SE534473C2 - Method of manufacturing a water-repellent cellulose textile and corresponding textile product - Google Patents
Method of manufacturing a water-repellent cellulose textile and corresponding textile product Download PDFInfo
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- SE534473C2 SE534473C2 SE1050031A SE1050031A SE534473C2 SE 534473 C2 SE534473 C2 SE 534473C2 SE 1050031 A SE1050031 A SE 1050031A SE 1050031 A SE1050031 A SE 1050031A SE 534473 C2 SE534473 C2 SE 534473C2
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- acid
- water
- textile
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- 239000004753 textile Substances 0.000 title claims abstract description 41
- 239000005871 repellent Substances 0.000 title claims abstract description 15
- 229920002678 cellulose Polymers 0.000 title claims abstract description 7
- 239000001913 cellulose Substances 0.000 title claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000203 mixture Substances 0.000 claims abstract description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002253 acid Substances 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 25
- 238000002444 silanisation Methods 0.000 claims description 11
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 10
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 229920006395 saturated elastomer Polymers 0.000 claims description 8
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 6
- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 claims description 5
- JDQDSEVNMTYMOC-UHFFFAOYSA-N 3-methylbenzenesulfonic acid Chemical compound CC1=CC=CC(S(O)(=O)=O)=C1 JDQDSEVNMTYMOC-UHFFFAOYSA-N 0.000 claims description 4
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 4
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 claims description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000004122 cyclic group Chemical group 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- RSKGMYDENCAJEN-UHFFFAOYSA-N hexadecyl(trimethoxy)silane Chemical group CCCCCCCCCCCCCCCC[Si](OC)(OC)OC RSKGMYDENCAJEN-UHFFFAOYSA-N 0.000 claims description 3
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 3
- 239000012736 aqueous medium Substances 0.000 claims description 2
- 239000004744 fabric Substances 0.000 abstract description 17
- 150000001875 compounds Chemical class 0.000 abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 238000005406 washing Methods 0.000 description 7
- 239000003377 acid catalyst Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 150000001282 organosilanes Chemical class 0.000 description 4
- 229920000742 Cotton Polymers 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000003599 detergent Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 230000035515 penetration Effects 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910006069 SO3H Inorganic materials 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 150000003961 organosilicon compounds Chemical class 0.000 description 2
- 238000007589 penetration resistance test Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- -1 ethyl,butyl Chemical group 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000005660 hydrophilic surface Effects 0.000 description 1
- 230000002706 hydrostatic effect Effects 0.000 description 1
- 238000004900 laundering Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000005180 public health Effects 0.000 description 1
- 150000004756 silanes Chemical group 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
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
- D06M13/144—Alcohols; Metal alcoholates
-
- 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
- D06M13/248—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 sulfur
- D06M13/256—Sulfonated compounds esters thereof, e.g. sultones
-
- 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
- D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
- D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
- D06M13/513—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond with at least one carbon-silicon bond
-
- 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
- D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
- D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
- D06M13/513—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond with at least one carbon-silicon bond
- D06M13/5135—Unsaturated compounds containing silicon atoms
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/03—Non-macromolecular organic compounds
- D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
- D21H17/13—Silicon-containing compounds
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
- D21H19/12—Coatings without pigments applied as a solution using water as the only solvent, e.g. in the presence of acid or alkaline compounds
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
- D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/16—Sizing or water-repelling agents
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
En metod för att tillverka en vattenavvisande cellulosatextil och en cellulosatextil tillverkadmed en sådan metod. Metoden omfattar; tillhandahålla med en lösning av en syra med pKa<1.0 i en C2-C4 alkohol valfritt innehållande vatten; tillhandahålla med enalkylalkoxisilanförening; effektivt blanda lösningen och alkylalkoxisilanföreningen för atttillverka en silaniserande komposition; kontakta cellulosatexilen med den silaniserandekompositionen; härda cellulosatextilen kontaktad med kompositionen vid en temperaturav 1o0°C eller högre tills den är huvudsakligen torr; valfritt skölja den behandlade textilenmed ett vatteninnehållande media för att ta bort syran och valfritt torka den tvättbehandlade textilen. A method of making a water-repellent cellulose fabric and a cellulose fabric made by such a method. The method includes; providing with a solution of an acid with pKa <1.0 in a C2-C4 alcohol optionally containing water; provide with enalkylalkoxysilane compound; effectively mixing the solution and the alkylalkoxysilane compound to produce a silanizing composition; contacting the cellulose textile with the silanizing composition; curing the cellulosic fabric contacted with the composition at a temperature of 100 ° C or higher until it is substantially dry; optionally rinsing the treated fabric with a water-containing media to remove the acid and optionally drying the wash-treated fabric.
