Aqueous composition for improving abrasion resistance

Abstract

The invention relates to a formulation which is used on textile surfaces, tissues, non-crimp fabrics, knitted fabrics, fibers, non-woven fabrics and weft knitted fabrics and which demonstrates an improved resistance to abrasion. The invention also relates to a process of preparing a formulation for improving abrasion resistance of textiles and the process of treating textiles, non-woven fabrics and leather articles for improving abrasion resistance.

Claims

1. A process for improving the abrasion resistance of textile materials, comprising: providing a dispersion that includes, a) 10 to 90% by weight of a wax-containing aqueous dispersion, b) 90 to 10% by weight of an aqueous polymer dispersion wherein the water content of the dispersions is respectively from 20 to 95%, and the waxes of said wax-containing aqueous dispersions have melting points of between 20-120° C., wherein said aqueous polymer dispersion is a polyurethane dispersion or polyacrylate dispersion applying the dispersion to a textile material.

2. The process according to claim 1, wherein the waxes of said wax-containing aqueous dispersions have melting points of between 20-80° C.

3. The process according to claim 1, wherein said waxes are selected from the group consisting of paraffins, silicone waxes, ester waxes, and combinations thereof.

4. The process according to claim 1, further comprising additives selected from the groups consisting of cross-linking agents, defoaming agents, processing aids, plasticizers, or other polymer dispersions.

5. The process according to claim 1, wherein the textile material is dilour nonwovens.

6. The process according to claim 1, wherein the textile material is textiles in the automotive field.

Description

DESCRIPTION OF THE INVENTION

(1) It is to be understood that the ranges and limits mentioned herein include all ranges located within the prescribed limits (i.e., subranges). For instance, a range from 20° to 120° C. also includes ranges from 20° to 100° C., 20° to 0° C., 33° to 113° C. and 35.3° to 99.6° C. Further, a a range of from 20 to 95% also includes ranges from 20 to 80%, 30 to 95%, 33 to 93%, and 33.3 to 90.3% as examples.

(2) The above object is achieved by a formulation for improving the abrasion resistance of textile materials that includes the following components:

(3) a) 10 to 90% by weight of a wax-containing aqueous dispersion,

(4) b) 90 to 10% by weight of an aqueous polymer dispersion

(5) wherein the water content of the dispersions is respectively from 20 to 95%, and the waxes have melting points of <120° C.

(6) A process for improving the abrasion resistance of textile materials includes providing a dispersion that includes, a) 10 to 90% by weight of a wax-containing aqueous dispersion, b) 90 to 10% by weight of an aqueous polymer dispersion wherein the water content of the dispersions is respectively from 20 to 95%, and the waxes of said wax-containing aqueous dispersions have melting points of between 20-120° C., wherein said aqueous polymer dispersion is a polyurethane dispersion or polyacrylate dispersion; and applying the dispersion to a textile material.

(7) Surprisingly, it has been found that the combinations of aqueous wax dispersions, in which the bulk of the wax component have melting points of <120° C., preferably from 20° to 120° C., more preferably from 20° to 100°, and most preferably from 20° to 80° with aqueous polymer dispersions show a significantly greater improvement in abrasion resistance than is observed with the individual components.

(8) All previous attempts to solve the problem of low abrasion resistance of textiles, especially dilour nonwovens, using finishing or coating agents so far have not provided a satisfactory result. Therefore, with untreated dilour nonwovens, the requirements of car manufacturers, even with high-quality fiber blends, cannot be met currently. Therefore, finishing is absolutely necessary in order to be able to deliver dilour nonwovens in accordance with specifications.

(9) By the finishing with a mixture according to the invention consisting of aqueous wax dispersions in combination with the aqueous polymer dispersion, it is now possible to improve the abrasion resistance so that a level is reached that previously could only be reached with much more expensive materials (taffeta fabrics). With formulations according to the invention, it thereby becomes possible that dilour nonwovens with a subsequent application by a standard method in the textile industry can be employed also in high-quality automotive segments, such as the “upper-middle class.”

