US3592684A - Nylon and polyester fibers having improved soil resistance - Google Patents

Abstract

POLYAMIDE AND POLYESTER FIBERS ARE RENDERED HIGHLY RESISTANT TO SOILING BY APPLYING TO THE FIBERS DURING THE MANUFACTURE THEREOF A FINISH COMPRISED OF A WATER SOLUBLE LUBRICATING AGENT AND A ZIRCONIUM COMPOUND, AND SUBSEQUENTLY SCOURING THE FIBERS TO REMOVE SUBSTANTIALLY ALL OF THE LUBRICATING AGENT WHILE A MAJOR PORTION OF THE ZIRCONIUM COMPOUND REMAINS ADHERED TO THE FIBER.

Description

3,592,684 NYLON AND POLYESTER FIBERS HAVEIG IMPROVED SOIL RESISTANCE Andrew I. Smith, Pensacola, Fla., assignor to Monsanto Company, St. Louis, M0.

N Drawing. Continuation-impart of application Ser. No. 568,724, July 29, 1966. This application Dec. 26, 1968, Ser. No. 787,269

Int. Cl. D06m 11/04 US. Cl. 117102L 6 Claims ABSTRACT OF THE DISCLOSURE Polyamide and polyester fibers are rendered highly resistant to soiling by applying to the fibers during the manufacture thereof a finish comprised of a Water soluble lubricating agent and a zirconium compound, and subsequently scouring the fibers to remove substantially all of the lubricating agent While a major portion of the zirconium compound remains adhered to the fiber.

CROSS-REFERENCE TO RELATED APPLICATION This application is a continuation-in-part of my copending application Ser. No. 568,724, filed July 29, 1966, now abandoned.

BACKGROUND OF THE INVENTION (1) Field of the invention This invention relates polyamide and polyester fibers and textile articles produced therefrom which are highly resistant to soiling, and to a method for treating the fibers during the manufacture thereof in order to render the finished textile article soil resistant.

(2) Description of the prior art Soiling of synthetic and natural fibers has always been recognized as a problem by the textile industry. The recent popularity of synthetic fibers for use in carpets and especially for carpets and other textile goods in light or patsel colors has caused the consumer and the industry to become even more aware of the problem. As a consequence, the synthetic fiber industry has attempted to improve the soil resistance of its products by modifying the fiber composition either internally with fiber additives or externally by the application of special finishes.

Polyamide and polyester fibers, in particular, have found extensive use in textile carpet goods, and many attempts have been made to increase their resistance to soiling. One of the most promising methods prior to this invention has involved the treatment of finished carpets with dispersions of microparticles, such as silica or the oxides of aluminum, titanium, and zirconium. The treatment of finished carpets, however, requires additional processing steps and equipment at the carpet mill, and results in additional expense to the consumer. It would, therefore, be far more desirable for the fiber producer to treat the fibers during the manufacture thereof, especially if such a treatment could be carried out on existing equipment and at minimum additional expense.

SUMMARY OF THE INVENTION According to this invention, polyamide and polyester fibers can be rendered soil resistant by applying to the fibers a finish comprised of (A) a water-soluble lubricating agent and (B) a zirconium compound selected from the group consisting of hydrous zirconia and water-soluble salts of zirconium, drying the treated fibers, and subsequently scouring the fiber to remove substantially all of United States Patent 3,592,684 Patented July 13, 1971 the lubricating agent while a major portion of the zirconium compound remains adhered to the fiber. The watersoluble lubricating agent is preferably an alkylene oxide derivative selected from the group consisting of alkylene glycol, polyalkylene glycol, substituted alkyl, aryl, and alkylaryl poly(oxyalkylene) glycol, and alkylene glycolfatty acid condensation products. The lubricant and the zirconium compound are applied to the fiber from an aqueous solution in an amount suificient to deposit on the fiber from 0.2 to 20 percent of the lubricating agent and from 0.05 to 1.0 percent of zirconium, based on the weight of the fiber. The process employed is not only relatively inexpensive and simple, but is readily adaptable to continuous production line manufacture of such fibers.

