Background of the Invention

Technical Field

This invention relates to aqueous compositions containing fluorochemical oil- and water-repellent agents. This invention also relates to agents that improve fluorine efficiency of fluorochemical oil- and water-repellent agents. This invention also relates to processes for providing oil- and water-repellency to fibrous substrate materials.

Description of the Related Art

Water-, oil- and soil-repellent finishes containing fluorochemical agents or compositions are well known. A considerable disadvantage of such finishes, however, is their high price. So-called "extenders" have therefore been developed in order to reduce cost. Modified synthetic resins, waxes, paraffin emulsions, and similar products have been used for this purpose.

U.S. Pat. No. 3,849,521 (Kiri oto et al.) describes oil- and water-repellent compositions containing a polymer containing fluoroalkyl-containing monomer units and an additive copolymer containing monomer units having the formula

CRιR ₂ =CR ₂ COOR4 wherein R-,, R ₂ and R ₃ represents hydrogen atoms or methyl groups, and R ₄ represents a C ₈ alkyl group; and monomer units having the formula:

CH ₂ =CR ₅ CONHCH ₂ OH wherein R ₅ represents a hydrogen atom or a methyl group. U.S. Pat. No. 4,834,784 (Deiner et al.) describes the use of blocked isocyanate compounds as extenders, the isocyanate compound before blocking being diphenylmethane diisocyanate or an isocyanate compound having a molecular weight of at least 450.

Summary of the Invention

This invention provides fluorine-efficient oil- and water-repellent compositions comprising:

(A) a fluorochemical oil- and water-repellent agent;

(B) a copolymer extender comprising

(i) polymerized units derived from a monomer of Formula V:

CR,R ₂ =CR ₃ R ₄ (V) wherein each of R _{l f} R ₂ , R ₃ and .^ independently represents hydrogen, halogen, or an organic group such as alkyl, carboxyl, or acyloxyalkyl (i.e., -C0 ₂ alkyl) ; and

(ii) polymerized units derived from a monomer of Formula VII:

CH ₂ =CR ₅ X (VII)

wherein R ₅ represents a hydrogen atom or a methyl group, and X represents a moiety comprising a functional group that can interact with a fibrous substrate; and

(C) a blocked isocyanate extender.

This invention also provides substrates treated with a fluorine-efficient composition as described above, and methods of improving the fluorine-efficiency of a fluorochemical oil- and water-repellent agent, comprising the step of formulating the fluorochemical agent with components (B) and (C) described above.

The compositions of the invention comprise at least one member of each of two classes of extenders. The combination improves the fluorine-efficiency of fluorochemical agents, and thus reduces the cost of fluorochemical treatment, to a greater extent than would be expected based on the properties of each individual class of extenders.

Detailed Description of the Invention Component (A) in a composition of the invention is a fluorochemical oil- and water-repellent agent generally comprising a plurality of fluoroaliphatic (i.e.,

R _f ) groups. Such agents are well known to those skilled in

the art, and many (e.g., SCOTCHGARD™ fabric protector, 3M) are commercially available as ready-made formulations.

In general, fluorochemical agents useful in this invention comprise fluorochemical compounds or polymers containing one or more fluoroaliphatic groups R _f , which are fluorinated, stable, inert, non-polar, preferably saturated, monovalent and both oleophobic and hydrophobic. R _f preferably contains at least about 3 carbon atoms, more preferably 3 to about 20 carbon atoms, and most preferably about 6 to about 14 carbon atoms. R _f can contain straight chain, branched chain, or cyclic fluorinated alkylene groups or combinations thereof or combinations thereof with straight chain, branched chain, or cyclic alkylene groups. R _f is preferably free of polymerizable olefinic unsaturation and can optionally contain catenary heteroatoms such as oxygen, divalent or hexavalent sulfur, or nitrogen. It is preferred that R _f contain about 40% to about 78% fluorine by weight, more preferably about 50% to about 78% fluorine by weight. The terminal portion of the R _f group contains a fully fluorinated terminal group. This terminal group preferably contains at least 7 fluorine atoms, e.g., CF ₃ CF ₂ CF ₂ -, (CF ₃ ) ₂ CF-, -CF ₂ SF ₅ , or the like. Perfluorinated aliphatic groups (i.e., those of the formula C _n F _2n+1 ) are the most preferred embodiments of R _f . Examples of fluorochemical agents include, for example, R _f -containing urethanes, ureas, esters, amines (and salts thereof) , amides, acids (and salts thereof) , carbodiimides, guanidines, allophanates, biurets, and compounds containing two or more of these groups, as well as mixtures and blends thereof.

