HK1125120B - Polymeric extenders for surface effects - Google Patents

Description

Polymeric extenders for surface effects

Technical Field

The use of the polymeric extender composition improves the performance of the treating agent to provide a surface effect to the treated substrate.

Background

Various compositions are known for use as treating agents for substrates to provide surface effects. Surface effects include water repellency, stain resistance, and other effects that 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 treating agents typically contain pendant perfluoroalkyl groups having three or more carbon atoms that provide oil and water repellency when the composition is applied to the surface of a fibrous substrate. Perfluoroalkyl groups are typically attached to non-fluorine containing polymerizable groups through various linking groups. The resulting monomers are then typically copolymerized with other monomers that impart other advantageous properties to the substrate. Various special monomers may be added to impart improved crosslinkability, latex stability, and substantivity. This particular combination is directed to the desired use, as the various ingredients may impart some properties in addition to the desired properties, which may be undesirable. These polymers are typically sold as aqueous emulsions for ease of application to fibrous substrates. U.S. Pat. No. 6,479,605 discloses a fluorinated copolymer useful for treating fibrous substrates to provide oil and water repellency.

Various attempts have been made to increase the oil and water repellency imparted to substrates by treatment agents and their durability while reducing the amount of fluorinated polymer required, i.e., to improve the efficacy and performance of the treatment agent. One method is to add blocked isocyanate or melamine resins. However, these components are used in limited amounts because they tend to adversely affect the hand (feel) of the fibrous substrate. Another approach is to use various extender polymers. The extender polymer is typically a hydrocarbon polymer in an aqueous emulsion that is blended with the fluorinated polymer emulsion prior to application to the substrate.

U.S. patent 6,309,752 discloses compositions comprising a fluorochemical agent (fluorochemicalagent), a copolymeric extender comprising two different polymeric units, and a blocked isocyanate extender, wherein the extender combination provides a greater degree of improvement in the fluorine efficiency (fluorinefficency) of the fluorochemical agent than either extender alone. The two different polymerized units are (1) optionally halogenated polymerizable olefinic compounds; and (2) an olefinic compound containing functional groups reactive with the fabric. It has been found that blocked isocyanate extenders tend to adversely affect the hand of the fibrous substrate.

There is a need for polymer compositions that significantly improve the performance of surface effect agents. In particular, there is a need for compositions that improve the performance of fluorinated polymer treating agents that provide repellency and other surface effects to substrates while reducing the amount of fluorinated polymer required. The present invention provides such a composition.

Summary of The Invention

The present invention relates to a polymeric extender composition for use with an agent that provides a surface effect when applied to a substrate, said composition comprising monomers copolymerized in the following percentages by weight:

(a) from about 5% to about 90% of a monomer of formula I:

R₁-OC(O)-C(R)＝CH₂ (I)

(b) from about 5% to about 85% of vinylidene chloride, vinyl acetate or mixtures thereof,

(c) from about 0.5% to about 3% of a monomer of formula II:

HO-CH₂-NH-C(O)-C(R)＝CH₂ (II)

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

HO-CH₂CH₂-OC(O)-C(R)＝CH₂ (III)

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

H-(OCH₂CH₂)_m-O-C(O)-C(R)＝CH₂ (IV)

(f) from 0% to about 25% of methyl methacrylate, vinylbenzyl chloride, styrene, or mixtures thereof,

wherein the content of the first and second substances,

each R is independently H or CH₃；

R₁Is a straight or branched or cyclic alkyl chain containing from 4 to 18 carbon atoms, and

m is from 2 to about 10.

The present invention also relates to a method of treating a substrate comprising contacting the substrate with a composition comprising i) an agent that provides a surface effect and ii) a polymeric extender composition as described above.

The present invention also relates to substrates treated with a composition comprising i) an agent that provides a surface effect and ii) a polymeric extender composition as described above.

Detailed Description

Trademarks and trade names are indicated herein by capital letters. The present invention relates to extender polymer compositions useful for improving the performance of treating agents that provide surface effects to substrates. In particular, the extender compositions are useful for improving the performance of fluorinated polymers in imparting durability to fibrous substrates. The fibrous substrates include paper, non-woven fabrics, leather, carpets, fibers, textiles and fabrics or hybrid fabrics. "Fabric" refers to natural or synthetic fabrics composed of fibers such as cotton, rayon, silk, wool, polyester, polypropylene, polyolefin, nylon, and aramid (e.g., "NOMEX" and "KEVLAR"), or blends thereof. "hybrid fabric" refers to a fabric made from 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 may also be a blend of two or more natural fibers or two or more synthetic fibers.

The addition of the extender polymer compositions of the present invention to the surface treatment composition prior to application to the fibrous substrate imparts superior surface properties as well as desirable properties of low yellowing, soft hand and longer durability to the fibrous substrate. These combined compositions may be applied to the fibrous substrate as a dispersion in water or other solvent before, after, or during the application of other treatment chemicals.

When so applied, it has been found that the extender compositions of the present invention used in combination with the fluorinated polymer treatment agent increase the durability of surface properties, particularly oil and water repellency, in fibrous substrates. In addition, the use of the extender composition increases fluorine efficiency by allowing the use of lower levels of fluorinated polymer. This is desirable because fluorinated polymer surface treatments tend to be expensive.

The extender polymer compositions of the present invention are prepared by conventional emulsion polymerization processes. Typically, such copolymers are prepared by the copolymerization of two or more monomers in an aqueous medium, and the resulting dispersion or emulsion is stabilized with a surfactant. The surfactants used to stabilize the emulsion during its formation and during polymerization can be conventional cationic, nonionic and/or anionic emulsifiers or mixtures thereof. The polymerization may be conveniently initiated by any free radical initiator such as 2, 2' -azobis (2-amidinopropane) dihydrochloride sold under the trade name "VAZO" by naulter dupont de Nemours and company, Wilmington, Delaware, da.

The aqueous dispersion resulting from mixing the extender composition dispersion with the fluorinated polymer dispersion is applied to the surface of the fibrous substrate by known methods to impart oil, stain and water repellency and other surface effects. Examples of such fluorinated polymer dispersions are ZONYL, available from Navelanduop, Inc. (E.I. du Pont de Nemours and Company, Wilmington, Delaware), located in Wilmington, Delaware, OLEOPHOBOL, available from Ciba Specialty Chemicals, Langwoid, Germany, ASAHI GARD, available from Asahi glass Company, Ltd, Tokyo, Japan, located in Langmuig, UNIDYNE, available from Daikin America, Inc., Orangenburg, Organin, located in Nemous, Inc., UNIDYNE, available from Empedox, Inc., located in 3 Bay, St.3M, Inc., located in West, Nanolen, Nanolex, located in Minn, Naylex, located in Nanolex, Inc. The addition of the extender composition of the present invention is particularly characterized by high fluorine efficiency and high durability of the finish (finish) on the substrate.

The extender polymer compositions of the present invention comprise a copolymer comprising monomers copolymerized in the following weight percentages:

(a) from about 5% to about 90% of a monomer or mixture of monomers of formula I:

R₁-OC(O)-C(R)＝CH₂ (I)

(b) from about 5% to about 85% of vinylidene chloride, vinyl acetate or mixtures thereof,

(c) from about 0.5% to about 3% of a monomer of formula II:

HO-CH₂-NH-C(O)-C(R)＝CH₂ (II)

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

HO-CH₂CH₂-OC(O)-C(R)＝CH₂ (III)

and

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

H-(OCH₂CH₂)_m-O-C(O)-C(R)＝CH₂ (IV)

(f) from 0% to about 25% of methyl methacrylate, vinylbenzyl chloride, styrene, or mixtures thereof,

wherein the content of the first and second substances,

each R is independently H or CH₃；

R₁Is a straight or branched alkyl chain containing from about 4 to about 18 carbon atoms, and

m is from 2 to about 10.

The term "(meth) acrylate" refers herein to methacrylate, acrylate or a mixture of both.

The monomer (a) of formula I required in the present invention is an alkyl (meth) acrylate having a chain length of from about 4 to about 18 carbon atoms or a mixture thereof. It is added to the polymerization in a proportion of 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 straight, branched, and cyclic alkyl groups. Examples of such monomers include stearyl (meth) acrylate, lauryl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, and the like. Of the foregoing examples, stearyl acrylate and stearyl methacrylate are most preferred.

