EP1544331A1 - Polyester fibres, process for their production and their use. - Google Patents
Polyester fibres, process for their production and their use. Download PDFInfo
- Publication number
- EP1544331A1 EP1544331A1 EP04027655A EP04027655A EP1544331A1 EP 1544331 A1 EP1544331 A1 EP 1544331A1 EP 04027655 A EP04027655 A EP 04027655A EP 04027655 A EP04027655 A EP 04027655A EP 1544331 A1 EP1544331 A1 EP 1544331A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- polyester
- polyester fibers
- fibers according
- epoxy composition
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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
-
- 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 hydrolysis resistance, in particular monofilaments, which are particularly useful in applications for Processing and / or storage of food can be used.
- polyester fibers in particular monofilaments for technical Applications, in most cases when using high mechanical and or be subjected to thermal loads.
- Exposure to chemical and other environmental factors affecting the material must oppose sufficient resistance. With all these burdens
- the material needs a good dimensional stability and constancy of the force-elongation properties have as long as possible periods of use.
- Molding compounds with high chemical and physical resistance and their Use for fiber production are known. Widely used materials for it are polyester. It is also known to use these polymers with other materials combine, for example, to set the hydrolysis resistance targeted.
- the present invention was the The object of the invention is to provide polyester fibers which are excellent Have hydrolytic stability and are suitable for the production of Food commodities, such as conveyor belts or sieves, are suitable.
- polyester fibers in particular Monofilaments, provided on the one hand during processing and / or storage can be used by food and the one opposite the unmodified and an equal number of carboxyl groups having polyester have improved hydrolysis resistance.
- the invention relates to polyester fibers containing free carboxyl groups of less than 3 meq / kg, containing with an epoxy composition at least one epoxidized fatty acid ester having an epoxide content of at least 1.5% by weight, based on the composition, has been stabilized are.
- the fiber-forming polyesters may be of any nature, as long as they are in the Melt are deformable and the fiber for the particular application lend desired properties.
- thermoplastic polyesters and / or aromatic liquid crystalline Polyesters are known per se.
- polyesters such as polycarbonate or aliphatic / aromatic Polyester, e.g. Polybutylene terephthalate, polycyclohexanedimethylterephthalate, Polyethylene naphthalate or in particular polyethylene terephthalate, but also completely aromatic, liquid-crystalline polyesters, such as Polyoxibenzonaphtoat.
- Building blocks of thread-forming polyesters are preferred Diols and dicarboxylic acids, or correspondingly structured oxycarboxylic acids.
- Main acid constituent of the polyesters is terephthalic acid or cyclohexanedicarboxylic acid, but also other aromatic and / or aliphatic or Cycloaliphatic dicarboxylic acids may be suitable, preferably para or transitive aromatic compounds, e.g. 2,6-naphthalene or 4,4'-biphenyldicarboxylic acid, but also p-hydroxybenzoic acid.
- aliphatic Dicarboxylic acids e.g. Adipic acid or sebacic acid are preferably used in 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.
- Preferred are aliphatic diols having from two to four carbon atoms, in particular ethylene glycol; furthermore preferred are cycloaliphatic diols, such as 1,4-cyclohexanedimethanol.
- polyesters which contain recurring structural units which are derived from an aromatic dicarboxylic acid and a aliphatic and / or cycloaliphatic diol.
- thermoplastic polyesters are selected in particular from the group consisting of polyethylene terephthalate, polyethylene naphthalate, Polybutylene naphthalate, polypropylene terephthalate, polybutylene terephthalate, Polycyclohexanedimethanol terephthalate, polycarbonate or a copolycondensate containing polybutylene glycol, terephthalic acid and Naphthalenedicarboxylic.
- thermoplastic polyesters used are aromatic, liquid crystalline polyesters, in particular polyesters containing p-hydroxybenzoate units.
- the inventively stabilized polyester moldings show a significant Reduction of the degradation tendency of the polyester, so that, for example Lifes of monofilaments can be achieved that of Monofilaments based on extremely durable fiber materials, such as Polyarylene sulfides or oxides, are equivalent.