Useful fluorochemical polymers containing R _f groups include copolymers of fluorochemical aerylate and/or methacrylate monomers with co-polymerizable monomers, including fluorine-containing and fluorine-free monomers, such as methyl methacrylate, butyl acrylate, octadecylmethacrylate, acrylate and methacrylate esters of poly(oxyalkylene) polyol oligomers and polymers, e.g., poly(oxyethylene)glycol dimethacrylate, glycidyl methacrylate, ethylene, vinyl acetate, vinyl chloride, vinylidenechloride, vinylidenefluoride, acrylonitrile, vinylchloroacetate, isoprene, chloroprene, styrene.

butadiene, vinylpyridine, vinyl alkyl ethers, vinyl alkyl ketones, acrylic and ethacrylic acid, 2-hydroxyethyl acrylate , N-methylolacrylamide,

2-(N,N,N-trimethylammonium)ethyl methacrylate and the like. Particular fluorochemical agents include those described in Patent Nos. 2,803,615 (Ahlbrecht et al.), 2,934,450 (Brown), 3,068,187 (Bolstad et al.) , 3,094,547 (Heine), 3,329,661 (Smith et al.), 3,341,497 (Sherman et al.), 3,398,182 (Guenthner et al.), 3,458,571 (Tokoli) , 3,462,296 (Raynolds et al.), 3,574,791 (Sherman et al.),

3,728,151 (Sherman et al.), 3,896,251 (Landucci), 3,916,053 (Sherman et al.), 4,013,627 (Temple), 4,024,178 (Landucci), 4,029,585 (Dettre) , 4,034,964 (Sherman et a1.) , 4,144,367 (Landucci), 4,160,777 (Loudas) , 4,165,338 (Katsushi a et al.), 4,190,545 (Marshall), 4,215,205 (Landucci), 4,264,484 )Patel), 4,325,857 (Champaneria et al.), 4,340,749 (Patel) , 4,401,780 (Steel), 4,426,476 (Chang), 4,525,305 (Patel), 4,525,423 (Lynn et al.), 4,529,658 (Schwartz et al.), 4,540,497 (Chang et al.) , 4,560,487 (Brinkley) , 4,564,366 (Patel), 4,565,641 (Chang et al.), 4,566,981 (Howells) , 4,579,924 (Schwartz et al.), 4,582,882 (Lynn et al.), 4,606,737 (Stern), 4,668,406 (Chang), 4,668,726 (Howells), Atty's Docket No. 44348USA6A (commonly assigned and filed of even date) , each of which is incorporated herein by reference.

Component (B) in a composition of the invention is a copolymer extender comprising

(i) polymerized units derived from a monomer of Formula V:

wherein each of Rj, R ₂ , R ₃ , and R ₄ independently represents hydrogen, halogen, or an organic group; and (ii) polymerized units derived from a monomer of Formula VII:

CH ₂ =CR ₅ X (VII)

wherein R ₅ is hydrogen or methyl and X is a moiety comprising a functional group that can interact with a fibrous substrate.

Examples of monomers of Formula V include general classes of ethylenic compounds capable of free-radical polymerization, such as lower olefinic hydrocarbons, optionally halogenated, such as ethylene, propylene, isobutene, 3-chloro-2-isobutene, butadiene, isoprene, chloro and dichlorobutadienes, fluoro and difluorobutadienes, 2,5-dimethyl-l,5-hexadiene; vinyl, allyl or vinylidene halides such as vinyl or vinylidene chloride, vinyl or vinylidene fluoride, allyl bromide, allyl chloride, methallyl chloride; styrene and its derivatives such as vinyltoluene, oi- ethylstyrene, α-cyanomethylstyrene, divinylbenene, N-vinylcarbazole; vinyl esters such as vinyl acetate, vinyl propionate, vinyl isobutyrate, vinyl succinate, vinyl stearate, divinylcarbonate; allyl esters such as allyl acetate and allyl heptanoate; alkylvinyl or alkylallyl ethers such as cetyl vinyl ether, dodecyl vinyl ether, isobutyl vinyl ether, ethyl vinyl ether, 2-chloroethyl vinyl ether, tetrallyloxyethane; vinyl alkyl ketones such as vinyl methyl ketone; unsaturated acids such as acrylic, α-chloro acrylic, α-fluoro acrylic, crotonic, maleic, fumaric, itaconic, and citraconic acids, and anhydrides and esters thereof such as dimethyl maleate, ethyl crotonate, acid methyl maleate, acid butyl itaconate, and vinyl, allyl, methyl, ethyl, butyl, isobutyl, hexyl, 2-ethylhexyl, chlorohexyl, octyl, lauryl, or stearyl acrylates and methacrylates; olefinic silanes such as vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, and methacryloyloxypropyl trimethoxysilane; nitriles such as acrylonitrile, methacrylonitrile, 2-chloroacrylonitrile, 2-cyanoethylacrylate, methylene glutaronitrile, vinylidene cyanide, alkyl cyanoacrylates such as isopropyl cyanoacrylate; (tris)-acryloyl-hexahydro-s-triazine; special acrylates such as butanediol dimethacrylate, dicyclopentenyl acrylate, ethoxylated bisphenol A dimethacrylate, isobornyl acrylate and methacrylate, trimethylopropane triacrylate, allyl methacrylate;

