AU2006269600B2

AU2006269600B2 - Polymeric extenders for surface effects

Info

Publication number: AU2006269600B2
Application number: AU2006269600A
Authority: AU
Inventors: John J. Fitzgerald; Ying Wang
Original assignee: EI Du Pont de Nemours and Co
Current assignee: EIDP Inc
Priority date: 2005-07-06
Filing date: 2006-06-28
Publication date: 2011-11-24
Anticipated expiration: 2026-06-28
Also published as: AU2006269600A1

Abstract

A polymer extender composition comprising monomers copolymerized in the following percentages by weight: (a) from about 5% to about 90% of a monomer of the formula (I): R-OC(O)-C(R)=CH (b) from about 5% to about 85% of vinylidene chloride, vinyl chloride, vinyl acetate, or a mixture thereof, (c) from about 0.5% to about 3% of a monomer of the formula (II): HO-CH-NH-C(O)-C (R)=CH (d) from about 0.5% to about 3% of a monomer of the formula (III ) HO-CHCH-OC(O)-C (R)=CH and (e) from about 1% to about 5% of a monomer of the formula (IV): H-(OCHCH)-O-C(O)-C(R)=CH (f) from 0% to about 25% of methyl methacrylate, vinylbenzyl chloride, styrene or a mixture thereof, wherein each R is independently H or CH; R is a linear or branched or cyclic alkyl chain having from about 4 to about 18 carbon atoms, and m is 2 to about 10.

Description

WO 2007/008416 PCT/US2006/025135 TITLE POLYMERIC EXTENDERS FOR SURFACE EFFECTS FIELD OF THE INVENTION Polymeric extender compositions are employed to improve the 5 performance of treating agents which provide surface effects to treated substrates. Background of the Invention Various compositions are known to be useful as treating agents to provide surface effects to substrates. Surface effects include repellency to 10 moisture, soil, and stains, and other effects, which are particularly useful for fibrous substrates such as fibers, fabrics, textiles, carpets, paper, leather, and other such substrates. Many such treating agents are fluorinated polymers or copolymers. Fluorinated polymer compositions having utility as fibrous substrate 15 treating agents generally contain pendant perfluoroalkyl groups of three or more carbon atoms, which provide oil- and water-repellency when the compositions are applied to fibrous substrate surfaces. The perfluoroalkyl groups are generally attached by various connecting groups to polymerizable groups not containing fluorine. The resulting monomer is 20 then generally copolymerized with other monomers, which confer additional favorable properties to the substrates. Various specialized monomers may be incorporated to impart improved cross-linking, latex stability and substantivity. Since each ingredient may impart some potentially undesirable properties in addition to its desirable ones, the 25 specific combination is directed to the desired use. These polymers are generally marketed as aqueous emulsions for easy application to the fibrous substrates. US Patent 6,479,605 discloses a fluorinated copolymer useful for treating fibrous substrates to provide oil repellency and water repellency. 1 Various attempts have been made to increase the oil- and water repellency imparted to the substrate and its durability while reducing the amount of fluorinated polymer required, i.e., boost the efficiency or performance of the treating agent. One method is to incorporate blocked isocyanates or melamine 5 resins. However, only limited amounts can be used because these ingredients tend to adversely affect the handle (the feel) of the fibrous substrates. Another method is the use of various extender polymers. These are typically hydrocarbon polymers in aqueous emulsions, which are blended with the fluorinated polymer emulsion before application to the substrate. 10 US Patent 6,309,752 discloses compositions comprising a fluorochemical agent, a copolymer extender comprising two distinct polymerized units, and a blocked isocyanate extender, wherein the extenders in combination improve the fluorine efficiency of the fluorochemical agent to a greater degree than either of the extenders alone. The two distinct polymerized units are (1) 15 optionally halogenated polymerizable ethylenic compounds, particularly acrylates; and (2) ethylenic compounds containing a functional group that can react with a fabric. It has been found that blocked isocyanate extenders tend to adversely affect the hand (feel) of the fibrous substrate. There is a need for polymer compositions, which significantly improve the 20 performance of surface effect agents. In particular, there is a need for compositions which improve the performance of fluorinated polymer treating agents for substrates to provide repellency and other surface effects while reducing the amount of fluorinated polymer required. The present invention provides such a composition. 25 Summary of the Invention The present invention provides a polymer composition comprising monomers copolymerized in the following percentages by weight: (a) from about 5% to about 90% of a monomer of formula 1:

R

1

-OC(O)-C(R)-CH

2 30 (b) from about 5% to about 85% of vinylidene chloride, vinyl chloride, vinyl acetate, or a mixture thereof, (c) from about 0.5% to about 3% of a monomer of formula II: 2

HO-CH

2

-NH-C(O)-C(R)=CH

2 (II) (d) from about 0.5% to about 3% of a monomer of formula III

HO-CH

2

CH

2

-OC(O)-C(R)-CH

2 (1l1) and 5 (e) from about 1% to about 5% of a monomer of formula IV:

H-(OCH

2

CH

2 )m-O-C(O)-C(R)=CH 2 (IV) (f) from 0% to about 25% of methyl methacrylate, vinylbenzyl chloride, styrene or a mixture thereof, wherein 10 each R is independently H or CH 3 ; R1 is a linear or branched or cyclic alkyl chain having from about 4 to about 18 carbon atoms, and m is 2 to about 10, said composition increasing the fluorine efficiency in treatment of a substrate by 15 permitting use of lower levels of fluorinated surface treating agents providing durable oil repellency and water repellency, such that the fluorine content of a blend of said composition with a fluorinated surface treating agent is from about 1.5% to about 6.6%. by weight of the blend. The present invention further provides a method of treating a substrate 20 comprising contacting the substrate with a composition comprising i) an agent which provides a surface effect and ii) a polymer composition as described above. The present invention further provides a substrate treated by a composition comprising i) an agent which provides a surface effect and li) a 25 polymer composition as described above. Detailed Description of the Invention Trademarks and tradenames are indicated herein by capitalization. This invention comprises an extender polymer composition useful for improving the performance of treating agents that provide surface effects to substrates. In 30 particular, the extender composition is useful for improving the performance of fluorinated polymers in imparting durable 3 WO 2007/008416 PCT/US2006/025135 properties to fibrous substrates. The fibrous substrates include paper, nonwovens, leather, carpet, fibers, textiles, and fabrics or fabric blends. By "fabrics" is meant natural or synthetic fabrics, or blends thereof, composed of fibers such as cotton, rayon, silk, wool, polyester, 5 polypropylene, polyolefins, nylon, and aramids such as "NOMEX" and "KEVLAR." By "fabric blends" is meant fabric made of two or more types of fibers. Typically these blends are a combination of at least one natural fiber and at least one synthetic fiber, but also can be a blend of two or more natural fibers or of two or more synthetic fibers. 10 Superior surface properties, along with desirable properties of low yellowing, soft hand and improved durability, can be imparted to fibrous substrates by the addition of the inventive extender polymer composition to surface treating agent composition before application to the fibrous substrates. These combined compositions can be applied to the fibrous 15 substrates in the form of a dispersion in water or other solvent either before, after or during the application of other treatment chemicals. When so applied, the extender composition of the present invention in combination with a fluorinated polymer-treating agent has been found to increase the durability of surface properties, especially oil- and water 20 repellency, in fibrous substrates. Further, use of the extender composition increases fluorine efficiency by permitting use of lower levels of the fluorinated polymer. This is desirable because fluorinated polymer surface treating agents tend to be expensive. The extender polymer compositions of this invention are prepared 25 by conventional emulsion polymerization techniques. Generally, such copolymers are prepared by copolymerization of two or more monomers in an aqueous media with the resulting dispersion or emulsion stabilized using a surfactant. The surfactant employed to stabilize the emulsion during its formation and during polymerization can be a conventional 30 cationic, nonionic, and /or anionic emulsifying agent or mixtures thereof. The polymerization is conveniently initiated by any free radical initiators such as 2,2'-azobis(2-amidinopropane) dihydrochloride, which is sold by 4 WO 2007/008416 PCT/US2006/025135 E. 1. du Pont de Nemours and Company, Wilmington, Delaware, commercially under the name of "VAZO". The aqueous dispersions produced by mixing the extender composition dispersion with a fluorinated polymer dispersion are applied to 5 the surfaces of fibrous substrates by known methods to impart oil-, soil and water-repellency and other surface effects. Examples of these fluoropolymer dispersions are ZONYL available from E. I. du Pont de Nemours and Company, Wilmington, DE; OLEOPHOBOL from Ciba Specialty Chemicals, Langweid, Germany; ASAHI GARD from Asahi 10 Glass Company, Ltd., Tokyo, Japan; UNIDYNE from Daikin America, Inc., Orangeburg, NY; SCOTCHGARD from 3M Company, St. Paul, MN; and NANO TEX from Nanotex, Emeryville, CA. A distinguishing feature of the inclusion of the extender compositions of the present invention is high fluorine efficiency and high durability of the finish on the substrate. 15 The extender polymer composition of the present invention comprises a copolymer comprising monomers copolymerized in the following percentages by weight: (a) from about 5% to about 90% of a monomer, or mixture of monomers, of formula I: 20 R 1

