[go: up one dir, main page]

EP3556914A1 - Corps moulé cellulosique régénéré et procédé de fabrication de corps moulé cellulosique régénéré - Google Patents

Corps moulé cellulosique régénéré et procédé de fabrication de corps moulé cellulosique régénéré Download PDF

Info

Publication number
EP3556914A1
EP3556914A1 EP18168510.8A EP18168510A EP3556914A1 EP 3556914 A1 EP3556914 A1 EP 3556914A1 EP 18168510 A EP18168510 A EP 18168510A EP 3556914 A1 EP3556914 A1 EP 3556914A1
Authority
EP
European Patent Office
Prior art keywords
silk protein
cellulose
recombinant
dope
shaped body
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.)
Withdrawn
Application number
EP18168510.8A
Other languages
German (de)
English (en)
Inventor
Sigrid Redlinger
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.)
Lenzing AG
Original Assignee
Lenzing AG
Chemiefaser Lenzing AG
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 Lenzing AG, Chemiefaser Lenzing AG filed Critical Lenzing AG
Priority to EP18168510.8A priority Critical patent/EP3556914A1/fr
Priority to PCT/EP2019/058783 priority patent/WO2019201639A1/fr
Publication of EP3556914A1 publication Critical patent/EP3556914A1/fr
Withdrawn legal-status Critical Current

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
    • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • 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
    • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • D01F2/06—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from viscose
    • D01F2/08—Composition of the spinning solution or the bath

