NZ516745A

NZ516745A - A method of imparting stain resistance to a differentially dyeable textile surface and the article produced thereby

Info

Publication number: NZ516745A
Application number: NZ516745A
Authority: NZ
Inventors: Markus Baumann; Ranier Heinz; Klaus Stark
Original assignee: Markus Baumann; Ei Du Pont De Nemours And Company; Ranier Heinz; Klaus Stark
Priority date: 1999-07-08
Filing date: 2000-07-07
Publication date: 2004-04-30
Also published as: AU5920300A; MXPA02000210A; CA2378676A1; WO2001004408A1; CA2378676C; NZ530205A; WO2001004408A8; BR0012348A; JP2003504531A; AU777574B2

Abstract

A method for treating an article having a textile surface with a stainblocker composition, the textile surface being formed from at least two types of nylon yarns, wherein at least one type of nylon yarn is dyeable by an acid dyestuff and at least one other type of nylon yarn is dyeable by a cationic dyestuff, the method comprising the sequential steps of: (a) dyeing the textile surface of the article with an acidic dyestuff and a cationic dyestuff; (b) passing the textile surface of the article through an aqueous bath containing a stainblocker composition and a surfactant, the bath having a temperature from above seventy to ninety-five degrees Celsius (70 to 95°C), the textile surface remaining in the bath for about five (5) to about thirty (30) seconds; (c) removing excess water from the textile surface of the article; (d) passing the article through an ambient temperature zone; and (e) rinsing the textile surface of the article with water, and thereafter suctioning and drying the same, such that substantially the entire textile surface of the article is coated with a stainblocker composition whereby the textile surface has a stain resistance of 9 or higher on the AATCC Red 40 Stain Scale.