The desired monomer (b) is vinylidene chloride, vinyl acetate or mixtures thereof. It is added to the polymerization in a proportion of about 5% to about 85%. Preferably, the proportion of monomer (b) in the copolymer is between about 5% and about 50% by weight.

The monomers (c), (d) and (e) together function to improve the durability of the treating agent. The monomer (c) is N-methylolacrylamide or methacrylamide. N-methylolacrylamide is preferred. It is added to the polymerization in a proportion of about 0.5% to about 3%, preferably about 0.7% to about 1.5%. The monomer (d) is hydroxyethyl (meth) acrylate. It is added to the polymerization in a proportion of about 0.5% to about 3%, preferably about 0.7% to about 1.5%. Monomer (e) is an ethoxylated (meth) acrylate wherein the number of ethoxy groups is from 2 to about 10. Preferably from about 4 to about 10 ethoxy groups. It is added to the polymerization in a proportion of 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 fibrous substrate treating agents. Of particular note are fluorinated polymers that can be used as treating agents to provide repellency properties to the surface of the substrate being treated. 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, more preferably from about 1: 2 to about 2: 1. The blend has a fluorine content of about 1.5% to about 6.6% by weight, preferably about 2.0% to about 4.0% by weight. The fluorinated polymer treating agent is any of those used to produce surface effects, particularly oil and water repellency, on fibrous substrates. It includes fluorinated compounds or polymers containing one or more fluoroaliphatic groups (herein Rf groups) that are fluorinated, stable, inert, non-polar, preferably saturated, monovalent, and both oleophobic and hydrophobic. The R is_fThe group preferably contains at least 3 carbon atoms, more preferably 3 to about 20 carbon atoms, and most preferably about 6 to about 14 carbon atoms. R_fThe groups may contain linear or branched or cyclic fluorinated alkylene groups or combinations thereof. R_fThe end of the radical being of formula C_nF_2n+1Wherein n is from about 3 to about 20.

Examples of such fluorinated polymers preferably include those containing R_fPolyurethanes and poly (meth) acrylates. Particularly preferred are fluorinated (meth) acrylate monomers and copolymerizableA copolymer of a monovinyl compound or a conjugated diene of (1). The copolymerizable monovinyl compounds include alkyl (meth) acrylates, vinyl esters of fatty acids, styrene and alkylstyrenes, vinyl halides, vinylidene halides, alkyl esters, vinyl alkyl ketones, and acrylamides. The conjugated diene is preferably 1, 3-butadiene. Representative compounds in the foregoing classes include methyl, propyl, butyl, 2-hydroxypropyl, 2-hydroxyethyl, isoamyl, 2-ethylhexyl, octyl, decyl, lauryl, cetyl and stearyl acrylates and methacrylates; vinyl acetate, vinyl propionate, vinyl caprylate, vinyl laurate, vinyl stearate, styrene, alpha-methylstyrene, p-methylstyrene, vinyl fluoride, vinyl chloride, vinyl bromide, vinylidene fluoride, vinylidene chloride, allyl heptanoate, allyl acetate, allyl octanoate, allyl hexanoate, vinyl methyl ketone, vinyl ethyl ketone, 1, 3-butadiene, 2-chloro-1, 3-butadiene, 2, 3-dichloro-1, 3-butadiene, isoprene, N-methylolacrylamide, N-methylolmethacrylamide, glycidyl acrylate, glycidyl methacrylate, and polyoxymethylene.

The blend composition comprising the fluorinated polymer and the extender polymer of the present invention applied to the fibrous substrate may optionally contain a blocked isocyanate (added after copolymerization, i.e., as a blended isocyanate) to further enhance durability. An example of a blocked isocyanate is hydrophopol XAN available from Ciba Specialty Chemicals, High Point, NJ. Other commercially blocked isocyanates are also suitable for use herein. The desirability of adding the blocked isocyanate depends on the particular application of the copolymer. For most of the presently contemplated applications, it need not 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.

Blend compositions comprising fluorinated polymers and the extender compositions of the present invention may optionally further comprise other components such as treatments or finishes to achieve other surface effects or additives commonly used with such treatments or finishes. Such other components include compounds or compositions that provide surface effects such as easy iron, shrinkage control, anti-wrinkle, permanent press, moisture control, softness, strength, anti-slip, anti-static, anti-rub, anti-pilling, anti-stain (stain repellency), stain release (stain release), soil repellency, soil release (stain release), water repellency, oil repellency, odor release, antimicrobial, sun protection, and the like. One or more such treatments or finishes may be combined with the blend composition and applied to the fibrous substrate. Other additives commonly used with such treatments or extenders may also be present, such as surfactants, pH adjusters, cross linkers, wetting agents, wax extenders and other additives well known to those skilled in the art. Suitable surfactants include anionic, cationic and nonionic. Preferred anionic surfactants are sodium dodecyl sulfate available as DUPONOL WAQE from Witco Corporation, Greenwich, CT, Greenwich, Conn.

In particular, the blend composition comprising the fluorinated polymer and the extender polymer of the present invention applied to the fibrous substrate may optionally further comprise a softening agent (added after copolymerization) to further enhance hand. The desirability of adding the softening agent depends on the particular application of the copolymer. Examples of softeners may be selected from softener products of Wacker chemistry (Wacker Chemical) such as WACKERFINISH WR 1300, WACKER FINISH CT 34E, WACKER FINISH WT1650, JETSOFT NFS, powersfot AE 38 and wetsft AOP or softeners 2-8031 from Silicone of Dow Chemical. Amounts of up to 1% by weight may be added.

When the above-described blends of extender polymer compositions with fluorinated polymer compositions are applied to a fibrous substrate, optional other extender compositions may also be included in the application to obtain certain combinations of benefits. An example of such an optional additional extender polymer composition is disclosed in co-pending U.S. provisional application 60/607,612(CH-2996), filed on 7.9.2004. When such optional extenders are added to the foregoing extender polymers of the present invention, the percentages given above for components (a), (b), (c), (d) and (e) of the present invention will apply to the entire extender polymer composition.

The present invention also relates to a method of treating a substrate comprising contacting the surface of the substrate with an effective amount of a composition comprising the extender composition of the invention as described above and a treating agent which provides a surface effect when applied to the substrate. Preferably, the treating agent is a fluorinated polymer. The blended combination is applied to the fibrous substrate to be treated from an aqueous dispersion either alone or in admixture with other textile treatments, finishes or additives as described above. The dispersion is typically applied to the fibrous substrate by spraying, dipping, padding or other well known methods. After removal of excess liquid, e.g., by squeeze rolls, the treated fibrous substrate is dried and then cured by heating to, e.g., 100 ℃ to 190 ℃ for at least 30 seconds, typically about 60 to about 240 seconds. Such curing enhances the durability of oil, water and stain repellency and repellency. While these curing conditions are typical, some industrial devices can operate outside of these ranges due to their specific design characteristics. The fluorine content of the treated fibrous substrate is from about 0.05% to about 0.5% by weight.

The present invention also relates to substrates treated with a composition as described above comprising i) an agent providing a surface effect and ii) an extender copolymer of the invention as described above. The composition may also contain optional agents to provide other surface effects as described above, optional additives as described above commonly used in substrate treatment, optional blocked isocyanates as described above, and optional other different extender compositions. As previously mentioned, such substrates include fibers, paper, non-woven fabrics, leather, textiles and fabrics or hybrid fabrics. "Fabric" includes natural or synthetic fabrics composed of cotton, rayon, silk, wool, polyester, polypropylene, polyolefin, nylon, and aramid (e.g., "NOMEX" and "KEVLAR"). "hybrid fabric" refers to a fabric made from 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 may also be a blend of two or more natural fibers or 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.

In particular, the compositions, methods, and treated substrates of the present invention are useful for enhancing the surface properties of such substrates, particularly oil, water, and stain repellency, while reducing the amount of fluorinated polymer used. The repellency properties are more durable than when fluorinated polymers are applied without the presence of extender and are effective on a variety of fibrous substrates. The repellency is effective simultaneously with a variety of other surface effects. The treated substrates of the present invention may be used in a variety of applications such as textiles, garments, uniforms, protective apparel, apparel and the like. The extender copolymers of the present invention are advantageous in that they impart a highly durable, low yellowing, and soft hand repellent coating to a wide range of fibrous substrates such as fabrics or mixed fabrics, while reducing the amount of fluorinated polymer used. The material costs for producing the compositions of the present invention are lower than current (meth) acrylate copolymers, for example by reducing the amount of expensive fluorinated polymer needed to provide the desired surface effect.

