EP3271508B1 - Fluorfreie hydrophobierung - Google Patents

Fluorfreie hydrophobierung Download PDF

Info

Publication number
EP3271508B1
EP3271508B1 EP16709022.4A EP16709022A EP3271508B1 EP 3271508 B1 EP3271508 B1 EP 3271508B1 EP 16709022 A EP16709022 A EP 16709022A EP 3271508 B1 EP3271508 B1 EP 3271508B1
Authority
EP
European Patent Office
Prior art keywords
mixture according
water
free
acid
available
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
EP16709022.4A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP3271508A1 (de
Inventor
Herbert Bachus
Matthias Bauer
Andreas Otterbach
Peter Will
Robert Zyschka
Konrad Nostadt
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.)
CHT Germany GmbH
Original Assignee
CHT Germany 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 CHT Germany GmbH filed Critical CHT Germany GmbH
Priority to PL16709022T priority Critical patent/PL3271508T3/pl
Publication of EP3271508A1 publication Critical patent/EP3271508A1/de
Application granted granted Critical
Publication of EP3271508B1 publication Critical patent/EP3271508B1/de
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
    • D06M15/568—Reaction products of isocyanates with polyethers
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/12—Hydrophobic properties

Definitions

  • the present invention describes fluorine-free cationic polyurethane dispersions, their production and use on textile surfaces, woven fabrics, scrims, knitted fabrics, fibers, nonwovens and knitted fabrics in order, together with a fluorine-free wax dispersion, to significantly increase the water-repellent effects and the wash resistance.
  • Textile materials are used for a wide variety of applications. However, their absorbency and permeability to water are undesirable in many applications. These properties are disadvantageous for outdoor textiles such as rainwear and tarpaulins or textiles that are permanently outdoors such as awnings and geotextiles. Since it is not possible to find a technically adequate and economically acceptable solution to the problem simply by choosing the textile material, these textiles are treated with water-repellent agents. For a long time, perfluorinated acrylate systems and the equipment based on them dominated the market. Such fluorine-containing surface treatments not only allow excellent water repellency, but also bring oil and dirt-repellent effects with them. Despite these technical properties, the perfluorinated coatings are now on withdrawal as they are considered persistent and bioaccumulative ( M. Santen, U. Kallee, Chemistry for Any Weather, Greenpeace eV, 2012, p. 5 ).
  • the majority of the polyurethane dispersions on the market are anionic. These anionic dispersions carry, for example, carboxylate or sulfonate groups, which are firmly polymerized into the polymer structure and thus contribute to the fact that both the hydrophobicity of such dispersions on the textile and the wash resistance are significantly impaired.
  • cationic dispersions which have been dispersed with the aid of a volatile acid, this problem does not arise, since the acid evaporates and the amino groups under normal drying conditions thus no longer exist in their protonated form.
  • the term volatile acid is defined in such a way that it has a boiling point of up to 180 ° C., preferably up to 150 ° C., at normal pressure.
  • Cationic polyurethane dispersions have also been known to the person skilled in the art for a long time and have already been described frequently in the literature.
  • Colloid Polymer Science (2004) 283, pp. 209-218 the influences of amine content, proportion of crosslinkers and ionizing agents in relation to particle size and viscosity in cationic polyurethane dispersions were investigated and described.
  • polytetrahydrofuran (PTMG) with a molar mass of 1000g / mol was used as the diol component.
  • PTMG polytetrahydrofuran
  • An application to textiles is not described in this document.
  • the reactions to quaternary amino groups described are also disadvantageous with regard to water repellency and permanence.
  • WO 2012 058534 A highlights the advantages of Jeffcat® DPA compared to N-methyldiethanolamine (NMDEA) with regard to the dispersion stability of cationic polyurethane dispersions.
  • NMDEA N-methyldiethanolamine
  • Polytetrahydrofurans, polypropylene glycols and a polyester diol based on hexanediol, neopentyl glycol and adipic acid were used as the diol component.
  • This document describes applications of such dispersions in inkjet printing, glass fiber and paper sizes and in electroplating. Applications to textiles, however, were not mentioned.
  • Cationic polyurethane dispersions which were produced from highly hydrophobic polyester diols are also not described therein.
  • Solvent-based polyacrylates are used in DE 1238215 A1 systems of this type cannot be used in the textile industry because of their disadvantageous process and environmental influences.
  • EP 2 411 575 B1 mentions the use of terpolymers based on alkyl acrylates, chlorine-containing vinyl compounds and styrene derivatives in combination with waxes as aqueous dispersions.