Definitions

  • the invention relates to regenerated cellulosic molded articles and to a process for producing regenerated cellulosic molded articles, in which a spinnable textile pulp comprising cellulose and a recombinant silk protein is produced, the textile pulp is extruded through spinnerets, and the extruded textile pulp is precipitated in a spinning bath form cellulosic shaped body, wherein the spinning bath contains a coagulant for the cellulose, which does not dissolve the cellulose and the recombinant silk protein substantially.
  • Silk chemically linked to a protein composed of amino acids through peptide bonds, is a naturally occurring animal fiber that has always been valued for its high strength and as the only natural continuous fiber. For example, silk has been used for about 5,000 years to produce luxurious fabrics with outstanding strength and wearing properties.
  • the object of the invention is therefore to provide a process for the production of cellulosic moldings which makes possible a large-scale processing and incorporation of silk protein in cellulosic fibers.
  • the invention has the task of providing regenerated cellulosic molded body with incorporated silk protein, which can be produced inexpensively and procedurally simple and have improved fiber properties.
  • the invention solves the stated problem with regard to the method in that the recombinant silk protein is added to the spinnable dope before extrusion.
  • the recombinant silk protein is added to the spinnable dope before extrusion, detrimental long residence times of the proteins in the dope can be prevented and degradation of these proteins can be largely avoided.
  • the addition of the silk protein to the spinning mass can be implemented particularly easily on an industrial scale, since the preparation and preparation of the spinnable dope can be carried out as in a conventional viscose, modal or lyocell process, without significant modifications to the process are necessary. Due to the distribution of the silk protein in the spinning mass, it can also be achieved that the silk protein after extrusion and the precipitation of the spinning mass is incorporated into the shaped bodies in the cellulosic matrix of the cellulosic shaped bodies.
  • a regenerated cellulosic shaped body in particular a fiber, a filament (continuous fiber), a foil, a powder or a microbead, which by a xanthate method (such as the viscose or modal method) or a Direct release (as the lyocell / amine oxide) were prepared is understood.
  • silk proteins are understood as meaning both fibroins and spidroins, the fiber-forming proteins of silk and spider silk.
  • fibroins are characterized by an amino acid sequence with the regularly recurring sequence motif GSGAGA, while spidroins have the characteristic sequence motif GGY.
  • biotechnologically produced proteins are therefore among recombinant silk proteins
  • Amino acid sequences such as fibroins or spidroins have designated.
  • recombinant spider silk proteins are proteins which have at least 80%, preferably at least 90% homology to spidroin proteins.
  • the recombinant spider silk proteins in particular as previously described, have a homology to the spidroin1 or spidroin2 protein from Nephila clavipes, preferably to the MaSp1, MaSp2, MiSp1 or MiSp2 protein.
  • Is the recombinant spider silk protein a polypeptide having an amino acid sequence represented by the formula (1): (GA or A) m (GGX or GPGGZ), wherein X and Z are selected from amino acids and m is greater than 2, especially greater than 5,
  • a cellulosic fiber can be created in which a spider silk protein is incorporated with as natural-like properties as possible, whereby the cellulosic fiber can obtain advantageous properties of the spider silk.
  • X is preferably A, Y or Q
  • Z is preferably A, Y, S or V.
  • the letters G, A, P, Y, Q, S and V stand for the amino acids glycine, alanine, proline, tyrosine, glutamine, serine and valine.
  • polypeptides having the amino acid sequence represented by the above formula it is possible to achieve the ⁇ -sheet structures which are particularly preferred for the spider silk.
  • the proteins in this case have a block copolymer in which the two basic sequences according to the above formula, namely poly (A) or poly (GA) and GGX or GPGGZ alternate.
  • Proteins of the formula (1) can accordingly have, for example, the sequences (GA) m GGX, A m GGX, (GA) m GPGGZ or A m GPGGZ.
  • the method according to the invention may be particularly distinguished when the aforementioned recombinant silk proteins have an average molecular weight of at least 10 kDa, in particular at least 40 kDa, preferably at least 60 kDa. Proteins with too few amino acids can not develop sufficient fiber-forming properties.
  • the process of the invention can be further improved as the degradation of the proteins can be significantly reduced in the spinning mass.
  • the security of the process is further increased.
  • Such an addition immediately before the extrusion of the dope can be done for example via an inline mixing unit.
  • a particularly high process stability and reproducibility can be achieved if the content of cellulose and recombinant silk protein is at least 5% by weight, in particular at least 10% by weight, based on the spinning mass.
  • the spin bath additionally contains a coagulant for the silk protein, in particular an alcohol
  • a coagulant for the silk protein in particular an alcohol
  • Preferred alcohols may be, for example, methanol, ethanol or isopropanol. Very stable process conditions can thus be achieved.
  • the invention can be characterized in a lyocell process, cellulose being dissolved in a mixture of water and NMMO to produce the spinning mass, and the spinning bath having a mixture of water and NMMO.
  • the mixing ratio of water to NMMO in the spinning bath differs significantly from the mixing ratio in the spinning mass and is in particular in a range in which a solution of cellulose is not possible (outside the solution window).
  • a lyocell process modified by the addition of silk protein, as described above, can be characterized in particular by high process reliability, since the subsequent addition of the protein prior to the extrusion of the spinning mass can markedly reduce the tendency to exothermic reactions in the dope.
  • the silk protein is preferably added in the form of a solution or aqueous suspension, for example in aqueous amine oxide, to the ready-spinnable cellulose solution (spinning mass) prepared according to the lyocell method.
  • the dope is extruded through an air gap into a spin bath containing aqueous amine oxide and alcohol, such as methanol, ethanol or isopropanol.
  • a spin bath with hot (> 60 ° C) aqueous amine oxide may be used.
  • the extrusion and the precipitation in the spinning bath subsequent washing steps take place preferably with hot water or superheated steam to promote structural transformation of the silk protein, particularly to form ⁇ -sheets.
  • NSF wet abrasion strength value
  • the invention may advantageously be distinguished by a viscose or modal process, a cellulose derivative, in particular cellulose xanthate, being dissolved in sodium hydroxide solution, and the spinning bath preferably having a mixture of water, sulfuric acid, sodium sulfate or ammonium sulfate and zinc sulfate for producing the spinning composition.
