IE51502B1 - Imparting anti-soiling properties to fibres - Google Patents

Description

The invention relates generally to the conditioning of fibers, esp. textile fibers. It relates particularly to a process for rendering such fibers anti-soiling. .

Chemical compositions are universally applied to S fiber surfaces to improve subsequent processing and handling of the fibers, and/or to impart a particular property thereto Such compositions generally provide lubrication, prevent static build-up, and afford a slight cohesion between adjacent fibers. Exactly what is applied depends in large measure upon the nature -- i.e., the chemical composition -of the fibers, the particular stage in the processing or handling thereof, and the end use in view. For example, compositions denominated spin finishes are applied to synthetic fiber tows, usually after stretching thereof, and IS frequently prior to subsequent processing thereof, including crimping, drying, cutting into staple lengths, carding, drawing, roving, and spinning. Such compositions generally provide lubrication, prevent static build-up, and afford a slight cohesion between adjacent fibers.

The application of chemical compositions to fibers is usually accomplished by contacting the fibers in the form of a tow, a yarn, or cut staple with a solution or an emulsion containing the desired chemical composition, employing standard padding,spraying (or overspraying) techniques.

For quite some time a need has existed in the industry for an effective means to impart anti-soiling properties to fibers, especially those which are used in the fabrication of floor coverings such as carpets and the like.

As a result of considerable research, a number of expedients have been proposed and numerous finish compositions and methods have been developed -- all of which are found wanting in one or more important aspects. That is to say, those which result in the imparting of low-, instead of antisoiling properties to the treated fibers are unacceptable in todays market, which requires products of the highest quality. Moreover, fluorochemical compositions such as Scotchguardand Zepel C, which do impart anti-soiling properties to fibers, are not only very expensive, but often interfere with proper processing of the fibers. As a consequence, the use of such materials is effectively limited to oversprays for finished products such as carpets.

Neutralized phosphate esters of aliphatic alcohols are not new, nor is the utilization of such materials as fiber finishes. In this regard, the following references are considered pertinent. 51503 A. U. S. 2,742,379 discloses amine salts of alkyl esters of pentavalent phosphorus acids and their application to hydrophobic, non-cellulosic fibers in order to impart antistatic properties thereto. The alkyl chains have from 8 to 18 carbon atoms therein, and the esters are prepared by reacting 2 moles of alcohol with one mole of phosphoric 'pentoxide. Not disclosed or even remotely suggested is that anti-soiling properties may be imparted to such fibers if the neutralized phosphate ester has from 12 to 22 carbon atoms in the aliphatic ID chain -- less than 12 carbon atoms being unsatisfactory for this purpose -- and if the ester is prepared by reacting 3 moles of alcohol with one mole of phosphoric pentoxide.

B. U. S. 3,639,233 discloses the employment of a phosphoric acid ester of an ethylene oxide adduct of a is Co to C,n alkyl alcohol as an essential component of a O c U fiber finish composition. In this art, phosphate esters of alkyl alcohols whether ethoxylated or not are considered as essentially equivalent, the choice of one or the other depending upon consideration of water dispersibility and io emulsifying properties, which normally increase upon the introduction of a polyglycol chain. In this regard, b'.S. 3,639,235 teaches the especial utility of the phosphoric acid esters of 2 to 8 mole ethylene oxide adducts of aliphatic alcohols. In sharp contradistinction thereto is the IS recognition in the present invention that even short polyglycol chains on the aliphatic alcohol destroy anti-soiling properties. (See Example 3, infra.) The primary object of the present invention is to provide a process for rendering fibres, especially textile fibres, i anti-soiling. Related objects are to provide acrylic and polyamide fibers which are efficiently handled and readily processed, and which possess anti-soiling properties.

The primary object of the invention is achieved by the provision of a process which comprises applying to fibers, esp. textile fibers, an effective amount of neutralized phosphate ester of an aliphatic alcohol having from 12 to 22 carbon atoms in the chain, the ester having been prepared by reacting about 3 moles of alcohol with one mole of phosphoric pentoxide. Especially advantageous results are achieved when such aliphatic alcohol is a monohydric alcohol, and when this aliphatic monohydric alcohol is saturated. Highly efficacious results are obtained when a low-soiling spreading agent, such as a sodium dialkyl sulfosuccinate, is employed in admixture with the neutralized phosphate ester of the aliphatic alcohol.