  • the use of styrene-containing polymers is unsuitable because of the tendency of these compounds to yellow, and halogen-containing substances are also undesirable in the textile industry for ecological reasons.
  • Vinyl esters of cooking acids as a component of copolymer wax dispersions have been used in EP 1 424 433 B1 mentioned, but are unfavorable due to the high price.
  • H-siloxanes to make textiles water repellent is no longer available DE 1231663 A1 known.
  • wrinkle-free finishes can be achieved at the same time (cf. also US 3032442 A ).
  • these systems have the serious disadvantage that elemental hydrogen can be released during textile finishing, which represents a considerable process risk.
  • they require anhydrous, flammable solvents and toxicologically questionable catalysts and are therefore not applicable in the textile industry.
  • EP 2 152 957 B1 suspends the described component DE 10211549 B9 also in connection with alkyl-modified organosiloxanes.
  • a combination of zirconium paraffin wax and H-siloxane is used in GB 1287745 A1 described, but application from organic, flammable solvents and with highly reactive catalysts is not acceptable for safety reasons at the time of registration.
  • JP 2006-124866 A1 reports on the use of a non-functionalized polydimethylsiloxane in combination with crosslinking agents to make textile materials water-repellent.
  • the crosslinker is preferably based on a carbodiimide.
  • EP 1 108 765 B1 describes carboxy-functional silicones as water repellants for furs and leather, optionally together with paraffins.
  • the disadvantage is that - applied to textile materials - they would lose their water-repellent effect at the latest after a household wash with a commercially available alkaline detergent, since the necessary acid groups are then deprotonated.
  • the authors also describe a dispersion process in which the silicone is first reacted with a base and then dispersed in a mixture of water and an organic solvent, from which this solvent must then be removed by distillation.
  • EP 1 035 200 A2 describes a wiping cloth finished with one or more hydrophobic components with the aim of producing a water-repellent film on an automobile surface treated with it, the hydrophobic finish being transferred from the textile to the surface wiped off with it.
  • the authors also state that the amount of emulsifier chosen for such a system should not be too high, since otherwise the hydrophobizing effect is lost. Accordingly, the smallest possible amounts of surface-active substances are advantageous.
  • compositions based on technical stearyl stearate (C18 / C18 with C16 components) which, in combination with silicone waxes and optionally other waxes, achieve good hydrophobicity.
  • the example compositions only provide sufficient water repellency through the addition of further substances, such as the formaldehyde-containing melamine resin Freepel® 1200 (Example 1) or in the remaining examples through the addition of a blocked isocyanate.
  • Formaldehyde is classified as carcinogenic in Europe at the time of registration; blocked Isocyanates are also toxicologically questionable.
  • a typical blocking agent namely butanone oxime, is classified as a cmr substance.
  • a fluorine-free cationic polyurethane dispersions are known as an additive in mixtures with fluorine-free wax and / or paraffin dispersions for impregnation and / or coating of textile fabrics, the polyurethane being produced by the reaction of one or more hydrophobic diols and one or more hydroxyl-containing tertiary amino compounds, one or more diisocyanates, with or without the addition of solvents and conversion of the polymeric reaction product obtained into water with the aid of volatile acid and suitable emulsifying auxiliaries.
  • An essential part of the technical teaching here is the use of blocking agents, which mostly have CMR properties and are therefore toxicologically questionable. Since such blocking agents have to be split off at high temperatures, their use is also disadvantageous from an energetic point of view.
  • cationic, fluorine-free wax and / or paraffin-containing dispersions can be significantly improved in their water-repellent effect if the cationic, fluorine-free polyurethane dispersions are added to them.
  • a first embodiment of the present invention relates to a mixture containing a fluorine-free, cationic cmr-free polyurethane dispersion and a fluorine-free wax and / or paraffin dispersion for hydrophobing, in particular for impregnating and / or coating textile fabrics, the polyurethane being produced by reacting one or more several hydrophobic polymeric diols with an average molecular weight of 1000 to 5000 g / mol and one or more hydroxyl-containing tertiary amino compounds, one or more diisocyanates, with or without the addition of solvents, and conversion of the polymeric reaction product obtained into water with the aid of volatile acid and suitable emulsifying auxiliaries , in particular if the dispersion is free from pbt substances and / or is free from blocking agents, in particular cmr blocking agents.