It is therefore an object of this invention to provide a process for treating polyamide and polyester fibers during the manufacture thereof in order to impart soil resistant properties to textile articles produced from the fibers.

It is a further object of this invention to provide a finish composition which when applied to melt spun polyamide and polyester fibers facilitates the drawing and processing of these fibers into finished textile articles having exceptional resistance to soiling.

DESCRIPTION OF THE PREFERRED EMBODIMENTS Among the alkylene glycols which may be employed in the process of the present invention are those containing 2 to 20 carbon atoms. Illustrative of such glycols are ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, hexamethylene glycol, decamethylene glycol, glycerine, hexylene glycol, 1,5-pentane diol, e-ethyl-l, 3-hexane diol, 2- ethyl-2-butyl-1, 3-propane diol, 2,2-diethyl-l, 3 propane diol, neopentyl glycol. The preferred alkylene glycol for use in the process of the present invention is triethylene glycol.

The preferred polyalkylene glycols are the polyethylene and polypropylene glycols which have a relatively low molecular weight of from about 200 to 2000 and which are liquid at below about 60 C.

Substituted aryl poly(oxyalkylene) glycols generally useful in the practice of this invention are of the type described in detail in US. Patent 3,333,983, where the products are disclosed to be useful as antistatic agents and lubricants for synthetic and natural fibers. In the preparation of these substituted glycols, an aromatic compound containing at least one phenolic hydroxy group is condensed with from about 9 to 19 moles of ethylene oxide per phenolic hydroxy group to form an aryl phenoxypoly- (oxyethylene) glycol. A particularly useful and preferred compound is obtained by condensing a methyl benzyl phenol with 9 to 15 moles of ethylene oxide.

Useful alkylene oxide-fatty acid condensation products include those obtained by reacting from 9 to 18 moles of ethylene oxide with one mole of a fatty acid having from 12 to 18 carbon atoms. A particularly preferred compound is polyethylene glycol molecular Weight (M.W.) 600' monooleate.

Sufiicient lubricant must be applied to permit processing of the fiber into yarn and finished textile articles. The optimum amount of any particular lubricant required de pends upon the compound selected since the various compounds have different lubricating properties.

It is contemplated that lubricating agents other than those enumerated above may be used in combination with the zirconium compounds according to the teaching of this invention with good results. This invention is accordingly not intended to be limited to any specific lubricating agents, but may include generally those lubricants which meet the critical requirements of being watersoluble and unreactive with both the fiber substrate and the zirconium compounds.

In a preferred embodiment of the present invention, there is added to the fiber in conjunction with the watersoluble lubricant mentioned above, either hydrous Zirconia or a water-soluble salt of zirconium. This zirconium compound may be added prior to, with, or subsequent to the application of the lubricant. Generally, it is more convenient to add the lubricant and the zirconium salt simultaneously. Among the water-soluble zirconium salts which are useful in the process of the present invention are zirconium acetate, zirconium chloride, zirconium bromide, zirconium oxalate, zirconium sulfate, and the like. The zirconium compound should be added to the fiber in an amount sufficient to provide at least 0.05 percent of zirconium, measured as zirconium dioxide, based on the weight of the fiber. Generally, the zirconium compound is added in an amount sufficient to provide between 0.05 percent and 1.0 percent of the zirconium onto the fiber. Amounts greater than 1.0 percent of the zirconium may be added to the fiber; however, the benefits accruing from the application of such additional amounts do not warrant it economically.