-OC(O)-C(R)=CH

2 (b) from about 5% to about 85% of vinylidene chloride, vinyl chloride, vinyl acetate, or a mixture thereof, (c) from about 0.5% to about 3% of a monomer of the formula II:

HO-CH

2 -NH-C(O)-C (R)=CH 2 (1I) 25 (d) from about 0.5% to about 3% of a monomer of the formula Ill

HO-CH

2

CH

2 -OC(O)-C (R)=CH 2 (1ll) and (e) from about I % to about 5% of a monomer of the formula IV:

H-(OCH

2

CH

2 )m-O-C(O)-C(R)=CH 2 (IV) 30 (f) from 0% to about 25% of methyl methacrylate, vinylbenzyl chloride, styrene or a mixture thereof, 5 WO 2007/008416 PCT/US2006/025135 wherein each R is independently H or CH 3 ;

R

1 is a linear or branched alkyl chain having from about 4 to about 18 carbon atoms, and 5 m is 2 to about 10. The term "(meth)acrylate" is used herein to mean either methacrylate, acrylate, or a mixture of the two. The required monomer (a) of formula I in the present invention is one or a mixture of alkyl (meth)acrylates having chain lengths of from 10 about 4 to about 18 carbons. These are added to the polymerization in proportions from about 5% to about 90%. Preferably the proportion of monomer (a) in the copolymer is between about 40% and about 85 % by weight. As used herein, "alkyl" refers to linear, branched-chain and cyclic alkyl groups. Examples of such monomers include stearyl (meth)acrylate, 15 lauryl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, and others. Of the foregoing, stearyl acrylate and stearyl methacrylate are most preferred. The required monomer (b) is vinylidene chloride, vinyl chloride, 20 vinyl acetate or a mixture thereof. It is added to the polymerization in proportions from about 5% to about 85%. Preferably the proportion of monomer (b) in the copolymer is between about 5 % and about 50 % by weight. Monomers (c), (d) and (e) act together to improve the durability of 25 the treating agent. Monomer (c) is N-methylol acrylamide or methacrylamide. N-methylol acrylamide is preferred. It is added to the polymerization in proportions from about 0.5% to about 3%, preferably from about 0.7% to about 1.5%. Monomer (d) is a hydroxyethyl (meth)acrylate. It is added to the polymerization in proportions from about 30 0.5% to about 3%, preferably from about 0.7% to about 1.5%. Monomer (e) is an ethoxylated (meth)acrylate wherein the number of ethoxy groups is between 2 and about 10. Between about 4 and about 10 ethoxy groups 6 WO 2007/008416 PCT/US2006/025135 are preferred. It is added to the polymerization in proportions from about 1 % to about 5%, preferably about 1.5% to about 3%. The extender composition described above is then blended with any of a variety of known treating agents for fibrous substrates. Of 5 particular interest are fluorinated polymers useful as treating agents to provide repellency properties to the surface of treated substrates. The copolymer dispersion is blended with the fluorinated polymer in a ratio of from about 0.5:10 to about 6:1, preferably from about 1:3 to about 3:1, and more preferably from about 1:2 to about 2:1. The fluorine content of the 10 blend is from about 1.5% to about 6.6% by weight, preferably from about 2.0% to about-4.0% by weight. The fluorinated polymer treating agents are any of those used for creating surface effects on a fibrous substrate, in particular oil- or water-repellency. These include fluorinated compounds or polymers containing one or more fluoroaliphatic groups (designated 15 here as Rf groups) which are fluorinated, stable, inert, non-polar, preferably saturated, monovalent and both oleophobic and hydrophobic. The Rf groups preferably contain at least 3 carbon atoms, more preferably 3 to about 20 carbon atoms, and most preferably about 6 to about 14 carbon atoms. The Rf groups may contain straight or branched chain or 20 cyclic fluorinated alkylene groups or combinations thereof. The terminal portion of the Rf groups is a perfluorinated aliphatic group of the formula CnF 2 ne+ wherein n is from about 3 to about 20. Examples of such fluorinated polymers preferably include Rf containing polyurethanes and poly(meth)acrylates. Especially preferred 25 are copolymers of fluorochemical (meth)acrylate monomers with a co polymerizable monovinyl compound or a conjugated diene. The co polymerizable monovinyl compounds include alkyl (meth)acrylates, vinyl esters of aliphatic acids, styrene and alkyl styrene, vinyl halides, vinylidene halides, alkyl esters, vinyl alkyl ketones, and acrylamides. The conjugated 30 dienes are preferably 1,3-butadienes. Representative compounds within the preceding classes include the methyl, propyl, butyl, 2-hydroxypropyl, 2-hydroxyethyl, isoamyl, 2-ethylhexyl, octyl, decyl, lauryl, cetyl, and octadecyl acrylates and methacrylates; vinyl acetate, vinyl propionate, 7 WO 2007/008416 PCT/US2006/025135 vinyl caprylate, vinyl laurate, vinyl stearate, styrene, alpha methyl styrene, p-methylstyrene, vinyl fluoride, vinyl chloride, vinyl bromide, vinylidene fluoride, vinylidene chloride, allyl heptanoate, allyl acetate, allyl caprylate, allyl caproate, vinyl methyl ketone, vinyl ethyl ketone, 1,3-butadiene, 2 5 chloro-1,3-butadiene, 2,3-dichloro-1,3-butadiene, isoprene, N methylolacrylamide, N-methylolmethacrylamide, glycidyl acrylate, glycidyl methacrylate, and polyoxymethacrylates. The blended composition comprising a fluorinated polymer and the extender polymer of the present invention applied to the fibrous substrate 10 may optionally contain a blocked isocyanate to further promote durability, added after copolymerization (i.e., as a blended isocyanate). An example of a blocked isocyanate is HYDROPHOBOL XAN available from Ciba Specialty Chemicals, High Point, NJ. Other commercially available blocked isocyanates are also suitable for use herein. The desirability of 15 adding a blocked isocyanate depends on the particular application for the copolymer. For most of the presently envisioned applications, it does not need to be present to achieve satisfactory cross-linking between chains or bonding to the substrate. When added as a blended isocyanate, amounts up to about 20% by weight may be added. 20 The blended composition comprising a fluorinated polymer and the extender composition of the present invention optionally further comprises additional components such as treating agents or finishes to achieve additional surface effects, or additives commonly used with such agents or finishes. Such additional components comprise compounds or 25 compositions that provide surface effects such as no iron, easy to iron, shrinkage control, wrinkle free, permanent press, moisture control, softness, strength, anti-slip, anti-static, anti-snag, anti-pill, stain repellency, stain release, soil repellency, soil release, water repellency, oil repellency, odor control, antimicrobial, sun protection, and similar effects. One or 30 more such treating agents or finishes can be combined with the blended composition and applied to the fibrous substrate. Other additives commonly used with such treating agents or finishes may also be present such as surfactants, pH adjusters, cross linkers, wetting agents, wax 8 WO 2007/008416 PCT/US2006/025135 extenders, and other additives known by those skilled in the art. Suitable surfactants include anionic, cationic, and nonionic. Preferred is an anionic surfactant such as sodium lauryl sulfonate, available as DUPONOL WAQE from Witco Corporation, Greenwich, CT. 5 In particular, the blended composition comprising a fluorinated polymer and the extender polymer of the present invention applied to the fibrous substrate may further comprise a softener to further promote hand, added after copolymerization. The desirability of adding a softener depends on the particular application for the copolymer. The examples of 10 softener can be chosen from Wacker Chemical softener products such as WACKER FINISH WR 1300, WACKER FINISH CT 34E, WACKER FINISH WT 1650, JETSOFT NFS, POWERSOFT AE 38 and WETSOFT AOP, or from Dow Chemical, Silicone softener 2-8031. Amounts up to 1 % by weight may be added. 15 Optionally, when the above blend of extender polymer composition and fluoropolymer composition are applied to fibrous substrates, other extender compositions may also be included in the application to obtain some combination of benefits. One example of such an optional additional extender polymer composition is that disclosed in co-pending 20 US Provisional Application 60/607,612, filed September 7, 2004 (CH-2996). When such an optional extender is added to the previously described inventive extender polymer, the percentages given above for the inventive ingredients (a), (b), (c), (d) and (e) shall apply to the total extender polymer composition. 