Test methods 1-Fabric treatment

The fabric is treated with the copolymer blend using a conventional pad bath (immersion) process. The fabrics were treated using a treatment bath containing 0.1 to 0.5% by weight of a fluorinated polymer treatment agent blended with an extender copolymer of the present invention (hereinafter copolymer blend) as detailed in the tables in the examples section. The fluorinated polymer used in blending with the non-fluorinated copolymer extender is commercially available as ZONYL from Navell DuPont, Wilmington, Del., located in Wilmington, Del. After application the fabric is cured at about 160 ℃ for 1-3 minutes and after treatment and curing it is "left" overnight for about 15-18 hours.

Test method 2 Water repellency

The water repellency of the treated substrates was determined according to the DuPont (DuPont) technology Laboratory Method (DuPont Technical Laboratory Method) as described in the TEFLON Global Specifications and Quality Control Tests (TEFLON Global Specifications and Quality Control Tests) information package. This test measures the ability of a treated substrate to resist wetting by aqueous liquids. Drops of water-alcohol mixtures with different surface tensions were placed on the fabric and the degree of surface wetting was visually assessed. This test provides a rough indication of water resistance soil. The higher the water repellency rating, the better the treated substrate's ability to resist contamination by water-resistant materials. The composition of the standard test liquids is given in table 1 below. A scale of 1-6 is sometimes used for convenience. The grade numbers in 0.5 increments were obtained by subtracting 0.5 from the grade numbers of the test liquids in table 1.

TABLE 1

Standard test liquid

Number of water repellency grades	Composition of isopropyl alcohol	Volume percent of distilled water
			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

Test method 3-Water repellency-spray method rating

The water repellency can be further determined by the spray test method. The treated fabric samples were tested for water repellency according to AATCC standard test method 22-1996 using the following procedure: the fabric samples treated with the aqueous polymer dispersion as described above were conditioned at 23 ℃ + 20% relative humidity and 65 ℃ + 10% relative humidity for at least 2 hours. The fabric sample was fastened to a plastic/metal embroidery ring so that the fabric was smooth and wrinkle free. The loop was placed on a test stand with the fabric facing up. 250mL of 80 + -2 deg.F (27 + -1 deg.C) water was then poured into a test funnel that sprayed the water onto the fabric surface. Once the water in the funnel is drained, the embroidery ring is beaten with the fabric facing down and against a hard object, rotated 180 degrees and beaten again. The beaded or wet surfaces were compared to the AATCC standard as described in the AATCC technical manual. The wetter the surface, the lower the grade number, and the poorer the repellency. 100 for no wetting, 90 for light wetting (three small beads), 80 for wetting with several (10) beads at the point of impingement, 70 for partial wetting of the upper surface of the fabric, 50 for total wetting of the upper surface of the fabric, and 0 for total wetting of the upper and lower surfaces of the fabric. A rating of 15, 25, 35, 45, 55, 60, 65, 75 or 85 indicates a performance that is between the above scoring scales.

Test method 4 oil repellency

The treated fabric samples were tested for oil repellency according to the modification of AATCC standard test method 118 using the following procedure: the fabric samples treated with the aqueous polymer dispersion as described above were conditioned at 23 ℃ + 20% relative humidity and 65 ℃ + 10% relative humidity for at least 2 hours. A series of organic liquids as shown in table 2 below were then added drop wise to the fabric sample. Starting with the lowest numbered test liquid (repellency rating 1), one drop (about 5mm in diameter or 0.05mL in volume) was added to each of three locations separated by at least 5 mm. The droplets were observed for 30 seconds. If at the end of this period two of the three droplets are still spherical in shape and there is no wicking around the droplet, three drops of one numbered liquid are added to the adjacent locations and observed for the same 30 seconds. This procedure was continued until the result of one of the test liquids was that two of the three droplets failed to remain spherical to hemispherical or wetting or wicking occurred.

The oil repellency rating of the fabric was the largest numbered test liquid for which two of the three droplets remained spherical to hemispherical and did not wick within 30 seconds. Generally, treated fabrics with a rating of 6 or more are considered good to excellent; fabrics with a rating of 1 or greater may be useful in certain applications. The grade numbers in 0.5 increments were obtained by subtracting 0.5 from the grade numbers of the test liquids in table 2.

TABLE 2

Oil repellency test liquid

Number of oil repellency grades	Test solutions
		1	NUJOL refined mineral oil
2	Nujol/n-hexadecane in a volume ratio of 65/35 at 21 DEG C
		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, and represents mineral oil having a Saybolt viscosity of 360/390 at 38 ℃ and a specific gravity of 0.880/0.900 at 15 ℃.

Test method 5-Wash resistance

The fabric samples were laundered according to the international standard which specifies the home laundering procedure used in the textile test. The fabric samples were loaded into a front opening horizontal drum (model a, WASCATOR Form71MP-Lab) of an automatic washing machine and a ballast load was added to a total dry load of 4 pounds. Commercial detergent (AATCC 1993 standard reference detergent WOB) was added, the washing machine was programmed to high water, warm water (105 ° F, 41 ℃) and rinsed 2 times for 13 minutes after a 15 minute normal wash cycle, then spun dry for 2 minutes. The samples and ballast were washed a specified number of times (5HW for 5 washes, 20HW for 20 washes, etc.). After the wash was complete, the wet fabric samples were allowed to air dry and then ironed on each side for 30 seconds with a flat iron having a surface temperature of 135-.

Examples

In the tables below, the term "fluorochemical" is used to refer to the fluorinated polymer prior to combination with the extender composition of the present invention.

Example 1

An aqueous emulsion was prepared by mixing the following components: 96g of hot deionized water (50-60 ℃ C.), 3.2g of ETHOQUAD 18/25 (available from Akzo Nobel, Chicago, IL.), 4.6g of tridecyl alcohol 5-ethylene oxide adduct (ETHOX TDA-5, available from Esaxox Chemicals, Greenville, SC, located in Greenville, N.), 30g of stearyl methacrylate, 1.25g of N-methylolacrylamide, 0.68g of 2-hydroxyethyl methacrylate, 1.25g of poly (oxyethylene) 7 methacrylate, 0.34g of dodecanethiol, and 19.36g of dipropylene glycol were then charged to 500mL four necks equipped with a mechanical stirrer, thermocouple thermometer, and quench condenser (-5 to-10 ℃ C.). The batch was flushed into the flask with 10g of hot deionized water and purged with nitrogen for 30 minutes or until the temperature was below 30 ℃. Then 30g of vinylidene chloride was added to the reaction flask and mixed for 5 minutes. 0.34g of "VAZO" 56WSP (E.I. du Pont de Nemours and Company, Wilmington, Delaware) dissolved in 10g of deionized water was then added to initiate polymerization. The mixture was heated to 50 ℃ over thirty minutes and held for 8 hours. After polymerization 0.46g of duponollaqe (available from witcok corporation,greenwich, Conn.) was mixed with the product at room temperature. The resulting polymer extender latex (dispersion in water) weighed 206g and had a solids content of 27.92%. T is_m＝25.36℃，δH＝23.93J/g。

The latex obtained above was blended with commercially available fluoropolymers ZONYL8300, ZONYL 8412 and ZONYL8932 from Navelanduon DuPont, Wilmington, Delaware, respectively, in Wilmington, Delaware, Del, to perform performance tests. The ratio of extender to fluoropolymer contained in the blend is from 3: 1 to 1: 1. The blend with ZONYL fluoropolymer was applied to a 100% nylon fabric using test method 1 above. For the data in tables 4 and 5, the treatment bath contained 20-50g/L of the blended product. For the data in Table 6, the treatment bath contained 10-15g/L of fluorinated polymer and the ratio of extender to fluorinated polymer for example 1 is shown in Table 6. The treatment bath also contained 2g/L of wetting agent ALKANOL 6112 (available from Navell DuPont, Wilmington, Delaware, E.I. du Pont de Nemours and Company, Wilmington, Delaware). After application the fabric was cured at 160 ℃ for about 2 minutes. After treatment and curing, the fabric is allowed to "rest". The treated fabrics were tested for their oil repellency, water repellency, and ratings by the spray method using test methods 2, 3, 4, and 5 above. The results are shown in tables 4 to 6.