  • the invention describes the chemistry of the fluorine-free cationic polyurethane dispersions and their preparation, which, in combination with cationic, fluorine-free wax dispersions, contribute to a significant improvement in the water-repellent effects while at the same time improving the wash permanence and doing without the use of blocking agents.
  • the cationic polyurethane dispersions are prepared by reacting one or more hydrophobic polymeric diols or one or more hydrophobic polyester diols with one or more Tertiary amino compounds containing hydroxyl groups, one or more diisocyanates, with or without the addition of solvents and the dispersion of the polymeric reaction product obtained in water with the aid of volatile acid and suitable emulsifying auxiliaries.
  • the dispersion in water can take place either by the “transfer process” known per se or, when solvents are used, by the “solvent process” known per se.
  • chain lengthening can take place by reaction of isocyanate groups still free with amines either in water or in a solvent.
  • diamines which carry two amino groups that are reactive with isocyanate groups, or three-dimensional crosslinking takes place through amines which contain at least three amino groups that are reactive with isocyanate groups.
  • Chain lengthening also takes place when no amine is added, since free isocyanate groups present hydrolyze to amino groups and can then react further with another free isocyanate group. Amines which have only one isocyanate-reactive amino group can also be reacted as chain terminators.
  • hydrophobic silicone carbinols and polycarbonate diols are suitable as hydrophobic polymeric diols.
  • polycaprolactones and polytetrahydrofurans can also be used as starting materials.
  • Polyethylene glycols, polypropylene glycols and EO / PO block polymers, on the other hand, are unsuitable.
  • hydrophobic polyester diols used with particular preference for this invention were synthesized according to the prior art by an acidic esterification of one or more dicarboxylic acids with one or more diols themselves and consist of monomeric units with either on the diol and / or on the dicarboxylic acid side have at least 9 carbon atoms and thus a relatively low density of ester groups.
  • Suitable dicarboxylic acids are aliphatic, cycloaliphatic and aromatic dicarboxylic acids having at least 4 carbon atoms. Succinic acid, glutaric acid, glutaric anhydride, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, dimeric fatty acids, phthalic acid, phthalic acid and phthalic acid are particularly preferred.
  • Suitable diols are aliphatic, cycloaliphatic and aromatic diols with a total of at least 4 carbon atoms.
  • the hydrophobic polyester diols produced from the above-mentioned dicarboxylic acids and diols by means of acid esterification according to the prior art have a calculated (average) molecular mass of ⁇ 7000 g / mol, preferably from 1000 to 5000 g / mol.
  • diisocyanates examples include tetramethylene diisocyanate, hexamethylene diisocyanate, dodecanemethylene diisocyanate, 1,4 diisocyanato-cyclohexane, 3-isocyanatomethyl-3,3,5-tri-methylcyclohexyl isocyanate (isophorone diisocyanate), 4,4'-diisocyanatocyclohexylmethane, 4,4'-diisocyanato-3,3 '-dimethyl-dicyclohexylmethane, 4,4'-diisocyanatocyclohexyl propane - (2,2), 1,4 diisocyanatobenzene, 2,4 or 2,6 diisocyanatotoluene or mixtures of these isomers, 4,4'-2,4', or 2 , 2 'diisocyanatodiphenylmethane or mixtures of these isomers, 4,4'
  • Catalysts based on tertiary amines such as 1,4-diazabicyclo [2.2.2] octane (DABCO) and diazabicycloundecene (DBU) and compounds of transition metals are preferred.
  • DABCO 1,4-diazabicyclo [2.2.2] octane
  • DBU diazabicycloundecene
  • Bismuth compounds such as Bismuth neodecanoate, manganese or zinc compounds such as zinc ethyl hexanoate.
  • Amino alcohols with a tertiary amino group are also incorporated during the synthesis of the polyester polyurethane in order to achieve a good dispersion quality with the smallest possible particle size when converted into water.
  • Amines with at least one tertiary amino group are required, which are converted into an ionic group by protonation with a preferably volatile acid and which makes a decisive contribution to good dispersion quality.
  • Aliphatic hydroxy compounds such as N, N-dimethylethanolamine, N, N, N'-trimethyl-N'-hydroxyethyl bisaminoethyl ether (Jeffcat® ZF-10), N, N-bis (3-dimethylaminopropyl) -N-isopropanolamine (Jeffcat ® ZR50), 2- (2-dimethylaminoethoxy) ethanol (Jeffcat® ZR-70), N, N, N'-trimethylaminoethylethanolamine (Jeffcat® Z 110).
  • Aliphatic N-alkyldialkanolamines such as, for example, N-methyldiethanolamine, N-methyldipropanolamine, or ethoxylated N-methyldiethanolamine, are particularly preferred.
  • Compounds which, in addition to 2 hydroxyl groups, also contain at least one tertiary amino group which cannot be incorporated into the polymer backbone but remain in a lateral position are very particularly preferred.
  • Examples are N- (3-dimethylaminopropyl) -N, N-diethanolamine), N- (3-dimethylaminopropyl) -N, N-diisopropanolamine (Jeffcat® DPA), or N, N bis (2-hydroxyethyl) -isonicotinamide.
