EP1544331B1 - Polyester fibres, process for their production and their use. - Google Patents
Polyester fibres, process for their production and their use. Download PDFInfo
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- EP1544331B1 EP1544331B1 EP04027655A EP04027655A EP1544331B1 EP 1544331 B1 EP1544331 B1 EP 1544331B1 EP 04027655 A EP04027655 A EP 04027655A EP 04027655 A EP04027655 A EP 04027655A EP 1544331 B1 EP1544331 B1 EP 1544331B1
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- Prior art keywords
- polyester
- weight
- polyester fibers
- fibers according
- epoxide
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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
- 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
Definitions
- the present invention relates to polyester fibers having high resistance to hydrolysis, in particular monofilaments, which can be used in particular in applications for processing and / or preserving foodstuffs.
- polyester fibers in particular monofilaments for technical applications, are in most cases subjected to high mechanical and / or thermal stresses during use.
- the material must have good dimensional stability and constancy of force-elongation properties over as long as possible usage periods.
- Molding compositions with high chemical and physical resistance and their use for fiber production are known. Commonly used materials for this are polyesters. It is also known to combine these polymers with other materials, for example, to set the hydrolysis resistance targeted.
- polyester-based chemical fibers are approved for contact with food.
- polyesters are prone to hydrolytic degradation.
- polyethylene terephthalate molding compositions containing a polyolefin copolymer, the glycidyl ester of an ethylenically unsaturated carboxylic acid and the barium salt of a long-chain fatty acid.
- the present invention has the object to provide polyester fibers which have excellent hydrolytic stability and which are suitable for the production of food commodities such as conveyor belts or sieves.
- the present invention provides polyester fibers, in particular monofilaments, which on the one hand can be used in the processing and / or storage of foodstuffs and which have one opposite to the other unmodified and having a same carboxyl group number having polyester improved hydrolysis resistance.
- the invention relates to polyester fibers having a content of free carboxyl groups of less than 3 meq / kg, which have been stabilized with an epoxy composition comprising at least one epoxidized fatty acid ester having an epoxide content of at least 1.5 wt.%, Based on the composition.
- the fiber-forming polyesters may be of any nature as long as they are melt-formable and impart to the fiber the properties desired for the particular application.
- thermoplastic polyesters and / or aromatic liquid crystalline polyesters are known per se.
- polyesters such as polycarbonate or aliphatic / aromatic polyesters such as polybutylene terephthalate, polycyclohexanedimethyl terephthalate, polyethylene naphthalate or especially polyethylene terephthalate, but also completely aromatic, liquid crystalline polyesters such as Polyoxibenzonaphtoat.
- Building blocks of thread-forming polyesters are preferably diols and dicarboxylic acids, or appropriately constructed oxycarboxylic acids.
- the main acid constituent of the polyesters is terephthalic acid or cyclohexanedicarboxylic acid, but other aromatic and / or aliphatic or cycloaliphatic dicarboxylic acids may also be suitable, preferably para or transitive aromatic compounds, for example 2,6-naphthalenedicarboxylic acid or 4,4'-biphenyldicarboxylic acid, but also p-hydroxybenzoic acid.
- Aliphatic dicarboxylic acids such as adipic acid or sebacic acid are preferably used in combination with aromatic dicarboxylic acids.
- Typical suitable dihydric alcohols are aliphatic and / or cycloaliphatic and / or aromatic diols, for example ethylene glycol, propanediol, 1,4-butanediol, 1,4-cyclohexanedimethanol but also hydroquinone.
- polyesters which have repeating structural units which are derived from an aromatic dicarboxylic acid and an aliphatic and / or cycloaliphatic diol.
- thermoplastic polyesters used are in particular selected from the group consisting of polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polypropylene terephthalate, polybutylene terephthalate, polycyclohexanedimethanol terephthalate, polycarbonate or a copolycondensate comprising polybutylene glycol, terephthalic acid and naphthalenedicarboxylic acid units.
- thermoplastic polyesters used are aromatic, liquid-crystalline polyesters, in particular polyesters comprising p-hydroxybenzoate units.
- the inventively stabilized polyester moldings show a significant reduction in the degradation tendency of the polyester, so that, for example, lifetimes of monofilaments can be achieved, which are equivalent to those of monofilaments based on highly resistant fiber materials, such as polyarylene sulfides or oxides.
- the polyesters used according to the invention usually have Solution viscosities (IV values) of at least 0.60 dl / g, preferably from 0.60 to 1.05 dl / g, particularly preferably from 0.62 to 0.93 dl / g, (measured at 25 ° C in Dichloroacetic acid (DCE)).
- IV values Solution viscosities
- the hydrolysis stabilizers used according to the invention give the polyester fibers excellent hydrolysis protection without being toxic.
- hydrolysis stabilizers used according to the invention can be prepared by simply mixing the components.
- the epoxidized fatty acid esters used as hydrolysis protectors used in the invention are derived from any fatty acids which are esterified with any, preferably aliphatic alcohols.
- the fatty acids have six to thirty carbon atoms, especially ten to twenty carbon atoms.
- the epoxidized fatty acid esters used to prepare the hydrolysis stabilizers used in the invention have at least one double bond. This may be in the alcohol part or preferably in the acid part. It is also fatty acid esters with multiple double bonds used as starting materials. These compounds are, in particular, esters of the so-called omega fatty acids which are found, for example, in fish oils.
- the alcohols may be tertiary, secondary or primary aliphatic alcohols and typically have from one to ten carbon atoms.
- Preferably used hydrolysis stabilizers comprise a) epoxidized fatty acid alkyl esters and b) epoxidized fatty acid glycerides.
- the epoxidized fatty acid glycerides used as component b) are derived from any fatty acids which are esterified with glycerol or partially esterified.
- the fatty acids Preferably, the fatty acids have six to thirty carbon atoms, in particular ten to twenty carbon atoms.
- the fatty acids are preferably unsaturated and may have one or more double bonds.
- Epoxidized fatty acid glycerides which are particularly suitable for preparing the hydrolysis protection agent used according to the invention are epoxidized soybean oil, epoxidized linseed oil, epoxidized rapeseed oil, epoxidized sunflower oil and epoxidized fish oil.
- the epoxidized fatty acid esters used are preferably the thermally stable C 1 -C 8 -alkyl esters, in particular the 2-ethylhexyl esters, unsaturated fatty acids or fatty acid mixtures of rapeseed oil, linseed oil, soybean oil or fish oil.
- the epoxidized products can be prepared by per se known epoxidation of the corresponding starting materials (esters or glycerides) with per compounds, such as peracids or hydrogen peroxide, or with activated oxygen, for example with ozone.