A particularly attractive aspect of the process of the present invention is that it brings about improvement in the soil resistance of fibers which have previously been drawn. Thus, it is a relatively simple matter to apply the process of this invention to the production line manufacture of fibers at a place subsequent to the drawing step. For example, when melt spun fibers are produced in the spin-draw process, the fibers may be treated in accordance with the process of this invention after the drawing and prior to the step in which the fibers are wound on a bobbin for storage. In my copending application Ser. No. 568,724, filed July 29, 1966 and now abandoned, there is disclosed a process for treating polyamide fibers to improve their soil resistance by coating the fiber with a glycol finish compound and thereafter drawing the fiber between 3.5 and 5.5 times over a draw pin heated to a temperature of 135 C. to 220 C. It has been found that the soil resistance of the yarns produced by the process described in said copending application may be even further improved by further treating the fibers in accordance with the process of this invention. In such a case, two relatively simple process steps, that is, applying glycol to the fiber and drawing the fiber and thereafter applying a water-soluble finish and a zirconium compound in accordance with the process of this invention results in polyamide fibers which are greatly improved in their soil resistance over heretofore known fibers.

The present invention may likewise be practiced on undrawn fibers by applying the water-soluble finish and Zirconium compounds to the fibers at a step prior to or during the drawing step. In this event, no other finishes are required in the production of the melt spun fibers.

The fibers treated in accordance with this invention are characterized in that they contain on the surface thereof from 0.2 to percent by weight of a selected lubricating agent and from about 0.05 to 1.0 percent by weight of a zirconium compound analyzed as zirconium dioxide. Fibers thus treated are processed into the desired textile goods such as fabrics, sweaters, and carpets by weaving, knitting, and tufting using conventional equipment and procedures. The finished goods are generally subjected to a wet treatment such as dyeing, bleaching, scouring, etc. before being readied for the ultimate consumer. During this treatment, substantially all of the water-soluble lubricant applied to the fiber is removed, while generally from 15 to about 50 percent of the zirconium compound is removed leaving a major portion of the originally applied zirconium compound on the surface of the fiber.

The final fiber product which demonstrates improved soil resistance is characterized only by containing a small amount of Zirconium tightly affixed to the fiber surface. The amount of zirconium remaining in general is from about 0.03 to 0.85 percent by weight, analyzed as zirconium dioxide.

It is contemplated that the treated fibers containing the selected Water-soluble lubricant and the zirconium compound may be dyed or scoured while in a yarn or staple form and before being processed into the final textile end product. In this event, it will be necessary to reapply a lubricating finish to the yarn or staple to facilitate further processing. In order that the soil resistant properties imparted to the fibers by the process of this invention are not defeated, care should be taken to select a lubricating finish which is water-soluble and which can be removed from the final textile product by simple wet treatment.

Fibers useful in the practice of this invention include primarily the polyamides and polyesters, although other melt spun fibers, such as the polyolefins are also considered to be within the scope of this invention. The polyamide fibers, generally known as nylons, are the high molecular weight linear polymers which contain recurring carbonamide groups as an integral part of the main polymer chain separated by at least two carbon atoms. Broadly speaking, nylon polymers are of two general types. One type of nylon is obtainable from polymerizable monoaminomonocarboxylic acids and their amideforming derivatives, for example, e-caprolactam and apyrrolidone known generically in their polymerized form as nylon-6 and nylon-4, respectively. The other type of commercial nylon is obtainable from suitable primary or secondary diamines and suitable dicarboxylic acids or amide-forming derivatives thereof. Among the latter type are polymers formed by the reaction of tetramethylene diamine, pentamethylene diamine, hexamethylene diamine and the like with adipic acid, suberic acid, sebacic acid and the like. The polymerization product of hexamethylene diamine and adipic acid has the generic name of Nylon-66.

The polyesters and copolyesters are those produced by heating one or more glycols of the series HO(CH OH, where n in an integer of from 2 to 10, with one or more dicarboxylic acids or ester-forming derivatives thereof. Of particular interest is the polyethylene terephthalate fiber which has found widespread commercial acceptance in woven, knitted, and tufted goods.

In the examples, carpet samples were blank-dyed by boiling for 60 minutes at a 35:1 liquor to carpet ratio in water containing 0.25 percent of an anionic surfactant detergent. After cooling, the carpet pieces were washed well seven times with deionized water using for each wash about a 20:1 liquor to carpet ratio. The carpet samples were squeezed well by hand after each washing, but particularly after the last washing and permitted to dry in the atmosphere for at least 40 hours before the soiling tests were made.