acrylamides and methacrylamides; mono or di (meth)acrylates of glycols or polyalkylene glycols such as ethylene glycol dimethacrylate, triethylene glycol acrylate, mono, di, and polyacrylates and methacrylates of methoxypolyethylene glycols and polyethylene glycols of various molecular weights (available as CARBOWAX™) , block copolymers of ethylene oxide and propylene oxide endcapped by hydroxy groups (available as PLURONIC™) , tetramethyleneoxide glycols (available as TERATHANE™) , amino or diamino- terminated polyethers (available as JEFFAMINE™) ; mono, di, and polyacrylates and methacrylates of siloxane mono-, di-, or polyols such as l,3-bis(4-hydroxybutyl)tetramethyl disiloxane (Petrarch Systems, Bristol, PA); VP-1610 siloxane diol (Wacker - Germany) ; Q4-3667 siloxane diol (Dow Corning) ; Q4-3557 siloxane diol (Dow Corning) ; acrylamides and methacrylamides of siloxane mono, di, or polyamines such as 1,3-bis(y-aminopropyl)tetramethyl disiloxane (Petrarch Systems) ; DC-531 siloxane polyamine (Dow Corning) ; DC-536 siloxane polyamine (Dow Corning) ; and others described in U.S. Pat. No. 4,728,571 (Clemens et al.), the disclosure of which is incorporated herein by reference.

A particularly preferred class of monomers of Formula V is acrylate monomers of Formula IX

CRg ^CRgCOORc, (IX) wherein R^, R ₇ , and R ₈ independently represent a hydrogen atom or a methyl group, and Rg represents a C ₈ alkyl group. Preferred among this class are alkyl crotonates, alkyl acrylates and alkyl methacrylates such as methyl acrylate, methyl methactylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, isoamyl acrylate, isoamyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, octyl methacrylate, lauryl acrylate, lauryl methacrylate, cetyl acrylate, or cetyl methacrylate.

The copolymer extender also comprises polymerized units derived from a monomer of Formula VII. Suitable monomers of Formula VII include those comprising a functional group that can interact with a fibrous substrate by, for example, physical entanglement, covalent bonding by

way of nucleophilic, electrophilic, ionic, free radical or like reactions between the copolymer and the substrate, or ionic bonding. Wool, leather, paper, cotton, and nylon variously comprise hydroxyl, amino, carboxyl, and carboxamido groups. For the purposes of the instant specification and claims, "a functional group that can interact with a fibrous substrate" designates a group that can interact with a fabric by any of the above-described mechanisms. Such groups can be easily selected by those skilled in the art as a function of the particular fibrous substrate that is intended to be treated with the composition of the invention. Representative groups suitable for interacting with a substrate include polymerizable olefin, olefin that can undergo a hydrosilation reaction, epoxy, amino, hydroxy, halo, haloformyl, aziridino, acid groups such as carboxy, sulfo, sulfino, sulfeno, dihydroxyphosphinyl, and hydroxyphosphinilidene, alkali metal and alkaline-earth metal salts thereof, amine salts thereof, quaternary ammonium salts thereof and the like, or amino and quaternary ammonium groups and salts thereof with, e.g., the above-listed types of acids.

Examples of suitable functionalized monomers include N-methylol acrylamide; N-methylol methacrylamide; aziridinyl acrylate and methacrylate; diacetone acrylamide and methacrylamide; methylolated diacetone acrylamide and methacrylamide; 2-hydroxy-3-chloropropyl acrylate and methacrylate; hydroxy (C ₂ to C ₄ ) alkyl acrylates and methacrylates; maleic anhydride; butadiene; isoprene; chloroprene; allyl alcohol; allyl glycolate; isobutenediol; allyloxyethanol; o-allyl phenol; divinyl carbinol; glycerol α-allylether, acrylamide; methacrylamide; maleamide; maleimide; N-cyanoethyl acrylamide; N-isopropyl acrylamide; glyoxal bis-acrylamide; metal salts of acrylic acid and methacrylic acid; vinylsulfonic and styrene p-sulfonic acids and their metal salts; monoallylamine; vinylpyridines; N-vinylpyrrolidone;

2-acrylamido-2-methylpropanesulfonic acid (AMPS) and its salts; vinyl azlactones; glycidyl acrylate and methacrylate; allyl glycidyl ether; acrolein;

N,N-dimethylaminoethyl acrylate and methacrylate;

N-tert-butylaminoethyl methacrylate; allyl methacrylate; diallyl maleate; vinyltriethoxysilane; vinyltrichlorosilane; and the like.

Preferred functionalized monomers of Formula VII include those of Formula XI:

CH ₂ =CR ₅ CONHCH ₂ OH (XI)

wherein R ₅ represents a hydrogen atom or a methyl group. Copolymers comprising such monomers are described in U.S.