- the epoxide content of the hydrolysis stabilizer used according to the invention can likewise vary within a wide range, but amounts to at least 1.5% by weight of oxygen, based on the total amount of epoxidized components.
- the epoxide content is in the range of 1.5 to 15% by weight, more preferably 4 to 8% by weight.
- the amount ratio of component a) to b) can vary within wide limits. Typically, the amount of component a) 90 to 10 wt.% And the amount of component b) 10 to 90 wt.%, Based on the total amount of components a) and b).
- the type and amount of components a) and b) are preferably chosen so that liquid products are obtained.
- the hydrolysis protection agent used according to the invention preferably also contains at least one carbodiimide as component c).
- the hydrolysis protection agent preferably comprises 90 to 10% by weight of component a), 9.9 to 60% by weight of component b) and 0.1 to 30% by weight of component c) (based on the total amount of components a) to c)).
- the NCN content here is at least 2.0% by weight, based on the total amount of components a) to c).
- hydrolysis protection agent which consists exclusively of components a) and b).
- the amount of epoxide composition added in the preparation of the polyester fibers according to the invention or in the preparation of the polyester should be chosen such that the desired content of free carboxyl groups is from 0 to 3 meq / kg, preferably not more than 2 meq / kg polyester.
- the amount of epoxy composition can be chosen so that after setting the desired content of free carboxyl groups virtually all epoxy groups are consumed.
- the amount of epoxy composition is 0.05 to 30% by weight, based on the polyester fiber.
- 0.1 to 10 wt.% are used.
- polyester fibers are to be understood as meaning any polyester-containing fibers.
- filaments or staple fibers which consist of several individual fibers, but in particular monofilaments.
- polyester fibers according to the invention can be prepared by processes known per se.
- the amount of the epoxy composition should be chosen so that the content of free carboxyl groups in the polyester fiber does not exceed 3 meq / kg.
- the amount of the epoxy composition is to be chosen so that the content of free carboxyl groups in the polyester fiber does not exceed 3 meq / kg.
- the polyester filament formed is drawn one or more times.
- polyester fibers according to the invention can be present in any desired form, for example as multifilaments, as staple fibers or in particular as monofilaments.
- the titer of the polyester fibers according to the invention can likewise vary within wide limits. Examples are 100 to 45,000 dtex, in particular 400 to 7,000 dtex.
- polyester raw material can be used. This typically has levels of free carboxyl groups of 15 to 50 meq / kg of polyester. Preference is given to using polyester raw materials produced by solid phase condensation; in these, the content of free carboxyl groups is typically 5 to 20 meq / kg, preferably less than 8 meq / kg of polyester.
- an already hydrolysis-stabilized polyester raw material can also be used to produce the polyester fibers according to the invention.
- the stabilizer mixture comprising components a) and b) was added during the polycondensation and / or at least one of the monomers.
- this polyester raw material has a content of carboxyl groups of less than or equal to 3 meq / kg.
- the hot polymer filament is cooled, e.g. in a cooling bath, preferably in a water bath, and then wound up or peeled off.
- the removal speed is greater than the injection rate of the polymer melt.
- polyester fiber produced in this way is then preferably subjected to a post-drawing, particularly preferably in several stages, in particular a two- or three-stage post-drawing, with a total draw ratio of 3: 1 to 8: 1, preferably 4: 1 to 6: 1.
- the take-off speed is usually 10 to 100 meters per minute, preferably 10 to 40 meters per minute.
- polyester fibers according to the invention may contain, in addition to the hydrolysis stabilizer, further auxiliaries.
- auxiliaries include processing aids, antioxidants, plasticizers, lubricants, pigments, matting agents, viscosity modifiers or crystallization accelerators.
- 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.
- polyester fibers according to the invention are used in particular for the production of articles used in the processing and / or storage of foodstuffs.
- polyester fibers of the invention are preferably used for the production of fabrics, in particular fabrics, which are used in the food processing industry.
- polyester fibers in the form of monofilaments according to the invention relates to their use as conveyor belts or as components of conveyor belts in the food processing industry.
- PET polyethylene terephthalate
- hydrolysis stabilizer hydrolysis stabilizer
- PET a solid-phase-condensed type having free carboxyl group content of about 7 meq / kg was used.
- the hydrolysis stabilizer used was a mixture of epoxidized fatty acid alkyl esters and epoxidized fatty acid glycerides (test product Synbio Hystab from Shufer-Additivsysteme GmbH, Slevogtweg 10, 67122 Altrip).
Abstract
Description
Die vorliegende Erfindung betrifft Polyesterfasern mit hoher Hydrolysebeständigkeit, insbesondere Monofilamente, die sich insbesondere in Anwendungen zur Verarbeitung und/oder Aufbewahrung von Lebensmitteln einsetzen lassen.The present invention relates to polyester fibers having high resistance to hydrolysis, in particular monofilaments, which can be used in particular in applications for processing and / or preserving foodstuffs.
Es ist bekannt, dass Polyesterfasern, insbesondere Monofilamente für technische Anwendungen, in den meisten Fällen beim Gebrauch hohen mechanischen und oder thermischen Belastungen unterworfen werden. Hinzu kommen in vielen Fällen Belastungen durch chemische und andere Umgebungseinflüsse, denen das Material einen ausreichenden Widerstand entgegensetzen muss. Bei all diesen Belastungen muss das Material eine gute Dimensionsstabiliät und Konstanz der Kraft-Dehnungseigenschaften über möglichst lange Benutzungszeiträume aufweisen.It is known that polyester fibers, in particular monofilaments for technical applications, are in most cases subjected to high mechanical and / or thermal stresses during use. In addition, in many cases, exposure to chemical and other environmental influences to which the material must oppose sufficient resistance. For all these loads, the material must have good dimensional stability and constancy of force-elongation properties over as long as possible usage periods.
Ein Beispiel für technische Anwendungen, bei denen die Kombination hoher mechanischer, thermischer und chemischer Beanspruchungen vorliegt, ist der Einsatz von Monofilamenten in Filtern, Sieben oder als Förderbänder. Dieser Einsatz verlangt ein Monofilamentmaterial mit ausgezeichneten mechanischen Eigenschaften, wie hohem Anfangsmodul, Reißfestigkeit, Knoten- und Schlingenfestigkeit, sowie eine hohe Abriebfestigkeit verbunden mit einer hohen Hydrolyseresistenz, um den hohen Beanspruchungen bei dessen Einsatz zu widerstehen und um eine ausreichende Standzeit der Siebe oder Förderbänder zu gewährleisten.An example of technical applications where the combination of high mechanical, thermal and chemical stresses is present is the use of monofilaments in filters, screens or conveyors. This use requires a monofilament material having excellent mechanical properties such as high initial modulus, tear strength, knot and loop strength, and high abrasion resistance combined with a high resistance to hydrolysis to withstand the high stresses involved in its use and sufficient durability of the screens or conveyors guarantee.