Examples 2 to 7

The procedure of example 1 was followed except that stearyl methacrylate and vinylidene chloride were used in varying amounts as shown in table 3 below. The solids content and melting point are also given in table 3.

TABLE 3

Product composition 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 content	27.39	28.98	30.02	27.73	25.5	28.04
Tm(℃)/δH(J/g)	30.09/42.78	31.39/32.52	31.76/35.36	30.47/73.31	15.26/15.18

^*StMA ═ stearyl methacrylate, VDC ═ vinylidene chloride

The extender was blended with ZONYL fluoride, applied to nylon fabric and tested as described in example 1. The results are given in tables 4-6.

Comparative example A

An aqueous emulsion was prepared by mixing the following components: 96g of hot deionized water (50-60 deg.C), 3.2g of ETHOQUAD 18/25 (available from Akzo Nobel, Chicago, IL), 4.6g of tridecyl alcohol 5-ethylene oxide adduct (ETHOX TDA-5, available from Esaxox Chemicals, Greenville, SC, located in Greenville, N.), 60g of stearyl methacrylate, 1.25g of poly (oxyethylene) 7 methacrylate, 1.25g of 1.25g N-hydroxymethylacrylamide, 0.68g of 2-hydroxyethyl methacrylate, 0.34g of dodecanethiol, and 19.36g of dipropylene glycol, were then charged to a 500mL four-necked flask equipped with a mechanical stirrer, thermocouple thermometer, and quench condenser (-5 to-10 deg.C.). The batch was flushed into the flask with 10g of hot deionized water and purged with nitrogen for 30 minutes. 0.34g of "VAZO" 56WSP (E.I. du Pont de Nemours and company, Wilmington, Delaware) dissolved in 10g of deionized water was then added to initiate polymerization. The mixture was heated to 50 ℃ over thirty minutes and held for 8 hours. After polymerizationAn aqueous solution of 0.46g DUPONOL WAQE (available from Witco Corporation, Greenwich, Conn.) from Wekett Corporation, Greenwich, Conn.) was mixed with the product at room temperature. The resulting polymer extender latex (dispersion in water) weighed 206g and had a solids content of 27.92%. T is_m32.86 ℃ and. delta.H 39.27J/g. The extender was blended with ZONYL fluoride, applied to nylon fabric and tested as described in example 1. The results are given in tables 4-6.

Comparative example B

An aqueous emulsion was prepared by mixing the following components: 167g of hot deionized water (50-60 ℃ C.), 0.7g of ETHOQUAD 18/25 (available from Akzo Nobel, Chicago, IL.), 2.9g of tridecyl alcohol 5-ethylene oxide adduct (ETHOX TDA-5, available from Esaxox Chemicals, Greenville, SC, located in Greenville, N.C.), 3.33g of poly (oxyethylene) 7 methacrylate, 3.33g N-hydroxymethylacrylamide, 1.67g of 2-hydroxyethyl methacrylate, 0.1g of dodecylmercaptan, and 16.67g of 2-methyl-2, 4-pentanediol, which were then charged to a 1L autoclave. The autoclave was sealed and evacuated/purged with nitrogen three times. Then 30g of vinylidene chloride were added. 0.34g of "VAZO" 56WSP (E.I. du Pont de Nemours and Company, Wilmington, Delaware) dissolved in 10g of deionized water was then added to initiate polymerization. The mixture was heated to 50 ℃ over thirty minutes and held for 8 hours with the stirrer rotating at 150 RPM. The resulting latex was filtered through a milk filter. The extender was blended with ZONYL fluoride, applied to nylon fabric and tested as described in example 1. The results are given in tables 4-6.

TABLE 4

Fluorine compounds	ZONYL 8932	ZONYL 8932	ZONYL 8932	ZONYL 8932
					EXAMPLES extenders	Comparative example B	1	Comparative example A	Is free of
F% by weight (based on the treated fabric)	0.093	0.097	0.1	0.19
					Oil repellency
Initially, the process is started	6	6	5	6
					5HW	5	6	-	3
20HW	1	6	3	1
Water repellency
					Initially, the process is started	6	6	6	6
5HW	6	6	-	6
					20HW	6	6	6	6
					Spray method rating
Initially, the process is started	100	100	100	100
					5HW	80	90	-	70
20HW	75	80	80	70

Note: a scale of 1-6 for water and oil repellency in test method 2 was used.

The results show that the copolymer of example 1 has better performance than the copolymers of comparative examples a and B when similar fluorine content is used. Better performance was obtained when the extender of example 1 was used, even when the fluorine content was only 50, compared to the fluoropolymer without extender.

The data in tables 5A, 5B, and 5C show that the blend formulations containing the extenders of examples 1-7 provide comparable or better performance on nylon fabrics than the fluorochemical without extender and a 50% reduction in fluorine usage. These data also show that the extenders of examples 1-7 provide comparable or better performance than the control examples when the same fluorine content is used.

TABLE 6

Fluorine-containing compound	ZONYL8932	ZONYL8932	ZONYL8300	ZONYL8300	ZONYL8300	ZONYL8412	ZONYL8412	ZONYL8412
									Extender/fluorochemical ratio of example 1	1/1	2/1	0.6/1	1/1	2/1	0.6/1	1/1	2/1
									Oil repellency
Initially, the process is started	7.5	7.5	7.5	7.5	5.5	7.5	7.5	6.5
									10 HW-ironing	6.5	6.5	5.5	6.5	5.5	5.5	5.5	4.5
20 HW-ironing	2.5	4.5	1.5	2.5	4.5	1.5	3.5	3.5
Water repellency
									Initially, the process is started	12	12	12	11.5	9.5	12	11.5	10.5
10 HW-ironing	10.5	10.5	9.5	10.5	9.5	8.5	10.5	6.5
									20 HW-ironing	5	6.5	4.5	5.5	6.5	4.5	6.5	5.5
									Spray method rating
Initially, the process is started	100	100	100	100	90	100	100	100
									10 HW-ironing	90	100	80	80	90	80	90	90
20 HW-ironing	60	70	50	70	70	50	60	70

The data in Table 6 shows that the combination of the extender of example 1 with different ZONYL products in different ratios gives effective performance on nylon.

Examples 8 to 13

An extender composition was prepared following the procedure of example 1, except that the surfactants and solvents shown in table 7 below were used. The resulting extenders were blended with commercially available fluoropolymers ZONYL8300, ZONYL 8412 and ZONYL8932 from Navelanduon DuPont, Wilmington, Delaware, respectively, located in Wilmington, Del.A. for performance testing. The ratio of extender to ZONYL was 1: 1.

Blends with various ZONYL fluoropolymers were applied to 100% nylon fabric using test method 1 above. The treatment bath contains 20-50g/L of the blended product. The treatment bath also contained 2g/L of wetting agent ALKANOL 6112 (available from Navell DuPont, Wilmington, Delaware, E.I. du Pont de Nemours and Company, Wilmington, Delaware). After application the fabric was cured at 160 ℃ for about 2 minutes. After treatment and curing, the fabric is allowed to "rest". The treated nylon was tested for oil repellency, water repellency, and spray rating using test methods 2, 3, 4, and 5 above. The results are listed in tables 8A, 8B and 8C.