Pat. No. 3,849,521 (Kirimoto et al.) incorporated herein by reference. Other suitable copolymers can be prepared by methods well known to those skilled in the art.

Component (C) in a composition of this invention is a blocked isocyanate. Suitable isocyanates for use

(before blocking) include aromatic diisocyanates such as 4,4'-methylenediphenylenediisocyanate, 4,6-di-(trifluoromethyl)-1,3-benzene diisocyanate, 2,4-tolunediisocyanate, 2,6-toluene diisocyanate, o, m, and p-xylylene diisocyanate, 4,4,-diisocyanatodiphenylether, 3,3'-dichloro-4,4'-diisocyanatodiphenylmethane, 4,5'-diphenyldiisocyanate, 4,4'-diisoc ^' yanatodibenzyl, 3,3,-dimethoxy-4,4,-diisocyanatodiphenyl, 3,3'-dimethyl-4,4'-diisocyanatodiphenyl, 2,2,-dichloro-5,5,-dimethoxy-4,4'-diisocyanato diphenyl, 1,3-diisocyanatobenzene, 1,2-naphthylene diisocyanate, 4-chloro-l,2-naphthylene diisocyanate, 1,3-naphthylene diisocyanate, and l,8-dinitro-2,7-naphthylene diisocyanate; alicyclic diisocyanates such as 3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate; aliphatic diisocyanates such as methylenediisocyanate, 1,6-hexamethylenediisocyanate ,

2,2,4-trimethyl-l,6-hexamethylenediisocyanate, and 1,2-ethylenediisocyanate; aliphatic triisocyanates such as 1,3,6-hexamethylenetriisocyanate; aromatic polyiisocyanates such as polymethylenepolyphenylisocyanate (PAPI) ; and cyclic diisocyanates such as isophorone diisocyanate (IPDI) .

Also useful are isocyanates containing internal isocyanate-derived moieties such as biuret-containing tri-isocyanates such as that available from Mobay as

DESMONDUR™ N-100, isocyanurate-containing tri-isocyanates such as that available from Huls AG, Germany, as IPDI-1890, and azetedinedione-containing diisocyanates such as that available from Bayer as DESMONDUR™TT. Also, triisocyanates such as tri-(4-isocyanatophenyl)-methane (available from Bayer as DESMONDUR™R) are suitable.

Another suitable class of isocyanates is isocyanate-functional low molecular weight polyurethanes. These polyurethanes are prepared by reacting a polyfunctional, aliphatic, cycloaliphatic, araliphatic or aromatic polyisocyanate, such as, for example, hexamethylene-l,6-diisocyanate, the various isomers of tolulene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate and the like, with a low molecular weight polyol having at least 2, preferably at least 3 hydroxyl groups. Suitable low molecular weight polyols include trimethylolpropane, 1,3,5-hexanetriol, glycerol, pentaerythritol, propylene glycol, hexylene glycol and diethylene glycol. Also suitable are other low molecular weight polyhydroxy compounds, such as triethanolamine.

These low molecular weight polyurethanes can be prepared by reacting a polyol with an excess of polyisocyanate. The equivalent ratio of hydroxyl to isocyanato groups in the reaction is preferably at least 1:1.3, more preferably 1:1.5 to 2.5.

The above-described isocyanates are used in a composition of the invention in the form of "blocked isocyanates", i.e., the reaction product of an isocyanate and a blocking agent, wherein the blocking agent is removable from the isocyanate under thermal conditions such as those employed during cure of a substrate treated with a compound containing the blocked isocyanato group. Conventional isocyanate blocking agents include arylalcohols (e.g., phenol, cresols, nitrophenols, o- and p-chlorophenol, naphthols, 4-hydroxybiphenyl) ; C ₂ to C ₈ alkanone oximes (e.g. acetone oxime, butanone oxime) ; arylthiols (e.g., thiophenol) ; organic active hydrogen compounds (e.g.; diethyl malonate, acetylacetone, ethyl acetoacetate, ethyl cyanoacetate, e-caprolactam) ; sodium bisulfite; and hydroxylamine. Particularly preferred blocked isocyanates include those blocked with C ₂ to C ₈

alkanone oxi es, particularly butanone oxime. Such blocked isocyanates can be de-blocked at a relatively low temperature, for example during the process of curing a substrate that has been treated with the composition comprising the blocked isocyanate.

Some of the above-described blocked isocyanates are disclosed in U.S. Pat. No. 4,834,764 (Deiner et al.) the disclosure of which is incorporated herein by reference. Others can be prepared by methods well known to those skilled in the art.

A composition of the invention comprises the fluorochemical agent in an amount effective to impart repellent properties to a fibrous substrate treated with the composition. The amount of fluorochemical agent that constitutes an effective amount can be easily determined by those skilled in the art and depends on the particular fluorochemical agent used and on the amounts of the copolymer and blocked isocyanate extenders used. The copolymer extender and the blocked isocyanate extender are present in a combined amount effective to improve the fluorine efficiency of the fluorochemical agent. Each extender is preferably present in an amount such that the improvement in fluorine efficiency is greater than the improvement provided by either extender alone.

