CA2259364A1 - Water-based sulfonated polymer compositions - Google Patents

Abstract

A method for the preparation of sulfonated polymer compositions wherein water dispersible isocyanate-terminated polyurethane prepolymers are reacted in the presence of aqueous polyvinyl dispersions which may contain active hydrogen atoms. The invention is further directed to a water-based sulfonated polyurethane polyvinyl hybrid latex wherein a sulfonated polyurethane is used as a seed for the polymerization of ethylenically unsaturated monomers and a method for preparing the same. The inventive compositions develop interpenetrating polymer networks or may form core-shell type structures, and are characterized as having enhanced mechanical and adhesion properties.

Description

W O 98/06768 PCTrUS97114386 WATER-BASED SULFONATED POLYMI~R COMPOSITIONS

Field Of The Invention r This invention relates to water-based poly~ners, specifically to a method S for the ~lepa.dLion of water-based sulfonated polymer compositions having enh~nt~ed mechanical and adhesion ~vpellies.

Rq~l~round Of The Invention There are several patents which disclose the ~le~ lion of water-based sulfonated polymer compositions:
U.S. Pat. No. 5,334,690 (Hoechst Aktiengesellschaft) discloses water-based sulfonated polyule~ e-urea polymers which can be combined with and are in general compatible with other aqueous polymer dispersions.
U.S. Pat. No. 4,888,383 (E.I. DuPont De Nemours and C~ ~ly) discloses a process wher,~in water-based polyurethane-urea modified acrylic polymers are p~cpared by reacting amine and/or hydrazide functional polyacrylic polymers withisocyanate t~rmin~te~l polyurethane prepolymers.
U.S. Pat. No. 4,491,646 (Ashland) discloses adhesives wherein hydroxyl functional polyvinyl polymers are blended with water dispersible polyfunctional iso-;y~,ale~.
Other related patents include U.S. Pat. No. 5,371,133 (National Starch), U.S. Pat. No. 5,200,463 (Huels), U.S. Pat. No. 5,204,404 (DuPont), U.S. Pat. No.5,173,526 (Air Products & Chemicals, Inc.) and U.S. Pat. No. 5,071,904 (PPG).

S~mr-:lry Of The Invention The present invention discloses water-based sulfonated polymer compositions comprising:
A) at least one water-based sulfonated polyurethane-urea polymer compri~in~:
1) at least one polyisocyanate; and 2) at least one sulfonated polyester polyol wherein the sulfonate groups are present in the form of alkali metal salts;

B) at least one aqueous polyvinyl dispersion compri~ing;
1) at least one ethylenically nncz~ r~te~1 monomer;
2) and optionally, at least one free radically reactive protective colloid c~ mpri~in~ active hydrogen atoms, and optionally, C) at least one sulfonated polyurethane-vinyl polymer composition which is the reaction product of, I) at least one isocyanate-t~",li~ d polyurethane prepolymer CO~
a) at least one polyisocyanate; and b) at least one sulfonated polyester polyol wherein the snlfon~te groups are present in the form of alkali metal salts, with 2) an aqueous polyvinyl dispersion comprixin~;
a3 at least one ethylenically l-.-x~ tPd monomer, and 1 5 optionally, b) at least one free radically reactive protective colloid compri~in~ active hydrogen atoms.
Su~prisingly, the sulfonated polymer compositions have enhanced me~h~nical and adhesion ~lu~ Lies and show stability at pH values greater than about 20 2Ø It is sllrmi~ecl that some of these unique properties can be attributed to the development of interpenetrating polymer n~ Lv~ lks and the sulfonate character located in the polyol segm~nt of the polyu,eLlla~e polymer.
The illV~ iVe compositions are useful as adhesives, binders, coatings and primers on any substrate including paper, wood, metals, concrete, glass, cloth and 25 synthetic polymers, and are useful in applications including fiber grass sizing, woodworking, automotive, film l~minslting and in the m~nllfs~cture of shoes.
In another aspect, the present invention discloses a method for the preparation of sulfonated polymer compositions wherein isocyanate t~nnin~ted polyurethane prepolymers are dispersed in a~ueous polyvinyl dispersions which may 30 contain primary amines, secondary ~min~s, p~ laly hydroxyl groups, secondary hydroxyl groups and form~mi-le groups. The method comprising:

