WO2016185195A1 - Treatment of fabrics and textiles - Google Patents

Treatment of fabrics and textiles Download PDF

Info

Publication number
WO2016185195A1
WO2016185195A1 PCT/GB2016/051413 GB2016051413W WO2016185195A1 WO 2016185195 A1 WO2016185195 A1 WO 2016185195A1 GB 2016051413 W GB2016051413 W GB 2016051413W WO 2016185195 A1 WO2016185195 A1 WO 2016185195A1
Authority
WO
WIPO (PCT)
Prior art keywords
fabric
group
solution
wetting
metal salt
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.)
Ceased
Application number
PCT/GB2016/051413
Other languages
English (en)
French (fr)
Inventor
Nicholas Brown
David John Ellis
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.)
Nikwax Ltd
Original Assignee
Nikwax Ltd
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
Priority claimed from GBGB1508527.7A external-priority patent/GB201508527D0/en
Priority to US15/574,608 priority Critical patent/US10633788B2/en
Priority to JP2018512501A priority patent/JP6930965B2/ja
Priority to ES16724452T priority patent/ES2888623T3/es
Priority to BR112017024619-8A priority patent/BR112017024619B1/pt
Priority to CN201680028932.4A priority patent/CN107690493B/zh
Application filed by Nikwax Ltd filed Critical Nikwax Ltd
Priority to KR1020177034112A priority patent/KR102623691B1/ko
Priority to EP16724452.4A priority patent/EP3298192B1/en
Priority to CA2985934A priority patent/CA2985934C/en
Priority to PL16724452T priority patent/PL3298192T3/pl
Publication of WO2016185195A1 publication Critical patent/WO2016185195A1/en
Anticipated expiration legal-status Critical
Priority to CONC2017/0012981A priority patent/CO2017012981A2/es
Ceased legal-status Critical Current

Links

Classifications

    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/01Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
    • D06M15/03Polysaccharides or derivatives thereof
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/184Carboxylic acids; Anhydrides, halides or salts thereof
    • D06M13/188Monocarboxylic acids; Anhydrides, halides or salts thereof
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10Repellency against liquids
    • D06M2200/12Hydrophobic properties

