US20240133115A1 - Method for conferring durable water repellence to woven or non-woven fabric and water repellent composition - Google Patents

Method for conferring durable water repellence to woven or non-woven fabric and water repellent composition Download PDF

Info

Publication number
US20240133115A1
US20240133115A1 US18/554,781 US202218554781A US2024133115A1 US 20240133115 A1 US20240133115 A1 US 20240133115A1 US 202218554781 A US202218554781 A US 202218554781A US 2024133115 A1 US2024133115 A1 US 2024133115A1
Authority
US
United States
Prior art keywords
composition
fabric
acrylic ester
water
ethylene glycol
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.)
Pending
Application number
US18/554,781
Inventor
Theodorus Matheus Maria VERWEERDEN
Lucienne BOLLEN-BOUVRIE
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.)
Lamoral Holding BV
Original Assignee
Lamoral Holding BV
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 Lamoral Holding BV filed Critical Lamoral Holding BV
Assigned to LAMORAL HOLDING B.V. reassignment LAMORAL HOLDING B.V. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BOLLEN-BOUVRIE, Lucienne, VERWEERDEN, Theodorus Matheus Maria
Publication of US20240133115A1 publication Critical patent/US20240133115A1/en
Pending legal-status Critical Current

Links

Images

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
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating 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
    • D06M13/224—Esters of carboxylic acids; Esters of carbonic acid
    • D06M13/2246—Esters of unsaturated carboxylic acids
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06C—FINISHING, DRESSING, TENTERING OR STRETCHING TEXTILE FABRICS
    • D06C7/00—Heating or cooling textile fabrics
    • 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
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/08—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with halogenated hydrocarbons
    • 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
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating 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
    • D06M13/144—Alcohols; Metal alcoholates
    • D06M13/148—Polyalcohols, e.g. glycerol or glucose
    • 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
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating 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
    • D06M13/224—Esters of carboxylic acids; Esters of carbonic acid
    • D06M13/236—Esters of carboxylic acids; Esters of carbonic acid containing halogen atoms
    • 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
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/244—Treating 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 sulfur or phosphorus
    • D06M13/282—Treating 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 sulfur or phosphorus with compounds containing phosphorus
    • D06M13/292—Mono-, di- or triesters of phosphoric or phosphorous acids; Salts thereof
    • 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
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating 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 nitrogen
    • D06M13/395—Isocyanates
    • 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
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • 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
    • D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
    • D06M23/10—Processes in which the treating agent is dissolved or dispersed in organic solvents; Processes for the recovery of organic solvents thereof
    • 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
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/32—Polyesters
    • 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
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
    • D10B2331/04—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyesters, e.g. polyethylene terephthalate [PET]
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00—Physical properties
    • D10B2401/02—Moisture-responsive characteristics
    • D10B2401/021—Moisture-responsive characteristics hydrophobic