Description
The invention relates to a method of making a cellulosic textile water-repellent and to acellulosic textile made water-repellent by the method.
BACKGROUND OF THE INVENTION A number of methods of making cellulosic textile water-repellent are known in the art. Acellulosic textile has a substantially hydrophilic surface rich in hydroxyl groups whichattract water molecules and bind them by weak hydrogen bonds. By transforming thesehydroxyl groups into groups that do not attract water molecules or by barring access ofwater molecules to them a cellulosic textile can be made water-repellent. Agentsproposed for use in these methods include fluorinated hydrocarbons and organosiliconcompounds of various kinds.
A drawback with cellulosic textiles made water-repellent by most state-of-the-artmethods is their poor washing stability, in particular when washed in household orlaundry washing machines using alkaline washing media at elevated temperatures (>25°C). ln order to achieve persistent water-repellency the formation of covalent bondsbetween the hydroxyl groups of the textile and the water-repellent coating is desired.
The use of fluorinated hydrocarbons has been proven effective, but is highly undesireddue to its negative impact on the environment and on human health.
The use of non-fluorinated organosilicon compounds is advantageous from anenvironmental and public health point of view. A problem with the organosilanes is thatthey are reactive and prone to undergo condensation reactions that lead to polymericstructures and gel formation of the coating compositions. The polymerization reactionleads to a decrease in the number of available silanol (Si-OH) groups that can be used forcovalent attachment of the silanes to the textile surface. Also, the washing stabilityachieved with methods utilizing non-fluorinated compounds has not been satisfactory.
U.S. 2009/0206296 A1 discloses an organosilane composition comprising an organosilane,an acid catalyst, a solvent, and water and its use in a method for making a cotton fabricwater-repellent. The method comprises applying the composition to the fabric and dryingthe fabric in an automatic laundering and drying system, such as at a temperature of 135°F (57 °C), or at ambient temperature. The pH of the composition is disclosed to be 1.5 orhigher.
EP 1 400 625 A2 discloses a process of treating the surface of a cellulosic substrate,comprising contacting the substrate with an organosilane of the general formula(Xlzi-h-Si-Rn, wherein R is a hydrocarbon chain of from Cy to C20 and X is a Cl to C4 alkoxygroup. The treatment is carried out in an aqueous or alcoholic environment. The treatedsubstrate is cured at a temperature of from 40 °C to 150 °C. lO OBJECTS OF THE INVENTION An object of the invention is to provide a method of making a cellulosic textilepermanently water-repellent so that it can be washed in household or laundry washingmachines.
Another object of the invention is to provide method of this kind, which is attractive froman economic and environmental standpoint.
Another object of the invention is to provide a method of this kind, which is suitable andadvantageous for industrial scale treatment of cellulosic textile.
Still another object of the invention is to provide a water-repellent cellulosic textile.
An additional object ofthe invention is to provide a silanization composition for cellulosictextiles.
Further objects of the invention will become evident from the following short descriptionof the invention and preferred embodiments thereof as well as from the appended claims.
SUMMARY OF THE INVENTION According to the present invention is disclosed a method of making a cellulosic textilewater-repellent. The method comprises providing a solution of an acid of pKa <1.0 in a C2-C4 alcohol optionally comprising water; providing an alkyltrialkoxysilane; efficiently mixingthe solution and the alkyltrialkoxysilane to produce a silanization composition; contactingthe cellulosic textile with the silanization composition; curing the cellulosic textilecontacted with the composition at a temperature of 100 °C or more until substantially dry;optionally rinsing the treated textile with an aqueous media to remove the acid; optionallydrying the rinsed treated textile.