- 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 protectants used according to the invention confer the Polyester fibers provide excellent protection against hydrolysis without being toxic Act.
- the hydrolysis protective agents used according to the invention can be prepared by simple Mixing the components are made.
- hydrolysis protection agent used according to the invention epoxidized fatty acid esters are derived from any fatty acids with any, preferably aliphatic alcohols are esterified.
- the fatty acids have six to thirty carbon atoms, in particular ten to twenty carbon atoms.
- the for the production of Hydrolysis protectants used according to the invention used epoxidized Fatty acid esters have at least one double bond. This can be in the Alcohol part or preferably located in the acid part. There are also fatty acid esters with several double bonds can be used as starting materials. In these Compounds are, in particular, esters of the so-called omega fatty acids, which occur for example in fish oils.
- the alcohols can tertiary, secondary or primary aliphatic alcohols are and generally have 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 that 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 preferred unsaturated and may have one or more double bonds.
- epoxidized fatty acid glycerides 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 preparation of the epoxidized products can by known per se 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, done.
- the epoxide content of the hydrolysis stabilizer used according to the invention can also vary widely, but is at least 1.5 wt.% To Oxygen, based on the total amount of epoxidized components.
- the epoxide content is in the range of 1.5 to 15 weight percent, in particular from 4 to 8% by weight.
- the quantitative ratio of component a) to b) can be in a wide range vary. Typically, the amount of component a) is 90 to 10% by weight. and the amount of component b) is 10 to 90% by weight, based on the Total amount of components a) and b).
- the nature and amount of the components a) and b) are preferably chosen so that liquid products are obtained.
- the hydrolysis protection agent used according to the invention preferably still contains at least one carbodiimide as component c).
- the hydrolysis-protecting agent preferably has 90 to 10 % By weight of component a), 9.9 to 60% by weight of component b) and 0.1 to 30% by weight Component c) (based on the total amount of components a) to c)).
- the NCN content is at least 2.0 wt.%, Based on the Total amount of components a) to c).
- hydrolysis protection agent which exclusively consists of the components a) and b).
- polyester fibers of the invention or in the Production of the polyester added amount of epoxy composition is so too Choose the desired content of free carboxyl groups from 0 to 3 mval / kg, preferably not more than 2 meq / kg polyester.
- the amount of epoxy composition can be chosen so that after the setting of the desired content of free carboxyl groups practically all epoxide groups are consumed.
- the amount of epoxy composition is 0.05 to 30 wt%, based on the polyester fiber.
- polyester fibers are any polyesters to understand containing fibers.
- Examples include filaments or staple fibers, which consist of several individual Consist of fibers, but in particular monofilaments.
- polyester fibers according to the invention can be prepared by processes known per se getting produced.
- 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 epoxy composition is to be chosen so the content of free carboxyl groups in the polyester fiber is not 3 meq / kg exceeds.
- the formed polyester filament one or more times stretched.
- 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 also be in wide Ranges vary. Examples are 100 to 45,000 dtex, especially 400 up to 7,000 dtex.
- monofilaments whose cross-sectional shape is round, oval or n-sided, where n is greater than or equal to 3.
- polyester fibers according to the invention may be a commercial Polyester raw material can be used. This typically has levels of free carboxyl groups of 15 to 50 meq / kg of polyester. To be favoured used by solid phase condensation polyester raw materials used; at the content of free carboxyl groups is typically 5 to 20 m / kg, preferably less than 8 meq / kg of polyester.
- polyester raw material For the preparation of the polyester fibers according to the invention but also already hydrolysis stabilized polyester raw material can be used. In its production was the stabilizer mixture containing components a) and b) during the Polycondensation and / or added to at least one of the monomers.
- This Polyester raw material already has a content of Carboxyl groups of less than or equal to 3 meq / kg.
- the hot Polymer thread After pressing the polymer melt through a spinneret is the hot Polymer thread cooled, e.g. in a cooling bath, preferably in a water bath, and then wound up or peeled off.
- the peel rate is this is greater than the injection rate of the polymer melt.
- the polyester fiber thus produced is then preferably a Post-drawing, particularly preferably in several stages, in particular one two- or three-stage re-drawing, with a total draw ratio from 3: 1 to 8: 1, preferably 4: 1 to 6: 1.