Description

<div class="application article clearfix" id="description"> WO 01/04408 PCT/USDO/ 51 TITLE A METHOD OF IMPARTING STAIN RESISTANCE TO A DIFFERENTIALLY DYEABLE TEXTILE SURFACE AND THE ARTICLE PRODUCED THEREBY 5 BACKGROUND OF THE INVENTION Field of the Invention The invention relates to a continuous method for treating a textile surface made of differentially dyeable nylon yarns with a stainblocker 10 composition to impart stain resistance thereto, and to the article produced thereby. Description of the Prior Art In the industrial production of articles having a textile surface thereon, such 15 as a broadloom carpet or carpet tiles, it is common to treat such articles with a composition to impart added desirable properties thereto, such as resistance to staining by a variety of agents, e.g. foods or beverages. Some especially troublesome stains are coffee, black tea and red wine. 20 In the industrial production of such articles it is also common to use differentially dyeable nylon yarns. By the term wdifferentially dyeable" it is meant that the article contains yarns having at least two different dyeabilities, such as acid dyeable yarn and cationic ("cat") dyeable yarn. Often a 25 desired aesthetic effect in a carpet is possible only by combining yarns of these two different dyeabilities. Both dyeabilities are available in various dye depths, such as light, regular, deep and extra deep acid dye and light and regular cat dye. 30 Compositions referred to as "stainblockers" are commonly applied to non-differentially dyeable carpets or carpet tiles to impart stain resistance. There is presently available both a continuous process and a discontinuous, or batch-wise, process for applying a 35 stainblocker composition to a carpet made of non-dif ferentially dyeable yarns. WO 01/04408 PCT/US00/18589 Continuous Conventional Process The steps of a conventional process for applying a stainblocker composition to a textile surface (such as a broadloom carpet) made of non-dif ferentially dyeable yarns are listed in Figure 3. In the 5 conventional continuous process a running line of colored carpet (colored as by dyeing or printing), after rinsing and suction hydroextraction, is passed through an aqueous liquid treatment bath containing a stainblocker composition and a surfactant. The temperature of the bath is in the range from 10 twenty to sixty degrees Celcius (20 to 60 °C). The residence time of the carpet in the bath is usually not adjusted as an independent critical parameter but is instead a function of the speed of the carpet line. After removal from the bath the carpet passes through a steam chamber wherein it is exposed to 15 saturated steam for about sixty to ninety (60 to 90) seconds. Thereafter, conventional finishing steps for the carpet typically include: a suction hydroextraction operation where residual liquid is vacuumed from the carpet; a cold water rinse operation (either by spraying or passing the carpet 20 through a dip trough); another suction hydroextraction operation; and a final drying. Batch-wise Conventional Process The batch-wise process for applying the stainblocker composition and a surfactant to a textile surface made of non-differentially dyeable yarns 25 (such as a broadloom carpet) is termed the "winch/beck" I process. In the batch-wise winch/beck process discrete dyed carpets are immersed in a vat having a bath including a stainblocker composition and a surfactant. The temperature of the bath in the batch-wise winch/beck process is slightly 30 higher than in the continuous process, in the range from seventy to seventy-five degrees Celcius (70 to 75 °C), and the residence time in the bath is on the order of twenty minutes. After removal from the bath, the carpet is subjected to the conventional finishing steps such as rinsing with cold water 35 in situ, or after unloading from the hot application bath, 2 WO 01/04408 PCT/US00/18589 rinsed by spray bar followed by a vacuum extraction operation to ensure no residual stainblocker is left. In both the continuous process and the batch-wise process the stainblocker composition is preferably of the anionic 5 functionalized type, and more preferably, of the sulphone resole type having nonionic functionality. Tile Production To produce carpet tiles treated with a stainblocker composition it is common practice first to treat a broadloom carpet with a stainblocker composition in one of 10 the manners specified, and after a backing is applied, to cut the broadloom carpet into pieces of the desired size to form carpet tiles. Stainblockers Suitable anionic functionalized type stainblocker compositions include sulphonated phenol 15 formaldehyde condensate types, maleic acid anhydride types, acrylate dispersions and mixtures thereof. Anionic functionalized type stainblocker compositions should be present between three weight percent (3 wt%) and five weight percent (5 wt.%) based on the weight of the nylon carpet 20 fiber. When anionic functionalized type stainblocker compositions are used, the pH of the bath must be adjusted to between 2 and 5. Examples of commercially available anionic functionalized type stainblocker compositions are available from E. I. Du 25 Pont de Nemours and Company, Wilmington, Delaware, under the trademarks SR 300, SR 400 and SR 500; from Du Pont de Nemours International S. A., Geneva, Switzerland, under the trademark NRD 334; from Allied Colloids, Bradford/West Yorkshire, U.K., under the trademark Alguard RD; and from Bayer AG, Leverkusen, 30 Germany, under the trademark Baygard DT. When sulphone resole type stainblocker compositions with nonionic functionality are used, they should be present at between four weight percent (4 wt. %) and six weight percent (6 wt. %) based on the weight of the nylon carpet fiber, and 35 the pH must be adjusted to between 6 and 7.5. An example of a commercially available sulphone resole type stainblocker 3 WO 01/04408 PCT/USOO/18589 composition with nonionic functionality is available from E. I. Du Pont de Nemours and Company, Wilmington, Delaware under the trademark Zelan 8236. The pH of the treatment bath may be adjusted by known 5 acid donor additives such as acetic acid, citric acid and sulfamic acid. Surfactants A surfactant may be added to the stainblocker bath separately or may be included as part of the stainblocker composition. The surfactant may be anionic, 10 amphoteric or nonionic in nature. Preferably, the surfactant used will be either an alkylated diphenyl oxide disulfonate sodium salt, alone or in combination with an alkylnaphtalene sulfonic acid formaldehyde condensate sodium salt. The surfactant is generally added to the bath at a rate of between 15 one (1) and four (4) grams per liter. Suitable surfactants are available from E. I. Du Pont de Nemours and Company, Wilmington, Delaware under the trademark Zelan 50; from Dow Chemical Company, Midland, Michigan, under the trademark Dowfax 3B2; or from BASF AG, Ludwigshafen, Germany, under the 20 trademark Primasol NF. Problem With Conventional Methods for Differentially Dyeable Textile Surfaces Unfortunately, when either the continuous process or the batch-wise process is used to apply a stainblocker composition to a broadloom carpet containing 25 differentially dyeable yarns the cationic dyestuff "bleeds" from the cat dyeable yarn into the surrounding stainblocker treatment bath, resulting in an unacceptable visual color change. Low Liquor Method The only publicly known system to 30 apply a stainblocker composition to a differentially dyeable carpet is a method known as the "low liquor" method. Using the "low liquor" method a differentially dyeable carpet may attain at least a modest degree of stain resistance. In the "low liquor" method a cold-foamed liquor including a 35 stainblocker composition and a fluorocarbon material are co-applied topically to the carpet. Thereafter the carpet is 4 WO 01/04408 PCT/US00/18589 dried, without steam or water rinse. In the past, the stainblocker composition typically utilized was the acrylate dispersion sold by 3M Corporation under the trademark "FX-661", while the fluorocarbon material typically utilized was 5 those sold by 3M Corporation under the trademarks "FC-3611", "FC-3602" or "FC-1395". However, the low liquor method is useful only with a carpet having a very low "wet pick-up", on the order of fifteen to twenty percent (15-20%). Wet pick-up (wpu) is the ratio of the weight of the liquid picked-up by 10 the carpet from a treatment bath to the weight of the carpet. Moreover, with the low liquor method, the stainblocker composition penetrates into only about the upper twenty-five percent (25%) of the height of the pile elements of a differentially dyeable carpet. This depth of stainblocker 15 penetration is not believed to be sufficient to impart a high degree of stain resistance. Accordingly, in view of the foregoing, it is believed advantageous to provide a process for treating an article 20 having a textile surface containing differentially dyeable nylon yarns, such as a broadloom carpet or carpet tiles, to impart a high degree of stain resistance thereto, while maintaining good color stability. 