The cellulosic textile can be contacted with the silanization composition in any suitablemanner, such as by dipping, padding application by roller or brush, and spraying. Thesilanization composition can be brought in contact with the textile in a manner so as tosubstantially fully wet (soak) the textile or only wet the textile to a desired depth from theface of the textile to which it is applied.
The method ofthe invention can be incorporated in a textile production process, e.g. byusing a standard padding process, impregnation process, spraying process, and coatingprocess.
I\/lost preferred C1-C4 alcohols ofthe invention are isopropanol and tert-butanol and theirmixtures. Ethanol, n-propanol, butanol-1 and/or butanol-2 are also preferred. lt is preferred for the alkyltrialkoxysilane of the invention to be of the general formulaR1(OR2)3Si, wherein Rl is straight, branched or cyclic, saturated or unsaturated Cg-CZZ alkyl.RZ is methyl, ethyl, butyl, tert-butyl or isopropyl. Rl is preferably straight and saturated to allow better packing of the chains at the textile interface, but branched, cyclic and/or non-saturated chains are also conceivable. More preferred is an alkyltrialkoxysilane wherein Rlis straight or branched Clz-Clg alkyl. I\/lost preferred is alkyltrialkoxysilane wherein Rl isstraight or branched C14-C16 alkyl, in particular hexadecyltrimethoxysilane. ln the method ofthe invention the acid component acts as a catalyst. While acid catalysiscan be provided, in principle, by a wide range of inorganic and organic acids, a catalystacid of a pKa of <1.5, in particular of <1.0, which is substantially non-volatile at ambientpressure and temperatures up to 200 °C, is preferred. Organic sulfonic acids meet thisrequirement and have been found to be particularly useful in the method ofthe invention.A preferred acid of the invention thus is an organic sulfonic acid, in particular one selectedfrom the group consisting of benzenesulfonic acid, p-toluenesulfonic acid, m-toluenesulfonic acid, naphthalenesulfonic acid, camphor sulfonic acid, andmethanesulfonic acid.
An important feature of the method of the invention is the curing temperature, which is atleast 100 °C, preferably at least 120 °C, more preferred at least 140 °C or 150 °C, and evenup to 200 °C.The curing time is about inversely proportional to the curing temperature.Thus, curing at higher temperatures can be carried out in a correspondingly shorter time,such as in a few minutes or in about from 1 min to 3 min in a pre-heated oven at atemperature of from 150 °C to 200 °C. A person skilled in the art will realize that airconvection during drying, the thickness and density ofthe fabric, and other physicalparameters ofthe fabric, will influence the curing time at a given drying temperature. lnselecting the drying conditions, consideration should also be given to the stability of thedye or dyes by which the fabric has been coloured. According to the method oftheinvention, the curing is continued until the fabric is substantially dry, that is, has a contentof solvent below 5 % by weight and even below 2 % by weight. ln this application, "drying"includes evaporation of solvent other than water; "substantially dry" means substantiallydevoid of water and/or solvent.
Since the preferred acid catalyst ofthe invention is substantially non volatile, it has to beremoved from the fabric after curing. The acid catalyst of the invention is easily removedfrom the fabric by rinsing with water, optionally containing tensides such as commonlyused machine washing detergents.
According to a preferred aspect of the invention the water content of the silanizationcomposition is 5.0 % by weight or less, in particular 0.5 % or less. A low water content willpromote the reaction of the alkyltrialkoxysilane with cellulose hydroxyl groups on thefabric.
One embodiment of the invention comprises the following steps in applying the methodof the invention in the context of a standard industrial application process such as apadding process, impregnation process, a spraying process, a coating process or anexhaust process. First, the acid catalyst of the invention and the solvent of the inventionare mixed until complete dissolution ofthe catalyst. Then the alkyltrialkoxysilanecomponent ofthe invention is blended into the solution ofthe catalyst. The composition is applied onto the fabric. The fabric is passed through a curing station, such as an oven keptat a temperature of 150 °C to 200 °C for approximately 1-3 minutes.