- polyester fibers according to the invention As particularly advantageous for the production of the polyester fibers according to the invention it has been proven, if at a melt temperature in the range of 285 to 315 ° C and a delay of 2: 1 to 6: 1 is worked.
- the take-off speed is usually 10-100 m per minute, preferably 10 - 40 m per minute.
- polyester fibers of the invention can be used in addition to the hydrolysis stabilizer still contain other auxiliaries.
- auxiliaries are processing aids, Antioxidants, plasticizers, lubricants, pigments, matting agents, Viscosity modifier or crystallization accelerator.
- 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 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 of the invention are used in particular for the production Objects involved in the processing and / or storage of food used.
- polyester fibers according to the invention for the production of Fabrics, in particular of woven fabrics, used in the used in the food processing industry.
- polyester fibers according to the invention in the form of Monofilaments 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 containing free Carboxyl groups of about 7 meq / kg used.
- Hydrolysestabilisator was a mixture of epoxidized fatty acid alkyl esters and epoxidized fatty acid glycerides used (test product Synbio Hystab the Fa. Schfer-Additivsysteme GmbH, Slevogtweg 10, 67122 Altrip).
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Artificial Filaments (AREA)
- Belt Conveyors (AREA)
- Woven Fabrics (AREA)
- Polyesters Or Polycarbonates (AREA)
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 hydrolysis resistance, in particular monofilaments, which are particularly useful in applications for Processing and / or storage of food can be used.
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, in most cases when using high mechanical and or be subjected to thermal loads. In addition, in many cases Exposure to chemical and other environmental factors affecting the material must oppose sufficient resistance. With all these burdens The material needs a good dimensional stability and constancy of the force-elongation properties have as long as possible periods of use.
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 as conveyor belts. This use requires a monofilament material with excellent mechanical properties Features, such as high initial modulus, tear strength, knot and Sling resistance, as well as a high abrasion resistance combined with a high Hydrolyseresistenz to the high stresses in its use Resist and to ensure adequate service life of the screens or conveyor belts 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 compounds with high chemical and physical resistance and their Use for fiber production are known. Widely used materials for it are polyester. It is also known to use these polymers with other materials combine, 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, as in the manufacture or processing of Food filters or conveyor belts are used in processes that in elevated temperatures and in which hot and humid environments are present. Polyester-based chemical fibers are approved for contact with food. When used in hot and humid environments, however, polyester tends 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 this adverse behavior of To slow or completely avoid polyesters. A possible measure is the reduction in the number of free carboxyl groups.
Der Verschluss von Carboxylgruppen mit Carbodiimiden ist bekannt, beispielsweise aus den DE-A-39 30 845, DE-A-41 08 278, EP-A-417,717 und EP-A-503,421.The closure of carboxyl groups with carbodiimides is known, for example from DE-A-39 30 845, DE-A-41 08 278, EP-A-417,717 and EP-A-503,421.
Aus der US-A-4,016,142 ist bekannt, dass der Gehalt an freien Carboxylgruppen in Polyestern durch Zusatz von einem Glycidylether reduziert werden kann.From US-A-4,016,142 it is known that the content of free carboxyl groups in Polyesters can be reduced by addition of a glycidyl ether.
In der US-A-4,284,540 werden Polyethylenterephthalat-Formmassen beschrieben, die ein Polyolefin-Copolymer, den Glycidylester einer ethylenisch ungesättigten Carbonsäure und das Bariumsalz einer langkettigen Fettsäure enthalten.In the US-A-4,284,540 polyethylene terephthalate molding compositions are described, a polyolefin copolymer, the glycidyl ester of an ethylenically unsaturated Carboxylic acid and the barium salt of a long-chain fatty acid.
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 a excellent hydrolytic stability. However, the compounds used are problematic for use with food.
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 was the The object of the invention is to provide polyester fibers which are excellent Have hydrolytic stability and are suitable for the production of Food commodities, such as conveyor belts or sieves, are suitable.