25 SUMMARY OF THE INVENTION In a first aspect the present invention is directed to a continuous method for treating an article having a textile surface made of differentially dyeable nylon yarns with a stainblocker composition to impart stain resistance thereto. 30 This method (the "hot shock" method) comprises the sequential steps of: (a) dyeing the textile surface of the article with an acid dyestuff and a cationic dyestuff,- (b) passing the textile surface of the article through a 35 bath containing a stainblocker composition and a surfactant, the bath having a temperature in the 5 WO 01/04408 PCT/US00/18589 range from seventy to ninety-five degrees Celsius (70 to 95 °C), the textile surface remaining in the bath for about five (5) to about thirty (30) seconds; (c) removing excess water from the textile surface of the article; (d) passing the article through an ambient temperature zone; and (e) rinsing the textile surface of the article with water, and thereafter suctioning and drying the same, such that substantially the entire textile surface of the article is coated with a stainblocker composition, whereby the textile surface has a stain resistance of 9 or higher on the AATCC Red 40 Stain Scale. Preferably, the excess water is removed by passing the textile article through a pair of nip rolls to control the level of wet pick-up between two hundred and six hundred percent (200-600%). The textile article preferably remains in the cooling zone for twenty (2 0) to one hundred twenty (12 0) seconds. In the instance where the article is a pile surface structure having a plurality of pile elements, substantially the entire height of each pile element is coated with the stainblocker composition whereby the pile surface structure has a stain resistance of 9 or higher on the AATCC Red 4 0 Stain Scale. In this method, if the stainblocker composition is of the sulphone resole type having nonionic functionality (as is preferred) the stainblocker composition is present between four percent (4%) and six percent (6%) based on the weight of the nylon yarns, and the pH of the stainblocker bath is between six (6) and seven and one-half (7.5). Alternatively, if the stainblocker composition is of the anionic functionalized type, such as that selected from the group consisting of sulphonated phenol formaldehyde condensate type, WO 01/04408 PCT/US00/18589 maleic acid anhydride type, acrylate dispersions and mixtures thereof, the stainblocker is present between three percent (3%) and five percent (5%) based on the weight of the nylon yarns; and the pH of the stainblocker bath is between two (2) 5 and five (5). -o-O-o- In another embodiment the present invention is a method (the "infra-red" method) of treating articles having a textile 10 surface (such as broadloom carpets or carpet tiles) with a stainblocker composition to impart stain resistance thereto. The textile surface of the articles may be made of either differentially dyeable nylon yarns or acid-dyeable nylon yarns. 15 The textile surface of the article is colored with acid dyestuffs and cationic dyestuffs (in the case of an article made of differentially dyeable nylon yarns) or with acid dyestuffs (in the case of an article made of acid-dyeable nylon yarns). The coloring may be accomplished either by 20 dyeing or by screen or spray printing. After coloring, this embodiment of the method comprises the sequential steps of: (a) applying a stainblocker composition to the textile surface of the article, the stainblocker composition having a temperature from twenty to ninety-five 25 degrees Celsius (20 to 95 °C); (b) drying the article in a drying zone having a temperature in the range from seventy-five degrees Celsius to ninety-five degrees Celsius (75-95 °C) for a time sufficient to allow the stainblocker 30 composition to react with the nylon yarn in the textile surface; and (c) rinsing the textile surface of the article with water, and thereafter drying the same, such that substantially the entire textile surface of the 35 article is coated with a stainblocker composition whereby the 7 WO 01/04408 PCT/US00/18589 textile surface has a stain resistance of 9 or higher on the AATCC Red 40 Stain Scale. A broadloom carpet (with the backing thereon) may be cut into pieces to form carpet tiles either before or after it is 5 colored, or after the final drying step. When the article is in the form of carpet tiles, the tiles lay loosely upon and are conveyed by a transport belt through the stainblocker application. For carpet tiles the stainblocker composition is applied using a flood process by a 10 flood applicator. Broadloom carpets may be transported by any suitable transport mechanism and the stainblocker composition can be applied by any appropriate application device. Preferably, the drying zone of step c) uses infra-red energy to dry the textile article. Preferably, the 15 temperature of the drying zone is in the range from eighty degrees Celsius to eighty-five degrees Celsius (80-85 °C). In this method, if the stainblocker composition is of the sulphone resole type having nonionic functionality (as is preferred) the stainblocker composition is present between one 20 and one-half percent (1.5%) and six percent (6%), and more preferably, between two percent (2%) and three percent (3%) , based on the weight of the nylon yarns. The pH of the stainblocker bath is between six (6) and seven and one-half (7.5). Alternatively, if the stainblocker composition is of 25 the anionic functionalized type, such as that selected from the group consisting of sulphonated phenol formaldehyde condensate type, maleic acid anhydride type, acrylate dispersions and mixtures thereof, the stainblocker is present between one percent (1%) and five percent (5%) based on the 30 weight of the nylon yarns; and the pH of the stainblocker bath is between two (2) and five (5). -o-O-o- In another aspect the invention is directed an article having a textile surface formed from at least two types of 35 dyeable nylon yarns. At least one type of nylon yarn is dyeable by an acid dyestuff and at least one other type of 8 WO 01/04408 PCT/USOO/18589 nylon yarn is dyeable by a cationic dyestuff. In accordance with the present invention the textile surface of the article is coated with a stainblocker composition such that the textile surface has a stain resistance of 9 or higher on the 5 AATCC Red 40 Stain Scale. In a preferred embodiment the article takes the form of a pile surface structure wherein the textile surface is defined by a plurality of upstanding pile elements formed from the two types of dyeable nylon yarns. Substantially the entire height of each pile element is coated 10 with the stainblocker composition. The dyeable nylon yarns may be bulked continuous filament yarns or staple spun yarns. The pile elements may be formed in such a way that each pile element includes both a nylon yarn dyeable by an acid dyestuff 15 and a nylon yarn dyeable by a cationic dyestuff. Alternately, the pile elements may be formed such that at least some of the pile elements are formed from a nylon yarn dyeable by an acid dyestuff and at least others of the pile elements are formed from a nylon yarn dyeable by 20 a cationic dyestuff. BRIEF DESCRIPTION OF THE DRAWINGS The invention will be more fully understood from the following detailed description thereof, taken in 25 connection with the accompanying drawings, which form a part of this application and in which: Figure 1 is a side view of a pile surface structure in accordance with the present invention; Figures 2A and 2B are respective schematic 30 representations of the steps of methods for treating an article having a textile surface with a stainblocker in accordance with the present invention, wherein the representation (Figure 2A) of the "hot shock" process of one embodiment of the present invention extends along the upper 35 edge of the drawing sheet, while the representation (Figure 2B) of the "infra-red" process of another embodiment of the 9 WO 01/04408 PCT/USOO/18589 present invention extends along the lower edge of the drawing sheet; and. Figure 3 is a block diagram representation of a conventional method for applying a stainblocker conposition to 5 a textile surface made of non-differentially dyeable yarns; and Figures 4A and 4B are respective schematic representations of the steps of methods for treating an article having a textile surface with a stainblocker in 10 accordance with the present invention, wherein