According to another preferred aspect of the invention, the silanization composition ofthe invention is prepared immediately prior to its application to a textile, in particular byblending a premixed solution ofthe acid catalyst of the invention in the solvent oftheinvention with the alkyltrialkoxysilane ofthe invention immediately prior to application toa textile. Such blending and application are preferably carried out in a continuous manner.
According to the present invention is also disclosed a water-repellent cellulosic textileobtained or obtainable by the method ofthe invention.
According to a further preferred aspect of the invention is disclosed a cellulose textilehydrophobization composition comprising or substantially consisting of analkyltrialkoxysilane of the general formula R1(OR2)3Si, wherein Rl is straight or branched,saturated or unsaturated Cg-CZZ alkyl, in particular C12 to C18 alkyl, and RZ is methyl, ethyl,butyl, tertbutyl or isopropyl; a C2-C4 alcohol; an organic sulfonic acid; optionally water. ltis preferred for the organic sulfonic acid to be selected from the group consisting ofbenzenesulfonic acid, p-toluenesulfonic acid, m-toluenesulfonic acid, naphthalenesulfonicacid, camphor sulfonic acid, or methanesulfonic acid. A water content of 5 % by weight orless, in particular of 0.5 % or less is preferred.
Also preferred for the composition is to comprise from 2 % by weight to 10 % by weight,more preferred from 2 % by weight to 5 % by weight of alkyltrialkoxysilane, and from 0.05% by weight to 1.0 % by weight, more preferred from 0.1 % by weight to 0.5 % by weight,of organic sulfonic acid.
The invention will now be described in more detail by reference to a number of preferredembodiments, which are given as an exemplification ofthe invention but should not beunderstood as limiting the scope ofthe invention.
DESCRIPTION OF PREFERRED EMBODIMENTSMaterials Ethanol 99.5 %, Kemetyl AB 2-Propanol, Sigma Aldrich 2-I\/|ethyl-2-propanol, Sigma Aldrich Benzenesulfonic acid, Sigma Aldrich p-Toluenesulfonic acid, Sigma Aldrich Oxalic acid, Sigma Aldrich Camphorsulfonic acid, Sigma AldrichHexadecyltrimethoxysilane, Evonik Degussa Chemicals Determination of resistance to surface wetting (spray test) of fabrics European Standard EN 24 920 (ISO 4920:1981). Principle: A specified amount of water issprayed on a textile specimen mounted on a ring. The specimen is disposed at an angle of45° in respect to the nozzle. The centre ofthe standardized nozzle is disposed at a givendistance above the centre ofthe specimen. A given amount of water is filled in a reservoirdisposed above the nozzle and in communication with it. The spray rating is determinedvisually and/or photographically. The five-step spray rating scale of ISO 5 -ISO 1corresponds to 100 %, 90 %, 80 %, 70 %, and 50 %, respectively, of the specimen havingwithstood wetting.
Determination of resistance to water penetration - Hydrostatic pressure test International Standard ISO 811-1981. Principle: The textile specimen is subjected to asteadily increasing pressure of water on one face until penetration occurs in three places.The pressure at which the water penetrates the fabric at the third place is noted. A highpenetration pressure value thus signifies a high resistance to water penetration.
Si/anization procedure To the alcohol (94.65 g) in a 250 ml glass beaker was added 0.35 g of the organic acidcatalyst. The catalyst was dissolved by stirring the solvent for 5 min. Into the clear solutionof the catalyst in the alkohol was injected 5.0 g of hexadecyltrimethoxysilane undervigorous stirring to form the liquid silanization composition. Stirring was continued for thetime period indicated in Table 1 (Textile Contact Delay: 30 sec, 180 sec or 1800 sec) .
A 2 g piece of dyed cotton textile was immersed in the silanization composition for 10 secand dried in a preheated oven at the temperature and for the time given in Table 1.
The water-repellency properties of the treated textile before and after washing with anaqueous solution of a household detergent (Skona®, pH > 10) were evaluated (washingtemperature 60 °C) by testing the textile with the standardized tests SS-EN 24 920 and ISO811-1981. The results are summarized in Ex. 1-14 inTable 1 below.