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.With the present invention polyester fibers, in particular Monofilaments, provided on the one hand during processing and / or storage can be used by food and the one opposite the unmodified and an equal number of carboxyl groups having polyester have 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 containing free carboxyl groups of less than 3 meq / kg, containing with an epoxy composition at least one epoxidized fatty acid ester having an epoxide content of at least 1.5% by weight, based on the composition, has been stabilized are.
Bevorzugt werden Polyesterfasern mit einem Gehalt an freien Carboxylgruppen von
kleiner gleich 3 mval/kg, die mit einer Epoxidzusammensetzung enthaltend
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 in the Melt are deformable and the fiber for the particular application lend desired properties.
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 of these are fiber-forming polyesters such as polycarbonate or aliphatic / aromatic Polyester, e.g. Polybutylene terephthalate, polycyclohexanedimethylterephthalate, Polyethylene naphthalate or in particular polyethylene terephthalate, but also completely aromatic, liquid-crystalline polyesters, such as Polyoxibenzonaphtoat. Building blocks of thread-forming polyesters are preferred Diols and dicarboxylic acids, or correspondingly structured oxycarboxylic acids. Main acid constituent of the polyesters is terephthalic acid or cyclohexanedicarboxylic acid, but also other aromatic and / or aliphatic or Cycloaliphatic dicarboxylic acids may be suitable, preferably para or transitive aromatic compounds, e.g. 2,6-naphthalene or 4,4'-biphenyldicarboxylic acid, but also p-hydroxybenzoic acid. aliphatic Dicarboxylic acids, e.g. Adipic acid or sebacic acid are preferably used in 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. Preferred are 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 contain recurring structural units which are derived from an aromatic dicarboxylic acid and a 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 are selected in particular from the group consisting of polyethylene terephthalate, polyethylene naphthalate, Polybutylene naphthalate, polypropylene terephthalate, polybutylene terephthalate, Polycyclohexanedimethanol terephthalate, polycarbonate or a copolycondensate containing polybutylene glycol, terephthalic acid and Naphthalenedicarboxylic.
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 containing 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 of the degradation tendency of the polyester, so that, for example Lifes of monofilaments can be achieved that of Monofilaments based on extremely durable fiber materials, such as Polyarylene sulfides or oxides, are equivalent.
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 protectants used according to the invention confer the Polyester fibers provide excellent protection against hydrolysis without being toxic Act.
Die erfindungsgemäß eingesetzten Hydrolyseschutzmittel können durch einfaches Vermischen der Komponenten hergestellt werden.The hydrolysis protective agents used according to the invention can be prepared by simple Mixing the components are made.
Die als erfindungsgemäß verwendetes Hydrolyseschutzmittel eingesetzten epoxidierten Fettsäureester leiten sich von beliebigen Fettsäuren ab, die mit beliebigen, vorzugsweise aliphatischen Alkoholen verestert sind.The hydrolysis protection agent used according to the invention epoxidized fatty acid esters are derived from any fatty acids with any, preferably aliphatic alcohols are esterified.
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, in particular ten to twenty carbon atoms. The for the production of Hydrolysis protectants used according to the invention used epoxidized Fatty acid esters have at least one double bond. This can be in the Alcohol part or preferably located in the acid part. There are also fatty acid esters with several double bonds can be used as starting materials. In these Compounds are, in particular, esters of the so-called omega fatty acids, which occur for example in fish oils. The alcohols can tertiary, secondary or primary aliphatic alcohols are and generally have 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 that 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 preferred 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.For the preparation of the hydrolysis protective agent used according to the invention particularly suitable epoxidized fatty acid glycerides 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 preparation of the epoxidized products can by known per se 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, done.
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 also vary widely, but is at least 1.5 wt.% To Oxygen, based on the total amount of epoxidized components. Preferably, the epoxide content is in the range of 1.5 to 15 weight percent, in particular from 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 quantitative ratio of component a) to b) can be in a wide range vary. Typically, the amount of component a) is 90 to 10% by weight. and the amount of component b) is 10 to 90% by weight, 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 nature and amount of the 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 still 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-protecting agent preferably has 90 to 10 % By weight of component a), 9.9 to 60% by weight of component b) and 0.1 to 30% by weight 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 is at least 2.0 wt.%, 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 exclusively consists of the 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 in the production of polyester fibers of the invention or in the Production of the polyester added amount of epoxy composition is so too Choose the desired content of free carboxyl groups from 0 to 3 mval / 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 the setting of the desired content of free carboxyl groups practically all epoxide groups are consumed.
