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

Abstract

To provide a method for conferring durable water repellence to woven or non-woven fabric.SOLUTION: This method comprises 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, and (2) heating the treated fabric to 120-200°C. Further such a composition and fabric treated with such a composition are disclosed.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a method for imparting durable water repellency to a woven or nonwoven fabric, a composition for imparting durable water repellency to a woven or nonwoven fabric, and a woven or nonwoven fabric treated with said composition. [Background technology]

[0002] Methods for imparting durable water repellency to woven or nonwoven fabrics are known in the art. To date, providing durable water repellency to fabrics has relied on highly effective and durable fluorocarbon-based treatments. However, the toxicity and environmental persistence of by-products such as fluorosurfactants and derivatives based on C8 and C6 fluorosurfactants make this an unacceptable combination despite their superior performance. Today, many fluorine-free coatings have a short life span. Water repellent rain shells break down into functional wind shells long before the garment itself wears out.

[0003] JP2020153057 describes vinyl-based polymerization of specific divinyl compounds with molecular weights of 600 or more, including chemical bonding of vinyl polymers to polyester fabrics. An additional film is applied that includes fluorinated copolymers or acrylic monomers polymerized with perfluoroalkyl groups having 6 or fewer carbon atoms. The additional film is crosslinked by melamine resin.

[0004] EP 3919673 describes a special fabric surface that resembles the surface of a lotus leaf and mimics its water repellent properties. This artificial lotus-like surface can be treated with commonly known water repellents.

[0005] WO2016 / 000831 describes a composition for application to textiles to impart water repellency, in which three different acrylate monomers, one of which contains fluorine, are polymerized to a polyacrylate with the aid of an azo initiator. Apart from the polyacrylate thus obtained, the composition contains a wax. DISCLOSURE OF THEINVENTION [Problem to be solved by the invention]

[0006] The present invention provides a method and textile treatment composition for imparting durable water repellency to woven or nonwoven fabrics that can impart excellent washing, durable water repellency to textile products without the need to incorporate fluorine components for water repellency or to use silicone, isocyanate or melamine boosters. The method is for imparting durable water repellency to woven or nonwoven fabrics, resulting in a durable, long-lasting water repellent coating on the fabric that remains unaffected even after 100 or more machine washes. [Means for solving the problem]

[0007] For this purpose, the method comprises the steps of: i) treating the fabric with a silicone-free aqueous composition, the composition comprising: a. an aqueous solvent comprising at least 80 w / w% water and up to 20 w / w% of a water-miscible organic solvent containing at least two functional OH groups; and b. A 1 is H or CH3, A 2 is C1-C 30 As a hydrocarbon which may have a linear or branched, saturated or unsaturated, alicyclic or aromatic ring, represented by formula 1: 0.1 to 40 w / w % of an acrylic acid ester having a molecular weight of 1000 to 2000 μg / cm2, the acrylic acid ester being dissolved, emulsified or dispersed in the aqueous solvent; ii) heating the treated fabric to 120-200°C.

[0008] According to the method of the present invention, the water-miscible solvent participates in a chemical reaction with the acrylate ester through its functional OH group.

[0009] The heat treatment step ii) initiates an esterification reaction (transesterification) between the water-miscible solvent molecule and the acrylic ester. A covalent bond COC is formed between one of the at least two OH groups of the water-miscible solvent molecule and 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, which allows the ester to bond with the textile fibers by means of this OH group via hydrogen bridges. Thus, by "functional OH group" it is meant that the group is capable of forming the COC bond. Conditions are selected such that the above reaction or reactions can occur, for example at an acidic pH.

[0010] Without being bound by any scientific explanation, it is assumed that the transesterification reaction proceeds and the aqueous solvent molecules are converted to the acrylate ester CH2=C(A 1 ) esterified with the COO moiety (or moiety), A 2 It is also possible for the moiety to become covalently attached to the terminal OH group. In the latter case, A 2 The moiety is attached to the textile fiber through hydrogen bridges of its newly acquired terminal OH group. The transesterification reaction results in both incomplete and complete esterification processes, both of which are related to the hydrophobic A moiety attached to it through hydrogen bridges. 2 Since the result of the heat treatment is that the A2 moieties become bonded to the fabric, this process is also considered a curing process.