  • the silk protein is supplied in the form of a heated silk-sodium-containing sodium hydroxide solution directly in front of the spinneret to the spinning mass.
  • the silk protein can be supplied to the dope in the form of a solution of silk protein in formic acid.
  • the invention achieves the stated object with regard to the regenerated cellulosic shaped body in that a regenerated cellulosic shaped body, in particular a fiber, a filament, a foil or a microsphere, is produced by a method according to one of claims 1 to 8.
  • the regenerated cellulosic shaped body which contains a cellulosic matrix forming the shaped body has at least one recombinant silk protein, wherein the recombinant silk protein is incorporated in the cellulose matrix
  • spider proteins on a large industrial scale can be prepared in cellulosic shaped bodies, in particular fibers, in a simple manner. be spun.
  • the cellulosic molded body contains spider silk proteins, in particular peptides having an amino acid sequence according to the aforementioned formula (1): (GA or A) m (GGX or GPGGZ), wherein X and Z are selected from amino acids and m is greater than 2. All other embodiments of the invention are equivalent to those described above for the method.
  • the shaped body according to the invention preferably has previously mentioned recombinant silk proteins which have an average molecular weight of at least 10 kDa, in particular of at least 40 kDa, preferably of at least 60 kDa.
  • a cellulosic molded body produced in this way may be distinguished, for example, by the fact that the shaped body is dyeable for acid dyes.
  • Acid dyes are anionic dyes which undergo electrovalent bonds with the amino group. Namely, cellulosic shaped bodies without modification are not dyeable for such dyes, while natural, protein-based fibers, e.g. Wool and silk, and polyamides have a high dyeability by acid dyes.
  • Mixed yarns or mixtures of cellulosic and natural fibers, such as wool, in textiles could therefore be dyed in the past only in a very complex manner in a common process, which usually high production costs.
  • the moldings according to the invention can now advantageously be used in mixtures with natural fibers, and thus high-quality blended yarns and blended textiles can be created, since a common dyeability is made possible by the incorporated silk protein in the cellulosic molded body.
  • cellulosic molded bodies with incorporated silk proteins can have an increased antibacterial and antimicrobial effect.
  • fibers of the present invention may be suitable for use in hygienic or medical products (such as wound dressings) in which delay or prevention of biofilm formation is desired.
  • the recombinant silk protein is additionally present in a proportion of 1 to 90% by weight, based on the cellulose in the molding, then a molding with sufficient stability in the cellulose matrix can be created. If the proportion of 1 to 40 wt .-%, in particular 3 to 25 wt .-%, so can To ensure that the strength of the cellulosic moldings is not adversely affected by the silk protein and at the same time the silk protein is present in sufficient quantity to develop the beneficial properties.
  • the shaped body is a lyocell fiber and in particular has a strength of at least 12 cN / tex, preferably of at least 25 cN / tex, then a cellulosic fiber with the above-mentioned advantages can be provided which has sufficient strength for a plurality of Offers applications.
  • a regenerated cellulosic molded body can be created, which has a wet abrasion resistance (NSF) of at least 50 U / dtex, or preferably greater than 200 U / dtex.
  • NSF wet abrasion resistance
  • the regenerated cellulosic fibers with incorporated silk proteins according to any one of claims 9 to 12 can be particularly advantageous in textile fabrics or nonwovens.
  • the fibers according to the invention may be suitable as blended yarns, yarn blends or fiber blends with natural fibers or consisting of natural fibers, such as wool or silk, in textile fabrics or nonwovens.
  • a procedurally simple processing of the mixed textiles, such as a common dyeing is made possible by the fibers of the invention.
  • the regenerated cellulosic moldings according to the invention according to one of claims 9 to 12 are particularly advantageous for the production of hygiene articles, in particular face masks, wipes, diapers or sanitary napkins and for the production of medical articles, such as wound dressings, dressings or tampons.
  • the silk proteins incorporated in the fibers can provide antibacterial and / or antimicrobial action and improve hygiene.
  • the formation of biofilms on the surface of such products can be advantageously prevented or delayed.
  • Table 1 example additive Silk protein [% by weight] spinning bath Titre [dtex] Strength [cN / tex] Strain [%] NSF [U / dtex] 1 without - water 1.61 34.1 10.2 50 2 5 Water 80 ° C 1.59 34.4 11.5 175 3 5 60% methanol 1.58 34.9 11.4 210 4 10 Water 80 ° C 1.62 34.2 11.2 302 5 10 methanol 1.61 34.9 11.8 325
  • the NSF value was determined with the Delta 100 scrubber marketed by Lenzing Instruments under the following test conditions: 8.2 ml / min water flow rate, 500 rpm spin speed, 50 ° chafe angle, 70 mg bias weight; Filament stocking from Baur GmbH & KG, Tistr. 34, D-42369 Wuppertal.
  • aqueous lyophilized slurries or solutions of silk protein in formic acid (10% by weight of spider silk protein in distilled water or formic acid) were added to the lyocell spinning mass and fibers with 5, 10 and 20% by weight of silk protein were produced.
  • the silk protein amounts refer to mass fraction of the silk protein on the fiber-forming substance.
  • a viscose solution containing 8.7% by weight of cellulose, 5.2% by weight of alkali and 2.3% by weight of sulfur, having a maturity index of 15 hottenroth and a falling ball viscosity of 75 seconds (determined in accordance with Zellchemie-Merkblatt III / 5 / E) was spun into a regeneration bath containing 100 g / l sulfuric acid, 330 g / l sodium sulfate or ammonium sulfate and 15 g / l zinc sulfate by spinneret.
  • the spinneret had 1053 holes of 50 ⁇ m in diameter.
  • To the viscose spinning solution was added 0.5% by weight of a nitrogen-containing auxiliary.
  • a draw in the secondary bath (92 ° C, 15 g / l sulfuric acid) of about 75%.
  • the take-off speed is 30 m / min.
  • Silk protein levels refer to the mass fraction of the silk protein on the fiber-forming substance.
  • aqueous solutions of spider silk protein (10% by weight of spider silk protein in distilled water) were added to the viscose solution before the spinneret as described above.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Artificial Filaments (AREA)
EP18168510.8A 2018-04-20 2018-04-20 Corps moulé cellulosique régénéré et procédé de fabrication de corps moulé cellulosique régénéré Withdrawn EP3556914A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP18168510.8A EP3556914A1 (fr) 2018-04-20 2018-04-20 Corps moulé cellulosique régénéré et procédé de fabrication de corps moulé cellulosique régénéré
PCT/EP2019/058783 WO2019201639A1 (fr) 2018-04-20 2019-04-08 Corps moulés cellulosiques régénérés et procédé de fabrication de corps moulés cellulosiques régénérés