TABLE 7

Example #	Surface active agent	Trade name (Source)	Solvent(s)	% solids content in latex
					8	Octadecylmethyl (polyoxyethylene (15) ammonium chloride, secondary alcohol ethoxylate	ETHOQUAD 18/25 (available from Akzo Nobel, Chicago, IL)), TERGITOL 15-S-20 (available from Union Carbide, Danbury, Conn.))	Dipropylene glycol methyl ether acetate	28％
9	Polyethylene glycol esters	MAZAR MEPEG 600MS (available from mosaic chemical Inc., Gurmee, IL, Gurmee, Ill.)	Hexanediol	32.55％
					10	Polyethylene glycol ester/AVITEXR	MAZAR MEPEG 600MS (from mosaic chemical Inc., Gurmee, IL, Gurmee, Ill.)/AVITEX R (from Klien, Holly, Mt., North Carolina)(Clariant，Mt.Holly，NC))	Hexanediol	31.74％
11	Alcohol ethoxylate/octadecyl methyl (polyoxyethylene (15) ammonium chloride/avitex xr)	ETHOX TDA-5 (available from Ethox Chemicals, Greenville, SC) from Ishoque, Greenville, N.C./ETHOQUAD 18/25 (available from Akzo Nobel, Chicago, IL) from Chicago, Ill.)/AVITEX R (available from claiant, Mt.Holly, N.C.)	Dipropylene glycol	28.08％
					12	Polyglycol ester/alkanolamine hydrochloride mixtures	MAZAR MEPEG 600MS (available from mosaic Chemical Co., Ltd., Gurmee, Ill.) (Mazar Chemical)	Hexanediol	32.79％
		Inc., Gurmee, IL))/AVITEX 2153 (available from DuPont, Wilmington, DE, Wilmington, Del.)

13

Polyethylene glycol ester/di (hydrogenated tallow) dimethyl ammonium chloride

MAZAR MEPEG 600MS (from Mazar chemical Inc., Gurmee, IL) located in Gurmee, Ill./ARQUAD 2HT 75 (from Akzo Nobel, Chicago, IL) located in Chicago, Ill.)

Hexanediol

32.73％

TABLE 8A

ZONYL 8412+ EXAMPLE bulking agent	Is free of	1	8	9	10	11	12	13
									Oil repellency
Initially, the process is started	6	6.5	6.5	6	7	6.5	4.5	5
									20 HW-ironing	3	5	4	5	4.5	5.5	1	2
									Water repellency
Initially, the process is started	12	12	12	11	12	12	8.5	8.5
									20 HW-ironing	8.5	7.5	7	7	8	8	5	6
									Spray method rating
Initially, the process is started	100	90	80	90	100	90	70	90
									20 HW-ironing	70	70	70	70	75	75	70	80

TABLE 8B

ZONYL8932 + EXAMPLE extender	Is free of	1	8	9	10	11	12	13
									Oil repellency
Initially, the process is started	6.5	8	6.5	6.5	7	7	6.5	7.5
									20 HW-ironing	4	6.5	5	5.5	4	4.5	6	5
									Water repellency

Initially, the process is started	12	12	12	12	12	12	12	12
									20 HW-ironing	8	10.5	8.5	9	9	10.5	9	9
									Spray method rating
Initially, the process is started	100	100	100	100	100	100	100	100
									20 HW-ironing	80	80	80	70	70	70	80	70

TABLE 8C

ZONYL8300 + EXAMPLE extender	Is free of	1	8	9	10	11	12	13
									Oil repellency
Initially, the process is started	7	7	6	5.5	6.5	6	3.5	4
									20 HW-ironing	4	4.5	2	3.5	4	4	0.5	2
									Water repellency
Initially, the process is started	11.5	12	10	10	11	10.5	6.5	8.5
									20 HW-ironing	8.5	9	6	7	8	7.5	5	6
									Spray method rating
Initially, the process is started	100	100	90	100	90	100	80	90
									20 HW-ironing	70	70	70	70	70	70	70	70

The data in tables 8A, 8B, and 8C show that the extender compositions of examples 1 and 8-13 are effective at providing durable repellency with half the fluorine content when prepared with various surfactants and solvents. The fluorine content of the compositions with extender present was 50% of those without extender present.

Example 14

An aqueous emulsion was prepared by mixing the following components: 80g of hot deionized water (50-60 ℃), 1.6g of ARMEEN DM18D (commercially available from Akzo Nobel, Chicago, Ill.), 60g of ethylhexyl methacrylate, 10g of poly (oxyethylene) 7 methacrylate, 2g N-methylolacrylamide, 0.3g of dodecanethiol, 1g of acetic acid, and 0.3g of a 2% sodium chloride solution and 20g of hexanediol were charged to a 500mL four-necked flask equipped with a mechanical stirrer, thermocouple thermometer, and quench condenser (-5 to-10 ℃). The batch was flushed into the flask with 80g of hot deionized water and purged with nitrogen for 30 minutes or until the temperature was below 30 ℃. Then 10g of vinylidene chloride was added to the reaction flask and mixed for 5 minutes. 0.4g of "VAZO" 56WSP (E.I. du Pont de Nemours and company, Wilmington, Delaware) dissolved in 10g of deionized water was then added to initiate polymerization. The mixture was heated to 50 ℃ over a half hour and held for 8 hours. The resulting polymer extender latex (dispersion in water) weighed 250g and had a solids content of 28.87%. This was then blended with ZONYL8300 and ZONYL8932, fluorinated polymers available from Navelanduop, Wilmington, Delaware, at a ratio of 2: 1 extender to fluorinated polymer for ZONYL8932 and 1: 1 extender to fluorinated polymer for ZONYL 8300. The blend was applied to nylon fabric using test method 1 above. The treatment bath contains 0.133% to 0.15% fluorine. Nylon was tested for repellency using test methods 2, 3, 4 and 5 above. The results are listed in tables 10A and 10B.

Examples 15-17, comparative example C

Latex extenders were synthesized following the same procedure as in example 14, except that the monomer amounts listed in table 9 were used.

TABLE 9

Examples	15	16	17	Comparative example C
					Monomer g
Poly (oxyethylene) 7 methacrylate	5	10	3	10
					Ethylhexyl methacrylate	70	65	50	70
Vinylidene chloride	5	5	27	0
					% solids content in latex	28.42％	29.04％	27.76％	28.87％

The extender and the product of control example C were blended with ZONYL8932 and ZONYL8300 fluorinated polymer at a ratio of 2: 1 extender to fluorinated polymer.

The blend was applied to 100% nylon fabric using test method 1 above. The treatment bath contains 20-50g/L of the blending product. The treatment bath also contained 2g/L of wetting agent ALKANOL 6112 (available from Navell DuPont, Wilmington, Delaware, U.S.A.). After application the fabric was cured at about 160 ℃ for 2 minutes. After treatment and curing, the fabric is allowed to "rest". The nylons were tested for oil, water and spray method ratings and wash durability using test methods 4, 2, 3 and 5 above. Results for ZONYL 8932/extender blends are set forth in Table 10A and results for ZONYL 8300/extender blends are set forth in Table 10B.

TABLE 10A

EXAMPLES extenders	Comparative example C	14	15	16	17
						Oil repellency
Initially, the process is started	6	6	5.5	6	5.5
						20 HW-ironing	3.5	5.5	4.5	4.5	4.5

						Water repellency
Initially, the process is started	10.5	10.5	10	11	10
						20 HW-ironing	7	7.5	8.5	8.5	8.5
						Spray method rating
Initially, the process is started	100	100	100	100	100
						20 HW-ironing	60	75	70	70	80

TABLE 10B

EXAMPLES extenders	Comparative example C	14	15	16	17
						Oil repellency
Initially, the process is started	5.5	6	6	6	5
						20 HW-ironing	0	4	4	0	0.5
						Water repellency
Initially, the process is started	10.5	7.5	9.5	6	5.5
						20 HW-ironing	5	4	6	4	5
						Spray method rating
Initially, the process is started	80	85	100	90	80
						20 HW-ironing	70	70	70	60	75

The data in Table 10A show that the presence of vinylidene chloride in the extender copolymers of examples 14-17 blended with ZONYL8932 improves performance compared to control example C without vinylidene chloride. The data in table 10B show that the presence of vinylidene chloride in the extender copolymers of examples 14-17 blended with ZONYL8300 improves oil repellency and spray method rating compared to control example C without vinylidene chloride.