the steps of the "hot shock" process (Figure 4A) of one embodiment of the present invention extend along the left hand side of the drawing sheet, while the steps of the "infra-red" process (Figure 4B) of another embodiment of the present invention 15 extend along the right hand side of the drawing sheet. DETAILED DESCRIPTION OF THE INVENTION Throughout the following detailed description similar reference numerals refer to similar elements in all figures of 2 0 the drawings. The present invention is broadly directed to methods for applying a stainblocker composition to any article having a textile surface to impart stain resistance thereto and to articles produced thereby. The textile surface may be one 25 that is formed from at least two types of dyeable nylon yarns. At least one type of nylon yarn is dyeable by acid dyestuffs and at least one other type of nylon yarn is dyeable by cationic ("cat") dyestuffs. A textile surface that contains yarns having at least two different dyeabilities, such as 30 cationic dyeable yarn and acid dyeable yarn, is termed "differentially dyeable". Alternatively, the textile surface may be "acid-dyeable", that is, a surface that is formed only from nylon yarns that are dyeable using acid dyestuffs. In accordance with the present invention the textile 35 surface of the article is coated with a stainblocker 10 WO 01/04408 PCT/US00/18589 composition such that the textile surface has a stain resistance of 9 or higher on the AATCC Red 4 0 Stain Scale. The most preferred form of an article 10 in accordance with the present invention is illustrated in Figure 1. In Figure 1 the article 10 is embodied by a carpet 10C whose textile surface 12 is defined by a plurality of upstanding pile elements 12P. The pile elements 12P extend above a backing 14. The carpet 10C may be a full broadloom size, or (once the backing is applied) may be cut into the form of "carpet tiles". As is appreciated by those in the art, "carpet tiles" are, in the typical case, generally square pieces of carpet having dimensions on the order of fifty-by-fifty centimeters (50 x 50 cm.). Of course, tiles may take other shapes and exhibit any desired range of sizes. As the result of treatment of the carpet 10C (in either broadloom or tile form) with either embodiment to be described herein, substantially the entire height 12H of each pile element 12P has a coating 16 of a stainblocker composition thereon. It should be noted that although in practice the coating 16 of stainblocker composition would be invisible, for purposes of illustration the presence of the coating 16 is represented in Figure 1 by relatively bold lines on the contours of the pile elements 12P. Since the textile surface 12 of the carpet IOC illustrated in Figure 1 is defined by the plurality of upstanding pile elements 12P, the carpet 10C is hereinafter be referred to as a "pile surface structure". This nomenclature serves to distinguish the illustrated pile surface structure 10C from alternative forms of carpet structures in which the textile surface is defined by a textile fabric. These alternative forms of carpet structures also lie within the contemplation of the invention. An example of one such alternative form of carpet structure is the carpet disclosed in International Publication WO 97/01665 (Vinod). The pile elements 12P defining the textile surface of the pile surface structure IOC may be either cut pile (as 11 WO 01/04408 PCT/USOO/18589 illustrated in the right hand portion of Figure 1) or loop pile (as illustrated in the left hand portion of Figure 1). The pile elements 12P may be produced by any suitable known carpet forming process, such as tufting, weaving or knitting. 5 In the case of a differentially dyeable pile surface structure, each pile element 12P, however produced, may be comprised entirely of either acid dyeable nylon yarns or cat dyeable nylon yarns. Alternately, each pile element 12P may comprise a combination of both acid dyeable nylon yarns or cat 10 dyeable nylon yarns. The nylon material may be nylon 6,6 or nylon 6 or any of the various copolymers thereof. The yarn is either a bulked continuous filament yarn or a staple spun yarn. In the case of an acid-dyeable pile surface structure 15 each pile element 12P in the pile surface structure 10C is formed only from nylon yarns that are dyeable using acid-dye. The backing 14 for the pile surface structure 10C may be implemented using any convenient materials. A preferred backing construction is a synthetic latex/chalk filler 2 0 compound. -o-O-o- A first embodiment of the method of the present invention, termed the "hot shock" process, by which the pile surface structure 10C (or the textile surface of any article) 25 is treated with a stainblocker composition will now be described in connection with the schematic representation of Figure 2A and the corresponding block diagram representation of Figure 4A. This embodiment of the process of the present invention is implemented in a continuous, as opposed to batch-30 wise, manner. After being made using any known carpet-forming process the undyed pile surface structure 10C is dyed in a dye bath 20 containing both cationic dyestuffs and acid dyestuffs. The cat dyeable nylon yarns and the acid dyeable nylon yarns that 35 form the pile elements 12P are each colored by the appropriate 12 WO 01/04408 PCT/US00/18589 dyestuff so that both types of yarns may contribute to the visual aesthetic properties of the pile surface structure 10C. The process conditions for the dye bath 20 are suitable for the dyes chosen for use. Some commercially available acid 5 dyes that may be suitable for use in the dye bath 20 include those sold by Ciba Specialty Chemicals, Inc., Basel, Switzerland, under the trademark Tectilon; by DyStar Textilfarben, Leverkusen, Germany under the trademark Telon; by Clariant (Switzerland) Ltd., Basel, Switzerland under the 10 trademark Nylosan; and by Crompton & Knowles, Charlotte, North Carolina, under the trademark Nylanthren. Some commercially available cationic dyes that may be suitable for use in the dye bath 2 0 include those sold by Ciba Specialty Chemicals, Inc., Basel, Switzerland, under the trademark Maxilon; by 15 DyStar Textilfarben, Leverkusen, Germany, under the trademark Astrazon; by Clariant (Switzerland) Ltd., Basel, Switzerland, under the trademark Sandocryl; and by Crompton & Knowles, Charlotte, North Carolina, under the trademark Sevron. After dyeing, the pile surface structure 10C passes 20 through a cold water rinsing step 21 and a hydroextraction step 22 to remove residual dyes and chemicals. Any conventional arrangement for suctioning liquid from a carpet may be used to perform the hydroextraction step. Both these steps are similar to corresponding steps of the continuous 25 process of the prior art. If dyeing of the pile surface structure occurs at an earlier time, the pile surface structure must be prewet (as at the water rinsing step 21) and the water extracted (as at step 22) before the stainblocker is applied. 30 After hydroextraction the pile surface structure 10C passes through a hot aqueous liquid treatment bath 24 containing a stainblocker composition and a surfactant. Although the same stainblocker compositions and surfactants as are used in the conventional continuous process as earlier 35 described are used in the treatment bath 24, it has been found that if the temperature of the treatment bath 24 and dwell 13 WO 01/04408 PCT/USOO/l8589 time of the pile surface structure 10C therein are in accord with the teachings of the present invention bleeding of cationic dyestuff from the cat dyeable yarn does not occur. In accordance with the present invention the temperature 5 of the hot treatment bath 24 is in the range from about seventy to about ninety-five degrees Celsius (70 to 95 °C). More preferably, the temperature is in the range from about eighty to about ninety degrees Celsius (80 to 90 °C). The temperature of the hot bath 24 is maintained by direct or 10 indirect heating with automatic control. A suitable system useful for the application step 24 is that manufactured under the name "hot shock applicator" by Eduard Kuesters Maschinenfabrik GmbH & Co. KG, Krefeld, Germany, comprising a low volume dip trough and a steam-supplied plate heat 15 exchanger with electronic temperature control. The pile surface structure IOC should remain in the bath 24 for a residence time in the range from about five (5) to about thirty (30) seconds, and more preferably, in the range from about ten (10) to about fifteen (15) seconds. 