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP18168510.8A EP3556914A1 (fr) 2018-04-20 2018-04-20 Corps moulé cellulosique régénéré et procédé de fabrication de corps moulé cellulosique régénéré

Publications (1)

Publication Number Publication Date
EP3556914A1 true EP3556914A1 (fr) 2019-10-23

Family

ID=62134046

Family Applications (1)

Application Number Title Priority Date Filing Date
EP18168510.8A Withdrawn EP3556914A1 (fr) 2018-04-20 2018-04-20 Corps moulé cellulosique régénéré et procédé de fabrication de corps moulé cellulosique régénéré

Country Status (2)

Country Link
EP (1) EP3556914A1 (fr)
WO (1) WO2019201639A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110886025B (zh) * 2019-12-17 2022-07-05 上海里奥纤维企业发展有限公司 一种溶剂法高湿模量蛋白纤维及其制备方法
CN116288770B (zh) * 2022-12-30 2025-02-07 宜宾惠美纤维新材料股份有限公司 一种含蛋白的莱赛尔纤维及其制备方法

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19841649A1 (de) 1998-09-11 2000-04-27 Thueringisches Inst Textil Verfahren zur Herstellung und produktorientierten Verarbeitung von konzentrierten Lösungen fibrillärer Proteine in NMMNO-Monohydrat
WO2006002827A1 (fr) 2004-06-25 2006-01-12 Technische Universitaet Muenchen Proteines d'origine naturelle et matieres fabriquees a partir de celles-ci
WO2006008163A2 (fr) 2004-07-22 2006-01-26 Technische Universitaet Muenchen Proteines de soies d'araignees recombinees
CN102851777B (zh) * 2012-10-11 2014-05-14 湖州珠力纳米材料科技开发有限公司 蚕丝蛋白共混再生纤维素纤维的制备方法
CN105803568A (zh) * 2014-12-30 2016-07-27 上海水星家用纺织品股份有限公司 一种蚕丝蛋白纤维的制备方法
WO2016149414A1 (fr) 2015-03-16 2016-09-22 Bolt Threads, Inc. Fibres de soie améliorées
CN107142542A (zh) * 2017-07-06 2017-09-08 青岛百草新材料股份有限公司 一种蚕丝蛋白再生纤维素纤维及其制备方法
WO2017188430A1 (fr) 2016-04-28 2017-11-02 Ｓｐｉｂｅｒ株式会社 Fibroïne modifiée