Vorzugsweise wählt man jedoch größere Mengen, um eine Depotwirkung zu erzielen.Preferably, however, one chooses larger amounts to a depot effect achieve.
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 wt%, 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 any polyesters to understand containing fibers.
Beispiele dafür sind Filamente oder Stapelfasern, die aus mehreren einzelnen Fasern bestehen, insbesondere jedoch Monofilamente sind. Examples include filaments or staple fibers, which consist of several individual Consist of 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 getting produced.
Gegenstand der Erfindung ist auch ein Verfahren zur Herstellung der
erfindungsgemäßen Polyesterfasern umfassend die Maßnahmen:
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:
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 epoxy composition is to be chosen so the content of free carboxyl groups in the polyester fiber is not 3 meq / kg exceeds.
In einer bevorzugten Ausführungsform der erfindungsgemäßen Verfahren wird das gebildete Polyesterfilament ein- oder mehrfach verstreckt.In a preferred embodiment of the inventive method is the formed polyester filament one or more times stretched.
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 also be in wide Ranges vary. Examples are 100 to 45,000 dtex, especially 400 up to 7,000 dtex.
Besonders bevorzugt werden Monofilamente, deren Querschnittsform rund, oval oder n-eckig ist, wobei n größer gleich 3 ist.Particularly preferred are monofilaments whose cross-sectional shape is round, oval or n-sided, 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.For the preparation of the polyester fibers according to the invention may be a commercial Polyester raw material can be used. This typically has levels of free carboxyl groups of 15 to 50 meq / kg of polyester. To be favoured used by solid phase condensation polyester raw materials used; at the content of free carboxyl groups is typically 5 to 20 m / 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.For the preparation of the polyester fibers according to the invention but also already hydrolysis stabilized polyester raw material can be used. In its production was the stabilizer mixture containing components a) and b) during the Polycondensation and / or added to at least one of the monomers. This Polyester raw material already 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 is the hot Polymer thread cooled, e.g. in a cooling bath, preferably in a water bath, and then wound up or peeled off. The peel rate is this 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 thus produced is then preferably a Post-drawing, particularly preferably in several stages, in particular one two- or three-stage re-drawing, with a total draw ratio from 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, wherein 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.As particularly advantageous for the production of the polyester fibers according to the invention it has been proven, if at a melt temperature in the range of 285 to 315 ° C and a delay of 2: 1 to 6: 1 is worked.
Die Abzugsgeschwindigkeit beträgt üblicherweise 10 - 100 m pro Minute, vorzugsweise 10 - 40 m pro Minute.The take-off speed is usually 10-100 m per minute, preferably 10 - 40 m 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 of the invention can be used in addition to the hydrolysis stabilizer still contain other auxiliaries. Examples are processing aids, Antioxidants, plasticizers, lubricants, pigments, matting agents, Viscosity modifier or crystallization accelerator.
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 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 of the invention are used in particular for the production Objects involved in the processing and / or storage of food used.
Bevorzugt werden die erfindungsgemäßen Polyesterfasern zur Herstellung von Flächengebilden, insbesondere von Geweben, eingesetzt, welche in der lebensmittelverarbeitenden Industrie eingesetzt werden. Preference is given to the polyester fibers according to the invention for the production of Fabrics, in particular of woven fabrics, used in the 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 according to the invention in the form of Monofilaments 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 used mixed in the extruder, melted and through a 12 hole spinneret 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 to monofilaments, stretched twice (first drawing in a water bath at 80 ° C; second Stretching in a water bath at 90 ° C), as well as in the hot air channel at 235 ° C heat set. The total stretch 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 containing free Carboxyl groups of about 7 meq / kg used.
