HK1110364B - Hydrocarbon extenders for surface effect compositions - Google Patents

Description

Hydrocarbon extender for surface effect compositions

Technical Field

Hydrocarbon polymers are used as extenders to improve the performance of the treating agents which provide surface effects to the treated substrate.

Background

A wide variety of compositions are known to be used as treating agents to provide surface effects to substrates. Surface effects include resistance to wetting, stain release and other effects that are particularly useful for fibrous substrates such as fabrics, textiles, fabrics, carpets, paper, leather and other such substrates. Many such treating agents are fluorinated polymers or copolymers.

Fluorinated polymer compositions useful as fiber substrate treating agents typically contain a pendant perfluoroalkyl group of three or more carbon atoms that provides oil and water repellency when applied to the surface of the fiber substrate. The perfluoroalkyl group is typically attached to a non-fluorine containing polymerizable group through various linking groups. The resulting monomer is then typically copolymerized with other monomers that impart additional advantageous properties to the matrix. Various specialized monomers can be incorporated to produce improved crosslinking, latex stability and substantivity. Since each component may produce undesirable characteristics in addition to desirable ones, the specific combination is directed to the desired use. These polymers are generally marketed as aqueous emulsions which are easy to apply to the fibrous substrate.

Various efforts have been made to improve the oil and water repellency imparted to the substrate and its durability while reducing the amount of fluorinated polymer required, i.e., to improve the performance of the treatment. One method is to incorporate blocked isocyanate or melamine resins. However, the amount that can be used is only limited, as these components tend to adversely affect the hand (feel) of the fibrous matrix. Another approach is to use various extender polymers. The polymer is typically a hydrocarbon polymer in the form of an aqueous emulsion which is mixed with the fluorinated polymer emulsion prior to use in the matrix.

US patent 3,657,173 discloses emulsions suitable for imparting oil and/or water repellency to a substrate, the emulsions containing a fluorinated polymer and a larger amount of a halogenated solvent, a smaller amount of an alkanol and water. Optionally, the emulsion may also contain at least one non-fluorine-containing polymer (i.e., extender polymer) that is free of non-vinyl fluorine atoms or non-fluorinated conjugated dienes. Examples of extender polymers are 2-hydroxyethyl or 2-hydroxypropyl acrylate or methacrylate; and n-lauryl methacrylate or 2-ethylhexyl methacrylate. It is generally considered advantageous to include in all of these polymers a small amount of units derived from N-methylolacrylamide or N-methylolmethacrylamide and glycidyl acrylate or methacrylate in order to improve the durability of the polymer solids to washing or dry cleaning.

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

Summary of The Invention

The present invention includes a polymer composition for use with a treating agent that provides a surface effect to a substrate, the polymer composition comprising the following monomers copolymerized in the following percentages by weight:

(a) from about 60% to about 94% of a monomer or mixture of monomers of formula I:

[CH₃-(CH₂)_p][CH₃(CH₂)_n]CHCH₂-OC(O)-C(R)＝CH₂(I) and are and

(b) from about 5% to about 20% of a monomer or mixture of monomers of formula II:

H-(OCH₂CH₂)_m-O-C(O)-C(R)＝CH₂(II)

(c) from about 0% to about 3% of a monomer or mixture of monomers of formula III:

HO-CH₂-NH-C(O)-C(R)＝CH₂(III)

(d) from about 0% to about 20% of a monomer or mixture of monomers of formula IV:

R¹-OC(O)-C(R)＝CH₂(IV)

(e) from about 0% to about 2% of ethylene glycol dimethacrylate, and

(f) from about 0% to about 10% of a monomer or mixture of monomers of formula V:

R_f-CH₂CH₂-OC(O)-C(R)＝CH₂(V)

wherein

Each R is independently H or CH₃；

R¹Is an alkyl chain of from 1 to about 18 carbon atoms;

n is 1 to about 10;

p is 1 to about 20;

m is 2 to about 10, and

R_fis a linear or branched perfluoroalkyl group of 2 to about 20 carbon atoms, or mixtures thereof.

The present invention also includes a method of treating a substrate comprising contacting the substrate with a composition comprising a treating agent that provides a surface effect when applied to a substrate and the above composition.

The present invention also includes substrates treated with a composition comprising a treating agent that provides a surface effect when applied to a substrate and the above composition.

Detailed Description

Trademarks are indicated herein by capitalization.

The present invention includes a polymer composition for improving the durability properties of a treating agent that provides a surface effect to a substrate. In particular, the extender composition can be used to improve the performance of the fluorinated polymer in imparting durable resistance to the fibrous matrix. The fibrous matrix comprises fibers, fabrics, paper, non-wovens, leather, carpet, fabrics, fabric blends, or combinations thereof. By "textile" is meant natural or synthetic fabrics or mixtures thereof, including fibers such as cotton, rayon, silk, wool, polyester, polypropylene, polyolefins, nylon, and aramids such as "NOMEX" and "KEVLAR". By "fabric blend" is meant a fabric made from two or more types of fibers. Typically, these mixtures are a combination of at least one natural fiber and at least one synthetic fiber, but may also be a mixture of two or more natural fibers or two or more synthetic fibers.

By adding the extender polymer composition of the present invention to the surface treatment agent prior to application to the fibrous substrate, the fibrous substrate can be given the desirable characteristics of excellent long-lasting surface activity, as well as low yellowing and good durability. These combined mixtures may be applied to the fiber matrix as a dispersion in water or other solvent before, after, or during the application of other treatment chemicals.

When so applied, the extender polymer compositions of the present invention in combination with the fluorinated polymer treatment agent are found to improve especially the durability of surface properties, particularly water and oil repellency, by as much as 50% in the fiber matrix after washing. The durability of the resistance is improved compared to other known supplement compositions. Moreover, the use of the replenisher composition of the present invention increases the efficacy of fluorine by allowing the use of lower levels of fluorinated polymer.

The extender polymer compositions of the present invention can be prepared by conventional emulsion polymerization techniques, such as those used to prepare fluorinated polymers. Typically, such copolymers are prepared by copolymerizing two or more monomers in an aqueous medium with the resulting dispersion or emulsion stabilized with a surfactant. Optionally, the copolymerization is carried out by solution polymerization, wherein an organic water-soluble solvent such as an alcohol or glycol is added to the aqueous medium to improve the solubility of the monomers. Surfactants used to stabilize the emulsion during formation and during polymerization are conventional anionic, cationic and/or nonionic emulsifiers. The polymerization is generally initiated by an azo initiator, such as 2, 2' -azobis (2-amidinopropane) dihydrochloride. These initiators are sold under the trade name "VAZO" by E.I. du Pont de Nemours and company, Wilmington, Delaware.

The aqueous dispersion mixture produced by mixing the extender composition dispersion with the fluorinated polymer dispersion is applied to the surface of the fibrous substrate by known methods to produce oil, soil and water repellency and other surface effects. A significant feature of the use of the fluorinated polymer-extender compositions of the present invention is the high durability of the protective layer on the fabric.

The composition of the present invention comprises a copolymer comprising the following monomers copolymerized in the following percentages by weight:

(a) from about 60% to about 94% of a monomer or mixture of monomers of formula I:

[CH₃-(CH₂)_p][CH₃(CH₂)_n]CHCH₂-OC(O)-C(R)＝CH₂(I)

(b) from about 5% to about 20% of a monomer or mixture of monomers of formula II:

H-(OCH₂CH₂)_m-O-C(O)-C(R)＝CH₂(II)

(c) from about 0% to about 3% of a monomer or mixture of monomers of formula III:

HO-CH₂-NH-C(O)-C(R)＝CH₂(III)

(d) from about 0% to about 20% of a monomer or mixture of monomers of formula IV:

R¹-OC(O)-C(R)＝CH₂(IV)

(e) from about 0% to about 2% of ethylene glycol dimethacrylate, and

(f) from about 0% to about 10% of a monomer or mixture of monomers of formula V

R_f-CH₂CH₂-OC(O)-C(R)＝CH₂(V)

Wherein each R is independently H or CH₃；

R¹Is an alkyl chain of from 1 to about 18 carbon atoms;

n is 1 to about 10;

p is 1 to about 20 and m is 2 to about 10, and

R_fis a linear or branched perfluoroalkyl group of 2 to about 20 carbon atoms, or mixtures thereof.