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19841649A1 (de) 1998-09-11 2000-04-27 Thueringisches Inst Textil Verfahren zur Herstellung und produktorientierten Verarbeitung von konzentrierten Lösungen fibrillärer Proteine in NMMNO-Monohydrat
WO2006002827A1 (fr) 2004-06-25 2006-01-12 Technische Universitaet Muenchen Proteines d'origine naturelle et matieres fabriquees a partir de celles-ci
WO2006002853A1 (fr) 2004-06-25 2006-01-12 Technische Universitaet Muenchen Synthese de soie d'araignee et/ou de proteines flagelliformes
WO2006008163A2 (fr) 2004-07-22 2006-01-26 Technische Universitaet Muenchen Proteines de soies d'araignees recombinees
CN102851777B (zh) * 2012-10-11 2014-05-14 湖州珠力纳米材料科技开发有限公司 蚕丝蛋白共混再生纤维素纤维的制备方法
CN105803568A (zh) * 2014-12-30 2016-07-27 上海水星家用纺织品股份有限公司 一种蚕丝蛋白纤维的制备方法
WO2016149414A1 (fr) 2015-03-16 2016-09-22 Bolt Threads, Inc. Fibres de soie améliorées
WO2017188430A1 (fr) 2016-04-28 2017-11-02 Ｓｐｉｂｅｒ株式会社 Fibroïne modifiée
CN107142542A (zh) * 2017-07-06 2017-09-08 青岛百草新材料股份有限公司 一种蚕丝蛋白再生纤维素纤维及其制备方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
HIRANO S ET AL: "Wet-spun blend biofibers of cellulose-silk fibroin and cellulose-chitin-silk fibroin", CARBOHYDRATE POLYM, APPLIED SCIENCE PUBLISHERS, LTD. BARKING, GB, vol. 1-47, no. 2, 1 February 2002 (2002-02-01), pages 121 - 124, XP004310248, ISSN: 0144-8617, DOI: 10.1016/S0144-8617(01)00171-0 *

Also Published As

Publication number Publication date
WO2019201639A1 (fr) 2019-10-24

Similar Documents

Publication Publication Date Title
DE69203731T2 (de) Zu Fasern verspinnbare Lösungen von Seidenraupen-Fibroin.
EP2981639B1 (fr) Fibres en polysaccharides à pouvoir élevé de formation de fibrilles et leur procédé de fabrication
DE69131924T2 (de) Verfahren zum Spinnen von Polypeptidfasern
DE69705303T2 (de) Verbundfasern, solche fasern enthaltende wundverbände und verfahren zu ihrer herstellung
EP2981640B1 (fr) Fibres en polysaccharides et leur procédé de fabrication
DE60125964T2 (de) Gekräuselte faser und verfahren zu deren herstellung
DE10007794A1 (de) Polymerzusammensetzung und daraus hergestellter Formkörper
EP2329074B1 (fr) Procédé de traitement de corps moulés cellulosiques
KR101385275B1 (ko) 라이오셀 스테이플 섬유의 제조 방법 및 이로부터 제조되는 라이오셀 스테이플 섬유
EP0797696B2 (fr) Procede de fabrication de fibres cellulosiques
DE69028729T2 (de) Elastische Polyurethanfaser
EP0683827B1 (fr) Procede de fabrication de corps moules en cellulose
EP1537261B1 (fr) Procede de fabrication de corps moules cellulosiques
WO2019201639A1 (fr) Corps moulés cellulosiques régénérés et procédé de fabrication de corps moulés cellulosiques régénérés
DE2151345A1 (de) Verfahren zur Herstellung von hochveredelten,gekraeuselten Rayon-Faeden und -Stapelfasern
EP2235253B1 (fr) Procédé de traitement de corps moulés cellulosiques
DE2607996C2 (de) Hydrophile Fasern und Fäden aus einem Acrylnitrilpolymerisat
CN116837476A (zh) 一种持久抗菌再生纤维素纤维及其制备方法
KR101904771B1 (ko) 라이오셀 섬유 및 그 제조방법
DE2402444A1 (de) Garne mit mattem aussehen auf der basis von synthetischen polymeren und verfahren zu ihrer herstellung
DE69315664T2 (de) Verfahren zum Spinnen von Polypeptidfasern aus Lösungen von Lithiumthiocyanat und flüssigem Phenol
DE10037983B4 (de) Polymerzusammensetzung und daraus hergestellter Formkörper mit einem Gehalt an Alkaloid
EP3868929B1 (fr) Corps moulé, comportant de l'élastane incorporé dans la cellulose et procédé de fabrication
EP1354914A1 (fr) Composition polymérique avec un polymère biodégradable et une substance, un ou des extraits et/ou un ou des composés essentiels d'herbes de la famille des Asteraceae
CN105420925A (zh) 以静电喷浆制备具有防霉、抗菌及除臭功能纤维素不织布的方法

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): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

17P Request for examination filed

Effective date: 20200423

RBV Designated contracting states (corrected)

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

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

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20200603