Table 1Ex. WR- WP- Wash Solvent Catalyst Textile Drying Dryingtest* test** Contact Temp., Time,Delay, sec °C min 1 100 455 0 EtOH, Bz-SO3H 30 150 370 100 1 99.5%50 50 2 2 100 435 0 EtOH 3070 110 1 95 %50 60 2 3 70 350 0 18070 100 150 60 2 4 100 480 0 180070 100 150 70 2 5 100 410 0 2-Methy|- 3070 180 1 2-propanol50 150 250 135 350 180 450 120 5 6 100 420 0 18070 130 150 160 250 160 370 230 450 150 5 7 100 365 0 180070 150 150 140 250 170 370 240 450 150 5 8 100 420 0 2-Propanol Bz-SO3H 30 15070 170 150 110 250 140 350 150 450 95 5 9 100 415 0 18070 140 150 120 250 130 350 180 450 100 5 10 100 410 0 180070 160 150 130 250 130 350 150 450 110 5 11 100 385 0 2-Propanol p-Toluene- 30 150100 260 1 SO3H70 190 250 90 4 12 100 330 0 Oxaficacfi 30100 150 170 90 250 80 4 13 100 290 0 Camphow 30100 205 1 SO3H80 180 250 130 4 14 100 450 0 30 200100 190 170 80 270 150 4 * Water Repellency Test EN 24920; **Water Penetration Resistance Test ISO 811 Use of hydrochloric acid as a Catalyst A silanization procedure was carried out as above, but instead of organic acid catalysteither 0.04 M or 12 M hydrochloric acid (HCl) was used. Aqueous HCl catalyst solution asindicated in Table 2 was dissolved in 94.9 g isopropanol and blended with 5.0 g ofhexadecyltrimethoxysilane for 2 minutes. A 2 g piece of dyed cotton textile was immersedin the silanization composition for 10-20 sec and dried in a preheated oven at 150 °C for 3minutes. The water-repellency properties of the treated textile before and after washingwith an aqueous solution of a household detergent (Skona®, pH > 10) were evaluated(washing temperature 60 °C) by testing the textile with the standardized tests SS-EN 24 920 and ISO 811. The results are summarised in Ex. 15-17 in the Table 2 below.
Table 2Ex. WR- WP- Wash Solvent Catalyst Textile Drying Dryingtest* test** Contact Temp., Time,Delay, sec °C min15 0 0 0 2-Propanol HCl (0,04 M) 60 150 31 0,1 ml16 70-80 388 0 2-Propanol HCl (12 M) 6070 350 1 0,1 ml17 100 500 0 2-Propanol HCl (12 M) 6080-90 388 1 1 ml * Water Repellency Test EN 24920; **Water Penetration Resistance Test ISO 811
Claims (15)
1. A method of making a cellulosic textile water-repellent, comprising: providing a solution of an acid of pKa <1.0 in a C2-C4 alcohol optionally comprising water;providing an alkyltrialkoxyosilane; efficiently mixing the solution and thealkyltrialkoxysilane to produce a silanization composition; contacting the cellulosic textilewith the silanization composition; curing the cellulosic texile contacted with thecomposition at a temperature of 100 °C or more until substantially dry; optionally rinsingthe treated textile with an aqueous media to remove the acid; optionally drying the rinsedtreated textile.
2. The method of claim 1, wherein the C2-C4 alcohol is selected from isopropanol andtert-butanol.
3. The method of claim 1 or 2, wherein the alkyltrialkoxysilane is of the general formulaR1(OR2)3Si, wherein Rl is straight, branched or cyclic, saturated or non-saturated Cg-CZZalkyl, and RZ is methyl, ethyl, butyl, tert-butyl or isopropyl.
4. The method of claim 3, wherein Rl is straight or branched Clz-Clg alkyl.
5. The method of claim 3, wherein Rl is straight or branched C14-C16 alkyl.
6. The method of claim 3, wherein the alkyltrialkoxysilane is hexadecyltrimethoxysilane.
7. The method of any of claims 1 to 6, wherein the acid is an organic sulfonic acid.
8. The method of claim 7, wherein the organic sulfonic acid is selected from the groupconsisting of benzenesulfonic acid, p-toluenesulfonic acid, m-toluenesulfonic acid, naphthalenesulfonic acid, camphor sulfonic acid, methanesulfonic acid.