One of the related objects of the invention is achieved by the provision of an acrylic fiber having antisoiling properties, the fiber having incorporated thereon a finish comprising from about 0.1 to 1 percent by weight of the neutralized phosphate ester of a saturated aliphatic monohydric alcohol having from 12 to 22 carbon atoms in the chain, the ester having been prepared by reacting about 3 moles of alcohol with one mole of phosphoric pentoxide. Highly advantageous results are achieved when a low-soiling spreading agent -- esp. a sodium dialkyl sulfosuccinate in an amount sufficient to provide from 1 to about 10 percent by weight- of the incorporated finish -is employed in admixture with the neutralized phosphate ester of the saturated aliphatic monohydric alcohol.

Another related object of the invention is achieved by the provision of a polyamide fibre having anti-soiling neutralized phosphate ester of a saturated aliphatic monohydric alcohol having from 12 to 22 carbon atoms in the chain, the ester having been prepared by reacting about 3 moles of alcohol with one mole of phosphoric pentoxide. Highly advantageous results are achieved when a low-soiling spreading agent -- esp. a sodium dialkyl sulfosuccinate in an amount sufficient to provide from about 1 to about 10 percent by weight of the incorporated finish is employed in admixture with the neutralized phosphate ester of the saturated aliphatic monohydric alcohol.

IP For a more complete understanding of the present invention, reference should be made to the following detailed description of the preferred embodiments thereof.

The neutralized phosphate ester of an aliphatic alcohol having from 12 to 22 carbon atoms in the chain, as S' employed in the present invention, is one of many available commercially. Such are commonly prepared by reacting the chosen aliphatic alcohol with P2°5> which results in the formation of a mixture of mono- and diester. The residual acidity of this reaction product is then neutralized, as with caustic or an amine. The chosen aliphatic alcohol may be saturated or unsaturated; and it may have a straight chain or a branched configuration. Although monohydric alcohols have been especially advantageously employed, polyhydric alcohols are not considered to be lacking in utility. In any zy event, it is essential that the aliphatic chain be no shorter than 12 carbon atoms and that there be no polyglycol branches (howsoever short) on the. aliphatic alcohol chain, since either condition will vitiate the otherwiseimparted anti-soiling properties, as is evidenced by the specific Examples, infra^ 5150 Moreover, the ester should be prepared by reacting about 3 moles of alcohol with one mole of phosphoric pentoxide.

The fibers to which anti-soiling properties are imparted are advantageously any of the textile fibers, especially man-made textile fibers such as acrylic and polyamide. Of particular importance are (a) acrylic fibers which have been spun from solutions of acrylonitrile polymers in inorganic solvents (see, e.g., U.S. 2,916,348 and U.S. 2,558,730) or organic solvents (see Knudsen, Textile Research Journal, 33, 13-20 (1963) ); and (b) polyamide fibers such as polycaprolactam which are melt spun employing standard techniques well known in the art (see Moncrieff, Man Made Fibers, John Wiley § Sons, Inc., Sth Ed., pp. 326 - 335 and 543 - 561 (1970) ).

The neutralized phosphate ester of the aliphatic alcohol is efficaciously applied to the fibers as a solution or dispersion, esp. as an aqueous dispersion, by any of a number of standard means such as spraying padding, or the like, at virtually any stage in the processing of the tow, staple or spun fibers, advantageously after streathing thereof, or after the fabrication of the fibers or a yarn containing them into a finished construction, such as a floor covering (e.g., a carpet). To be effective in. imparting anti-soiling properties to the fibers, the neutralized phosphate ester 7. of the aliphatic alcohol is employed in an amount sufficient to provide from about 0.1 to about 2 percent by weight, based upon the weight of the fibers. When acrylic fibers are utilized, the effective amount of neutralized phosphate ester is from about 0.1 to about 1 percent by weight; when polyamide fibers such as polycaprolactam are utilized, the effective amount of neutralized phosphate ester is from about 0.2 to about 2 percent by weight.

In order to enhance the uniformity of application of the neutralized phosphate ester of the aliphatic alcohol, a low soiling spreading agent is beneficially employed in simple admixture therewith. This spreading agent, which is conveniently and advantageously provided in an amount sufficient to provide from about 1 to about 10 percent by weight of the incorporated fiber finish, is profitably a sodium dialkyl sulfosuccinate, esp. the dioctyl, di-isobutyl, diamyl, dihexyl, di-tridecyl, or di-octadecyl. Such spreading agents are disclosed in U. S. 3,306,850 and U. S. 3,428,560. Other spreading agents which might be employed are sulfo succinamates, as well as sodium alkyl naphthalene sulfonate.

