des Polyesters zu rechnen ist. Beispiele dafür sind der Einsatz in Sieben, Filtern oder in Förderbändern.The fibers of the invention can be used in all industrial fields. They are preferably used in applications in which increased wear due to mechanical stress and hydrolytic degradation of the polyester is to be expected. Examples include the use in screens, filters or in conveyor belts.
Bevorzugt werden die erfindungsgemäßen Fäden zur Herstellung von Flächengebilden, insbesondere von Geweben, eingesetzt, welche in Sieben eingesetzt werden.The threads according to the invention are preferably used for the production of fabrics, in particular fabrics, which are used in screens.
Eine weitere Verwendung der erfindungsgemäßen Fäden in der Form von Monofilamenten betrifft deren Einsatz als Förderbänder oder als Komponenten von Förderbändern.Another use of the filaments of the invention in the form of monofilaments relates to their use as conveyor belts or as components of conveyor belts.
Besonders bevorzugt sind Verwendungen der erfindungsgemäßen Fäden in Sieben, die zum Einsatz in der Trocknerpartie von Papiermaschinen vorgesehen sind.Particularly preferred are uses of the threads of the invention in screens, which are intended for use in the dryer section of paper machines.
Diese Verwendungen sind ebenfalls Gegenstand der vorliegenden Erfindung.These uses are also the subject of the present invention.
Die nachfolgenden Beispiele erläutern die Erfindung ohne diese zu begrenzen.The following examples illustrate the invention without limiting it.
Eingesetzt wurde ein thermoplastischer, elastomerer Polyetherester (Heraflex E-Type; Radici/Chignolo d'Isola, Italien) sowie ein unterschiedliche Carbodiimide und TPE-E enthaltender Materbatch (Fa. Rhein Chemie, Mannheim, Deutschland).A thermoplastic, elastomeric polyetherester (Heraflex E-type, Radici / Chignolo d'Isola, Italy) and a different carbodiimide and TPE-E containing Materbatch (Rhein Chemie, Mannheim, Germany) were used.
Unmittelbar vor der Einzugszone eines Extruders wurde dem TPE-E der Masterbatch in einer solchen Menge zugemischt, so dass das Carbodiimid in der nachfolgend beschriebenen Menge in die Spinnmasse eingebracht wurde. Dazu wurde der polymere Masterbatch gravimetrisch dem TPE-E Schnitzelstrom im Einzugsrohr des Extruders zudosiert, im Extruder aufgeschmolzen und vermischt, über eine Spinnpumpe einem Spinnpack zugeführt und durch feine Lochdüsen gedrückt. Anschließend wurden die erhaltenen Filamente in einem Wasserbad abgeschreckt, mehrfach unter Temperatureinwirkung verstreckt und mittels einer Spulmaschine auf Scheibenspulen aufgespult.Immediately before the feed zone of an extruder, the masterbatch was added to the TPE-E in such an amount that the carbodiimide was introduced into the dope in the amount described below. For this purpose, the polymeric masterbatch was gravimetrically metered into the TPE-E Schnitzelstrom in the feed tube of the extruder, melted in the extruder and mixed, fed via a spinning pump to a spin pack and pressed through fine hole nozzles. Subsequently, the resulting filaments were quenched in a water bath, stretched several times under the action of temperature and wound on disc coils by means of a winding machine.
Die Verfahrensbedingungen wurden in allen Fällen so gewählt, dass Monofilamente von etwa 0,40 mm Durchmesser mit annähernd gleichen Textilwerten erzielt wurden.
Die eingesetzten Carbodiimide sind in der Tabelle 1 und die verfahrenstechnischen Daten sowie die erhaltenen Textilwerte der Monofilamente sind in der Tabelle 2 aufgeführt.
2) gemessen in Anlehnung an DIN
3) gemessen in Anlehnung an DIN
4) gemessen in Anlehnung an DIN
5) nach 32-stündiger Behandlung mit Wasserdampf von 4,2 bar
The carbodiimides used are shown in Table 1 and the process data and the resulting textile values of the monofilaments are listed in Table 2.
2) measured on the basis of DIN
3) measured in accordance with DIN
4) measured on the basis of DIN
5) after treatment with steam at 4.2 bar for 32 hours
Bei den Versuchen zeigte sich, dass sich mit niedermolekularem Carbodiimid keine brauchbaren Monofilamente herstellen ließen (starke Rauchentwicklung). Die übrigen Textilwerte der verschiedenen Varianten sind weitgehend gleich.The experiments showed that it was not possible to produce useful monofilaments with low molecular weight carbodiimide (strong smoke development). The other textile values of the different variants are largely the same.