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

The essential formula I monomers (a) in the present invention are one or a mixture of branched alkyl (meth) acrylates having from about 6 to about 34 carbon atoms in the alkyl chain. It is added to the polymerization in a proportion of about 60% to about 94% by weight. The proportion of monomer (a) in the copolymer is preferably between about 70% and about 90%. The branched alkyl (meth) acrylate is preferably 2-ethylhexyl (meth) acrylate.

The essential monomer (b) of formula II in the present invention is one or a mixture of ethoxylated (meth) acrylates in which the number of ethoxy groups is between 2 and about 10. From about 5 to about 10 ethoxy groups are preferred. It is added to the polymerization in a proportion of about 5% to about 20% by weight. The proportion of monomer (b) in the extender copolymer is preferably between about 8% and about 15% by weight.

The optional monomer (c) of formula III in the present invention is N-methylolacrylamide, N-methylolmethacrylamide or a mixture of the two. N-methylolacrylamide is preferred. It is added to the polymerization in a proportion of 0% to about 3%. About 1% by weight is preferred. Such monomers are often used to help improve the durability of the barrier properties imparted to the treated substrate.

Optional monomer (d) of formula IV is a linear alkyl chain (meth) acrylate having from 1 to about 18 carbon atoms therein. Methyl methacrylate is preferred. It is added to the polymerization in a proportion of from 0 to about 20% by weight. About 12% by weight is preferred.

Optional monomer (e) is ethylene glycol dimethacrylate, [ CH ]₂CH(CH₃)C(O)OCH₂CH₂]₂. It is added to the polymerization in a proportion of from 0 to about 2% by weight. About 0.5% by weight is preferred. The inclusion of monomers (d) and (e) increases the flexibility to accommodate a variety of specific substrates while maintaining effective performance.

Optional monomer (f) of formula V is a perfluoro (meth) acrylate having a linear or branched perfluoroalkyl group of about 2 to about 20 carbon atoms or a mixture thereof. Preferably, perfluoroalkyl CF₃CF₂(CF₂)_x-having from about 6 to about 18 carbon atoms, or mixtures thereof. Perfluoro (meth) acrylates of the formula: CF (compact flash)₃CF₂(CF₂)_xC₂H₄OC(O)-C(CH₃)＝CH₂Wherein x is 6, 8, 10, 12, 14, 16 and 18, their respective relative amounts in the mixture are 33%, 24%, 12%, 6%, 2%, 1% and 0.5%, respectively, and the monomer has an average molecular weight of about 583. It is added to the polymerization in a proportion of about 0 to about 10%, preferably 0%. The presence of such monomers in the mixture may improve compatibility with the fluorochemical treatment.

The above-described copolymer dispersion is then mixed with any of various known fiber matrix treating agents. Examples of fluorinated polymer treatments are ZONYL available from e.i. du Pont DE Nemours and company, Wilmington, DE; OLEPHOBOOL from Ciba specialty Chemicals, Langweid, Germany; from Asahi GlassCoASAHI GARD by mpany, ltd., Tokyo, Japan; UNIDYNE available from Daikin America, Inc., Orangeburg, NY; SCOTCHGARD available from 3M Company, st. paul, MN; and NANO TEX available from Nanotex, Emeryville, CA. Of particular interest are fluorinated polymers that are useful as treating agents to impart repellency properties to the treated substrate. The copolymer is mixed with the fluorinated polymer in a ratio of from about 1: 10 to about 6: 1, preferably from about 1: 3 to about 3: 1, and more preferably from about 2: 1 to about 1: 2. The fluorine content of the mixture 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 treatment is any fluorinated polymer treatment used to impart water and oil repellency on a fibrous substrate. These fluorinated polymeric treatments include compositions containing one or more fluoroaliphatic groups (referred to herein as R)_fRadical) fluorochemical treatment polymer that is fluorinated, stable, inert, non-polar, preferably saturated, monovalent, and oleophobic and hydrophobic. The R is^fThe group preferably contains at least 3 carbon atoms; more preferably from 3 to 20 carbon atoms and most preferably from about 6 to about 14 carbon atoms. The R is^fThe radicals may contain linear or branched or cyclic fluorinated alkylene groups or combinations thereof. R^fThe terminal part of the radical being of formula C_nF_2n+1 perfluoroaliphatic group, wherein n is from about 3 to about 20.

Such fluorinated polymers include those containing R_fPoly (meth) acrylates of (a) to (b). Particularly preferred are copolymers of fluorine-containing (meth) acrylate monomers with a copolymerizable monovinyl compound or conjugated diene. The copolymerizable monovinyl compounds include alkyl (meth) acrylates, vinyl esters of fatty acids, styrene and alkylstyrenes, vinyl halides, 1-dihaloethylene, alkyl esters, vinyl alkyl ketones, and acrylamides. The conjugated diene is preferably 1, 3-butadiene. Representative compounds within 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-methylstyreneVinyl fluoride, vinyl chloride, vinyl bromide, 1-difluoroethylene, 1-dichloroethylene, 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 acrylate.

The blended composition comprising the fluorinated polymer and the extender polymer of the present invention applied to the fibrous matrix optionally further comprises a blocked isocyanate (i.e., a blended isocyanate) added after copolymerization to improve durability. An example of a suitable blocked isocyanate is hydrophopol XAN available from Ciba specialty chemicals, High Point, NJ. Other commercially available blocked isocyanate liquids may also be used herein. The desirability of adding the blocked isocyanate depends on the particular application for the copolymer. For most of the presently envisioned applications, satisfactory crosslinking between chains or bonding to fibers is achieved, which need not be present. When added as a mixed isocyanate, amounts up to 20% by weight are added.

The blended composition comprising the fluorinated polymer and the extender polymer of the present invention may optionally further comprise additional components such as treating agents or polishes (finishes) to achieve additional surface effects. Such additional components comprise compounds or compositions capable of imparting to a surface, for example, a non-ironing, easy-to-iron, shrink-resistant, wrinkle-free, durable pressure-resistant, moisture-resistant, soft, strong, non-slip, anti-static, anti-snag, anti-pilling, anti-staining, anti-smudging, stain-removing, water-repellent, oil-repellent, anti-odor, anti-microbial, sun-protective, and the like effect. One or more such treating agents or polishes may be mixed with the mixed composition and applied to the fibrous substrate. Other additives used with such treatments or polishes, such as surfactants, pH adjusters, cross-linkers, wetting agents, wax extenders, and other additions known to those skilled in the art, may also be present. Moreover, other supplement compositions may be included to obtain beneficial combinations.

The present invention also includes a method of treating a substrate comprising contacting the surface of the substrate with an effective amount of a composition comprising the replenisher composition of the present invention described above and a treating agent that produces a surface effect on the substrate when applied to the substrate. Preferably, the treating agent is a fluorinated polymer. The mixed composition, alone or in combination with other fabric treatment agents, polishes or additives as described above, is applied to the fibrous substrate from an aqueous dispersion. For example, when treating synthetic fibers, humectants such as ALKANOL 6112 from E.I. du Pont DE Nemours and Company, Wilmington, DE, may be used. As another example, when treating cotton or blended cotton fibers, a wrinkle resistant resin such as PERMAFRESH EFC available from Omnova Solutions, Chester, SC may be used. As an additional example, when treating nonwoven fibers, a wax extender such as FREEPEL 1225WR available from Omnova Solutions Chester, SC may be used. Antistatic agents, such as ZELEC KC from Stepan, Northfield, IL, or humectants, such as hexanol, are also suitable. The dispersion may be 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 matrix is dried and then cured by heating, e.g., to about 100 c to about 190 c, for at least 30 seconds, typically about 60 to about 240 seconds. Such curing improves oil, water and soil repellency and durability of the barrier. While these curing conditions are typical, certain commercial equipment can operate outside of these ranges due to its particular design features. The treated fibrous matrix has a fluorine content of about 0.05% to about 0.5% by weight.