[0011] However, it is clear that the compositions of the present invention do not include acrylate polymers, i.e. polymers containing a plurality of acrylate monomers, in particular three or more, polymerized together, for example by the use of an azo initiator.Furthermore, it is clear from the above definition that said acrylic esters do not contain fluorine groups.

[0012] Suitable acrylic esters as defined above for step i)b. are known in the art, for example Unidyne XF series (Daikin, Japan).

[0013] Heat treatment transforms the fibers into hydrophobic A 2 The resulting fabric stably bonds the moieties and acquires very strong and long-lasting water repellency.

[0014] Water-miscible solvents can contain more than two functional OH groups, but the presence of two functional OH groups is preferred.Therefore, the water-soluble aqueous solvent is preferably an organic water-miscible solvent 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.Most preferred is tripropylene glycol.

[0015] It is preferred that the aqueous solvent comprises at least 0.1 w / w% water miscible solvent, preferably at least 0.2 w / w%.

[0016] The aqueous solvent preferably contains 90-99.9 w / w% water and 0.1-10 w / w% water-miscible solvent, 95-99.8 w / w% water and 0.2-5 w / w% water-miscible solvent, or 95-99 w / w% water and 1-5 w / w% miscible organic solvent.

[0017] The composition preferably contains 0.2 to 20 w / w %, more preferably 0.5 to 10 w / w %, and even more preferably 1 to 6 w / w % of the acrylic acid ester.

[0018] For optimal water repellency, the surface tension of the coating should be approximately 25 mN / m 2 For this purpose, A 2 The moiety is preferably alkyl. 2 The -CH2- moiety preferably has 12 to 24 carbon atoms, more preferably 12 to 21 carbon atoms, and even more preferably 18 carbon atoms. 2 The terminal -CH3 has a force of 22 mN / m 2 This means that a higher -CH3 content leads to a coating with lower surface tension and stronger water repellency. A higher -CH3 content can be obtained by increasing the number of branches of the hydrocarbon chain. Therefore, A 2 Although the moiety may be linear, the moiety is preferably branched.

[0019] The coating applied to the fabric according to the above method has been found to remain very stably attached to the fabric. It has been observed that the fabric remains perfectly preserved during 100 wash cycles followed by drying in a tumble dryer operated with a normal drying program, i.e., including heat (or during drying in a tumble dryer operated with a normal drying program, i.e., including heat, after 100 wash cycles). However, when dried without heat (so-called "line drying"), it has been observed that the coating begins to wear off after about 10 wash cycles.

[0020] The coating could be further improved by including a polyisocyanate having at least three crosslinking isocyanate groups in the aqueous composition. Surprisingly, the presence of the polyisocyanate resulted in a significant increase in the stability of the coating, and no noticeable wear occurred after 30 washing cycles, followed by line drying. The functional OH groups of both the water-miscible solvent molecules and the acrylic esters containing functional OH groups as a result of the above transesterification reaction, as well as the A2 moieties thus obtained with functional OH groups, are covalently bonded to the polyisocyanate, resulting in a crosslinked network of hydrophobic carbohydrate moieties, the crosslinked network being formed by the mutual linking of polyisocyanate molecules linked to each other via covalent bonds with the functional OH groups of the water-miscible solvent molecules. As these molecules contain two or more functional OH groups, they each function to link the polyisocyanate molecules to each other, form hydrogen bridge bonds with the fabric fibers, and provide functional groups to the acrylic esters of the A2 moieties.

[0021] The polyisocyanate may be, for example, aromatic or aliphatic, and suitable polyisocyanates are known in the art. Since the polyisocyanate is an aqueous composition, e.g., water-based, it is preferred that the polyisocyanate is blocked by a blocking group known in the art, e.g., phenol, nonylphenol, methylethylketoxime (MEKO), alcohol, epsilon-caprolactam, amide, imidazole, or pyrazole. JP2020007657 describes a water repellent and a textile treatment composition containing such a blocked polyisocyanate. In order for the blocked polyisocyanate to be activated, i.e., to become unblocked, the water is first removed, e.g., by drying, followed by a heating step. A very attractive isocyanate is the aliphatic hexamethylene-1,6-diisocyanate, especially the trimer based on HDI trimer (Kowa, New York, USA).