Als Hydrolysestabilisator wurde ein Gemisch epoxidierter Fettsäurealkylester und epoxidierter Fettsäureglyceride eingesetzt (Versuchsprodukt Synbio Hystab der Fa. Schäfer-Additivsysteme GmbH, Slevogtweg 10, 67122 Altrip).As Hydrolysestabilisator was a mixture of epoxidized fatty acid alkyl esters and epoxidized fatty acid glycerides used (test product Synbio Hystab the Fa. 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. In the table below, the dosages used in the individual experiments, the content of free carboxyl groups of the stabilized product and the residual strength after 80 hours of treatment in a moist-hot environment at 135 ° C (hydrolysis resistance) are compiled.
Claims (15)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10359763 | 2003-12-19 | ||
DE10359763A DE10359763B4 (en) | 2003-12-19 | 2003-12-19 | Polyester fibers, process for their preparation and their use |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1544331A1 true EP1544331A1 (en) | 2005-06-22 |
EP1544331B1 EP1544331B1 (en) | 2009-09-09 |
Family
ID=34485495
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP04027655A Not-in-force EP1544331B1 (en) | 2003-12-19 | 2004-11-22 | Polyester fibres, process for their production and their use. |
Country Status (7)
Country | Link |
---|---|
US (1) | US20050137299A1 (en) |
EP (1) | EP1544331B1 (en) |
JP (1) | JP2005179879A (en) |
AT (1) | ATE442469T1 (en) |
DE (2) | DE10359763B4 (en) |
ES (1) | ES2332718T3 (en) |
PT (1) | PT1544331E (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2015047988A1 (en) * | 2013-09-30 | 2015-04-02 | 3M Innovative Properties Company | Compositions, wipes, and methods |
CN105579630A (en) * | 2013-09-30 | 2016-05-11 | 3M创新有限公司 | Fibers, wipes, and methods |
EP3052697A1 (en) * | 2013-09-30 | 2016-08-10 | 3M Innovative Properties Company | Fibers and wipes with epoxidized fatty ester disposed thereon, and methods |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
JP5542085B2 (en) * | 2011-03-31 | 2014-07-09 | 帝人株式会社 | Method for producing pretreated polyester fiber |
JP5542084B2 (en) * | 2011-03-31 | 2014-07-09 | 帝人株式会社 | Polyester fiber for rubber reinforcement |
ES2619029T3 (en) * | 2011-10-14 | 2017-06-22 | Galata Chemicals Llc | Plasticizers derived from renewable raw material |
US20150005420A1 (en) * | 2012-02-08 | 2015-01-01 | Dow Global Technologies Llc | Plasticizer compositions and methods for making plasticizer compositions |
GB201310837D0 (en) | 2013-06-18 | 2013-07-31 | Dupont Teijin Films Us Ltd | Polyester film -IV |
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 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4016142A (en) * | 1966-11-09 | 1977-04-05 | Millhaven Fibers, Ltd. | Process for the control of carboxyl end groups in fiber-forming polyesters |
JPS62243825A (en) * | 1986-04-17 | 1987-10-24 | Asahi Chem Ind Co Ltd | Production of polyester filament yarn |
JPH09263688A (en) * | 1996-03-28 | 1997-10-07 | Toray Ind Inc | Polyester composition, monofilament and woven fabric for industrial use |
US20040214984A1 (en) * | 2003-04-24 | 2004-10-28 | Keep Gerald Timothy | Stabilized polyester fibers and films |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BE618033A (en) * | 1961-06-01 | |||
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 |
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 |
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 |
-
2003
- 2003-12-19 DE DE10359763A patent/DE10359763B4/en not_active Expired - Fee Related
-
2004
- 2004-11-22 ES ES04027655T patent/ES2332718T3/en active Active
- 2004-11-22 DE DE502004010034T patent/DE502004010034D1/en active Active
- 2004-11-22 PT PT04027655T patent/PT1544331E/en unknown
- 2004-11-22 AT AT04027655T patent/ATE442469T1/en not_active IP Right Cessation
- 2004-11-22 EP EP04027655A patent/EP1544331B1/en not_active Not-in-force
- 2004-12-15 US US11/013,114 patent/US20050137299A1/en not_active Abandoned
- 2004-12-17 JP JP2004365326A patent/JP2005179879A/en not_active Withdrawn
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4016142A (en) * | 1966-11-09 | 1977-04-05 | Millhaven Fibers, Ltd. | Process for the control of carboxyl end groups in fiber-forming polyesters |
JPS62243825A (en) * | 1986-04-17 | 1987-10-24 | Asahi Chem Ind Co Ltd | Production of polyester filament yarn |
JPH09263688A (en) * | 1996-03-28 | 1997-10-07 | Toray Ind Inc | Polyester composition, monofilament and woven fabric for industrial use |
US20040214984A1 (en) * | 2003-04-24 | 2004-10-28 | Keep Gerald Timothy | Stabilized polyester fibers and films |
Non-Patent Citations (2)
Title |
---|
PATENT ABSTRACTS OF JAPAN vol. 012, no. 122 (C - 488) 15 April 1988 (1988-04-15) * |
