Nothing Special   »   [go: up one dir, main page]

EP1842944B1 - Biodegradable binding twine - Google Patents

Biodegradable binding twine Download PDF

Info

Publication number
EP1842944B1
EP1842944B1 EP07105204A EP07105204A EP1842944B1 EP 1842944 B1 EP1842944 B1 EP 1842944B1 EP 07105204 A EP07105204 A EP 07105204A EP 07105204 A EP07105204 A EP 07105204A EP 1842944 B1 EP1842944 B1 EP 1842944B1
Authority
EP
European Patent Office
Prior art keywords
oder
und
core material
biodegradable
fibers
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.)
Active
Application number
EP07105204A
Other languages
German (de)
French (fr)
Other versions
EP1842944B9 (en
EP1842944A2 (en
EP1842944A3 (en
EP1842944B3 (en
Inventor
Karl-Heinz Eispert
Thomas Schönung
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
GARNTEC GmbH
Original Assignee
GARNTEC GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by GARNTEC GmbH filed Critical GARNTEC GmbH
Publication of EP1842944A2 publication Critical patent/EP1842944A2/en
Publication of EP1842944A3 publication Critical patent/EP1842944A3/en
Application granted granted Critical
Publication of EP1842944B1 publication Critical patent/EP1842944B1/en
Publication of EP1842944B3 publication Critical patent/EP1842944B3/en
Publication of EP1842944B9 publication Critical patent/EP1842944B9/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/02—Yarns or threads characterised by the material or by the materials from which they are made
    • D02G3/04—Blended or other yarns or threads containing components made from different materials
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/22—Yarns or threads characterised by constructional features, e.g. blending, filament/fibre
    • D02G3/36—Cored or coated yarns or threads

Definitions

  • the present patent application relates to a biodegradable yarn of a core material of biodegradable natural fibers and / or man-made fibers and a shell of a biodegradable plastic.
  • Yarns are used for example in the form of tie cords in hop growing; their use is also in other areas z. B. in viticulture, the construction industry or packaging industry possible.
  • iron wires are used as a climbing aid for hop plants in hop growing.
  • the plant can grow upwards and thus reach the desired heights, while hopping up to about 8 meters.
  • the wires are knotted in the hop garden at the top of a cross wire and just below in the immediate vicinity of the hop plant stuck in the ground.
  • the wire is cut by hand or machine down with the hop plant just above the ground and also topped off with the hop plant.
  • the wire is shredded together with the plant remains of the hop plant and spent on the fields for rotting or rusting.
  • a new hop wire is attached to each hop plant as described above.
  • the hops are currently made of iron, usually of ST 37 and have a round cross section with a diameter of 1.1 and 1.5 mm.
  • the hop plant needs a certain surface roughness on the wire surface in order to be able to hold tight to the wire. In the conventional iron wire, this surface roughness results from the manufacturing process and resulting flash rust.
  • a first disadvantage is its very high specific gravity.
  • Another disadvantage is that when chopping the wire a very high wear on the chopping knives occurs.
  • hop spikes A particular disadvantage is the so-called "hop spikes".
  • hop farmer drives the shredded material from his farm to the fields with the tractor and wagon with the pieces of iron wire approx. 2 to 5 centimeters long, it regularly happens that such "hop spikes” fall on the road.
  • driving over these "hop spikes” with the car they then drill into the tires and cause high damage.
  • the DE-OS 23 44 221 describes support cords for plants from z. B. polyolefin. A cross-sectional change is to be achieved by a melt fracture induced in the extrusion. However, this leads to strength variations over the length of the string. In addition, although the surface achievable by melt fracture is deformed, it is still smooth so that plants will find insufficient support.
  • the DE 198 00 842 C2 describes a plastic thread formed as a monofilament, wherein the monofilament is made of a polypropylene and treated on the surface to reduce the surface smoothness, wherein the plastic thread made of biodegradable modified polypropylene and is stretched to increase the strength, and wherein the Surface of the plastic thread is reduced by profiling and / or chemical and physical processes.
  • the present invention is therefore based on the object to provide an improved yarn with controllable biodegradability and compostability and excellent tensile strength and elongation at break.
  • the present invention thus provides a biodegradable and compostable yarn containing a core material of natural fibers and / or man-made fibers and comprising a shell material of biodegradable and compostable biopolymers.
  • the materials forming the core of the yarn according to the invention are those of natural fibers such as cotton, flax, hemp, sisal, jute, coconut, bast, ramie and / or man-made fibers, for example natural polymers such as viscose, cellulose , Lyocell and / or Tencel, as well as fibers of biodegradable and compostable aliphatic and / or partially aromatic polyester amides and / or aliphatic and / or partially aromatic polyesters.
  • the core fibers are selected from natural fibers consisting of cotton, flax (linen), hemp, sisal, cellulose and / or jute.
  • the materials forming the core are particularly preferably natural fibers of sisal, since sisal has a natural water-repellent action.
  • biodegradable and compostable means biodegradable and compostable yarns according to the invention which are completely biodegradable and compostable according to DIN EN 13 432.
  • the yarn according to the invention disintegrates after a certain, predeterminable time and is converted under composting conditions by the bacteria and microbes in the soil into natural waste products, so that in this case even a natural fertilization is achieved.
  • the time required for the yarn of the present invention to fully degrade is limited (e.g., by the weight fraction of shell material, based on the total weight of the yarn of the invention), i.e., adjustable.
  • the yarn according to the invention can be defined in terms of its degradation time to each individual application.
  • the tear strength of the yarn according to the invention can also be adjusted to any particular application.
  • acids can also be used in the form of derivatives such as, for example, acid chlorides or esters, both as monomers and as oligomeric esters.
  • the yarn according to the invention has the advantage that by the use of natural fibers, such as cotton, flax, hemp, sisal, jute, ramie and coconut, and / or man-made fibers of natural polymers, such as viscose (a definition of these terms eg in Römpp Chemie Lexikon, 9th edition, Thieme Verlag, Stuttgart , under the relevant keywords) and the envelope material from biopolymers because of the biodegradability of the yarn according to the invention a soil contamination is avoided, whereby the planting period is increased.
  • the yarn of the present invention is sufficiently durable to ensure its durability throughout the growing season because it can withstand the rainfall during that time.
  • the Envelope-forming biopolymeric material can be biopolymeric materials of starch (for example corn starch, potato starch, wheat starch, rice starch, tapioca starch, sorghum starch, manioc starch, pea starch, modified starches, starch degradation products), cyclodextrins, polylactic acid, biodegradable resins, milk protein, casein, sugar, Vegetable oils, cellulose (for example cellulose acetate), aliphatic and / or (partially) aromatic polyesters (for example those described above), polyhydroxyalkanoates and / or polyvinyl alcohol / starch mixtures.
  • starch for example corn starch, potato starch, wheat starch, rice starch, tapioca starch, sorghum starch, manioc starch, pea starch, modified starches, starch degradation products
  • cyclodextrins polylactic acid, biodegradable resins, milk protein, casein, sugar, Vegetable oils,
  • the shell material is selected from vegetable biopolymeric materials and / or petroleum-based biopolymeric materials.
  • the shell material is selected, for example, from starch, polylactic acid, cellulose, mixtures of aromatic and aliphatic polyesters and / or polyvinyl alcohol / starch mixtures.
  • These biodegradable and compostable shell materials may further comprise other components, provided that the yarn according to the invention has the complete biodegradability and compostability according to DIN EN 13 432.
  • Such shell materials are commercially available, for example under the trade name biomat from Pro-Tech, ECOFLEX from BASF, Materbi from Novamont, Natureflex from Inovia Films, or Biophan from Treofan.
  • the proportion of the biopolymeric shell material, based on the total weight of the yarn according to the invention, is usually 5 to 40 wt .-%, preferably 10 to 30 wt .-%, in particular 15 to 25 wt .-%.
  • the core material of the yarn according to the invention is subjected to one or more of the above-mentioned shell materials.
  • the time period until the onset of the decomposition process of the yarn according to the invention can be precisely controlled in terms of time.
  • the time period until the onset of the decomposition process of the yarn according to the invention can be adjusted by suitable choice of the composition of the wrapping material, for example the mixing ratio of the wrapping materials used.
  • the shell material preferably comprises a mixture of vegetable and petroleum-based biopolymers in a ratio of 1: 1 to 1: 5, in particular 1: 2 to 1: 4, more preferably 1: 2 to 1: 3.
  • the vegetable biopolymers used may be, for example, starch, cellulose and / or vegetable oils; the petroleum-based biopolymers used are, for example, polyhydroxyalkanoates or polyesters.
  • the shell material consists of a mixture of vegetable biopolymers such as corn starch and petroleum-based biopolymers such as polyhydroxyalkanoates or polyesters in the ratio of 1: 3. This ensures that the yarn according to the invention has a start of decomposition of within six months.
  • the shell material consists of a mixture of vegetable biopolymers such as corn starch and petroleum-based biopolymers such as polyhydroxyalkanoates or polyesters in a ratio of 1: 2. This ensures that the yarn according to the invention has a decomposition start within four months. Other Mixing conditions can lead to an extension or shortening of the mining time.
  • the application of the wrapping material to the core material of the yarn according to the invention can be done for example by wrapping, welding, fusing, gluing, machine bonding, shrinking or dip coating.
  • the wrapping material may be wrapped in the form of a film around the core material.
  • the film of the enveloping material may have a thickness in a range between 0.001 and 0.2 mm, preferably in a range of 0.01 to 0.1 mm, in particular in a range of 0.02 to 0.08 mm.
  • an envelope can in another embodiment be made using a tubular film blowing device, wherein the envelope is inflated onto the core material.
  • the yarn according to the invention can be produced, for example, by using textile processing methods known per se, such as spinning, twisting, braiding, crocheting, bobbins, knitting, weaving and / or knitting, for example in the form of staple yarns (spun yarns) ) or filament yarns present core materials of natural fibers and / or man-made fibers of natural polymers are combined or solidified as a fiber, so that a strength of the yarn of the invention of at least 450 N is achieved.
  • textile processing methods known per se such as spinning, twisting, braiding, crocheting, bobbins, knitting, weaving and / or knitting, for example in the form of staple yarns (spun yarns) ) or filament yarns present core materials of natural fibers and / or man-made fibers of natural polymers are combined or solidified as a fiber, so that a strength of the yarn of the invention of at least 450 N is achieved.
  • Lyocell is the generic term for solvent-spun cellulose fibers produced by the NMMO or lyocell process. Lyocell fibers are available, for example, from Lenzing AG and Courtaulds Fibers, Coventry / Great Britain. Tencel fibers are a further development and also available from the company Courtaulds. Tencel is a registered trademark. These fibers have the advantage that their dry strength is higher than any other commercial cellulose staple fiber; when wet, this strength is even more pronounced. Dry, the strength is twice as high as conventional viscose fibers and wet three times as high.
  • the core material can be applied with an adhesive before application of the wrapping material.
  • adhesive material according to the invention are those which combine with the core material and the shell material and are biodegradable.
  • adhesives based on starch or based on polyvinyl alcohol These are known to those skilled in the art and commercially available. For example, the following may be mentioned: starch-based planatol-based adhesives, polyvinyl alcohol-based dispersions, e.g. Helmitin adhesive L 93 / 22-01 from Forbo Helmitin, or the dispersion adhesive Adhesin from Henkel.
  • an adhesive can increase the tensile strength of the yarn according to the invention and improve the bond between the core material and the casing.
  • the adhesive is in a proportion of 5 to 30 wt .-%, based on the weight of the core material, applied.
  • the application amount is in a range of 5 to 20, ideally 7 to 10 wt .-%.
  • the yarn according to the invention can, for example, achieve a tensile strength of at least 500 N and an elongation at break of not more than 4%.
  • the applied adhesive can be firmly incorporated into the core material.
  • the adhesive is pressed into the fibers of the core material using a rope-making machine, whereby the strength of the yarn according to the invention increases significantly.
  • the application of the shell material to the core material takes place, for example, by melting, a natural roughness develops on the surface of the yarn according to the invention, thereby improving plant growth along the yarn according to the invention.
  • the melting of the shell material according to the invention for example, at temperatures between 50 and 200 ° C, preferably between 80 and 150 ° C, in particular between 100 and 130 ° C, depending on the shell material used.
  • the yarn according to the invention can have a wide variety of geometric shapes, for example round, flat, polygonal, oval, etc. Ideally, however, the yarn according to the invention has a round shape.
  • the thickness of the yarn according to the invention may be in a range of 0.5 to 10 mm, preferably 1 to 8 mm, in particular 2 to 6 mm.
  • the yarn of the invention has an S twist. This supports the growth of the plant and can be generated, for example, using a rope machine. In this case, lay lengths in a range of 0.5 to 4 cm, preferably 1 to 3 cm, in particular 1.5 to 2.5 cm have proven to be favorable.
  • sisal cord with a diameter of about 2.5 mm and a basic strength of about 400 N.
  • the sisal cord is unrolled by a flyer from the supply spool and pulled through a glue bath, the excess glue before leaving the glue station of the cord is stripped off.
  • the sisal cord becomes a 2 cm wide and 0.03 mm thick biopolymer Wannerra film WBA 2000 wrapped and pulled through a Nipper and pressed.
  • the wrapped cord is fused together by means of hot air and solidified and, by turning back the cord / rope machine, its final strength of more than 500 N and its roughened surface are obtained.