25 The present invention further comprises a method of treating substrates comprising contacting the surface of the substrate with an effective amount of a composition comprising an extender composition of the present invention as described above and a treating agent which provides a surface effect when applied to a substrate. Preferably the 30 treating agent is a fluorinated polymer. The blended combination is applied to the fibrous substrate to be treated from aqueous dispersions, either alone or in a mixture with other textile treatment agents, finishes or additives as described above. The dispersions are generally applied to 9 WO 2007/008416 PCT/US2006/025135 fibrous substrates by spraying, dipping, padding, or other well-known methods. After excess liquid has been removed, for example by squeeze rolls, the treated fibrous substrate is dried and then cured by heating, for example, to 100*C to 1900C, for at least 30 seconds, typically from about 5 60 to about 240 seconds. Such curing enhances oil-, water- and soil repellency and durability of the repellency. While these curing conditions are typical, some commercial apparatus may operate outside these ranges because of its specific design features. The treated fibrous substrate has a fluorine content of from about 0.05% to about 0.5% by 10 weight. The present invention further comprises substrates treated with the above-described composition comprising i) a treating agent which provides a surface effect and ii) the extender copolymer of the present invention as described above. The composition also can contain optional 15 agents to provide additional surface effects as described above, optional additives commonly used in treating substrates as described above, optional blocked isocyanate as described above, and optional additional distinct extender compositions. As previously noted such substrates include fibers, paper, nonwovens, leather, textiles, and fabrics or fabric 20 blends. "Fabrics" includes natural or synthetic fabrics composed of fibers of cotton, rayon, silk, wool, polyester, polypropylene, polyolefins, nylon, and aramids such as "NOMEX" and "KEVLAR." By "fabric blends" is meant fabric made of two or more types of fibers. Typically these blends are a combination of at least one natural fiber and t least one synthetic 25 fiber, but also can be a blend of two or more natural fibers or of two or more synthetic fibers. Preferably, the substrate has been treated with a composition comprising an extender composition of the present invention and a fluorinated polymer such as a polyurethane or poly(meth)acrylate. Specifically, the composition, method and treated substrates of the 30 present invention are useful to enhance surface properties, in particular oil-, water- and soil-repellency, of the above-described substrates while reducing the amount of fluorinated polymer employed. The repellency property is more durable than applications of fluorinated polymer without 10 WO 2007/008416 PCT/US2006/025135 the extender present, and is effective for various fibrous substrates. The repellency property is effective with a variety of other surface effects. The treated substrates of the present invention are useful in a variety of applications such as for textiles, clothing, uniforms, protective garments, 5 furnishings and the like. The extender copolymers of the present invention are advantageous in that they give highly durable, low yellowing and soft hand repellent finishes over a wide range of fibrous substrates, such as fabrics or fabric blends, while using a reduced level of the fluorinated polymer. The inventive compositions are made at lower materials cost 10 than the current (meth)acrylate copolymers, for example by reducing the amount of the expensive fluorinated polymer required to provide the desired surface effects. Test Method 1 - Fabric Treatment The fabric was treated with the copolymer blend using a 15 conventional pad bath (dipping) process. A bath containing 0.1 to 0.5% by weight of the fluorinated polymer-treating agent blended with the extender copolymer of the present invention (hereinafter copolymer blend), as detailed in the Tables in the Example section, was used to treat fabrics. The fluoropolymers used for blending with the non-fluorinated copolymer 20 extenders were commercial ZONYL products that are available from E. I. du Pont de Nemours and Company, Wilmington, DE. After application, the fabrics were cured at approximately 160 0C for 1 - 3 minutes, and allowed to "rest" after treatment and cure. The resting time employed was overnight, about 15 - 18 hours. 25 Test Method 2 - Water Repellency The water repellency of a treated substrate was measured according to the DuPont Technical Laboratory Method as outlined in the TEFLON Global Specifications and Quality Control Tests information packet. The test determines the resistance of a treated substrate to 30 wetting by aqueous liquids. Drops of water-alcohol mixtures of varying surface tensions are placed on the fabric and the extent of surface wetting 11 WO 2007/008416 PCT/US2006/025135 is determined visually. The test provides a rough index of aqueous stain resistance. The higher the water repellency rating, the better the resistance the finished substrate has to staining by water-based substances. The composition of standard test liquids is shown in the 5 following Table 1. Sometimes a 1 - 6 scale was used for convenience. Ratings of 0.5 increments are determined by subtracting one half from the numbers in Table 1 for borderline passing of the test liquid. Table I Standard Test Liquids Water Composition, Vol. % Repellency Isopropyl Distilled Water Rating Number Alcohol 1 2 98 2 5 95 3 10 90 4 20 80 5 30 70 6 40 60 7 50 50 8 60 40 9 70 30 10 80 20 11 90 10 12 100 0 10 Test Method 3 - Water Repellency - Spray Ratinq Water repellency can be further tested by utilizing the spray test method. The treated fabric samples were tested for water repellency by following the AATCC standard Test Method No. 22-1996, conducted as follows: A fabric sample, treated with an aqueous dispersion of polymer 15 as previously described, is conditioned for a minimum of 2 hours at 23 0 C + 20% relative humidity and at 650C + 10% relative humidity. The fabric sample is securely fastened on a plastic/metal embroidery hoop such that the fabric is wrinkle-free. The hoop is placed on the testing stand so that the fabric is facing up. Then 250 mL of water at 80 ± 2*F (27 ±1oC) is 20 poured into the testing funnel allowing the water to spray onto the fabric 12 WO 2007/008416 PCT/US2006/025135 surface. Once the water has run through the funnel, the hoop is rapped against the edge of a solid object with the fabric facing down, rotated 180 degrees and rapped again. The spotted or wetted surface is compared with the AATCC standards found in the AATCC Technical Manual. The 5 more wet the surface, the lower the number and the poorer the repellency. A 100 denotes no wetting, a 90 denotes slight wetting (three small spots), an 80 denotes wetting signified by several (10) spots at the spray points, a 70 denotes partial wetting of the upper fabric surface, a 50 denotes wetting of the entire upper fabric surface, and a 0 denotes complete 10 wetting of the lower and upper fabric surface. A rating of 15, 25, 35, 45, 55, 60, 65, 75 or 85 indicates performance intermediate between the above-described rankings. Test Method 4 - Oil Repellency The treated fabric samples were tested for oil repellency by a 15 modification of AATCC standard Test Method No. 118, conducted as follows: A fabric sample, treated with an aqueous dispersion of polymer as previously described, is conditioned for a minimum of 2 hours at 230C + 20% relative humidity and 650C + 10% relative humidity. A series of organic liquids, identified below in Table 2, are then applied drop wise to 20 the fabric samples. Beginning with the lowest numbered test liquid (Repellency Rating No. 1), one drop (approximately 5 mm in diameter or 0.05 mL volume) is placed on each of three locations at least 5 mm apart. The drops are observed for 30 seconds. If, at the end of this period, two of the three drops are still spherical in shape with no wicking around the 25 drops, three drops of the next highest numbered liquid are placed on adjacent sites and similarly observed for 30 seconds. The procedure is continued until one of the test liquids results in two of the three drops failing to remain spherical to hemispherical, or wetting or wicking occurs. The oil repellency rating of the fabric is the highest numbered test 30 liquid for which two of the three drops remained spherical to hemispherical, with no wicking for 30 seconds. In general, treated fabrics with a rating of 6 or more are considered good to excellent; fabrics having 13 WO 2007/008416 PCT/US2006/025135 a rating of one or greater can be used in certain applications. Ratings of 0.5 increments are determined by subtracting one-half from the number in Table 2 for borderline passing of the text liquid. Table 2 5 Oil Repellency Test Liquids Oil Repellency Rating Number Test Solution 1 NUJOL Purified Mineral Oil 2 65/35 Nujol/n-hexadecane by volume at 210C 3 n-hexadecane 4 n-tetradecane 5 n-dodecane 6 n-decane 7 n-octane 8 n-heptane Note: NUJOL is a trademark of Plough, Inc., for a mineral oil having a Saybolt viscosity of 360/390 at 380C and a specific gravity of 0.880/0.900 at 15*C. Test Method 5 - Wash Durability 10 The fabric samples were laundered according to International Standard specifies domestic washing procedure for textile testing. Fabric samples are loaded into a horizontal drum, front-loading type (Type A, WASCATOR Fom7l MP-Lab) of automatic washing machine with a ballast load to give a total dry load of 4 lb. A commercial detergent is added 15 (AATCC 1993 standard Reference Detergent WOB) and the washer programmed with high water level with warm water (105 'F, 41 C), 15 minutes normal wash cycle followed by 2 times 13 minutes rinse and then 2 minutes spin dry. The sample and ballast are washed a designated number of times (5HW for 5 washes, 20HW for 20 washes etc.). After 20 washing is complete, the wet fabric samples are dried in air, then ironed with a flatbed press at a surface temperature of 135 - 160 C, 30 seconds on each side. 14 WO 2007/008416 PCT/US2006/025135 EXAMPLES In the Tables hereinafter, the term "fluorochemical" is used to identify the fluorinated polymer prior to its combination with the extender composition of the present invention. 