(10) The wax dispersions consist of waxes based on natural, semi-synthetic, synthetic waxes. Natural waxes can be distinguished into mineral, vegetable and animal waxes, all of which can be employed according to the invention. Vegetable waxes include, for example, carnauba or Japan waxes, mineral waxes include, for example, ceresin or montan waxes (raw montan waxes, acid waxes, ester waxes, partially saponified ester waxes, emulsifier-containing ester waxes, fully saponified montan waxes). Beeswax, lanolin may be mentioned as examples of animal waxes. Synthetic waxes are those based on polyalkylene (polyethylene, polypropylene, polyolefin waxes), silicone waxes, polyol ether esters, Fischer-Tropsch waxes, oxidized PE and HDPE waxes, paraffins, amide waxes, such as ethylenebis(stearoyldiamide). Semisynthetic waxes are chemically modified waxes from native sources, such as hydrogenated jojoba and Sasol waxes. The waxes can consist of a combination of the waxes set forth above.

(11) The polymer dispersions include polymers and/or copolymers as a single component or in mixtures, selected from the groups of polyacrylates, polyurethanes, polybutadienes, polystyrenes, polyethylene terephthalates, polyesters, and silicone polymers.

(12) Both from the aforementioned waxes and from the polymers, aqueous dispersions with water contents of 20-95% by weight are prepared according to the respective state of the art and by methods known to the skilled person. It is advantageous to provide formulations according to the invention with the lowest possible water contents in order to save transport costs and to expend as little energy as possible for drying. In addition, water-based systems offer the advantage of having very low VOC values and to be more ecologically sustainable as compared to solvent-based systems. VOC is an abbreviation for volatile organic compounds and is a collective term for organic, i.e., carbon-containing, substances that are very volatile and are present as a gas already at low temperatures (e.g., room temperature).

(13) The aqueous formulations of the invention on the basis of a mixture of wax and polymer dispersion are applied to the textile substrates in textile-technical processes, forced applications, especially coating, such as in an application bath, finishing by padding, spray method, foam-paste application, monofilament application and/or dyeing, but also by extraction methods. In suitable methods, such as padding, foam or paste application and spray method, a backside latex application for a stronger reinforcement of the material can be affected in the same step.

(14) Textile materials may include all textile sheets, fabrics, scrims, knitted fabrics, fibers, nonwovens and weft-knitted fabrics as well as leather can be treated as substrates with the dispersion formulation according to the invention to improve their scuff resistance and abrasion resistance. Preferably, the textile materials may be dilour nonwovens and textiles in the automotive field can be treated with the formulation by applying the dispersion formulation to these textile materials for improving abrasion resistance.

(15) The dispersion may include additives selected from the groups consisting of cross-linking agents, defoaming agents, processing aids, plasticizers, or other polymer dispersions.

EXAMPLES

(16) Raw Materials Employed

(17) Beiphob zeroF=wax dispersion based on waxes/silicone waxes with melting points of 65-68° C. and 30-32° C., available from CHT R. Beitlich GmbH, Tübingen, Germany.

(18) Polyavin PEN=polyethylene dispersion based on an HD polyethylene having a melting point of 135-137° C., available from CHT R. Beitlich GmbH, Tübingen, Germany.

(19) Intermediate product NLDPE=polyethylene dispersion based on polyethylene with melting points of 104-108° C. and 90-92° C., available from CHT R. Beitlich GmbH, Tübingen, Germany.

(20) Tubicoat Primer LE=cationic, hydrophobic polyurethane dispersion giving a very soft film, available from CHT R. Beitlich GmbH, Tübingen, Germany.

(21) Arristan CPU=cationic, hydrophilic polyurethane dispersion giving a soft film, available from CHT R. Beitlich GmbH, Tübingen, Germany.

(22) Erlapon SOL=emulsion based on a polydimethylsiloxane, available from CHT R. Beitlich GmbH, Tübingen, Germany.

(23) Lustraffin SA 88=emulsion on the basis of a paraffin with a melting point of 60-62° C. and wax components having a melting point of 102-110° C., available from CHT R. Beitlich GmbH, Tübingen, Germany.