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Textile Engineering (AREA)
  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
  • Biological Depolymerization Polymers (AREA)
  • Materials For Medical Uses (AREA)

Abstract

A yarn consists of material that is both biologically degradable and suitable for composting. The core material is a natural fiber. The sleeve is a biopolymer that is both biologically degradable and suitable for composting. The core is sisal. The sleeve is poly-lactic acid. The ratio of the sleeve material to core material is in the range 5 to 40%. Further claimed is a process to produce a cord whose core material is a natural fiber and/or a man-made fiber with a sleeve winding that is both biologically degradable and suitable for composting. The sleeve is bonded to the core by exposure to hot air.

Description

Die vorliegende Patentanmeldung betrifft ein biologisch abbaubares Garn aus einem Kernmaterial aus biologisch abbaubaren Naturfasern und/oder Chemiefasern und einer Hülle aus einem biologisch abbaubaren Kunststoff.The present patent application relates to a biodegradable yarn of a core material of biodegradable natural fibers and / or man-made fibers and a shell of a biodegradable plastic.

Garne werden beispielsweise in Form von Bindeschnüren im Hopfenanbau verwendet; ihr Einsatz ist aber auch in anderen Gebieten z. B. im Weinbau, der Bauindustrie oder Verpackungsindustrie möglich.Yarns are used for example in the form of tie cords in hop growing; their use is also in other areas z. B. in viticulture, the construction industry or packaging industry possible.

Gegenwärtig werden im Hopfenanbau überwiegend Drähte aus Eisen als Kletterhilfe für Hopfenpflanzen eingesetzt. An den Drähten kann die Pflanze nach oben wachsen und damit die gewünschten Höhen, beim Hopfen bis zu ungefähr 8 Metern, erreichen.At present, mainly iron wires are used as a climbing aid for hop plants in hop growing. On the wires, the plant can grow upwards and thus reach the desired heights, while hopping up to about 8 meters.

Die Drähte werden in der Hopfengartenanlage oben an einem Querdraht verknotet und unten in unmittelbarer Nähe der Hopfenpflanze knapp in den Boden gesteckt. Bei der Ernte des Hopfens wird der Draht von Hand oder maschinell unten mit der Hopfenpflanze knapp über der Erde abgeschnitten und oben ebenfalls mit der Hopfenpflanze abgerissen.The wires are knotted in the hop garden at the top of a cross wire and just below in the immediate vicinity of the hop plant stuck in the ground. When harvesting the hops, the wire is cut by hand or machine down with the hop plant just above the ground and also topped off with the hop plant.

In der Hopfenpflückmaschine wird der Draht zusammen mit den Pflanzenresten der Hopfenpflanze klein gehäckselt und zum Verrotten bzw. Verrosten auf die Felder verbracht. Bevor dann im nächsten Frühjahr die Hopfenpflanze erneut auszutreiben beginnt, wird für jede Hopfenpflanze wieder ein neuer Hopfendraht wie oben beschrieben angebracht.In the hop-picking machine, the wire is shredded together with the plant remains of the hop plant and spent on the fields for rotting or rusting. Before the hops plant begins to drive out again next spring, a new hop wire is attached to each hop plant as described above.

Die Hopfendrähte sind derzeit aus Eisen, und zwar in der Regel aus ST 37 und haben einen runden Querschnitt mit einem Durchmesser von 1,1 und 1,5 mm. Die Hopfenpflanze benötigt, um sich gut an den Draht festhalten zu können, eine bestimmte Oberflächenrauhigkeit auf der Drahtoberfläche. Bei dem herkömmlichen Eisendraht ergibt sich diese Oberflächenrauhigkeit durch den Herstellprozess und dadurch entstehenden Flugrost.The hops are currently made of iron, usually of ST 37 and have a round cross section with a diameter of 1.1 and 1.5 mm. The hop plant needs a certain surface roughness on the wire surface in order to be able to hold tight to the wire. In the conventional iron wire, this surface roughness results from the manufacturing process and resulting flash rust.

Der üblicherweise verwendete Eisendraht besitzt jedoch wesentliche Nachteile.However, the iron wire commonly used has significant disadvantages.

Ein erster Nachteil ist sein sehr hohes spezifisches Gewicht. Ein größerer Hopfenbauer besitzt ca. 100.000 Hopfenpflanzen, d.h. er muss jedes Jahr 100.000 Drähte neu anbringen. Hier hat er ungeheuere Gewichte zu transportieren und auch zu tragen.A first disadvantage is its very high specific gravity. A larger hop farmer owns about 100,000 hop plants, i. he has to rewire 100,000 wires every year. Here he has immense weights to transport and carry too.

Ein weiterer Nachteil ist der relativ hohe Preis.Another disadvantage is the relatively high price.

Ebenfalls nachteilig ist, dass beim Häckseln des Drahts ein sehr hoher Verschleiß an den Häckselmessern auftritt.Another disadvantage is that when chopping the wire a very high wear on the chopping knives occurs.