Examples 18 to 21

First (a)70g of 2-ethylhexyl methacrylate, (b)10g of poly (oxyethylene) 7 methacrylate, (c)2g of a 48% aqueous N-methylolacrylamide solution, 0.3g of dodecanethiol, 20g of hexanediol, 1.6g of ARMEEN DM18D, 1.0g of acetic acid, 3g of a 2% aqueous salt (NaCl) solution and 80g of hot deionized water (50-60 ℃) were emulsified and then charged into a four-necked flask equipped with a stirrer, a thermocouple thermometer and a water condenser. The batch was flushed into the flask with 75g of hot deionized water and purged with nitrogen at 65 ℃ for 30 minutes. 0.08g of "VAZO" 56WSP (E.I. du Pont de Nemours and Company, Wilmington, Delaware) dissolved in 2g of deionized water was then added to initiate polymerization. The temperature of the mixture spontaneously rose to 79 ℃ in about 12 minutes and then began to drop. The temperature controller was reset to 70 ℃ and the feed was stirred under nitrogen for 4 hours. The resulting polymer extender latex (dispersion in water) weighed 251g and had a solids content of 31.7%. This extender was mixed with the extenders of examples 1, 9, 10 and 11, respectively, in a 1: 1 ratio to produce the extender mixtures referred to herein as the products of examples 18, 19, 20 and 21.

This extender mixture was then blended with ZONYL8932 fluorochemical at a ratio of extender to fluorinated polymer of 2: 1. The blend was applied to 100% cotton twill fabric using test method 1 above. The treatment bath contained 45g/L of the blend, 1g/L of blocked isocyanate HYDROPHOBOL XAN from Ciba specialty Chemicals, High Point, NC, and 70g/L of anti-wrinkle resin PERMAFRESH EFC from Omnova Solutions, Chester, SC, located at Chester, south Carolina. After application the fabric was cured at 330 ℃ for 3 minutes. After treatment and curing, the fabric is allowed to "rest". The treated cotton was tested for oil repellency, water repellency and spray method ratings and wash durability using test methods 4, 2, 3 and 5 above. For comparison, when no extender is present, the treatment bath contains 15g/L or 30g/L ZONYL8932, and the other treatment bath components are the same. The results are listed in table 11.

TABLE 11

ZONYL8932 + EXAMPLE extender	18	19	20	21	15g/L ZONYL8932, no extender	30g/L ZONYL8932, no extender
Oil repellency
							Initially, the process is started	7	7	7	7	5	6
20HWLTD	6	6	6	6	2	4
Water repellency
							Initially, the process is started	12	12	12	12	7	10
20HWLTD	10	10	9	11	5	7.5
Spray method rating
							Initially, the process is started	100	100	100	100	100	100
20HWLTD	80	85	80	85	75	80

The results in table 11 show that fluorine efficacy was obtained using a mixture of the extender composition and the fluorinated polymer. Superior performance is obtained compared to fluorinated polymers that have about three times higher fluorine content than the blend in the absence of the extender composition.

Example 22

An aqueous emulsion was prepared by mixing the following components: 96g of hot deionized water (50-60 ℃ C.), 3.2g of ETHOQUAD 18/25 (available from Akzo Nobel, Chicago, IL.), 4.6g of tridecyl alcohol 5-ethylene oxide adduct (ETHOX TDA-5, available from Esaxox Chemicals, Greenville, SC, located in Greenville, N.C.), 30g of stearyl methacrylate, 15g of methyl methacrylate, 1.25g N-hydroxymethylacrylamide, 0.68g of 2-hydroxyethyl methacrylate, 1.25g of poly (oxyethylene) 7 methacrylate, 0.34g of dodecanethiol, and 19.36g of dipropylene glycol were charged to a 500mL four-necked flask equipped with a mechanical stirrer, thermocouple thermometer, and quench condenser (-5 to-10 ℃ C.). The batch was flushed into the flask with 10g of hot deionized water and purged with nitrogen for 30 minutes or until the temperature was below 30 ℃. Then 15g of vinylidene chloride was added to the reaction flask and mixed for 5 minutes. 0.34g of "VAZO" 56WSP (E.I. du Pont de Nemours and Company, Wilmington, Delaware) dissolved in 10g of deionized water was then added to initiate polymerization. The mixture was heated to 50 ℃ over a half hour and held for 8 hours. After polymerization, 0.46g of DUPONOL WAQE (available from Witco Corporation, Greenwich, Conn.) in water was mixed with the product at room temperature. The resulting polymer extender latex (dispersion in water) weighed 202.65g and had a solids content of 28.74%.

Example 23

An aqueous emulsion was prepared by mixing the following components: 96g of hot deionized water (50-60 ℃ C.), 3.2g of ETHOQUAD 18/25 (available from Akzo Nobel, Chicago, IL.), 4.6g of tridecyl alcohol 5-ethylene oxide adduct (ETHOX TDA-5, available from Esaxox Chemicals, Greenville, SC, located in Greenville, N.C.), 30g of stearyl methacrylate, 15g of vinyl acetate, 1.25g N-hydroxymethylacrylamide, 0.68g of 2-hydroxyethyl methacrylate, 1.25g of poly (oxyethylene) 7 methacrylate, 0.34g of dodecanethiol, and 19.36g of dipropylene glycol were charged to a 500mL four-necked flask equipped with a mechanical stirrer, thermocouple thermometer, and quench condenser (-5 to-10 ℃ C.). The batch was flushed into the flask with 10g of hot deionized water and purged with nitrogen for 30 minutes or until the temperature was below 30 ℃. Then 15g of vinylidene chloride was added to the reaction flask and mixed for 5 minutes. 0.34g of "VAZO" 56WSP (E.I. du Pont de Nemours and Company, Wilmington, Delaware) dissolved in 10g of deionized water was then added to initiate polymerization. The mixture was heated to 50 ℃ over a half hour and held for 8 hours. After polymerization, 0.46g of DUPONOL WAQE (available from Witco Corporation, Greenwich, Conn.) in water was mixed with the product at room temperature. The resulting polymer extender latex (dispersion in water) weighed 196.4g and had a solids content of 25.91%.

Example 24

An aqueous emulsion was prepared by mixing the following components: 96g of hot deionized water (50-60 ℃ C.), 3.2g of ETHOQUAD 18/25 (available from Akzo Nobel, Chicago, IL.), 4.6g of tridecyl alcohol 5-ethylene oxide adduct (ETHOX TDA-5, available from Esaxox Chemicals, Greenville, SC, located in Greenville, N.), 30g of stearyl methacrylate, 1.25g of N-methylolacrylamide, 0.68g of 2-hydroxyethyl methacrylate, 1.25g of poly (oxyethylene) 7 methacrylate, 0.34g of dodecanethiol, and 19.36g of dipropylene glycol were then charged to 500mL four necks equipped with a mechanical stirrer, thermocouple thermometer, and quench condenser (-5 to-10 ℃ C.). The batch was flushed into the flask with 10g of hot deionized water and purged with nitrogen for 30 minutes or until the temperature was below 30 ℃. Then 30g of vinyl acetate was added to the reaction flask and mixed for 5 minutes. 0.34g of "VAZO" 56WSP (E.I. du Pont de Nemours and Company, Wilmington, Delaware) dissolved in 10g of deionized water was then added to initiate polymerization. The mixture was heated to 50 ℃ over a half hour and held for 8 hours. After polymerization, 0.46g of DUPONOLWAQE (available from Witco corporation, Greenwich, Conn.) in water was mixed with the product at room temperature. The resulting polymer extender latex (dispersion in water) weighed 201.56g and had a solids content of 28.47%.

Example 25

An aqueous emulsion was prepared by mixing the following components: 96g of hot deionized water (50-60 ℃ C.), 3.2g of ETHOQUAD 18/25 (available from Akzo Nobel, Chicago, IL.), 4.6g of tridecyl alcohol 5-ethylene oxide adduct (ETHOX TDA-5, available from Ethox Chemicals, Greenville, SC, Greenville, N.C.), 30g of stearyl methacrylate, 15g of vinylbenzyl chloride (vinylbenzyl chloride methyl), 1.25g of 1.25g N-hydroxymethylacrylamide, 0.68g of 2-hydroxyethyl methacrylate, 1.25g of poly (oxyethylene) 7 methacrylate, 0.34g of dodecyl mercaptan, and 19.36g of dipropylene glycol were placed in a 500mL four-necked flask equipped with a mechanical stirrer, thermometer, and quench condenser (-5 to-10 ℃ C.). The batch was flushed into the flask with 10g of hot deionized water and purged with nitrogen for 30 minutes or until the temperature was below 30 ℃. Then 15g of vinylidene chloride was added to the reaction flask and mixed for 5 minutes. 0.34g of "VAZO" 56WSP (E.I. du Pont de Nemours and Company, Wilmington, Delaware) dissolved in 10g of deionized water was then added to initiate polymerization. The mixture was heated to 50 ℃ over a half hour and held for 8 hours. After polymerization, 0.46g of DUPONOL WAQE (available from Witco Corporation, Greenwich, Conn.) in water was mixed with the product at room temperature. The resulting polymer extender latex (dispersion in water) weighed 202.33g and had a solids content of 27.13%.