The present invention also includes a substrate treated with the above composition comprising i) a surface effect generating treatment agent and ii) the above extender copolymer of the present invention. The composition may also contain the optional agents described above that produce additional surface effects, the optional additives described above that are typically used to treat the substrate, the optional blocked isocyanates described above, and optionally additional unique extender compositions. As previously mentioned, such substrates include paper, non-woven fabrics, leather, fabrics, textiles, fabrics, fiber blends, or combinations thereof. "textiles" include natural or made from cotton, rayon, silk, wool, polyester, polypropylene, polyolefin, nylon, and aramids such as "NOMEX" and "KEVLAR". By "fabric blend" is meant a fabric made from two or more types of fibers. Typically, these mixtures are a combination of at least one natural fiber and at least one synthetic fiber, but may also be a mixture of two or more natural fibers and two synthetic fibers. Preferably, the matrix has been treated with a composition comprising the extender of the present invention and a fluorinated polymer such as a polyurethane or poly (meth) acrylate.

In particular, the copolymer compositions, methods and treated substrates of the present invention are useful for improving surface properties, particularly oil-, water-and soil-repellent properties of the aforementioned substrates, while reducing the amount of fluorinated polymer used. The repellency is more durable than the application of fluorinated polymer treatments with other extenders and is effective for a variety of fabric substrates. Along with various other surface effects, the protective properties are effective. The treated fabric substrates of the present invention can be used in a variety of applications such as fabrics, garments, uniforms, protective garments, furniture and the like. The copolymers of the present invention are advantageous because they have high durability, low yellowing protection polishing when applied to various fabric substrates, low levels of fluorinated polymer when combined with fluorinated polymer treatment agents. Compared with the existing acrylate copolymer, the composition of the invention can be prepared at lower material cost.

Test method

The following tests were used to evaluate the examples herein

Test methods 1-Fabric treatment

The fabric is treated with the copolymer blend using a conventional dip bath (impregnation) process. Baths containing 0.2 to 5% by weight of a fluorinated polymeric treatment agent, as specified in the tables in the examples section, in combination with the extender copolymer of the invention (hereinafter copolymer mixture) were used to treat fabrics, such as cotton, non-woven formed fabrics and nylon fabrics, in combination with the indicated blocked isocyanate (0 to 2%). A mixture containing 30 to 45g/L of copolymer was used. Fluorochemical treatments for mixing with the non-fluorinated polymer extenders of the present invention are commercially available ZONYL products from E.I. DuPont DE Nemours and Company, Wilmington, DE. After use, the woven fabric is cured at about 160 ℃ for 1-3 minutes and the nonwoven fabric is cured at 100 ℃ and 170 ℃ for 2-4 minutes. The fabric was allowed to "rest" after treatment and curing.

Test method 2 Water repellency

The water repellency of the treated substrates was measured according to the DuPont Technical Laboratory Method outlined in TEFLON (R) Global Specifications and Quality Control Tests information packet or AATCC standard Test Method No. 193-2004. This test uses an aqueous liquid to determine the resistance of the treated substrate to wetting. Drops of water-alcohol mixtures of different surface tensions were placed on the fabric and the degree of surface wetting was determined visually. The test provides a rough index of water staining resistance. The higher the waterproof rating, the better the resistance of the finished substrate to staining by water-based bodies. The compositions of the standard test liquids are shown in the table below.

TABLE 1

Standard test liquid

Test method 3-Water resistance-spray rating

Further tests for water repellency can be performed using the spray test method. The treated fabric samples were tested by AATCC standard Test Method No.22-1996, as performed below. The aqueous dispersion of the polymer was allowed to stand at 23 ℃ plus 20% relative humidity to 65 ℃ plus 10% relative humidity for 2 hours. The fabric is securely fastened to the plastic/metal embroidery hoop so that the fabric is wrinkle-free. The embroidery hoop is placed on a shelf so that the fabric is facing upward. 250ml of water at 80 + -2 deg.F (27 + -1 deg.C) was then poured into the funnel to spray the water onto the fabric surface. Once the water passes through the funnel, the edge of the solid object is tapped, the fabric is turned downwards, rotated 180 degrees and tapped again. The spotted or wet surfaces were compared to the AATCC standard in AATCC Technical Manual. The wetter the surface, the smaller the number and the lower the protection. 100 indicates no wetting, 90 indicates light wetting (three small spots), 80 indicates wetting at the spray point by several (10) spots, 70 indicates partial wetting of the upper fabric surface, 50 indicates wetting of the entire upper fabric surface, and 0 indicates complete wetting of the lower and upper fabric surfaces.

Test method 4-oil repellency

The treated fabric samples were tested for oil repellency using a modified AATCC standard Test Method No.118, as performed below. The fabric treated with the aqueous dispersion of the polymer described above was left for 2 hours at 23 ℃ + 20% relative humidity-65 ℃ + 10% relative humidity. A series of organic liquids identified in table I were then added dropwise to the fabric sample. Starting with the lowest numbered test liquid (protective rating No.1), a drop (approximately 5mm in diameter or 0.05mL in volume) is placed at three points spaced at least 5mm apart. The drop was observed for 30 seconds. If, at the end, two of the three drops are still spherical and are not wicked around the drop, three drops of one of the highest encoded liquids are placed at adjacent sites and again observed for 30 seconds. This operation is continued until one of the test liquids eventually causes two of the three drops to fail to remain spherical to hemispherical or wetting or wicking occurs.

The oil repellency rating of the fabric was the highest encoded test liquid for which two of the three drops remained spherical to hemispherical and were not wicked for 30 seconds. In general, treated fabrics with a rating of 6 or higher are considered good to excellent; fabrics having a rating of 1 or higher may be used in certain applications.

TABLE 2

Oil repellency test liquid

Oil repellency rating number	Test solutions
		1	NUJOL Purified Mineral Oil
2	63/35 NUJOL/n-hexadecane (vol.), 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, a 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-impact protection method

The water repellency can be further tested by impact testing. The treated fabric samples were tested for water repellency by the following AATCC standard test method No.42-2000, as performed below. The fabric samples treated with the aqueous dispersion of the foregoing copolymer mixture were placed at 23 ℃ + 20% relative humidity-65 ℃ + 10% relative humidity for 2 hours. The fabric swatches were securely held on a flat surface so that the fabric was wrinkle free. A piece of blotter paper of the same size as the fabric was placed behind the fabric. 500mL of water at 80 + -2 deg.F (27 + -1 deg.C) was then poured onto the funnel to spray the water onto the fabric surface. Once the water passed through the funnel, the blotter paper was weighed. Weight gain of less than half a gram is considered to be very good.

Test method 6-washing method

The fabric samples were washed according to the U.S. home Laundering Method outlined in the TEFLON Global Specifications and Quality Control Tests data bag. The fabric samples were loaded into a KENMORE automatic washing machine and simultaneously with ballast to provide a total dry load of 4Ib. (1.0 kg). Commercial Detergent (AATCC 1993Standard Reference Detergent WOB) was added and the washer was filled with warm water at high water level (105 ℃ F.) (41 ℃). Using a 12-minute standard wash cycle followed by a rinse and spin cycle, the sample and ballast are washed for a specified number of times (5 HW-5 washes, 10 HW-10 washes, etc.). Between wash cycles, the samples were not dried.

After washing was complete, the fabric sample and ballast were transferred to a KeNMORE automatic dryer and dried at the high/cotton gear for 45 minutes to achieve an outlet temperature of 155 ℃ and 160 ℃ F. (68-71 ℃ C.).

Examples

The following materials were used in the indicated examples.

ARMEEN DM-12D is N, N-dimethyldodecylamine available from Akzo Chemicals Inc., Chicago, IL.

ARMEEN DM-18D is N, N-dimethyloctadecylamine available from Akzo Chem icals Inc., Chicago, IL.

VAZO 56WSP is 2, 2' -azobis (2-amidinopropane) dihydrochloride, an azo polymerization initiator available from e.i. du Pont DE Nemours and Company, Wilmington, DE.

ZONYL7700, ZONYL8315, ZONYL8932, and ZONYL 8300 are each fluorochemical treatments available from E.I. du Pont DE Nemours and Company, Wilmington, DE for use as textile treatments.