Definitions

  • the invention relates to a method for conferring durable water repellence to woven or non-woven fabric, to a composition for conferring durable water repellence to woven or non-woven fabric and to woven or non-woven fabric treated with the said composition.
  • JP2020153057 describes a vinyl-based polymerisation of a specific divinyl compound with a molecular weight of 600 or more involving chemical bonding of the vinyl polymer to polyester fabric.
  • An additional film is applied, comprising a fluorinated copolymer or an acrylic monomer that is polymerized with a perfluoroalkyl group having 6 or less carbon atoms.
  • the additional film is crosslinked by a melamine resin.
  • EP3919673 describes a special fabric surface that resembles the surface of lotus flower leaves to mimic the water repellence thereof. This artificial lotus-like surface can be treated by commonly known water repellents.
  • WO2016/000831 describes a composition for application on textiles to confer water repellence, wherein three different acrylate monomers, one of which containing fluorine, are polymerized to a polyacrylate by the aid of an azo initiator. Apart from the thus obtained polyacrylate, the composition comprises a wax.
  • the present invention provides method for conferring durable water repellence to woven or non-woven fabric and a fibre treatment composition that can impart water repellence having excellent washing durability to a fibre product without the need to incorporate fluor components for water repellence, and without the need for use of silicone, isocyanates or melamine boosters.
  • the present method for conferring durable water repellence to woven or non-woven fabric results in a highly durable and sustainable water repellent coating on the fabric, that remains unaffected even after 100 or more rounds of machine washing.
  • the method comprises the following steps:
  • a 1 is H or CH 3
  • a 2 is C 1 -C 30 linear or branched, saturated or unsaturated hydrocarbon that may have an alicyclic or aromatic ring, the acrylic ester being dissolved, emulsified or dispersed in the aqueous solvent,
  • the water miscible solvent participates in a chemical reaction with the acrylic ester through the functional OH groups thereof.
  • a (trans)esterification reaction is initiated between a water miscible solvent molecule and the acrylic ester.
  • a covalent C—O—C bond is formed between one of the at least two OH groups of the water miscible solvent molecule and with the oxygen of the C ⁇ O group of the acrylic ester of formula 1. Since the water miscible solvent molecule has at least two functional OH groups, the acrylic ester acquires a functional OH group, enabling the said ester to bond with the fabric fibre by this OH group through hydrogen bridging.
  • ‘functional OH group’ is therefore meant that the said group is capable of forming the said C—O—C bond.
  • the conditions are chosen such, that the above reaction or reactions can take place, e.g. at acid pH.
  • the transesterification reaction proceeds, wherein the aqueous solvent molecule becomes esterified with the CH 2 ⁇ C(A 1 )COO moiety of the acrylate ester, and the A 2 moiety to become covalently linked to a terminal OH group.
  • the A 2 moiety binds to the fibric fibre by hydrogen bridging of its newly acquired terminal OH group.
  • the transesterification reaction results in both, i.e. an incomplete and a complete esterification process, both resulting in the fibre acquiring a hydrophobic A 2 moiety bound thereto through hydrogen bridging. Since the result of the heat treatment is that the A 2 moieties become bound to the fabric, this step is also to be regarded as a curing step.
  • composition of the present invention does not comprise an acrylate polymer, i.e. a polymer comprising a plurality of acrylate monomers, in particular three or more, polymerized to one another, e.g. by the use of an azo initiator.
  • an acrylate polymer i.e. a polymer comprising a plurality of acrylate monomers, in particular three or more, polymerized to one another, e.g. by the use of an azo initiator.
  • acrylic ester is free of fluorine groups.
  • Suitable acrylic esters as defined above for step i)b. are known in the art, such as Unidyne XF series (Daikin, Japan).
  • the heat treatment results in a fabric, the fibres of which comprising hydrophobic A 2 moieties stably bound thereto through hydrogen bridging, therewith acquiring a very strong and sustainable water repellence.
  • the water miscible solvent can comprise more than 2 functional OH groups, but the presence of 2 functional OH groups is preferred.
  • the water soluble aqueous solvent is preferably an organic water miscible solvent, more preferably chosen from the group, consisting of: ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol dimethyl ether, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol, tripropylene glycol monomethyl ether, polypropylene glycol and hexylene glycol
  • the aqueous solvent preferably comprises at least 0.1 w/w % of the water miscible solvent, preferably at least 0.2 w/w %.
  • the aqueous solvent preferably comprises 90-99.9 w/w % water and 0.1-10 w/w % of the water miscible solvent, more preferably 95-99.8 w/w % water and 0.2-5 w/w % of the water miscible solvent, or 95-99 w/w % water and 1-5 w/w % miscible organic solvent.
  • the composition preferably comprises 0.2-20 w/w % acrylic ester, more preferably 0.5-10 w/w %, even more preferably 1-6 w/w %.
  • the surface tension of the coating should be about 25 mN/m 2 .
  • the A 2 moiety is preferably alkyl.
  • the A 2 moiety of the acrylic ester preferably has 12 to 24 carbon atoms, more preferably 12 to 21 carbon atoms, even more preferably 18 carbon atoms.
  • a —CH 2 — moiety confers about 31 mN/m 2
  • a terminal —CH 3 confers 22 mN/m 2 . This means that a higher —CH 3 content will result in a coating with a lower surface tension and therewith to a stronger water repellence.
  • a higher —CH 3 content can be obtained by increasing the number of branches in the hydrocarbon chain. Therefore, although the A 2 moiety can be linear, the said moiety is preferably branched.
  • the coating could be further improved by including a polyisocyanate having at least 3 crosslinking isocyanate groups in the aqueous composition. It was surprisingly found that the presence of polyisocyanate resulted in a significant increased stability of the coating, without any noticeable wear after 30 washing cycles followed by line drying.
  • the functional OH groups of both the water miscible solvent molecules and of the acrylic ester comprising a functional OH group as a result of the above described transesterification reaction, as well as the A 2 moiety with a functional OH group obtained this way are covalently bound to the polyisocyanate, resulting in a crosslinked web of hydrophobic carbohydrate moieties, the web being formed by interconnection of the polyisocyanate molecules linked to one another via covalent linkage with the functional OH groups of the water miscible solvent molecules. Since these molecules comprise 2 or more functional OH groups, these function to link polyisocyanate molecules to one another, to form a hydrogen bridge bond with the fabric fibre, and to provide a functional group to the acrylic ester of the A 2 moiety, respectively.
  • the polyisocyanate can e.g. be aromatic or aliphatic, and suitable polyisocyanates are known in the art. Since the polyisocyanate is in an aqueous composition, e.g. water-based, the polyisocyanate is preferably blocked, e.g. by blocking groups known in the art, such as phenol, nonyl phenol, methylethylketoxime (MEKO), alcohols, ⁇ -caprolactam, amides, imidazoles, or pyrazoles.
  • JP2020007657 describes a fibre treatment composition containing a water repellent and such a blocked polyisocyanate. In order for the blocked polyisocyanates to become active, i.e.