Definitions

  • the present invention relates to a novel combination of reagents for use in an improved process for applying a wetting effect to a textile or fabric and for preparing fabrics for the application of a water repellent.
  • it relates to a novel combination of reagents that together form a wetting system that when applied to a textile or fabric and on low temperature drying of the textile continues to provide a re-wetting effect to the textile but on raising the temperature of the textile above a certain temperature the re-wetting effect is lost.
  • the padding process is an immersion process that consists essentially of two steps.
  • the first step known as the "dip" is when the fabric is immersed in the required liquid in a padding tank to achieve thorough impregnation of the fabric.
  • the fabric is passed under a submerged roller in the padding tank full of the required liquid, which may be a dye or water-repellent agent.
  • the second step consists of passing the fabric out of the padding tank and then between two rollers, known as pad mangles, to squeeze out air and force liquid into the fibres of the fabric or material.
  • the pad mangles As the fabric passes through the pad mangles, at speeds of up to 50m per minute, the excess liquid squeezed out is sent back along the fabric. For the process to be effective and even, sufficient liquor needs to be adsorbed on to the fabric before excess is squeezed out by a mangle.
  • a wetting system for providing a wetting effect to a fabric or textile comprising a solution of an alkyl polyglucoside (APG) in combination with a solution of a Group 4 metal salt.
  • APG alkyl polyglucoside
  • Such a wetting system can be applied to fabrics made of natural fibres such as cotton or wool, or to fabrics made of man-made fibres such as polyester or nylon.
  • a wetting agent is a substance that provides the effect of increasing the ability of a liquid to penetrate or spread over the surface of a material such as a fabric or textile cloth.
  • wetting agents in the padding tank or bath to increase the pick-up of the bath liquor and to promote uniformity of absorption.
  • a wetting agent may also be applied to the textile before the immersion in the bath.
  • the alkyl polyglucoside acts as the wetting agent and the Group 4 metal salt serves to deactivate the wetting effect of the APG when combined together and heated above a certain temperature.
  • [001 1 ] 'In combination' refers to the fact that the solution of APG can be applied to a fabric with, for example, a dye and then the fabric is dried at low temperature, after which the solution of the Group 4 metal salt with, for example, a water repellent treatment is applied to the fabric, after which the fabric is dried at a high temperature, i.e. at least 100°C.
  • the solution of the APG and the solution of the Group 4 metal salt may be applied to the fabric simultaneously.
  • Each of the two components of the wetting system may be utilised as part of other treatments and still be effective in contributing to the provision of a wetting effect to a fabric.
  • the solution of a Group 4 metal salt may form part of a water repellent treatment.
  • Suitable water repellent treatments include waxes, silicones, stearic acid-melamine based systems, reactive polyurethanes, dendrimer chemistries, hydrophobic alkyl chain fluorinated compounds such as polymers based upon C6 and C8 fluorotelomer- derived acrylates.
  • Alkyl polyglycosides are a class of non-ionic surfactants derived from sugars and fatty alcohols. When derived from glucose they are known as alkyl polyglucosides.
  • the alkyl polyglucoside has a hydrophilic end to the molecule having a formula (C 6 Hi 0 O5) n , where n is at least 1, for example at least 2. In embodiments, n is less or equal to 20.
  • the alkyl polyglucoside also has a hydrophobic end to the molecule comprising an alkyl group, R, typically having from 4 to 20 carbon atoms, preferably from 8 to 16 carbon atoms.
  • the alkyl group may comprise 4 to 6 carbons, 8 to 10 carbons, 8 to 12 carbons, 10 to 12 carbons, 10 to 16 carbons or 16 to 18 carbons.
  • the alkyl polyglucoside can be represented overall by the formula H(C 6 Hi 0 O5) n OR:
  • Alkyl polyglucosides are produced by direct synthesis from higher monofunctional alcohols and powdered glucose, in particular anhydrous glucose or glucose monohydrate in the presence of an acid catalyst at an elevated temperature.
  • the reaction chamber is maintained at reduced pressure.
  • Alkyl polyglucosides are available commercially from The Dow Chemical
  • the Group 4 metal salt preferably comprises a titanium, zirconium or hafnium salt of a carboxylic acid.
  • the carboxylic acid salt may be selected from acetate, acetylacetonate, acrylate, lactate and stearate.
  • the most preferred Group 4 metal salt is zirconium acetate. Suitable salt preparations are available commercially from MEL Chemicals (UK), Dixon Chew (UK) and Dorf-Ketal Chemicals (India).
  • Zirconium acetate is available as a 22% w/w solution in water and acetic acid.
  • the ratio of the Group 4 metal salt, preferably zirconium acetate, to the alkyl polyglucoside is preferably in the region of 10: 1 to 15 : 1.
  • the wetting system to a fabric it is dried at a temperature of at least 100°C, i.e. from 100°C to 160°C, preferably from 100°C to 140°C, most preferably from 110°C to 135°C, the ability of the fabric to absorb water, i.e. to be re- wet, is lost.
  • a process for producing a wetting or re-wetting effect on a textile or fabric comprising applying a wetting system to the fabric that comprises a solution of an alkyl polyglucoside in combination with a solution of a Group 4 metal salt and subsequently drying the fabric at a low temperature, i.e. less than 100°C.
  • Low temperature drying may be carried out at from 20°C to 80°C, preferably from 50°C to 60°C.
  • the solution of the alkyl polyglucoside and the solution of the Group 4 metal salt may be applied simultaneously to the textile or fabric.
  • the fabric may be dried at a low temperature after the application of the alkyl polyglucoside solution, and before applying the solution of the Group 4 metal salt.
  • the fabric may then be dried at a temperature of from 100°C to 160°C, preferably from 100°C to 140°C, most preferably from 110°C to 135°C.
  • the solution of the alkyl polyglucoside and the solution of the Group 4 metal salt are applied to the fabric sequentially, the solution of the alkyl polyglucoside may be applied together with a dye in order to colour the fabric. After low temperature drying, the solution of the Group4 metal salt may be applied to the fabric together with a water repellent treatment, after which the fabric is dried at a temperature of from 100°C to 160°C.
  • the advantage of the wetting system of the invention is that at low temperature drying the re-wetting effect is preserved. As a consequence the wetting system does not subsequently inhibit the attainment of good water-repellent properties for the textile or fabric.
  • the water repellent treatment may thus be successfully applied to the fabric in the pad tank or bath.
  • a solution comprising of 5g of a mixture of alkyl polyglucosides based on natural fatty alcohol C12-C 14 (Glucopon 600 CUSP, BASF Chemicals) and 5 g of Titanium Lactate (ammonium salt)(Tyzor LA, Dorf Ketal) in distilled water (1000 g) was used as a bath solution to apply the water repellent Texfin WR- F (Textile Chemicals) to a sample of polyester microfiber (weight of 120 g/m 2 ) using a Mathis HVF350 Laboratory Padder.
  • the Texfin WR-NF was introduced to the bath solution at a level of 200 g/1 and the pH was adjusted to a range of 4 to 5 using acetic acid at a level of 0.5 to 1.0 g/1.
  • the fabric was passed through the final bath solution at a rate of 4 metres per minute and passed through the mangle at a nip pressure of 4 bar. The pickup of the fabric was measured to be 56% of its dry weight.
  • An oil in water macroemulsion was prepared using 220g of polydimethylsiloxane, viscosity 100 centistoke (Dow Corning 200 Fluid, lOOCST) as the oil phase (22% w/w) and a mixture of 44 g C8 to C16 fatty alcohol glucoside (Plantacare 818UP, BASF Chemicals) in 736g deionised water.
  • the emulsion was produced by mechanical means using a laboratory high shear mixer operating at 21,000 rpm and the resultant oil droplet size in the emulsion was below 7 microns.
  • the emulsion was further diluted in deionised water at a ratio of 1 part emulsion to 4 parts water.
  • a sample of lightweight polyamide microfibre fabric (weight 75g/m 2 ) was fully immersed in the diluted emulsion for a period of ten minutes. After this, zirconium acetate (22% solution, Mel Chemicals) and acetic acid (80% technical grade) were added at a rate of 1.25% and 2.5% of the solution weight, respectively.
  • the fabric was left immersed for a further ten minutes before removing and allowing to drip dry, i.e. at ⁇ 100°C.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Silicon Polymers (AREA)
PCT/GB2016/051413 2015-05-18 2016-05-17 Treatment of fabrics and textiles Ceased WO2016185195A1 (en)