PATENT ABSTRACTS OF JAPAN vol. 1998, no. 02 30 January 1998 (1998-01-30) * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2015047988A1 (en) * | 2013-09-30 | 2015-04-02 | 3M Innovative Properties Company | Compositions, wipes, and methods |
CN105579630A (en) * | 2013-09-30 | 2016-05-11 | 3M创新有限公司 | Fibers, wipes, and methods |
EP3052697A1 (en) * | 2013-09-30 | 2016-08-10 | 3M Innovative Properties Company | Fibers and wipes with epoxidized fatty ester disposed thereon, and methods |
US9982128B2 (en) | 2013-09-30 | 2018-05-29 | 3M Innovative Properties Company | Fibers, wipes, and methods |
Also Published As
Publication number | Publication date |
---|---|
US20050137299A1 (en) | 2005-06-23 |
PT1544331E (en) | 2009-11-23 |
DE502004010034D1 (en) | 2009-10-22 |
JP2005179879A (en) | 2005-07-07 |
ES2332718T3 (en) | 2010-02-11 |
ATE442469T1 (en) | 2009-09-15 |
DE10359763B4 (en) | 2007-11-22 |
DE10359763A1 (en) | 2005-07-28 |
EP1544331B1 (en) | 2009-09-09 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0503421B1 (en) | Polyester fibres modified with carbodiimides and process for their preparation | |
DE10359763B4 (en) | Polyester fibers, process for their preparation and their use | |
DE69731290T2 (en) | SPONTANEABLE FIBERS | |
DE69817212T2 (en) | COPOLYESTER-BINDER FIBERS | |
EP2632985B1 (en) | Use of polymer blends for producing slit film tapes | |
DD297670A5 (en) | CARBODIMIDED MODIFIED POLYESTER FIBERS AND METHOD FOR THE PRODUCTION THEREOF | |
EP1637633A1 (en) | Polyester fibres, method for their production and their use. | |
DE4307392C1 (en) | Hydrolysis resistant monofilament prepn. - comprises drawing soln. contg. polyester obtd. from 1,4-cyclohexane:di:methanol and phthalic acid or 1,4-cyclohexane di:carboxylic acid, stabiliser, and (co)polymer of ethylene] terephthalate, | |
DE4410399A1 (en) | Abrasion-resistant polyester blend with increased processing safety, monofilaments made of it and their production and use | |
EP3158115A1 (en) | Monofilaments having high abrasion resistance and dimensional stability and low glideability, textile fabrics composed thereof and use thereof | |
DE2703051A1 (en) | HYDROPHILIC POLYESTER FEMES | |
EP1835055A1 (en) | Polyester threads, method for their manufacture and application thereof | |
DE19805153A1 (en) | Biodegradable coating agents | |
DE102005033350A1 (en) | Polyester fibers, process for their preparation and their use | |
EP0779382B1 (en) | Hydrolysis resistant polyester fibres and filaments, masterbatches and production process of polyester fibres and filaments | |
EP0761847B1 (en) | Paper-making machine fabrics, filters and reinforcement structures for elastomers containing monofilaments from copolyesters | |
DE19828517C2 (en) | Monofilaments based on polyethylene-2,6-naphthalate | |
WO1983003432A1 (en) | Draw-textured, base-dyeable polyester yarn | |
EP2499283B1 (en) | Spun-dyed hmls monofilaments, production thereof and use thereof | |
EP0991689B1 (en) | Thread-forming, chain-branched polyesters and copolyesters | |
DE19948977C2 (en) | Polymer compositions and their use | |
DE4334492A1 (en) | Low-pill and flame-retardant polyester mixtures containing phosphorus and silicon, processes for their production and structures formed therefrom | |
DE19963242C1 (en) | Multi-component monofilament comprises core of polyethylene naphthalate, liquid crystal polymer(s), polybutylene terephthalate and sealant and polyphenylene sulfide shell | |
DE19915683A1 (en) | Polyester fibers and filaments and process for their manufacture | |
EP2063003A1 (en) | Hydrolysis resistant, equipped filaments, method for their manufacture and application thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LU MC NL PL PT RO SE SI SK TR |
|
AX | Request for extension of the european patent |
Extension state: AL HR LT LV MK YU |
|
17P | Request for examination filed |
Effective date: 20051222 |
|
AKX | Designation fees paid |
Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LU MC NL PL PT RO SE SI SK TR |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LU MC NL PL PT RO SE SI SK TR |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D Free format text: NOT ENGLISH |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D |
|
REF | Corresponds to: |
Ref document number: 502004010034 Country of ref document: DE Date of ref document: 20091022 Kind code of ref document: P |
|
REG | Reference to a national code |
Ref country code: SE Ref legal event code: TRGR |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: NV Representative=s name: PATENTANWAELTE SCHAAD, BALASS, MENZL & PARTNER AG |
|
REG | Reference to a national code |