(24) Tubicoat A 19=acrylate-based plastic dispersion, giving a very soft film, available from CHT R. Beitlich GmbH, Tübingen, Germany.

(25) Tubicoat A 41=acrylate-based plastic dispersion, giving a rigid film, available from CHT R. Beitlich GmbH, Tübingen, Germany.

(26) Tubicoat ZWE=emulsion on the basis of a paraffin having a melting point of 60° C., available from CHT R. Beitlich=GmbH, Tübingen, Germany.

(27) Tubicoat AOS=foaming agent for foam finishing techniques, available from CHT R. Beitlich GmbH, Tübingen, Germany.

(28) To improve comparability, all formulations were adjusted to a solids content of 20% by weight by the addition of water.

(29) The product was applied in the form of an unstable foam by a foam-padding method. The fabric was passed vertically from top to bottom through a foam-padding machine. As a foaming agent, respectively, 7 g/l Tubicoat AOS was added to the liquor, and the foam weight per liter was adjusted to 40 g/l.

(30) The experiments were performed on a dilour nonwoven in accordance with TL 52442. This is a needle-punched nonwoven made from spun-dyed polyester fibers, with 11 dtex, which has been thermo-mechanically fixed.

(31) The abrasion resistance of the finished fabrics was tested with a Taber Rotary Abraser 5135 available from Taber Industries, North Tonawanda, United States, according to DIN provision DIN EN ISO 5470.

Experimental Series 1: Concentration Series (According to the Invention)

(32) TABLE-US-00001 TABLE 1a Raw fabric 1 2 3 4 5 6 [g/l] [g/l] [g/l] [g/l] [g/l] [g/l] [g/l] Beiphob 0 10 25 50 100 150 250 zeroF Tubicoat 0 3.2 8 16 32 48 80 Primer LE Water 0 6.8 17 34 68 102 170

(33) Solids content of the formulations=20% by weight

(34) TABLE-US-00002 TABLE 1b Sample designation Raw fabric Formulation 1 Formulation 2 Cycles 1000 1000 1000 1000 1000 1000 Abrasion wheels H18 H18 H18 H18 H18 H18 Additional weight 1000 g/ 1000 g/ 1000 g/ 1000 g/ 1000 g/ 1000 g/ wheel wheel wheel wheel wheel wheel Weight before test in mg 6094.9 5843.7 6318.9 5872.9 5853.7 5661.8 Weight after test in mg 5885.3 5618.8 6141.7 5616.8 5648.8 5437.9 Weight loss in mg 209.60 224.90 177.20 256.10 204.90 223.90 Weight loss in % 3.44 3.85 2.80 4.36 3.50 3.95 Average weight loss in % 3.64 3.58 3.73

(35) TABLE-US-00003 TABLE 1c Sample designation Formulation 3 Formulation 4 Formulation 5 Cycles 1000 1000 1000 1000 1000 1000 Abrasion wheels H18 H18 H18 H18 H18 H18 Additional weight 1000 g/ 1000 g/ 1000 g/ 1000 g/ 1000 g/ 1000 g/ wheel wheel wheel wheel wheel wheel Weight before test in mg 5877 5869.3 6153.1 6181.6 6319.9 6281.5 Weight after test in mg 5733.4 5690.4 6077.9 6115.1 6248.1 6234.4 Weight loss in mg 143.6 178.9 75.2 66.5 71.8 47.1 Weight loss in % 2.44 3.05 1.22 1.08 1.14 0.75 Average weight loss in % 2.75 1.15 0.95

(36) TABLE-US-00004 TABLE 1d Sample designation Formulation 6 Cycles 1000 1000 Abrasion wheels H18 H18 Additional weight 1000 g/ 1000 g/ wheel wheel Weight before test in mg 6531.6 6646.2 Weight after test in mg 6492 6618.4 Weight loss in mg 39.6 27.8 Weight loss in % 0.61 0.42 Average weight loss in % 0.51

(37) On the basis of Tables 1a-1d, it can be seen that the average percentage weight loss in the Taber test is within a range of 1% or below from formulation 4, which corresponds to a quantity employed of 200 g/l with its total solids concentration of 20%. As compared to unfinished fabrics, this means an improvement of 65% or more.