Ein besonderer Nachteil sind die sogenannten "Hopfen-Spikes". Wenn der Hopfenbauer mit dem Traktor und Wagen das Häckselgut mit den ca. 2 bis 5 Zentimeter langen Eisendrahtstücken von seinem Bauernhof auf die Felder fährt, kommt es regelmäßig vor, dass solche "Hopfen-Spikes" auf die Strasse fallen. Beim Überfahren dieser "Hopfen-Spikes" mit dem PKW bohren sich diese dann in die Reifen und führen zu hohen Schäden.A particular disadvantage is the so-called "hop spikes". When the hop farmer drives the shredded material from his farm to the fields with the tractor and wagon with the pieces of iron wire approx. 2 to 5 centimeters long, it regularly happens that such "hop spikes" fall on the road. When driving over these "hop spikes" with the car, they then drill into the tires and cause high damage.

Ein weiterer großer Nachteil ist die Anreicherung von umweltschädigenden Stoffen im Erdreich.Another major disadvantage is the accumulation of environmentally harmful substances in the soil.

Für die anderen oben angegebenen Anwendungsgebiete gilt bei Verwendung von Metalldrähten im Wesentlichen das gleiche.Essentially the same applies to the other fields of application given above when metal wires are used.

Zur Abhilfe der beschriebenen Probleme sind schon vielfach Kunststofffäden aus Monofilen oder multifile Fäden beschrieben worden. Keine der beschriebenen Fäden hat sich in der Praxis jedoch durchsetzen können. Dies liegt daran, dass bei allen Fäden aus Kunststoff jeweils nur eines der beschriebenen Vielzahl an Problemen mehr oder weniger gut gelöst wurde, die anderen jedoch geblieben sind.To remedy the problems described plastic threads of monofilaments or multifilament threads have been described many times. However, none of the described threads has prevailed in practice. This is because with all threads made of plastic only one of the described variety of problems was solved more or less well, but the others have remained.

So ist in der DE 34 17 543 A1 ein Monofilament zur Heraufführung von Hopfen beschrieben. Hier allerdings wird eine höchst umweltschädigende Mischung aus Kunststoffen eingesetzt, nämlich eine Mischung aus Polyolefinen und Styrolpolymer. Von Styrol ist bekannt, dass es in Verdacht steht, Krebs zu erzeugen.So is in the DE 34 17 543 A1 described a monofilament for the production of hops. Here, however, a highly polluting mixture of plastics is used, namely a mixture of polyolefins and styrene polymer. Styrene is known to cause cancer.

Die DE-OS 23 44 221 beschreibt Stützschnüre für Pflanzen aus z. B. Polyolefin. Eine Querschnittsveränderung soll durch einen bei der Extrusion herbeigeführten Schmelzbruch erreicht werden. Dies allerdings führt zu Festigkeitsschwankungen über die Länge der Schnur. Darüber hinaus ist die durch Schmelzbruch erreichbare Oberfläche zwar deformiert, aber dennoch nach wie vor glatt, so dass Pflanzen nur ungenügend Halt finden.The DE-OS 23 44 221 describes support cords for plants from z. B. polyolefin. A cross-sectional change is to be achieved by a melt fracture induced in the extrusion. However, this leads to strength variations over the length of the string. In addition, although the surface achievable by melt fracture is deformed, it is still smooth so that plants will find insufficient support.

Die DE 198 00 842 C2 beschreibt einen Kunststofffaden, der als Monofilament ausgebildet ist, wobei das Monofilament aus einem Polypropylen besteht und an der Oberfläche zur Verringerung der Oberflächenglätte behandelt ist, wobei der Kunststofffaden aus biologisch abbaubarem modifiziertem Polypropylen besteht und zur Festigkeitserhöhung verstreckt ist, und wobei die Oberfläche des Kunststofffadens durch Profilierung und/oder chemische und physikalische Prozesse verringert ist.The DE 198 00 842 C2 describes a plastic thread formed as a monofilament, wherein the monofilament is made of a polypropylene and treated on the surface to reduce the surface smoothness, wherein the plastic thread made of biodegradable modified polypropylene and is stretched to increase the strength, and wherein the Surface of the plastic thread is reduced by profiling and / or chemical and physical processes.

Der vorliegenden Erfindung liegt daher die Aufgabe zugrunde, ein verbessertes Garn mit steuerbarer biologischer Abbaubarkeit und Kompostierbarkeit sowie ausgezeichneter Reißfestigkeit und Reißdehnung bereitzustellen.The present invention is therefore based on the object to provide an improved yarn with controllable biodegradability and compostability and excellent tensile strength and elongation at break.

Außerdem soll ein Verfahren zur Herstellung derartiger Garne beschrieben werden.In addition, a method for producing such yarns will be described.

Überaschenderweise wurde erfindungsgemäß festgestellt, dass durch Kombination eines Kernmaterials aus biologisch abbaubaren und kompostierbaren Naturfasern und/oder Chemiefasern mit einem Hüllmaterial aus biologisch abbaubaren und kompostierbaren Biopolymeren ein Garn mit steuerbarer biologischer Abbaubarkeit und Kompostierbarkeit sowie ausgezeichneter Reißfestigkeit und Reißdehnung erhalten werden kann.Surprisingly, according to the invention, it has been found that by combining a core material of biodegradable and compostable natural fibers and / or man-made fibers with a shell material of biodegradable and compostable biopolymers, a yarn having controllable biodegradability and compostability as well as excellent tear strength and elongation at break can be obtained.

Gegenstand der vorliegenden Erfindung ist somit ein biologisch abbaubares und kompostierbares Garn, das ein Kernmaterial aus Naturfasern und/oder Chemiefasern enthält und ein Hüllmaterial aus biologisch abbaubaren und kompostierbaren Biopolymeren umfasst.The present invention thus provides a biodegradable and compostable yarn containing a core material of natural fibers and / or man-made fibers and comprising a shell material of biodegradable and compostable biopolymers.

Erfindungsgemäß handelt es sich bei den den Kern des erfindungsgemäßen Garns bildenden Werkstoffen um solche aus Naturfasern wie beispielsweise Baumwolle, Flachs (Leinen), Hanf, Sisal, Jute, Kokos, Bast, Ramie und/oder Chemiefasern beispielsweise aus natürlichen Polymeren wie z.B. Viskose, Cellulose, Lyocell und/oder Tencel, sowie Fasern von biologisch abbaubaren und kompostierbaren aliphatischen und/oder teilaromatischen Polyesteramiden und/oder aliphatischen und/oder teilaromatischen Polyestern.According to the invention, the materials forming the core of the yarn according to the invention are those of natural fibers such as cotton, flax, hemp, sisal, jute, coconut, bast, ramie and / or man-made fibers, for example natural polymers such as viscose, cellulose , Lyocell and / or Tencel, as well as fibers of biodegradable and compostable aliphatic and / or partially aromatic polyester amides and / or aliphatic and / or partially aromatic polyesters.

In einer bevorzugten Ausführungsform der vorliegenden Erfindung sind die Kernfasern aus Naturfasern, die aus Baumwolle, Flachs(Leinen), Hanf, Sisal, Cellulose und/oder Jute bestehen, ausgewählt. Besonders bevorzugt handelt es sich erfindungsgemäß bei den den Kern bildenden Materialien um Naturfasern aus Sisal, da Sisal eine natürliche wasserabweisende Wirkung hat.In a preferred embodiment of the present invention, the core fibers are selected from natural fibers consisting of cotton, flax (linen), hemp, sisal, cellulose and / or jute. According to the invention, the materials forming the core are particularly preferably natural fibers of sisal, since sisal has a natural water-repellent action.

Unter dem Begriff "biologisch abbaubar und kompostierbar" werden erfindungsgemäße biologisch abbaubare und kompostierbare Garne verstanden, die vollständig gemäß DIN EN 13 432 biologisch abbaubar und kompostierbar sind.The term "biodegradable and compostable" means biodegradable and compostable yarns according to the invention which are completely biodegradable and compostable according to DIN EN 13 432.

Das erfindungsgemäße Garn zerfällt nach einer bestimmten, vorgebbaren Zeit und wird unter Kompostierbedingungen durch die Bakterien und Mikroben im Erdreich in natürliche Ausscheidungsprodukte umgewandelt, so dass hierbei sogar noch eine natürliche Düngung erreicht wird.The yarn according to the invention disintegrates after a certain, predeterminable time and is converted under composting conditions by the bacteria and microbes in the soil into natural waste products, so that in this case even a natural fertilization is achieved.

Die Zeit, die das erfindungsgemäße Garn bis zum vollständigen Abbau benötigt, ist in Grenzen (beispielsweise durch den Gewichtsanteil an Hüllmaterial, bezogen auf das Gesamtgewicht des erfindungsgemäßen Garns) einstellbar, d.h. das erfindungsgemäße Garn kann definiert in seiner Abbauzeit auf jeden einzelnen Anwendungsfall eingestellt werden.The time required for the yarn of the present invention to fully degrade is limited (e.g., by the weight fraction of shell material, based on the total weight of the yarn of the invention), i.e., adjustable. The yarn according to the invention can be defined in terms of its degradation time to each individual application.

Durch Variation beispielsweise des Kernmaterials kann ferner die Reißfestigkeit des erfindungsgemäßen Garns ebenfalls auf jeden speziellen Anwendungsfall eingestellt werden.By varying, for example, the core material, the tear strength of the yarn according to the invention can also be adjusted to any particular application.