  • Volatile organic and / or inorganic acids are preferably used as acids for protonating the amino groups, since the evaporation of the acid in conventional drying processes can significantly increase the hydrophobicity and permanence.
  • formic acid, propionic acid or hydrochloric acid are therefore preferred and acetic acid is very particularly preferred for the purposes of the invention.
  • diamines are used as chain extenders. These are preferably aliphatic and / or cycloaliphatic diamino compounds.
  • Polyamines with a functionality of three or more can optionally also be used as crosslinkers in order to achieve a certain degree of branching.
  • suitable diamines are ethylenediamine, 1,2- and 1,3-propylenediamine, 1,4-tetramethylenediamine, 1,6 hexamethylenediamine, 2,2,4- and 2,4,4-trimethylhexamethylenediamine, or mixtures of these isomers.
  • cycloaliphatic diamino compounds are examples of cycloaliphatic diamino compounds.
  • chain extenders can be dispensed with entirely. Chain extension then takes place via the partial hydrolysis of free isocyanate groups to form amino groups.
  • suitable solvents are aprotic solvents that cannot react with isocyanate. They are preferably ketones, esters and ethers. Examples of ketones are acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone. Examples of esters are isopropyl acetate, butyl acetate, methoxypropyl acetate (Dowanol® PMA) and dipropylene glycol methyl ether acetate (Dowanol® DPMA). An example of ethers is dipropylene glycol dimethyl ether (Propylene glycol® DME, Proglyde® DMM).
  • Suitable dispersing auxiliaries must not have any significant surface activity and therefore not have a good wetting effect.
  • Long-chain, hardened fatty alcohols are therefore preferred higher degree of ethoxylation such as stearyl alcohol x 25 EO (Lutensol® AT 25) or ethoxylated fatty acid esters such as hydrogenated castor oil x 60 EO (Simulsol®1294) or C30 wax alcohol x 40 EO (Unithox® 480)
  • the cationic polyurethane dispersions are used exclusively in combination with known fluorine-free, wax and / or paraffin dispersions used for hydrophobing textiles. In this case, preferably between 3 and 50% by weight, particularly preferably between 4 and 30% by weight, and very particularly preferably between 6 and 24% by weight of such a cationic polyurethane dispersion are added to the wax dispersions.
  • a fluorine-free wax dispersion that does not require the use of cmr substances, the in DE 102013209 170A formulation mentioned under embodiment 2.
  • the haptic assessment was divided into five levels of softness (very soft, soft, moderate, stiff, very stiff).
  • a laboratory pad from Walter Mathis AG was used for equipment.
  • the samples were dried in a "Mathis Labdryer” laboratory frame provided with a "Programmer LTE" control unit.
  • the liquor pick-up of the samples is defined as the percentage increase in mass due to the liquor and was determined by weighing the samples before and after finishing. It was around 73% for the material used.
  • the textile pattern used was: 100% polyester marine, item number 1816 (fabric weight of 115 g / m 2 ), available from Dolinschek GmbH, Eichhalde 15, 72393 Burladingen.
  • Beitlich GmbH DABCO: available from Sigma Aldrich Desmophen® C2200: polycarbonate diol, 2000 g / mol available from Bayer MaterialScience AG Ethylenediamine: available from BASF SE Acetic acid 60%: available from Brenntag GmbH Acetic acid 100%: available from Brenntag GmbH HANSA® ADD 4090: silicone carbinol, available from CHT R.
  • Table 1A Polyester based on adipic acid PES 1 * PES 2 * PES 3 * PES 4 Adipic acid 652 610 597 189 Neopentyl glycol 494 1.6 hexanediol 525 535 Pripol® 2033 843 Phosphorous acid 4th 4th 4th 4th CHT defoamer SI 1.2 1.2 1.2 1.2 Jeffcat® DPA 12 12 12 12 calculated molecular mass approx.
  • 220 g of the polymeric diol are placed in a 500 ml reaction vessel equipped with a stirrer, thermometer and reflux condenser and heated to 80 ° C. with 0.1 kg of catalyst and the amounts of solvent given in Tables 2A-2C.
  • the amounts of diisocyanates indicated in the table are then added at 80 ° C. and the mixture is stirred until a constant NCO content is reached.
  • the stated amount of the tertiary amino compounds containing hydroxyl groups is then added and the mixture is again stirred until a constant NCO content is reached.
  • the specified amount of a volatile, anhydrous acid is then added and the mixture is stirred until homogeneous.
  • the homogeneous prepolymer is then transferred, with vigorous stirring, to a 2 l reaction vessel in which the specified amounts of soft water, Sarabid®200LL and CHT-Defoamer® K50 at a temperature of approx. 10 ° C are placed.
  • a separately prepared solution consisting of the specified amounts of the amines and water is added in order to extend the chain.
  • the mixture is then slowly heated to 40 ° C. and stirred there for 120 minutes before the cationic polyurethane dispersion is cooled back down to room temperature.