Experimental Series 2: Variation of the Ratio of Wax Dispersion to Polyurethane Dispersion

(38) TABLE-US-00005 TABLE 2a 7 8 9 10 11 12 13 14 [g/l] [g/l] [g/l] [g/l] [g/l] [g/l] [g/l] [g/l] Beiphob zeroF 132 112 100 92 72 52 32 0 Tubicoat 0 20 32 40 60 80 100 132 Primer LE Water 68 68 68 68 68 68 68 68 200 200 200 200 200 200 200 200

(39) Solids content of the formulations=20% by weight

(40) TABLE-US-00006 TABLE 2b Sample designation Formulation 7 Formulation 8 Formulation 9 Cycles 1000 1000 1000 1000 1000 1000 Abrasion wheels H18 H18 H18 H18 H18 H18 Additional weight 1000 g/ 1000 g/ 1000 g/ 1000 g/ 1000 g/ 1000 g/ wheel wheel wheel wheel wheel wheel Weight before test in mg 5958.4 6251.1 6284 6560.9 6029.5 6035.1 Weight after test in mg 5849.8 6127.9 6205.7 6467 5974.8 5965.6 Weight loss in mg 108.60 123.20 78.30 93.90 54.70 69.50 Weight loss in % 1.82 1.97 1.25 1.43 0.91 1.15 Average weight loss in % 1.90 1.34 1.03

(41) TABLE-US-00007 TABLE 2c Sample designation Formulation 10 Formulation 11 Formulation 12 Cycles 1000 1000 1000 1000 1000 1000 Abrasion wheels H18 H18 H18 H18 H18 H18 Additional weight 1000 g/ 1000 g/ 1000 g/ 1000 g/ 1000 g/ 1000 g/ wheel wheel wheel wheel wheel wheel Weight before test in mg 5917.1 6009.4 5917.1 6009.4 6421.6 5933.9 Weight after test in mg 5881.3 5982.8 5881.3 5982.8 6389.8 5895.1 Weight loss in mg 35.80 26.60 35.80 26.60 31.80 38.80 Weight loss in % 0.61 0.44 0.61 0.44 0.50 0.65 Average weight loss in % 0.52 0.52 0.57

(42) TABLE-US-00008 TABLE 2d Sample designation Formulation 13 Formulation 14 Cycles 1000 1000 1000 1000 Abrasion wheels H18 H18 H18 H18 Additional weight 1000 g/ 1000 g/ 1000 g/ 1000 g/ wheel wheel wheel wheel Weight before test in mg 5802.7 6226.4 6114.9 6041 Weight after test in mg 5783.5 6176.4 6000.9 5893.5 Weight loss in mg 19.20 50.00 114.00 147.50 Weight loss in % 0.33 0.80 1.86 2.44 Average weight loss in % 0.57 2.15

(43) On the basis of Tables 2a-2d, it is apparent from the formulations 7 and 14, which are not according to the invention, that improvements in a mixture can be achieved neither by the sole use of the wax dispersion nor by the sole use of the polymer dispersion. It is also apparent that significant improvements in abrasion can be achieved only through the combination according to the invention of the two individual components. The best results are achieved with the formulations 9-13, representing the range of the mixing ratio of wax/polyurethane dispersion from about 3:1 to 1:3.

Experimental Series 3: Examination of Further Additives, Such as Polyethylene Dispersions, and of an Emulsion Based on Polydimethylsiloxane

(44) In experimental series 3, the influence of the melting point of the waxes as well as that of emulsions on PDMS is examined (formulations according to the invention: 16, 17, 18; formulations not according to the invention: 15, 19, 20).