Werden als Kernmaterial biologisch abbaubare und kompostierbare Fasern aus aliphatischen und/oder teilaromatischen Polyesteramiden und/oder aliphatischen und/oder teilaromatischen Polyestern verwendet, kann es sich bei diesen um die folgenden Polymere handeln:

  • Aliphatische und/oder teilaromatische Polyester:
    1. A) aus aliphatischen bifunktionellen Alkoholen, bevorzugt linearen C2 bis C10-Dialkoholen wie beispielsweise Ethandiol, Butandiol, Hexandiol oder besonders bevorzugt Butandiol und/oder gegebenenfalls cycloaliphatischen bifunktionellen Alkoholen, bevorzugt mit 5 oder 6 C-Atomen im cycloaliphatischen Ring, wie beispielsweise Cyclohexandimethanol, und/oder teilweise oder vollständig statt der Diole monomeren oder oligomeren Polyolen auf der Basis von Ethylenglykol, Propylenglykol, Tetrahydrofuran oder Copolymeren daraus mit Molekulargewichten bis 4000, bevorzugt bis 1000, und/oder gegebenenfalls geringen Mengen verzweigten bifunktionellen Alkoholen, bevorzugt C3-C12-Alkyldiolen, wie beispielsweise Neopentylglykol, und zusätzlich gegebenenfalls geringen Mengen höherfunktionellen Alkoholen wie beispielsweise 1,2,3-Propantriol oder Trimethylolpropan sowie aus aliphatischen bifunktionellen Säuren, vorzugsweise C2-C12-Alkyldicarbonsäuren, wie beispielsweise und bevorzugt Bernsteinsäure, Adipinsäure und/oder gegebenenfalls aromatischen bifunktionellen Säuren wie beispielsweise Terephthalsäure, Phthalsäure, Naphthalindicarbonsäure und zusätzlich gegebenenfalls geringen Mengen höherfunktionellen Säuren wie beispielsweise Trimellitsäure oder
    2. B) aus säure- und alkoholfunktionalisierten Bausteinen, vorzugsweise mit 2 bis 12 C-Atomen in der Alkylkette beispielsweise Hydroxybuttersäure, Hydroxyvaleriansäure, Milchsäure, oder deren Derivaten, beispielsweise ε-Caprolacton oder Dilactid,
      oder einer Mischung und/oder einem Copolymer enthaltend A und B,
      wobei die aromatischen Säuren nicht mehr als 50 Gew.-% Anteil, bezogen auf alle Säuren, ausmachen.
      Aliphatische und/oder teilaromatische Polyesteramide:
    3. C) aus aliphatischen bifunktionellen Alkoholen, bevorzugt linearen C2 bis C10-Dialkoholen wie beispielsweise Ethandiol, Butandiol, Hexandiol oder besonders bevorzugt Butandiol und/oder gegebenenfalls cycloaliphatischen bifunktionellen Alkoholen, vorzugsweise mit 5 bis 8 C-Atomen im cycloaliphatischen Ring, wie beispielsweise Cyclohexandimethanol, und/oder teilweise oder vollständig statt der Diole monomeren oder oligomeren Polyolen auf der Basis von Ethylenglykol, Propylenglykol, Tetrahydrofuran oder Copolymere daraus mit Molekulargewichten bis 4000, bevorzugt bis 1000, und/oder gegebenenfalls geringen Mengen verzweigten bifunktionellen Alkoholen, vorzugsweise mit C2-C12-Alkyldicarbonsäuren, wie beispielsweise Neopentylglykol und zusätzlich gegebenenfalls geringen Mengen höherfunktionellen Alkoholen wie beispielsweise 1,2,3-Propantriol, Trimethylolpropan sowie aus aliphatischen bifunktionellen Säuren wie beispielsweise und bevorzugt Bernteinsäure, Adipinsäure und/oder gegebenenfalls aromatischen bifunktionellen Säuren wie beispielsweise Terephthalsäure, Isophthalsäure, Naphthalindicarbonsäure und zusätzlich gegebenenfalls geringen Mengen höherfunktionellen Säuren wie beispielsweise Trimellitsäure oder
    4. D) aus säure- und alkoholfunktionalisierten Bausteinen, vorzugsweise mit 2 bis 12 C-Atomen in der Kohlenstoffkette, beispielsweise Hydroxybuttersäure, Hydroxyvaleriansäure, Milchsäure oder deren Derivaten, beispielsweise ε-Caprolacton oder Dilactid,
      oder einer Mischung und/oder einem Copolymer enthaltend C) und D),
      wobei die aromatischen Säuren nicht mehr als 50 Gew.-% Anteil. bezogen auf alle Säuren, ausmachen,
    5. E) einem Amidanteil aus aliphatischen und/oder cycloaliphatischen bifunktionellen und/oder gegebenenfalls geringen Mengen verzweigten bifunktionellen Aminen, bevorzugt sind lineare aliphatische C2 bis C10-Diamine, und zusätzlich gegebenenfalls geringen Mengen höherfunktionellen Aminen, unter den Aminen bevorzugt Hexamethylendiamin, Isophorondiamin und besonders bevorzugt Hexamethylendiamin, sowie aus linearen und/oder cycloaliphatischen bifunktionellen Säuren, vorzugsweise mit 2 bis 12 C-Atomen in der Alkylkette bzw. C5- oder C6-Ring im Falle von cycloaliphatischen Säuren, bevorzugt Adipinsäure, und/oder gegebenenfalls geringen Mengen verzweigten bifunktionellen und/oder gegebenenfalls aromatischen bifunktionellen Säuren wie beispielsweise Terephthalsäure, Isophthalsäure, Naphthalindicarbonsäure und zusätzlich gegebenenfalls geringen Mengen höherfunktionellen Säuren, vorzugsweise mit 2 bis 10 C-Atomen, oder
    6. F) aus einem Amidanteil aus säure- und aminfunktionalisierten Bausteinen, vorzugsweise mit 4 bis 20 C-Atomen in der cycloaliphatischen Kette, bevorzugt ω-Laurinlactam, ε-Caprolactam, besonders bevorzugt ε-Caprolactam,
oder einer Mischung enthaltend E) und F) als Amidanteil, wobei
der Esteranteil C) und/oder D) mindestens 20 Gew.-%, bezogen auf die Summe aus C), D), E) und F) beträgt, vorzugsweise der Gewichtsanteil der Esterstrukturen 20 bis 80 Gew.-%, der Anteil der Amidstrukturen 80 bis 20 Gew.-% beträgt.If biodegradable and compostable fibers of aliphatic and / or partially aromatic polyesteramides and / or aliphatic and / or partly aromatic polyesters are used as the core material, these may be the following polymers:
  • Aliphatic and / or partially aromatic polyesters:
    1. A) from aliphatic bifunctional alcohols, preferably linear C 2 to C 10 dialcohols such as ethanediol, butanediol, hexanediol or more preferably butanediol and / or optionally cycloaliphatic bifunctional alcohols, preferably having 5 or 6 carbon atoms in the cycloaliphatic ring, such as cyclohexanedimethanol , and / or partially or completely instead of the diols of monomeric or oligomeric polyols based on ethylene glycol, propylene glycol, tetrahydrofuran or copolymers thereof with molecular weights up to 4000, preferably up to 1000, and / or optionally small amounts of branched bifunctional alcohols, preferably C 3 -C 12- Alkyldiolen, such as neopentyl glycol, and additionally optionally small amounts of higher functionality alcohols such as 1,2,3-propanetriol or trimethylolpropane and aliphatic bifunctional acids, preferably C 2 -C 12 alkyl dicarboxylic acids, such as and preferably Bernst acid, adipic acid and / or optionally aromatic bifunctional acids such as terephthalic acid, phthalic acid, naphthalenedicarboxylic acid and additionally optionally small amounts of higher-functional acids such as trimellitic acid or
    2. B) from acid- and alcohol-functionalized building blocks, preferably having 2 to 12 carbon atoms in the alkyl chain for example, hydroxybutyric acid, hydroxyvaleric acid, lactic acid, or their derivatives, for example ε-caprolactone or dilactide,
      or a mixture and / or a copolymer comprising A and B,
      wherein the aromatic acids constitute not more than 50% by weight, based on all acids.
      Aliphatic and / or partly aromatic polyesteramides:
    3. C) from aliphatic bifunctional alcohols, preferably linear C 2 to C 10 dialcohols such as ethanediol, butanediol, hexanediol or more preferably butanediol and / or optionally cycloaliphatic bifunctional alcohols, preferably having 5 to 8 carbon atoms in the cycloaliphatic ring, such as cyclohexanedimethanol and / or partially or completely instead of the diols monomeric or oligomeric polyols based on ethylene glycol, propylene glycol, tetrahydrofuran or copolymers thereof with molecular weights up to 4000, preferably up to 1000, and / or optionally small amounts of branched bifunctional alcohols, preferably with C 2 - C 12 -alkyldicarboxylic acids, such as neopentyl glycol and additionally optionally small amounts of higher functional alcohols such as 1,2,3-propanetriol, trimethylolpropane and aliphatic bifunctional acids such as and preferably Bernteinsäure, adipic acid and / or geg optionally aromatic bifunctional acids such as terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid and additionally optionally small amounts of higher functional acids such as trimellitic acid or
    4. D) from acid- and alcohol-functionalized building blocks, preferably with 2 to 12 C atoms in the carbon chain, for example hydroxybutyric acid, hydroxyvaleric acid, lactic acid or derivatives thereof, for example ε-caprolactone or dilactide,
      or a mixture and / or a copolymer comprising C) and D),
      wherein the aromatic acids not more than 50 wt .-% share. based on all acids, make up,
    5. E) an amide portion of aliphatic and / or cycloaliphatic bifunctional and / or optionally small amounts of branched bifunctional amines, preferably linear aliphatic C 2 to C 10 diamines, and additionally optionally small amounts of higher functional amines, among the amines preferably hexamethylenediamine, isophoronediamine and especially preferably hexamethylenediamine, as well as linear and / or cycloaliphatic bifunctional acids, preferably branched with 2 to 12 C-atoms in the alkyl chain or C 5 - or C 6 ring in the case of cycloaliphatic acids, preferably adipic acid, and / or optionally small amounts bifunctional and / or optionally aromatic bifunctional acids such as terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid and additionally optionally small amounts of higher-functional acids, preferably having 2 to 10 carbon atoms, or
    6. F) from an amide moiety of acid- and amine-functionalized building blocks, preferably with 4 to 20 C atoms in the cycloaliphatic chain, preferably ω-laurolactam, ε-caprolactam, particularly preferably ε-caprolactam,
or a mixture containing E) and F) as Amidanteil, wherein
the ester fraction C) and / or D) is at least 20% by weight, based on the sum of C), D), E) and F), preferably the proportion by weight of the ester structures is from 20 to 80% by weight, the proportion of Amide structures 80 to 20 wt .-% is.