Formmassen mit hoher chemischer und physikalischer Beständigkeit und deren Einsatz zur Faserherstellung sind bekannt. Verbreitet verwendete Materialien dafür sind Polyester. Es ist auch bekannt, diese Polymere mit anderen Materialien zu kombinieren, um beispielsweise die Hydrolysebeständigkeit gezielt einzustellen.Molding compositions with high chemical and physical resistance and their use for fiber production are known. Commonly used materials for this are polyesters. It is also known to combine these polymers with other materials, for example, to set the hydrolysis resistance targeted.
In der industriellen Produktion, wie bei der Herstellung oder Verarbeitung von Lebensmitteln werden Filter oder Förderbänder in Prozessen eingesetzt, die bei erhöhten Temperaturen ablaufen und in denen feucht-heiße Umgebungen vorliegen. Chemiefasern auf Polyesterbasis sind für den Kontakt mit Lebensmitteln zugelassen. Beim Einsatz in feucht-heißen Umgebungen neigen Polyester jedoch zum hydrolytischen Abbau.In industrial production, such as in the production or processing of food, filters or conveyor belts are used in processes that take place at elevated temperatures and in hot and humid environments. Polyester-based chemical fibers are approved for contact with food. However, when used in hot humid environments, polyesters are prone to hydrolytic degradation.
Es gibt bereits eine Reihe von Ansätzen, um dieses nachteilige Verhalten von Polyestern zu verlangsamen oder ganz zu vermeiden. Eine mögliche Maßnahme besteht in der Verringerung der Anzahl freier Carboxylgruppen.There are already a number of approaches to slow down or avoid this adverse behavior of polyesters. One possible measure is to reduce the number of free carboxyl groups.
Der Verschluss von Carboxylgruppen mit Carbodiimiden ist bekannt, beispielsweise aus den
Aus der
In der
Die bislang verfolgten Ansätze führen zu stabilisierten Polyestern mit einer ausgezeichneten Hydrolysestabilität. Allerdings sind die eingesetzten Verbindungen für die Anwendung mit Lebensmitteln problematisch.The hitherto pursued approaches lead to stabilized polyesters with excellent hydrolytic stability. However, the compounds used are problematic for use with foods.
Ausgehend von diesem Stand der Technik lag der vorliegenden Erfindung die Aufgabe zugrunde, Polyesterfasern bereitzustellen, die eine ausgezeichnete Hydrolysestabilität aufweisen und die sich für die Herstellung von Lebensmittelbedarfsgegenständen, wie Förderbändern oder Sieben, eignen.Based on this prior art, the present invention has the object to provide polyester fibers which have excellent hydrolytic stability and which are suitable for the production of food commodities such as conveyor belts or sieves.
Mit der vorliegenden Erfindung werden Polyesterfasern, insbesondere Monofilamente, bereitgestellt, die einerseits bei der Verarbeitung und/oder Lagerung von Lebensmitteln eingesetzt werden können und die eine gegenüber dem unmodifizierten und eine gleiche Carboxylgruppenanzahl aufweisenden Polyester verbesserte Hydrolysebeständigkeit aufweisen.The present invention provides polyester fibers, in particular monofilaments, which on the one hand can be used in the processing and / or storage of foodstuffs and which have one opposite to the other unmodified and having a same carboxyl group number having polyester improved hydrolysis resistance.
Die Erfindung betrifft Polyesterfasern mit einem Gehalt an freien Carboxylgruppen von weniger als 3 mval/kg, die mit einer Epoxidzusammensetzung enthaltend mindestens einen epoxidierten Fettsäureester mit einem Epoxidgehalt von mindestens 1,5 Gew. %, bezogen auf die Zusammensetzung, stabilisiert worden sind.The invention relates to polyester fibers having a content of free carboxyl groups of less than 3 meq / kg, which have been stabilized with an epoxy composition comprising at least one epoxidized fatty acid ester having an epoxide content of at least 1.5 wt.%, Based on the composition.
Bevorzugt werden Polyesterfasern mit einem Gehalt an freien Carboxylgruppen von kleiner gleich 3 mval/kg, die mit einer Epoxidzusammensetzung enthaltend
- a) epoxidierte Fettsäureester, und
- b) epoxidierte Fettsäureglyceride,
- a) epoxidized fatty acid esters, and
- b) epoxidized fatty acid glycerides,
Die faserbildenden Polyester können beliebiger Natur sein, solange diese in der Schmelze verformbar sind und der Faser die für den jeweiligen Anwendungszweck gewünschten Eigenschaften verleihen.The fiber-forming polyesters may be of any nature as long as they are melt-formable and impart to the fiber the properties desired for the particular application.
Diese thermoplastischen Polyester und/oder aromatischen flüssig-kristallinen Polyester sind an sich bekannt.These thermoplastic polyesters and / or aromatic liquid crystalline polyesters are known per se.
Beispiele dafür sind faserbildende Polyester wie Polycarbonat oder aliphatisch/aromatische Polyester, wie z.B. Polybutylenterephthalat, Polycyclohexandimethylterephthalat, Polyethylennaphthalat oder insbesondere Polyethylenterephthalat, aber auch vollständig aromatische, flüssig-kristalline Polyester, wie Polyoxibenzonaphtoat. Bausteine von fadenbildenden Polyestern sind vorzugsweise Diole und Dicarbonsäuren, bzw. entsprechend aufgebaute Oxycarbonsäuren. Hauptsäurebestandteil der Polyester ist Terephthalsäure oder Cyclohexandicarbonsäure, aber auch andere aromatische und/oder aliphatische bzw. cycloaliphatische Dicarbonsäuren können geeignet sein, vorzugsweise para- oder transständige aromatische Verbindungen, wie z.B. 2,6-Naphthalindicarbonsäure oder 4,4'-Biphenyldicarbonsäure, aber auch p-Hydroxy-benzoesäure. Aliphatische Dicarbonsäuren, wie z.B. Adipinsäure oder Sebacinsäure werden vorzugsweise in Kombination mit aromatischen Dicarbonsäuren eingesetzt.Examples thereof are fiber-forming polyesters such as polycarbonate or aliphatic / aromatic polyesters such as polybutylene terephthalate, polycyclohexanedimethyl terephthalate, polyethylene naphthalate or especially polyethylene terephthalate, but also completely aromatic, liquid crystalline polyesters such as Polyoxibenzonaphtoat. Building blocks of thread-forming polyesters are preferably diols and dicarboxylic acids, or appropriately constructed oxycarboxylic acids. The main acid constituent of the polyesters is terephthalic acid or cyclohexanedicarboxylic acid, but other aromatic and / or aliphatic or cycloaliphatic dicarboxylic acids may also be suitable, preferably para or transitive aromatic compounds, for example 2,6-naphthalenedicarboxylic acid or 4,4'-biphenyldicarboxylic acid, but also p-hydroxybenzoic acid. Aliphatic dicarboxylic acids such as adipic acid or sebacic acid are preferably used in combination with aromatic dicarboxylic acids.