The soiling and cleaning procedure set forth in the examples may be described as follows: 2-inch squares of the blank dyed carpets were soiled by tumbling at 60 r.p.m. for one hour with 15 weight percent of synthetic soil in a one-gallon wide mouth jar containing internal bafiles to insure adequate mixing. The samples were thereafter cleaned in two steps; first, the samples were vacuumed with a nozzle attached to a laboratory vacuum line through a length of rubber pressure tubing. The samples were cleaned three times in each direction. All easily removed dirt was taken off in this step. The second step consisted of vacuuming the samples with a hand vacuum cleaner through a half-inch diameter adaptor on the end of the cleaner hose. Again, the samples were vacuumed three times in each direction with overlap of the adaptor path. The synthetic soil which was used in this soiling test and which is thought to be representative of a cross section of soil across the United States has the following composition:

Percent Sifted sawdust 52.5 Sifted peat moss 22.3 Calcium carbonate 10.9 Animal charcoal powder 6.6 Silica 2.1 Cement 2.1 Kaolin clay 2.1 Mineral oil 1.1 Furnace black 0.2 Red iron oxide 0.1

EXAMPLE I This example illustrates the soil resistance of untreated polyamide fibers. Commercial carpet yarn (68 filaments, 1250 denier) was prepared by draw texturing yarn spun with one percent of commercial finish. The yarn was plied triple and made into carpet on polyurethane backing. After scouring at 71 C. for 30 minutes at a 30:1 liquor to carpet ratio in an aqueous solution containing 0.5 percent tetrasodium pyrophosphate and 0.5 percent detergent, the sample was blank-dyed, washed and soiled as described above. The green tristimulus values of the unsoiled and soiled samples were 85.2 and 40.3 percent, respectively. The percent loss in brightness of the yarn due to retained soil was therefore 52.6 percent.

EXAMPLE II Carpet yarn was made in a manner similar to that described in Example I with the exception that the finish 95/5 triethylene glycol, polyethylene glycol M.W. 600 mono-oleate, was applied to the yarn in an amount sufficient to provide 4.8 percent triethylene glycol, polyethylene glycol M.W. 600 mono-oleate mixture, based on the weight of the yarn, to the yarn. Thereafter, the yarn was treated with a 3.0 percent zirconium solution which was applied uniformly by means of a finish Wheel. The zirconium solution. was prepared by dissolving 6.0 grams of hydroxylamine sulfate in 453 ml. of water. This solution was added with good stirring to 40.9 grams of a 22 percent solution of zirconium acetate. The pH of the solution was 3.9 and the solids content of the solution was 3.0 percent. The ZrO content of the yarn after treatment was 0.31 percent. The yarn was made into carpet on polyurethane backing and soiled after being blank-dyed as described above. 'The brightness values before and after soiling were 82.7 and 46.0 percent. The percent loss in brightness was 44.4 compared to 52.6 for the control yarn of Example I.

EXAMPLE III Yarn prepared as in Example II with the 95/5 triethylene glycol, polyethylene glycol M.W. 600 monooleate mixture, was coated uniformly after draw texturing with 4.1 weight percent of triethylene glycol by the application of 50% aqueous triethylene glycol solution with the use of a finish wheel.

Thereafter, a 3.0 percent zirconium solution as described in Example II was applied uniformly to the yarn in an amount sufficient to provide 0.29 weight percent of zirconium dioxide on the yarn. The yarn was made into carpet, blank-dyed and soiled as described above. The brightness values before and after soiling were 84.2 and 49.6 percent. The percent loss in brightness was 41.1 as compared to 52.6 percent for the untreated control yarn of Example I.