Priority Applications (10)

Application Number Priority Date Filing Date Title
PL16724452T PL3298192T3 (pl) 2015-05-18 2016-05-17 Obróbka tkanin i wyrobów włókienniczych
EP16724452.4A EP3298192B1 (en) 2015-05-18 2016-05-17 Treatment of fabrics and textiles
ES16724452T ES2888623T3 (es) 2015-05-18 2016-05-17 Tratamiento de telas y textiles
BR112017024619-8A BR112017024619B1 (pt) 2015-05-18 2016-05-17 Sistema de umectação e processo para a produção de um efeito de umectação ou reumectação sobre um têxtil ou tecido
CN201680028932.4A CN107690493B (zh) 2015-05-18 2016-05-17 布料与织物的处理方法
US15/574,608 US10633788B2 (en) 2015-05-18 2016-05-17 Treatment of fabrics and textiles
KR1020177034112A KR102623691B1 (ko) 2015-05-18 2016-05-17 패브릭 및 텍스타일 처리
JP2018512501A JP6930965B2 (ja) 2015-05-18 2016-05-17 ファブリック及びテキスタイルの処理方法
CA2985934A CA2985934C (en) 2015-05-18 2016-05-17 A wetting system for providing a wetting effect to a fabric or textile
CONC2017/0012981A CO2017012981A2 (es) 2015-05-18 2017-12-18 Tratamiento de telas y textiles

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
GB1508527.7 2015-05-18
GBGB1508527.7A GB201508527D0 (en) 2015-05-18 2015-05-18 Novel formulation
GB1607178.9 2016-04-25
GB201607178 2016-04-25

Publications (1)

Publication Number Publication Date
WO2016185195A1 true WO2016185195A1 (en) 2016-11-24

Family

ID=56069161

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB2016/051413 Ceased WO2016185195A1 (en) 2015-05-18 2016-05-17 Treatment of fabrics and textiles

Country Status (15)

Country Link
US (1) US10633788B2 (enExample)
EP (1) EP3298192B1 (enExample)
JP (1) JP6930965B2 (enExample)
KR (1) KR102623691B1 (enExample)
CN (1) CN107690493B (enExample)
BR (1) BR112017024619B1 (enExample)
CA (1) CA2985934C (enExample)
CL (1) CL2017002921A1 (enExample)
CO (1) CO2017012981A2 (enExample)
ES (1) ES2888623T3 (enExample)
MA (1) MA42108A (enExample)
PL (1) PL3298192T3 (enExample)
PT (1) PT3298192T (enExample)
TW (1) TWI699470B (enExample)
WO (1) WO2016185195A1 (enExample)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019147266A1 (en) * 2018-01-26 2019-08-01 Hewlett-Packard Development Company, L.P. Three-dimensional printing