The present invention, especially its primary and related objects and multiple benefits, may be better understood by referring to the'following examples, which are set forth for illustrative purposes only.

Example 1 Acrylic carpet fiber was stock dyed to a yellow shade, oversprayed with 8¾ water, carded, spun into carpet yarn, and tufted into a carpet of level loop construction. No processing lubricant or antistat was used. Test samples of 2 x 2 size were cut and the face sprayed with 7% water and dispersed therein 0.5% finish solids (percentages are based on the weight of the carpet sample). The samples were dried for 2 hours at 115°C and let cool for 10 minutes at ambient temperature. All samples of one series were then shaken with an excess of soil in a glass jar for 10 minutes. The samples were then vacuum cleaned. The soil consisted of carpet sweepings from a vacuum cleaner (through 100-mesh screen) with 0.65% carbon black and 0.65% Nujol mineral oil added. The reflectance at 700mu was determined in a Large Sphere Color Eye.

The percent reflectance R was converted into the Kubelka-Munk 15 function K/S which equals (1-R)i/2R and is an app'roximate measure of colorant (or dirt in this case) concentration. By subtracting K/S obtained on an unsoiled carpet piece of the same kind from the K/S of a soiled sample, a comparative reading of the amount of dirt on each sample can be obtained. Experimental data on hydrogenated tallow alcohol (HTA containing 4% C,„, 30% Ci4, 65% Ci4, 1% Cso) phosphate salts are shown in Table I. DEA = diethanolamine: TEA = Triethanolamine.

All of the phosphate esters of the present invention which are formed in the instant and following examples were prepared using a molar ratio of alcohol to phosphoric pentoxide of 3/1.

TABLE I Series No Oversprav K/S AK/S 4K/S Change Soil Control, 1 None (unsoiled) 0.0526 Water only (Control) 0.538 0.485 30 HTA Phosphate K-salt 0.291 0.238 - 51 HTA Phosphate DEA salt 0.502 0.449 -7 7 Water Only (Control) 0.645 0.592 HTA Phosphate K-salt 0.441 0.388 - 55 HTA Phosphate Na-salt 0.414 0.561 -59 35 HTA Phosphate TEA salt 0.481 0.428 -28 HTA Phos. Morpholine salt 0.440 0.387 -35 Ii : can be seen that all over spray finishes applied decrease t! soiling, i.e. have antisoiling properties.

In Table II, a similar comparison is shown between phosphate esters of different alkyl chain length. The chains are unbranched except where indicated.

TABLE II Series No Overspray K/S ΔΚ/S Soil ΔΚ/S Change from Control, % 3 None (Unsoiled) 0.0526 Water Only (Control) 0.537 0.484 5 Ce-Cio Alcohol Phosphate 1.535 1.482 + 206 K-salt Iso-Cto Alcohol Phosphate 1.570 1.517 +213 K-salt Lauryl Alcohol Phosphate 0.469 0.416 -14 10 K-salt It can be seen that the phosphate esters made from Ca-Cio alcohols lead to more soiling than the control. Contrary to this', lauryl (Cu alcohol phosphate imparts antisoiling properties..

Example 2 Acrylic carpet was made from stock dyed (yellow) fiber but the carpet construction in this series was cut pile. Otherwise, the experimental steps and tests were the same as described in Example 1 Table III shows data confirming that C8-Ci0 alcohol phosphates do no confer antisoiling properties but Ci2 (lauryl) alcohol phosphate doe Furthermore, C14 and hydrogenated tallow (Ci*-C20)alcohol phosphates are shown to be antisoiling finishes.

TABLE III Series No Overspray K/S ΔΚ/S Soil ΔΚ/S Change From Control 4 None (Unsoiled) 0.0691 25 Water Only (Control) 0.858 0.789 Ca-Cxo Alcoh. Phos. K-salt 1.883 1.814 +130 iso-Cic Alcoh. Phos. K-salt 1.920 1.851 +135 Lauryl Alcoh. Phos. K-salt 0.797 0.728 -8 5 Water Only (Control) 0.631 0.562 C,„ Alcoh. Phos. K-salt 0.450 0.381 -32 30 Cia-C2tl (HTA) Phos. K-salt 0.475 0.406 -28 Example 3 The sample preparation was the same as in Examples 1 and 2, ΑΠ samples are stock dyed (yellow). The carpet construction is noted in the table. This example is to demonstrate the deleterious effect of ethoxylation on the alkyl alcohol. In other words, phosphated polyglycol alkyl esters do not show antisoiling properties.