Typische geeignete zweiwertige Alkohole sind aliphatische und/oder cycloaliphatische und/oder aromatische Diole, beispielsweise Ethylenglykol, Propandiol, 1,4-Butandiol, 1,4-Cyclohexandimethanol aber auch Hydrochinon. Bevorzugt sind aliphatische Diole, die zwei bis vier Kohlenstoffatome aufweisen, insbesondere Ethylenglykol; weiterhin bevorzugt sind cycloaliphatische Diole, wie 1,4-Cyclohexandimethanol.Typical suitable dihydric alcohols are aliphatic and / or cycloaliphatic and / or aromatic diols, for example ethylene glycol, propanediol, 1,4-butanediol, 1,4-cyclohexanedimethanol but also hydroquinone. Preference is given to aliphatic diols having from two to four carbon atoms, in particular ethylene glycol; furthermore preferred are cycloaliphatic diols, such as 1,4-cyclohexanedimethanol.
Bevorzugt werden Polyester eingesetzt, die wiederkehrende Struktureinheiten aufweisen, die sich ableiten von einer aromatischen Dicarbonsäure und einem aliphatischen und/oder cycloaliphatischen Diol.Preference is given to using polyesters which have repeating structural units which are derived from an aromatic dicarboxylic acid and an aliphatic and / or cycloaliphatic diol.
Bevorzugt eingesetzte thermoplastische Polyester werden inbesondere ausgewählt aus der Gruppe bestehend aus Polyethylenterephthalat, Polyethylennaphthalat, Polybutylennaphthalat, Polypropylenterephthalat, Polybutylenterephthalat, Polycyclohexandimethanolterephthalat, Polycarbonat oder einem Copolykondensat enthaltend Polybutylenglykol-, Terephthalsäure- und Naphthalindicarbonsäureeinheiten.Preferred thermoplastic polyesters used are in particular selected from the group consisting of polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polypropylene terephthalate, polybutylene terephthalate, polycyclohexanedimethanol terephthalate, polycarbonate or a copolycondensate comprising polybutylene glycol, terephthalic acid and naphthalenedicarboxylic acid units.
Weitere bevorzugt eingesetzte thermoplastische Polyester sind aromatische, flüssigkristalline Polyester, inbesondere Polyester enthaltend p-Hydroxybenzoateinheiten.Further preferred thermoplastic polyesters used are aromatic, liquid-crystalline polyesters, in particular polyesters comprising p-hydroxybenzoate units.
Die erfindungsgemäß stabilisierten Polyesterformkörper zeigen eine signifikante Verringerung der Abbauneigung des Polyesters, so dass beispielsweise Lebensdauern von Monofilamenten erzielt werden können, die denen von Monofilamenten auf der Basis von äußerst beständigen Fasermaterialien, wie Polyarylensulfiden oder -oxiden, gleichwertig sind.The inventively stabilized polyester moldings show a significant reduction in the degradation tendency of the polyester, so that, for example, lifetimes of monofilaments can be achieved, which are equivalent to those of monofilaments based on highly resistant fiber materials, such as polyarylene sulfides or oxides.
Die erfindungsgemäß eingesetzten Polyester weisen üblicherweise Lösungsviskositäten (IV-Werte) von mindestens 0,60 dl/g, vorzugsweise von 0,60 bis 1,05 dl/g, besonders bevorzugt von 0,62 - 0,93 dl/g, auf (gemessen bei 25°C in Dichloressigsäure (DCE)).The polyesters used according to the invention usually have Solution viscosities (IV values) of at least 0.60 dl / g, preferably from 0.60 to 1.05 dl / g, particularly preferably from 0.62 to 0.93 dl / g, (measured at 25 ° C in Dichloroacetic acid (DCE)).
Die erfindungsgemäß eingesetzten Hydrolyseschutzmittel verleihen den Polyesterfasern einen ausgezeichneten Hydrolyseschutz ohne dabei toxisch zu wirken.The hydrolysis stabilizers used according to the invention give the polyester fibers excellent hydrolysis protection without being toxic.
Die erfindungsgemäß eingesetzten Hydrolyseschutzmittel können durch einfaches Vermischen der Komponenten hergestellt werden.The hydrolysis stabilizers used according to the invention can be prepared by simply mixing the components.
Die als erfindungsgemäß verwendetes Hydrolyseschutzmittel eingesetzten epoxidierten Fettsäureester leiten sich von beliebigen Fettsäuren ab, die mit beliebigen, vorzugsweise aliphatischen Alkoholen verestert sind.The epoxidized fatty acid esters used as hydrolysis protectors used in the invention are derived from any fatty acids which are esterified with any, preferably aliphatic alcohols.
Vorzugsweise weisen die Fettsäuren sechs bis dreißig Kohlenstoffatome auf, insbesondere zehn bis zwanzig Kohlenstoffatome. Die zur Herstellung der erfindungsgemäß verwendeten Hydrolyseschutzmittel eingesetzten epoxidierten Fettsäureester weisen mindestens eine Doppelbindung auf. Diese kann sich im Alkoholteil oder vorzugsweise im Säureteil befinden. Es sind auch Fettsäureester mit mehreren Doppelbindungen als Ausgangsmaterialien einsetzbar. Bei diesen Verbindungen handelt es sich insbesondere um Ester der sogenannten omega-Fettsäuren, die beispielsweise in Fischölen vorkommen. Die Alkohole können tertiäre, sekundäre oder primäre aliphatische Alkohole sein und weisen in der Regel ein bis zehn Kohlenstoffatome auf.Preferably, the fatty acids have six to thirty carbon atoms, especially ten to twenty carbon atoms. The epoxidized fatty acid esters used to prepare the hydrolysis stabilizers used in the invention have at least one double bond. This may be in the alcohol part or preferably in the acid part. It is also fatty acid esters with multiple double bonds used as starting materials. These compounds are, in particular, esters of the so-called omega fatty acids which are found, for example, in fish oils. The alcohols may be tertiary, secondary or primary aliphatic alcohols and typically have from one to ten carbon atoms.