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998010134A1 (en) * 1996-09-04 1998-03-12 Kimberly-Clark Worldwide, Inc. Method and composition for treating substrates for wettability
US20040121680A1 (en) * 2002-12-23 2004-06-24 Kimberly-Clark Worldwide, Inc. Compositions and methods for treating lofty nonwoven substrates
EP2267216A1 (de) * 2009-06-27 2010-12-29 Cognis IP Management GmbH Verwendung von wässerigen Wachsdispersionen zur Verbesserung der mechanischen Eigenschaften von Textilfasern
WO2016058781A1 (de) * 2014-10-15 2016-04-21 Wacker Chemie Ag Zusammensetzungen von aminosiloxanen, alkoxysiliciumverbindungen und metallcarboxylaten

Family Cites Families (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3993830A (en) * 1972-04-28 1976-11-23 Colgate-Palmolive Company Soil-release finish
US4537594A (en) * 1983-07-22 1985-08-27 Fogarty P.L.C. Processed feathers
US4795675A (en) * 1986-09-17 1989-01-03 Staley Continental Enhanced transfer printability treatment method and composition
DE19516963A1 (de) * 1995-05-12 1996-11-14 Stockhausen Chem Fab Gmbh Verfahren zur Behandlung von Häuten, Fellen, Ledern und Pelzen mit Tensiden zur Verbesserung der Hydrophobierwirkung und zur Angleichung qualitativ unterschiedlichen wet-blue-Materials
DE19904496A1 (de) * 1999-02-04 2000-08-10 Wacker Chemie Gmbh Wäßrige Cremes von Organosiliciumverbindungen
ATE365789T1 (de) * 2000-05-22 2007-07-15 Procter & Gamble Kit zur textilpflege
JP2004530052A (ja) * 2001-02-22 2004-09-30 クロムプトン コーポレイション 撥水性繊維製品仕上品及びその製造方法
US7018945B2 (en) * 2002-07-02 2006-03-28 Kimberly-Clark Worldwide, Inc. Composition and method for treating fibers and nonwoven substrates
DE102005029627A1 (de) * 2005-06-23 2007-01-04 Basf Ag Verfahren zur Herstellung von Leder
FR2894997A1 (fr) * 2005-12-19 2007-06-22 Rhodia Recherches & Tech Support fibreux comprenant un revetement silicone
US20090029140A1 (en) * 2006-02-03 2009-01-29 Basf Se Process for treating substrates
FR2903113A1 (fr) * 2006-06-30 2008-01-04 Rhodia Recherches & Tech Emulsion huile dans eau d'aminosiloxanes
CN101680159A (zh) * 2007-05-22 2010-03-24 巴斯夫欧洲公司 处理表面的方法
CN103946446B (zh) * 2011-11-29 2017-02-22 道康宁公司 氨基官能有机硅乳液
US20140308229A1 (en) * 2011-11-29 2014-10-16 Dow Corning Corporation Aminofunctional Silicone Emulsions For Fiber Treatments
CN103572604B (zh) * 2012-07-20 2016-01-27 广东德美精细化工股份有限公司 一种防水防油剂及其制备方法和应用
CN103966031A (zh) * 2014-05-30 2014-08-06 于文 一种环保型皮革清洁护理剂及其制备方法
CN104450343A (zh) * 2014-11-17 2015-03-25 青岛厚科信息工程有限公司 一种可长期保存的洗涤剂
CN104532556B (zh) * 2015-01-29 2017-01-11 偃师然合生物材料有限公司 一种高耐碱型纺织精练剂及其制备方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998010134A1 (en) * 1996-09-04 1998-03-12 Kimberly-Clark Worldwide, Inc. Method and composition for treating substrates for wettability
US20040121680A1 (en) * 2002-12-23 2004-06-24 Kimberly-Clark Worldwide, Inc. Compositions and methods for treating lofty nonwoven substrates
EP2267216A1 (de) * 2009-06-27 2010-12-29 Cognis IP Management GmbH Verwendung von wässerigen Wachsdispersionen zur Verbesserung der mechanischen Eigenschaften von Textilfasern
WO2016058781A1 (de) * 2014-10-15 2016-04-21 Wacker Chemie Ag Zusammensetzungen von aminosiloxanen, alkoxysiliciumverbindungen und metallcarboxylaten