Ref country code: PT Ref legal event code: SC4A Free format text: AVAILABILITY OF NATIONAL TRANSLATION Effective date: 20091117 |
|
REG | Reference to a national code |
Ref country code: RO Ref legal event code: EPE |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: AT Payment date: 20091113 Year of fee payment: 6 Ref country code: CH Payment date: 20091124 Year of fee payment: 6 Ref country code: DE Payment date: 20091120 Year of fee payment: 6 Ref country code: ES Payment date: 20091123 Year of fee payment: 6 Ref country code: FI Payment date: 20091113 Year of fee payment: 6 Ref country code: SE Payment date: 20091112 Year of fee payment: 6 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2332718 Country of ref document: ES Kind code of ref document: T3 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: PL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20090909 Ref country code: SI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20090909 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 20091112 Year of fee payment: 6 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20090909 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FD4D |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20090909 Ref country code: EE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20090909 Ref country code: CZ Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20090909 Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20100109 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20091201 Year of fee payment: 6 Ref country code: GB Payment date: 20091119 Year of fee payment: 6 Ref country code: IT Payment date: 20091124 Year of fee payment: 6 Ref country code: RO Payment date: 20091214 Year of fee payment: 6 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20090909 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MC Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20091130 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 20091110 Year of fee payment: 6 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20090909 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: PT Payment date: 20100419 Year of fee payment: 6 |
|
26N | No opposition filed |
Effective date: 20100610 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20091210 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BG Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20091130 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20091122 |
|
REG | Reference to a national code |
Ref country code: PT Ref legal event code: MM4A Free format text: LAPSE DUE TO NON-PAYMENT OF FEES Effective date: 20110523 |
|
BERE | Be: lapsed |
Owner name: TEIJIN MONOFILAMENT GERMANY G.M.B.H. Effective date: 20101130 |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: V1 Effective date: 20110601 |
|
REG | Reference to a national code |
Ref country code: SE Ref legal event code: EUG |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: HU Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20100310 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20101122 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: PT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20110523 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20101130 Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20101130 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST Effective date: 20110801 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: TR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20090909 Ref country code: NL Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20110601 Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20101130 Ref country code: AT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20101122 Ref country code: FI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20101122 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R119 Ref document number: 502004010034 Country of ref document: DE Effective date: 20110601 Ref country code: DE Ref legal event code: R119 Ref document number: 502004010034 Country of ref document: DE Effective date: 20110531 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20101123 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20101130 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: RO Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20101122 Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20101122 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20101122 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20120220 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20101123 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20110531 |