CA 022~9364 1998-12-29 W O 98/0676X PCTrUS97114386 A) forming a water dispersible isocyanate-t~rmin~tef1 polyurethane prepolymer by rç~qcting;
1) at least one polyisocyanate; and 2) at least one sulfonated polyester polyol wherein the sulfo groups are present in the form of aLkali metal salts;
B) forming an aqueous polyvinyl dispersion by free radically polymeri_ing;
1) at least one ethylenically unsaturated monomer; and optionally, 2) at least one free radically reactive protective colloid cc-mpri.~in~
active hydrogen atoms; and then 10 C) dispersing the product of A) into B).
In another aspect, the present invention discloses a water based sulfonated polymer composition and a method of making the same by seed emulsion polymeri7~tion. The composition comprises the reaction product of:
a) at least one sulfonated polyurethane dispersion;
b) at least one aqueous ethylenically unsaturated monomer pre-emulsion comprising at least one ethylenically unsaturated monomer; and c) an initi~tor.
The method of p~p~ing the same comprises the steps of:
a) forming an aqueous pre-emulsion comprising at least one ethylenically unsaturated monomer pre-emulsion comprising at least one ethylenically ullsaLuldl~d monomer and op$ionally at least one snrf~-t~nt and b) reacting said aqueous pre-emulsion with at least one sulfonated polyurethane dispersion optionally in the presence of an initi~tor solution and optionally in the presence of a reducer solution.
In another aspect, the present invention discloses a polyurethane/polyvinyl hybrid latex and a method of making the same by seed emulsion polymerization. The hybrid latex comprises the seed emulsion polymerization reaction of:
a) at least one sulfonated polyulc;Lll~ e dispersion, the polyurethane serving as a seed;

WO 98/067~8 PCT~US97/14386 b) at least one aqueous ethylenically un~,aLul2lt~d monomer pre-emulsion comprising at least one ethylenically ~lnczttnr~tec~
monomer; and at least one free radical; . .;

Brief Description of the D. ~ o~
Figure 1 is a graph showing the seed polyu~ e particle size distribution (dotted line) as a fimction of the final hybrid latex particle distribution (solid line), for the latex (water based sulfonated polymer composition) prepared in Example 6.
Figure 2 is a graph showing the seed polyurethane particle size distribution (dotted line) as a function of the f~al hybrid latex particle distribution (solid line), for the latex (water based sulfonated polymer composition) prepared in Example 7.

15 Detailed Descrip~ion Of The l~vention The sulfonated polymer compositions have enhanced mechz~nic z~l and adhesion properties colllpaled to their corresponding water-based sulfonated polyurethane-urea polymers, aqueous polyvinyl dispersions and their simple blends. For the purposes of the present application, polyvinyl dispersions include dispersions of 20 addition polym~ri~zltion products of ethylencially unsaturated monomers including, but not limited to (meth)acrylate monomers. Also, polyurethane refers in the presentapplication to a polymer co..~ ;t-g more than one urethane group and is int~n-1e~ to include polyurethanes contztining urea groups as well (polyurethane-ureas). It is sllrmi~ed that some ofthese unique plo~c~lies can be atEributed to the formation of 25 interpenetrating polymer networks. The term "interpenetrating polymer n~;L~c ,1~'' is defined as a cros~linked and/or semi cro~linke~l system comprising at least two similzlr or different polymers. IPNs are further described in the "Handbook of Adhesives", Irving Skeist, 3rd edition, chapter 1, page 18, Van Nostrzmd, NY, 1990.
For the the purposes of the present application, "hybrid" denotes a 30 polymer comprised of two or more ~ imilzlr polymers. The ~ Similz1r polymers may or may not be covalent linked.