  • a very attractive isocyanate is a trimer based on aliphatic hexamethylene-1,6-diisocyanate, in particular HDI trimer (Kowa, NY, US).
  • the weight ratio acrylic ester:isocyanate is 100:5-100, preferably 100:30-80, more preferably 100:50-70, most preferably 100:60. It was found that a relatively high ratio acrylic ester:isocyanate results in the most stable coating.
  • the heating is preferably performed at 130-200° C., more preferably 140-200° C., more preferably 145-200° C. 180° C., even more preferably at 145-180° C., still even more preferably at 150-170° C. and most preferably around 160° C. It has been found that such a heating step result in an excellent reaction between the components (water miscible solvent, and acrylic ester, and if present, the polyisocyanate) and binding to the fabric. In case of the presence of a blocked polyisocyanate in the composition, the said polyisocyanate becomes unblocked at such a temperature as well.
  • the optimal heating temperature may also depend on the treated fabric.
  • the heating temperature is preferably kept below 140° C., in particular around 130° C., since above the said temperature, deformation of the material can take place.
  • the drying temperature is preferably higher, as described above, most preferably around 160° C.
  • the heating step can be performed by exposure of the treated fabric to a hot air stream, or by residing in a heat chamber, or e.g. by ironing. The skilled person will be aware of the proper temperature choice.
  • the heating step is preferably performed for 30 seconds to 10 minutes, preferably for 1-3 minutes.
  • the fabric as treated in step i) is dried before being subjected to the heating step ii).
  • a pre-drying step becomes particularly important in the presence of a polyisocyanate, since the crosslinking reaction is preferably to be performed in a water free environment. In case there is no isocyanate present in the composition, it becomes also possible to combine the heating with the drying. However, drying can usually take place at a lower temperature than heating. Heating is preferably as described above, e.g. between 120° C. and 200° C., or at 145-200° C., whereas drying preferably takes place preferably between 100 and 140° C., preferably below 140° C. Such a pre-drying step may therefore be more energy saving. Drying is preferably carried out for about 1-10 minutes, preferably about 1-3 minutes.
  • the composition is free of silicon and/or melamine compounds, and for the sole function of water repellence, the composition is preferably fluorine free as well. This means that there are no compounds present in the composition that have fluorine groups in their molecular backbone.
  • the composition of the invention comprises in an attractive embodiment a fluorinated C 2 -C 20 alkyl compound comprising a terminal acryl group, as e.g. is described in JP2020153057, and as are known in the art, e.g. The Unidyne TG Series (Daikin, Japan).
  • this fluor acrylic ester will be susceptible to the transesterification reaction with the water miscible solvent as the fluorine free acrylic ester of formula 1 as described above, and will therefore result in a fluorinated hydrocarbon moiety bound to the fabric fibre through hydrogen bridging, and be able to participate in the crosslinking with the polyisocyanate, if present.
  • the fluorinated alkyl compound is defined as the fluorine free acrylic ester of formula 1, wherein for the fluorinated compound, the A2 moiety is a C 6 -C 20 alkyl, 1 to 6 of the carbon atoms being fully substituted with fluorine.
  • the term ‘fully substituted with fluorine’ means that all the H atoms of the respective carbon atom have been replaced by a fluorine atom.
  • a saturated terminal carbon atom will, when fully substituted, have three fluorine atoms, and a saturated internal carbon, i.e.
  • the fluorine groups can be scattered throughout the alkyl backbone.
  • Such compounds are e.g. known from WO2016/096128.
  • the A 2 of the fluorinated compound is a C 6 alkyl, all 6 of the carbon atoms being fully substituted with fluorine.
  • —CF 2 — groups Since the surface tension of —CF 2 — groups is 18 mN/m 2 , and of terminal —CF 2 and —CF 3 groups is 15 mN/m 2 and 6 mN/m 2 , respectively, a branched fluorinated alkyl compound with terminal —CF 2 and —CF 3 groups, in particular —CF 3 groups is preferred.
  • the composition preferably comprises in w/w % an equal amount of both non-fluorinated and fluorinated acrylic esters.
  • the composition preferably comprises 0.2-20 w/w % acrylic ester, more preferably 0.5-10 w/w %, even more preferably 1-6 w/w % of the fluorinated C 2 -C 20 alkyl compound.
  • the weight ratio of isocyanate, if present, to acrylic acid is determined by the sum of both the fluorinated and fluor free acrylic esters present in the composition.
  • the method of the invention can also be applied to fabric fibres before being assembled to a fabric or textile, instead of treatment of the fabric or textile.
  • a similar water repellence is obtained when a fabric or textile is produced from such treated fibres.
  • the fibres and/or the fabric is preferably chosen from polyester, polyamide, acrylate, ultra high molecular weight polyethylene (e.g. Dyneema, DSM, Netherlands), cotton or aramide or a mixture of two or more thereof. It was found that the repellent coating was stably and strongly bonded to these types of fabric.
  • the fabric preferably comprises polyester and/or polyamide, more preferably polyester.
  • the treatment of step i) is preferably chosen from dipping the fabric in the composition, or spraying the composition onto the fabric.
  • Dipping means that the fabric is immersed in the composition. Dipping is preferred, but spraying is a very attractive home appliance, where the fabric can be sprayed from an aerosol comprising the composition, whereafter the heat treatment can be performed by ironing.
  • the treated fabric is preferably dipped and padded subsequently, in order to remove superfluous liquid composition.
  • the invention relates to a composition for conferring durable water repellence to woven or non-woven fabric as described above.
  • the invention relates to fibres, woven or non-woven fabric as described herein, treated with the composition, in particular as described herein.
  • the arrows reflect the transportation direction of the fabric 1, guided by guidance rollers 2.
  • the process is continuous, e.g. without interruption.
  • Fabric 1 is immersed in a bath 3 comprising the composition 4 of the invention. After leaving the bath 3, the fabric 4 passes through two padding rolls 5, squeezing the superfluous liquid composition from the fabric.
  • the fabric is dried with hot air in drying chamber 6, where the temperature is e.g. 130° C., and eventually enter a heating chamber, where the temperature is e.g. 160° C.
  • Oil repellence is measure after washing 100 times of samples as described above according to the AATCC118 method 118-1997.
  • the fabric sample was cut 15 ⁇ 15 cm from the reel and by dipping the fabric for 1 minute in the coating emulsion.
  • the uncoated fabric was weighed in duplo. After dipping, the coated sample was placed on a rubber sleeve of a manual coating unit (RK prints) for the padding process. With a smooth roller with a weight of 10 kg the excess of emulsion was squeezed out by 2 times rolling the roller over the fabric.
  • the samples were dried in an oven with forced air ventilation for 3 minutes at 130° C.; subsequently the sample was cured for 1 minute at 160° C. After curing, the sample was weighted in duplo again.
  • oil repellence for examples 3, 4, 8-10 as measured according to AATCC118 was grade 5-6 after 100-120 times washing followed by the above tumble drying.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Dispersion Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Paints Or Removers (AREA)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)