5 Example I A water emulsion was prepared by mixing the following: 96 g of hot deionized H 2 0 (50 - 60"C), 3.2 g of ETHOQUAD 18/25 (available from Akzo Nobel, Chicago, IL), 4.6 g of tridecyl alcohol 5-ethylene oxide adduct (ETHOX TDA-5, available from Ethox Chemicals, Greenville, SC), 30 g of 10 stearyl methacrylate, 1.25 g of N-methylolacrylamide, 0.68 g of 2 hydroxyethyl methacrylate, 1.25 g of poly(oxyethylene)7 methacrylate, 0.34 g of dodecyl mercaptan and 19.36 g of dipropylene glycol, and then charged to a 500 mL of four-necked flask equipped with mechanic stir, thermocouple thermometer and chiller condenser (-5 to -10 'C). The 15 charge was rinsed into the flask with 10 g of hot deionized water and purged with nitrogen for 30 minutes or until the temperature is below 30 *C. 30 g of vinylidene chloride was then charged to the reaction flask and mixed for 5 minutes. Then, 0.34 g of "VAZO" 56 WSP (E. . du Pont de Nemours and Company, Wilmington, DE) dissolved in 10 g deionized 20 water was added to initiate polymerization. The mixture was heated to 50 'C over a period of thirty minutes and maintained for 8 hours. Following the polymerization a water solution of 0.46 g of DUPONOL WAQE (available from Witco Corporation, Greenwich, Conn.) was mixed with the product at room temperature. The resulting polymer extender 25 latex (dispersion in water) weighed 206 g with solids content of 27.92%. Tm = 25.36 0 C and 8H = 23.93 J/g. The above-resulted latex was separately blended with commercially available fluoropolymers, ZONYL 8300, ZONYL 8412, and ZONYL 8932 from E. 1. du Pont de Nemours and Company, Wilmington, DE for 30 performance tests. The blends contained a ratio of extender to fluoropolymer of from 3:1 to 1:1. The blend with ZONYL fluoropolymers were applied to 100% nylon fabric using Test Method I described above. 15 WO 2007/008416 PCT/US2006/025135 The bath contained 20-50g/L of the blended product for the data in Tables 4 and 5. For the data in Table 6, the bath contained 10-1 5g/L of the fluorinated polymer and the ratio of the extender of Example 1 to fluorinated polymer was as shown in Table 6. A wetting agent 5 ALKANOL 6112 (available from E. 1. du Pont de Nemours and Company, Wilmington, DE) was also included in the bath at 2 g/L. After application, the fabrics were cured at about 160 0 C for about 2 minutes. The fabric was allowed to "rest" after treatment and cure. The treated fabric was tested for oil repellency, water repellency and spray repellency using Test 10 Methods 2, 3, 4 and 5 described above. Results are listed in Tables 4 - 6. Example 2 - 7 The procedure of Example 1 was followed, except for using different amounts of stearyl methacrylate and vinylidene chloride as shown below in Table 3. The solid content and melting point are also included in 15 Table 3. Table 3. Product Compositions and DSC Data Example# 2 3 4 5 6 7 StMA* 45 50 55 40 15 20 VDC* 15 10 5 20 45 40 Solid % 27.39 28.98 30.02 27.73 25.5 28.04 Tm (0C)/ 30.09/ 31.39/ 31.76/ 30.47/ 15.26/ 5H( J/g) 42.78 32.52 35.36 73.31 15.18 *StMA = stearyl methacrylate, VDC = vinylidene chloride The extenders were blended with ZONYL fluorochemicals, applied to 20 nylon fabric, and tested as described in Example 1. Results are in Tables 4 - 6. Comparative Example A A water emulsion was prepared by mixing the following: 96 g of hot deionized H 2 0 (50 - 60'C), 3.2 g of ETHOQUAD 18/25 (available from 25 Akzo Nobel, Chicago, IL), 4.6 g of tridecyl alcohol 5-ethylene oxide adduct 16 WO 2007/008416 PCT/US2006/025135 (ETHOX TDA 5 from Ethox Chemicals, Greenville, SC), 60 g of stearyl methacrylate, 1.25 g of poly(oxyethylene)7 methacrylate, 1.25 g of N methylolacrylamide, 0.68 g of 2-hydroxyethyl methacrylate, 0.34 g of dodecyl mercaptan and 19.36 g of dipropylene glycol, and then charged to 5 a 500 mL of four-necked flask equipped with mechanic stir, thermocouple thermometer and chiller condenser (-5 to -10 *C). The charge was rinsed into the flask with 10 g of hot deionized water and purged with nitrogen for 30 minutes. Then, 0.34 g of "VAZO" 56 WSP (E. 1. du Pont de Nemours and Company, Wilmington, DE) dissolved in 10 g deionized water was 10 added to initiate polymerization. The mixture was heated to 50 0 C over a period of 30 minutes and maintained for 8 hours. Following the polymerization a water solution of 0.46 g of DUPONOL WAQE (available from Witco Corporation, Greenwich, Conn.) was mixed with the product at room temperature. The resulting polymer extender latex (dispersion in 15 water) weighed 206 g with solids content of 27.92%. Tm was 32.86 oC and 5H was 39.27 J/g. The extender was blended with ZONYL fluorochemicals, applied to nylon fabric, and tested as described in Example 1. Results are in Tables 4 - 6. Comparative Example B 20 A water emulsion was prepared by mixing the following: 167 g of hot deionized H 2 0 (50 - 60'C), 0.7 g of ETHOQUAD 18/25 (available from Akzo Nobel, Chicago, IL), 2.9g of tridecyl alcohol 5-ethylen oxide adduct (ETHOX TDA-5, Ethox Chemicals, Greenville, SC), 3.33 g of poly(oxyethylene)7 methacrylate, 3.33g of N-methylolacrylamide, 1.67 g of 25 2-hydroxyethyl methacrylate, 0.1 g of dodecyl mercaptan and 16.67 g of 2 methyl-2,4-pentanediol, and then charged to a 1 L autoclave. The autoclave was sealed and evacuated / filled with nitrogen three times. 30 g of vinylidene chloride was then charged. Then, 0.34 g of "VAZO" 56 WSP (E. I. du Pont de Nemours and Company, Wilmington, DE) dissolved 30 in 10 g deionized water was added to initiate polymerization. The mixture was heated to 50 *C over a period of 30 minutes and maintained for 8 hours with agitator at 150 RPM. The resulting latex extender was filtered 17 WO 2007/008416 PCT/US2006/025135 through a milk filter. The extender was blended with ZONYL fluorochemicals, applied to nylon fabric, and tested as in Example 1. Results are in Tables 4 - 6. Table 4 Fluorochemical ZONYL 8932 ZONYL ZONYL 8932 ZONYL 8932 8932 Example Extender Comparative 1 Comparative none Ex. B Ex. A F% weight based on 0.093 0.097 0.1 0.19 treated fabric Oil Repellency initial 6 6 5 6 5HW 5 6 - 3 20HW 1 6 3 1 Water Repellency initial 6 6 6 6 5HW 6 6 - 6 20HW 6 6 6 6 Spray Repellency initial 100 100 100 100 5HW 80 90 - 70 20HW 75 80 80 70 5 Note: Tested using a scale of 1 - 6 for water and oil repellency in Test Method 2. The results showed that the copolymer of Example 1 provided better performance than that of Comparative Examples A and B when employing similar levels of fluorine. Compared to the fluoropolymer 10 without extender, better performance was obtained when the extender of Example I was used, even with only 50% of fluorine present. 18 WO 2007/008416 PCT/US2006/025135 a) 0) CoI COOt o.o L 6EW 0 a) 0) a T-C[O 0) LO 0 C) 0)LOo L 0) 0) 'ttl o 1 oCD - N to 0) q) 0) C) I CU 0 0) 0)) 0) C*) o C 0) a) 0 0Y) Ct O C"Jc C o0 >- ED) C 6Z C0 a -: Cj-U a) C: ZXU N uO c)WS WO 2007/008416 PCT/US2006/025135 (D rl CLO Nc ~ LO 6D EWu 0 0OC I-. NC I-, LC) ~C) L O CO ItN 0CD I- co CD co P-_oCC C) 0) NCq C1 C ) : 7- C\J N C) ~CCD .~~( 0CC') 6 zO z~ c t CO 0 0C 0o a) > - W C) C)L LL 0 + ~ ~ 0 0)C LC N) N~ N a) N WO 2007/008416 PCT/US2006/025135 0) oO c.m C)C to 0) 00 EWLL 0 C)= CU co0 C 0 0) C 0D)0 0) 0 C 0) S0) OC 0) a) 600\ 0) 0) co t Cto o)O 0) 00 C C\ CLOcoC 0) 0) t o N t 0 L Oo a) 0) c CCo ~CTJ ) "a) 2 0 2 0 0 00 - co -~ _ u- Cm LL 0 + w=a) N) 0 ) C )C 0 w N M WO 2007/008416 PCT/US2006/025135 The data in Tables 5A, 5B, and 5C showed that the blended formulation containing the extender of Examples 1 through 7 provided comparable or better performance with 50% fluorine reduction compared to the fluorochemical without extender on nylon fabric. The data also showed that the extenders of Examples 5 through 7 provided comparable or better performance than Comparative Examples A and B at the same level of fluorine. Table 6 Fluoro- ZONYL ZONYL ZONYL ZONYL ZONYL ZONYL ZONYL ZONYL chemical 8932 8932 8300 8300 8300 8412 8412 8412 Ratio of 1/1 2/1 0.6/1 1/1 2/1 0.6/1 1/1 2/1 Extender of Ex. 1/ Fluoro chemical Oil Repellency initial 7.5 7.5 7.5 7.5 5.5 7.5 7.5 6.5 1OHW-iron 6.5 6.5 5.5 6.5 5.5 5.5 5.5 4.5 20HW-iron 2.5 4.5 1.5 2.5 4.5 1.5 3.5 3.5 Water Repellency initial 12 12 12 11.5 9.5 12 11.5 10.5 1OHW-iron 10.5 10.5 9.5 10.5 9.5 8.5 10.5 6.5 20HW-iron 5 6.5 4.5 5.5 6.5 4.5 6.5 5.5 Spray Repellency initial 100 100 100 100 90 100 100 100 1OHW-iron 90 100 80 80 90 80 90 90 20HW-iron 60 70 50 70 70 50 60 70 The data in Table 6 demonstrated that the combination of the 10 extender of Example 1 and different ZONYL products at different ratios achieved effective performance on nylon. Examples 8 - 13 The extender compositions were prepared following the procedure of Example 1 except for using different surfactants and solvents as listed 22 WO 2007/008416 PCT/US2006/025135 in Table 7. The resulting extenders were separately blended with commercially available fluoropolymers, ZONYL 8300, ZONYL 8412, and ZONYL 8932 from E. I. du Pont de Nemours and Company, Wilmington, DE for performance tests. The ratio of extender to ZONYL was 1:1. 