CA 022~9364 l998-l2-29 W 098/06768 PCT~US97/14386 s In the present invention, when isocyanate-termin~t~cl polyurethane prepolymers are dispersed in aqueous polyvinyl dispersions, which may contain active hydrogen atoms such as primary amines, secondary ~min~c, primary hydroxyl groupsand secondary hydroxyl groups, the isocyanate Lt~ ecl polyurethane prepolymer 5 dispersions interact with the aqueous polyvinyl dispersions to form IPNs and cro~link~(l networks. The frequency of such int~r~ctions can be influenced by the quantity of isocyanate and active hydrogen atoms present in the respective polymer dispersions. It is possible to increase the crosslink density using a structured aqueous polyvinyl dispersion wherein active hydrogen atoms are distributed on the surface of the particle. A
10 structured particle can be generated when ethylenically uns~ Lled monomers, co~ls-i " i I ~p; active hydrogen atoms, are added at the end of the free radical emulsion polymerization process. It is believed that such a particle morphology improves the collision frequency of the isocyanate/active hydrogen atom reaction to increase the composition's crosslink density.
The dispersed particles can contain a complex mixture of polymers consisting of sulfonated polyurethane-urea polymers, polyvinyl polymers and sulfonated polyurethane-vinyl polymers. The complex particle llliX~Ul~S can be formed when subst~nti~lly ~ imil~r or substantially dirr~ lll polymers diffuse and interact or crosslink with adjacent particles. Such diffusion processes may generate particles having 20 polyrners within the particle that are different when compare with polymers on the surface of the particle. Examples include particles having substantially polyvinyl based polymers on the surface of predominantly polyurethane-urea based particles or substantially polyurethane-urea based polymers on the surface of predo. . . i ~ y polyvinyl based particles. Such surface layers may be continuous or non-continuous and 25 can vary in thickness. If a particle's surface layer has a substantial thickness, as well as being continuous, then the particle approaches a core-shell type structure.
The isocyanate-t~rrnin~te-l polyurethane prepolymers of the present invention may be formed using monoisocyanates and polyisocyanates. The isocyanates may be linear aliphatic, cyclic aliphatic, aromatic and ll~ixLu~t;s thereof. Exarnples of 30 commercially available polyisocyanates include V~st~n~t6i) IPDI which is isophorone diisocyanate from HULS America Inc. (PiscaL~w~y, NJ), TMXDT(~) which is W 098/06768 PCTnUS97/14386 tetramethylxylene diisocyanate from Cyanarnid (Wayne, NJ), Luxate~ HM which is he~methylene diisocyanate from Olin Corporation (Starnford, CN), diphenylmethanediisocyanate from Upjohn Polyrner Chemicals (~ 7~o~ MI), Desmodur(g) W which is dicyclohexylmethane-4,4'-diisocyanate from Bayer Corporation (Pittsburgh, PA) and S toluene diisocyanate CIDI). The preferred diisocyanates are hP~methylene diisocyanate, isophorone diisocyanate and their lllixlw. s.
If des*ed, small guantities of polyisocyanates which have an isocyanate content greater than 2.1 may be used. Additionally, modified polyisocyanates which are prepared from hexamethylene diisocyanate, isophorone diisocyanate and toluene 10 diisocyanate may also be used. Said polyisocyanates can have functionalities including urethanes, uretdiones, isocyanurates, biurets and mixlulcs thereof.
The sulfonated polyester polyol component used in the preparation of the isocyanate-t(~rminzlt~?-1 polyurethane prepolymer can have hydroxyl numbers, as det~rmint~-l by ASTM tiesi~n~tion E-222-67 (Method B), in a range from about 20 to about 140, and preferably from about 40 to about 110. The polyols may be forrned ~,vith components such as diacids, diols, sulfonate diols and sulfonate diacids. Such polyols and their pl~dLion are further described in U.S. Pat. No. 5,334,690, incorporated herein by reference. The ~l~rt;;ll~ d sulfonated polyester polyols are based on 5-sulfoisophthalic acid monosodium salt, adipic acid and 1,6-hexanediol and/or diethylene 20 glycol. It is believed that the sulfonate character, which is present in the polyol segment, enhances the polymer's dispersibility and stability at reduced pH.