Abstract

Disclosed is a method for conferring durable water repellence to woven or non-woven fabric, comprising the steps of: (1) treating the fabric with an aqueous composition, the composition comprising (a) an aqueous solvent comprising at least 80 w/w % water, and 20 w/w % or less of a water miscible organic solvent comprising at least two functional OH groups, and (b) 0.1-40 w/w % of an acrylic ester having the formula 1: wherein A1 is H or CH3, and A2 is C1-C30 linear or branched, saturated or unsaturated hydrocarbon that may have an alicyclic or aromatic ring, the acrylic ester being dissolved, emulsified or dispersed in the aqueous solvent, (2) heating the treated fabric to 120-200° C. Further such a composition and fabric treated with such a composition are disclosed.
Figure US20240133115A1-20240425-C00001

Description

  • The invention relates to a method for conferring durable water repellence to woven or non-woven fabric, to a composition for conferring durable water repellence to woven or non-woven fabric and to woven or non-woven fabric treated with the said composition.
  • Methods for conferring durable water repellence to woven or non-woven fabric are known in the art. Up to now, the provision of durable water repellence to fabric has relied on fluorocarbon-based treatments that are highly effective and extraordinarily durable. However, the by-products such as fluor surfactants and derivatives based on C8 and C6 fluor surfactants are toxic and persist in the environment, a combination that makes it unacceptable despite its excellent performance. Many coatings that are fluor-free today have a short life span. A water repellent rain shell functionally degrades into a wind shell long before the garment itself wears out.
  • JP2020153057 describes a vinyl-based polymerisation of a specific divinyl compound with a molecular weight of 600 or more involving chemical bonding of the vinyl polymer to polyester fabric. An additional film is applied, comprising a fluorinated copolymer or an acrylic monomer that is polymerized with a perfluoroalkyl group having 6 or less carbon atoms. The additional film is crosslinked by a melamine resin.
  • EP3919673 describes a special fabric surface that resembles the surface of lotus flower leaves to mimic the water repellence thereof. This artificial lotus-like surface can be treated by commonly known water repellents.
  • WO2016/000831 describes a composition for application on textiles to confer water repellence, wherein three different acrylate monomers, one of which containing fluorine, are polymerized to a polyacrylate by the aid of an azo initiator. Apart from the thus obtained polyacrylate, the composition comprises a wax.
  • The present invention provides method for conferring durable water repellence to woven or non-woven fabric and a fibre treatment composition that can impart water repellence having excellent washing durability to a fibre product without the need to incorporate fluor components for water repellence, and without the need for use of silicone, isocyanates or melamine boosters. The present method for conferring durable water repellence to woven or non-woven fabric results in a highly durable and sustainable water repellent coating on the fabric, that remains unaffected even after 100 or more rounds of machine washing.
  • To this end, the method comprises the following steps:
      • i) treating the fabric with an aqueous composition, the composition comprising:
        • a. an aqueous solvent comprising at least 80 w/w % water, and 20 w/w % or less of a water miscible organic solvent comprising at least two functional OH groups, and
        • b. 0.1-40 w/w % of an acrylic ester having the formula 1:
  • Figure US20240133115A1-20240425-C00002
  • wherein A1 is H or CH3, and A2 is C1-C30 linear or branched, saturated or unsaturated hydrocarbon that may have an alicyclic or aromatic ring, the acrylic ester being dissolved, emulsified or dispersed in the aqueous solvent,
      • ii) heating the treated fabric to 120-200° C.
  • According to the method of the present invention, the water miscible solvent participates in a chemical reaction with the acrylic ester through the functional OH groups thereof.
  • By the heat treatment step ii), a (trans)esterification reaction is initiated between a water miscible solvent molecule and the acrylic ester. A covalent C—O—C bond is formed between one of the at least two OH groups of the water miscible solvent molecule and with the oxygen of the C═O group of the acrylic ester of formula 1. Since the water miscible solvent molecule has at least two functional OH groups, the acrylic ester acquires a functional OH group, enabling the said ester to bond with the fabric fibre by this OH group through hydrogen bridging. With ‘functional OH group’ is therefore meant that the said group is capable of forming the said C—O—C bond. The conditions are chosen such, that the above reaction or reactions can take place, e.g. at acid pH.
  • Without being bound to any scientific explanation, it is also possible that the transesterification reaction proceeds, wherein the aqueous solvent molecule becomes esterified with the CH2═C(A1)COO moiety of the acrylate ester, and the A2 moiety to become covalently linked to a terminal OH group. In the latter case, the A2 moiety binds to the fibric fibre by hydrogen bridging of its newly acquired terminal OH group. It is also possible that the transesterification reaction results in both, i.e. an incomplete and a complete esterification process, both resulting in the fibre acquiring a hydrophobic A2 moiety bound thereto through hydrogen bridging. Since the result of the heat treatment is that the A2 moieties become bound to the fabric, this step is also to be regarded as a curing step.
  • It is however clear that the composition of the present invention does not comprise an acrylate polymer, i.e. a polymer comprising a plurality of acrylate monomers, in particular three or more, polymerized to one another, e.g. by the use of an azo initiator. Further, by the above definition, it is also clear that the said acrylic ester is free of fluorine groups.
  • Suitable acrylic esters as defined above for step i)b. are known in the art, such as Unidyne XF series (Daikin, Japan).
  • The heat treatment results in a fabric, the fibres of which comprising hydrophobic A2 moieties stably bound thereto through hydrogen bridging, therewith acquiring a very strong and sustainable water repellence.
  • The water miscible solvent can comprise more than 2 functional OH groups, but the presence of 2 functional OH groups is preferred. Accordingly, the water soluble aqueous solvent is preferably an organic water miscible solvent, more preferably chosen from the group, consisting of: ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol dimethyl ether, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol, tripropylene glycol monomethyl ether, polypropylene glycol and hexylene glycol. Most preferred is tripropylene glycol.
  • The aqueous solvent preferably comprises at least 0.1 w/w % of the water miscible solvent, preferably at least 0.2 w/w %.
  • The aqueous solvent preferably comprises 90-99.9 w/w % water and 0.1-10 w/w % of the water miscible solvent, more preferably 95-99.8 w/w % water and 0.2-5 w/w % of the water miscible solvent, or 95-99 w/w % water and 1-5 w/w % miscible organic solvent.
  • The composition preferably comprises 0.2-20 w/w % acrylic ester, more preferably 0.5-10 w/w %, even more preferably 1-6 w/w %.
  • For optimal water repellence, the surface tension of the coating should be about 25 mN/m2. To this end, the A2 moiety is preferably alkyl. The A2 moiety of the acrylic ester preferably has 12 to 24 carbon atoms, more preferably 12 to 21 carbon atoms, even more preferably 18 carbon atoms. A —CH2— moiety confers about 31 mN/m2, whereas a terminal —CH3 confers 22 mN/m2. This means that a higher —CH3 content will result in a coating with a lower surface tension and therewith to a stronger water repellence. A higher —CH3 content can be obtained by increasing the number of branches in the hydrocarbon chain. Therefore, although the A2 moiety can be linear, the said moiety is preferably branched.