2 0 As to the stainblocker compositions themselves, sulphone resole type stainblocker compositions with nonionic functionality (in the appropriate weight percentages and with appropriate pH adjustment) are preferred. Anionic functionalized type stainblocker compositions (also in the 25 appropriate weight percentages and with appropriate pH adjustment) may also be used. As earlier discussed the pH of the treatment bath may be adjusted by known acid donor additives such as acetic acid, citric acid and sulfamic acid. Preferred surfactants again include appropriate amounts of an 30 alkylated diphenyl oxide disulfonate sodium salt, alone or in combination with an alkylnaphtalene sulfonic acid formaldehyde condensate sodium salt. When the stainblocker composition is of the sulphone resole type having nonionic functionality the stainblocker 35 composition is present between four percent (4%) and six percent (6%) based on the weight of the nylon yarns, and the 14 WO 01/04408 PCT/US00/18589 pH of the stainblocker bath is between six (6) and seven and one-half (7.5). After exiting the hot treatment bath 24 excess water is removed from the pile surface structure 10C. To this end the 5 pile surface structure 10C passes through a pair of nip rolls 26. Preferably, the rolls 26 adjust the wet pick-up of the pile surface structure 10C to between two hundred percent (200%) and six hundred percent (600%) and more preferably, to about three hundred percent (300%). The pressure between the 10 nip rolls 26 may be varied in order to find the optimal wet pick-up for a given carpet construction and process. Expedients other than nip rolls may be used to remove the excess moisture. Thereafter, the pile surface structure 10C passes through 15 an ambient temperature zone 28 in which the pile surface structure 10C cools toward the ambient air temperature. Preferably, the pile surface structure 10C remains in the cooling zone 28 for between twenty (20) to one hundred twenty (120) seconds, and more preferably, between twenty (20) to 20 forty (40) seconds. It should be noted that in accordance with this invention the pile surface structure 10C is not subjected to a steaming step, as in the prior art continuous process. After undergoing treatment in the hot bath 24 and cooling 25 in the air cooling zone the pile surface structure 10C is subjected to the conventional finishing steps normally used in the continuous immersion process of the prior art. Such finishing steps would include a suction operation 30, a cold water rinse operation 32, and another suction operation 34. 30 Finally, the pile surface structure 10C is dried in an oven 36 and collected by a take-up roll 38. EXAMPLES 1-3 Test Methods The following test methods were used in the 35 Examples 1-3 below to measure carpet samples made according to the "hot shock" embodiment of the invention as well as control 15 WO 01/04408 PCT/US00/18589 samples for stain resistance, color stability and dyelightfastness. Kool-Aid® Soft Drink Stain Resistance Standard Test (Standardized AATCC Test Method 175-1991: Red 40 Stain Rating 5 Scale) This impact tester method simulates a "household accident" with a spill dropped from table height onto a carpet. Staining Agent: The staining agent is a ninety (90) gram per thousand (1000) cc water solution of cherry-flavored, 10 sugar-sweetened Kool-Aid ® soft drink. The solution is permitted to reach room temperature (22 ± 2 °C) before use. An alternative staining agent is a solution containing 0.1 gram/liter FD&C Food Red 40 dyestuff, one (1) gram/liter citric acid, and ten (10) gram/liter sugar. 15 Equipment: A specially designed impact tester is used to apply the staining agent to the specimens under test. The impact tester comprises a cylinder (of plastic or glass) that is 28 cm high with a 6.5 cm inside diameter. A massive piston nine (9) cm in length weighing four hundred (4 00) grams is 20 received on the inside of the cylinder. The piston is made from a plastic material (PVC or PTFE) . The piston is vertically movable within the cylinder by a bolt fitted to the piston. The bolt projects through a four (4) mm vertical slot in the cylinder. A small (seven (7) mm diameter) hole is 25 drilled through the cylinder two cm from the bottom for injecting staining agent. ProcedureTest samples, measuring ten (10) cm square, are cut from each pile surface structure under test. The impact tester is centered on each sample and the plastic 30 piston lifted and fixed in position by the bolt in the slot. Using a syringe twenty (20) cc of the staining agent is injected through the small hole over the surface of the sample. The plastic piston is released and drops freely onto the carpet sample. The impact corresponds to the impact of a 35 cup of liquid falling from the table height [eighty (80) cm]. The impact tester is removed and the sample is left, 16 WO 01/04408 PCT/US00/18589 undisturbed, in a horizontal position for twenty-four (24 ± 4) hours. Without damaging the pile, the sample is rinsed thoroughly with tap water at about twenty degrees Celsius (20 °C), centrifuged to remove any excess water and dried in a 5 forced air oven at maximum of seventy-five degrees Celsius (75 °C) . Each sample is evaluated for staining, using the AATCC Red 40 Stain Scale. According to this scale stains are rated on a scale of 1 to 10, with ml" designating heavy staining and 10 "10" designating no staining. A sample receiving a rating of "9" is considered to have acceptable stain resistance. Coffee Stain Resistance Standard Test This test is substantially identical to the Kool-Aid® soft drink test, except that the staining agent is a twenty gram per liter 15 (20 g/1) solution of an instant coffee (e.g. Nescafe® Gold coffee, with no additives such as milk, cream or sugar) at a temperature of sixty degrees Celsius (60 °C). Color Measurement Color measurements were made using the international standard color measurement method promulgated by 20 "Commission Internationale de L'Eclairage" (Paris, France), (International Society for Illumination/Lighting), ("CIE") using standard color coordinates of both the CIELAB L*a*b* and the CIELAB L*C*h color space: nL" designates the lightness coordinate; "a" designates the red/green coordinate (+a 25 indicating red, -a indicating green) ; "b" designates the yellow/blue coordinate (+b indicating yellow, -b indicating blue); and "C" designates the chroma coordinate, the perpendicular distance from the lightness axis (more distance indicating more chroma). 30 Dyefastness Dyelightfastness is measured according to standardized test method DIN 54004 (ISO 105 B02). This method is based on scale of 1 to 8, according to standardized "bluescale" of eight different blue wool dyestuffs, dyed on a wool fabric, which are joint into the light exposure process 35 together with the test specimen (1-very poor, 8-very high lightfastness). 17 WO 01/04408 PCT/US00/18589 EXAMPLES 1-3 The pile surface structure in Example 1 and Controls la-lc were a loop construction containing three different filament yarn types having regular cationic, light 5 cationic and deep acid dyeabilities. The deep acid dyeable yarns were dyed green. The regular and light cationic dyeable yarns were dyed orange in two color steps. Control la was treated by conventional batch-wise winch/beck process. Control lb was treated by conventional 10 continuous application. Control lc is an untreated control carpet. Example 1 was treated by the method of the present invention. The temperature of bath was eighty-five degrees Celsius (85 °C), the residence time of the article in the bath was ten (10) seconds, and the time in the ambient temperature 15 zone was thirty (30) seconds. In Example 1 and Controls la-lb the stainblocker composition was ZELAN® 8236 (DuPont) and the surfactant used was ZELAN® 50 (DuPont). The stainblocker composition was applied at 5.5% of pile weight and pH values were adjusted 20 with acetic acid. Control la was treated for twenty minutes at pH 6.8 and at a temperature of 75°C. Control lb was treated at pH 6.8 and steamed afterwards. The wet pick-up was 400%. Example 1 was treated as described above at a pH of 6.8. Control lc was not treated in order to compare color 25 stability and dyelightfastness. After treating with the stainblocker composition Example 1 and Controls la-lb were water rinsed, hydroextracted and dried. After dyeing, Example 1 and Controls la-lb were each tested for color stability and dyelightfastness by the test 30 methods described above. The results are reported in Table 1. As can be seen from Table 1 Example 1 shows smallest deviation in color saturation (C* values). Also, the dyelightfastness resulting from each application method was good. 35 18 WO 01/04408 PCT/US00/18589 TABLE 1 No. L* a* b* C* Dyelightfastness Control la 46.74 -1.09 +10.39 10.45 5-6 Control lb 46.70 -1.44 +13.09 13.17 5-6 Example 1 46.43 -1.95 +14.74 14 . 