Optionally, non-sulfonated polymeric diols may be used in combination with the sulfonated polyester polyols. Such polyols may have lly~o~yl numbers in a range from about 20 to about 140, and preferably from about 40 to about 110. The non-25 sulfonated polymeric polyols may include polyester polyols, polyether polyols,polycarbonate polyols, polyu~ e polyols, polyacetal polyols, polyacrylate polyols, polycaprolactone polyols, polye~ .ide polyols, polythioether polyols, and mixtures thereof.
Alkylene diols may also be used in the pr~udlion of the isocyanate -3Q tf rtninzlte(1 prepolymers. The alkylene diols may have hydroxyl numbers in a range fromabout 130 to about 1250, and preferably from about 950 to about 1250. The ~IcÇellcd CA 022~9364 1998-12-29 W O 98/06768 PCTrUS97/14386 alkylene diols include 1,4-butanediol, 1,6-hexanediol and 2-methyl-1,3-propanediol and may be present in the isocyanate t~rmin~e~l polyurethane prepolymer in a range from about 0.1% by weight to about 10.0% by weight, and preferably from about 0.5% byweight to about 5.0% by weight, based on 100 parts of total prepolymer solids.
Higher functional polyols may be used in the pl~ation of the polyul~Lll~le-urea polymers. Suitable examples include glycerol, trimethylolpropane, 1,2,4-butane triol, I ,2,6-hexane triol and mixtures thereof. The pL~r~ d higherfunctional polyol is trimethylolpropane. Said polyols may be present in a range from about 0.1% by weight to about 1.0% by weight, and preferably from about 0.3% by 10 weight to about 0.7% by weight, based on 100 parts oftotal isocyanate-t~rmin~ht polyurethane prepolymer solids.
Optionally, dihydroxy carboxylic acids may be used when pl~ g the isocyanate-t~rrnin~te~l poly~LIeLll~le prepolymer. A preferred dihydroxy carboxylic acid is dimethylolpropionic acid. The dihydroxy carboxylic acid component may be present 15 in a range from about 0.05% by weight to about 1.0% by weight, and preferably from about 0.2% by weight to about 0.5% by weight, based on 100 parts total polyult;lll~le prepolymer solids.
~eutralization of the dihydroxy carboxylic acid groups can be accomplished with compounds such as alkali metal hydroxides, organic tertiary ~mines, 20 ammonia and mixtures thereof. Preferred neutralizing agents are sodium hydroxide and triethylamine. Conversion of the acid groups to ionic groups (salts) can be accomplished before, or at the same time, that, the isocyanate terrnin:~te-l polyurethane prepolymer has been dispersed in the polyvinyl dispersion mixture.
The isocyanate-t~rmin~t~fl polyurethane prepolymer is prepared by 25 reacting a stoichiometric excess of polyisocyanate with said polyol components. The reactants are in such proportions that the resulting percent isocyanate may be in a range from about 1.0% by weight to about 10.0% by weight, and preferably from about 2.0%
by weight to about 5.0% by weight, based on 100 parts total of isocyanate terrnin~t~cl polyurethane prepolymer solids. The prepolymers may be processed at tempcldlules in 30 a range from about 30~C to about 110~C, and preferably from about 65~C to about 85~C.
Additionally, small quantities of catalysts may be used to accelerate the CA 022~9364 1998-12-29 W O 98/06768 PCT~US97114386 hydroxy/isocyanate reaction. The catalysts can be present in a range from about 0.05%
by weight to about 2.0% by weight, and preferably from about 0.13% by weight to about 0.15% by weight, based on 100 parts total isocyanate-tPrminzttc~l polyurethane prepolymer solids. An exarnple includes MetacureTN' T-12 w~tich is an organic tin S compound from Air Products and Chemicals, Inc. (Allentown, PA).
The ethylenically lln~t~lr~ted monomers can include monow~s~ dLed monomer~, polyunsaturated monomers and ~ wes thereof. Examples include methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, n-propylacrylate, iso-propyl acrylate, methyl methacrylate, butyl methacrylate, vinyl acetate, vinyl propionate, vinyl 10 ethers, ethylenically unsaturated filmPr~Ps, ethylenically wl~aLul~led maleates, styrene, acrylonitrile, acryl~tmi~les, but~tnediol diacrylate, hP.sc~n~liol diacrylate, ethylene glycol dimethacrylate, trimethylolpropane triacrylate and pentaerythritol triacrylate.