5 The blends with each ZONYL fluoropolymers were applied to 100% nylon fabric using Test Method 1 described above. The bath contained 20-50 g/L of the blended product. A wetting agent ALKANOL 6112 (available from E. I. du Pont de Nemours and Company, Wilmington, DE) was also included in the bath at 2 g/L. After application, the fabrics were 10 cured at about 1600C for about 2 minutes. The fabric was allowed to "rest" after treatment and cure. The treated nylon was tested for oil repellency, water repellency and spray repellency using Test Methods 2, 3, 4 and 5 described above. Results are listed in Tables 8A, 8B, and 8C. 23 WO 2007/008416 PCT/US2006/025135 Table 7 Ex. # Surfactant Brand name (availability) Solvent % Solids in Latex 8 Octadecylmethyl(poly ETHOQUAD 18/25 Dipropylene 28% oxyethylene (15) (available from Akzo glycol methyl ammonium chloride, Nobel, Chicago, IL), ether acetate Secondary alcohol TERGITOL 15-S-20 ethoxylate (available from Union Carbide, Danbury, Conn.) 9 Polyethylene Glycol MAZAR MEPEG 600MS Hexylene 32.55% Ester (available from Mazar glycol Chemical Inc., Gurmee, IL) 10 Polyethylene Glycol MAZAR MEPEG 600MS Hexylene 31.74% Ester/ AVITEX R (available from Mazar glycol Chemical Inc., Gurmee, IL) /AVITEX R (available from Clariant, Mt. Holly, NC) 11 Alcohol ethoxylate/ ETHOX TDA-5 (available Dipropylene 28.08% Octadecylmethyl(poly from Ethox Chemicals, glycol oxyethylene (15) Greenville, SC)/ ammonium chloride,! ETHOQUAD 18/25 AVITEX R (available from Akzo Nobel, Chicago, IL)/ AVITEX R (available from Clariant, Mt. Holly, NC) 12 Polyethylene Glycol MAZAR MEPEG 600MS Hexylene 32.79% Ester/ Alkylolamine (available from Mazar glycol Hydrochloride Chemical Inc., Gurmee, IL) mixture / AVITEX 2153 (available from DuPont, Wilmington, DE) 13 Polyethylene Glycol MAZAR MEPEG 600MS Hexylene 32.73% Ester/ (available from Mazar glycol Di(hydrogenated Chemical Inc., Gurmee, IL) tallow) dimethyl / ARQUAD 2HT 75 ammonium chloride (available from Akzo Nobel, Chicago, IL) 24 WO 2007/008416 PCT/US2006/025135 Table 8A ZONYL 8412 none 1 8 9 10 11 12 13 +Example Extender Oil Repellency initial 6 6.5 6.5 6 7 6.5 4.5 5 20HW-iron 3 5 4 5 4.5 5.5 1 2 Water Repellency initial 12 12 12 11 12 12 8.5 8.5 20HW-iron 8.5 7.5 7 7 8 8 5 6 Spray Repellency initial 100 90 80 90 100 90 70 90 20HW-iron 70 70 70 70 75 75 70 80 Table 8B ZONYL 8932 none 1 8 9 10 11 12 13 +Example Extender Oil Repellency initial 6.5 8 6.5 6.5 7 7 6.5 7.5 20HW-iron 4 6.5 5 5.5 4 4.5 6 5 Water Repellency initial 12 12 12 12 12 12 12 12 20HW-iron 8 10.5 8.5 9 9 10.5 9 9 Spray Repellency initial 100 100 100 100 100 100 100 100 20HW-iron 80 80 80 70 70 70 80 70 5 25 WO 2007/008416 PCT/US2006/025135 Table 8C ZONYL 8300 none 1 8 9 10 11 12 13 +Example Extender Oil Repellency initial 7 7 6 5.5 6.5 6 3.5 4 20HW-iron 4 4.5 2 3.5 4 4 0.5 2 Water Repellency . initial 11.5 12 10 10 11 10.5 6.5 8.5 20HW-iron 8.5 9 6 7 8 7.5 5 6 Spray Repellency initial 100 100 90 100 90 100 80 90 20HW-iron 70 70 70 70 70 70 70 70 The data in Tables 8A, 8B and 8C demonstrated that the extender compositions of Examples 1 and 8-13 were effective to provide durable 5 repellency using half the fluorine level when prepared using a variety of surfactants and solvents. The fluorine level of the compositions having extenders present was 50% of those having no extender present. Example 14 A water emulsion was prepared by mixing the following: 80 g of hot 10 deionized H 2 0 (50 - 60*C), 1.6 g of ARMEEN DMI8D (available from Akzo Nobel, Chicago, IL), 60 g of ethylhexyl methacrylate, 10 g of poly(oxyethylene)7 methacrylate, 2 g of N-methylolacrylamide, 0.3 g of dodecyl mercaptan, I g of acetic acid, 0.3 g of 2% sodium chloride solution and 20 g of hexylene glycol, and then charged to a 500 ml of four 15 necked flask equipped with mechanic stir, thermocouple thermometer and chiller condenser (-5 to -10 *C). The charge was rinsed into the flask with 80 g of hot deionized water and purged with nitrogen for 30 minutes or until the temperature is below 30 C. 10 g of vinylidene chloride was then charged to the reaction flask and mixed for 5 minutes. Then, 0.4 g of 26 WO 2007/008416 PCT/US2006/025135 "VAZO" 56 WSP (E. 1. du Pont de Nemours and Company, Wilmington, DE) dissolved in 10 g deionized water was added to initiate polymerization. The mixture was heated to 50 *C within half of an hour and maintained for 8 hours. The resulting polymer extender latex 5 (dispersion in water) weighed 250 g with solids content of 28.87%. It was then blended with commercially available fluorinated polymers, ZONYL 8300 and ZONYL 8932 from E. I. du Pont de Nemours and Company, Wilmington, DE at a ratio of 2:1 of extender to fluorinated polymer for ZONYL 8932 and at a ratio of 1:1 extender to fluorinated polymer for 10 ZONYL 8300. The blends were applied to nylon fabric using Test Method 1 described above. The bath contained 0.133% - 0.15% of fluorine. The nylon was tested for repellency using Test Methods 2, 3, 4 and 5 described above. Results are listed in Tables 10A and 1OB. Example 15 - 17, Comparative Example C 15 Latex extenders were synthesized by following the same procedure as Example 14 except for using the amount of monomers listed in Table 9. Table 9 Example 15 16 17 Comparative Ex.C Monomer, g Poly(oxyethylene)7 5 10 3 10 methacrylate Ethylhexyl 70 65 50 70 methacrylate Vinylidene chloride 5 5 27 0 % Solid in Latex 28.42 % 29.04 % 27.76 % 28.87 % The extenders and Comparative Example C were blended with 20 ZONYL 8932 and ZONYL 8300 fluorinated polymers in a ratio of 2:1 of extender to fluorinated polymer. The blends were applied to 100% nylon fabric using Test Method 1 described above. The bath contained 20-50g/L of the blended product. A wetting agent ALKANOL 6112 (available from E. 1. du Pont de Nemours 25 and Company, Wilmington, DE) was also included in the bath at 2 g/L. 27 WO 2007/008416 PCT/US2006/025135 After application, the fabrics were cured at about 1600C for about 2 minutes. The fabric was allowed to "rest" after treatment and cure. The nylon was tested for oil repellency, water repellency and spray repellency and wash durability using Test Methods 4, 2, 3 and 5 described above. 5 Results are listed in Table 1 OA for ZONYL 8932/extender blends and in Table 1 OB for ZONYL 8300/extender blends. Table 10A Example Comparative 14 15 16 17 Extender Ex. C Oil Repellency initial 6 6 5.5 6 5.5 20HW - iron 3.5 5.5 4.5 4.5 4.5 Water Repellency Initial 10.5 10.5 10 11 10 20HW - iron 7 7.5 8.5 8.5 8.5 Spray Repellency initial 100 100 100 100 100 20HW - iron 60 75 70 70 80 Table 10B Example Comparative 14 15 16 17 Extender Ex. C Oil Repellency initial 5.5 6 6 6 5 20HW-iron 0 4 4 0 0.5 Water Repellency initial 10.5 7.5 9.5 6 5.5 20HW-iron 5 4 6 4 5 Spray Repellency initial 80 85 100 90 80 20HW-iron 70 70 70 60 75 28 WO 2007/008416 PCT/US2006/025135 The data in Table 1 OA showed that the presence of vinylidene chloride in the extender copolymer of Examples 14 -17 blended with ZONYL 8932 improved the performance compared to Comparative Example C that did not contain vinylidene chloride. The data in Table 1 0B 5 showed that the presence of vinylidene chloride in the extender copolymer of Examples 14 -17 blended with ZONYL 8300 improved the oil repellency and spray repellency compared to Comparative Example C that did not contain vinylidene chloride. Example 18 - 21 10 To begin, (a) 70 g of 2-ethylhexylmethacrylate; (b) 1Og of poly(oxyethylene)7 methacrylate; (c) 2 g of aqueous 48% N-methylol acrylamide; 0.3 g of dodecyl mercaptan, 20 g hexylene glycol, 1.6 g of ARMEEN DM 18D, 1.0g acetic acid, 3 g of aqueous 2% salt (NaCl) solution, and 80 g of hot (50-60 0 C) deionized water were emulsified and 15 then charged to a four-necked flask fitted with a stirrer, thermocouple thermometer, and water condenser. The charge was rinsed into the flask with 75 g of hot deionized water and purged with nitrogen at 65 0 C for 30 minutes. Then, 0.08 g of "VAZO" 56 WSP (E. 1. du Pont de Nemours and Company, Wilmington, DE) dissolved in 2 g deionized water was 20 added to initiate polymerization. The temperature of the mix rose spontaneously to 79 0 C over about 12 minutes, and then began to decline. The temperature controller was reset to 70*C, and the charge was stirred for 4 hours under nitrogen. The resulting polymer extender latex (dispersion in water) weighed 251 g with solids content of 31.7%. This 25 extender was mixed separately with the extenders of Examples 1, 9, 10 and 11 in a ratio of 1:1 to produce a mixture of extenders designated herein as Examples 18, 19, 20 and 21. This extender mixture was then blended with ZONYL 8932 fluorochemical in a ratio of 2:1 of extender to fluorinated polymer. The 30 blend was applied to 100% cotton twill fabric using Test Method I described above. The treating bath contained 45 g/L of the blend, I g/L of blocked isocyanate HYDROPHOBOL XAN from Ciba Specialty 29 WO 2007/008416 PCT/US2006/025135 Chemicals, High Point, NC, and 70 g/L anti-wrinkle resin, PERMAFRESH EFC from Omnova Solutions, Chester, SC. After application, the fabric was cured at 330'C for 3 minutes. The fabric was allowed to "rest" after treatment and cure. The treated cotton was tested for oil repellency, water 5 repellency and spray repellency and wash durability using Test Methods 4, 2, 3 and 5 described above. For comparison when no extender was present, the bath contained either 15 g/L or 30 g/L of ZONYL 8932 combined with the same bath components. Results are listed in Table 11. Table 11 ZONYL 8932 + 18 19 20 21 15 g/L 30 g/L Example extender ZONYL ZONYL 8932, no 8932, no extender extender Oil Repellency initial 7 7 7 7 5 6 20HW LTD 6 6 6 6 2 4 Water Repellency I initial 12 12 12 12 7 10 20HW LTD 10 10 9 11 5 7.5 Spray Repellency initial 100 100 100 100 100 100 20HW LTD 80 85 80 85 75 80 10 The results in Table 11 showed that fluorine efficiency was achieved by using a mixture of extender compositions with the fluorinated polymer. Superior performance was obtained compared to the fluorinated polymer having no extender composition present which had a fluorine level about three times higher than