Bevorzugt eingesetzte Hydrolysestabilisatoren enthalten a) epoxidierte Fettsäurealkylester und b) epoxidierte Fettsäureglyceride.Preferably used hydrolysis stabilizers comprise a) epoxidized fatty acid alkyl esters and b) epoxidized fatty acid glycerides.
Die als Komponente b) eingesetzten epoxidierten Fettsäureglyceride leiten sich von beliebigen Fettsäuren ab, die mit Glycerin verestert oder teilverestert sind. Vorzugsweise weisen die Fettsäuren sechs bis dreißig Kohlenstoffatome auf, insbesondere zehn bis zwanzig Kohlenstoffatome. Die Fettsäuren sind vorzugsweise ungesättigt und können ein- oder mehrere Doppelbindungen aufweisen.The epoxidized fatty acid glycerides used as component b) are derived from any fatty acids which are esterified with glycerol or partially esterified. Preferably, the fatty acids have six to thirty carbon atoms, in particular ten to twenty carbon atoms. The fatty acids are preferably unsaturated and may have one or more double bonds.
Zur Herstellung des erfindungsgemäß eingesetzten Hydrolyseschutzmittels besonders geeignete epoxidierte Fettsäureglyceride sind epoxidiertes Sojabohnenöl, epoxidiertes Leinöl, epoxidiertes Rüböl, epoxidiertes Sonnenblumenöl und epoxidiertes Fischöl.Epoxidized fatty acid glycerides which are particularly suitable for preparing the hydrolysis protection agent used according to the invention are epoxidized soybean oil, epoxidized linseed oil, epoxidized rapeseed oil, epoxidized sunflower oil and epoxidized fish oil.
Als epoxidierte Fettsäureester werden bevorzugt die thermisch stabilen C1-C8-Alkylester, insbesondere die 2-Ethylhexylester, ungesättigter Fettsäuren oder Fettsäuregemische der Rüböl, Leinöl, Sojaöl oder Fischöl zugrundeliegenden Fettsäuren eingesetzt.The epoxidized fatty acid esters used are preferably the thermally stable C 1 -C 8 -alkyl esters, in particular the 2-ethylhexyl esters, unsaturated fatty acids or fatty acid mixtures of rapeseed oil, linseed oil, soybean oil or fish oil.
Die Herstellung der epoxidierten Produkte kann durch an sich bekannte Epoxidierung der entsprechenden Ausgangsprodukte (Ester bzw. Glyceride) mit Perverbindungen, wie Persäuren oder Wasserstoffperoxid, oder mit aktiviertem Sauerstoff, beispielsweise mit Ozon, erfolgen.The epoxidized products can be prepared by per se known epoxidation of the corresponding starting materials (esters or glycerides) with per compounds, such as peracids or hydrogen peroxide, or with activated oxygen, for example with ozone.
Der Epoxidgehalt des erfindungsgemäß eingesetzten Hydrolysestabilisators kann ebenfalls in weiten Bereich schwanken, beträgt jedoch mindestens 1,5 Gew. % an Sauerstoff, bezogen auf die Gesamtmenge an epoxidierten Komponenten. Vorzugsweise bewegt sich der Epoxidgehalt im Bereich von 1,5 bis 15 Gew. %, insbesondere von 4 bis 8 Gew. %.The epoxide content of the hydrolysis stabilizer used according to the invention can likewise vary within a wide range, but amounts to at least 1.5% by weight of oxygen, based on the total amount of epoxidized components. Preferably, the epoxide content is in the range of 1.5 to 15% by weight, more preferably 4 to 8% by weight.
Das Mengenverhältnis von Komponente a) zu b) kann in weiten Bereichen schwanken. Typischerweise beträgt die Menge an Komponente a) 90 bis 10 Gew. % und die Menge an Komponente b) 10 bis 90 Gew. %, bezogen auf die Gesamtmenge an Komponenten a) und b).The amount ratio of component a) to b) can vary within wide limits. Typically, the amount of component a) 90 to 10 wt.% And the amount of component b) 10 to 90 wt.%, Based on the total amount of components a) and b).
Art und Menge der Komponenten a) und b) werden vorzugsweise so gewählt, dass flüssige Produkte erhalten werden.The type and amount of components a) and b) are preferably chosen so that liquid products are obtained.
Bevorzugt enthält das erfindungsgemäß eingesetzte Hydrolyseschutzmittel noch mindestens ein Carbodiimid als Komponente c).The hydrolysis protection agent used according to the invention preferably also contains at least one carbodiimide as component c).
In dieser Ausführungsform weist das Hydrolyseschutzmittel vorzugsweise 90 bis 10 Gew. % Komponente a), 9,9 bis 60 Gew. % Komponente b) und 0,1 bis 30 Gew. % Komponente c) auf (bezogen auf die Gesamtmenge an Komponenten a) bis c)).In this embodiment, the hydrolysis protection agent preferably comprises 90 to 10% by weight of component a), 9.9 to 60% by weight of component b) and 0.1 to 30% by weight of component c) (based on the total amount of components a) to c)).
Der NCN-Gehalt beträgt hierbei mindestens 2,0 Gew. %, bezogen auf die Gesamtmenge an Komponenten a) bis c).The NCN content here is at least 2.0% by weight, based on the total amount of components a) to c).
Besonders bevorzugt wird ein Hydrolyseschutzmittel eingesetzt, das ausschließlich aus den Komponenten a) und b) besteht.Particular preference is given to using a hydrolysis protection agent which consists exclusively of components a) and b).
Die bei der Herstellung der erfindungsgemäßen Polyesterfasern oder bei der Herstellung des Polyesters zugesetzte Menge an Epoxidzusammensetzung ist so zu wählen, dass sich der gewünschte Gehalt an freien Carboxylgruppen von 0 bis 3 mval/kg, vorzugsweise von nicht mehr als 2 mval/kg Polyester ergibt.The amount of epoxide composition added in the preparation of the polyester fibers according to the invention or in the preparation of the polyester should be chosen such that the desired content of free carboxyl groups is from 0 to 3 meq / kg, preferably not more than 2 meq / kg polyester.
Die Menge an Epoxidzusammensetzung kann dabei so gewählt werden, dass nach dem Einstellen des gewünschten Gehaltes an freien Carboxylgruppen praktisch sämtliche Epoxidgruppen verbraucht sind.The amount of epoxy composition can be chosen so that after setting the desired content of free carboxyl groups virtually all epoxy groups are consumed.