Et_ylenically unsaturated monomers co~ it~g anionic and/or ionic groups can be used. Examples of such monomers include acrylic acid, methacrylic acid, 15 fumaric acid, crotonic acid, itaconic acid, mesaconic acid, maleic acid, citraconic acid and/or their corresponding ionic groups. Said monomers may be in a range from about 0.1% by weight to about 25.0% by weight, and preferably from about 0.1% by weight to about 10.0% by weight, based on 100 parts total composition solids.
Ethylenically unsaturated monomers co~ g active hydrogen atoms 20 may also be used. The term "active hydrogen atoms" refers to hydrogens which display activity according to the Z~cwiLilloff test as described by Kohlerin, J. Am. ~*em. Soc., 49, 3181 (1927). Examples include hydroxyethyl acrylate, allyl alcohol, allyl amine, N-methylol acrylamide, mono-acrylic acid esters of glycols, itaconic acid and methyl-3-arninocrotonate .
Amine and hydroxyl functional protective colloids may be used to ~ e the aqueous polyvinyl dispersion of the present invention Suitable examples include the water dispersible polyvinyl alcohol-copoly(vinyl amine) polymers described in EP0599245 assigned to Air Products and Chemicals, Inc. (Allentown, PA). Such protective colloids may have an amine content in a range from about 0.5 meq. amine/gram to about 30 3.5 meq. amine/gram, and preferably from about 1.0 meq. amine/gram to about 3.0 meq.
arnine/gram. The number average molecular weight may be in a range from about CA 022~9364 1998-12-29 W O 98/~6768 PCTrUS97/14386 10,000 grams/mol. to about 350,000 grams/mol., and preferably from about 30,000 grams/mol. to about 250,000 grams/mol. Said colloids can be present in a range from about 0.1% by weight to about 20.0% by weight, and preferably from about 0.5% byweight to about 5.0% by weight, based on 100 parts total polyacrylic solids. It is 5 assumed grafting reactions occur during the emulsion polymer;7~tion process. The graft copolym~ri7~tion process is further described in "Polyvinyl Alcohol Developments", edited by C.A. Finch, John Wiley & Sons, New York, 1992, pp. 449-453.
Specialty monomers may also be incorporated into the aqueous polyvinyl dispersions and include the amino organo-silane coupling agente described in U.S. Pat.
No. 4,745,02g (PPG) and U.S. Pat. No. 5,236,982, (Owens-Corning), the imidazolidinone functional wet adhesion monomers described in U.S. Pat. No.
5,496,907, (H.B. Fuller Co., St. Paul, MN) and the Vinzlmern EF monomer which is N-ethenylform~mi~1e from Air Products Chemicals, Inc. (Allentown, PA).
When Vinamer EF ~onomers are incorporated into the agueous polyvinyl 15 dispersions, the bound ro~ a~ide group may be hydrolyzed to a primary amine using catalysts such as bases or acids including sodium hydroxide, hydrochloric acid and sulfuric acid. The resulting arnine functional polyvinyl can then be used as a reactive component in the process of the present invention.
The aqueous polyvinyls can be formed using m~t~ri~le and free radical 20 polymerization processes known in the art. For example, the free radical initiators, used in the addition polymerization process, may be water soluble, oil soluble or ~ Lules thereof. Exatnples include hydrogen peroxide, sodium persulfate, potassium persulfate, ammonium persulfate, 2,2-azobis (2,4-dimethylpents~n~nitrile), 2,2-azobis (2-methylpropanenitrile) and mixtures such as t-butylhydroperoxide, Fe-EDTA and 25 isoascorbic acid. Said initiators may be present in amounts from about 0.05% by weight to about 1.5% by weight, and preferably from about 0.1% by weight to about 0.5% by weight, based on 100 parts total solids. Also, oxicii7~ng catalysts may be used independently or in combination with reducing agents such as sodium forn ~ ehyde-sulfoxylate, ferrous salts, sodium dithionite, sodium hydrogen sulfite, sodium sulfite and 30 sodium thiosulfate. The redox catalysts may be present in amounts from about 0.05% by weight to about 1.5% by weight, preferably from about 0.1% by weight to about 0.5% by CA 022~9364 1998-12-29 weight, based on 100 parts total solids.