"Improvement in fluorine efficiency" as used herein designates an improvement in the repellent properties imparted by a fluorochemical agent per unit weight of fluorine in a composition comprising the agent, as those repellent properties are measured using the test procedures set forth below. Stated another way, an extender (or combination of extenders) improves the fluorine efficiency of a given fluorochemical agent if performance is improved by including the extender(s) in a composition containing the same or a lesser concentration of the fluorochemical agent.

Generally, the extenders are present in relative amounts between about 1:20 to about 20:1, preferably abut 1:4 to about 4:1, more preferably about 2:1 to abut 1:2, and most preferably about 1:1. Generally, the fluorochemical agent is present in an amount of about 20 to

about 2000, preferably 40 to about 900, and most preferably about 100 to about 400, parts by weight based on 100 parts by weight of the copolymer and the blocked isocyanate extenders combined. When a composition of the invention is applied as a treatment to a fibrous substrate, e.g., a fabric intended for use in a garment, it is preferred that a treated substrate comprise the fluorochemical agent in an amount of abut 0.1% to about 0.6% by weight based on the weight of the untreated substrate. Further, it is preferred that a treated substrate comprise the fluorochemical agent, the copolymer extender, and the blocked isocyanate extender in a total combined amount of about 0.1% to about 1% by weight based on the weight of the untreated substrate.

Knowing the amount of composition intended to be incorporated on the substrate, the percent pick-up of the substrate, and the mass of the substrate, a composition of the invention can be applied to a substrate by any suitable method. For example, a composition can be prepared in the form of an aqueous dispersion and the substrate treated therewith. A dispersion will generally contain water, an amount of composition effective to provide repellent properties to a substrate treated therewith, and an emulsifier in an amount effective to stablilize the dispersion. Water is preferably present in an amount of about 70 to about 900 parts by weight based on 100 parts by weight of the composition of the invention. The emulsifier is preferably present in an amount of about 1 to about 25 parts by weight, preferably about 5 to about 10 parts by weight, based on 100 parts by weight of the composition of the invention. Conventional cationic, nonionic, anionic, and zwitterionic emulsufiers are suitable.

In order to effect treatment of a substrate, the substrate can be immersed in the dispersion and agitated until it is saturated. The saturated substrate can then be run through a padder/roller to remove excess dispersion, dried in an oven at a relatively low temperature (e.g., 70°C) for a time sufficient to remove the dispersion medium (e.g., water, ethylene glycol, or a mixture thereof), and cured at a temperature and for a time sufficient to provide

a cured treated substrate. This curing process can be carried out at temperatures between 40°C and about 200°C depending on the particular composition used. In general, a temperature of about 155°C for period of about 5 minutes is suitable. The cured treated substrate can be cooled to room temperature and used as desired, e.g., incorporated or fashioned into a garment such as rainwear.

In order to improve fixing of a fluorinated compound of the invention to a substrate, it is sometimes advantageous to include in the dispersion certain additives, polymers, thermo-condensable products and catalysts capable of promoting interaction with the substrate. Among these are the condensates or precondensates of urea or melamine with formaldehyde (sometimes referred to herein as resins) .

Other auxilliary extenders can be used, either alone or in combination with each other. Suitable auxilliary extenders include paraffin; compositions containing alkylketenes or derivatives thereof; siloxanes; chlorohydrates of stearamidomethylpyridinium; condensates of fatty acids with melamine or urea derivatives (such as the product obtained on reacting stearic acid with hexamethoxymethylmelamine) , condensates of fatty acids with polyamides (such as the reaction product of stearic acid with diethylenetria ine) and their epichlorohydrin adductε. It is also possible to use salts of inorganic or organic acids such as aluminum stearate, zirconium acetate, zirconium oxychloride or Werner complexes such as chromium stearatochloride. If it is desired to improve the softness or

"hand" of a substrate treated with a composition of the invention, it is possible to use softeners, such as certain polyethylenes, polydimethylsiloxanes, modified hydrogenalkylpolysiloxanes, or other materials known to those skilled in the art.

In combination with compositions of this invention it is also possible to use auxilliary products such as polyglycols, colloids such as starch, dextrin, casein, sizing agents, fixing or retaining agents, materials to improve stain resistance, cleaning ability, fire proofing or antistatic properties, buffering agents,

fungicidal agents, optical bleaching agents, sequestering agents, mineral salts, surface-activity agents, or swelling agents to promote penetration. Particular suitable auxilliary products and amounts thereof can be easily selected by those skilled in the art.