Vorzugsweise wählt man jedoch größere Mengen, um eine Depotwirkung zu erzielen.Preferably, however, one chooses larger amounts in order to achieve a depot effect.
Typischerweise beträgt die Menge an Epoxidzusammensetzung 0,05 bis 30 Gew. %, bezogen auf die Polyesterfaser. Bevorzugt werden 0,1 bis 10 Gew. % verwendet.Typically, the amount of epoxy composition is 0.05 to 30% by weight, based on the polyester fiber. Preferably, 0.1 to 10 wt.% Are used.
Unter Polyesterfasern sind im Rahmen dieser Beschreibung beliebige Polyester enthaltende Fasern zu verstehen.For the purposes of this description, polyester fibers are to be understood as meaning any polyester-containing fibers.
Beispiele dafür sind Filamente oder Stapelfasern, die aus mehreren einzelnen Fasern bestehen, insbesondere jedoch Monofilamente sind.Examples are filaments or staple fibers, which consist of several individual fibers, but in particular monofilaments.
Die erfindungsgemäßen Polyesterfasern können nach an sich bekannten Verfahren hergestellt werden.The polyester fibers according to the invention can be prepared by processes known per se.
Gegenstand der Erfindung ist auch ein Verfahren zur Herstellung der erfindungsgemäßen Polyesterfasern umfassend die Maßnahmen:
- i) Vermischen von Polyestergranulat mit der oben definierten Epoxidzusammensetzung,
- ii) Extrudieren des Gemisches enthaltend Polyester und Epoxidzusammensetzung durch eine Spinndüse, und
- iii) Abziehen des gebildeten Filaments.
- i) mixing polyester granules with the above-defined epoxy composition,
- ii) extruding the mixture containing polyester and epoxy composition through a spinneret, and
- iii) stripping the formed filament.
Dabei ist die Menge der Epoxidzusammensetzung so zu wählen, dass der Gehalt von freien Carboxylgruppen in der Polyesterfaser 3 mval/kg nicht überschreitet.The amount of the epoxy composition should be chosen so that the content of free carboxyl groups in the polyester fiber does not exceed 3 meq / kg.
Die Erfindung betrifft ferner ein Verfahren zur Herstellung der erfindungsgemäßen Polyesterfasern umfassend die Maßnahmen:
- iv) Zuführen von Polyestergranulat, das vor oder während der Polykondensation mit der oben definierten Epoxidzusammensetzung vermischt worden ist, in einen Extruder, und
- ii) Extrudieren des Gemisches enthaltend Polyester und Epoxidzusammensetzung durch eine Spinndüse, und
- iii) Abziehen des gebildeten Filaments.
- iv) feeding polyester granules, which has been mixed before or during the polycondensation with the above-defined epoxy composition, into an extruder, and
- ii) extruding the mixture containing polyester and epoxy composition through a spinneret, and
- iii) stripping the formed filament.
Auch bei dieser Variante ist die Menge der Epoxidzusammensetzung so zu wählen, dass der Gehalt von freien Carboxylgruppen in der Polyesterfaser 3 mval/kg nicht überschreitet.Also in this variant, the amount of the epoxy composition is to be chosen so that the content of free carboxyl groups in the polyester fiber does not exceed 3 meq / kg.
In einer bevorzugten Ausführungsform der erfindungsgemäßen Verfahren wird das gebildete Polyesterfilament ein- oder mehrfach verstreckt.In a preferred embodiment of the process according to the invention, the polyester filament formed is drawn one or more times.
Die erfindungsgemäßen Polyesterfasern können in beliebiger Form vorliegen, beispielsweise als Multifilamente, als Stapelfasern oder insbesondere als Monofilamente.The polyester fibers according to the invention can be present in any desired form, for example as multifilaments, as staple fibers or in particular as monofilaments.
Der Titer der erfindungsgemäßen Polyesterfasern kann ebenfalls in weiten Bereichen schwanken. Beispiele dafür sind 100 bis 45.000 dtex, insbesondere 400 bis 7.000 dtex.The titer of the polyester fibers according to the invention can likewise vary within wide limits. Examples are 100 to 45,000 dtex, in particular 400 to 7,000 dtex.
Besonders bevorzugt werden Monofilamente, deren Querschnittsform rund, oval oder n-eckig ist, wobei n größer gleich 3 ist.Particular preference is given to monofilaments whose cross-sectional shape is round, oval or n-shaped, where n is greater than or equal to 3.
Zur Herstellung der erfindungsgemäßen Polyesterfasern kann ein handelsüblicher Polyester-Rohstoff verwendet werden. Dieser weist typischerweise Gehalte von freien Carboxylgruppen von 15 bis 50 mval/kg Polyester auf. Bevorzugt werden durch Festphasenkondensation hergestellte Polyester-Rohstoffe eingesetzt; bei diesen beträgt der Gehalt an freien Carboxylgruppen typischerweise 5 bis 20 mval/kg, bevorzugt weniger als 8 mval/kg Polyester.To prepare the polyester fibers of the invention, a commercial polyester raw material can be used. This typically has levels of free carboxyl groups of 15 to 50 meq / kg of polyester. Preference is given to using polyester raw materials produced by solid phase condensation; in these, the content of free carboxyl groups is typically 5 to 20 meq / kg, preferably less than 8 meq / kg of polyester.
Zur Herstellung der erfindungsgemäßen Polyesterfasern kann aber auch ein bereits hydrolysestabilisierter Polyester-Rohstoff verwendet werden. Bei dessen Herstellung wurde das Stabilisatorgemisch enthaltend Komponenten a) und b) während der Polykondensation und/oder mindestens einer der Monomeren zugesetzt. Dieser Polyester-Rohstoff weist bereits vor der Faserherstellung einen Gehalt von Carboxylgruppen von kleiner gleich 3 mval/kg auf.However, an already hydrolysis-stabilized polyester raw material can also be used to produce the polyester fibers according to the invention. During its preparation, the stabilizer mixture comprising components a) and b) was added during the polycondensation and / or at least one of the monomers. Even before fiber production, this polyester raw material has a content of carboxyl groups of less than or equal to 3 meq / kg.
Nach dem Verpressen der Polymerschmelze durch eine Spinndüse wird der heiße Polymerfaden abgekühlt, z.B. in einem Kühlbad, vorzugsweise in einem Wasserbad, und anschließend aufgewickelt oder abgezogen. Die Abziehgeschwindigkeit ist dabei größer als die Spritzgeschwindigkeit der Polymerschmelze.After pressing the polymer melt through a spinneret, the hot polymer filament is cooled, e.g. in a cooling bath, preferably in a water bath, and then wound up or peeled off. The removal speed is greater than the injection rate of the polymer melt.