  • a solution of 22 g of 60% hexamethylenediamine in 88 g of water is then added dropwise via a dropping funnel and the mixture is again stirred until homogeneous. 525 g of water are then slowly added to this mixture and the dispersion thus obtained is heated to 50.degree. After 2 hours at 50 ° C., the solvent is removed in vacuo. A finely divided dispersion is obtained with a pH of 10% dilution in distilled water of 8.31 and an active content of 33.25%
  • the wax dispersion WD was after DE 10 2013 209170 A , Embodiment 2, produced as follows: 700 g of Radia 7501®, 57.68 g of Licowax KPS®, 420 g of silicone polymer 2 and 57.68 g of Genamin 0-020® were placed together in a sufficiently dimensioned steel pail with an anchor stirrer, which was heated in a water bath. The mixture was heated to 90 ° C. and stirred until the constituents were homogeneously dissolved in one another. A mixture of 42 g of 60% strength by weight acetic acid in 2908.64 g of hot water was then slowly added with stirring.
  • the pre-emulsion thus obtained was mixed with 168 g of a 15% strength Lutensol AT 25® in water, circulated in a homogenizer for 15 min (200 bar, 80 ° C.) and drained into a separate vessel via a plate heat exchanger.
  • the silicone polymer 2 used therein was analogous to that also in DE 10 2013 209170 A mentioned regulation: 56.4 g of Dynasilan 1505® were placed in a four-necked flask equipped with a stirrer, dropping funnel, thermometer and reflux condenser and heated to 75.degree. 11.7 g of water were then added. The mixture was stirred at 85 ° C. for 3 hours and the cleavage alcohol was then distilled off. Then 1013 g of HANSA SW 3068® were added and the mixture was stirred until homogeneous. Then 2 g of tetrabutylphosphonium hydroxide (40% in water) were added and the mixture was stirred at 90 ° C. for 5 h.
  • the cationic polyurethane dispersions were acidified in the amounts stated in Tables 3A-3C with the amounts also stated of acetic acid 60, mixed with the wax dispersion and diluted with water.
  • the water repellency was determined according to DIN EN 24920 by the so-called spray test. In addition to the values 50, 70, 80, 90 and 100 listed in the standard, a complete, Double-sided wetting of the textile sample, with the adhering water also penetrating the non-irrigated areas by capillary forces, indicated with the value 0.
  • the finished textiles were subjected to a specified number of household washes in accordance with DIN EN ISO 6330 at 60 ° C.
  • Tables 4A-4C list the formulations F1-F33 which were tested therein for their water-repellent effect with a small amount used. They were applied to polyester at 25 g / l each on a laboratory pad and dried at 120 ° C. for 2 minutes. The liquor uptake and the spray values before and after the household washes are also listed in Tables 4A-4C below.
  • Dispersion F4 F12 F19 F20 F21 F28 F29 Fleet admission 73% 73% 73% 73% 73% 73% 73% 73% 73% 73% 73% 73% Drying temperature / 120 ° C 120 ° C 120 ° C 120 ° C 120 ° C Drying time 2 min 2 min 2 min 2 min 2 min 2 min 2 min Starting value 5 5 5 5 5 5 1 household wash at 60 ° C 5 5 5 5 5 5 2 household washes at 60 ° C 5 5 5 5 5 5 5 household washes at 60 ° C 5 5 5 5 5 5 10 household washes at 60 ° C 4th 4th 5 5 4th 5 5 5 5
  • Table 6 Water repellency and permanence when using the individual components: Table 6: Dispersion WD KPU4 KPU 11 KPU16 KPU17 KPU18 KPU23 KPU24 Fleet pick-up 73% 73% 73% 73% 73% 73% 73% 73% 73% 73% Drying temperature / 120 ° C 120 ° C 120 ° C 120 ° C 120 ° C 120 ° C Drying time 2 min 2 min 2 min 2 min 2 min 2 min 2 min 2 min 2 min 2 min 2 min 2 min 2 min 2 min Starting value 3 2 2 2 2 3 2 1 household wash at 60 ° C 2 2 2 2 2 2 2 household washes at 60 ° C 2 1 1 1 1 1 1 2 1 5 household washes at 60 ° C 1 0 0 0 0 0 0 10 household washes at 60 ° C 1 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
  • CN103628324 describes fluorine-free cationic polyurethane dispersions as an additive in mixtures with fluorine-free wax and / or paraffin dispersions for the impregnation and / or coating of textile fabrics. Analogously to the embodiment 1 mentioned there, the following dispersion not according to the invention was prepared for comparison purposes.
  • Stepanpol PD-195 polyester based on phthalic acid and diethylene glycol with an OH number of 200, available from NRC Nordmann Rassman GmbH TMP (Trimethylopropane flakes): available from Perstorp Oxo Belgium AB PEG 400: polyethylene glycol with 400 g / mol available from Ineos Oxide Belgium.
  • NMDEA N-methyldiethanolamine
  • BASF SE 3.5 Dimethylpyrazole: available from Sigma-Aldrich Sasolwax 6403: Paraffin with a melting point of 63-66 ° C available from Sasol Wax GmbH
  • Ethoquat C / 25 Cocoalkylmethyl polyoxyalkylene (15) ammonium chloride available from AkzoNobel
  • Table 7 Dispersion Example 1 from CN103628342 * Example 1 from CN103628342 * F14 F15 F22 Fleet pickup 73% 73% 73% 73% 73% Drying temperature 120 ° C 100 ° C 120 ° C 120 ° C Drying time 2 min 2 min 2 min 2 min 2 min Fixing temperature --- 180 ° C --- --- Fixing time --- 30 sec.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Paints Or Removers (AREA)
EP16709022.4A 2015-03-16 2016-03-08 Fluorfreie hydrophobierung Active EP3271508B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL16709022T PL3271508T3 (pl) 2015-03-16 2016-03-08 Bezfluorowa hydrofobizacja