  • It has been found that a coating applied to a fabric according to the above method remain very stably attached to the fabric. It was observed that the fabric remained fully preserved during 100 washing cycles, followed by drying in a tumble dryer operated with a regular drying program, i.e. involving heating. It was however observed that the coating started to wear after about 10 washing cycles when drying was performed without added heating (so-called “line drying”).
  • The coating could be further improved by including a polyisocyanate having at least 3 crosslinking isocyanate groups in the aqueous composition. It was surprisingly found that the presence of polyisocyanate resulted in a significant increased stability of the coating, without any noticeable wear after 30 washing cycles followed by line drying. The functional OH groups of both the water miscible solvent molecules and of the acrylic ester comprising a functional OH group as a result of the above described transesterification reaction, as well as the A2 moiety with a functional OH group obtained this way are covalently bound to the polyisocyanate, resulting in a crosslinked web of hydrophobic carbohydrate moieties, the web being formed by interconnection of the polyisocyanate molecules linked to one another via covalent linkage with the functional OH groups of the water miscible solvent molecules. Since these molecules comprise 2 or more functional OH groups, these function to link polyisocyanate molecules to one another, to form a hydrogen bridge bond with the fabric fibre, and to provide a functional group to the acrylic ester of the A2 moiety, respectively.
  • The polyisocyanate can e.g. be aromatic or aliphatic, and suitable polyisocyanates are known in the art. Since the polyisocyanate is in an aqueous composition, e.g. water-based, the polyisocyanate is preferably blocked, e.g. by blocking groups known in the art, such as phenol, nonyl phenol, methylethylketoxime (MEKO), alcohols, ε-caprolactam, amides, imidazoles, or pyrazoles. JP2020007657 describes a fibre treatment composition containing a water repellent and such a blocked polyisocyanate. In order for the blocked polyisocyanates to become active, i.e. to become unblocked, the water is to be removed first, e.g. by drying, followed by a subsequent heating step. A very attractive isocyanate is a trimer based on aliphatic hexamethylene-1,6-diisocyanate, in particular HDI trimer (Kowa, NY, US).
  • The weight ratio acrylic ester:isocyanate is 100:5-100, preferably 100:30-80, more preferably 100:50-70, most preferably 100:60. It was found that a relatively high ratio acrylic ester:isocyanate results in the most stable coating.
  • In step ii), the heating is preferably performed at 130-200° C., more preferably 140-200° C., more preferably 145-200° C. 180° C., even more preferably at 145-180° C., still even more preferably at 150-170° C. and most preferably around 160° C. It has been found that such a heating step result in an excellent reaction between the components (water miscible solvent, and acrylic ester, and if present, the polyisocyanate) and binding to the fabric. In case of the presence of a blocked polyisocyanate in the composition, the said polyisocyanate becomes unblocked at such a temperature as well.
  • The optimal heating temperature may also depend on the treated fabric. In case of e.g. an ultra high molecular weight polyethylene, the heating temperature is preferably kept below 140° C., in particular around 130° C., since above the said temperature, deformation of the material can take place. For other fabrics that are more temperature resistant, the drying temperature is preferably higher, as described above, most preferably around 160° C. The heating step can be performed by exposure of the treated fabric to a hot air stream, or by residing in a heat chamber, or e.g. by ironing. The skilled person will be aware of the proper temperature choice. The heating step is preferably performed for 30 seconds to 10 minutes, preferably for 1-3 minutes.
  • It is preferred that the fabric as treated in step i) is dried before being subjected to the heating step ii). Such a pre-drying step becomes particularly important in the presence of a polyisocyanate, since the crosslinking reaction is preferably to be performed in a water free environment. In case there is no isocyanate present in the composition, it becomes also possible to combine the heating with the drying. However, drying can usually take place at a lower temperature than heating. Heating is preferably as described above, e.g. between 120° C. and 200° C., or at 145-200° C., whereas drying preferably takes place preferably between 100 and 140° C., preferably below 140° C. Such a pre-drying step may therefore be more energy saving. Drying is preferably carried out for about 1-10 minutes, preferably about 1-3 minutes.
  • In a very attractive embodiment, the composition is free of silicon and/or melamine compounds, and for the sole function of water repellence, the composition is preferably fluorine free as well. This means that there are no compounds present in the composition that have fluorine groups in their molecular backbone.
  • However, in order to provide a stable and wear resistant coating that is not only water repellent but also oil repellent, the composition of the invention comprises in an attractive embodiment a fluorinated C2-C20 alkyl compound comprising a terminal acryl group, as e.g. is described in JP2020153057, and as are known in the art, e.g. The Unidyne TG Series (Daikin, Japan). By including such a fluor acrylic ester in the composition, this fluor acrylic ester will be susceptible to the transesterification reaction with the water miscible solvent as the fluorine free acrylic ester of formula 1 as described above, and will therefore result in a fluorinated hydrocarbon moiety bound to the fabric fibre through hydrogen bridging, and be able to participate in the crosslinking with the polyisocyanate, if present.
  • By the provision of such a fluorinated acrylic ester, not only water repellence, but also oil repellence is obtained. Very attractively, the fluorinated alkyl compound is defined as the fluorine free acrylic ester of formula 1, wherein for the fluorinated compound, the A2 moiety is a C6-C20 alkyl, 1 to 6 of the carbon atoms being fully substituted with fluorine. The term ‘fully substituted with fluorine’ means that all the H atoms of the respective carbon atom have been replaced by a fluorine atom. A saturated terminal carbon atom will, when fully substituted, have three fluorine atoms, and a saturated internal carbon, i.e. flanked by two adjacent carbon atoms by a single bond, will have two fluorine atoms. This means that the fluorine groups can be scattered throughout the alkyl backbone. Such compounds are e.g. known from WO2016/096128. Very attractively, the A2 of the fluorinated compound is a C6 alkyl, all 6 of the carbon atoms being fully substituted with fluorine.
  • Since the surface tension of —CF2— groups is 18 mN/m2, and of terminal —CF2 and —CF3 groups is 15 mN/m2 and 6 mN/m2, respectively, a branched fluorinated alkyl compound with terminal —CF2 and —CF3 groups, in particular —CF3 groups is preferred.
  • The composition preferably comprises in w/w % an equal amount of both non-fluorinated and fluorinated acrylic esters. The composition preferably comprises 0.2-20 w/w % acrylic ester, more preferably 0.5-10 w/w %, even more preferably 1-6 w/w % of the fluorinated C2-C20 alkyl compound. In case of the presence of a fluorinated acrylic ester, the weight ratio of isocyanate, if present, to acrylic acid is determined by the sum of both the fluorinated and fluor free acrylic esters present in the composition.