Alle als Säuren genannten Monomere können auch in Form von Derivaten wie beispielsweise Säurechloride oder Ester, sowohl als Monomere als auch als oligomere Ester, eingesetzt werden.All monomers mentioned as acids can also be used in the form of derivatives such as, for example, acid chlorides or esters, both as monomers and as oligomeric esters.

Das erfindungsgemäße Garn hat den Vorteil, dass durch die Verwendung von Naturfasern, wie beispielsweise Baumwolle, Flachs(Leinen), Hanf, Sisal, Jute, Ramie und Kokos, und/oder Chemiefasern aus natürlichen Polymeren, wie beispielsweise Viskose (eine Definition dieser Begriffe findet sich z.B. im Römpp Chemie Lexikon, 9. Auflage, Thieme Verlag, Stuttgart , unter den entsprechenden Stichwörtern) sowie des Hüllmaterials aus Biopolymeren wegen der biologischen Abbaubarkeit des erfindungsgemäßen Garns eine Bodenbelastung vermieden wird, wodurch der Bepflanzungszeitraum erhöht wird. Andererseits ist das erfindungsgemäße Garn anders als Papierbänder so ausreichend beständig, dass seine Haltbarkeit über die gesamte Wachstumsperiode gewährleistet ist, weil es den Niederschlägen während dieser Zeit standhält.The yarn according to the invention has the advantage that by the use of natural fibers, such as cotton, flax, hemp, sisal, jute, ramie and coconut, and / or man-made fibers of natural polymers, such as viscose (a definition of these terms eg in Römpp Chemie Lexikon, 9th edition, Thieme Verlag, Stuttgart , under the relevant keywords) and the envelope material from biopolymers because of the biodegradability of the yarn according to the invention a soil contamination is avoided, whereby the planting period is increased. On the other hand, unlike paper tapes, the yarn of the present invention is sufficiently durable to ensure its durability throughout the growing season because it can withstand the rainfall during that time.

Um das Kernmaterial des erfindungsgemäßen Garns herum befindet sich ein Überzug aus einem biopolymeren Material. Bei dem das Hüllmaterial bildenden biopolymeren Material kann es sich um biopolymere Materialien aus Stärke (beispielsweise Maisstärke, Kartoffelstärke, Weizenstärke, Reisstärke, Tapiokastärke, Sorghumstärke, Maniokstärke, Erbsenstärke, modifizierte Stärken, Stärkeabbauprodukte), Cyclodextrinen, Polymilchsäure, biologisch abbaubaren Harzen, Milcheiweiß, Casein, Zucker, Pflanzenölen, Cellulose (beispielsweise Celluloseacetat), aliphatischen und/oder (teil)aromatischen Polyestern (beispielsweise den oben beschriebenen), Polyhydroxyalkanoaten und/oder Polyvinylalkohol/Stärke-Mischungen handeln. Vorzugsweise ist das Hüllmaterial aus pflanzlichen biopolymeren Materialien und/oder erdölbasierenden biopolymeren Materialien ausgewählt. In einer bevorzugten Ausführungsform ist das Hüllmaterial beispielsweise aus Stärke, Polymilchsäure, Cellulose, Gemischen aus aromatischen und aliphatischen Polyestern und/oder Polyvinylalkohol/Stärke-Mischungen ausgewählt. Diese biologisch abbaubaren und kompostierbaren Hüllmaterialien können ferner andere Bestandteile umfassen, vorausgesetzt, dass das erfindungsgemäße Garn die vollständige biologische Abbaubarkeit und Kompostierbarkeit gemäß DIN EN 13 432 aufweist. Derartige Hüllmaterialien sind beispielsweise im Handel erhältlich, z.B. unter der Handelsbezeichnung biomat von der Firma Pro-Tech, ECOFLEX von der Firma BASF, Materbi von der Firma Novamont, Natureflex von der Firma Inovia Films, oder Biophan von der Firma Treofan.Around the core material of the yarn according to the invention is a coating of a biopolymeric material. In that the Envelope-forming biopolymeric material can be biopolymeric materials of starch (for example corn starch, potato starch, wheat starch, rice starch, tapioca starch, sorghum starch, manioc starch, pea starch, modified starches, starch degradation products), cyclodextrins, polylactic acid, biodegradable resins, milk protein, casein, sugar, Vegetable oils, cellulose (for example cellulose acetate), aliphatic and / or (partially) aromatic polyesters (for example those described above), polyhydroxyalkanoates and / or polyvinyl alcohol / starch mixtures. Preferably, the shell material is selected from vegetable biopolymeric materials and / or petroleum-based biopolymeric materials. In a preferred embodiment, the shell material is selected, for example, from starch, polylactic acid, cellulose, mixtures of aromatic and aliphatic polyesters and / or polyvinyl alcohol / starch mixtures. These biodegradable and compostable shell materials may further comprise other components, provided that the yarn according to the invention has the complete biodegradability and compostability according to DIN EN 13 432. Such shell materials are commercially available, for example under the trade name biomat from Pro-Tech, ECOFLEX from BASF, Materbi from Novamont, Natureflex from Inovia Films, or Biophan from Treofan.

Der Anteil des biopolymeren Hüllmaterials, bezogen auf das Gesamtgewicht des erfindungsgemäßen Garns, beträgt üblicherweise 5 bis 40 Gew.-%, vorzugsweise 10 bis 30 Gew.-%, insbesondere 15 bis 25 Gew.-%.The proportion of the biopolymeric shell material, based on the total weight of the yarn according to the invention, is usually 5 to 40 wt .-%, preferably 10 to 30 wt .-%, in particular 15 to 25 wt .-%.

Üblicherweise wird das Kernmaterial des erfindungsgemäßen Garns mit einem oder mehreren der obengenannten Hüllmaterialien beaufschlagt. Durch Wahl und/oder Zusammensetzung der geeigneten Materialien für das Hüllmaterial lässt sich die Zeitdauer bis zum Einsetzen des Zersetzungsprozesses des erfindungsgemäßen Garns zeitlich genau steuern. In einer bevorzugten Ausführungsform kann die Zeitdauer bis zum Einsetzen des Zersetzungsprozesses des erfindungsgemäßen Garns durch geeignete Wahl der Zusammensetzung des Hüllmaterials, beispielsweise des Mischungsverhältnisses der verwendeten Hüllmaterialien, eingestellt werden. Vorzugsweise weist das Hüllmaterial eine Mischung aus pflanzlichen und erdölbasierenden Biopolymeren in einem Verhältnis von 1:1 bis 1:5, insbesondere 1:2 bis 1:4, noch besser 1:2 bis 1:3 auf. Bei den verwendeten pflanzlichen Biopolymeren kann es sich beispielsweise um Stärke, Cellulose und/oder Pflanzenöle handeln, die verwendeten erdölbasierenden Biopolymere sind beispielsweise Polyhydroxyalkanoate oder Polyester. In einer speziellen Ausführungsform der vorliegenden Erfindung besteht das Hüllmaterial aus einer Mischung aus pflanzlichen Biopolymeren wie z.B Maisstärke und erdölbasierenden Biopolymeren wie Polyhydroxyalkanoaten oder Polyestern im Verhältnis von 1:3. Hierdurch wird erreicht, dass das erfindungsgemäße Garn einen Zersetzungsbeginn von innerhalb von sechs Monaten aufweist.Usually, the core material of the yarn according to the invention is subjected to one or more of the above-mentioned shell materials. By choice and / or composition of the suitable materials for the shell material, the time period until the onset of the decomposition process of the yarn according to the invention can be precisely controlled in terms of time. In a preferred embodiment, the time period until the onset of the decomposition process of the yarn according to the invention can be adjusted by suitable choice of the composition of the wrapping material, for example the mixing ratio of the wrapping materials used. The shell material preferably comprises a mixture of vegetable and petroleum-based biopolymers in a ratio of 1: 1 to 1: 5, in particular 1: 2 to 1: 4, more preferably 1: 2 to 1: 3. The vegetable biopolymers used may be, for example, starch, cellulose and / or vegetable oils; the petroleum-based biopolymers used are, for example, polyhydroxyalkanoates or polyesters. In a specific embodiment of the present invention, the shell material consists of a mixture of vegetable biopolymers such as corn starch and petroleum-based biopolymers such as polyhydroxyalkanoates or polyesters in the ratio of 1: 3. This ensures that the yarn according to the invention has a start of decomposition of within six months.