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102015204736.9A DE102015204736A1 (de) 2015-03-16 2015-03-16 Fluorfreie Hydrophobierung
PCT/EP2016/054908 WO2016146437A1 (de) 2015-03-16 2016-03-08 Fluorfreie hydrophobierung

Publications (2)

Publication Number Publication Date
EP3271508A1 EP3271508A1 (de) 2018-01-24
EP3271508B1 true EP3271508B1 (de) 2020-10-28

Family

ID=55521696

Family Applications (1)

Application Number Title Priority Date Filing Date
EP16709022.4A Active EP3271508B1 (de) 2015-03-16 2016-03-08 Fluorfreie hydrophobierung

Country Status (7)

Country Link
EP (1) EP3271508B1 (ko)
KR (1) KR102437958B1 (ko)
CN (1) CN107429478B (ko)
DE (1) DE102015204736A1 (ko)
ES (1) ES2848849T3 (ko)
PL (1) PL3271508T3 (ko)
WO (1) WO2016146437A1 (ko)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3497166A1 (en) 2016-08-12 2019-06-19 3M Innovative Properties Company Fluorine-free fibrous treating compositions, treated substrates, and treating methods
EP3470573A1 (de) * 2017-10-16 2019-04-17 Werner & Mertz GmbH Verfahren zur herstellung eines textilen artikels mit hydrophobierter textiler oberfläche durch plasmabehandlung und nasschemische behandlung
CN114197210B (zh) * 2021-12-21 2024-03-19 赛得利（福建）纤维有限公司 一种疏水改性的粘胶纤维及其制备方法
CN116084205A (zh) * 2022-12-06 2023-05-09 浙江氟信新材料科技有限公司 一种纸张无氟防水剂及其制备方法