87 5-6 Control lc 46.31 -2.15 +15.78 15.96 6 Example 2 and Controls 2a-2c The pile surface structure in Example 2 and Controls 2a-2c was a velour construction 5 containing four different filament nylon yarn types having regular acid, extra deep acid, regular cationic and light cationic dyeabilities. The pile surface structure was dyed to grey and orange colors. The regular acid dyeable yarn was light gray, the extra deep acid dyeable yarn was dark gray, 10 the regular cationic dyeable yarn was dark orange, and the light cationic dyeable yarn was light orange. Example 2 and Controls 2a-2c were performed exactly as Example 1 and Controls la-lc. After dyeing, the carpet sample pieces were each tested for stain resistance using both the Kool-Aid® soft 15 drink stain resistance test and the coffee stain resistance test. The results are reported in Table 2. The results show little difference between the samples, also the stain resist properties of Example 2 are the best overall. Due to the special fine four component color pattern in 20 this carpet, a color measurement could not be done, the samples were only visually compared. TABLE 2 Kool-Aid Coffee Control 2a 10 9-10 Control 2b 10 9 Example 2 10 10 Control 2c 1 1 19 WO 01/04408 PCT/US00/18589 Example 3 and Controls 3a-3c These examples demonstrated the application of stainblocker compositions on cationic dyeable nylon carpets. Example 3 and Controls 3a-3c were performed exactly as Example 1 and Controls la-lc. In Example 3 and Controls 3a-3c the pile surface structure was a velour construction of one hundred percent cationic dyeable nylon yarn. The carpet was orange in color. The samples were each tested for color stability and dyelightfastness by the test methods described above. The results are reported in Table 3. These results demonstrate the small deviation in color saturation of the hot-shock treated carpet sample piece (compare Controls 3a, 3b and Example 3 to Control 3c) . Also these results showed improved dyelightfastness of hot shock treated carpet sample piece Example 3c compared to Examples 3a and 3b. TABLE 3 No. L* a* b* C* Dyelightfastness Control 3a 61.97 +34.56 +39.75 52 .67 4-5 . Control 3b 58.96 +37.78 +47.88 60.99 4-5 Example 3 58.01 +39.75 +48.86 62.99 5-6 Control 3c 57.79 +40.07 +49.78 63.90 5-6 Discussion of Results Example 1 and Example 3 showed the smallest measured color deviation from the untreated control samples. Also in Example 2, where only a visual rating was feasible, the sample treated according to the above-described method showed the smallest color change from the control color. In all three examples application of the stainblocker conposition using a bath having a temperature and with dwell times in accordance with the "hot shock" embodiment of the present invention resulted in the lowest and still acceptable color change on the cationic dyeable yarn components. This is believed to be the first industry applicable method to treat nylon differential dye carpets with stainblocker chemicals 20 WO 01/04408 PCT/US00/18589 without unacceptable color loss on the cationic dyeable yarn. In all cases good stainblocking results were received. The dyelightfastness results were even one-half (1/2) to one (1) note better than after standard application methods. -o-O-o- The "hot shock" process as above described, although advantageous for use with broadloom carpets, is not particularly advantageous for use with carpet tiles. Accordingly, the alternative embodiment, termed the "infrared" process, may be used when the pile surface structure is implemented in the form of either broadloom carpet or carpet tiles. The "infra-red" process by which the pile surface structure (or the textile surface of any article) is described in connection with the schematic representation of Figure 2B and the corresponding block diagram representation of Figure 4B. In the infra-red process embodiment of the present invention the stainblocker composition is also applied in a continuous, as opposed to batch-wise, manner. In a typical implementation, after being made using any known carpet-forming process, an undyed pile surface structure 10C is colored in a color applicator 16A (such as a dye bath). The color is fixed in a color fixator 16B (such as a steamer). If the pile surface structure 10C is formed from differentially dyeable yarns, the dye bath contains a mixture of both acid dyestuffs and cationic dyestuffs. The acid dyeable nylon yarns and the cat dyeable nylon yarns that form the pile elements are each colored by the appropriate dyestuff so that both types of yarns may contribute to the visual aesthetic properties of the pile surface structure. On the other hand, if the pile surface structure 10C is formed only from acid dyeable yarns, the dye bath contains only acid dyestuffs and the acid-dyeable nylon yarns that form the pile elements are appropriately colored by that dyestuff. The process conditions for the dye bath are suitable for the dyes chosen for use. Some commercially available acid 21 WO 01/04408 PCT/US00/18589 dyes that may be suitable for use in the dye bath include those sold by Ciba Specialty Chemicals, Inc., Basel, Switzerland, under the trademark Tectilon; by DyStar Textilfarben, Leverkusen, Germany under the trademark Telon; by Clariant (Switzerland) Ltd., Basel, Switzerland under the trademark Nylosan; and by Yorkshire Chemicals, Leeds, UK, under the trademark Nylanthren. Some commercially available cationic dyes that may be suitable for use in the dye bath include those sold by Ciba Specialty Chemicals, Inc., Basel, Switzerland, under the trademark Maxilon; by DyStar Textilfarben, Leverkusen, Germany, under the trademark Astrazon; by Clariant (Switzerland) Ltd., Basel, Switzerland, under the trademark Sandocryl; and by Yorkshire Chemicals, Leeds, UK, under the trademark Sevron. It should be understood that the dye(s) appropriate for the pile surface structure 10C may also be applied using either a screen printing or a spray printing technique. After dyeing, if the pile surface structure IOC remains in a broadloom form it is conveyed through the stainblocker application process using a suitable guiding devices typically used in the art. However, it should be understood that it lies within the contemplation of the invention to cut the broadloom carpet (assuming that it is provided with a backing) into tiles before entering the stainblocker application process. To this end devices for backing and cutting the carpet are diagrammatically indicated in the dashed-line path shown in Figure 2B. It also lies within the contemplation of the invention to cut the broadloom (with backing) into the form of tiles prior to dyeing. If the pile surface structure 10C is cut into tiles (either before or after coloring) the tiles are advanced through the stainblocker application process using any commercially available transport belt conveyor. The dyed pile surface structure 10C (in either the broadloom or the carpet tile form) passes through a cold water 22 WO 01/04408 PCT/U S00/18589 rinsing step 21 and a hydroextraction step 22 to remove residual dyes and chemicals. Any conventional arrangement for suctioning liquid from a carpet may be used to perform the suctioning step. Both these steps are similar to corresponding steps of the conventional continuous process. If coloring of the pile surface structure occurs at an earlier time, the pile surface structure must be prewet (as at the water rinsing step 21) and the water extracted (as at step 22) before the stainblocker is applied. After suctioning the pile surface structure passes through an application device 24' where a stainblocker composition (with a surfactant, if used) is applied. In accordance with this embodiment of the present invention the temperature of the stainblocker composition is in the range from about twenty to about ninety-five degrees Celsius (20 to 95 °C). More preferably, the temperature is in the range from about twenty to about twenty-five degrees Celsius (2 0 to 25 °C) . For pile surface structure in the form of carpet tiles that are lying loosely on the transport belt a suitable system useful for the application step 241 is a flood applicator such as that manufactured by Eduard Kuesters Maschinenfabrik GmbH & Co. KG, Krefeld, Germany ("Kuesters"). By the term "flood applicator" it is meant that a running line of dyed carpet tiles is passed through a "gutter" that contains the stainblocker composition. A calculated amount of stainblocker composition is applied continuously by the "waterfall/weir" principle onto the carpet. For a pile surface structure in the form of a_broadloom carpet held by the guiding device, the stainblocker composition can be applied by any appropriate application device, such as: a dip trough (with nip rolls at the delivery end) ; a flood applicator; a foam applicator; the device manufactured by Kuesters and sold as "Flexnip"; or, the device manufactured by Kuesters and sold as "Fluidyer" . 