Example 1

Initially, 70g of 2-ethylhexyl methacrylate; 10g of poly (oxyethylene) 7 methacrylate; 2g of N-methylol-acrylamide containing 48% water; 0.3g dodecanethiol, hexanediol, 1.6g ARMEEN DM18D, 1.0g acetic acid, 3g of a 2% aqueous salt (NaCl) solution and 80g of hot (50-60 ℃ C.) deionized water were emulsified and then loaded into a four-necked flask equipped with a stirrer, a thermocouple thermometer and a water condenser. The charge was flushed into the flask with 75g of hot deionized water and purged with nitrogen at 65 ℃ for 30 minutes. Then, 0.08g of "VAZO" 56WSP (e.i. du Pont DE Nemoursand Company, Wilmington, DE) dissolved in 2g of deionized water was added to initiate polymerization. The temperature of the mixture naturally rose to 79 ℃ over about 12 minutes and then began to drop. The temperature controller was reset at 70 ℃ and the charge was stirred under nitrogen for 4 hours. The resulting polymer extender emulsion (dispersion in water) weighed 251g and had a solids content of 31.7%. This was mixed with commercially available fluorochemical treatments ZONYL7700, ZONYL8315 and ZONYL8932 from E.I. du Pont DE Nemours and Company, Wilmington, DE, respectively, at a 1: 2 fluorochemical treatment to extender ratio.

A mixture with ZONYL7700 was applied to a 100% polypropylene nonwoven substrate using the method of test method 1. The entire 32g/L of the mixed product was used in the padding bath. The product mixture contained 31% ZONYL7700 and 69% non-fluorinated extender, which resulted in a product mixture containing about 2.3% fluorine. About 5g/L of wetting agent (hexanol) was used in the padding bath. An anti-static ZELEK KC of about 2g/L from Stepan, Northfield, IL was also used in the padding bath. After application, the nonwoven fibrous web was cured at about 100 ℃ for 4 minutes. After treatment and curing, the fabric is allowed to "rest". The polypropylene nonwoven fabric was tested for water repellency using test method 2 described above. In the same manner, ZONYL 7200 in the absence of extender was applied to the substrate for comparison. The results are shown in table 3.

The blend with ZONYL8315 was applied to a 100% polyester nonwoven using the fiber fabric treatment method described in test method 1 above. 20g/L of the product mixture was used in a padding bath. The product mixture contained about 2.7% fluorine. About 15g/L of a wax extender FREEPEL 1225WR from Omnova solutions, Chester, SC was used. After application, the nonwoven fibrous web was cured at about 170 ℃ for about 2 minutes. After treatment and curing, the fabric is allowed to "rest". The polyester nonwoven fabric was tested for water repellency, spray resistance, and impact protection using test methods 2, 3, and 5 described above. In the same manner, ZONYL8315 without extender was applied to the substrate for comparison. The results are shown in Table 4.

The mixture with ZONYL8932 was applied to a 100% nylon fiber fabric using test method 1 described above. The bath contained 45g/L of the product mixture. The product mixture contained about 3.5% fluorine. For one sample, the bath contained 0-1g/L of blocked isocyanate. The blocked isocyanate used was hydrophopal XAN, Ciba Specialty Chemicals, highpoint, NG. The bath also contains 2g/L of wetting agent. The humectant is ALKANOL 6112 available from E.I. du Pont DE Nemours and Company, Wilmington, DE. After application, the fiber fabric was cured at about 160 ℃ for 3 minutes. After treatment and curing, the fabric is allowed to "rest". The nylon was tested for oil repellency, water repellency, and spray repellency using test methods 4, 2, and 3 described above. In the same manner, ZONYL8932 without extender was applied to the matrix for comparison. The results are shown in Table 5.

Example 2

Following the procedure of the example except that 4g of BRIJ 58 from Uniqema, New Castle, DE was also added prior to emulsification. The product was a 33.1% solids emulsion of 252g of polymer extender which was mixed with the fluorochemical treatment in a 1: 2 ratio of fluorochemical treatment to extender and applied to polypropylene and polyester nonwovens as described in example 1. The fiber fabric was tested as described in example 1. The results are shown in tables 3 and 4.

Comparative example A

Initially, (a)80g of 2-ethylhexyl methacrylate; (c)3.3g of N-methylolacrylamide containing 48% water; (e)0.4 ethylene glycol dimethacrylate; 1.6g ARMEEN DM18D, 1.0g acetic acid, 3g 2% saline (NaCl) solution and 135g warm (40-50 ℃) water were emulsified and then loaded into a four-necked flask equipped with a stirrer, thermocouple thermometer and dry ice or water condenser. The charge was flushed into the flask with 20g of cold deionized water and purged with nitrogen at 50 ℃ for 30 minutes. The nitrogen was then switched to a slow purge and 19gm of acetone was added. Then, 0.02g of "VAZO" 56WSP (E.I. du Pont DE Nemours and Company, Wilmington, DE) was added to initiate polymerization. The temperature rises linearly up to 70 ℃ in about 30 minutes. The temperature continued to rise to 73 ℃ over the next 10-12 minutes. The charge was stirred at 70 ℃ for 3.5 hours under nitrogen. The resulting polymer emulsion weighed 244g and had a solids content of 31.4%. This was mixed with a commercially available fluorochemical treatment as listed in table 5 at a ratio of extender to fluorochemical treatment of about 2: 1. The compound was applied to a nylon fiber fabric and tested as in example 1. The results are shown in Table 5.

Comparative example B

Initially, (a)80g of 2-ethylhexyl methacrylate; (c)3.3g of N-methylol-acrylamide containing 48% water; 1.6g ARMEEN DM18D, 1.0g acetic acid, 3g 2% saline (NaCl) aqueous solution and 135g warm (40-50 ℃) water were emulsified and then loaded into a four-necked flask equipped with a stirrer, thermocouple thermometer and dry ice or water condenser. The charge was flushed into the flask with 20g of cold deionized water and purged with nitrogen at 50 ℃ for 30 minutes. The nitrogen was then switched to a slow purge and 19gm of acetone was added. Then, 0.02g of "VAZO" 56WSP (E.I. du Pont DE Nemours and Company, Wilmington, DE) was added to initiate polymerization. The temperature rises linearly up to 70 ℃ in about 30 minutes. The temperature continued to rise to 73 ℃ over the next 10-12 minutes. The charge was stirred at 70 ℃ for 3.5 hours under nitrogen. The resulting polymer emulsion weighed 242g and had a solids content of 31.2%. This was mixed with commercially available fluorochemical treatments listed in tables 4 and 5 at a ratio of extender to fluorochemical treatment of about 2: 1. The compound was applied to a polyester nonwoven substrate and a nylon fiber fabric and tested as in example 1. The results are shown in tables 4 and 5.

TABLE 3

Polypropylene nonwoven fabric

Fluorochemical treatment agent	ZONYL 7700	ZONYL 7700	ZONYL 7700
				Example supplements	Is free of	1	2
				Water-proof property
Initial	11	11	11
Resistance to fogging
				Initial	90	90	90

Table 3 illustrates the efficacy of the supplement of the present invention. The baths used to treat the nonwovens contained less than 40% fluorochemical treatment agent when the extender of examples 1 and 2 was present, as compared to no extender, but maintained the performance of the treatment.

TABLE 4

Polyester nonwoven fabric

Fluorochemical treatment agent	ZONYL 8315	ZONYL 8315	ZONYL 8315	ZONYL 8315
					Example supplements	Is free of	1	2	Comparative example B
Water-proof property
					Initial	8	8	8	6
Resistance to fogging
					Initial	80	80	80	70
Impact resistance
					Initially (gram)	0.32	0.1	0.1	0.3
Standard deviation of	0.15474	0.16258	0.00577	0.00577

Table 4 illustrates the efficacy of the supplement of the present invention. The fluorochemical treatment for treating the nonwoven contained less than 25% fluorochemical treatment when the extender of examples 1 and 2 was present, but maintained the performance of the treatment, as compared to when the extender was not present. Also, the supplements of examples 1 and 2 performed better at the same fluorine level than comparative example B.