The ethylenically unsaturated monomers are polymerized using free radical polymerization techniques known in the art. The free radical initi~tors can be added all at once, slowly over time or as a partial initial charge with the r~mz~in-l~r being added slowly over time.
Free radical polym~ri7~tion may be conducted at tempc~dlul~s in a range from about 5~C to about 85~C, and preferably from about 25~C to about 80~C.
The water-based sulfonated polymer compositions of the present invention are formed using a method wherein isocyanate-tf rmin~ted polyulel~
prepolymers are dispersed in an aqueous polyvinyl dispersion which may contain primary ~mine~, secondary amines, primary hydroxyl groups~ secondary hydroxyl groups and form~mide groups. It is also possible to disperse the isocyanate-termin~7tefi polyurethane prepolyrner in water and then immerli~tely blend with the aqueous polyvinyl dispersion. Optionally, the aqueous poly~inyl dispersion may be added to a neat or water dispersed isocyanate-termin~t~d polyurethane prepolymer. The ~ imilz~r polymers are suitably combined at temperature in a range from about 25~C to about 95~C, preferably from about 45~C to about 75~C.
If amine functional aqueous polyvinyl dispersions are used, the polymer components may be blended using an equivalence ratio of amine active hydrogen toisocyanate in a range from about 1:10 to about 10:5, and preferably from about 1:5 to about 5:1.
If desired, water soluble compounds co.,~ primary and/or secondary amines may be reacted with the polymer mixture of the invention. Suitable examples include monoethanolamine, ethylen~ mine, diethylene triamine and ammonia.
The water-based sulfonated polymer compositions may have viscosities in a range from about 10 mPa.s to about 1,000 mPa.s, and preferably from about 10 mPa.s to about 500 mPa.s. The particle size distribution may be monomodal or multimodal and generally will have a mean diameter in a range from about 0.01 microns to about 2.0 mlcrons.
The water-based sulfonated polymer compositions may have a solids content in the range from about 20% by weight to about 70% by weight, and preferably CA 022~9364 1998-12-29 from about 3 5% by weight to about 55% by weight of the total composition.
The dried sulfonated polymer compositions may have single or multiple glass transition (Tg.) telllptildLul~;, in a range from about -100~C to about +200~C.
The present invention is also directed to a water based sulfonated polymer composition which may be used, inter alia, for fiberglass sizing and a method for m~kin~
the same. The water-based sulfonated polyuleLhalle polyvinyl hybrid latex of the present invention comprises the reaction product of at least one sulfonated polyurethanedispersion, at least one aqueous ethylenically uns~Luldl~d monomer pre-emulsion comprising at least one ethylenically ~uls~LuldL~d monomer and at least one free radical 10 initiator, such as those disclosed above.
The present invention is also directed to a water-based sulfonated poly~ner composition comprising particles, the particles comprising a core and a surface wherein the core and surface comprise substantially dirr~ l~lll polymers, the core comprising at least one polymer selected from the group con~i~tinp of sulfonated polyurethane 15 polymers and sulfonated polyurethane-urea polymers and l~ ules thereof, the surface comprising predomin~ntly polyvinyl polymers. The composition may be formed from the free radical seed emulsion polymeri7~tion of at least one ethylencially unsaturated monomer in the presence of a sulfonated polyurethane or polyu,cLh~lle-urea dispersion, the polyuleLlla~le serving as a seed.
Sulfonated polyurethane dispersions such as those been disclosed in U.S.