[0022] The weight ratio acrylic ester:isocyanate is 100:5 to 100, preferably 100:30 to 80, more preferably 100:50 to 70, and most preferably 100:60. It has been found that higher ratios of acrylic ester:isocyanate result in the most stable coatings.

[0023] In step ii), heating is carried out at 130-200°C, more preferably 140-200°C, more preferably 145-200°C 180°C, even more preferably 145-180°C, even more preferably 150-170°C and most preferably around 160°C. Such heating steps have been found to result in excellent reaction between the components (water-miscible solvent, acrylate ester and, if present, polyisocyanate) and bonding to the fabric. If a blocked polyisocyanate is present in the composition, said polyisocyanate similarly becomes unblocked at such temperatures.

[0024] The optimum heating temperature may also depend on the treated fabric. For example, in the case of ultra-high molecular weight polyethylene, the heating temperature is preferably kept below 140°C, especially around 130°C, since above said temperature deformation of the material may occur. For other fabrics that are more heat resistant, the drying temperature is preferably higher, as mentioned above, most preferably around 160°C. The heating step can be carried out by exposing the treated fabric to a hot air current or by being in a heat chamber or by ironing, for example. The skilled person will know the appropriate temperature selection. Preferably, the heating step is carried out for 30 seconds to 10 minutes, preferably 1 to 3 minutes.

[0025] The fabric treated in step i) is preferably dried before being subjected to the heating step ii). Such a pre-drying step is particularly important in the presence of polyisocyanates, since the crosslinking reaction is preferably carried out in a water-free environment. In the absence of isocyanates in the composition, it is also possible to combine heating and drying. However, drying can usually be carried out at a lower temperature than heating. Heating is preferably carried out, as described above, for example between 120°C and 200°C or at 145-200°C, while drying is preferably carried out between 100-140°C, preferably below 140°C. Such a pre-drying step therefore allows to save more energy. Preferably, drying is carried out for about 1-10 minutes, preferably for about 1-3 minutes.

[0026] In a very attractive embodiment, the composition is free of silicon and / or melamine compounds and, for the sole function of water repellency, it is preferred that the composition is likewise free of fluorine, meaning that there are no compounds in the composition that have fluorine groups in their molecular skeleton.

[0027] However, the compositions of the present invention use fluorinated C2-C acrylate copolymers containing terminal acrylic groups, as described, for example, in JP2020153057 and known in the art, to provide stable abrasion resistant coatings that are not only water repellent but also oil repellent. 20 In an attractive embodiment, alkyl compounds, such as Unidyne TG series (Daikin, Japan), are included. By including such fluorine acrylic ester in the composition, this fluorine acrylic ester is susceptible to transesterification with water-miscible solvents as the fluorine-free acrylic ester of formula 1 as described above, and thus leads to fluorinated hydrocarbon moieties bonded to fabric fibers through hydrogen bridges, and can participate in crosslinking with polyisocyanates, if present.

[0028] By providing such a fluorinated acrylic ester, not only water repellency but also oil repellency can be obtained. Very attractively, the fluorinated alkyl compound is a fluorine-free acrylic ester of formula 1 (for the fluorinated compound, the A2 moiety is C6-C 20 A2 is defined as a C6 alkyl, with 1 to 6 of the carbon atoms being fully substituted with fluorine. The term "fully substituted with fluorine" means that all H atoms of the respective carbon atoms are replaced by fluorine atoms. A saturated terminal carbon atom, when fully substituted, will have three fluorine atoms, and a saturated internal carbon, i.e. a carbon sandwiched between two adjacent carbon atoms by a single bond, will have two fluorine atoms. This means that the fluorine groups are scattered throughout the alkyl backbone. Such compounds are known, for example, from WO2016 / 096128. Very attractively, the fluorine compound A2 is a C6 alkyl, with all six of the carbon atoms being fully substituted with fluorine.