the blends having the extender 15 present. Example 22 A water emulsion was prepared by mixing the following: 96 g of hot deionized water (50 - 60 0 C), 3.2 g of ETHOQUAD 18/25 (available from Akzo Nobel, Chicago, IL), 4.6 g of tridecyl alcohol 5-ethylene oxide adduct 30 WO 2007/008416 PCT/US2006/025135 (ETHOX TDA-5, available from Ethox Chemicals, Greenville, SC), 30 g of stearyl methacrylate, 15 g of methyl methacrylate, 1.25 g of N methylolacrylamide, 0.68 g of 2-hydroxyethyl methacrylate, 1.25 g of poly(oxyethylene)7 methacrylate, 0.34 g of dodecyl mercaptan and 19.36 5 g of dipropylene glycol. It was then charged to a 500 ml four-necked flask equipped with mechanical stirrer, thermocouple thermometer and chiller condenser (-5 to -10 0C). The charge was rinsed into the flask with 10 g of hot deionized water and purged with nitrogen for 30 minutes or until the temperature was below 30 C. 15 g of vinylidene chloride was then 10 charged to the reaction flask and mixed for 5 minutes. Then, 0.34 g of "VAZO" 56 WSP (E. I. du Pont de Nemours and Company, Wilmington, DE) dissolved in 10 g deionized water was added to initiate polymerization. The mixture was heated to 50 0C within a half hour and maintained for 8 hours. Following the polymerization a water solution of 15 0.46 g of DUPONOL WAQE (available from Witco Corporation, Greenwich, CT) was mixed with the product at room temperature. The resulting polymer extender latex (dispersion in water) weighed 202.65 g with solids content of 28.74%. Example 23 20 A water emulsion was prepared by mixing the following: 96 g of hot deionized water (50 - 600C), 3.2 g of ETHOQUAD 18/25 (available from Akzo Nobel, Chicago, IL), 4.6 g of tridecyl alcohol 5-ethylene oxide adduct (ETHOX TDA-5, available from Ethox Chemicals, Greenville, SC), 30 g of stearyl methacrylate, 15 g of vinyl acetate, 1.25 g of N-methylolacrylamide, 25 0.68 g of 2-hydroxyethyl methacrylate, 1.25 g of poly(oxyethylene)7 methacrylate, 0.34 g of dodecyl mercaptan and 19.36 g of dipropylene glycol. It was then charged to a 500 ml four-necked flask equipped with mechanical stirrer, thermocouple thermometer and chiller condenser (-5 to -10 *C). The charge was rinsed into the flask with 10 g of hot deionized 30 water and purged with nitrogen for 30 minutes or until the temperature was below 30 'C. 15 g of vinylidene chloride was then charged to the reaction flask and mixed for 5 minutes. Then, 0.34 g of "VAZO" 56 WSP 31 WO 2007/008416 PCT/US2006/025135 (E. 1. du Pont de Nemours and Company, Wilmington, DE) dissolved in 10 g deionized water was added to initiate polymerization. The mixture was heated to 50 *C within a half hour and maintained for 8 hours. Following the polymerization a water solution of 0.46 g of DUPONOL WAQE 5 (available from Witco Corporation, Greenwich, Conn.) was mixed with the product at room temperature. The resulting polymer extender latex (dispersion in water) weighed 196.4 g with solids content of 25.91%. Example 24 A water emulsion was prepared by mixing the following: 96 g of hot 10 deionized water (50 - 60*C), 3.2 g of ETHOQUAD 18/25 (available from Akzo Nobel, Chicago, IL), 4.6 g of tridecyl alcohol 5-ethylene oxide adduct (ETHOX TDA-5, available from Ethox Chemicals, Greenville, SC), 30 g of stearyl methacrylate, 1.25 g of N-methylolacrylamide, 0.68 g of 2 hydroxyethyl methacrylate, 1.25 g of poly(oxyethylene)7 methacrylate, 15 0.34 g of dodecyl mercaptan and 19.36 g of dipropylene glycol. It was then charged to a 500 ml four-necked flask equipped with mechanical stirrer, thermocouple thermometer and chiller condenser (-5 to -10 *C). The charge was rinsed into the flask with 10 g of hot deionized water and purged with nitrogen for 30 minutes or until the temperature was below 20 30 C. 30 g of vinyl acetate was then charged to the reaction flask and mixed for 5 minutes. Then, 0.34 g of "VAZO" 56 WSP (E. 1. du Pont de Nemours and Company, Wilmington, DE) dissolved in 10 g deionized water was added to initiate polymerization. The mixture was heated to 50 0 C within half of an hour and maintained for 8 hours. Following the 25 polymerization a water solution of 0.46 g of DUPONOL WAQE (available from Witco Corporation, Greenwich, Conn.) was mixed with the product at room temperature. The resulting polymer extender latex (dispersion in water) weighed 201.56 g with solids content of 28.47%. Example 25 30 A water emulsion was prepared by mixing the following: 96 g of hot deionized water (50 - 600C), 3.2 g of ETHOQUAD 18/25 (available from 32 WO 2007/008416 PCT/US2006/025135 Akzo Nobel, Chicago, IL), 4.6 g of tridecyl alcohol 5-ethylene oxide adduct (ETHOX TDA-5, available from Ethox Chemicals, Greenville, SC), 30 g of stearyl methacrylate, 15 g of vinylbenzyl chloride methyl, 1.25 g of N methylolacrylamide, 0.68 g of 2-hydroxyethyl methacrylate, 1.25 g of 5 poly(oxyethylene)7 methacrylate, 0.34 g of dodecyl mercaptan and 19.36 g of dipropylene glycol. It was then charged to a 500 ml four-necked flask equipped with mechanical stirrer, thermocouple thermometer and chiller condenser (-5 to -10 0 C). The charge was rinsed into the flask with 10 g of hot deionized water and purged with nitrogen for 30 minutes or until the 10 temperature was below 30 *C. 15 g of vinylidene chloride was then charged to the reaction flask and mixed for 5 minutes. Then, 0.34 g of "VAZO" 56 WSP (E. 1. du Pont de Nemours and Company, Wilmington, DE) dissolved in 10 g deionized water was added to initiate polymerization. The mixture was heated to 50 "C within a half hour and 15 maintained for 8 hours. Following the polymerization a water solution of 0.46 g of DUPONOL WAQE (available from Witco Corporation, Greenwich, Conn.) was mixed with the product at room temperature. The resulting polymer extender latex (dispersion in water) weighed 202.33 g with solids content of 27.13%. 20 Example 26 A water emulsion was prepared by mixing the following: 96 g of hot deionized water (50 - 60'C), 3.2 g of ETHOQUAD 18/25 (available from Akzo Nobel, Chicago, IL), 4.6 g of tridecyl alcohol 5-ethylene oxide adduct (ETHOX TDA-5, available from Ethox Chemicals, Greenville, SC), 30 g of 25 stearyl methacrylate, 15 g of styrene, 1.25 g of N-methylolacrylamide, 0.68 g of 2-hydroxyethyl methacrylate, 1.25 g of poly(oxyethylene)7 methacrylate, 0.34 g of dodecyl mercaptan and 19.36 g of dipropylene glycol. It was then charged to a 500 ml four-necked flask equipped with mechanical stirrer, thermocouple thermometer and chiller condenser (-5 to 30 -10 0 C). The charge was rinsed into the flask with 10 g of hot deionized water and purged with nitrogen for 30 minutes or until the temperature was below 30 C. 15 g of vinylidene chloride was then charged to the reaction 33 WO 2007/008416 PCT/US2006/025135 flask and mixed for 5 minutes. Then, 0.34 g of "VAZO" 56 WSP (E. 1. du Pont de Nemours and Company, Wilmington, DE) dissolved in 10 g deionized water was added to initiate polymerization. The mixture was heated to 50 C within a half hour and maintained for 8 hours. Following 5 the polymerization a water solution of 0.46 g of DUPONOL WAQE (available from Witco Corporation, Greenwich, Conn.) was mixed with the product at room temperature. The resulting polymer extender latex (dispersion in water) weighed 206 g with solids content of 26.39%. Example 27 10 A mixture of 96 g of hot deionized water (50'- 60'C), 3.2 g of ETHOQUAD 18/25 (available from Akzo Nobel, Chicago, IL), 4.6 g of tridecyl alcohol 5-ethylene oxide adduct (ETHOX TDA-5, available from Ethox Chemicals, Greenville, SC), 30 g of butyl methacrylate, 1.25 g of N methylolacrylamide, 0.68 g of 2-hydroxyethyl methacrylate, 1.25 g of 15 poly(oxyethylene)7 methacrylate, 0.34 g of dodecyl mercaptan and 19.36 g of dipropylene glycol was charged to a 500 ml four-necked flask equipped with mechanical stirrer, thermocouple thermometer and chiller condenser (-5 to -10 'C). The charge was rinsed into the flask with 10 g of hot deionized water and purged with nitrogen for 30 minutes or until the 20 temperature was below 30 0 C. 30 g of vinylidene chloride was then charged to the reaction flask and mixed for 5 minutes. Then, 0.34 g of "VAZO" 56 WSP (E. I. du Pont de Nemours and Company, Wilmington, DE) dissolved in 10 g deionized water was added to initiate polymerization. The mixture was heated to 50 0 C within a half hour and 25 maintained for 8 hours. Following the polymerization a water solution of 0.46 g of DUPONOL WAQE (available from Witco Corporation, Greenwich, Conn.) was mixed with the product at room temperature. The resulting polymer extender latex (dispersion in water) weighed 205.15 g with solids content of 28.04%. 