In addition to providing oil- and water- repellent properties to substrates, the compositions of the invention can also be used to provide anti-adhesion properties and to protect substrates against solvents or certain aggresive chemicals. They can also be used for applications such as stain resistance, soil resistance, soil release and stain release on textiles, paper, or leather. Further, they can be used for imparting properties such as antistatic, antipilling, mold release, corrosion inhibition, or anti-fouling properties.

Substrates treated with compositions of the invention were tested by the test methods set forth below.

Water Spray Test (SR) The resistance of a treated substrate to wetting with water was measured using AATCC Test Method 22-1977, "Water Repellency: Spray Test" as described in American Association of Textile Chemists and Colorists Technical Manual, 1977, 5J3, 245. Samples are rated on a scale of 0 to 100, with 0 indicating complete wetting of the upper and lower surfaces of the substrate and 100 indicating no wetting.

Oil Repellency Test (OR) The oil repellency of a substrate treated with a compound of the invention was measured using AATCC Test Method 118-1975, "Oil Repellency: Hydrocarbon Resistance Test" as described in AATCC Technical Manual, 1977, 53, 223. This test measures the resistance of a substrate to wetting by a series of hydrocarbon liquids with a range of surface tensions. The values reported range from 0 (least repellent) to 8 (most repellent) .

Launderinq Procedure

The procedure set forth below was used to prepare treated substrate samples designated in the examples below as "5x Laundered" or "5 Laund". A 230 g sample of generally square, 400 cm ² to about 900 cm ² sheets of treated substrate was placed in a washing machine along with a ballast sample (1.9 Kg of 8 oz fabric in the form of generally square, hemmed 8100 cm ² sheets). Conventional detergent ("TIDE", 46 g) is added and the washer is filled to high water level with hot water (49°C ± 3°C). The substrate and ballast load is washed five times using a 12-minute normal wash cycle and the substrate and the ballast are dried together in a conventional clothes dryer set on the "heat" setting for about 45 minutes. The dry substrate is pressed using a hand iron set at the temperature recommended for the particular substrate fabric.

Dry Cleaning Procedure Substrate samples designated in the examples below as "Dry Cleaned" were treated as set forth in AATCC Test Method 7-1975, note 8.1

The following describes the preparation of extenders and fluorochemical agents used in the Examples that follow. Also described below are several commercially available fluorochemical agents that are used in the Examples.

Intermediate A

2-Butanone oxime (26.1 g, 0.3 mol, available from Servo Company, the Netherlands, as SERVOXIME™ Y-250) was added at room temperature over about 30 minutes to PAPI (40.8 g, 0.3 equivalents, a polyphenylpolyisocya-nate, Upjohn, equivalent weight 136 with a chemical structure

CH, CH

NCO NCO n NCO

wherein average n = 0.7)

The reaction temperature was increased to 60°C and maintained for two hours. The reaction mixture was then diluted to 40% solids in ethyl acetate using about 86 g ethyl acetate. A clear, brown organic solution was obtained.

In a separate flask was placed MARLOWET™ 5401 cationic emulsifier (5.7 g, 10 percent by weight based on total solids, Hiils, Germany) , ethylene gylcol (35 g, 60% by weight on total solids) and deionized water (171 g, 300% by weight on total solids) . This solution was warmed to about 40°C and under very vigorous mixing added to the organic solution, also at about 40°C. A milky pre-emulsion was obtained, which was passed three times through a MANTON-GAULIN™ emulsifier at about 40°C and 300 bar pressure. The solvent was removed under reduced pressure. A slightly brown dispersion was obtained. This dispersion was diluted to 20% solids and filtered and stored.

Intermediate B 2-Ethylhexyl methacrylate (59,4 g, 0.3 mol) ,

N-methylolacrylamide (1.5 g, 0.014 mol), ETHOQUAD™ 18/25 cationic emulsifier (Akzo, the Netherlands, 3 g, about 5% by weight on total solids), tertiary dodecyl mercaptan (.15 g, about 0.25% by weight on total solids) and V-50™ initiator ([2,2'-azobis[2-methylpropanimidamide]- dihydrochloride, Wako, Japan] 0.12 g, about 0.2% by weight on total solids) and deionized water (140 g) were mixed. The mixture was deaereated and then heated at 75°C for 16 hours. A nearly transparent dispersion was obtained.

Intermediate C

A dispersion was prepared as described in U.S. Pat. No. 3,068,187 (Bolstad et al.. Example 5), containing a graft copolymer of a fluorinated monomer and a fluorine-free comonomer.

Intermediate D

A mixture of N-ethyl perfluorooctylsulfonamido- ethanol (ETFOSE, 40.8 g, 0.3 equivalents) dry ethyl acetate (100 g) and 4 drops of dibutyltindilaurate was heated at reflux (about 78°C) for 4 hours. 2-Ethylhexanol (13 g, 0.1

mol) was then added and the reation was continued at reflux for another 6 hours. A clear, brown solution was obtained. The reaction product was emulsified following the procedure described in Intermediate A above. A slightly brown dispersion was obtained, which was further diluted with water to 20% solids filtered, and stored.