  • The method of the invention can also be applied to fabric fibres before being assembled to a fabric or textile, instead of treatment of the fabric or textile. A similar water repellence is obtained when a fabric or textile is produced from such treated fibres.
  • The fibres and/or the fabric is preferably chosen from polyester, polyamide, acrylate, ultra high molecular weight polyethylene (e.g. Dyneema, DSM, Netherlands), cotton or aramide or a mixture of two or more thereof. It was found that the repellent coating was stably and strongly bonded to these types of fabric. To this end, the fabric preferably comprises polyester and/or polyamide, more preferably polyester.
  • The treatment of step i) is preferably chosen from dipping the fabric in the composition, or spraying the composition onto the fabric. Dipping means that the fabric is immersed in the composition. Dipping is preferred, but spraying is a very attractive home appliance, where the fabric can be sprayed from an aerosol comprising the composition, whereafter the heat treatment can be performed by ironing. In an industrial setting, the treated fabric is preferably dipped and padded subsequently, in order to remove superfluous liquid composition.
  • In another aspect, the invention relates to a composition for conferring durable water repellence to woven or non-woven fabric as described above.
  • In still another aspect, the invention relates to fibres, woven or non-woven fabric as described herein, treated with the composition, in particular as described herein.
  • The invention will now be further illustrated by way of examples and figure, showing a possible industrial set up for the method of the invention.
  • The arrows reflect the transportation direction of the fabric 1, guided by guidance rollers 2. The process is continuous, e.g. without interruption. Fabric 1 is immersed in a bath 3 comprising the composition 4 of the invention. After leaving the bath 3, the fabric 4 passes through two padding rolls 5, squeezing the superfluous liquid composition from the fabric. The fabric is dried with hot air in drying chamber 6, where the temperature is e.g. 130° C., and eventually enter a heating chamber, where the temperature is e.g. 160° C.
    • EXAMPLES Water Repellence
  • Samples of PES 1 fabric 135 gr/m2 and PES 2 fabric 190 gr/m2 (MB Sportswear, Eindhoven Netherlands) were washed 100 times according to the method of Iso 6330 3G or 4H.
  • After washing, the water repellence is measured by the ISO 4920 (version 2012-12) spray method
    • Commercial Washing Cycles
  • The water repellence measured by the Iso 4920 spray method after washing 120 times according to the method of using a commercial washing machine of the type Miele Twindos (Germany) using the program Express 2.0 and the detergent Colour 15 Reus extra strong against stains, extra clean (Henkel, Germany). The program specifications and the contents of the detergent are given in tables 1 and 2, respectively.
  • TABLE 1
    Washing program
    washing time
    6 min.
    rinsing time 14 min.
    pumping time 14 min.
    spinning time 1 min.
    washing cycle time 27 min.
    load 2-3 kg
    temperature 30° C.
  • TABLE 2
    Ingredients detergent
      anionic surface active agents (5-15%)
    soap (<5%)
    non ionic surface active agents
    phoshonates
    parfumes
    hexl cynnamal
    conservation agents
    methylisothiazolinone
    benzisothiazolinone
    enzymes
    • Oil Repellence
  • Oil repellence is measure after washing 100 times of samples as described above according to the AATCC118 method 118-1997.
    • Sample Preparation
  • The fabric sample was cut 15×15 cm from the reel and by dipping the fabric for 1 minute in the coating emulsion. The uncoated fabric was weighed in duplo. After dipping, the coated sample was placed on a rubber sleeve of a manual coating unit (RK prints) for the padding process. With a smooth roller with a weight of 10 kg the excess of emulsion was squeezed out by 2 times rolling the roller over the fabric.
  • The samples were dried in an oven with forced air ventilation for 3 minutes at 130° C.; subsequently the sample was cured for 1 minute at 160° C. After curing, the sample was weighted in duplo again.
  • Possible compositions for use in examples 1-8 are given in table 3. The experiment have been performed with the compositions given in table 4.
  • In examples 1, 3, 5-10, a polyester woven fabric PES 135 gr/m2 (‘pique’) (MB Sportswear, Eindhoven Netherlands) was used, whereas in examples 2 and 4 195 gr/m2 ‘smooth’ (MB Sportswear, Eindhoven Netherlands) was used.
  • It was observed that all examples, after the washing cycles and drying in a tumble dryer (AEG Lavatherm Protex plus, AEG, Germany, with the program setting ‘cotton extra dry’) retained their water repellence. Grade iso 5 was measured for all samples before the first washing and after 100 or 120 times washing. Grade 5 means that no sticking or wetting of the upper surface was observed.
  • The same was true for examples 1 and 3 when the dipping was replaced by spraying and the padding was replaced by tumbling in a tumble dryer as described above. Heating was performed by ironing at 150° C. (level**) for example 1 and at 200° C. (level***) for example 2, in conformity with the ironing prescriptions of the fabric manufacturer. Also for these samples, Grade iso 5 was measured for all samples before the first washing and after 100 or 120 times washing.
  • The oil repellence for examples 3, 4, 8-10 as measured according to AATCC118 was grade 5-6 after 100-120 times washing followed by the above tumble drying.
  • TABLE 3
    Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7 Ex. 8 Ex. 9 Ex. 10
    Compositions w/w %
    Acrylic Unidyne 0.1-2.0  6.0-10.0 0.1-2.0 3.0-5.0 0.1-2.0 0.1-2.0 0.1-2.0 0.1-2.0 0.1-2.0 0.1-2.0
    ester XF5000
    Series
    (Daikin,
    Japan)
    Water Tripropylene 0.1-05 0.5-5.0 0.1-0.5 0.5-5.0 0.1-0.5 0.1-0.5 0.1-0.5 0.1-0.5 0.1-0.5 0.1-0.5
    miscible glycol
    solvent (Sigma
    Aldrich
    US)
    Fluorinated Unidyne TG — — 0.1-2.0 3.0-5.0 0.1-2.0 0.1-2.0 0.1-2.0
    alkyl Series
    (Daikin,
    Japan)
    Poly- Rudolf, 0.06-1.2  0.03-0.6 0.01-0.2  0.06-1.2  0.03-0.6  0.01-0.2 
    isocyanate Imprafix
    Demi water 97.5-99.8 85-93.5 95.5-99.7   85-93.5 96.3-99.8 96.9-99.8 97.3-99.8 94.3-99.6 94.9-99.7 95.3-99.7
    Total solids 0.1-2.5  6.0-15.0 0.3-4.5  6.5-15.0 0.26-3.7  0.23-3.1  0.21-2.7  0.36-5.7  0.33-5.1  0.31-4.7 
    (%)
  • TABLE 4
    Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7 Ex. 8 Ex. 9 Ex. 10
    Compositions w/w %
    Acrylic ester Unidyne XF5000 Series 1 6 1 3 1 1 1 1 1 1
    (Daikin, Japan)
    Water miscible Tripropylene glycol 0.2 2.1 0.2 2.1 0.2 0.2 0.2 0.2 0.2 0.2
    solvent (Sigma Aldrich US)
    Fluorinated alkyl Unidyne TG Series — — 1 3 — — — 1 1 1
    (Daikin, Japan)
    Polyisocyanate Rudolf, Imprafix 0.6 0.3 0.1 0.6 0.3 0.1
    Demi water 98.8 91.9 98.9 94.9 99.8 99.5 98.7 97.2 97.5 97.7
    Total solids (%) 1.2 8.1 2.2 8.1 1.8 1.5 1.3 2.8 2.5 2.3
  • It was however observed that in case of line drying, i.e. without heating the dried fabric, a coating that has been subjected to crosslinking with polyisocyanate remained stably bound as compared to the results for all coatings after tumble drying, whereas the coatings without comprising the isocyanate (NCO) crosslinkages tended to loosen from the fabric after 10-12 washing cycles, see table 5. It was observed that a weight ratio acrylic ester:polyisocyanate of above 30 gave the best bonding.
  • TABLE 5
    0 3 6 9 12 15 18 21 24 27 30
    Example 1 (no NCO) 5 5 5 5 4 3 3 3 2 2 2
    Example 5 (100:60) 5 5 5 5 5 5 5 5 5 5 5
    Example 6 (100:30) 5 5 5 5 5 4, 5 3 3 3 2 3
    Example 7 (100:10) 5 5 5 5 5 4 4, 5 4 3 3 2