23 WO 01/04408 PCT/US00/18589 The speed of the transport mechanism controls the time during which the pile surface structure is within the bath. For broadloom carpet, transport speed in the range from eight to fifteen (8 to 15) meters per minute is sufficient to keep the broadloom carpet within the bath for an appropriate period of time. For carpet tiles, transport speed in the range from two to five (2 to 5) meters per minute is sufficient to keep each tile within the bath for an appropriate period of time. As to the stainblocker compositions themselves, sulphone resole type stainblocker compositions with nonionic functionality (in the appropriate weight percentages and with appropriate pH adjustment) are preferred. Anionic functionalized type stainblocker compositions (also in the appropriate weight percentages and with appropriate pH adjustment) may also be used. As earlier discussed the pH of the treatment bath may be adjusted by known acid donor additives such as acetic acid, citric acid and sulfamic acid. Preferred surfactants again include appropriate amounts of an alkylated diphenyl oxide disulfonate sodium salt, alone or in combination with an alkylnaphtalene sulfonic acid formaldehyde condensate sodium salt. When the stainblocker composition is of the sulphone resole type having nonionic functionality the stainblocker composition is present between one and one-half percent (1.5%) and six percent (6%) based on the weight of the nylon yarns, and the pH of the stainblocker bath is between six (6) and seven and one-half (7.5). After exiting the applicator 24' the pile surface structure (either broadloom or tiles) is passed through a drying zone 281. Conveniently, the drying zone 28' is defined within a heating device. The temperature within the drying zone is in the range from seventy-five degrees Celsius to ninety-five degrees Celsius (75-95 °C) . More preferably, the temperature within the drying zone is in the range from eighty to eighty-five degrees Celsius (80-85 °C). 24 WO 01/04408 PCT/US00/18589 In the drying zone 28' the stainblocker composition is allowed to react with the nylon yarn in the textile surface. It is while the pile surface structure is heated to the temperature of the drying zone [i.e., in the range from 5 seventy-five degrees Celsius to ninety-five degrees Celsius (75-95 °C), and more preferably, in the range from eighty to eighty-five degrees Celsius (80-85 °C)] that the fiber structure becomes very open and the stainblocker is allowed to react with the fiber. The pile surface structure should 10 remain in this temperature environment for a time sufficient to permit the stainblocker to enter into and react with the nylon yarn in the textile surface, without the dye bleeding from the fiber. The time required for the pile surface structure to reach this temperature depends upon the 15 temperature of the stainblocker composition bath and the speed of the pile surface structure through the process. For typical stainblocker temperatures and transport speeds this residence time is in the range from about five (5) to about twenty (20) seconds, and more preferably, in the range from 20 about ten (10) to about fifteen (15) seconds. In the preferred instance infra-red energy is used to raise the temperature of the carpet in the drying zone. Suitable for use as the heating device within which the drying zone is defined is an infra-red oven such as that manufactured by 25 Babcock Textilmaschinen GmbH, Seevetal, Germany; Brueckner Trockentechnik GmbH and Co., KG, Leonberg, Germany; or Fleissner GmbH and Co., Egelsbach, Germany. It should be noted that in accordance with this invention the pile surface structure is not subjected to a steaming step 30 where bleeding of cationic dyestuff from the cat dyeable yarn would occur, as in the conventional continuous process. After undergoing treatment in the application device 24' and drying in the heating device 28' the pile surface structure is subjected to the conventional finishing steps 35 normally used in the continuous process. Such finishing steps would include a cold water rinse operation 32 and a suction 25 WO 01/04408 PCT/US00/18589 operations 34. A suction operation before the cold rinse could also be performed. Finally, the pile surface structure is dried in a drying oven 36 and suitably collected, as by a take-up roll (in the case of a broadloom carpet) or a 5 collection bin (in the case of carpet tiles). The take-up or collection bin is not illustrated in Figure 2B. If desired, after final drying in the oven 36, a broadloom carpet may be backed and then cut into tiles of desired size. 10 EXAMPLES 4-5 TEST METHODS The same Test Methods as were used in connection with Examples 1 through 3 were used in the Examples 4 and 5 below to measure carpet samples made according to the "infra-red" embodiment of the invention as well as control 15 samples for stain resistance, color stability and dyelightfastness. EXAMPLES 4a-4c Examples 4a-4c were performed to demonstrate the invention on overprinted carpet tiles. The carpet tiles were made of acid dyeable yarn. 20 In all of Examples 4a-4c the stainblocker was ZELAN® 8236 and the surfactant ZELAN® 50. The amount of ZELAN® 8236 was 5.0% of pile weight, the wet pickup was 400%. pH values were adjusted with citric acid to 6.3. The stainblocker composition was applied by flood process at a temperature of 25 seventy-six degrees Celsius (76 °C). The tiles were cured for ten (10) seconds at eighty degrees Celsius (80 °C) in an infra-red heater. In all of Examples la-c the residual moisture after printing was forty percent (40%). Example la was one hundred percent (100%) overprinted before treating 30 with the stainblocker composition. Example lb was forty percent (40%) overprinted and Example lc was an un-overprinted control carpet. After treating the tile sample pieces 4a-4c were water rinsed, extracted and dried. After dyeing, the tile sample pieces were each tested for 35 stainblocker performance (Kool-Aid test: cold rinsed, coffee 26 WO 01/04408 PCT/USOO/18589 test: after cleaned) by standard test methods. The results are reported in Table 4. As can be seen the stainblocker results of Examples 4a, 4b, and 4c were excellent. 5 TABLE 4 Example No. Kool- Coffee Aid After Cold cleaned rinsed 4a 10 10 4b 10 10 4c 10 9-10 Discussion of Results In all three examples application of the stainblocker composition using a flood applicator and an infra-red oven in accordance with the present invention resulted in all cases in excellent stairiblocking results. 10 Examples 5a-5d Examples 5a-5d were performed to demonstrate the invention on differentially dyeable nylon carpets. The carpet in Examples 5a-5d was a loop construction containing three different filament yarn types having deep acid, regular cationic, and light cationic dyeabilities. The 15 carpet was of blue (acid dyeable yarn) and orange (cationic dyeable yarn) color. Example 5a was treated by conventional winch/beck process. Example 5b was treated by conventional continuous application. Example 5c was treated by the infrared process of the present invention. Example 5d was an 20 untreated control carpet. In all of Examples 5a-5c ZELAN® 8236 (DuPont) as stainblocker and ZELAN® 50 (DuPont) as surfactant were used. In Examples 5a and 5b the amount of ZEIAN® 8236 was 5.5% and in Example 5c the amount of ZELAN® 8236 was 3.0% of carpet 25 pile weight. pH values were adjusted with acetic acid. Example 5a was treated for twenty minutes at pH 6.8 and at a temperature of seventy-five degrees Celsius (75 °C). Example 2b was treated at pH 6.8 and steamed afterwards. The wet pick-up was 450%. Example 2c was treated as described above 27 WO 01/04408 PCT/USOO/18589 at a pH of 6.8. Example 2d was treated in order to compare stainblocking performance, color stability and dyelightfastnesses. After treating the carpet sample pieces 5a-5c were water 5 rinsed, hydroextracted and dried. After drying, the carpet sample pieces were each tested for Kool-Aid staining, color stability and dyelightfastness by the test methods described above. The results are reported in Table 5. 10 TABLE 5 Example No. Kool-Aid C* Dyelightfastness 5a 10 11.12 5-6 5b 10 13.96 5-6 5c 10 15.87 6 5d 1-2 16.44 6 C* value (saturation, the higher the C* value the richer is the color) Discussion of Results As can be seen (compare Examples 5a, 5b to 5c and 5a, 5b, 5c to 5d) the infra-red process-15 treated carpet sample 5c shows the same excellent stainblocking results although a smaller amount of stainblocker has been used. These results (compare Examples 5a, 5b, 5c to 5d) also show smallest deviation in color saturation (C* values) of carpet specimen 5c. Also, as can be 20 seen by comparing Examples 5a, 5b and 5c to 5d, the dyelightfastnesses at all application methods are good. 28 </div>