TABLE 5

Nylon

Fluorochemical treatment agent	ZONYL 8932	ZONYL 8932	ZONYL 8932	ZONYL 8932	ZONYL 8932
						Example supplements	Is free of	Comparative example A	Comparative example B	1	1
Oil repellency				Note 1
						Initial	6	5.5	6	6	5
5HW	3	2	2	6	4
						10HW	2	1	0	5	2
Water-proof property
						Initial	11	10	10.5	12	10

5HW	8	5	4	11	7
						10HW	4	4	3	9	4
Resistance to fogging
						Initial	100	90	90	100	100
5HW	50	50	50	75	80
						10HW	50	50	50	70	50

^＊Note 1: in example 1, a small amount of blocked isocyanate was added

^＊＊5HW ═ 5 washes; 10HW ═ 10 washes

Table 5 illustrates the efficacy of the supplement of the present invention. The bath used to treat nylon contained 50% less fluorochemical treatment agent than when the extender of the examples was used, but maintained durability of the performance of the treatment, compared to the absence of the extender. The supplement of example 1 performed better at the same fluorine level compared to comparative examples a and B. The performance of example 1 and its durability were excellent. The use of blocked isocyanates improves the protection compared to the use of no blocked isocyanate.

Example 3

Initially, (a)60g of 2-ethylhexyl methacrylate; (b)10g of poly (oxyethylene) 7 methacrylate; (c)2g of N-methylol-acrylamide containing 48% water; (d)10g of methyl methacrylate; 0.3g dodecanethiol, 20g hexanediol, 1.6g ARMEEN DM18D, 1.0g acetic acid, 3g 2% aqueous salt (NaCl) and 80g hot (50-60 ℃ C.) water were emulsified and then loaded into a four-necked flask equipped with a stirrer, thermocouple thermometer and water condenser. The charge was flushed into the flask with 75g of hot deionized water and purged with nitrogen at 65 ℃ for 30 minutes. Then, 0.08g of "VAZO" 56WSP (E.I. du Pont DE Nemours and Company, Wilmington, DE) dissolved in 2g of deionized water was added to initiate polymerization. The temperature spontaneously rose to 80 ℃ and then began to drop. The temperature controller was reset at 70 ℃ and the charge was stirred under nitrogen for 3.5 hours. The resulting polymer supplement emulsion weighed 255g and had a solids content of 31.6%. This was mixed with a commercially available fluorochemical treatment listed in table 6 below at a 2: 1 ratio of extender to fluorochemical treatment and applied to a 100% cotton fiber fabric using the fabric treatment method described in test method 1 above. Generally, 45g/L of the mixed product was used in a padding bath. The mixed product contains 2.2-3.5% fluorine. Blocked isocyanates are used in the padding bath. The isocyanate level is between 5 and 10 g/L. An anti-wrinkle resin, PERMAFRESH EFC from Omnova Solutions, Chester, SC, was included in an amount of 60 g/L. After application, the fabric was cured at about 160 ℃ for 30 minutes. After treatment and curing, the fabric is allowed to "rest". The fabrics were tested for water repellency, oil repellency, and spray repellency using test methods 2-5 described above. After washing according to test method 6 described above, the fabrics were again tested for water repellency, oil repellency and spray repellency in the same manner. The results are shown in table 6. Comparative examples a and B were applied to 100% cotton fabric in the same manner as in example 3, and tested, washed and retested. The results are also shown in table 6. Comparative examples a and B are not able to provide the durability of fluorochemical treatments as the present supplements.

Example 4

Initially, (a)67g of 2-ethylhexyl methacrylate; (b)10g of poly (oxyethylene) 7 methacrylate; (c)2g of N-methylol-acrylamide containing 48% water; (f)3g ZONYLTM (E.I.du Pont DE Nemours and Company, Wilmington, DE); 0.3g dodecanethiol, 20g hexanediol, 1.6g ARMEEN DM18D, 1.0g acetic acid, 3g 2% salt (NaCl) in water and 80g hot (50-60 ℃ C.) deionized water were emulsified and then loaded into a four-necked flask equipped with a stirrer, thermocouple thermometer and water condenser. The charge was flushed into the flask with 75g of hot deionized water and purged with nitrogen at 65 ℃ for 30 minutes. Then, 0.08g of "VAZO" 56WSP (E.I. du Pont DE Nemours and Company, Wilmington, DE) dissolved in 2g of deionized water was added to initiate polymerization. The temperature spontaneously increased to 77 ℃ and then began to drop. The temperature controller was reset at 70 ℃ and the charge was stirred under nitrogen for 3.5 hours. The resulting polymer supplement emulsion weighed 252g and had a solids content of 31.6%. This was mixed with a commercially available fluorochemical treatment listed in table 6 below at a 2: 1 ratio of extender to fluorochemical treatment. The mixture was applied to 100% cotton fabric, washed and retested as described in example 3. The results are shown in table 6. The inclusion of fluorinated monomers in the extender does not appear to increase the effectiveness of the copolymer extender.

Example 5

To begin with, (a)63g of 2-ethylhexyl methacrylate; (b)10g of poly (oxyethylene) 7 methacrylate; (c)2g of N-methylol-acrylamide containing 48% water; (f)7g ZONYL (E.I.du Pont DE Nemours and Company, Wilmington, DE); 0.3g dodecanethiol, 20g hexanediol, 1.6g ARMEEN DM18D, 1.0g acetic acid, 3g 2% salt (NaCl) in water, and 80g hot (50-60 ℃ C.) deionized water were emulsified and then loaded into a four-necked flask equipped with a stirrer, thermocouple thermometer, and water condenser. The charge was flushed into the flask with 75g of hot deionized water and purged with nitrogen at 65 ℃ for 30 minutes. Then, 0.08g of "VAZO" 56WSP (E.I. du pont DE Nemours and Company, Wilmington, DE) dissolved in 2g of deionized water was added to initiate polymerization. The temperature spontaneously increased to 77 ℃ and then began to drop. The temperature controller was reset at 70 ℃ and the charge was stirred under nitrogen for 3.5 hours. The resulting polymer supplement emulsion weighed 253g and had a solids content of 31.5%. This was mixed with a commercially available fluorochemical treatment listed in table 6 below at a 2: 1 ratio of extender to fluorochemical treatment. The mixture was applied to 100% cotton fabric, tested, washed and retested as described in example 3. The results are shown in table 6. The inclusion of fluorinated monomers in the extender does not appear to increase the effectiveness of the copolymer extender.

Example 6

Initially, (a)70g of 2-ethylhexyl methacrylate; (b)10g of poly (oxyethylene) 7 methacrylate; (c)2g of N-methylol-acrylamide containing 48% water; (e)0.3g ethylene glycol dimethacrylate; 1.6g ARMEEN DM18D, 1.0g acetic acid, 0.3g dodecanethiol, 20g hexanediol, 3g 2% salt (NaCl) in water and 80g hot (50-60 ℃ C.) deionized water were emulsified and then loaded into a four-necked flask equipped with a stirrer, thermocouple thermometer and water condenser. The charge was flushed into the flask with 75g of hot deionized water and purged with nitrogen at 65 ℃ for 30 minutes. Then, 0.08g of "VAZO" 56WSP (E.I. du Pont DE Nemours and Company, Wilmington, DE) dissolved in 2g of deionized water was added to initiate polymerization. The temperature spontaneously increased to 79 ℃ and then began to drop. The temperature controller was reset at 70 ℃ and the charge was stirred under nitrogen for 3.5 hours. The resulting polymer supplement emulsion weighed 252g and had a solids content of 32.2%. This was mixed with a commercially available fluorochemical treatment listed in table 6 below at a 2: 1 ratio of extender to fluorochemical treatment. The mixture was applied to 100% cotton fabric, tested, washed and retested as described in example 3. The results are shown in table 6.