EXAMPLE IV Yarn prepared as in Example 11 was treated after drawtexturing with 3.0 percent zirconium solution as described in Example II so that the yarn contained 0.29 percent of zirconium dioxide solids distributed uniformly on the yarn surface. Immediately after the zirconium addition, a 50% aqueous triethylene glycol solution was applied uniformly to the yarn in an amount sufficient to provide 7.8 weight percent triethylene glycol on the yarn. The yarn was made into carpet and treated as described above. The brightness values of the yarn were 82.0 and 51.0 percent before and after soiling, respectively. The percent loss in brightness was 37.8.

EXAMPLE V EXAMPLE VI Yarn prepared as described in Example H was treated after draw texturing and securing with aqueous colloidal zirconia to give two yarns, one containing 0.45 weight percent and another containing 0.90 weight percent zirconia solids on the yarn surface. No glycol or polyethylene glycol lubricant was applied to either of these yarns. The yarn was made up into carpets, blank dyed, and soiled as described above. The percent loss in brightness of these samples was 46.6 and 41.0 percent, respectively both significantly greater than the 37.6 loss experienced by the yarn treated with both zirconia and a glycol according to Example V. This demonstrates the interaction between the zirconium compound and the lubricant and the advantage of the combination over zirconium alone.

EXAMPLE VII A series of yarn samples were prepared according to the method of Example 11, with the exception that the yarns were treated with polyethylene glycol mono-oleate M.W. 1000 and the aqueous zirconium solution as described in Example II. Carpet samples constructed from the treated yarns were blank dyed, soiled, and measured for brightness before and after soiling as described above. The amounts of zirconium (as ZrO and polyethylene glycol mono-oleate M.W. 1000 applied to the yarn samples and the results of the boiling tests are given below:

Percent on yarn Brightness Polyethylene glycol Percent mono-oleate Original soiled loss The above data illustrate the improvement in soil resistance to be obtained by treating yarn spun with watersoluble lubricant with small amounts of ZrO and polyethylene glycol mono-oleate M.W. 10 00. The percent loss in brightness was about 43 for the treated samples compared to 53 for the untreated control. Similar results may be obtained by substituting a polypropylene glycol for the polyethylene glycol mono-oleate M.W. 1000.

EXAMPLE VIII The procedure of Example II was repeated applying polyethylene glycol M.W. 600 mono-oleate and zirconium acetate to the yarn from a single bath at three different concentrations. The amount of zirconium remaining on the yarn after blank-dyeing to remove the water-soluble lubricant was measured with the following results:

Molecular \veight=600.

In the following examples, polyamide polymer flake containing no titanium dioxide and having a relative viscosity of 50 was melt spun to produce a 17 filament yarn bundle of 1000 total denier. Deionized water was applied to the spun yarn in order to prepare finish-free spin cakes. Four spin cakes were plied together for draw texturing with the application of various finishes to provide a final yarn of 68 filaments and about 1200 denier. Carpet samples made from the textured yarns were scoured and blank dyed and evaluated for soiling as described above. The following examples illustrate the efiect of specific finish compositions on the soiling propensity of the final carpet, and thereby further demonstrate the advantages of the method of the instant invention over the prior art.

EXAMPLE IX Sample 1 A zirconium acetate solution equivalent to 3.0 percent of the oxide was applied in an amount suflicient to coat the yarn with 0.17 percent of the oxide.

Sample 3 A zirconium acetate-hydroxylamine sulfate solution described in Example II was applied in an amount suificient to deposit 0.30 percent of the oxide on the yarn.

Sample 4 A 3.0 percent suspension of colloidal zirconia was applied in an amount suflicient to deposit 0.43 percent zirconia solids on the yarn.

Carpets prepared from the above yarns were blank dyed and evaluated for soiling with the following results:

Brightness Percent Original Soiled B loss It is apparent from the above results that there is no appreciable ditference between the samples and that the application of zirconium to yarn finished with the conventional water-insoluble finish has no significant affect on the soiling characteristics of the yarn.