Family Cites Families (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2758946A (en) 1952-09-23 1956-08-14 Gen Electric Silicone water-repellent compositions
US2785145A (en) 1954-07-01 1957-03-12 American Cyanamid Co Siliconate-aminoplast compositions and textiles coated therewith
US3032442A (en) 1955-04-15 1962-05-01 American Cyanamid Co Process of finishing textiles with silicone-colloidal melamine resin mixtures, composition and resultant article
NL236360A (ko) 1958-02-20
NL284874A (ko) 1961-10-31
GB1287745A (en) 1968-12-18 1972-09-06 Permashield Chemicals Ltd Water repellant fabric-treating composition
DE4222483A1 (de) 1992-07-09 1994-01-13 Pfersee Chem Fab Organosiloxane mit Stickstoff enthaltenden und mit Äthergruppierungen enthaltenden Resten
DE4401544A1 (de) 1994-01-20 1995-07-27 Basf Lacke & Farben Polyurethanharze, Verfahren zu ihrer Herstellung sowie ihre Verwendung in wasserverdünnbaren Überzugsmitteln
EP0674039A3 (de) * 1994-03-22 1999-11-24 Bayer Ag Verfahren zur Textilbeschichtung
US6140412A (en) 1996-09-12 2000-10-31 Nicca Chemical Co., Ltd. Waterproofing agent for ink jet printing paper
KR100287126B1 (ko) * 1998-09-17 2001-04-16 최근배 양이온성 폴리우레탄 프리폴리머의 제조 방법, 상기 프리폴리머로부터 제조되는 수분산성 폴리우레탄 또는 폴리우레탄 우레아의 제조 방법 및 그의 용도.
EP1035200B1 (en) 1999-03-06 2006-09-27 Soft 99 Corporation Wet cloth for cleaning, water repellent finish and polishing of automobile paint film
DE19959949A1 (de) 1999-12-13 2001-06-21 Bayer Ag Hydrophobierung mit carboxylgruppenhaltigen Polysiloxanen
DE10211549B9 (de) 2002-03-15 2004-11-25 Rudolf Gmbh & Co. Kg Chemische Fabrik Zubereitungen auf Basis von Wasser und/oder organischen Lösemitteln und deren Anwendung als Appretur auf Flächengebilden
EP1543191B1 (en) 2002-03-15 2011-10-12 Teijin Aramid B.V. Finish composition for treating yarns
KR100536445B1 (ko) 2002-11-26 2005-12-16 에어 프로덕츠 폴리머, 엘.피. 고급 비닐 에스테르의 공중합체로부터 유도된 수계 소수성배리어 코팅
JP2005132917A (ja) * 2003-10-29 2005-05-26 Kanebo Ltd 生分解性ポリエステル系成形体用の処理剤
WO2006038466A1 (ja) * 2004-10-05 2006-04-13 Adeka Corporation 水分散型ポリウレタン組成物
JP2006124866A (ja) 2004-10-28 2006-05-18 Ohara Palladium Kagaku Kk 繊維用加工剤およびそれを用いた繊維製品ならびに繊維布帛類の加工方法
DE102007020790B4 (de) 2007-05-03 2009-10-01 Rudolf Gmbh & Co. Kg Chemische Fabrik Fluorkohlenstoffpolymer-freie Zubereitungen auf Basis von Wasser und/oder organischen Lösemitteln und deren Anwendung als Appretur auf Flächengebilden sowie danach erhaltene textile Substrate
JP5251035B2 (ja) * 2007-08-21 2013-07-31 Ｄｉｃ株式会社 繊維基材用インクジェット受理剤、及びそれを用いたインクジェット記録媒体
DE102009014699A1 (de) 2009-03-27 2010-10-07 Carl Freudenberg Kg Verfahren zur Herstellung einer reaktiven Polyurethan-Emulsion
EP2233633A1 (de) 2009-03-28 2010-09-29 Huntsman Textile Effects (Germany) GmbH Fluorfreie wässrige Dispersion für die Behandlung von textilen Flächengebilden
CN101929076A (zh) * 2010-09-02 2010-12-29 安庆中大化学科技有限公司 一种合成革用水性浆料
EP2632965B1 (en) 2010-10-29 2017-04-26 Lubrizol Advanced Materials, Inc. Aqueous cationic polyurethane dispersions
DE102013209170A1 (de) 2013-05-17 2013-09-12 Cht R. Beitlich Gmbh Wasserabweisende Effekte auf textilen Oberflächen
CN103628324A (zh) * 2013-12-02 2014-03-12 广东德美精细化工股份有限公司 无氟防水剂及其制备方法、纺织品

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Also Published As

Publication number Publication date
CN107429478B (zh) 2020-05-05
CN107429478A (zh) 2017-12-01
EP3271508A1 (de) 2018-01-24
ES2848849T3 (es) 2021-08-12
WO2016146437A1 (de) 2016-09-22
PL3271508T3 (pl) 2021-04-19
KR102437958B1 (ko) 2022-08-30
DE102015204736A1 (de) 2016-09-22
KR20170125843A (ko) 2017-11-15