Example 7

Initially, (a)70g of 2-ethylhexyl methacrylate; (b)10g of poly (oxyethylene) 7 methacrylate; (c)2g of N-methylol-dimethacrylate containing 48% water; 1.6g ARMEEN DM18D, 1.0g acetic acid, 0.3g dodecanethiol, 20g hexanediol, 3g 2% salt (NaCl) in water and 80g hot (50-60 ℃ C.) deionized water were emulsified and then loaded into a four-necked flask equipped with a stirrer, thermocouple thermometer and water condenser. The charge was flushed into the flask with 75g of hot deionized water and purged with nitrogen at 65 ℃ for 30 minutes. Then, 0.08g of "VAZO" 56WSP (E.I. du pont DE Nemours and Company, Wilmington, DE) dissolved in 2g of deionized water was added to initiate polymerization. The temperature spontaneously increased to 79 ℃ and then began to drop. The temperature controller was reset at 70 ℃ and the charge was stirred under nitrogen for 3.5 hours. The resulting polymer supplement emulsion weighed 251g and had a solids content of 31.7%. This was mixed with a commercially available fluorochemical treatment as listed in table 6 at a 2: 1 ratio of extender to fluorochemical treatment. The mixture was applied to 100% cotton fabric, tested, washed and retested as described in example 3. The results are shown in table 6.

Example 8

To begin with, (a)55g of 2-ethylhexyl methacrylate; (b)10g of poly (oxyethylene) 7 methacrylate; (c)2g of N-methylol-acrylamide containing 48% water; (d)15g stearyl methacrylate; 0.3g dodecanethiol, 20g hexanediol, 1.6g Armeen DM18D, 1.0g acetic acid, 3g 2% salt (NaCl) solution and 80g hot (50-60 ℃ C.) deionized water were emulsified and then loaded into a four-necked flask equipped with a stirrer, thermocouple thermometer and water condenser. The charge was flushed into the flask with 75g of hot deionized water and purged with nitrogen at 65 ℃ for 30 minutes. Then, 0.08g of "VAZO" 56WSP (E.I. du Pont DE Nemours and Company, Wilmington, DE) dissolved in 2g of deionized water was added to initiate polymerization. The temperature spontaneously increased to 77 ℃ and then began to drop. The temperature controller was reset at 70 ℃ and the charge was stirred under nitrogen for 3.5 hours. The temperature controller was reset at 70 ℃ and the charge was stirred under nitrogen for 3.5 hours. The resulting polymer supplement emulsion weighed 241g and had a solids content of 31.3%. This was mixed with a commercially available fluorochemical treatment listed in table 6 below at a 2: 1 ratio of extender to fluorochemical treatment. The mixture was applied to 100% cotton fabric, tested, washed and retested as described in example 3. The results are shown in table 6.

Example 9

Initially, (a)70g of 2-ethylhexyl methacrylate; (b)7g of poly (oxyethylene) 7 methacrylate; (c)2g of N-methylol-acrylamide containing 48% water; 0.3g dodecanethiol, 20g hexanediol, 1.6g ARMEEN DM18D, 1.0g acetic acid, 3g 2% salt (NaCl) in water and 80g hot (50-60 ℃ C.) deionized water were emulsified and then loaded into a four-necked flask equipped with a stirrer, thermocouple thermometer and water condenser. The charge was flushed into the flask with 75g of hot deionized water and purged with nitrogen at 65 ℃ for 30 minutes. Then, 0.08g of "VAZO" 56WSP (E.I. du Pont DE Nemours and Company, Wilmington, DE) dissolved in 2g of deionized water was added to initiate polymerization. The temperature of the mixture spontaneously rose to 79 ℃ in about 15 minutes and then began to drop. The temperature controller was reset at 70 ℃ and the charge was stirred under nitrogen for 3.5 hours. The resulting polymer supplement emulsion weighed 249g and had a solids content of 30.7%. This was mixed with a commercially available fluorochemical treatment as listed in table 6 at a 2: 1 ratio of extender to fluorochemical treatment. The mixture was applied to 100% cotton fabric, tested, washed and retested as described in example 3. The results are shown in table 6.

Example 10

Initially, (a)70g of 2-ethylhexyl methacrylate; (b)10g of poly (oxyethylene) 7 methacrylate; 1.6g ARMEEN DM18D, 1.0g acetic acid, 0.3g dodecanethiol, 20g hexanediol, 3g 2% salt (NaCl) in water and 80g hot (50-60 ℃ C.) deionized water were emulsified and then loaded into a four-necked flask equipped with a stirrer, thermocouple thermometer and water condenser. The charge was flushed into the flask with 75g of hot deionized water and purged with nitrogen at 65 ℃ for 30 minutes. Then, 0.08g of "VAZO" 56WSP (E.I. du Pont DE Nemours and Company, Wilmington, DE) dissolved in 2g of deionized water was added to initiate polymerization. The temperature spontaneously rose to 80 ℃ and then began to drop. The temperature controller was reset at 70 ℃ and the charge was stirred under nitrogen for 3.5 hours. The resulting polymer supplement emulsion weighed 251g and had a solids content of 31.9%. This was mixed with a commercially available fluorochemical treatment as listed in table 6 at a 2: 1 ratio of extender to fluorochemical treatment. The mixture was applied to 100% cotton fabric, tested, washed and retested as described in example 3. The results are shown in table 6.

Example 11

Initially, (a)60g of 2-ethylhexyl methacrylate; (b)10g of poly (oxyethylene) 7 methacrylate; (d)10g of methyl methacrylate; 0.3g dodecanethiol, 20g hexanediol, 1.6g Armeen DM18D, 1.0g acetic acid, 3g 2% salt (NaCl) in water and 80g hot (50-60 ℃ C.) deionized water were emulsified and then loaded into a four-necked flask equipped with a stirrer, thermocouple thermometer and water condenser. The charge was flushed into the flask with 75g of hot deionized water and purged with nitrogen at 65 ℃ for 30 minutes. Then, 0.08g of "VAZO" 56WSP (e.i. du Pont DE Nemours and company, Wilmington, DE) dissolved in 2g of deionized water was added to initiate polymerization. The temperature spontaneously rose to 78 ℃ and then began to drop. The temperature controller was reset at 70 ℃ and the charge was stirred under nitrogen for 3.5 hours. The resulting polymer supplement emulsion weighed 258g and had a solids content of 31.3%. This was mixed with a commercially available fluorochemical treatment as listed in table 6 at a 2: 1 ratio of extender to fluorochemical treatment. The mixture was applied to 100% cotton fabric, tested, washed and retested as described in example 3. The results are shown in table 6.

TABLE 6

100% cotton

Fluorochemical treatment agent	ZONYL8932	ZONYL8300	ZONYL8932	ZONYL8300	ZONYL8932	ZONYL8300	ZONYL8932	ZONYL8300	ZONYL8932	ZONYL8300	ZONYL8932	ZONYL8300	ZONYL8932	ZONYL8300
															Example supplements	1	1	A	A	B	B	2	2	3	3	4	4	5	5
Oil repellency
															Initial	7	7	6	4	5	6	6+	7	6+	6	7	7	7	7
5HW	6	6	2	2	1	4	6	6	6	6	6	6	6	6
															10HW	6	5	2	2	0	2	5	5	5	5	5	5	5	5
Water-proof property
															Initial	12	7	11	5	11	6	12	7	12	12	12	12	12	12
5HW	11	7	5	4	4	5	11	7	12	12	11	12	12	11
															10HW	11	6	4	4	3	4	9	5	7	7	10	7	10	8
Resistance to fogging
															Initial	100	100	90	90	100	100-	100	90	100-	100-	100	100	100	100
5HW	70	70-	50	50+	50	50	70-	50	50+	70	70-	50	70-	50+
															10HW	50	50	50	50	50	50	50	50/0	50	50	50	50	50	50

^＊5HW ═ 5 washes; 10HW ═ 10 washes

Table 6 (continue)

100% cotton

Fluorochemical treatment agent	ZONYL8932	ZONYL8300	ZONYL8932	ZONYL8300	ZONYL8932	ZONYL8932	ZONYL8932	ZONYL8932
									Example supplements	6	6	7	7	8	9	10	11
Oil repellency
									Initial	7	7	7	6	7	7	5+	7
5HW	5	6	5	5	6	5	5+	5
									10HW	5	5	5	4	5	4	3	3
20HW					1	2	2	2
									Water-proof property
Initial	12	12	12	12	12	12	12	9+
									5HW	10	7	9	6	9	8	11	9
10HW	8	5	8	5	9	7	5	5
									20HW					5	5	4	3
Resistance to fogging
									Initial	100	100-	100	100-	100	100	100	100
5HW	70-	50	50+	50	50+	70-	70+	70
									10HW	50	50	50	50	50	50	50+	50
20HW					50	50	50	0

^＊5HW ═ 5 washes; 10HW ═ 10 washes; 20 HW-20 washes

When applied at the same fluorine level, for the blends containing the supplements of examples 1-11, the treated fabrics performed longer after the specified number of washes than the blends containing comparative examples a and B, especially in terms of oil and water repellency.