EXAMPLE X The procedure of Example VII was repeated except the conventional finish was replaced with a completely watersoluble finish comprising a 7.5 percent aqueous solution of polyethylene glycol M.W. 600 mono-oleate, applied to give a draw-textured yarn containing 0.5 percent of the polyethylene glycol M.W. 600 mono-oleate lubricant. Three additional samples corresponding to Samples 2,

3, and 4 of Example VII were prepared in a like manner. Levels of zirconium applied to the yarn, and the results of the carpet soiling evaluation are shown below.

Carpet brightness Zirconium Percent level Original Soiled 13 loss The above data illustrate the reduction in percent brightness loss due to soiling resulting from the application of zirconium compounds over a water-soluble yarn finish. It is noted that the soiling characteristics of Sample 1 containing only the water-soluble were essentially the same as those described in Example VII for yarns containing the water-insoluble finish.

EXAMPLE XI The procedure of Example VII was repeated with the conventional finish replaced by a 7.5 percent aqueous solution of the methyl benzyl phenol-9 ethylene oxide (MBP-EO) applied to give a draw-textured yarn containing 1.0 percent finish. Three additional samples were prepared by applying zirconium to yarn in accordance with the procedures described for Samples 2, 3, and 4 of Example VII. Levels of zirconium applied to the yarn, and the results of the carpet soiling evaluation are shown below:

Carpet brightness Zirconium Percent Sample level Original Soiled B loss 1 Sample contained 0.57% of the MBP-EO.

The above data clearly demonstrates the improvement in soil resistance provided by the combination of zirconium compounds and a water-soluble yarn finish or lubricant.

The preceding examples illustrate a method for producing a soil-resistant carpet yarn by first applying to the yarn a water-soluble finish, such as polyalkylene glycols or ethylene oxide condensation products of phenolic derivatives, and thereafter applying zirconium from a solution or suspension. Although this two-step method provides very good results, a soil-resistant yarn can also be obtained by combining the zirconium and water-soluble finish into a single finish composition. The advantage of applying a. water-soluble finish in combination with zirconium rather than a conventional water-insoluble film finish is illustrated by the following example.

EXAMPLE XII Hydroxyl amine sulfate 3.60 Zirconium acetate 24.60 Acetic acid 1.50

Water 15.80

The finished yarn contained 1360 ppm. zirconium as determined by X-ray analysis. The yarn was draw-textured to give a carpet yarn of 1230 denier. Four ends were plied, bulked, and made into carpet samples for soiling tests. After soiling, the brightness of this sample was measured as 39.0. A second sample was prepared in an identical manner, except a water-soluble finish of the following composition was applied during spinnings:

Lbs.

Methyl benzyl phenol +9 ethylene oxide 43.50 Zirconium acetate 27.00 Hydroxyl amine sulfate 3.96 Acetic acid 1.50

- Water 225.50

The finish was applied at a rate sulficient to provide 1360 ppm. zirconium on the spun fiber. The carpet was produced as described above, and the brightness after soiling measured as 41.9, an improvement of 2.9 brightness units over the first sample.

It is apparent from the foregoing examples and data given in conjunction therewith that the process of the present invention provides significantly improved soilresistant fibers when compared to untreated fibers.

The foregoing examples illustrate the essential features of the invention as well as some of the manners in which it may be practiced. Various changes and modifications may be made in practicing the invention without departing from the spirit and scope thereof, and therefore, the invention should not be limited except as defined in the appended claims.

I claim:

1. A process of improving the soil resistance of polyamide and polyester fibers and articles produced therefrom comprising the steps of 2 (a) applying to the fibers an aqueous composition consisting essentially of from about 0.2 to 20 percent based on the weight of the fiber of a water-soluble lubricating agent being an alkylene oxide derivative selected from the group consisting of alkylene glycol, polyalkylene glycol, substituted alkyl and aryl poly (oxyalkylene) glycol, alkylene oxide-fatty acid condensation products, and mixtures thereof, and from about 0.05 to 1. 0 percent measured as zirconium dioxide and based on the weight of the fiber of a watersoluble zirconium compound selected from the group consisting of zirconium acetate, zirconium chloride, zirconium bromide, zirconium oxalate and zirconium sulfate;

(b) drying the fiber with the lubricating agent and zirconium compound thereon; and

(c) treating the fiber to remove substantially all the water-soluble lubricating agent while a major part of the zirconium compound remains adhered thereto.