Claims (21)

1-43. (canceled)
44. A method for conferring durable water repellence to woven or non-woven fabric, comprising the steps of:
i) treating the fabric with an aqueous composition free of silicon compounds, the composition comprising:
a. an aqueous solvent comprising at least 80 w/w % water, and 20 w/w % or less of a water miscible organic solvent comprising at least two functional OH groups, and
b. 0.1-40 w/w % of an acrylic ester having the formula 1:
Figure US20240133115A1-20240425-C00003
wherein A1 is H or CH3, and A2 is C1-C30 linear or branched, saturated or unsaturated hydrocarbon that may have an alicyclic or aromatic ring, the acrylic ester being dissolved, emulsified or dispersed in the aqueous solvent,
ii) heating the treated fabric to 120-200° C.
45. The method of claim 44, wherein the water miscible solvent is selected from the group consisting of ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol dimethyl ether, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol, tripropylene glycol monomethyl ether, polypropylene glycol and hexylene glycol.
46. The method of claim 44, wherein the aqueous solvent comprises 90-99.9 w/w % water and 0.1-10 w/w % of the water miscible solvent.
47. The method of claim 44, wherein the composition comprises 0.2-20 w/w % acrylic ester
48. The method of claim 44, wherein A2 of the acrylic ester has 12 to 24 carbon atoms.
49. The method of claim 44, further comprising a polyisocyanate comprising at least 3 crosslinkable isocyanate groups.
50. The method of claim 49, wherein the weight ratio acrylic ester:isocyanate is 100:5-100.
51. The method of claim 44, wherein the treated fabric of step i) is dried before step ii).
52. The method of claim 44, wherein the composition further comprises a fluorinated C2-C20 alkyl compound comprising a terminal acryl group.
53. The method of claim 52, wherein the composition comprises in w/w % an equal amount of both non-fluorinated and fluorinated acrylic esters.
54. The method of claim 44, wherein the fabric is selected from the group consisting of polyester, polyamide, acrylate, ultra high molecular weight polyethylene, cotton and aramide or a mixture of two or more thereof, the fabric preferably comprising polyester and/or polyamide, more preferably polyester.
55. A composition free of fluorine and silicon compounds for conferring durable water repellence to woven or non-woven fabric, the composition comprising
a. an aqueous solvent comprising at least 80 w/w % water, and 20 w/w % or less of a water miscible organic solvent comprising at least two functional OH groups, and
b. 0.1-40 w/w % of an acrylic ester having the formula 1:
Figure US20240133115A1-20240425-C00004
wherein A1 is H or CH3, and A2 is C1-C30 linear or branched, saturated or unsaturated hydrocarbon that may have an alicyclic or aromatic ring, the acrylic ester being dissolved, emulsified or dispersed in the aqueous solvent.
56. The composition of claim 55, wherein the water miscible solvent is selected from the group consisting of ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol dimethyl ether, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol, tripropylene glycol monomethyl ether, polypropylene glycol and hexylene glycol.
57. The composition of claim 55, wherein the aqueous solvent comprises 90-99.9 w/w % water and 0.1-10 w/w % of the water miscible solvent.
58. The composition of claim 55, wherein the composition comprises 0.2-20 w/w % acrylic ester.
59. The composition of claim 55, wherein A2 of the acrylic ester has 12 to 24 carbon atoms.
60. The composition of claim 55, further comprising a polyisocyanate comprising at least 3 crosslinkable isocyanate groups.
61. The composition of claim 60, wherein the weight ratio acrylic ester:isocyanate is 100:5-100.
62. A woven or non-woven fabric, treated with the composition of claim 55.
63. The woven or non-woven fabric of claim 62, wherein the fabric is selected from the group consisting of polyester, polyamide, acrylate, ultra high molecular weight polyethylene, cotton and aramide or a mixture of two or more thereof, the fabric preferably comprising polyester and/or polyamide, more preferably polyester.
US18/554,781 2021-04-08 2022-04-08 Method for conferring durable water repellence to woven or non-woven fabric and water repellent composition Pending US20240133115A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
NL2027946 2021-04-08
NL2027946A NL2027946B1 (en) 2021-04-08 2021-04-08 Method for conferring durable water repellence to woven or non-woven fabric and water repellent composition
PCT/NL2022/050198 WO2022216158A1 (en) 2021-04-08 2022-04-08 Method for conferring durable water repellence to woven or non-woven fabric and water repellent composition