Comparative example C

Initially, 3g of a 2% salt (NaCl) solution, 4.2g of hexanediol, 2g of ARMEEN DM18D, 6g of tridecyl alcohol ethoxylate (ETHAL TDA 5 from Ethox Chemicals, Greenville, C.) and 217g of water were loaded into a four-necked flask equipped with a stirrer, thermocouple thermometer and water condenser. The charge was purged with nitrogen at 65 ℃ for 30 minutes. Then, 0.06g of "VAZO" 56WSP (E.I. du Pont DE Nemours and company, Wilmington, DE) in 2g of water was added. Then, a mixture of (b)4g of poly (oxyethylene) 7 methacrylate, (d)76g of methyl methacrylate and 0.8g of dodecanethiol was slowly and stably added dropwise. The monomer mixture was added over about 80 minutes while maintaining the temperature at 65-67 ℃. The charge was then stirred at 70 ℃ for 2.5 hours. The resulting polymer emulsion weighed 309g and had a solids content of 28%. This was mixed with ZONYL8932 from E.I.du Pont de Nemours and Company at a 2: 1 ratio of extender to fluorochemical treatment. The product mixture contained 3.5% fluorine. The mixture was applied to 100% cotton fabric using the fabric treatment method described above in test method 1. 45g/L of the product mixture was used in a padding bath. Blocked isocyanates are also used in the padding bath. The isocyanate level is 5-10 g/L. An anti-wrinkle resin, PERMAFRESH EFC from Omnova Solutions, Chester, SC, was included in an amount of 60 g/L. After application, the fabric was cured at about 160 ℃ for 3 minutes. The fabric was allowed to "rest" after treatment and curing. The fabrics were tested for water repellency, oil repellency, and spray repellency using test methods 2-4 described above. After washing according to test method 6 above, the fabrics were retested for water repellency, oil repellency, and spray repellency in the same manner. The results are shown in table 7.

Comparative example D

Initially, 3g of 2% aqueous salt (NaCl), 4.2g of hexanediol, 2g of ARMEEN DM18D, 6g of tridecyl alcohol ethoxylate (ETHAL TDA 5 from Ethox Chemicals, Grenville, SC), and 217g of water were loaded into a four-necked flask equipped with a stirrer, thermocouple thermometer, and water condenser. The charge was purged with nitrogen at 65 ℃ for 30 minutes. Then, 0.06g of "VAZO" 56WSP (E.I. du Pont DE Nemours and company, Wilmington, DE) in 2g of water was added. Then, a slow, steady dropwise addition of a mixture of (b)4g of poly (oxyethylene) 7 methacrylate, (d)76g of methyl methacrylate, 2g of water, 48% N-methylol-acrylamide and 0.8g of dodecanethiol was started. The monomer mixture was added over about 80 minutes while maintaining the temperature at 65-67 ℃. The charge was then stirred at 70 ℃ for 2.5 hours. The resulting polymer emulsion weighed 311g and had a solids content of 28%. This was mixed with ZONYL8932 in a 2: 1 ratio of extender to fluorochemical treatment. The mixture was applied to 100% cotton fabric, tested, washed, and retested as described in comparative example C. The results are shown in table 7.

Comparative example E

Initially, 3g of 2% aqueous salt (NaCl), 4.2g of hexanediol, 2g of ARMEEN DM12D, 6g of tridecyl alcohol ethoxylate (ETHAL TDA 5 from Ethox Chemicals, Greenville, C.) and 217g of water were loaded into a four-necked flask equipped with a stirrer, thermocouple thermometer and water condenser. The charge was purged with nitrogen at 65 ℃ for 30 minutes. The nitrogen was then switched to a slow purge and a solution of 0.05g of potassium persulfate in 2g of water was added. Then, a mixture of (b)4g of poly (oxyethylene) 7 methacrylate, (d)76g of methyl methacrylate, and 0.3g of dodecanethiol was gradually and stably added dropwise. The monomer mixture was added over about 90 minutes while maintaining the temperature at 64-67 ℃. The charge was then stirred at 70 ℃ for 2.5 hours. The resulting polymer emulsion weighed 307g and had a solids content of 27.6%. This was mixed with ZONYL8932 in a 2: 1 ratio of extender to fluorochemical treatment. The mixture was applied to 100% cotton fabric, tested, washed, and retested as described in comparative example C. The results are shown in table 7.

TABLE 7

100% cotton

Fluorochemical treatment agent	ZONYL8932	ZONYL8932	ZONYL8932	ZONYL8932
					Examples of supplements	1	Comparative example C	Comparative example D	Comparative example E
Oil repellency
					Initial	7	5	5	6
5HW＊	6	3	4	4
					10HW＊	6	2	2	2
Water-proof property
					Initial	12	11	11	11
5HW＊	11	5	5	7
					10HW＊	11	4	4	5
Resistance to fogging
					Initial	100-	100-	100-	100-
5HW＊	70	70	70	70
					10HW＊	50	70-	50	50

^＊5HW ═ 5 washes; 10HW ═ 10 washes

When applied at the same level of fluorine, the treated fabric lasted better than the blend containing comparative examples C, D and E after the specified number of washes for the performance of the blend containing the supplement of example 1, especially in terms of oil and water repellency.

Comparative examples F and G

Comparative examples F and G are commercially available supplements, PHOBOOTEX JVA available from Ciba specialty Chemicals, High Point, NC and FREEPEL 1225WR available from Omnova Solutions Chester, SC. These extenders and the extender polymer of example 1 were each mixed with fluorochemical treatments ZONYL 8300 and ZONYL8932 from E.I. du Pont DE Nemonrs and Company, Wilmington, DE, at a ratio of 2: 1, respectively, to fluorochemical treatment. The mixture was applied to 100% cotton fabric using the method of test method 1. 45g/L of the product mixture was used in a padding bath. The product mixture contains 2.2-3.5% fluorine. Blocked isocyanates are also used in the padding bath. The isocyanate level is 5-10 g/L. An anti-wrinkle resin, PERMAFRESH EFC from Omnova Solutions, Chester, SC, was included in an amount of 60 g/L. After application, the fabric was cured at about 160 ℃ for 3 minutes. The fabric is allowed to "rest" after treatment and curing. The mixture was applied to 100% cotton fabric, tested, washed, and retested as described in example C. The results are shown in table 8.

TABLE 8

100% cotton

Fluorochemical treatment agent	ZONYL8932	ZONYL8300	ZONYL 8932	ZONYL 8932	ZONYL 8300	ZONYL 8300
							Example supplements	1	1	Comparative example F	Comparative example G	Comparative example F	Comparative example G
Oil repellency
							Initial	7	7	6	4	6	6
5HW＊	6	6	4	2	3	4
							10HW＊	5	6	2	1	1	1
Water-proof property
							Initial	12	12	11	6	12	12
5HW＊	12	8	7	4	5	6
							10HW＊	8	7	4	4	0	1
Resistance to fogging
							Initial	100	100	100	70	90	100
5HW＊	70-	50	50	50	50	50
							10HW＊	50	50	50	50	50/0	50/0

[0165] ^＊5HW ═ 5 washes; 10HW ═ 10 washes

For the blends containing commercial extenders (comparative examples F and G), the performance durability of the treated fabrics after the specified number of washes was not equal to the blend containing the fluorochemical treatment of the present extender (example 1).