34 WO 2007/008416 PCT/US2006/025135 Example 28 A mixture of 96 g of hot demonized water (50 - 60'C), 3.2 g of ETHOQUAD 18/25 (available from Akzo Nobel, Chicago, IL), 4.6 g of tridecyl alcohol 5-ethylene oxide adduct (ETHOX TDA-5, available from 5 Ethox Chemicals, Greenville, SC), 30 g of ethylhexyl methacrylate, 1.25 g of N-methylolacrylamide, 0.68 g of 2-hydroxyethyl methacrylate, 1.25 g of poly(oxyethylene)7 methacrylate, 0.34 g of dodecyl mercaptan and 19.36 g of dipropylene glycol was charged to a 500 ml four-necked flask equipped with mechanical stirrer, thermocouple thermometer and chiller 10 condenser (-5 to -10 'C). The charge was rinsed into the flask with 10 g of hot deionized water and purged with nitrogen for 30 minutes or until the temperature was below 30 *C. 30 g of vinylidene chloride was then charged to the reaction flask and mixed for 5 minutes. Then, 0.34 g of "VAZO" 56 WSP (E. I. du Pont de Nemours and Company, Wilmington, 15 DE) dissolved in 10 g deionized water was added to initiate polymerization. The mixture was heated to 50 0 C within a half hour and maintained for 8 hours. Following the polymerization a water solution of 0.46 g of DUPONOL WAQE (available from Witco Corporation, Greenwich, Conn.) was mixed with the product at room temperature. The 20 resulting polymer extender latex (dispersion in water) weighed 185.43 g with solids content of 29.26%. Example 29 A mixture of 96 g of hot deionized water (50 - 60*C), 3.2 g of ETHOQUAD 18/25 (available from Akzo Nobel, Chicago, IL), 4.6 g of 25 tridecyl alcohol 5-ethylene oxide adduct (ETHOX TDA-5, available from Ethox Chemicals, Greenville, SC), 30 g of lauryl methacrylate, 1.25 g of N methylolacrylamide, 0.68 g of 2-hydroxyethyl methacrylate, 1.25 g of poly(oxyethylene)7 methacrylate, 0.34 g of dodecyl mercaptan and 19.36 g of dipropylene glycol was charged to a 500 ml four-necked flask 30 equipped with mechanical stirrer, thermocouple thermometer and chiller condenser (-5 to -10 0 C). The charge was rinsed into the flask with 10 g of hot deionized water and purged with nitrogen for 30 minutes or until the 35 WO 2007/008416 PCT/US2006/025135 temperature was below 30 C. 30 g of vinylidene chloride was then charged to the reaction flask and mixed for 5 minutes. Then, 0.34 g of "VAZO" 56 WSP (E. 1. du Pont de Nemours and Company, Wilmington, DE) dissolved in 10 g deionized water was added to initiate 5 polymerization. The mixture was heated to 50 *C within a half hour and maintained for 8 hours. Following the polymerization a water solution of 0.46 g of DUPONOL WAQE (available from Witco Corporation, Greenwich, Conn.) was mixed with the product at room temperature. The resulting polymer extender latex (dispersion in water) weighed 185.14 g 10 with solids content of 27.92%. Example 30 A mixture of 96 g of hot deionized water (50 - 600C), 3.2 g of ETHOQUAD 18/25 (available from Akzo Nobel, Chicago, IL), 4.6 g of tridecyl alcohol 5-ethylene oxide adduct (ETHOX TDA-5, available from 15 Ethox Chemicals, Greenville, SC), 30 g of tridecyl methacrylate, 1.25 g of N-methylolacrylamide, 0.68 g of 2-hydroxyethyl methacrylate, 1.25 g of poly(oxyethylene)7 methacrylate, 0.34 g of dodecyl mercaptan and 19.36 g of dipropylene glycol was charged to a 500 ml four-necked flask equipped with mechanical stirrer, thermocouple thermometer and chiller 20 condenser (-5 to -10 'C). The charge was rinsed into the flask with 10 g of hot deionized water and purged with nitrogen for 30 minutes or until the temperature was below 30 C. 30 g of vinylidene chloride was then charged to the reaction flask and mixed for 5 minutes. Then, 0.34 g of "VAZO" 56 WSP (E. I. du Pont de Nemours and Company, Wilmington, 25 DE) dissolved in 10 g deionized water was added to initiate polymerization. The mixture was heated to 50 0C within a half hour and maintained for 8 hours. Following the polymerization a water solution of 0.46 g of DUPONOL WAQE (available from Witco Corporation, Greenwich, Conn.) was mixed with the product at room temperature. The 30 resulting polymer extender latex (dispersion in water) weighed 187.53 g with solids content of 27.2%. 36 WO 2007/008416 PCT/US2006/025135 Example 31 A mixture of 96 g of hot deionized water (50 - 60'C), 3.2 g of ETHOQUAD 18/25 (available from Akzo Nobel, Chicago, IL), 4.6 g of tridecyl alcohol 5-ethylene oxide adduct (ETHOX TDA-5, available from 5 Ethox Chemicals, Greenville, SC), 30 g of hexyl methacrylate, 1.25 g of N methylolacrylamide, 0.68 g of 2-hydroxyethyl methacrylate, 1.25 g of poly(oxyethylene)7 methacrylate, 0.34 g of dodecyl mercaptan and 19.36 g of dipropylene glycol was charged to a 500 ml four-necked flask equipped with mechanical stirrer, thermocouple thermometer and chiller 10 condenser (-5 to -10 *C). The charge was rinsed into the flask with 10 g of hot deionized water and purged with nitrogen for 30 minutes or until the temperature was below 30 "C. 30 g of vinylidene chloride was then charged to the reaction flask and mixed for 5 minutes. Then, 0.34 g of "VAZO" 56 WSP (E. 1. du Pont de Nemours and Company, Wilmington, 15 DE) dissolved in 10 g deionized water was added to initiate polymerization. The mixture was heated to 50 0C within a half hour and maintained for 8 hours. Following the polymerization a water solution of 0.46 g of DUPONOL WAQE (available from Witco Corporation, Greenwich, Conn.) was mixed with the product at room temperature. The 20 resulting polymer extender latex (dispersion in water) weighed 201.34 g with solids content of 29.5%. Example 32 A water emulsion was prepared by mixing the following: 96 g of hot deionized water (50 - 600C), 3.2 g of ETHOQUAD 18/25 (available from 25 Akzo Nobel, Chicago, IL), 4.6 g of tridecyl alcohol 5-ethylene oxide adduct (ETHOX TDA-5, available from Ethox Chemicals, Greenville, SC), 30 g of cyclohexyl methacrylate, 1.25 g of N-methylolacrylamide, 0.68 g of 2 hydroxyethyl methacrylate, 1.25 g of poly(oxyethylene)7 methacrylate, 0.34 g of dodecyl mercaptan and 19.36 g of dipropylene glycol. It was 30 then charged to a 500 ml four-necked flask equipped with mechanic stir, thermocouple thermometer and chiller condenser (-5 to -10 CC). The charge was rinsed into the flask with 10 g of hot deionized water and 37 WO 2007/008416 PCT/US2006/025135 purged with nitrogen for 30 minutes or until the temperature was below 30 'C. 30 g of vinylidene chloride was then charged to the reaction flask and mixed for 5 minutes. Then, 0.34 g of "VAZO" 56 WSP (E. I. du Pont de Nemours and Company, Wilmington, DE) dissolved in 10 g deionized 5 water was added to initiate polymerization. The mixture was heated to 50 0C within a half hour and maintained for 8 hours. Following the polymerization a water solution of 0.46 g of DUPONOL WAQE (available from Witco Corporation, Greenwich, Conn.) was mixed with the product at room temperature. The resulting polymer extender latex (dispersion in 10 water) weighed 203.37 g with solids content of 28%. The above-resulting latexes of Examples 22 to 32 were separately blended with commercially available fluoropolymer ZONYL 8932 from E. I. du Pont de Nemours and Company, Wilmington, DE for performance tests. The blends contained a ratio of extender to fluoropolymer of 1:1. 15 The blends with ZONYL fluoropolymer were applied to 100% nylon fabric using Test Method 1 described above. The bath contained 20-50g/L of the blended product for the data in Table 13 and the bath contained 10 15g/L of the fluorinated polymer. A wetting agent ALKANOL 6112 (available from E. 1. du Pont de Nemours and Company, Wilmington, DE) 20 was also included in the bath at 2 g/L. After application, the fabrics were cured at about 1600C for about 2 minutes. The fabric was allowed to "rest" after treatment and cure. The treated fabric was tested for oil repellency, water repellency and spray repellency using Test Methods 2, 3, 4 and 5 described above. Results are listed in Table 12. 25 38 WO 2007/008416 PCT/US2006/025135 C\ Cc) 00 ( ) r a) D 'I0)00 10 1000 C140 Co LO co m 0)00 100 000)-C m00 (0100 0 00 (0 LO CO0)0)00 O 10 000 a) 1010 10 10 00 CD C - 0 co I N 10 000I CO C0~ LO D C CDoL (01 C41Oc 000? ') DC N~ C-D C:)00 10 1 1110 6 000I 10lC U 00 CD) CD +~ 0) W 0 o 0 x )C) C) - C) C -NW _ _ )N 'oU EIClIY The results in Table 12 showed that comparing the extender of the present invention combined with fluorinated polymer to the same fluorinated polymer without extender present, better or comparable performance was obtained with use of the extenders with 60% of fluorine 5 present. Example 33 A water emulsion is prepared by mixing the following: 96 g of hot demonized H 2 0 (50 - 60'C), 3.2 g of ETHOQUAD 18/25 (available from Akzo Nobel, Chicago, IL), 4.6 g of tridecyl alcohol 5-ethylene oxide adduct 10 (ETHOX TDA 5 from Ethox Chemicals, Greenville, SC), 30 g of stearyl methacrylate, 1.25 g of poly(oxyethylene)7 methacrylate, 1.25 g of N methylolacrylamide, 0.68 g of 2-hydroxyethyl methacrylate, 0.34 g of dodecyl mercaptan and 19.36 g of dipropylene glycol, and then is charged to a I L autoclave. The autoclave is sealed and is evacuated/ filled with 15 nitrogen three times. 30 g of vinyl chloride is then charged. Then, 0.34 g of "VAZO" 56 WSP (E. 1. du Pont de Nemours and Company, Wilmington, DE) dissolved in 10 g deionized water is added to initiate polymerization. The mixture is heated to 50 *C over a period of 30 minutes and is maintained for 8 hours with agitator at 150 RPM. Following the 20 polymerization a water solution of 0.46 g of DUPONOL WAQE (available from Witco Corporation, Greenwich, Conn.) is mixed with the product at room temperature. The resulting latex extender is filtered through a milk filter. The extender is mixed with ZONYL 8932 at a ratio of extender to fluorinated polymer of 2:1. The blend is applied to 100% cotton fabric and 25 to nylon fabric, tested, laundered, and retested as in Example 11. The test results show durability of performance after washing the fabric, Where the terms "comprise", "comprises", "comprised" or "comprising" are used in this specification, they are to be interpreted as specifying the presence of the stated features, integers, steps or 30 components referred to, but not to preclude the presence or addition of one or more other feature, integer, step, component or group thereof. 40 Further, any prior art reference or statement provided in the specification is not to be taken as an admission that such art constitutes, or is to be understood as constituting, part of the common general knowledge in Australia. 5 40A