[0029] The surface tension of the -CF2- group is 18mN / m 2 The surface tensions of the terminal -CF2 and -CF3 groups are 15 mN / m 2 and 6mN / m 2 Therefore, branched alkyl fluoride compounds having terminal -CF2 and -CF3 groups, especially -CF3 groups, are preferred.

[0030] The composition preferably contains equal amounts of both non-fluorinated and fluorinated acrylic esters, by w / w %. The composition preferably contains 0.2-20 w / w % acrylic esters, more preferably 0.5-10 w / w %, and even more preferably 1-6 w / w % fluorinated C2-C 20 When fluorinated acrylic esters are present, the weight ratio of isocyanate (if present) to acrylic acid is determined by the sum of both fluorinated and fluorine-free acrylic esters present in the composition.

[0031] Instead of treating the fabric or textile, the method of the present invention can also be applied to textile fibers prior to assembly into a fabric or textile, and similar water repellency can be achieved when fabrics or textiles are made from such treated fibers.

[0032] The fibers and / or fabrics are preferably selected from polyester, polyamide, acrylate, ultra-high molecular weight polyethylene (e.g. Dyneema, DSM, Holland), cotton or aramid, or a mixture of two or more thereof. It has been found that the water-repellent coating is stably and strongly bonded to these types of fabrics. For this purpose, the fabrics preferably comprise polyester and / or polyamide, more preferably polyester.

[0033] The treatment in step i) is preferably selected 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 household appliance, and the fabric can be sprayed from an aerosol containing the composition, after which the heat treatment can be performed by ironing. In an industrial environment, the treated fabric is preferably dipped and subsequently padded to remove excess liquid composition.

[0034] In another aspect, the present invention relates to a composition, as described above, for imparting durable water repellency to a woven or nonwoven fabric.

[0035] In yet another aspect, the invention relates to fibers, woven fabrics, or nonwoven fabrics described herein that have been treated with a composition, particularly as described herein. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0036] The invention is further illustrated by examples and figures showing possible industrial setups for the inventive process.

[0037] The arrows reflect the conveying direction of the fabric 1, guided by guide rollers 2. The process is continuous, for example without interruptions. The fabric 1 is immersed in a bath 3 containing the composition 4 of the invention. After leaving the bath 3, the fabric 4 passes over two padding rolls 5, which squeeze the excess liquid composition from the fabric. The fabric is dried with hot air in a drying chamber 6, for example at a temperature of 130°C, and finally enters a heating chamber, where the temperature is for example 160°C.

[0038] Working Example <Water repellency> PES1 cloth 135gr / m 2 and PES2 fabric 190gr / m 2 (MB Sportswear, Eindhoven, The Netherlands) samples were washed 100 times according to method Iso 6330 3G or 4H.

[0039] After washing, water repellency is measured by the ISO 4920 (version 2012-12) spray method. Commercial Wash Cycle:

[0040] Water repellency measured by the Iso 4920 spray method after 120 washes according to the method using a commercial washing machine of the Miele Twindos (Germany) type with the program Express 2.0 and the detergent Colour Reus extra strong fort stains, extra clean (Henkel, Germany). The program specifications and detergent contents are shown in Tables 1 and 2, respectively. Table 1: Washing program TIFF2025072571000013.tif51170TIFF2025072571000014.tif64169

[0041] <Oil repellency> Oil repellency is measured according to AATCC Method 118-1997 after the samples have been washed 100 times as described above.

[0042] <Sample preparation> Fabric samples were cut from the reels measuring 15 x 15 cm by immersing the fabric in the coating emulsion for 1 minute. The uncoated fabric was weighed in duplo. After immersion, the coated samples were placed on the rubber sleeve of a manual coating unit (RK Print) for the padding process. Using a smooth roller weighing 10 kg, excess emulsion was squeezed out by rolling the roller twice over the fabric.

[0043] The samples were dried in an oven with forced air ventilation at 130° C. for 3 minutes, and then the samples were cured for 1 minute at 160° C. After curing, the samples were weighed again.

[0044] Table 3 shows compositions that can be used in Examples 1 to 8. Experiments were carried out with the compositions shown in Table 4.