TABLE IV Series No. Carpet Construct. Overspray K/S Δκ/S soil Δκ/S Change From Control 10 6 Cut Pile None (Unsoiled) 0.0691 Water Only (Control) 0.631 0.562 C-|2_Ci4 Alcoh.+3E0, Phos. K- 1.700 1.631 +190 ^16-C18 A1coh.+6E0, Phos. K- 1.811 1.742 +210 7 Cut Pile Water Only (Control) 0.660 0.591 15 Oleyl Alcoh.+5E0, Phos. K- 1.566 1.497 +153 +7E0, " K- 1.322 1.253 +11211 +9E0, K- 1.621 1.552 +163 8 Level Loop None (Unsoiled) 0.0526 Water Only (Control) 0.355 0.302 20 C1fi-C,8 Alcoh.+IOEO, Phos.K- 0.961 0.908 +200 ...... 15E0, Phos.K- 0.970 0.917 +204 ...... 20E0, Phos.K- 0.878 0.825 +173 Example 4 Acrylic carpet fibre was made with 0.2% hydrogenated tallow alcohol phosphate, K-salt as the finish applied to the tow, before crimping and cutting into staple. This fibre was oversprayed with 8% water, carded, spun into yarn, and tufted into a level loop carpet of natural colour (Sample 1). Another part of the staple was oversprayed with an additional 0.4% of the same finish besides 8% water and made into a level loop carpet (Sample 2) Both carpets were tested in the Tetrapod Accelerated Wear Tester in contact with carpet sweepings from a vacuum cleaner. Samples were removed after ,000; 15,000; and 30,000 drum rotations (cycles).

TABLE V Sample No. Unsoiled % Reflect. K/S 10,000 K/S 15,000 K/S 30,000 Cycles K/S K/S Increase Over unsoiled 1 73.55 0.0476 0.155 0.311 0.335 604 35 2 72.24 0.0533 0.152 0.234 0.245 360 It can be seen that an increase in the finish by a factor of 3 results in a decrease in soiling by a factor of 1.7. 502 Example 5 Nylon 6 carpet staple was made into a level-loop carpet. After piece dyeing (yellow) and drying, 1% hydrogenated tallow alcohol (HTA) phosphate, K-salt, dispersed in 3% water (percentages are based on carpet weight) were brushed into the face of a 2 x 2" (5.1 x 5.1 cm) piece of this carpet. After drying at 80°C for 2 hours, followed by 15 minutes at 115°C, and cooling for 10 minutes, this sample and a control (water brushed on and treated in a like manner) were shaken with soil (composition given in Ex. 1) in a glass jar for 10 minutes and then vacuum cleaned. The results of reflectance measurements are given in Table VI.

TABLE VI Finish K/S ΔΚ/S SoilAK/S Change from Control, % None (unsoiled) 0.0363 Water Only Control 0.155 0.119 HTA Phosphate K-salt 0.139 0.103 -13 Example 6 Two commercial level-loop acrylic heater type carpets containing 70% fibre of natural colour were floor tested. The natural fibre in Carpet No. 1 was made with 0.25% hydrogenated tallow alcohol phosphate, K-sal as the finish applied to the tow on the fibre production line before crimpinc and cutting into staple. The natural fibres in Carpet No. 2 was made in the same way, but with 0.25% n-octyl/n-decyl alcohol phosohate, K-salt, as the finish. Everything in fibre processing and carpet tufting was the same for both carpets. The two carpets were laid on the floor side-by-sidc in a heavy traffic area. After 22,000 steps and vacuum cleaning, the difference in soiling could clearly be seen. Carpet No. 2 had picked up significanly more soil than Carpet No. 1. Table VII shows reflectance measurements similar to those reported in the previous examples.

TABLE VII Unsoiled Soiled on Floor Carpet--- - ^K/S ^K/S Increase No. % Reflect. K/S ^Reflect K/S Soil Over Unsoiled, % 61.59 0.1198 54.46 0.1904 0.0706 59 61.80 0.1181 50.75 0.2390 0.1209 102 It can be seen that the carpet containing natural fibre with Cg-C^Q alcohol phosphate picked up 73% more dirt than the one containing the same proportion of natural fibre with hydrogenated tallow alcohol phosphat Example 7 Acrylic carpet fiber was made with 0.25¾ of a finish consisting of 95¾ hydrogenated tallow alcohol phosphate, K-salt, and 5¾ sodium dioctyl sulfosuccinate. The finish was applied to the tow, before crimping and cutting into staple. This fiber was oversprayed with 8¾ water, carded, spun into yarn, and tufted into a level-loop carpet of natural color (Sample 1). In a paralled experiment, the finish consisted of hydrogenated tallow alcohol phosphate only (Sample 2.). Both carpets were tested in the Tetrapod Accelerated Wear Tester in contact with carpet sweepings from a vacuum cleaner. Samples were removed after 10,000 and 20,000 drum rotations (cycles), vaccum cleaned, and reflectance measurements made for judgement of soil pickup. The addition of the spreading agent did not interefore with the low-soiling characteristics of the phosphate ester finish.