Claims

1. A polymer composition comprising monomers copolymerized in the following percentages by weight: (a) from about 5% to about 90% of a monomer of formula 1: 5 R 1 -OC(O)-C(R)=CH 2 (I) (b) from about 5% to about 85% of vinylidene chloride, vinyl chloride, vinyl acetate, or a mixture thereof, (c) from about 0.5% to about 3% of a monomer of formula 1l: HO-CH 2 -NH-C(O)-C(R)=CH 2 (11) 10 (d) from about 0.5% to about 3% of a monomer of formula Ill: HO-CH 2 CH 2 -OC(O)-C(R)=CH 2 (Il1) and (e) from about 1% to about 5% of a monomer of formula IV: H-(OCH 2 CH 2 )m-O-C(O)-C(R)=CH 2 (IV) 15 (f) from 0% to about 25% of methyl methacrylate, vinylbenzyl chloride, styrene or a mixture thereof, wherein each R is independently H or CH 3 ; Ri is a linear or branched or cyclic alkyl chain having from about 20 4 to about 18 carbon atoms, and m is 2 to about 10, said composition increasing the fluorine efficiency in treatment of a substrate by permitting use of lower levels of fluorinated surface treating agents providing durable oil repellency and water repellency, such that 25 the fluorine content of a blend of said composition with a fluorinated surface treating agent is from about 1.5% to about 6.6% by weight of the blend.

2. The composition of claim 1, wherein monomer (a) is stearyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, butyl (meth)acrylate, hexyl 41 (meth)acrylate, cyclohexyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, or a mixture thereof.

3. The composition of claim 1 or claim 2, wherein monomer (c) is N-methylolacrylamide, monomer (d) is hydroxyethyl methacrylate, 5 and monomer (e) is an ethoxylated (meth)acrylate wherein the number of ethoxy groups is between about 2 and about 10.

4. The composition of any one of claims 1 to 3, wherein the ratio of the composition to the fluorinated surface treating agent is from about 0.5:10 to about 6:1. 10

5. The composition of any one of claims 1 to 4, wherein the fluorinated surface treating agent is a fluorine-containing polyurethane, poly(meth)acrylate, polyvinyl, or polyvinylidene, or mixture thereof.

6. The composition of any one of claims 1 to 5, further containing a blocked isocyanate, at least one additional extender 15 composition, or an additive selected from the group consisting of a surfactant, emulsifier, pH adjuster, cross linker, wetting agent, and wax extender.

7. A method of treating a substrate comprising contacting the substrate with a composition of any one of claims 1 to 6. 20

8. The method of claim 7, wherein the substrate is a textile, fiber, fabric, paper, nonwoven, leather or combination thereof.

9. A substrate treated by the method of claim 7.

10. The substrate of claim 9, having a fluorine content of from about 0.05% to about 0.5% by weight. 25

11. The composition of any one of claims 1 to 6, substantially as hereinbefore described with reference to any one of the Examples. 42