Using the same synthetic procedure and emulsification method, Intermediate E was pepared. PAPI (40.8 g, 0.3 equivalent), N-methylperfluoro octylsulfonamidoethanol (44.7 g, 0.1 equivalent), and

2-butanone oxime (17.4 g, 0.2 mol) were reacted to obtain a fluorochemical urethane composition containing blocked isocyanate groups.

Intermediate F

LODYNE™ 921 C (149 g, 0.24 mol, a telomer mercaptan represented by the formula C _n F _2n+ ιCH ₂ CH ₂ SH where n = 6, 8, 10, 12, 14 . . . average n is about 10, available from Ciba-Geigy) , 2-butyn-l,4-diol (11 g, 0.13 mol) and hexafluoroxylene (100 g) were combined. The mixture was warmed to 62°C and a solution of VAZO™ 52 initiator [ (2,2'-azobis-(2,4-dimethylvaleronitrile) , 5 g, Du Pont)] in 10 g of dichloro ethane was added over a period of 4 hours. The reation was continued for 4 hours at 70°C. A hazy, slightly yellow reaction mixture was formed. Dry ethyl acetate (100 g) and trimethylhexa ethylenediisocyanate (22 g, 0.1 mol, TMDI, Bayer) were added and the reaction mixture was heated to 80°C. Dibutyltin dilaureate catalyst (0.2 g) was added. The reaction was continued for 8 hours at 95°C. DDI (51 g, 0.08 mol, dimer diisocyanate, Henkel) and methyldiethanolamine (6 g, 0.05 mol) were added. The reaction was continued at 90°C for 4 hours. A clear, brown solution was obtained. To 200 g of the solution, 101 g butyl acetate, 3.5 g acetic acid and 87 g ethylene glycol were added. The resulting organic solution was warmed to 75°C.

In a separate flask a solution of 5.2 g MARLOWET™ 5401 surfactant (about 5% by weight on total solids) in 463 g deionized water was heated to 75°C. Under vigorous stirring, this aqueous solution was added to the

organic solution. The pre-emulsion obtained was passed 5 times through a preheated MANTON-GAULIN™ emulsifier at about 70 to 75°C and 300 bar pressure. A microemulsion was obtained. All solvents were removed (at 50°C and about 5 mm Hg vaccuum) slightly brown dispersion was filtered and stored.

Intermediate G

N-Methylperfluorooctylsulfona idoethyl acrylate, (61.1 g, 0.1 mol), 2-mercaptoethanol (1.95 g, 0.025 mol), ethyl acetate 40 g and AIBN (0.12 g, 0.2% by weight on total solids) were mixed, deaerated, and heated at reflux (about 80°C) for 16 hours. The reaction mixture was cooled to room temperature. PAPI (10.2 g, 0.075 equivalent) was added together with 2 drops of dibutyltin dilaureate catalyst. The reaction mixture was heated at reflux for 5 hours. The reaction was then cooled to about 60°C and 4.35 g of 2-butanone oxime (0.05 mol) was added. The reaction was continued for 2 hours at 70°C. The reaction product was emulsified at 70°C using the procedure described in

Intermediate A. A slightly brown dispersion was obtained, filtered, and stored.

Intermediate H FC-217, a fluorochemical acrylate copolymer commercially available from 3M Company.

Intermediate I

FC-352, a fluorochemical carbodiimide containing composition commercially available from 3M Company.

Intermediate J

FC-353, a fluorochemical containing ester commercially available from 3M Company.

Intermediate K

N-Allylperfluorooctylsulfonamide (54 g, 0.1 equivalent), a polymethylhydrogensiloxane (12 g, 0.2 equivalents BAYSILONE-OL™ MH15 silicone, Bayer, of the formula

(CH ₃ ) ₃ SiO[(CH ₃ ) (H)SiO] _D Si(CH ₃ ) ₃

wherein n=40) and butyl acetate (60 g) were combined. The mixture was heated to 110°C and 1 mL of 1% solution of H ₂ Pt ₁₁₆ in 2-butanone is added. After 30 minutes Monylvinylester (2 g, 0.01 mol, VEORA™ 10, Shell) and 0.3 L of the 1% catalyst solution was added. The reaction was heated at 126°C for 1 hour. A slightly brown solution was obtained. The material was emulsified at 30°C using the procedure, ingredients, and amounts decribed in Intermediate H. A slightly brown dispersion was obtained, the pH was adjusted to 7, and the emulsifion was filtered and stored.

Intermediate L

FC-247, a composition containing a blend of a fluorochemical ester, a fluorochemical urethane, and a fluorochemical acrylate copolymer, commercially available from 3M Company.

Intermediate M FC-214, a composition containing a blend of a fluorochemical urethane and a fluorochemical copolymer, and commercially available from 3M Company.

Intermediate N FC-270, a composition containing a blend of a fluorochemical carbodiimide and a fluorochemical acrylate copolymer, commercially available from 3M Company.