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019147266A1 (en) * 2018-01-26 2019-08-01 Hewlett-Packard Development Company, L.P. Three-dimensional printing
US11795338B2 (en) 2018-01-26 2023-10-24 Hewlett-Packard Development Company, L.P. Three-dimensional printing

Also Published As

Publication number Publication date
BR112017024619A2 (pt) 2018-11-13
CA2985934A1 (en) 2016-11-24
TW201700827A (zh) 2017-01-01
EP3298192A1 (en) 2018-03-28
BR112017024619B1 (pt) 2022-03-29
MA42108A (fr) 2018-03-28
EP3298192B1 (en) 2021-06-23
ES2888623T3 (es) 2022-01-05
HK1252975A1 (zh) 2019-06-06
US10633788B2 (en) 2020-04-28
KR102623691B1 (ko) 2024-01-10
CN107690493A (zh) 2018-02-13
CA2985934C (en) 2022-05-10
US20180135241A1 (en) 2018-05-17
CO2017012981A2 (es) 2018-03-20
PL3298192T3 (pl) 2021-12-06
PT3298192T (pt) 2021-09-21
JP2018514664A (ja) 2018-06-07
CL2017002921A1 (es) 2018-09-28
TWI699470B (zh) 2020-07-21
KR20180030775A (ko) 2018-03-26
JP6930965B2 (ja) 2021-09-01
CN107690493B (zh) 2020-11-06

Similar Documents

Publication Publication Date Title
Leeder et al. Changes induced in the properties of wool by specific epicuticle modification
DE69016635T2 (de) Wasser- und ölabweisendes Behandlungsmittel.
DE2114517C3 (de) Verfahren und Vorrichtung zum Veredeln von cellulosehaltigem Textilgut
EP3704295B1 (en) Functional thermo-regulating textile additives and uses thereof
EP3298192B1 (en) Treatment of fabrics and textiles
US2750305A (en) Composition and method for hydrophobizing of textiles
HK1252975B (en) Treatment of fabrics and textiles
CN106758394B (zh) 一种改善经纱涂料染色效果的方法
Peters et al. The effect of solvents in wool dyeing
JP2012001849A (ja) 撥水性繊維集合体および撥水加工方法
EP1944408A2 (en) Method for forming a fabric with insect, water- and oilrepellent characteristics
DE1802187A1 (de) Hochmolekulares Polyaethylenglykol als Mittel zur Erhoehung des Aufnahmevermoegens von cellulosehaltigen Geweben
CN114575150A (zh) 一种芳香耐久型帽饰用纯棉布及其制备方法
CN106498721A (zh) 一种改善浆料浸透效率的方法
WO2006015744A1 (de) Verfahren zur ausrüstung von saugfähigen materialien
AT242096B (de) Verfahren zur Verbesserung der Gebrauchseigenschaften von Zellulosematerialien
JP2006052480A (ja) セルロース系繊維含有布帛の加工方法及びセルロース系繊維含有布帛
JPS642708B2 (enExample)
DE732231C (de) Verfahren zum Wasserabstossendmachen von Textilstoffen
CN106758195B (zh) 一种改善经纱上浆效果的方法
Steele Factors Affecting the Drying of Apparel Fabrics: Part III: Finishing Agents
DE2139026A1 (de) Verfahren und mittel zur stabilisierung von organopolysiloxan-emulsionen
DE2047872C3 (de) Verfahren zum Färben von bahnförmigem Textilgut aus synthetischen Fasern
Ali et al. Direct Inkjet Single Sided Hydrophobic Finishing of Textiles
AT522744A1 (de) Verfahren zum Bedrucken wenigstens eines textilen Substrats

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16724452

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2985934

Country of ref document: CA

WWE Wipo information: entry into national phase

Ref document number: 15574608

Country of ref document: US

ENP Entry into the national phase

Ref document number: 2018512501

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 20177034112

Country of ref document: KR

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: NC2017/0012981

Country of ref document: CO

Ref document number: 2016724452

Country of ref document: EP

REG Reference to national code

Ref country code: BR

Ref legal event code: B01A

Ref document number: 112017024619

Country of ref document: BR

ENP Entry into the national phase

Ref document number: 112017024619

Country of ref document: BR

Kind code of ref document: A2

Effective date: 20171116

WWW Wipo information: withdrawn in national office

Ref document number: NC2017/0012981

Country of ref document: CO