Die so hergestellte Polyesterfaser wird anschließend vorzugsweise einer Nachverstreckung, besonders bevorzugt in mehreren Stufen, insbesondere einer zwei- oder dreistufigen Nachverstreckung, mit einem Gesamtverstreckungsverhältnis von 3 : 1 bis 8 : 1, vorzugsweise 4 : 1 bis 6 : 1, unterzogen.The polyester fiber produced in this way is then preferably subjected to a post-drawing, particularly preferably in several stages, in particular a two- or three-stage post-drawing, with a total draw ratio of 3: 1 to 8: 1, preferably 4: 1 to 6: 1.
Nach der Verstreckung schließt sich vorzugsweise eine Thermofixierung an, wobei Temperaturen von 130 bis 280°C zum Einsatz kommen; dabei wird bei konstanter Länge gearbeitet oder es wird ein Schrumpf von bis zu 30 % zugelassen.After stretching preferably followed by a heat-setting, with temperatures of 130 to 280 ° C are used; it will be at constant Length worked or a shrinkage of up to 30% is allowed.
Als besonders vorteilhaft für die Herstellung der erfindungsgemäßen Polyesterfasern hat es sich erwiesen, wenn bei einer Schmelzetemperatur im Bereich von 285 bis 315°C und bei einem Verzug von 2 : 1 bis 6 : 1 gearbeitet wird.It has proven to be particularly advantageous for the preparation of the polyester fibers according to the invention, if working at a melt temperature in the range of 285 to 315 ° C and at a delay of 2: 1 to 6: 1.
Die Abzugsgeschwindigkeit beträgt üblicherweise 10 - 100 m pro Minute, vorzugsweise 10 - 40 m pro Minute.The take-off speed is usually 10 to 100 meters per minute, preferably 10 to 40 meters per minute.
Die erfindungsgemäßen Polyesterfasern können neben dem Hydrolysestabilisator noch weitere Hilfsstoffe enthalten. Beispiele dafür sind Verarbeitungshilfsmittel, Antioxidantien, Weichmacher, Gleitmittel, Pigmente, Mattierungsmittel, Viskositätsmodifizierer oder Kristallisationbeschleuniger.The polyester fibers according to the invention may contain, in addition to the hydrolysis stabilizer, further auxiliaries. Examples include processing aids, antioxidants, plasticizers, lubricants, pigments, matting agents, viscosity modifiers or crystallization accelerators.
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 Farbstoff-pigmente oder Titandioxid.Examples of pigments or matting agents are organic dye pigments or titanium dioxide.
Bespiele 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.
Die erfindungsgemäßen Polyesterfasern werden insbesondere zur Herstellung Gegenständen, die bei der Verarbeitung und/oder Aufbewahrung von Lebensmitteln eingesetzt werden, verwendet.The polyester fibers according to the invention are used in particular for the production of articles used in the processing and / or storage of foodstuffs.
Bevorzugt werden die erfindungsgemäßen Polyesterfasern zur Herstellung von Flächengebilden, insbesondere von Geweben, eingesetzt, welche in der lebensmittelverarbeitenden Industrie eingesetzt werden.The polyester fibers of the invention are preferably used for the production of fabrics, in particular fabrics, which are used in the food processing industry.
Eine weitere Verwendung der erfindungsgemäßen Polyesterfasern in der Form von Monofilamenten betrifft deren Einsatz als Förderbänder oder als Komponenten von Förderbändern in der lebensmittelverarbeitenden Industrie.Another use of the polyester fibers in the form of monofilaments according to the invention relates to their use as conveyor belts or as components of conveyor belts in the food processing industry.
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.
Die Komponenten Polyethylenterephthalat ("PET") und Hydrolysestabilisator wurden im Extruder vermischt, aufgeschmolzen und durch eine 12 Loch Spinndüse mit einem Lochdurchmesser von 1,10 mm bei einer Fördermenge von 292,3 g/min und einer Abzugsgeschwindigkeit von 32,7 m/min zu Monofilamenten versponnen, zweifach verstreckt (erste Verstreckung im Wasserbad bei 80°C; zweite Verstreckung im Wasserbad bei 90°C), sowie im Heißluftkanal bei 235°C thermofixiert. Die Gesamtverstreckung betrug 4,28 : 1. Der Enddurchmesser der Monofilamente betrug 0,40 mm.The components polyethylene terephthalate ("PET") and hydrolysis stabilizer were mixed in the extruder, melted and passed through a 12-hole spinnerette with a hole diameter of 1.10 mm at a flow rate of 292.3 g / min and a take-off speed of 32.7 m / min spun into monofilaments, stretched twice (first orientation in a water bath at 80 ° C., second orientation in a water bath at 90 ° C.), and heat-set in the hot-air channel at 235 ° C. The total draw was 4.28: 1. The final diameter of the monofilaments was 0.40 mm.
Als PET wurde eine festphasenkondensierte Type mit einem Gehalt an freien Carboxylgruppen von etwa 7 mval/kg eingesetzt.As the PET, a solid-phase-condensed type having free carboxyl group content of about 7 meq / kg was used.
Als Hydrolysestabilisator wurde ein Gemisch epoxidierter Fettsäurealkylester und epoxidierter Fettsäureglyceride eingesetzt (Versuchsprodukt Synbio Hystab der Fa. Schäfer-Additivsysteme GmbH, Slevogtweg 10, 67122 Altrip).The hydrolysis stabilizer used was a mixture of epoxidized fatty acid alkyl esters and epoxidized fatty acid glycerides (test product Synbio Hystab from Schäfer-Additivsysteme GmbH, Slevogtweg 10, 67122 Altrip).
In der nachfolgenden Tabelle sind die bei den einzelnen Versuchen verwendeten Dosierungen, der Gehalt an freien Carboxylgruppen des stabilisierten Produktes sowie die Restfestigkeit nach 80-stündiger Behandlung in feucht-heißer Umgebung bei 135°C (Hydrolyseresistenz) zusammengestellt.
[Gew. %]
[mval/kg]
[N]
[Wt. %]
[Meq / kg]
[N]
Claims (15)
- Polyester fibers having a free carboxyl group content of not more than 3 meq/kg which are stabilized by an epoxide composition comprising at least one epoxidized fatty acid ester having an epoxide content of not less than 1.5% by weight, based on the composition.
- Polyester fibers according to claim 1, characterized in that the epoxide composition comprisesa) epoxidized fatty acid esters, andb) epoxidized fatty acid glycerides,and has an epoxide content of not less than 1.5% by weight, based on the composition.
