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    • 专利摘要:
    A method of making a cellulosic water-repellent material and cellulosic material made water-repellent by such method. The method comprises; providing a solution of an acid of pKa 2-C4 alcohol optionally comprising water; providing an alkyltrialkoxyosilane; efficiently mixing the solution and the alkyltrialkoxysilane to produce a silanization composition; contacting the cellulosic material with the silanization composition; curing the cellulosic material contacted with the composition at a temperature of 100° C or more until substantially dry; optionally rinsing the treated material with an liquid media to remove the acid and optionally drying the rinsed treated material. The cellulosic water-repellent material is for example a cellulosic textile material.
    公开号:SE1050031A1
    申请号:SE1050031
    申请日:2010-01-14
    公开日:2011-07-15
    发明作者:Armando Cordova；Ali Naderi
    申请人:Organoclick Ab；
    IPC主号:
    专利说明:

    lO METHOD OF MAKING A CELLULOSIC TEXTILE WATER REPELLENT AND CORRESPONDINGTEXTILE FIELD OF THE INVENTION 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
    权利要求:
    Claims (15)
    [1] 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] 2. The method of claim 1, wherein the C2-C4 alcohol is selected from isopropanol andtert-butanol.
    [3] 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] 4. The method of claim 3, wherein Rl is straight or branched Clz-Clg alkyl.
    [5] 5. The method of claim 3, wherein Rl is straight or branched C14-C16 alkyl.
    [6] 6. The method of claim 3, wherein the alkyltrialkoxysilane is hexadecyltrimethoxysilane.
    [7] 7. The method of any of claims 1 to 6, wherein the acid is an organic sulfonic acid.
    [8] 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] 9. The method of any of claims 1 to 8, wherein the curing temperature is from 120 °C or150 °C to 200 °C.
    [10] 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] 11. A water-repellent cellulosic textile obtained or obtainable by the method of any ofclaims 1 to 10.
    [12] 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] 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] 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] 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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    同族专利:
    公开号 | 公开日
    WO2011086012A1|2011-07-21|
    SE534473C2|2011-09-06|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
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    US4349610A|1979-04-09|1982-09-14|Beloit Corporation|Method for waterproofing paper|
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    SE537807C2|2013-03-13|2015-10-20|Organoclick Ab|Method and formulation for obtaining fabrics that are water repellent and or repellent for water soluble dirt|
    WO2016025004A1|2014-08-15|2016-02-18|Halliburton Energy Services, Inc.|Hydrophobic surface treatment for use in subterranean formation operations|
    EP3380526A1|2015-11-26|2018-10-03|Organofuel Sweden AB|Environmentally friendly process for the preparation of nanocellulose and derivatives thereof|
    法律状态:
    2018-08-28| NUG| Patent has lapsed|
    优先权:
    申请号 | 申请日 | 专利标题
    SE1050031A|SE534473C2|2010-01-14|2010-01-14|Method of manufacturing a water-repellent cellulose textile and corresponding textile product|SE1050031A| SE534473C2|2010-01-14|2010-01-14|Method of manufacturing a water-repellent cellulose textile and corresponding textile product|
    PCT/EP2011/050066| WO2011086012A1|2010-01-14|2011-01-04|Method of making a cellulosic material water repellent and corresponding material|
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