In einer weiteren speziellen Ausführungsform der vorliegenden Erfindung besteht das Hüllmaterial aus einer Mischung aus pflanzlichen Biopolymeren wie z.B Maisstärke und erdölbasierenden Biopolymeren wie Polyhydroxyalkanoaten oder Polyestern im Verhältnis von 1:2. Hierdurch wird erreicht, dass das erfindungsgemäße Garn einen Zersetzungsbeginn innerhalb von vier Monaten aufweist. Andere Mischungsverhältnisse können zu einer Verlängerung oder Verkürzung der Abbauzeit führen.In a further specific embodiment of the present invention, the shell material consists of a mixture of vegetable biopolymers such as corn starch and petroleum-based biopolymers such as polyhydroxyalkanoates or polyesters in a ratio of 1: 2. This ensures that the yarn according to the invention has a decomposition start within four months. Other Mixing conditions can lead to an extension or shortening of the mining time.

Die Applikation des Hüllmaterials auf das Kernmaterial des erfindungsgemäßen Garns kann beispielsweise durch Umhüllen, Verschweißen, Verschmelzen, Verkleben, maschinelles Verbinden, Aufschrumpfen oder Tauchbeschichten erfolgen.The application of the wrapping material to the core material of the yarn according to the invention can be done for example by wrapping, welding, fusing, gluing, machine bonding, shrinking or dip coating.

In einer Ausführungsform der vorliegenden Erfindung kann das Hüllmaterial in Form einer Folie um das Kernmaterial herum gewickelt werden. Die Folie des Hüllmaterials kann dabei eine Dicke in einem Bereich zwischen 0,001 und 0,2 mm, vorzugsweise in einem Bereich von 0,01 bis 0,1 mm, insbesondere in einem Bereich von 0,02 bis 0,08 mm aufweisen.In one embodiment of the present invention, the wrapping material may be wrapped in the form of a film around the core material. The film of the enveloping material may have a thickness in a range between 0.001 and 0.2 mm, preferably in a range of 0.01 to 0.1 mm, in particular in a range of 0.02 to 0.08 mm.

Erfindungsgemäß haben sich beispielsweise Kordelmaschinen zum Wickeln des Hüllmaterials, das beispielsweise in Form von Folien vorliegt, auf das Kernmaterial als vorteilhaft erwiesen. Eine Umhüllung kann erfindungsgemäß in einer anderen Ausführungsform unter Verwendung einer Schlauchfolienblasvorrichtung erfolgen, wobei die Hülle auf das Kernmaterial aufgeblasen wird.According to the invention, for example, cordless machines for winding the wrapping material, which is present for example in the form of films, have proved to be advantageous on the core material. According to the invention, an envelope can in another embodiment be made using a tubular film blowing device, wherein the envelope is inflated onto the core material.

Wie oben ausgeführt, kann das erfindungsgemäße Garn beispielsweise hergestellt werden, indem unter Verwendung von an sich bekannten textilen Verarbeitungsverfahren, wie beispielsweise Spinnen, Zwirnen, Flechten, Häkeln, Klöppeln, Stricken, Weben und/oder Wirken, die beispielsweise in Form von Stapelfasergarnen (Spinnfasergarnen) oder Filamentgarnen vorliegenden Kernmaterialien aus Naturfasern und/oder Chemiefasern aus natürlichen Polymeren zusammengeführt oder als Faser verfestigt werden, so dass eine Festigkeit des erfindungsgemäßen Garns von mindestens 450 N erreicht wird.As stated above, the yarn according to the invention can be produced, for example, by using textile processing methods known per se, such as spinning, twisting, braiding, crocheting, bobbins, knitting, weaving and / or knitting, for example in the form of staple yarns (spun yarns) ) or filament yarns present core materials of natural fibers and / or man-made fibers of natural polymers are combined or solidified as a fiber, so that a strength of the yarn of the invention of at least 450 N is achieved.

Gute Ergebnisse wurden auch mit Lyocellfasern und Tencelfasern erzielt, die gesponnen, verzwirnt oder geflochten werden. Tencelfasern eignen sich gut. Lyocell ist der Gattungsbegriff für lösungsmittelgesponnene Cellulosefasern, die nach dem NMMO- bzw. Lyocell-Verfahren hergestellt werden. Lyocellfasern sind beispielsweise von den Firmen Lenzing AG und Courtaulds Fibres, Coventry/Großbritannien, erhältlich. Tencelfasern sind eine Weiterentwicklung und ebenfalls von der Firma Courtaulds erhältlich. Tencel ist ein eingetragenes Warenzeichen. Diese Fasern haben den Vorteil, dass ihre Trockenfestigkeit höher ist als die jeder anderen kommerziellen Cellulose-Stapelfaser, im nassen Zustand ist diese Festigkeit noch ausgeprägter. Trocken ist die Festigkeit zweimal so hoch wie bei herkömmlichen Viskosefasern und nass dreimal so hoch.Good results have also been obtained with lyocell fibers and tencel fibers that are spun, twisted or braided. Tencel fibers work well. Lyocell is the generic term for solvent-spun cellulose fibers produced by the NMMO or lyocell process. Lyocell fibers are available, for example, from Lenzing AG and Courtaulds Fibers, Coventry / Great Britain. Tencel fibers are a further development and also available from the company Courtaulds. Tencel is a registered trademark. These fibers have the advantage that their dry strength is higher than any other commercial cellulose staple fiber; when wet, this strength is even more pronounced. Dry, the strength is twice as high as conventional viscose fibers and wet three times as high.

In einer bevorzugten Ausführungsform kann das Kernmaterial vor Aufbringen des Hüllmaterials mit einem Kleber beaufschlagt werden. Als Klebematerial eignen sich erfindungsgemäß solche, die sich mit dem Kernmaterial und dem Hüllmaterial verbinden und biologisch abbaubar sind. Als Beispiele lassen sich Kleber auf Stärkebasis oder auf Basis von Polyvinylalkohol nennen. Diese sind dem Fachmann auf dem einschlägigen Fachgebiet bekannt und im Handel erhältlich. Beispielsweise lassen sich die folgenden nennen: Planatol-Kleber auf Stärkebasis, Dispersionen auf Basis von Polyvinylalkohol wie z.B. Helmitin Kleber L 93/22-01 der Firma Forbo Helmitin, oder der Dispersionskleber Adhesin der Fa. Henkel.In a preferred embodiment, the core material can be applied with an adhesive before application of the wrapping material. As adhesive material according to the invention are those which combine with the core material and the shell material and are biodegradable. Examples are adhesives based on starch or based on polyvinyl alcohol. These are known to those skilled in the art and commercially available. For example, the following may be mentioned: starch-based planatol-based adhesives, polyvinyl alcohol-based dispersions, e.g. Helmitin adhesive L 93 / 22-01 from Forbo Helmitin, or the dispersion adhesive Adhesin from Henkel.

Durch die Mitverwendung eines Klebers kann die Reißfestigkeit des erfindungsgemäßen Garns erhöht und die Verbindung zwischen Kernmaterial und Hülle verbessert werden. Beispielsweise wird der Kleber in einem Anteil von 5 bis 30 Gew.-%, bezogen auf das Gewicht des Kernmaterials, aufgetragen. Bevorzugt liegt die Auftragsmenge in einem Bereich von 5 bis 20, idealerweise zwischen 7 und 10 Gew.-%. Durch die Mitverwendung eines Klebers kann das erfindungsgemäße Garn beispielsweise eine Reißfestigkeit von mindestens 500 N und eine Reißdehnung von höchstens 4 % erreichen.The concomitant use of an adhesive can increase the tensile strength of the yarn according to the invention and improve the bond between the core material and the casing. For example, the adhesive is in a proportion of 5 to 30 wt .-%, based on the weight of the core material, applied. Preferably, the application amount is in a range of 5 to 20, ideally 7 to 10 wt .-%. By using an adhesive, the yarn according to the invention can, for example, achieve a tensile strength of at least 500 N and an elongation at break of not more than 4%.

Ferner kann bei Mitverwendung eines Klebers beispielsweise durch Wahl des geeigneten Herstellungsverfahrens des erfindungsgemäßen Garns der applizierte Kleber in das Kernmaterial fest eingearbeitet werden. So wird der Kleber beispielsweise nach Applikation auf das Kernmaterial unter Verwendung einer Seilereimaschine in die Fasern des Kernmaterials eingepresst, wodurch die Festigkeit des erfindungsgemäßen Garns deutlich steigt.Furthermore, when an adhesive is used, for example by selecting the suitable production method of the yarn according to the invention, the applied adhesive can be firmly incorporated into the core material. For example, after application to the core material, the adhesive is pressed into the fibers of the core material using a rope-making machine, whereby the strength of the yarn according to the invention increases significantly.