- Polyester fibers according to claim 2, characterized in that the epoxide composition consists ofa) 90% to 10% by weight of long-chain epoxidized fatty acid alkyl esters andb) 10% to 90% by weight of epoxidized fatty acid glycerides,and has an epoxidized content of not less than 1.5% by weight.
- Polyester fibers according to claim 1, characterized in that the epoxide composition comprisesa) 90% to 10% by weight of long-chain epoxidized fatty acid alkyl esters,b) 9.9% to 60% by weight of epoxidized fatty acid glycerides andc) 0.1 % to 30% by weight of carbodiimides,and has an epoxide content of not less than 1.5% by weight and an NCN group content of not less than 2.0% by weight.
- Polyester fibers according to claim 1, characterized in that the amount of epoxide composition is in the range from 0.1% to 10% by weight, based on the shaped polyester article.
- Polyester fibers according to claim 1, characterized in that the fiber is a monofilament.
- Polyester fibers according to claim 1, characterized in that the polyester comprises structural repeat units derived from an aromatic dicarboxylic acid and an aliphatic and/or cycloaliphatic diol, especially polyethylene terephthalate repeat units.
- Polyester fibers according to claim 1, characterized in that the polyester is a liquid crystal polyester.
- Process for producing the polyester fibers according to claim 1, the - process comprising the measures of:i) mixing polyester pellet with the epoxide composition according to claim 1, andii) extruding the mixture comprising polyester and epoxide composition through a spinneret die, andiii) withdrawing the resulting filament,with the proviso that the amount of epoxide composition is chosen such that the level of free carboxyl groups in the polyester fiber does not exceed 3 meq/kg.
- Process for producing the polyester fibers according to claim 1, the process comprising the measures of:iv) feeding an extruder with polyester pellet mixed with the epoxide composition according to claim 1 before or during the polycondensation, andii) extruding the mixture comprising polyester and epoxide composition through a spinneret die, andiii) withdrawing the resulting filament,with the proviso that the amount of epoxide composition is chosen such that the level of free carboxyl groups in the polyester fiber does not exceed 3 meq/kg.
- Process according to claim 10 or claim 11, characterized in that the polyester fiber is subjected to single or multiple drawing.
- Process according to claim 10 or claim 11, characterized in that the polyester fiber is produced using a polyester produced by solid state condensation.
- Use of polyester fibers according to claim 1 for producing articles used in food processing and/or storage.
- Use of polyester fibers according to claim 1 for producing sheetlike structures, especially wovens, used in the food-processing industry.
- Use of polyester fibers according to claim 1 in the form of monofilaments as conveyor belts or as components of conveyor belts in the food-processing industry.
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DE102004044326A1 (en) * | 2004-09-10 | 2006-03-16 | Mitsubishi Polyester Film Gmbh | Hydrolysis resistant film of a polyester with hydrolysis protection agent and process for their preparation and their use |
GB0915687D0 (en) | 2009-09-08 | 2009-10-07 | Dupont Teijin Films Us Ltd | Polyester films |
GB2488787A (en) * | 2011-03-07 | 2012-09-12 | Dupont Teijin Films Us Ltd | Stabilised polyester films |
JP5542084B2 (en) * | 2011-03-31 | 2014-07-09 | 帝人株式会社 | Polyester fiber for rubber reinforcement |
JP5542085B2 (en) * | 2011-03-31 | 2014-07-09 | 帝人株式会社 | Method for producing pretreated polyester fiber |
EP2766420B1 (en) * | 2011-10-14 | 2017-01-18 | Galata Chemicals LLC | Plasticizers derived from renewable feedstock |
KR102024408B1 (en) * | 2012-02-08 | 2019-09-23 | 다우 글로벌 테크놀로지스 엘엘씨 | Plasticizer compositions and methods for making plasticizer compositions |
GB201310837D0 (en) | 2013-06-18 | 2013-07-31 | Dupont Teijin Films Us Ltd | Polyester film -IV |
CN105593298A (en) * | 2013-09-30 | 2016-05-18 | 3M创新有限公司 | Compositions, wipes, and methods |
CN105579630B (en) * | 2013-09-30 | 2018-03-23 | 3M创新有限公司 | Fiber, cleaning piece and method |
WO2015047890A1 (en) * | 2013-09-30 | 2015-04-02 | 3M Innovative Properties Company | Fibers and wipes with epoxidized fatty ester disposed thereon, and methods |
GB201317551D0 (en) | 2013-10-03 | 2013-11-20 | Dupont Teijin Films Us Ltd | Co-extruded polyester films |
JP6360693B2 (en) * | 2014-03-14 | 2018-07-18 | 株式会社クラレ | Melt anisotropic aromatic polyester fiber with excellent light resistance |
GB201707356D0 (en) | 2017-05-08 | 2017-06-21 | Dupont Teijin Films U S Ltd Partnership | Hydrolysis resistant polyester film |
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BE618033A (en) * | 1961-06-01 | |||
US4016142A (en) * | 1966-11-09 | 1977-04-05 | Millhaven Fibers, Ltd. | Process for the control of carboxyl end groups in fiber-forming polyesters |
GB1093840A (en) * | 1965-11-29 | 1967-12-06 | Ici Ltd | Modified polyesters |
US3886104A (en) * | 1973-01-05 | 1975-05-27 | Gen Electric | Stabilized polyester compositions |
JPS62243825A (en) * | 1986-04-17 | 1987-10-24 | Asahi Chem Ind Co Ltd | Production of polyester filament yarn |
JP3001945B2 (en) * | 1990-09-20 | 2000-01-24 | ポリプラスチックス株式会社 | Polyester showing anisotropy when melted |
JP3228977B2 (en) * | 1991-03-14 | 2001-11-12 | ジョーンズ・マンヴィル・インターナショナル・インコーポレーテッド | Carbodiimide-modified polyester fiber and method for producing the same |
DE19540320A1 (en) * | 1995-10-28 | 1997-04-30 | Herberts & Co Gmbh | Nonionic emulsifiers |
JPH09263688A (en) * | 1996-03-28 | 1997-10-07 | Toray Ind Inc | Polyester composition, monofilament and woven fabric for industrial use |
US5753166A (en) * | 1996-04-29 | 1998-05-19 | Eastman Chemical Company | Process of making a non-circular cross-sectional fiber |
US6333363B1 (en) * | 1997-07-18 | 2001-12-25 | Nisshinbo Industries, Inc. | Method for obtaining polyester resin products having desired strength, and mixture used in said method |
US6818293B1 (en) * | 2003-04-24 | 2004-11-16 | Eastman Chemical Company | Stabilized polyester fibers and films |
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