Die Restfestigkeit nach 32 Stunden in 4,2 bar Wasserdampf nimmt demgegenüber mit dem Molekulargewicht des polymeren Carbodiimids zu.The residual strength after 32 hours in 4.2 bar of water vapor, in contrast, increases with the molecular weight of the polymeric carbodiimide.
Die Feststellung, dass mit zunehmendem Molekulargewicht des Carbodiimids die Hydrolysebseständigkeit ansteigt, zeigte sich auch bei geringeren Konzentrationen an polymerem Carbodiimid, wenn auch nicht so ausgeprägt wie im angeführten Beispiel. Die Beobachtungsergebnisse ließen sich auf Monofilamente aus TPE-E Polymeren mit verschiedenen Shorehärten übertragen.The finding that hydrolysis resistance increases with increasing molecular weight of the carbodiimide was also demonstrated at lower levels of polymeric carbodiimide, although not as pronounced as in the example given. The observation results could be transferred to monofilaments of TPE-E polymers with different Shore hardnesses.
Claims (11)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102007056631A DE102007056631A1 (en) | 2007-11-24 | 2007-11-24 | Resistant to hydrolysis, process for their preparation and their use |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP2063003A1 true EP2063003A1 (en) | 2009-05-27 |
Family
ID=40301250
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP08018593A Withdrawn EP2063003A1 (en) | 2007-11-24 | 2008-10-23 | Hydrolysis resistant, equipped filaments, method for their manufacture and application thereof |
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| Country | Link |
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| EP (1) | EP2063003A1 (en) |
| DE (1) | DE102007056631A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2460649A1 (en) * | 2010-12-02 | 2012-06-06 | Rhein Chemie Rheinau GmbH | Elastomer-fibre compound, method for producing and using same |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0735165A2 (en) * | 1995-03-31 | 1996-10-02 | Hoechst Trevira GmbH & Co. KG | High resistance core-sheath monofilaments for technical applications |
| EP0779382A1 (en) * | 1995-12-15 | 1997-06-18 | Hoechst Trevira GmbH & Co. KG | Hydrolysis resistant polyester fibres and filaments, masterbatches and production process of polyester fibres and filaments |
| US5885709A (en) * | 1991-03-14 | 1999-03-23 | Hoechst Aktiengesellschaft | Carbodiimide-modified polyester fiber and preparation thereof |
| DE19834008A1 (en) | 1998-07-29 | 2000-02-03 | Johns Manville Int Inc | Monofilament bicomponent threads of the core sheath type |
| US20060036012A1 (en) * | 2004-08-10 | 2006-02-16 | Hayes Richard A | Process for producing a wollastonite containing polyester and products and articles produced therefrom |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL272088A (en) * | 1960-12-02 | |||
| WO1989011507A1 (en) * | 1988-05-26 | 1989-11-30 | Allied-Signal Inc. | Thermoplastic polyester/elastomer grafted blends |
| DE502006005768D1 (en) * | 2005-09-21 | 2010-02-11 | Raschig Gmbh | Hydrolysestabilisatorformulierungen |
-
2007
- 2007-11-24 DE DE102007056631A patent/DE102007056631A1/en not_active Withdrawn
-
2008
- 2008-10-23 EP EP08018593A patent/EP2063003A1/en not_active Withdrawn
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5885709A (en) * | 1991-03-14 | 1999-03-23 | Hoechst Aktiengesellschaft | Carbodiimide-modified polyester fiber and preparation thereof |
| EP0735165A2 (en) * | 1995-03-31 | 1996-10-02 | Hoechst Trevira GmbH & Co. KG | High resistance core-sheath monofilaments for technical applications |
| DE19511853A1 (en) | 1995-03-31 | 1996-10-02 | Hoechst Trevira Gmbh & Co Kg | Heavy-duty core / sheath monofilaments for technical applications |
| EP0779382A1 (en) * | 1995-12-15 | 1997-06-18 | Hoechst Trevira GmbH & Co. KG | Hydrolysis resistant polyester fibres and filaments, masterbatches and production process of polyester fibres and filaments |
| DE19834008A1 (en) | 1998-07-29 | 2000-02-03 | Johns Manville Int Inc | Monofilament bicomponent threads of the core sheath type |
| US20060036012A1 (en) * | 2004-08-10 | 2006-02-16 | Hayes Richard A | Process for producing a wollastonite containing polyester and products and articles produced therefrom |
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|---|---|
| DE102007056631A1 (en) | 2009-05-28 |
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