Erfolgt die Aufbringung des Hüllmaterials auf das Kernmaterial beispielsweise durch Aufschmelzen, entsteht auf der Oberfläche des erfindungsgemäßen Garns eine natürliche Rauhigkeit, wodurch das Pflanzenwachstum an dem erfindungsgemäßen Garn entlang verbessert wird. Das Aufschmelzen des Hüllmaterials kann erfindungsgemäß beispielsweise bei Temperaturen zwischen 50 und 200 °C, vorzugsweise zwischen 80 und 150 °C, insbesondere zwischen 100 und 130°C, je nach verwendetem Hüllmaterial erfolgen.If the application of the shell material to the core material takes place, for example, by melting, a natural roughness develops on the surface of the yarn according to the invention, thereby improving plant growth along the yarn according to the invention. The melting of the shell material according to the invention, for example, at temperatures between 50 and 200 ° C, preferably between 80 and 150 ° C, in particular between 100 and 130 ° C, depending on the shell material used.

Das erfindungsgemäße Garn kann die verschiedensten geometrischen Formen haben, beispielsweise rund, flach, mehrkantig, oval usw. Idealerweise hat das erfindungsgemäße Garn jedoch eine runde Form. Die Dicke des erfindungsgemäßen Garns kann in einem Bereich von 0,5 bis 10 mm, vorzugsweise 1 bis 8 mm, insbesondere 2 bis 6 mm, liegen.The yarn according to the invention can have a wide variety of geometric shapes, for example round, flat, polygonal, oval, etc. Ideally, however, the yarn according to the invention has a round shape. The thickness of the yarn according to the invention may be in a range of 0.5 to 10 mm, preferably 1 to 8 mm, in particular 2 to 6 mm.

In einer bevorzugten Ausführungsform der vorliegenden Erfindung besitzt das erfindungsgemäße Garn eine S-Drehung. Diese unterstützt das Wachstum der Pflanze und kann beispielsweise unter Verwendung einer Seilereimaschine erzeugt werden. Erfindungsgemäß haben sich dabei Schlaglängen in einem Bereich von 0,5 bis 4 cm, vorzugsweise 1 bis 3 cm, insbesondere 1,5 bis 2,5 cm als günstig erwiesen.In a preferred embodiment of the present invention, the yarn of the invention has an S twist. This supports the growth of the plant and can be generated, for example, using a rope machine. In this case, lay lengths in a range of 0.5 to 4 cm, preferably 1 to 3 cm, in particular 1.5 to 2.5 cm have proven to be favorable.

Beispielexample

Ausgangsmaterial ist eine Sisalkordel mit einem Durchmesser von ca. 2,5 mm und einer Grundfestigkeit von ca. 400 N. Die Sisalkordel wird mittels eines Flyers von der Vorlagespule abgerollt und durch ein Leimbad gezogen, wobei der überflüssige Leim vor Verlassen der Leimstation von der Kordel abgestreift wird. Unmittelbar vor dem Einzug in eine handelsübliche Kordel-/Seilereimaschine, die so eingerichtet ist, dass das fertige Garn eine S-Drehung mit einer Schlaglänge von 1,5 cm erhält, wird die Sisalkordel mit einer 2 cm breiten und 0,03 mm starken biopolymeren Folie der Fa. Wenterra mit der Bezeichnung WBA 2000 umwickelt und durch einen Nipper gezogen und verpresst. Direkt nach Verlassen des Nippers wird die umwickelte Kordel mittels Heißluft miteinander verschmolzen und verfestigt und erhält durch das Rückdrehen der Kordel-/Seilereimaschine seine Endfestigkeit von mehr als 500 N und seine aufgeraute Oberfläche.Starting material is a sisal cord with a diameter of about 2.5 mm and a basic strength of about 400 N. The sisal cord is unrolled by a flyer from the supply spool and pulled through a glue bath, the excess glue before leaving the glue station of the cord is stripped off. Immediately prior to insertion into a commercial cord / ropemaking machine designed to give the finished yarn an S twist with a lay length of 1.5 cm, the sisal cord becomes a 2 cm wide and 0.03 mm thick biopolymer Wannerra film WBA 2000 wrapped and pulled through a Nipper and pressed. Immediately after leaving the nipper, the wrapped cord is fused together by means of hot air and solidified and, by turning back the cord / rope machine, its final strength of more than 500 N and its roughened surface are obtained.

Claims (7)

  1. Biodegradable and compostable twine, which contains a core material of natural fibres and/or synthetic fibres and comprises a cover material of biodegradable and compostable biopolymers.
  2. Twine according to claim 1, wherein the core material consists of sisal.
  3. Twine according to either claim 1 or claim 2, wherein the cover material consists of polylactic acid.
  4. Twine according to any one of the preceding claims, wherein the proportion of the cover material is 5 to 40 % by weight based on the total weight of the twine according to the invention.
  5. Method for the production of a twine according to any one of claims 1 to 4, wherein a cover material of biodegradable and compostable biopolymers is wrapped around a core material of natural fibres and/or synthetic fibres on a cording machine.
  6. Method according to claim 5, wherein the method further comprises the step of melting the cover material onto the core material.
  7. Method according to claim 6, wherein the melting is carried out by applying hot air.
EP07105204A 2006-04-07 2007-03-29 Biodegradable binding twine Active EP1842944B9 (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE102006016538A DE102006016538A1 (en) 2006-04-07 2006-04-07 Biodegradable binding yarns

Publications (5)

Publication Number Publication Date
EP1842944A2 EP1842944A2 (en) 2007-10-10
EP1842944A3 EP1842944A3 (en) 2008-05-28
EP1842944B1 true EP1842944B1 (en) 2010-05-26
EP1842944B3 EP1842944B3 (en) 2012-02-08
EP1842944B9 EP1842944B9 (en) 2012-07-25

Family

ID=38139803

Family Applications (1)

Application Number Title Priority Date Filing Date
EP07105204A Active EP1842944B9 (en) 2006-04-07 2007-03-29 Biodegradable binding twine

Country Status (6)

Country Link
EP (1) EP1842944B9 (en)
AT (1) ATE469253T1 (en)
DE (2) DE102006016538A1 (en)
DK (1) DK1842944T3 (en)
ES (1) ES2345677T7 (en)
PT (1) PT1842944E (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012077066A1 (en) 2010-12-10 2012-06-14 Luigi Lavazza S.P.A. Cartridge for preparing a liquid product
WO2012080908A1 (en) 2010-12-14 2012-06-21 Luigi Lavazza S.P.A. Cartridge for preparing a liquid product
WO2014097039A1 (en) 2012-12-21 2014-06-26 Luigi Lavazza S.P.A. Cartridge for preparing a liquid product, and process for production thereof
WO2014128658A1 (en) 2013-02-22 2014-08-28 Luigi Lavazza S.P.A. Cartridge, machine and system for the preparation of beverages and process for manufacturing the cartridge
WO2015193774A1 (en) 2014-06-18 2015-12-23 Luigi Lavazza S.P.A. Cartridge for preparing a liquid product and method for producing it
WO2016103104A1 (en) 2014-12-22 2016-06-30 Luigi Lavazza S.P.A. Cartridge for the preparation of liquid products

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102008016351B4 (en) 2008-03-29 2016-12-29 Perlon Nextrusion Monofil GmbH Use of biodegradable monofilaments in field and gardening
DE102008016350A1 (en) 2008-03-29 2009-10-01 Teijin Monofilament Germany Gmbh Monofilament polymeric component, useful e.g. as binding wire in the field, horticulture and floristry, and for the production of flower arrangements, floral skeins and wreaths, comprises one or more aliphatic polyester
ES2536582B1 (en) * 2013-11-25 2016-03-01 Plàstics Torner, S.L. Plastic binding, use of the tie and method to tie, gather or gather elements together
PE20190865A1 (en) 2016-08-02 2019-06-18 Fitesa Germany Gmbh SYSTEM AND PROCESS FOR THE PREPARATION OF POLYLACTIC ACID NON-WOVEN FABRICS
US11441251B2 (en) 2016-08-16 2022-09-13 Fitesa Germany Gmbh Nonwoven fabrics comprising polylactic acid having improved strength and toughness
AT520161B1 (en) * 2017-05-09 2020-02-15 Chemiefaser Lenzing Ag Carrier materials that can be degraded in the sea
ES1221442Y (en) * 2018-10-03 2019-02-26 Gold Fiber Europe S L BIODEGRADABLE FOOD CONTAINER
IT202000015400A1 (en) * 2020-06-26 2021-12-26 Linificio E Canapificio Nazionale S R L Soc Benefit PACKAGING FOR FOOD AND OTHER PRODUCTS
DE102020124303A1 (en) * 2020-09-17 2022-03-17 Cordenka Innovations GmbH tracking cord
DE102021106840A1 (en) 2021-03-19 2022-09-22 Frowin Puntsch Textile product and use of the textile product