Example 12

The extender of example 1 was mixed with ZONYL8932 in a 2: 1 ratio of extender to ZONYL8932, and with blocked isocyanate (1% by bath weight (owb)) and softener (1% owb). In this mixture ZONYL 8932: extender: softener: blocked isocyanate equals 2: 1: 0.2: 0.3. The blocked isocyanate used in this example was HYDROPHOBOLXAN (Ciba Specialty Chemicals, High Point, NC) and the softening agent used in this example was ARQUAD 2HT/75(Akzo-Nobel, McCook, IL). The formulated product was applied to 100% cotton fabric at a level of 45g/L in a pad bath using the method of test method 1. A60 g/L crease resist resin, PERMAFRESH EFC, available from Omnova Solutions, Chester, SC was included in the padding bath. After application, the fabric was cured at about 160 ℃ for about 3 minutes. After treatment and curing, the fabric is allowed to "rest". The water repellency, oil repellency, and spray resistance of the fabrics were determined using test methods 2-4 described above. After washing according to test method 6 above, the fabric was again tested for water repellency, oil repellency, and anti-fogging properties using the same methods. The results are shown in Table 9.

Example 13

The extender of example 1 was mixed with ZONYL8932 and blocked isocyanate (1% owb) in a 3: 6: 1 ratio of extender to fluorochemical treatment to blocked isocyanate. The formulated product was applied to 100% cotton fabric at a level of 30g/L in a pad bath using the method of test method 1. A60 g/L crease resist resin, PERMAFRESHEFC, available from Omnova Solutions, Chester, SC was included in the padding bath. After application, the fabric was cured at about 160 ℃ for about 3 minutes. After treatment and curing, the fabric is allowed to "rest". The water repellency, oil repellency, and spray resistance of the fabrics were determined using test methods 2-4 described above. After washing according to test method 6 above, the fabric was again tested for water repellency, oil repellency, and anti-fogging properties using the same methods. The results are shown in Table 9.

Example 14

The extender of example 1 was mixed with ZONYL8932 and blocked isocyanate (1% owb) in a ratio of extender to fluorochemical treatment to blocked isocyanate of 2: 1: 0.3. The formulated product was applied to 100% cotton fabric at a level of 45g/L in a pad bath using the method of test method 1. A60 g/L crease resist resin, PERMAFRESHEFC, available from Omnova Solutions, Chester, SC was included in the padding bath. After application, the fabric was cured at about 160 ℃ for about 3 minutes. After treatment and curing, the fabric is allowed to "rest". The water repellency, oil repellency, and spray resistance of the fabrics were determined using test methods 2-4 described above. After washing according to test method 6 above, the fabric was again tested for water repellency, oil repellency, and anti-fogging properties using the same methods. The results are shown in Table 9.

Example 15

The extender of example 1 was mixed with ZONYL8932 and blocked isocyanate (1% owb) in a ratio of extender to fluorochemical treatment to blocked isocyanate of 3: 1: 0.3. The formulated product was applied to 100% cotton fabric at a level of 30g/L in a pad bath using the method of test method 1. A60 g/L crease resist resin, PERMAFRESHEFC, available from Omnova Solutions, Chester, SC was included in the padding bath. After application, the fabric was cured at about 160 ℃ for about 3 minutes. After treatment and curing, the fabric is allowed to "rest". The water repellency, oil repellency, and spray resistance of the fabrics were determined using test methods 2-4 described above. After washing according to test method 6 above, the fabric was again tested for water repellency, oil repellency, and anti-fogging properties using the same methods. The results are shown in Table 9.

Example 16

The extender of example 1 was mixed with ZONYL8932 and blocked isocyanate (1% owb) in a ratio of extender to fluorochemical treatment to blocked isocyanate of 6: 1: 0.3. The formulated product was applied to 100% cotton fabric at a level of 30g/L in a pad bath using the method of test method 1. A60 g/L crease resist resin, PERMAFRESHEFC, available from Omnova Solutions, Chester, SC was included in the padding bath. After application, the fabric was cured at about 160 ℃ for about 3 minutes. After treatment and curing, the fabric is allowed to "rest". The water repellency, oil repellency, and spray resistance of the fabrics were determined using test methods 2-4 described above. After washing according to test method 6 above, the fabric was again tested for water repellency, oil repellency, and anti-fogging properties using the same methods. The results are shown in Table 9.

TABLE 9

100% cotton

Examples	ZONYL8932	12	13	14	15	16
							Oil repellency
Initial	6	7	6	7	6	2
							5HW＊	5	6	4.5	6.5	5	1
10HW＊	3	5	2.5	5	3	1
							20HW＊	1	3.5	2	4.5	1	0
Water-proof property
							Initial	12	12	12	12	12	5
5HW＊	7	11	8	11	6	4
							10HW＊	5	10	5	11	4	3

20HW＊	3	4	4	7	4	3
							Resistance to fogging
Initial	100	100	100	100	100	90
							5HW＊	50	50	50	80	50	50
10HW＊	50	50	50	50+	50	50
							20HW＊	50	50	50	50	50	50

^＊5HW ═ 5 washes; 10HW ═ 10 washes; 20 HW-20 washes

The results show that the supplement of the present invention can be used in a variety of formulations with and without emollients and can be used at a variety of application levels. When applied alone without any replenisher present, the fluorochemical treatment agent ZONYL8932 was applied at a level of 30g/L in a pad bath using the same conditions as examples 12-16.

The data demonstrates that examples 12-15 provide comparable or superior protective durability when a small percentage of fluorine is applied to the fabric. Example 16 had comparable spray protection with a fluorochemical treatment reduced to 1/6 compared to ZONYL8932 alone.

Claims (14)

1. A polymer extender composition comprising monomers copolymerized in the following percentages by weight:

(a) from 60% to 94% of a monomer or mixture of monomers of formula I:

[CH₃-(CH₂)_p][CH₃(CH₂)_n]CHCH₂-OC(O)-C(R)＝CH₂(I) and are and

(b) from 5% to 20% of a monomer or mixture of monomers of formula II:

H-(OCH₂CH₂)_m-O-C(O)-C(R)＝CH₂(II)

(c) 0% to 3% of a monomer or mixture of monomers of formula III:

HO-CH₂-NH-C(O)-C(R)＝CH₂(III)

(d) from 0% to 20% of a monomer or mixture of monomers of formula IV:

R¹-OC(O)-C(R)＝CH₂(IV)

(e) from 0% to 2% of ethylene glycol dimethacrylate, and

(f) from 0% to 10% of a monomer or mixture of monomers of formula V:

R_f-CH₂CH₂-OC(O)-C(R)＝CH₂(V)

wherein

Each R is independently H or CH₃；

R¹Is an alkyl chain of 1 to 18 carbon atoms;

n is 1 to 10;

p is 1 to 20;

m is 2 to 10, and

R_fis a linear or branched perfluoroalkyl group of 2 to 20 carbon atoms.

2. The composition of claim 1 wherein for monomer (f), R_fHaving the formula: CF (compact flash)₃CF₂(CF₂)_xWherein x is 6 to 18.

3. The composition of claim 1, wherein the composition further comprises a treating agent that provides a surface effect when applied to a substrate.

4. The composition of claim 3, wherein the surface effect is iron free, easy to iron, shrink resistant, wrinkle free, durable pressure resistant, moisture resistant, soft, strong, slip resistant, static resistant, snag resistant, pilling resistant, stain release, stain resistant, stain release, water repellent, oil repellent, odor resistant, antimicrobial, sun resistant.

5. The composition of claim 3, wherein the treating agent is a fluorinated polymer.

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

7. The composition of claim 1 or 5, wherein the composition comprises a blocked isocyanate or an additive selected from the group consisting of: surfactants, pH adjusters, cross-linking agents, softeners, and wax extenders.

8. A method of treating a substrate comprising contacting the substrate with a composition comprising i) a treatment agent that provides a surface effect and ii) the polymer extender composition of claim 1.

9. The method of claim 8, wherein the treatment agent is a fluorinated polymer.

10. The method of claim 8, wherein the ratio of the replenisher composition to fluorinated polymer is from 1: 10 to 6: 1.

11. The method of claim 8, wherein the matrix is a fibrous matrix.

12. A substrate treated by a composition comprising i) a treatment agent that provides a surface effect and ii) the polymer extender composition of claim 1.

13. The substrate of claim 12 which is a fibrous substrate.

14. The substrate of claim 12 having a fluorine content of 0.05% to 0.5% by weight.