9. The method of any of claims 1 to 8, wherein the curing temperature is from 120 °C or150 °C to 200 °C.
10. The method of any of claims 1 to 9, wherein the water content ofthe silanizationcomposition is 5.0 % by weight or less, in particular 0.5 % or less.
11. A water-repellent cellulosic textile obtained or obtainable by the method of any ofclaims 1 to 10.
12. A cellulose textile hydrophobization composition comprising or substantiallyconsisting of an alkyltrialkoxysilane ofthe general formula R1(OR2)3Si, wherein Rl isstraight or branched, saturated or non-saturated Cg-CZZ alkyl, in particular C12 to C18 alkyl,and RZ is methyl, ethyl, butyl, tertbutyl or isopropyl.; a C1-C4 alcohol; an organic sulfonicacid; optionally water. lO
13. The composition of claim 12, wherein the organic sulfonic acid is selected from thegroup consisting of benzenesulfonic acid, p-toluenesulfonic acid, m-toluenesulfonic acid,naphthalenesulfonic acid, camphor sulfonic acid, methanesulfonic acid.
14. The composition of any of claims 11 to 13 of a water content of 5 % by weight or less,in particular of 0.5 % or less.
15. The composition of any of claims 12 to 14, comprising from 2 % by weight to 10 % byweight, preferably from 2 % by weight to 5 % by weight of alkyltrialkoxysilane and from0.05 % by weight to 1.0 % by weight, preferably from 0.1 % by weight to 0.5 % by weightof organic sulfonic acid.
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| SE1050031A SE534473C2 (en) | 2010-01-14 | 2010-01-14 | Method of manufacturing a water-repellent cellulose textile and corresponding textile product |
| PCT/EP2011/050066 WO2011086012A1 (en) | 2010-01-14 | 2011-01-04 | Method of making a cellulosic material water repellent and corresponding material |
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| US10465336B2 (en) | 2013-03-13 | 2019-11-05 | Organoclick Ab | Method and composition obtaining textiles showing water-repellency and repellency against water soluble dirt |
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| DE102006013090A1 (en) * | 2006-03-20 | 2007-09-27 | Georg-August-Universität Göttingen | Composite material made of wood and thermoplastic material |
| US10012065B2 (en) | 2014-08-15 | 2018-07-03 | Halliburton Energy Services, Inc. | Hydrophobic surface treatment for use in subterranean formation operations |
| PL3380526T3 (en) * | 2015-11-26 | 2022-11-14 | Organofuel Sweden Ab | Environmentally friendly process for the preparation of nanocellulose and derivatives thereof |
| CA3203322A1 (en) | 2020-12-23 | 2022-06-30 | Armando Cordova | A composition for use as a coating |
| SE545404C2 (en) * | 2022-06-22 | 2023-08-01 | Organograph Ab | An electron conducting coating |
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| US4339479A (en) | 1966-01-24 | 1982-07-13 | Edward Robbart | Treatment of cellulose |
| US4349610A (en) * | 1979-04-09 | 1982-09-14 | Beloit Corporation | Method for waterproofing paper |
| US5073195A (en) | 1990-06-25 | 1991-12-17 | Dow Corning Corporation | Aqueous silane water repellent compositions |
| JPH11246846A (en) * | 1997-12-12 | 1999-09-14 | Toyota Motor Corp | Friction material and its production |
| JP3456956B2 (en) * | 2000-08-10 | 2003-10-14 | 株式会社飾一 | Fiber coating material and coating liquid used for it |
| FR2843759B1 (en) | 2002-08-20 | 2006-12-22 | Louis Rousseau | PROCESS FOR THE SURFACE TREATMENT OF HYDROPHILIC FIBERS OF A SUBSTRATE, NATURAL OR SYNTHETIC |
| WO2009103024A2 (en) | 2008-02-14 | 2009-08-20 | Dave Bakul C | Methods and compositions for improving the surface properties of fabrics, garments, textiles and other substrates |
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| US10465336B2 (en) | 2013-03-13 | 2019-11-05 | Organoclick Ab | Method and composition obtaining textiles showing water-repellency and repellency against water soluble dirt |
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| WO2011086012A1 (en) | 2011-07-21 |
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