METHOD FOR CONFERRING DURABLE WATER REPELLENCE TO WOVEN OR NON-WOVEN FABRIC AND WATER REPELLENT COMPOSITION

Abstract

Disclosed is a method for conferring durable water repellence to woven or non-woven fabric, comprising the steps of: (1) treating the fabric with an aqueous composition, the composition comprising (a) an aqueous solvent comprising at least 80 w/w % water, and 20 w/w % or less of a water miscible organic solvent comprising at least two functional OH groups, and (b) 0.1-40 w/w % of an acrylic ester having the formula 1: wherein A.sup.1 is H or CH.sub.3, and A.sup.2 is C.sub.1-C.sub.30 linear or branched, saturated or unsaturated hydrocarbon that may have an alicyclic or aromatic ring, the acrylic ester being dissolved, emulsified or dispersed in the aqueous solvent, (2) heating the treated fabric to 120-200? C. Further such a composition and fabric treated with such a composition are disclosed.

##STR00001##

Claims

1-43. (canceled)

44. A method for conferring durable water repellence to woven or non-woven fabric, comprising the steps of: i) treating the fabric with an aqueous composition free of silicon compounds, the composition comprising: a. an aqueous solvent comprising at least 80 w/w % water, and 20 w/w % or less of a water miscible organic solvent comprising at least two functional OH groups, and b. 0.1-40 w/w % of an acrylic ester having the formula 1: ##STR00003## wherein A.sup.1 is H or CH.sub.3, and A.sup.2 is C.sub.1-C.sub.30 linear or branched, saturated or unsaturated hydrocarbon that may have an alicyclic or aromatic ring, the acrylic ester being dissolved, emulsified or dispersed in the aqueous solvent, ii) heating the treated fabric to 120-200? C.

45. The method of claim 44, wherein the water miscible solvent is selected from the group consisting of ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol dimethyl ether, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol, tripropylene glycol monomethyl ether, polypropylene glycol and hexylene glycol.

46. The method of claim 44, wherein the aqueous solvent comprises 90-99.9 w/w % water and 0.1-10 w/w % of the water miscible solvent.

47. The method of claim 44, wherein the composition comprises 0.2-20 w/w % acrylic ester

48. The method of claim 44, wherein A.sup.2 of the acrylic ester has 12 to 24 carbon atoms.

49. The method of claim 44, further comprising a polyisocyanate comprising at least 3 crosslinkable isocyanate groups.

50. The method of claim 49, wherein the weight ratio acrylic ester:isocyanate is 100:5-100.

51. The method of claim 44, wherein the treated fabric of step i) is dried before step ii).

52. The method of claim 44, wherein the composition further comprises a fluorinated C.sub.2-C.sub.20 alkyl compound comprising a terminal acryl group.

53. The method of claim 52, wherein the composition comprises in w/w % an equal amount of both non-fluorinated and fluorinated acrylic esters.

54. The method of claim 44, wherein the fabric is selected from the group consisting of polyester, polyamide, acrylate, ultra high molecular weight polyethylene, cotton and aramide or a mixture of two or more thereof, the fabric preferably comprising polyester and/or polyamide, more preferably polyester.

55. A composition free of fluorine and silicon compounds for conferring durable water repellence to woven or non-woven fabric, the composition comprising a. an aqueous solvent comprising at least 80 w/w % water, and 20 w/w % or less of a water miscible organic solvent comprising at least two functional OH groups, and b. 0.1-40 w/w % of an acrylic ester having the formula 1: ##STR00004## wherein A.sup.1 is H or CH.sub.3, and A.sup.2 is C.sub.1-C.sub.30 linear or branched, saturated or unsaturated hydrocarbon that may have an alicyclic or aromatic ring, the acrylic ester being dissolved, emulsified or dispersed in the aqueous solvent.

56. The composition of claim 55, wherein the water miscible solvent is selected from the group consisting of ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol dimethyl ether, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol, tripropylene glycol monomethyl ether, polypropylene glycol and hexylene glycol.

57. The composition of claim 55, wherein the aqueous solvent comprises 90-99.9 w/w % water and 0.1-10 w/w % of the water miscible solvent.

58. The composition of claim 55, wherein the composition comprises 0.2-20 w/w % acrylic ester.

59. The composition of claim 55, wherein A.sup.2 of the acrylic ester has 12 to 24 carbon atoms.

60. The composition of claim 55, further comprising a polyisocyanate comprising at least 3 crosslinkable isocyanate groups.

61. The composition of claim 60, wherein the weight ratio acrylic ester:isocyanate is 100:5-100.

62. A woven or non-woven fabric, treated with the composition of claim 55.

63. The woven or non-woven fabric of claim 62, wherein the fabric is selected from the group consisting of polyester, polyamide, acrylate, ultra high molecular weight polyethylene, cotton and aramide or a mixture of two or more thereof, the fabric preferably comprising polyester and/or polyamide, more preferably polyester.

Description

EXAMPLES

Water Repellence

[0042] Samples of PES 1 fabric 135 gr/m.sup.2 and PES 2 fabric 190 gr/m.sup.2 (MB Sportswear, Eindhoven Netherlands) were washed 100 times according to the method of Iso 6330 3G or 4H.

[0043] After washing, the water repellence is measured by the ISO 4920 (version 2012-12) spray method

Commercial Washing Cycles

[0044] The water repellence measured by the Iso 4920 spray method after washing 120 times according to the method of using a commercial washing machine of the type Miele Twindos (Germany) using the program Express 2.0 and the detergent Colour 15 Reus extra strong against stains, extra clean (Henkel, Germany). The program specifications and the contents of the detergent are given in tables 1 and 2, respectively.