Similar Documents

Publication Publication Date Title
EP3271508B1 (de) Fluorfreie hydrophobierung
DE102009014699A1 (de) Verfahren zur Herstellung einer reaktiven Polyurethan-Emulsion
EP0919579B1 (de) Lagerstabile, selbstvernetzende Hybriddispersionen
EP0554747B1 (de) Beschichtungsmittel, ein Verfahren zu ihrer Herstellung und ihre Verwendung zur Herstellung von Beschichtungen
EP3074437B1 (de) Ausrüstungsmittel mit blockierten polyisocyanaten
DE4136618A1 (de) Wasserdispergierbare polyisocyanatgemische
DE102006039261A1 (de) Zugerichtetes Leder
WO1986002115A1 (en) Method for obtaining a coating for wash- and cleaning-resistant textiles comprised of reactive perfluoroalkyl rest-containing (co)polymers and/or precondensates
EP1629149A1 (de) Zubereitungen für die öl- und wasserabweisende ausrüstung von flächengebilden und deren anwendung
EP1571254A2 (de) Verfahren zur Herstellung eines lichtechten Syntheseleders und danach hergestellte Produkte
EP1193277A2 (de) Pulverförmige, wasserdispergierbare blockierte Polyisocyanataddukte, ein Verfahren zur Herstellung und ihre Verwendung
EP3580254B1 (de) Polymere zur hydrophoben und oleophoben textilausrüstung
EP0490150B1 (de) In Wasser dispergierbare, elektrolytstabile Polyetherester-modifizierte Polyurethanionomere
EP1263992A1 (de) Polysiloxane zur hydrophobierung
EP2419467B1 (de) Sphärische polyurethan-partikel und ihre verwendung
EP2118161A1 (de) Polyurethan-dispersionen auf basis von 2,2'-mdi
EP2308908B1 (de) Wäßrige Dispersion einer hitzehärtenden Polyurethankomposition
EP0452774B1 (de) Perfluoralkylgruppen enthaltende Pfropfcopolymerisate
EP0728785B1 (de) Wasserdispergierbare Polyisocyanatgemische
EP1264863A1 (de) Zusammensetzungen mit Polysiloxanen und weiteren Polymeren
EP1184400A1 (de) Mit Pyrazol oder Pyrazolderivaten blockierte aromatische Polyisocyanate, Verfahren zu deren Herstellung und Verwendung
EP0934964B1 (de) Allophanatgruppen enthaltende Polyurethan-Polyacrylat-Hybriddispersionen
WO2019242997A1 (de) Polyurethan-organopolysiloxane mit carbodiimid-gruppen
DE60219913T2 (de) Druckpaste sowie entsprechendes Textildruckverfahren
DE10228873A1 (de) Wässrige Polyurethan-Dispersionen

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

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

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

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20170816

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

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

17Q First examination report despatched

Effective date: 20181205

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: CHT GERMANY GMBH

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

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

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20200519

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

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

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

RIN1 Information on inventor provided before grant (corrected)

Inventor name: OTTERBACH, ANDREAS

Inventor name: ZYSCHKA, ROBERT

Inventor name: BAUER, MATTHIAS

Inventor name: WILL, PETER

Inventor name: BACHUS, HERBERT

Inventor name: NOSTADT, KONRAD

AK Designated contracting states

Kind code of ref document: B1

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

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: DE

Ref legal event code: R096

Ref document number: 502016011549

Country of ref document: DE

REG Reference to a national code

Ref country code: CH

Ref legal event code: NV

Representative=s name: SERVOPATENT GMBH, CH

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 1328338

Country of ref document: AT

Kind code of ref document: T

Effective date: 20201115

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20201028

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

Effective date: 20201028

Ref country code: NO

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: 20210128

Ref country code: RS

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: 20201028

Ref country code: PT

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: 20210301

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: 20210129

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: 20201028

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

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

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: 20210228

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: 20201028

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: 20210128

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: 20201028

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

Ref country code: HR

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: 20201028

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 502016011549

Country of ref document: DE

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

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20201028

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: 20201028

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: 20201028

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: 20201028

Ref country code: SM

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: 20201028

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: 20201028

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2848849

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20210812

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

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20201028

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

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

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20210729

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

Effective date: 20201028

Ref country code: AL

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: 20201028

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

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: 20201028

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: 20210308

Ref country code: IE

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

Effective date: 20210308

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

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: 20210228

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

Ref country code: FR

Payment date: 20230320

Year of fee payment: 8

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

Ref country code: TR

Payment date: 20230306

Year of fee payment: 8

Ref country code: PL

Payment date: 20230224

Year of fee payment: 8

Ref country code: BE

Payment date: 20230321

Year of fee payment: 8

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

Effective date: 20230502

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

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20201028

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; INVALID AB INITIO

Effective date: 20160308

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

Ref country code: IT

Payment date: 20230331

Year of fee payment: 8

Ref country code: ES

Payment date: 20230414

Year of fee payment: 8

Ref country code: CH

Payment date: 20230402

Year of fee payment: 8

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

Ref country code: AT

Payment date: 20240318

Year of fee payment: 9

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

Ref country code: MK

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: 20201028

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

Ref country code: DE

Payment date: 20240315

Year of fee payment: 9

Ref country code: GB

Payment date: 20240322

Year of fee payment: 9