2. A process according to claim 1 wherein the polyalkylene glycol has a molecular weight of from about 200 to 2000 and is selected from the group consisting of polyethylene glycol and polypropylene glycol.

3. A process according to claim 1 wherein the aryl poly(oxyalkylene) glycol is an ethylene oxide condensation product of an aromatic compound containing at least one phenolic hydroxy group with from about 9 to 19 moles of ethylene oxide per phenolic hydroxy group.

4. A process according to claim 1 wherein the alkylene glycol contains from 2 to about 20 carbon atoms.

5. A process of improving the soil resistance of polyamide and polyester fibers and articles produced therefrom comprising the steps of:

(a) contacting the fibers with an aqueous solution of a first water-soluble lubricating agent;

(b) drying the fibers with the first lubricating agent thereon;

. (c) contacting the dried fibers with an aqueous mixture consisting essentially of from about 0.2 to 20 percent based on the weight of the fiber of a second Watersoluble lubricating agent, said second water-soluble lubricating agent being an alkylene oxide derivative selected from the group consisting of alkylene glycol, polyalkylene glycol, substituted alkyl and aryl poly (oxyalkylene) glycol, alkylene oxide-fatty acid condensation products, and mixtures thereof, and from about 0.05 to 1.0 percent measured as zirconium dioxide and based on the weight of the fibers of a water-soluble zirconium compound selected from the group consisting of Zirconium acetate, zirconium chloride, zirconium bromide, zirconium oxalate and zirconium sulfate;

(d) drying the fiber with the second lubricating agent and zirconium compound therein; and

(e) treating the fibers to remove substantially all of the first and second lubricating agents while a major part of the zirconium compound remain adhered thereto.

6. A process of producing soil-resistant textile articles comprised of polyarnide and polyester fibers comprising the steps of:

(a) contacting the fibers with at least one soluble lubricating agent and a water-soluble zirconium compound in an aqueous media, said lubricating agent being an alkylene oxide derivative selected from the group consisting of alkylene glycol, polyalkylene glycol, substituted alkyl and aryl poly (oxyalkylene) glycol, alkylene oxide-fatty acid condensation products, and mixtures thereof, said lubricating agent being applied to the fiber in an amount from about 0.2 to 20 percent, based on the weight of the fibers, said zirconium compound being selected from the group consisting of zirconium acetate, zirconium chloride, zirconium bromide, zirconium oxalate and zirconium sulfate, said zirconium compound being applied to the fibers in an amount from about 0.05 to 1.0 percent measured as zirconium dioxide and based on the weight of the fiber;

(b) drying the fiber with the lubricating agent and zirconi'um compound thereon;

(c) processing the dried fiber into a textile article; and

(d) treating the textile article to remove substantially all of the water-soluble lubricating agent while a major portion of the zirconium compound remains adhered to the fiber.

Zirconium Chemicals, Dyeing and Finishing, Rayon and Synthetic Textiles, December 1950, pp. 81-83.

WILLIAM D. MARTIN, Primary Examiner J. E. MILLER, JR., Assistant Examiner US. Cl. X.R

8ll5.6; ll7138.8F, 138.8N, 139.5CI, 139.5CO 169R; 2528.9

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. g fi i Dated 1 13 1 1 Inventor(s) Andrew I. Smith N Col. 6, line 25, "securing" should read ---scouring-.

C01. 7. In the table in Example IX, Sample 4, the number "7. 98" in the "Original" Column should read "79. 8".

C01. 8, line 54, cancel "film".

Signed and sealed this 30th day of January 1973- (SEAL) Attest:

EDWARD M.FLETCHER,JR. ROBERT GOTTSCHALK Attesting Officer Commissioner of Patents FORM F'O-TOSO (10-69) USCOMM-DC 6037B-F'09 U 5 GOVERNMENT PRINTFNG OFHCE