Intermediate O Into a polymerization bottle was placed N-methyl perfluorooctylsulfonamidoethyl acrylate (30.6 g, about 0.050 mol, MeFOSEA) , 2-ethylhexyl acrylate (8.1, about 0.044 mol) 2-hydroxyethyl acrylate (0.7 g, about 0.006 mol) , 2 g ETHOQUAD™ 18/25 emulsifier. (Akzo, The Netherlands), tertiary dodecylmercaptan (0.2 g, 0.5% by weight on total monomers) , V-50™ initiator (2,2 ^! -azobis[2-methylpropanimidamide] , 0.08 g, Wako, Japan) , acetone (15 g) and deionized water (78 g) . The reaction mixture was deaerated and the polymerization bottle was capped and put into a launderometer at 70°C for

16 hours. The resulting nearly transparent dispersion was filtered and stored.

Intermediate P Following the procedure of Intermediate 0,

MeFOSEA, octadecyl methacrylate, and polydimethylsiloxane monomethacrylate (molecular weight of about 2000) in a molar ratio 80 to 15 to 5 were reacted. A nearly transparent dispersion was obtained.

Intermediate 0

Hexamethoxymethylmelamine (39 g, 0.1 mol, CYMEL™ 303, American Cyanamid) , a fluorochemical mercaptan with general formula C _n F _2n+1 CH ₂ CH ₂ SH (232 g, 0.4 mol, average n is about 10, average molecular weight is about 580, Atochem, France) and para-toluenesulfonic acid (0.42 g) were mixed and heated at 90°C. Methanol was evolved and removed by distillation. Over a 2 hour period the temperature was further raised to 180°C and kept at that temperature for 4 hours. After cooling to about 80°C, hexafluoroxylene solvent was added to make a 40% solids solution (in total, 348 g hexafluoroxylene was used) . A dispersion was prepared of this solution according to the procedure set forth in Intermediate F. The dispsersion was filtered and stored.

The above Intermediates were tested, according to the test methods mentioned above, by themselves and in combination with one extender or a combination of two extenders. Formulations were prepared and fabrics treated according to the general procedure set forth below:

Formulation and Treatment Procedure

A fluorochemical agent as described in Intermediates C-Q above is provided and formulated into a treatment bath containing a predetermined amount of each of the appropriate fluorochemical agent, the copolymer extender, and the blocked isocyanate extender such that the treatment can be made by a padding application at the indicated percent solids on fabric. After treatment, the substrate is dried and cured at 150°C for 10 min.

Objects and advantages of this invention are further illustrated by the following examples. The particular materials and amounts thereof recited in these examples, as well as other conditions and details, should not be construed to unduly limit this invention.

Examples 1-24 and Comparative Examples C-l to C-45

Fluorochemical agents were formulated with single extenders and combinations of extenders to treat a polyester/cotton 50/50 fabric at 0.4% total solids on fabric.

Results are shown in Table I below, wherein FC designates fluorochemical agent and weight percents indicate percent based on the combined weight of the fluorochemical agent and the extender or extenders.

TAB I fcont.)

20

20 10 10

TABLE I (cont.)

The results in Table 1 indicate that the compositions of the invention, comprising any of a wide

variety of fluorochemical agents in combination with a member of each of the two extender classes, give superior results compared to the compositions of the Comparative Examples comprising only one extender. Superior oil and water repellencies were obtained, and fluorine efficiency was improved relative to the Comparative Examples.

Examples 25-42 and Comparative Examples C-46 to C-72

As described in connection with Examples 1-24 above, formulations were prepared and used to treat 100% cotton fabrics at 0.6% total solids on fabric.

TABLE II

Weight % Weight % Weight Extender 1 Extender 2 Initial 5 Laund 1 Dryclean

EX. FC (Int. B) (Int. A) OR SR OR SR OR SR

Fluorochemical: Intermediate C

C-46 100

C-47 80 20

C-48 80 20

25 80 10 10

26 70 20 10

Fluorochemical: Intermediate D

20 10 10

Fluorochemical: Intermediate F

20 10 10

TA II tcont.ϊ

Fluorochemical: Intermediate H

Fluorochemical: Intermediate I

0 0

0 50

0 70

1 70 0 60

Fluorochemica

Fluorochemical: Intermediate O

TABLE II (cont.1

Fluorochemical: Intermediate 0

4 90 3 70

20 — 5 90 3 80

2- 4 100 3 90

10 10 5 100 4 90 20 10 4 100 4 90

The results in Table II indicate that some compositions of the invention afford superior results and increased fluorine efficiency compared to the corresponding compositions of the Comparative Examples even on cotton, a fabric known to be difficult to treat effectively.

Various modifications and alterations of this invention will become apparent to those skilled in the art without departing from the scope and spirit of this invention. It should be understood that this invention is not to be unduly limited to the embodiments set forth herein.