Example 26

An aqueous emulsion was prepared by mixing the following components: 96g of hot deionized water (50-60 ℃ C.), 3.2g of ETHOQUAD 18/25 (available from Akzo Nobel, Chicago, IL.), 4.6g of tridecyl alcohol 5-ethylene oxide adduct (ETHOX TDA-5, available from Esaxox Chemicals, Greenville, SC, located in Greenville, N.C.), 30g of stearyl methacrylate, 15g of styrene, 1.25g N-hydroxymethylacrylamide, 0.68g of 2-hydroxyethyl methacrylate, 1.25g of poly (oxyethylene) 7 methacrylate, 0.34g of dodecanethiol, and 19.36g of dipropylene glycol were charged to a 500mL four-necked flask equipped with a mechanical stirrer, thermocouple thermometer, and quench condenser (-5 to-10 ℃ C.). The batch was flushed into the flask with 10g of hot deionized water and purged with nitrogen for 30 minutes or until the temperature was below 30 ℃. Then 15g of vinylidene chloride was added to the reaction flask and mixed for 5 minutes. 0.34g of "VAZO" 56WSP (E.I. DuPont de Nemours and Company, Wilmington, Delaware) dissolved in 10g of deionized water was then added to initiate polymerization. The mixture was heated to 50 ℃ over a half hour and held for 8 hours. After polymerization, 0.46g of DUPONOL WAQE (available from Witco Corporation, Greenwich, Conn.) in water was mixed with the product at room temperature. The resulting polymer extender latex (dispersion in water) weighed 206g and had a solids content of 26.39%.

Example 27

96g of hot deionized water (50-60 ℃ C.), 3.2g of ETHOQUAD 18/25 (available from Akzo Nobel, Chicago, Ill.), 4.6g of tridecyl alcohol 5-ethylene oxide adduct (ETHOX TDA-5, available from Ethox Chemicals, Greenville, SC) located in Greenville, N.C.), 30g of butyl methacrylate, 1.25g N-hydroxymethyl acrylamide, 0.68g of 2-hydroxyethyl methacrylate, 1.25g of poly (oxyethylene) 7 methacrylate, 0.34g of dodecanethiol, and 19.36g of dipropylene glycol were charged to 500mL four-necked flask equipped with a mechanical stirrer, thermocouple thermometer, and quench condenser (-5 to-10 ℃ C.). The batch was flushed into the flask with 10g of hot deionized water and purged with nitrogen for 30 minutes or until the temperature was below 30 ℃. Then 30g of vinylidene chloride was added to the reaction flask and mixed for 5 minutes. 0.34g of "VAZO" 56WSP (E.I. du Pont de Nemours and Company, Wilmington, Delaware) dissolved in 10g of deionized water was then added to initiate polymerization. The mixture was heated to 50 ℃ over a half hour and held for 8 hours. After polymerization, 0.46g of DUPONOL WAQE (available from Witco Corporation, Greenwich, Conn.) in water was mixed with the product at room temperature. The resulting polymer extender latex (dispersion in water) weighed 205.15g and had a solids content of 28.04%.

Example 28

96g of hot deionized water (50-60 ℃ C.), 3.2g of ETHOQUAD 18/25 (available from Akzo Nobel, Chicago, Ill.), 4.6g of tridecyl alcohol 5-ethylene oxide adduct (ETHOX TDA-5, available from Ethox Chemicals, Greenville, SC) of Greenville, N.C.), 30g of ethylhexyl methacrylate, 1.25g N-hydroxymethyl acrylamide, 0.68g of 2-hydroxyethyl methacrylate, 1.25g of poly (oxyethylene) 7 methacrylate, 0.34g of dodecanethiol, and 19.36g of dipropylene glycol were charged to 500mL four-necked flask equipped with a mechanical stirrer, thermocouple thermometer, and quench condenser (-5 to-10 ℃ C.). The batch was flushed into the flask with 10g of hot deionized water and purged with nitrogen for 30 minutes or until the temperature was below 30 ℃. Then 30g of vinylidene chloride was added to the reaction flask and mixed for 5 minutes. 0.34g of "VAZO" 56WSP (E.I. du Pont de Nemours and Company, Wilmington, Delaware) dissolved in 10g of deionized water was then added to initiate polymerization. The mixture was heated to 50 ℃ over a half hour and held for 8 hours. After polymerization, 0.46g of DUPONOL WAQE (available from Witco Corporation, Greenwich, Conn.) in water was mixed with the product at room temperature. The resulting polymer extender latex (dispersion in water) weighed 185.43g and had a solids content of 29.26%.

Example 29

96g of hot deionized water (50-60 ℃ C.), 3.2g of ETHOQUAD 18/25 (available from Akzo Nobel, Chicago, Ill.), 4.6g of tridecyl alcohol 5-ethylene oxide adduct (ETHOX TDA-5, available from Ethox Chemicals, Greenville, SC) of Greenville, N.C.), 30g of lauryl methacrylate, 1.25g N-hydroxymethyl acrylamide, 0.68g of 2-hydroxyethyl methacrylate, 1.25g of poly (oxyethylene) 7 methacrylate, 0.34g of dodecanethiol, and 19.36g of dipropylene glycol were mixed and charged to a 500mL four-necked flask equipped with a mechanical stirrer, thermocouple thermometer, and quench condenser (-5 to-10 ℃ C.). The batch was flushed into the flask with 10g of hot deionized water and purged with nitrogen for 30 minutes or until the temperature was below 30 ℃. Then 30g of vinylidene chloride was added to the reaction flask and mixed for 5 minutes. 0.34g of "VAZO" 56WSP (E.I. du Pont de Nemours and Company, Wilmington, Delaware) dissolved in 10g of deionized water was then added to initiate polymerization. The mixture was heated to 50 ℃ over a half hour and held for 8 hours. After polymerization, 0.46g of DUPONOL WAQE (available from Witco Corporation, Greenwich, Conn.) in water was mixed with the product at room temperature. The resulting polymer extender latex (dispersion in water) weighed 185.14g and had a solids content of 27.92%.

Example 30

A mixture of 96g of hot deionized water (50-60 deg.C), 3.2g of ETHOQUAD 18/25 (available from Akzo Nobel, Chicago, Ill.), 4.6g of tridecyl alcohol 5-ethylene oxide adduct (ETHOX TDA-5 available from Ethox Chemicals, Greenville, SC) located in Greenville, N.C.), 30g of tridecyl methacrylate, 1.25g N-hydroxymethyl acrylamide, 0.68g of 2-hydroxyethyl methacrylate, 1.25g of poly (oxyethylene) 7 methacrylate, 0.34g of dodecyl mercaptan, and 19.36g of dipropylene glycol was charged to a 500mL four-necked flask equipped with a mechanical stirrer, thermocouple thermometer, and condenser (-5 to-10 deg.C.). The batch was flushed into the flask with 10g of hot deionized water and purged with nitrogen for 30 minutes or until the temperature was below 30 ℃. Then 30g of vinylidene chloride was added to the reaction flask and mixed for 5 minutes. 0.34g of "VAZO" 56WSP (E.I. du Pont de Nemours and Company, Wilmington, Delaware) dissolved in 10g of deionized water was then added to initiate polymerization. The mixture was heated to 50 ℃ over a half hour and held for 8 hours. After polymerization, 0.46g of DUPONOL WAQE (available from Witco Corporation, Greenwich, Conn.) in water was mixed with the product at room temperature. The resulting polymer extender latex (dispersion in water) weighed 187.53g and had a solids content of 27.2%.