(45) TABLE-US-00009 TABLE 3a 15 16 17 18 19 20 [g/l] [g/l] [g/l] [g/l] [g/l] [g/l] Beiphob zeroF 40 60 Polyavin PEN 100 Intermediate product NLDPE 100 Lustraffin SA 88 60 Tubicoat ZWE 60 Erlapon SOL 15 30 Tubicoat Primer LE 32 32 32 32 32 32 Water 34 34 54 54 36.5 78 200 200 200 200 200 200

(46) Solids content of the formulations=20% by weight

(47) TABLE-US-00010 TABLE 3b Sample designation Formulation 15 Formulation 16 Formulation 17 Cycles 1000 1000 1000 1000 1000 1000 Abrasion wheels H18 H18 H18 H18 H18 H18 Additional weight 1000 g/ 1000 g/ 1000 g/ 1000 g/ 1000 g/ 1000 g/ wheel wheel wheel wheel wheel wheel Weight before test in mg 6151.1 6107.7 5926.1 6318.3 5976.9 5999.5 Weight after test in mg 5994.9 5895.8 5773.6 6271.4 5961.7 5973.1 Weight loss in mg 156.20 211.90 152.50 46.90 15.20 26.40 Weight loss in % 2.54 3.47 2.57 0.74 0.25 0.44 Average weight loss in % 3.01 1.66 0.35

(48) TABLE-US-00011 TABLE 3c Sample designation Formulation 18 Formulation 19 Formulation 20 Cycles 1000 1000 1000 1000 1000 1000 Abrasion wheels H18 H18 H18 H18 H18 H18 Additional weight 1000 g/ 1000 g/ 1000 g/ 1000 g/ 1000 g/ 1000 g/ wheel wheel wheel wheel wheel wheel Weight before test in mg 5957.1 5510.5 5746.5 6085.9 6210.4 6028.9 Weight after test in mg 5923 5487.7 5652.5 5878.7 6039.2 5843.3 Weight loss in mg 34.10 22.80 94.00 207.20 171.20 185.60 Weight loss in % 0.57 0.41 1.64 3.40 2.76 3.08 Average weight loss in % 0.49 2.52 2.92

(49) Based on the Tables 3a-3c, it can be seen that the formulations 15, 19 and 20, which are not according to the invention, show virtually no or only insignificant abrasion improvements as compared to the raw fabric. This leads to the conclusion that neither polyethylene dispersions based on HD waxes nor the addition of PDMDS emulsions exhibit an effect in terms of abrasion improvement. Although, with formulation 16, based on a wax dispersion with LD polyethylenes, the average abrasion is improved, this is only by about 45% as compared to the raw fabric. Minimal weight losses by abrasion in a Taber test is obtained with formulations 17 and 18. Both formulations contain waxes or paraffins with melting points below 80° C.

Experimental Series 4: Examination of Further Product Classes

(50) In the experimental series, the effects of two acrylate dispersions and that of a hydrophilic cationic polyurethane dispersion are examined (according to the invention).

(51) TABLE-US-00012 TABLE 4a 21 22 23 [g/l] [g/l] [g/l] Beiphob zeroF 100 100 100 Tubicoat A 17 16 TUBICOAT A 41 19.2 Arristan CPU 32 Water 84 80.8 68 100 100 100

(52) Solids content of the formulations=20% by weight

(53) TABLE-US-00013 TABLE 4b Sample designation Formulation 21 Formulation 22 Formulation 23 Cycles 1000 1000 1000 1000 1000 1000 Abrasion wheels H18 H18 H18 H18 H18 H18 Additional weight 1000 g/ 1000 g/ 1000 g/ 1000 g/ 1000 g/ 1000 g/ wheel wheel wheel wheel wheel wheel Weight before test in mg 6070.7 6392.7 5447.8 6028.4 5553.1 5980.6 Weight after test in mg 6002.4 6368.3 5379.7 5950.2 5482.3 5948.8 Weight loss in mg 68.30 24.40 68.10 78.20 70.80 31.80 Weight loss in % 1.13 0.38 1.25 1.30 1.27 0.53 Average weight loss in % 0.75 1.27 0.90

(54) Based on the Tables 4a-4b, it can be seen that the formulations 21-23 based on wax dispersions in combination with hydrophilic polyurethane dispersions as well as two acrylate dispersions selected by way of example provide a significant improvement in abrasion resistance according to Taber. Here, the dispersions that form rather soft films on drying, such as Arristan CPU and Tubicoat A 17, show better results than those forming rather rigid films, such as Tubicoat A 41. Generally, however, the selection of the wax dispersion seems to show a greater influence than that of the polymer dispersion.