[0045] In Examples 1, 3, 5-10, polyester woven fabric PES 135gr / m 2 ('pique') (MB Sportswear, Eindhoven, The Netherlands) was used, whereas in Examples 2 and 4, 195 gr / m 2 'Smooth' (MB Sportswear, Eindhoven, The Netherlands) was used.

[0046] After a wash cycle and drying in a tumble dryer (AEG Lavatherm Protex plus, AEG, Germany, program setting "cotton extra dry"), all examples were observed to retain their water repellency. A grade of iso 5 was measured for all samples before the first wash and after 100 or 120 washes. Grade 5 means that no adhesion or wetting of the top surface was observed.

[0047] The same was true for Examples 1 and 3 when soaking was replaced by spraying and padding was replaced by tumbling in a tumble dryer as described above. Heating was performed by ironing according to the ironing instructions of the fabric manufacturer, e.g. at 150°C (level **) for Example 1 and 200°C (level ***) for Example 2. Also, the ISO 5 grade was measured for all samples before the first wash and after 100 or 120 washes.

[0048] The oil repellency of Examples 3, 4, 8-10, measured according to AATCC 118, was grade 5-6 after 100-120 washes followed by tumble drying as described above. TIFF2025072571000015.tif23551TIFF2025072571000016.tif23652