Example 8 In accordance with the procedure of Example 1 of the present application, acrylic carpet fiber was stock dyed to a yellow shade, oversprayed with 8¾ water, carded, spun into carpet yarn, and tufted into a carpet of level loop construction.

No processing lubricant or antistat was used. Test samples of 2 x 2 size were cut and the face sprayed with 7¾ water and dispersed therein 0.5¾ finish solids (percentages are based on the weight of the carpet sample). The samples were dried for 2 hours at 115° and let cool for 10 minutes at ambient temperature. All samples of one series were then shaken with an excess of soil in a glass jar for 10 minutes.

The samples were then vacuum cleaned. The soil consisted of carpet sweepings from a vacuum cleaner (through 100-mesh screen) with 0.65¾ carbon black and 0.65¾ Nujol mineral oil added. The reflectance at 700 mu was determined in a Large Sphere Color Eye. The percent reflectance R was converted into the Kubelka-Munk function K/S which equals (1-R)£/2R and is an approximate measure of colorant (or dirt in this case) concentration. By subtracting K/S obtained on an unsoiled carpet piece of the same kind from the K/S of a soiled sample, a comparative reading of the amount of dirt on each sample can be obtained. Experimental data on hydrogenated tallow alcohol (HTA containing 4Ϊ Cia, 30¾ Cig, 65¾ Cjo. 1¾ C,n) phosphate salts are shown in Table VIII below. Due to the presence of an additional filter in the Large Sphere Color Eye, the K/S values shown in Table VIII below are higher than those shown in Table I of Example I of the application, but there is strict comparability between the values in each group.

TABLE VIII Series No. Overspray % Reflectance K/S Δ K/S Soil 9 None (unsoiled) 35.28 0.594 HTA Phosphate, K- b salt, Alcohol P20g3/l 24.62 1.154 0.560 HTA Phosphate, Ksalt, Alcohol/P^O^/l 20.69 1.520 0.926 10 None (unsoiled) HTA Phosphate, K- 35.28 0.594 - 10 salt, Alcoholy^O^/l 24.16 1.190 0.596 HTA Phosphate, Ksalt, Alcohol/PzO^/l 20.45 1.547 0.953 HTA Phosphate, Ksalt, Alcohol/P-jOc//! , 20.41 1.552 0.958 Larger-scale product From Table VIII it can be seen that the carpet samples with the HTA phosphate made at a molar ratio of 2/1 are unacceptable in that they soil 60 - 65¾ more than those with HTA phosphate made at a molar ratio of 3/1.

Claims (9)

1. A process for imparting anti-soiling properties to fibres, comprising applying to the fibres the neutralized phosphate ester of an aliphatic alcohol having from 12 to 22 carbon atoms in the chain, the ester having been prepared by reacting about 3 moles of alcohol with one mole of phosphoric pentoxide, the neutralized phosphate ester being applied alone or in admixture with a spreading agent.

2. A process as claimed in claim 1, wherein the aliphatic alcohol is a monohydric alcohol.

3. A process as claimed in claim 2, wherein the aliphatic monohydric alcohol is saturated.

4. A process as claimed in claim 1, 2 or 3, wherein the amount of neutralized phosphate ester is from about 0.1 to 2 percent by weight based on the weight of the fibres.

5. A process as claimed in claim 1, 2, 3 or 4, wherein the neutralized phosphate ester or the neutralized phosphate ester/spreading agent mixture is applied in the form of an aqueous solution or dispersion.

6. A process as claimed in claim 1, 2, 3, 4 or 5, wherein the spreading agent is a sodium di alkyl sulphosuccinate.

7. A process as claimed in claim 6, wherein the succinate is the dioctyl, d-isobutyl, diamyl, dihexyl, di-tridecyl or di-octadecyl succinate.

8. A process for imparting anti-soiling properties to fibres, substantially as described herein by way of Example.

9. Fibre treated by a process according to any of claims 1 to 3 or 6.