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2344221A1 (en) 1973-09-01 1975-03-13 Rudolf Hiller Fa Support lines for plants, esp. hops and vines - with projections on extruded plastic strands to ensure a firm hold
FR2348988A1 (en) * 1976-04-20 1977-11-18 Inst Textile De France PROCEDURE FOR OBTAINING A FANTASY WIRE AND THREAD SO OBTAINED
HU187234B (en) 1983-05-13 1985-11-28 Kaposplast Kefe Es Mueanyagipa Hop guiding monofil
JPH086444Y2 (en) * 1990-03-16 1996-02-28 敏夫 阪中 String material for packing plant roots
DE19523490C2 (en) * 1995-06-28 1997-04-10 Werner & Pfleiderer Device and method for impregnating fiber strands with plastic material
WO1997043472A1 (en) * 1996-05-14 1997-11-20 Shimadzu Corporation Spontaneously degradable fibers and goods made by using the same
KR100504214B1 (en) * 1997-05-02 2005-07-28 카르길,인코포레이티드 Degradable polymer fibers, preparation, product, and methods of use
AU734539B2 (en) * 1998-01-06 2001-06-14 Aderans Research Institute, Inc. Bioabsorbable fibers and reinforced composites produced therefrom
DE19800842C2 (en) * 1998-01-13 2003-06-18 Gerhard Barich Synthetic thread
JP3323165B2 (en) * 1999-10-20 2002-09-09 ユニチカ株式会社 Biodegradable spun yarn with core-sheath structure and fabric comprising the same
US20030077444A1 (en) * 2001-05-10 2003-04-24 The Procter & Gamble Company Multicomponent fibers comprising starch and polymers
US20030134120A1 (en) * 2001-12-24 2003-07-17 Ibeks Technologies Co., Ltd. Natural fiber coated with chitosan and a method for producing the same
KR20050083171A (en) * 2001-12-24 2005-08-26 (주)아이벡스 Chitosan-contaning spun yarn and a method of producing the same
FR2853330B1 (en) * 2003-04-01 2005-08-26 Univ Bretagne Sud METHOD AND DEVICE FOR MANUFACTURING BIODEGRADABLE THREADS OR TWINE THREADS, THREADS OR TWINS OBTAINED THEREBY AND CORRESPONDING APPLICATIONS
DE10349110B3 (en) * 2003-05-28 2004-12-09 Daimlerchrysler Ag Rovings comprising Musaceae or banana plant fibers, used to reinforce composite automobile components, have limited contamination by processing aids
FR2868087B1 (en) * 2004-03-26 2006-06-09 Gilles Bruno Debat BIODEGRADABLE TWINE
ES2282021B1 (en) 2005-07-12 2008-07-01 Mimcord, S.A. RECYCLABLE GUARDIAN FOR VERTICAL CROPS.

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012077066A1 (en) 2010-12-10 2012-06-14 Luigi Lavazza S.P.A. Cartridge for preparing a liquid product
WO2012080908A1 (en) 2010-12-14 2012-06-21 Luigi Lavazza S.P.A. Cartridge for preparing a liquid product
US9422104B2 (en) 2010-12-14 2016-08-23 Luigi Lavazza S.P.A. Cartridge for preparing a liquid product
WO2014097039A1 (en) 2012-12-21 2014-06-26 Luigi Lavazza S.P.A. Cartridge for preparing a liquid product, and process for production thereof
WO2014128658A1 (en) 2013-02-22 2014-08-28 Luigi Lavazza S.P.A. Cartridge, machine and system for the preparation of beverages and process for manufacturing the cartridge
WO2015193774A1 (en) 2014-06-18 2015-12-23 Luigi Lavazza S.P.A. Cartridge for preparing a liquid product and method for producing it
EP3388363A1 (en) 2014-06-18 2018-10-17 Luigi Lavazza S.p.A. Cartridge for preparing a liquid product and method for producing it
WO2016103104A1 (en) 2014-12-22 2016-06-30 Luigi Lavazza S.P.A. Cartridge for the preparation of liquid products

Also Published As

Publication number Publication date
EP1842944B9 (en) 2012-07-25
PT1842944E (en) 2010-08-09
EP1842944A2 (en) 2007-10-10
ES2345677T7 (en) 2012-06-14
EP1842944A3 (en) 2008-05-28
DK1842944T3 (en) 2010-08-16
DE102006016538A1 (en) 2007-11-08
DE502007003898D1 (en) 2010-07-08
ES2345677T3 (en) 2010-09-29
ATE469253T1 (en) 2010-06-15
ES2345677T9 (en) 2012-12-26
EP1842944B3 (en) 2012-02-08

Similar Documents

Publication Publication Date Title
EP1842944B1 (en) Biodegradable binding twine
EP0799335B1 (en) Technical and non-technical textile products and packaging materials
EP2161374B1 (en) Synthetic turf
AT508721B1 (en) CELLULOSE FIBERS WITH IMPROVED DOSAGE ABILITY, METHOD FOR THE PRODUCTION THEREOF, AND THEIR USE FOR THE REINFORCEMENT OF COMPOSITE MATERIALS
EP2632985B1 (en) Use of polymer blends for producing slit film tapes
DE10206924A1 (en) Heat sealable filter materials
EP4267687A1 (en) Adhesive tape
JP6273575B2 (en) Lap net
JP2018028158A (en) Wrapping net and method for producing the same
JP6033691B2 (en) Lap net
DE102020108122B3 (en) Tubular knitted fabric and method for this
EP2919734A1 (en) Cotton wool bud
WO2019138093A1 (en) Molded body which has elastane incorporated into cellulose, and production method
DE102008016351B4 (en) Use of biodegradable monofilaments in field and gardening
EP0765210B1 (en) Method of producing a starting material for producing biologically degradable sacks and bags
EP4214356A1 (en) Biodegradable plant-training string
DE102021003374A1 (en) Pfianz- or growth cover
JP3911850B2 (en) Pete Moss alternative material
EP4298886A1 (en) Biodegradable mowing yarn
WO2022117837A1 (en) Net
DE4446054A1 (en) Biodegradable textile contains thermoplastic starch

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: A2

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC MT NL PL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL BA HR MK YU

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC MT NL PL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL BA HR MK RS

17P Request for examination filed

Effective date: 20081121

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 LT LU LV MC MT NL PL PT RO SE SI SK TR

17Q First examination report despatched

Effective date: 20090119

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 LT LU LV MC MT 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

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

REF Corresponds to:

Ref document number: 502007003898

Country of ref document: DE

Date of ref document: 20100708

Kind code of ref document: P

REG Reference to a national code

Ref country code: CH

Ref legal event code: NV

Representative=s name: BOHEST 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: 20100802

REG Reference to a national code

Ref country code: DK

Ref legal event code: T3

REG Reference to a national code

Ref country code: NL

Ref legal event code: T3

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2345677

Country of ref document: ES

Kind code of ref document: T3

LTIE Lt: invalidation of european patent or patent extension

Effective date: 20100526

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 FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20100526

Ref country code: LT

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: 20100526

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LV

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: 20100526

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: 20100526

Ref country code: FI

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: 20100526

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: 20100926

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: 20100526

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: 20100526

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: 20100827

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: 20100526

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: 20100526

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: 20100526

Ref country code: RO

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: 20100526

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

REG Reference to a national code

Ref country code: DE

Ref legal event code: R055

Ref document number: 502007003898

Country of ref document: DE

26N No opposition filed

Effective date: 20110301

PLCP Request for limitation filed

Free format text: ORIGINAL CODE: EPIDOSNLIM1

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 502007003898

Country of ref document: DE

Effective date: 20110228

PLCQ Request for limitation of patent found admissible

Free format text: ORIGINAL CODE: 0009231

LIM1 Request for limitation found admissible

Free format text: SEQUENCE NO: 1; FILED AFTER OPPOSITION PERIOD

Filing date: 20110428

PLCO Limitation procedure: reply received to communication from examining division + time limit

Free format text: ORIGINAL CODE: EPIDOSNLIR3

PLCR Communication despatched that request for limitation of patent was allowed

Free format text: ORIGINAL CODE: 0009245

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 502007003898

Country of ref document: DE

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: 20110331

REG Reference to a national code

Ref country code: DK

Ref legal event code: EBP

Ref country code: CH

Ref legal event code: PL

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20110329

REG Reference to a national code

Ref country code: DE

Ref legal event code: R056

Ref document number: 502007003898

Country of ref document: DE

Effective date: 20110921

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

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: 20100526

PLCN Payment of fee for limitation of patent

Free format text: ORIGINAL CODE: EPIDOSNRAL3

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: 20111229

PUAM (expected) publication of b3 document

Free format text: ORIGINAL CODE: 0009410

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN LIMITED

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20110331

Ref country code: PT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20111229

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20110331

REG Reference to a national code

Ref country code: CH

Ref legal event code: AEN

Free format text: BESCHRAENKUNGANTRAG GUTGEHEISSEN

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20110329

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20120405

Year of fee payment: 6

Ref country code: IE

Payment date: 20120317

Year of fee payment: 6

REG Reference to a national code

Ref country code: NL

Ref legal event code: T3

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 NON-PAYMENT OF DUE FEES

Effective date: 20110331

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20120321

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20120403

Year of fee payment: 6

Ref country code: BE

Payment date: 20120402

Year of fee payment: 6

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LV

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: 20120208

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 20120330

Year of fee payment: 6

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: 20110329

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20120321

Year of fee payment: 6

BERE Be: lapsed

Owner name: GARNTEC G.M.B.H.

Effective date: 20130331

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: 20100526

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: 20100826

REG Reference to a national code

Ref country code: NL

Ref legal event code: V1

Effective date: 20131001

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: 20100526

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 469253

Country of ref document: AT

Kind code of ref document: T

Effective date: 20130329

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20131129

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20130329

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20130331

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20130329

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20130402

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20131001

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20130329

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20140606

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: 20130330

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230508

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20240313

Year of fee payment: 18