[0049] However, in the case of line drying, i.e. without heating the drying fabric, it was observed that the coatings crosslinked with polyisocyanate remained stably bonded compared to the results of all coatings after tumble drying, while the coatings without isocyanate (NCO) crosslinks tended to flake off from the fabric after 10-12 wash cycles, see Table 5. It was observed that a weight ratio acrylate:polyisocyanate greater than 30 gave the best bond. TIFF2025072571000017.tif42169The following is the invention described at the beginning of the filing of this application. <Claim 1> 1. A method for imparting durable water repellency to a woven or nonwoven fabric, comprising the steps of: i) treating the fabric with an aqueous composition, the composition comprising: a. an aqueous solvent comprising at least 80 w / w% water and up to 20 w / w% of a water-miscible organic solvent containing at least two functional OH groups; and b. A1 is H or CH3, and A2 is a C1-C30 linear or branched, saturated or unsaturated, optionally alicyclic or aromatic hydrocarbon represented by formula 1: 0.1 to 40 w / w % of an acrylic acid ester having the formula: ii) heating the treated fabric to 120-200°C. <Claim 2> 2. The method of claim 1, 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. <Claim 3> 3. The method of claim 2, wherein the water-miscible solvent comprises tripropylene glycol. <Claim 4> 4. The method according to claim 1, wherein the aqueous solvent comprises 90 to 99.9 w / w % water and 0.1 to 10 w / w % water-miscible solvent, preferably 95 to 99.8 w / w % water and 0.2 to 5 w / w % water-miscible solvent, or 95 to 99 w / w % water and 1 to 5 w / w % water-miscible organic solvent. <Claim 5> 5. The method according to claim 1, wherein the composition comprises 0.2 to 20 w / w %, preferably 0.5 to 10 w / w %, more preferably 1 to 6 w / w % of an acrylic ester. <Claim 6> 6. The method according to claim 1, wherein the acrylic ester A2 has from 12 to 24 carbon atoms, preferably from 12 to 21 carbon atoms, more preferably from 18 carbon atoms. <Claim 7> 7. The method according to claim 1, wherein A2 of the acrylic ester is alkyl. <Claim 8> 7. The method according to claim 1, wherein the acrylic ester A2 is branched. <Claim 9> 9. The method of claim 1, further comprising a polyisocyanate containing at least three crosslinkable isocyanate groups. <Claim 10> 10. The method of claim 9, wherein the polyisocyanate is a water-based blocked polyisocyanate. <Claim 11> 11. The method according to claim 9 or 10, wherein the weight ratio of acrylic ester:isocyanate is 100:5-100, preferably 100:30-80, more preferably 100:50-70, and most preferably 100:60. <Claim 12> 12. The method according to any one of claims 1 to 11, wherein the treated fabric of step i) is dried before step ii). <Claim 13> The method according to claim 12, wherein the fabric is dried at 100 to 140°C. <Claim 14> The method according to any one of claims 1 to 13, wherein in step ii), the heating is carried out at 130 to 200°C, preferably 140 to 200°C, more preferably 145 to 200°C, further preferably 145 to 180°C, and further preferably 150 to 170°C. <Claim 15> The method according to any one of claims 1 to 14, wherein the heating step is carried out for 30 seconds to 10 minutes. <Claim 16> The method according to any one of claims 1 to 15, wherein the composition is free of silicone and melamine compounds. <Claim 17> The method according to any one of claims 1 to 16, wherein the composition is fluorine-free. <Claim 18> 17. The method of claim 1, wherein the composition further comprises a fluorinated C2-C20 alkyl compound containing a terminal acrylic group. <Claim 19> 19. The method of claim 18, wherein the fluorinated alkyl compound is a C6-C20 alkyl, and 1 to 6 of the carbon atoms are fully substituted with fluorine. <Claim 20> 20. The method according to claim 18 or 19, wherein the fluorinated alkyl compound is branched. <Claim 21> The method of any of claims 18 to 20, wherein the composition comprises, on a w / w % basis, equal amounts of both non-fluorinated and fluorinated acrylic esters. <Claim 22> 22. The method according to any one of claims 1 to 21, wherein the fibres are selected from polyester, polyamide, acrylate, ultra-high molecular weight polyethylene, cotton or aramid, or a mixture of two or more thereof, preferably comprising polyester and / or polyamide, more preferably polyester. <Claim 23> 23. The method according to any one of claims 1 to 22, wherein the treatment in step i) is selected from immersing the fabric in the composition or spraying the composition onto the fabric. <Claim 24> 24. The method according to any one of claims 1 to 23, wherein the treated fabric is padded before being dried or heated. <Claim 25> 1. A composition for imparting durable water repellency to a woven or nonwoven fabric, the composition comprising: a. an aqueous solvent comprising at least 80 w / w% water and up to 20 w / w% of a water-miscible organic solvent containing at least two functional OH groups; and b. A1 is H or CH3, and A2 is a C1-C30 linear or branched, saturated or unsaturated, optionally alicyclic or aromatic hydrocarbon represented by formula 1: 0.1 to 40 w / w% of an acrylic acid ester having the formula: The composition comprising: <Claim 26> 26. The composition of claim 25, 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. <Claim 27> 27. The composition of claim 26, wherein the water-miscible solvent comprises tripropylene glycol. <Claim 28> 28. The composition according to claim 25, wherein the aqueous solvent comprises 90 to 99.9 w / w% water and 0.1 to 10 w / w% of the water-miscible solvent, preferably 95 to 99.8 w / w% water and 0.2 to 5 w / w% of the water-miscible solvent, or 95 to 99 w / w% water and 1 to 5 w / w% of the miscible organic solvent. <Claim 29> 29. The composition according to claim 25, wherein the composition comprises an acrylic acid ester in an amount of 0.2 to 20 w / w %, preferably 0.5 to 10 w / w %, and more preferably 1 to 6 w / w %. <Claim 30> 30. The composition according to any one of claims 25 to 29, wherein the acrylic ester A2 has 12 to 24 carbon atoms, preferably 12 to 21 carbon atoms, more preferably 18 carbon atoms. <Claim 31> 31. The compound according to claim 25, wherein A2 of the acrylic ester is alkyl. <Claim 32> 32. The compound according to claim 25, wherein A2 of the acrylic ester is branched. <Claim 33> 33. The composition according to any one of claims 26 to 32, further comprising a polyisocyanate containing at least three crosslinkable isocyanate groups. <Claim 34> 34. The composition of claim 33, wherein the polyisocyanate is a water-based blocked polyisocyanate. <Claim 35> 34. The composition according to claim 32 or 33, wherein the weight ratio of acrylic ester:isocyanate is 100:5-100, preferably 100:30-80, more preferably 100:50-70, and most preferably 100:60. <Claim 36> 36. The composition according to any one of claims 25 to 35, wherein the composition is free of silicone and melamine compounds. <Claim 37> 37. The composition according to claim 25, wherein the composition is fluorine-free. <Claim 38> 37. The composition according to any one of claims 25 to 36, wherein the composition further comprises a fluorinated C2-C20 alkyl compound containing a terminal acrylic group. <Claim 39> 39. The composition of claim 38, wherein the fluorinated alkyl compound is a C6-C20 alkyl, and 1 to 6 of the carbon atoms are fully substituted with fluorine. <Claim 40> 40. The composition of claim 38 or 39, wherein the fluorinated alkyl compound is branched. <Claim 41> The composition of any one of claims 38 to 40, wherein the composition comprises equal amounts, on a w / w % basis, of both non-fluorinated and fluorinated acrylic esters. <Claim 42> A woven or nonwoven fabric treated with the composition of any one of claims 25 to 41. <Claim 43> 43. A woven or nonwoven fabric according to claim 42, wherein the fabric is selected from polyester, polyamide, acrylate, ultra high molecular weight polyethylene, cotton or aramid, or a mixture of two or more thereof, preferably the fabric comprises polyester and / or polyamide, more preferably polyester. [Brief description of the drawings]