Publications (1)

Publication Number Publication Date
US20240133115A1 true US20240133115A1 (en) 2024-04-25

Family

ID=75747003

Family Applications (1)

Application Number Title Priority Date Filing Date
US18/554,781 Pending US20240133115A1 (en) 2021-04-08 2022-04-08 Method for conferring durable water repellence to woven or non-woven fabric and water repellent composition

Country Status (9)

Country Link
US (1) US20240133115A1 (en)
EP (1) EP4320306A1 (en)
JP (1) JP2024513482A (en)
KR (2) KR20240026305A (en)
CN (1) CN117295860A (en)
BR (1) BR112023020680A2 (en)
CA (1) CA3216049A1 (en)
NL (1) NL2027946B1 (en)
WO (1) WO2022216158A1 (en)

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105793487B (en) * 2014-01-24 2017-11-07 日华化学株式会社 The manufacture method of dryingagent composition, water-repellancy fibre and water-repellancy fibre
TWI686439B (en) * 2014-07-04 2020-03-01 瑞士商亞克羅瑪智財公司 Fluorine-free water-repellent composition
CN107108455A (en) 2014-12-19 2017-08-29 默克专利股份有限公司 Fluorochemical
KR20220163534A (en) * 2017-03-07 2022-12-09 에이지씨 가부시키가이샤 Water repellent oil repellent article, method for producing same, and water repellent oil repellent agent composition
WO2019026593A1 (en) * 2017-07-31 2019-02-07 ダイキン工業株式会社 Water repellent composition
CN109023947A (en) * 2018-06-22 2018-12-18 杭州友博纺织品有限公司 Solution and its production technology and application method for the processing of fabric anti-pollution
JP7007683B2 (en) 2018-07-05 2022-01-25 明成化学工業株式会社 Methods for Manufacturing Fiber Treatment Compositions, Textile Treatment Kits, Textile Products, and Water Repellent Textile Products
EP3919673A4 (en) 2019-01-30 2023-05-03 Toray Industries, Inc. Water-repellent woven article, production method for same, and garment
JP7486985B2 (en) 2019-03-13 2024-05-20 ユニチカトレーディング株式会社 Woven and knitted fabrics and their manufacturing method
CN111576043B (en) * 2020-03-17 2022-09-02 宁波萌恒线业有限公司 Processing technology of waterproof yarn

Also Published As

Publication number Publication date
KR102638466B1 (en) 2024-02-20
JP2024513482A (en) 2024-03-25
EP4320306A1 (en) 2024-02-14
KR20240026305A (en) 2024-02-27
WO2022216158A1 (en) 2022-10-13
CN117295860A (en) 2023-12-26
CA3216049A1 (en) 2022-10-13
BR112023020680A2 (en) 2023-12-12
NL2027946B1 (en) 2022-10-20
KR20230158624A (en) 2023-11-20

Similar Documents

Publication Publication Date Title
US6451717B1 (en) Highly durable oil/water repellents for textiles
TWI462940B (en) Fluoropolymer emulsions
US5578688A (en) Antifouling agent
US7446145B2 (en) Water and oil repellent aqueous composition
US8993067B2 (en) Composition for oil- and/or water-repellent finishing of fiber materials
US20060052556A1 (en) Hydrocarbon extenders for surface effect compositions
JP5500068B2 (en) Antifouling agent composition, method for producing the same, and article treated using the same
KR20170134227A (en) Method for producing water repellent fiber product
JPH03172337A (en) Hydrophobic and oleophobic compound
CN102666970A (en) Fluoropolymers and surface treatment agent
CN114808455B (en) Environment-friendly fluorine-free fabric waterproof moisture permeable agent, preparation method and application
US20240133115A1 (en) Method for conferring durable water repellence to woven or non-woven fabric and water repellent composition
JPH0468006A (en) New copolymer and stainproofing agent
JPS636676B2 (en)
US7186273B2 (en) Treatment of textiles with fluorinated polyethers
JP3752713B2 (en) Fiber processing method with high friction durability
CN107592890B (en) Hydrophobic compounds and formulations containing them and their use
AU2002345239A1 (en) Treatment of textiles with fluorinated polyethers

Legal Events

Date Code Title Description
AS Assignment

Owner name: LAMORAL HOLDING B.V., NETHERLANDS

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:VERWEERDEN, THEODORUS MATHEUS MARIA;BOLLEN-BOUVRIE, LUCIENNE;REEL/FRAME:065962/0235

Effective date: 20231011

STPP Information on status: patent application and granting procedure in general

Free format text: DOCKETED NEW CASE - READY FOR EXAMINATION