TABLE-US-00001 TABLE 1 Washing program washing time 6 min. rinsing time 14 min. pumping time 14 min. spinning time 1 min. washing cycle time 27 min. load 2-3 kg temperature 30? C.

TABLE-US-00002 TABLE 2 Ingredients detergent anionic surface active agents (5-15%) soap (<5%) non ionic surface active agents phoshonates parfumes hexl cynnamal conservation agents methylisothiazolinone benzisothiazolinone enzymes

Oil Repellence

[0045] Oil repellence is measure after washing 100 times of samples as described above according to the AATCC118 method 118-1997.

Sample Preparation

[0046] The fabric sample was cut 15?15 cm from the reel and by dipping the fabric for 1 minute in the coating emulsion. The uncoated fabric was weighed in duplo. After dipping, the coated sample was placed on a rubber sleeve of a manual coating unit (RK prints) for the padding process. With a smooth roller with a weight of 10 kg the excess of emulsion was squeezed out by 2 times rolling the roller over the fabric.

[0047] The samples were dried in an oven with forced air ventilation for 3 minutes at 130? C.; subsequently the sample was cured for 1 minute at 160? C. After curing, the sample was weighted in duplo again.

[0048] Possible compositions for use in examples 1-8 are given in table 3. The experiment have been performed with the compositions given in table 4.

[0049] In examples 1, 3, 5-10, a polyester woven fabric PES 135 gr/m.sup.2 (pique) (MB Sportswear, Eindhoven Netherlands) was used, whereas in examples 2 and 4 195 gr/m.sup.2 smooth (MB Sportswear, Eindhoven Netherlands) was used.

[0050] It was observed that all examples, after the washing cycles and drying in a tumble dryer (AEG Lavatherm Protex plus, AEG, Germany, with the program setting cotton extra dry) retained their water repellence. Grade iso 5 was measured for all samples before the first washing and after 100 or 120 times washing. Grade 5 means that no sticking or wetting of the upper surface was observed.

[0051] The same was true for examples 1 and 3 when the dipping was replaced by spraying and the padding was replaced by tumbling in a tumble dryer as described above. Heating was performed by ironing at 150? C. (level**) for example 1 and at 200? C. (level***) for example 2, in conformity with the ironing prescriptions of the fabric manufacturer. Also for these samples, Grade iso 5 was measured for all samples before the first washing and after 100 or 120 times washing.

[0052] The oil repellence for examples 3, 4, 8-10 as measured according to AATCC118 was grade 5-6 after 100-120 times washing followed by the above tumble drying.

TABLE-US-00003 TABLE 3 Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7 Ex. 8 Ex. 9 Ex. 10 Compositions w/w % Acrylic Unidyne 0.1-2.0 6.0-10.0 0.1-2.0 3.0-5.0 0.1-2.0 0.1-2.0 0.1-2.0 0.1-2.0 0.1-2.0 0.1-2.0 ester XF5000 Series (Daikin, Japan) Water Tripropylene 0.1-05 0.5-5.0 0.1-0.5 0.5-5.0 0.1-0.5 0.1-0.5 0.1-0.5 0.1-0.5 0.1-0.5 0.1-0.5 miscible glycol solvent (Sigma Aldrich US) Fluorinated Unidyne TG 0.1-2.0 3.0-5.0 0.1-2.0 0.1-2.0 0.1-2.0 alkyl Series (Daikin, Japan) Poly- Rudolf, 0.06-1.2 0.03-0.6 0.01-0.2 0.06-1.2 0.03-0.6 0.01-0.2 isocyanate Imprafix Demi water 97.5-99.8 85-93.5 95.5-99.7 85-93.5 96.3-99.8 96.9-99.8 97.3-99.8 94.3-99.6 94.9-99.7 95.3-99.7 Total solids 0.1-2.5 6.0-15.0 0.3-4.5 6.5-15.0 0.26-3.7 0.23-3.1 0.21-2.7 0.36-5.7 0.33-5.1 0.31-4.7 (%)

TABLE-US-00004 TABLE 4 Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7 Ex. 8 Ex. 9 Ex. 10 Compositions w/w % Acrylic ester Unidyne XF5000 Series 1 6 1 3 1 1 1 1 1 1 (Daikin, Japan) Water miscible Tripropylene glycol 0.2 2.1 0.2 2.1 0.2 0.2 0.2 0.2 0.2 0.2 solvent (Sigma Aldrich US) Fluorinated alkyl Unidyne TG Series 1 3 1 1 1 (Daikin, Japan) Polyisocyanate Rudolf, Imprafix 0.6 0.3 0.1 0.6 0.3 0.1 Demi water 98.8 91.9 98.9 94.9 99.8 99.5 98.7 97.2 97.5 97.7 Total solids (%) 1.2 8.1 2.2 8.1 1.8 1.5 1.3 2.8 2.5 2.3

[0053] It was however observed that in case of line drying, i.e. without heating the dried fabric, a coating that has been subjected to crosslinking with polyisocyanate remained stably bound as compared to the results for all coatings after tumble drying, whereas the coatings without comprising the isocyanate (NCO) crosslinkages tended to loosen from the fabric after 10-12 washing cycles, see table 5. It was observed that a weight ratio acrylic ester:polyisocyanate of above 30 gave the best bonding.

TABLE-US-00005 TABLE 5 0 3 6 9 12 15 18 21 24 27 30 Example 1 (no NCO) 5 5 5 5 4 3 3 3 2 2 2 Example 5 (100:60) 5 5 5 5 5 5 5 5 5 5 5 Example 6 (100:30) 5 5 5 5 5 4, 5 3 3 3 2 3 Example 7 (100:10) 5 5 5 5 5 4 4, 5 4 3 3 2