[0050] FIG. 1 is an explanatory diagram of an embodiment.

Claims

1. 1. A method for imparting durable water repellency to a woven or nonwoven fabric, comprising the steps of: i) treating said fabric with an aqueous composition, said composition comprising: a. an aqueous solvent comprising at least 80 w / w % water and up to 20 w / w % of a water-miscible organic solvent containing at least two functional OH groups; and b.A １ is H or CH ３ And A ２ is C １ -C ３０ As a hydrocarbon which may have a linear or branched, saturated or unsaturated, alicyclic or aromatic ring, the formula 1: 0.1-40 w / w % of an acrylic acid ester having the formula: ii) heating the treated fabric to 120-200°C.

2. 2. The method of claim 1, 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.

3. The method of claim 2 , wherein the water-miscible solvent comprises tripropylene glycol.

4. 4. The method according to any one of claims 1 to 3, wherein the aqueous solvent comprises 90-99.9 w / w% water and 0.1-10 w / w% water-miscible solvent, preferably 95-99.8 w / w% water and 0.2-5 w / w% water-miscible solvent, or 95-99 w / w% water and 1-5 w / w% miscible organic solvent.

5. 5. The method according to any one of claims 1 to 4, wherein the composition comprises 0.2 to 20 w / w%, preferably 0.5 to 10 w / w%, more preferably 1 to 6 w / w% of an acrylic ester.

6. The acrylic acid ester A ２ The process according to any one of claims 1 to 5, wherein has 12 to 24 carbon atoms, preferably 12 to 21 carbon atoms, more preferably 18 carbon atoms.

7. The acrylic acid ester A ２ The method of any one of claims 1 to 6, wherein is alkyl.

8. The acrylic acid ester A ２ The method of any one of claims 1 to 6, wherein is branched.

9. The method of any one of claims 1 to 8, further comprising a polyisocyanate containing at least three crosslinkable isocyanate groups.

10. The method of claim 9, wherein the polyisocyanate is a water-based blocked polyisocyanate.

11. A process according to claim 9 or 10, wherein the weight ratio acrylate:isocyanate is from 100:5 to 100, preferably from 100:30 to 80, more preferably from 100:50 to 70, most preferably 100:

60.

12. A method according to any one of claims 1 to 11, wherein the treated fabric of step i) is dried prior to step ii).

13. The method of claim 12, wherein the fabric is dried at 100-140°C.

14. The method according to any one of claims 1 to 13, wherein in step ii) the heating is carried out at 130 to 200°C, preferably at 140 to 200°C, more preferably at 145 to 200°C, even more preferably at 145 to 180°C, even more preferably at 150 to 170°C.

15. A method according to any one of the preceding claims, wherein the heating step is carried out for between 30 seconds and 10 minutes.

16. The method according to any one of the preceding claims, wherein the composition is free of silicone and melamine compounds.

17. The method of any one of claims 1 to 16, wherein the composition is fluorine-free.

18. The composition comprises a fluorinated C ２ -C ２０ The method of any one of claims 1 to 16, further comprising an alkyl compound.