(55) In order to illustrate the effect of the synergistic mixture of a wax dispersion with a polymer dispersion once again clearly, the products previously used in combination are shown in a way not according to the invention as individual components in Tables 5a-5d.

Experimental Series 5: Use of the Products as Individual Components (not According to the Invention)

(56) TABLE-US-00014 TABLE 5a 24 25 26 27 28 29 30 31 [g/l] [g/l] [g/l] [g/l] [g/l] [g/l] [g/l] [g/l] Polyavin PEN 132 (HD) Intermediate 132 product NLDPE (LD) Lustraffin SA 80 88 Tubicoat ZWE 80 Erlapon SOL 100 TUBICOAT A 66 17 TUBICOAT A 79.2 41 Arristan CPU 132 Water 68 68 120 12 100 134 120.8 68 200 200 200 200 200 200 200 200

(57) Solids content of the formulations=20% by weight

(58) TABLE-US-00015 TABLE 5b Formulation Formulation Formulation Formulation Formulation Formulation Sample designation 24 24 25 25 26 26 Cycles 1000 1000 1000 1000 1000 1000 Abrasion wheels H18 H18 H18 H18 H18 H18 Additional weight 1000 g/ 1000 g/ 1000 g/ 1000 g/ 1000 g/ 1000 g/ wheel wheel wheel wheel wheel wheel Weight before test in 5844.4 5994 6147.3 6066 6163.9 6337.7 mg Weight after test in mg 5679.6 5768.3 6020.7 5950.2 6020.8 6238.6 Weight loss in mg 164.80 225.70 126.60 115.80 143.10 99.10 Weight loss in % 2.82 3.77 2.06 1.91 2.32 1.56 Average weight loss in % 3.29 1.98 1.94

(59) TABLE-US-00016 TABLE 5c Sample designation Formulation 27 Formulation 28 Formulation 29 Cycles 1000 1000 1000 1000 1000 1000 Abrasion wheels H18 H18 H18 H18 H18 H18 Additional weight 1000 g/ 1000 g/ 1000 g/ 1000 g/ 1000 g/ 1000 g/ wheel wheel wheel wheel wheel wheel Weight before test in mg 6222.8 6100.5 5882.9 5672.9 6530.7 6208.8 Weight after test in mg 6099.7 5992.6 5753 5501.8 6355.8 5966.5 Weight loss in mg 123.10 107.90 129.90 171.10 174.90 242.30 Weight loss in % 1.98 1.77 2.21 3.02 2.68 3.90 Average weight loss in % 1.87 2.63 3.29

(60) TABLE-US-00017 TABLE 5d Sample designation Formulation 30 Formulation 31 Cycles 1000 1000 1000 1000 Abrasion wheels H18 H18 H18 H18 Additional weight 1000 g/ 1000 g/ 1000 g/ 1000 g/ wheel wheel wheel wheel Weight before test in mg 5873.8 5986.8 6166.8 5815.9 Weight after test in mg 5613.9 5729.4 5966.3 5599.2 Weight loss in mg 259.90 257.40 200.50 216.70 Weight loss in % 4.42 4.30 3.25 3.73 Average weight loss in % 4.36 3.49

(61) Based on the Tables 5a-5d, it is clear that none of the tested products provides an improvement in abrasion resistance as a single component that goes beyond 50% in comparison to the raw fabric. Thus, the products as single components do not get even close to the values of the formulations according to the invention, which provide improvements in abrasion resistance according to Taber of sometimes in excess of 80% compared to the raw fabric.