Example 31

96g of hot deionized water (50-60 ℃ C.), 3.2g of ETHOQUAD 18/25 (available from Akzo Nobel, Chicago, Ill.), 4.6g of tridecyl alcohol 5-ethylene oxide adduct (ETHOX TDA-5, available from Ethox Chemicals, Greenville, SC) of Greenville, N.C.), 30g of hexyl methacrylate, 1.25g N-hydroxymethyl acrylamide, 0.68g of 2-hydroxyethyl methacrylate, 1.25g of poly (oxyethylene) 7 methacrylate, 0.34g of dodecyl mercaptan, and 19.36g of dipropylene glycol were mixed and charged to a 500mL four-necked flask equipped with a mechanical stirrer, thermocouple thermometer, and quench condenser (-5 to-10 ℃ C.). The batch was flushed into the flask with 10g of hot deionized water and purged with nitrogen for 30 minutes or until the temperature was below 30 ℃. Then 30g of vinylidene chloride was added to the reaction flask and mixed for 5 minutes. 0.34g of "VAZO" 56WSP (E.I. du Pont de Nemours and Company, Wilmington, Delaware) dissolved in 10g of deionized water was then added to initiate polymerization. The mixture was heated to 50 ℃ over a half hour and held for 8 hours. After polymerization, 0.46g of DUPONOL WAQE (available from Witco Corporation, Greenwich, Conn.) in water was mixed with the product at room temperature. The resulting polymer extender latex (dispersion in water) weighed 201.34g and had a solids content of 29.5%.

Example 32

96g of hot deionized water (50-60 ℃ C.), 3.2g of ETHOQUAD 18/25 (available from Akzo Nobel, Chicago, Ill.), 4.6g of tridecyl alcohol 5-ethylene oxide adduct (ETHOX TDA-5, available from Ethox Chemicals, Greenville, SC) of Greenville, N.C.), 30g of cyclohexyl methacrylate, 1.25g N-hydroxymethyl acrylamide, 0.68g of 2-hydroxyethyl methacrylate, 1.25g of poly (oxyethylene) 7 methacrylate, 0.34g of dodecyl mercaptan, and 19.36g of dipropylene glycol were mixed and charged to a 500mL four-necked flask equipped with a mechanical stirrer, thermocouple thermometer, and quench condenser (-5 to-10 ℃ C.). The batch was flushed into the flask with 10g of hot deionized water and purged with nitrogen for 30 minutes or until the temperature was below 30 ℃. Then 30g of vinylidene chloride was added to the reaction flask and mixed for 5 minutes. 0.34g of "VAZO" 56WSP (E.I. du Pont de Nemours and Company, Wilmington, Delaware) dissolved in 10g of deionized water was then added to initiate polymerization. The mixture was heated to 50 ℃ over a half hour and held for 8 hours. After polymerization, 0.46g of DUPONOL WAQE (available from Witco Corporation, Greenwich, Conn.) in water was mixed with the product at room temperature. The resulting polymer extender latex (dispersion in water) weighed 203.37g and had a solids content of 28%.

The latices of examples 22-32 obtained above were each blended with a commercial fluoropolymer ZONYL8932 from Navelandu DuPont, Wilmington, Delaware, located in Wilmington, Del. The ratio of extender to fluoropolymer contained in the blend was 1: 1. The blend with ZONYL fluoropolymer was applied to a 100% nylon fabric using test method 1 above. For the data in Table 13, the treatment bath contained 20-50g/L of the blended product and the bath contained 10-15g/L of the fluorinated polymer. The treatment bath also contained 2g/L of wetting agent ALKANOL 6112 (available from Navell DuPont, Wilmington, Delaware, E.I. du Pont de Nemours and Company, Wilmington, Delaware). After application the fabric was cured at 160 ℃ for about 2 minutes. After treatment and curing, the fabric is allowed to "rest". The treated fabrics were tested for oil repellency, water repellency, and spray rating using test methods 2, 3, 4, and 5 above. The results are listed in table 12.

The results in table 12 show that the extender of the present invention used in combination with a fluorinated polymer gives better or comparable performance with 60% fluorine when compared to the same fluorinated polymer in the absence of extender.

Example 33

An aqueous emulsion was prepared by mixing the following components: 96g of hot deionized water (50-60 ℃ C.), 3.2g of ETHOQUAD 18/25 (available from Akzo Nobel, Chicago, Ill.), 4.6g of tridecyl alcohol 5-ethylene oxide adduct (ETHOX TDA-5, available from Esaxox Chemicals, Greenville, SC, located in Greenville, N.), 30g of stearyl methacrylate, 1.25g of poly (oxyethylene) 7 methacrylate, 1.25g of 1.25g N-hydroxymethylacrylamide, 0.68g of 2-hydroxyethyl methacrylate, 0.34g of dodecanethiol, and 19.36g of dipropylene glycol, were then charged to a 1L autoclave. The autoclave was sealed and evacuated/purged with nitrogen three times. Then 30g of vinyl chloride were added. 0.34g of "VAZO" 56WSP (E.I. du Pont de Nemours and company, Wilmington, Delaware) dissolved in 10g of deionized water was then added to initiate polymerization. The mixture was heated to 50 ℃ over 30 minutes and held for 8 hours with the stirrer rotating at 150 RPM. After polymerization, 0.46g of DUPONOL WAQE (available from Witco Corporation, Greenwich, Conn.) in water was mixed with the product at room temperature. The resulting latex extender was filtered through a milk filter. The extender was mixed with ZONYL8932 in a ratio of 2: 1 extender to fluorinated polymer. The blends were applied to 100% cotton and nylon fabrics, tested, washed, and retested as in example 11. The test results show the durability of the performance after laundering the fabric.

Claims (14)

1. An extender polymer composition, said composition consisting of a copolymer comprising copolymerized monomers in the following weight percentages:

(a) 5% to 90% of a monomer of formula I:

R₁-OC(O)-C(R)＝CH₂ (I)

(b) 5-85% of vinylidene chloride, vinyl acetate or their mixture,

(c) 0.5% to 3% of a monomer of formula II:

HO-CH₂-NH-C(O)-C(R)＝CH₂ (II)

(d) 0.5% to 3% of a monomer of formula III:

HO-CH₂CH₂-OC(O)-C(R)＝CH₂ (III)

and

(e) 1% to 5% of a monomer of formula IV:

H-(OCH₂CH₂)_m-O-C(O)-C(R)＝CH₂ (IV)

(f) 0-25% of methyl methacrylate, vinylbenzyl chloride, styrene or a mixture thereof,

wherein the content of the first and second substances,

each R is independently H or CH₃；

R₁Is a straight or branched or cyclic alkyl chain containing from 4 to 18 carbon atoms, and

m is the number of 2-10,

the composition increases the fluorine efficiency of the surface treatment agent.

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

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

4. The composition of claim 1 further in combination with an agent that provides a surface effect when applied to a substrate, said surface effect being permanent press, easy press, shrinkage control, wrinkle resistance, permanent press, moisture control, softness, strength, skid resistance, antistatic, anti-scratch, anti-pilling, anti-staining, de-staining, anti-soiling, stain removal, water repellency, oil repellency, odor repellency, antimicrobial, or sunscreen.

5. The composition of claim 4, wherein the agent is a fluorinated polymer.

6. The composition of claim 5 wherein the fluorine content is from 1.5% to 6.6% by weight.

7. The composition of claim 5 wherein the ratio of extender composition to fluorinated polymer is from 0.5: 10 to 6: 1.

8. The composition of claim 5 wherein the fluorinated polymer is a fluorine-containing polyurethane, poly (meth) acrylate, polyethylene or polyvinylidene or mixtures thereof.

9. The composition of claim 1 or 5, further comprising a blocked isocyanate, at least one other extender composition or an additive selected from the group consisting of surfactants, emulsifiers, pH adjusters, cross linkers, wetting agents and wax extenders.

10. A method of treating a substrate comprising contacting the substrate with the composition of claim 7 having increased fluorine efficiency.

11. The method of claim 10, wherein the composition further comprises a blocked isocyanate, at least one other extender, or an additive selected from the group consisting of surfactants, emulsifiers, pH adjusters, cross linkers, wetting agents, and wax extenders.

12. The method of claim 10, wherein the substrate is a textile, fiber, fabric, paper, non-woven fabric, leather, or a combination thereof.

13. A substrate treated by the method of claim 10.

14. The substrate of claim 13 having a fluorine content of from 0.05% to 0.5% by weight.