19. The fluoroalkyl compound is ６ -C ２０ 19. The method of claim 18, wherein said alkyl is fully substituted with fluorine, said 1 to 6 carbon atoms being fully substituted with fluorine.

20. 20. The method of claim 18 or 19, wherein the fluorinated alkyl compound is branched.

21. The method of any of claims 18 to 20, wherein the composition comprises equal amounts, w / w %, of both non-fluorinated and fluorinated acrylic esters.

22. 22. The method according to any one of the preceding claims, wherein the fibres are selected from polyester, polyamide, acrylate, ultra-high molecular weight polyethylene, cotton or aramid, or a mixture of two or more thereof, preferably comprising polyester and / or polyamide, more preferably polyester.

23. The method according to any one of claims 1 to 22, wherein the treating in step i) is selected from immersing the fabric in the composition or spraying the composition onto the fabric.

24. A method according to any one of the preceding claims, wherein the treated fabric is padded before being dried or heated.

25. 1. A composition for imparting durable water repellency to a woven or nonwoven fabric, the composition comprising: a. an aqueous solvent comprising at least 80 w / w % water and up to 20 w / w % of a water-miscible organic solvent containing at least two functional OH groups; and b.A １ is H or CH ３ And A ２ is C １ -C ３０ As a hydrocarbon which may have a linear or branched, saturated or unsaturated, alicyclic or aromatic ring, the formula 1: 0.1 to 40 w / w % of an acrylic acid ester having the formula: The composition comprising:

26. 26. The composition of claim 25, 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.

27. 27. The composition of claim 26, wherein the water-miscible solvent comprises tripropylene glycol.

28. 28. The composition according to any one of claims 25 to 27, wherein said aqueous solvent comprises 90-99.9% w / w of water and 0.1-10% w / w of said water-miscible solvent, preferably 95-99.8% w / w of water and 0.2-5% w / w of said water-miscible solvent, or 95-99% w / w of water and 1-5% w / w of a miscible organic solvent.

29. 29. The composition according to any one of claims 25 to 28, wherein the composition comprises 0.2 to 20 w / w%, preferably 0.5 to 10 w / w%, more preferably 1 to 6 w / w% of an acrylic ester.

30. The acrylic ester A ２ A composition according to any one of claims 25 to 29, wherein has 12 to 24 carbon atoms, preferably 12 to 21 carbon atoms, more preferably 18 carbon atoms.

31. The acrylic acid ester A ２ The compound of any one of claims 25 to 30, wherein is alkyl.

32. The acrylic acid ester A ２ The compound according to any one of claims 25 to 31, wherein is branched.

33. The composition of any one of claims 26 to 32, further comprising a polyisocyanate containing at least three crosslinkable isocyanate groups.

34. The composition of claim 33, wherein the polyisocyanate is a water-based blocked polyisocyanate.

35. A composition according to claim 32 or 33, wherein the weight ratio acrylic ester:isocyanate is from 100:5 to 100, preferably from 100:30 to 80, more preferably from 100:50 to 70, most preferably 100:

60.

36. The composition of any one of claims 25 to 35, wherein the composition is free of silicone and melamine compounds.

37. The composition according to any one of claims 25 to 36, wherein the composition is fluorine-free.

38. The composition comprises a fluorinated C ２ -C ２０ The composition of any one of claims 25 to 36, further comprising an alkyl compound.

39. The fluoroalkyl compound is ６ -C ２０ The composition of claim 38, wherein said alkyl is alkyl and 1 to 6 of said carbon atoms are fully substituted with fluorine.

40. 40. The composition of claim 38 or 39, wherein the fluorinated alkyl compound is branched.

41. The composition of any one of claims 38 to 40, wherein the composition comprises equal amounts, in w / w %, of both non-fluorinated and fluorinated acrylic esters.

42. A woven or nonwoven fabric treated with the composition of any one of claims 25 to 41.

43. 43. A woven or nonwoven fabric according to claim 42, wherein the fabric is selected from polyester, polyamide, acrylate, ultra high molecular weight polyethylene, cotton or aramid, or a mixture of two or more thereof, preferably the fabric comprises polyester and / or polyamide, more preferably polyester.

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