Claims

<div class="application article clearfix printTableText" id="claims"> The claims defining the invention are as follows:

1. A method for treating an article having a textile surface with a stainblocker composition, the textile surface being formed from at least two types of nylon yarns, wherein at least one type of nylon yarn is dyeable by an acid dyestuff and at least one other type of nylon yarn is dyeable by a cationic dyestuff, the method comprising the sequential steps of: (a) dyeing the textile surface of the article with an acid dyestuff and a cationic dyestuff; (b) passing the textile surface of the article through an aqueous bath containing a stainblocker composition and a surfactant, the bath having a temperature from above seventy to ninety-five degrees Celsius (70 to 95° C), the textile surface remaining in the bath for about five (5) to about thirty (30) seconds; (c) removing excess water from the textile surface of the article; (d) passing the article through an ambient temperature zone; and (e) rinsing the textile surface of the article with water, and thereafter suctioning and drying the same, such that substantially the entire textile surface of the article is coated with a stainblocker composition whereby the textile surface has a stain resistance of 9 or higher on the AATCC Red 40 Stain Scale.

2. A method for treating an article having a textile surface with a stainblocker composition, the textile surface being formed from at least two types of dyeable nylon yarns, wherein at least one type of nylon yarn is dyeable by an acid dyestuff and at least one other type of nylon yarn is dyeable by a cationic dyestuff, the method comprising the step of: passing the textile surface of the article through a bath containing a stainblocker composition and a surfactant, the bath having a temperature from about seventy to ninety-five degrees Celsius (70 to 95°C), the textile surface remaining in the bath for about five (5) to about thirty (30) seconds, such that substantially the entire textile surface of the article is coated with a stainblocker composition, whereby the textile surface has a stain resistance of 9 or higher on the AATCC Red 40 Stain Scale. INTEOF°iceALOFTERTV " 5 JAN 2004 _ RECEIVED -29- 23/12/03,swopl 137spa2,29 I WE of^CFVH&PERTV I • 5 JAN 2004 L RECFI\/Fn

3. The method of claim 1 or claim 2, wherein the textile article is a pile MIUll structure having a plurality of pile elements thereon, the pile elements being formed from the first and the second types of nylon yarn, wherein substantially the entire height of each pile element is coated with a stainblocker composition whereby the pile surface structure has a stain resistance of 9 or higher on the AATCC Stain Rating Scale 40.

4. The method of any of claims 1 to 3, wherein the stainblocker composition comprises a stainblocker compound and a surfactant, and the stainblocker compound is of the anionic functionalized type.

5. The method of any one of claims 1 to 4, wherein the stainblocker composition is selected from the group consisting of sulphonated phenol formaldehyde condensate type, maleic acid anhydride type, acrylate dispersions and mixtures thereof; the stainblocker is present between three percent (3%) and five percent (5%) based o the weight of the nylon yarns; and the pH of the stainblocker bath is between two (2) and five (5).

6. The method of any one of claims 1 to 3, wherein the stainblocker composition comprises a stainblocker compound and a surfactant and the stainblocker compound is of the sulphone resole type having nonionic functionality.

7. The method of any one of claims 1 to 3 and 6, wherein the stainblocker composition is present between four precent (4%) and six percent (6%) based on the weight of the nylon yarns, and the pH of the stainblocker bath is between six (6) and seven and one-half (7.5).

8. The method of any one of claims 1 to 7, wherein the two types of dyeable nylon yarns are bulked continuous filament yarns.

9. The method of any one of claims 1 to 7, wherein the two types of dyeable nylon yarns are staple spun yarns. -30- 23/12/03,swopl 137spa2,30

10. The method of any one of claims 3 to 9, wherein at least some of the pile elements are formed both from a nylon yarn dyeable by an acid dyestuff and a nylon yarn dyeable by a cationic dyestuff.

11. The method of any one of claims 3 to 9, wherein at least some of the pile elements are formed from a nylon yarn dyeable by an acid dyestuff and at least others of the pile elements are formed from a nylon yarn dyeable by a cationic dyestuff.

12. An article having a textile surface formed from at least two types of nylon yarns, wherein at least one type of nylon yarn is dyeable by an acid dyestuff and at least one other type of nylon yarn is dyeable by a cationic dyestuff, and wherein the textile surface of the article is coated with a stainblocker composition substantially along its entire height, such that the surface has a stain resistance of 9 or higher on the AATCC Red 40 Stain Scale.

13. The article of claim 12, wherein the article is a pile surface structure and the textile surface is formed from a plurality of pile elements, the pile elements being formed from the first and second types of dyeable nylon yarns.

14. The article of claim 12 or claim 13, wherein the stainblocker composition comprises a stainblocker compound and a surfactant and the stainblocker compound is of the anionic functionalized type.

15. The article of any one of claims 12 to 14, wherein the stainblocker composition is selected from the group consisting of sulphonated phenol formaldehyde condensate type, maleic acid anhydride type, acrylate dispersions and mixtures thereof.

16. The article of claim 12 or claim 13, wherein the stainblocker composition comprises a stainblocker compound and a surfactant and the stainblocker compound is of the sulphone resole type having nonionic functionality.

17. The article of any one of claims 12 to 16, wherein the two types of dyeable nylon yarns are bulked continuous filament yarns. INTELLECTUAL "propfrtv OFFICE OF N.Z ~ 5 JAM 2004 RECEIVED -31 - /opll37spa2,31

18. The article of any one of claims 12 to 16, wherein the two types of dyeable nylon yarns are staple spun yarns.

19. The article of any one of claims 13 to 18, wherein at least some of the pile elements are formed from both a nylon yarn dyeable by an acid dyestuff and a nylon yarn dyeable by a cationic dyestuff.

20. The article of any one of claims 13 to 18, wherein at least some of the pile elements are formed from a nylon yarn dyeable by an acid dyestuff and at least others of the pile elements are formed from a nylon yarn dyeable by a cationic dyestuff.

21. An article produced by the method of claim 1.

22. The method of claim 1 or claim 2, or the article of claim 12, substantially as herein described with reference to any one of the Examples. Dated this 23rd day of December 2003 E.I. DU PONT DE NEMOURS AND COMPANY By their Patent Attorneys: CALLINAN LAWRIE -32-

23/12/03, swopll37spa2,32 </div>