Pat. No. 5,608,000 (Duan et al.), U.S. Pat. No. 5,610,232 (Duan et al.) are suitable for use in the present invention. Two sulfonated polyurethane dispersions which are embo~1iment~ of the above inventions, NP-4062-M or NP-4073, both of which are produced by the H.B. Fuller Company, are particularly suited for use in the present 25 invention although other sulfonated polyurethane dispersions may be used as well including sulfonated polyurethane-urea dispersions.
The aqueous ethylenically unsaturated monomer will preferably be chosen from among acrylate monomers, (meth)acrylate mon~ mer.c, (meth)acrylic monomers,vinyl monomers, allylic monomers, acrylamide monomers or ~ Lules thereof.
30 Examples include methyl acrylate, ethyl acrylate, isobutyl acrylate, n-propylacrylate, iso-propyl acrylate, butyl methacrylate, hç~nç-liol diacrylate, ethylene glycol dimethacrylate, trimethylol~l.,p~ule triacrylate and pentaerythritol triacrylate and lllixLul~;s thereof. Preferably, the emulsion comprising the monomer will comprise methyl meth~rrylate, n-butyl acrylate, hydroxy ethyl methacrylate and mixtures thereo~
However, any of the ethylenically unsdluldl~d monomers mentioned above such as 5 ethylenically lm~tllr~ted monomers cornpricing anionic and/or ionic groups, orethylenically unsaturated monomers cont~ining active hydrogen atoms may be used as well. A suitable s-lrf~- t~nt such as Pluronic L64 (m~mlf~ctured by BASF) or a combination of surfactants may be used in ple~ g the pre-emulsion In one embodiment the ratio of sulfonated poly~Lllalle solids to polyvinyl solids is from about 9:1 to about 1:9. Preferably, the ratio is from about 4:1 to about 1:4 and most preferably, the ratio is from about 4,1 to about 2:1.
The present invention is also directed to a water-based sulfonated polyurethane polyvinyl hybrid latex comprising polyurethane polyvinyl particles wherein the average particle size is at least 200 nm.
The water-based sulfonated polymer compositions formed via the seed emulsion polymeri7~tion are characterized by high lap shear strengths of at least about 350 psi.
The present invention is also directed to a method for plt;~ g the above-mentioned polyurethane polyvinyl latex hybrid. The method comprises the steps 20 of forming an aqueous pre-emulsion compri~ing at least one ethylenically lmc~tllrs~te~l monomer, the pre-emulsion compri~ing at least one acrylate and optionally a sllrf~rt~nt and reacting the aqueous pre-emulsion with at least one sulfonated polyurethane dispersion in the presence of at least one free radically ini~i~tr,r.
The aqueous polyvinyl pre-emulsion may be formed by dispersing 25 ethylenically ull:idluldled monomers in water, with a surfactant and ~git~ting the mixture.
The pol~ u~ haue polyvinyl latex dispersion is then formed by adding an initiator solution such as t-butyl hydrogen peroxide, a reducer solution such ashydrosulfite and the pre-emulsion to a polyurethane dispersion. ~ltrrn~tively, the initi~tr,r may already be present in the pre-emulsion or in the polyurethane dispersion.
30 The rnixture is allowed to react over a period of time at a t~ dlllre between 50~C and 100~C, preferably at 65~C.

CA 022~9364 l998-l2-29 W O 98/06768 PCTrUS97/14386 The characteristics of the water-based sulfonated polymer compositions may be modified by the addition of compounds including surfactants, defoaming agents, coalescing aids, fungicides, bactericides, polyfunctional cro~linking agents, plasticizers, thickenin~ agents, fillers, pi~ment~, reactive pi~ment~, dispersing agents for the S pigments, colors, perfume-like m~teri~l~, W stabilizers, seqllest~?ring agents, waxes, oils, fire lel~dail~ agents and organic solvents. Such materials may be introduced at any stage of the production process.
The present invention is further illustrated by the following examples.

EXAMPLI~S
In the examples, the following test methods were used.
Tensile Strength and ElongatiQn The polymer dispersions were cast to generated dried films having a thickness ina range from about 20 mils. to about 40 mils. Type V dogbones were cut with a Dewes 15 Gumbs Die and conditioned at least 24 hours in an environment having 50% relative hllmitlity at 23~C. The samples were run using ASTMD-638 at a crosshead speed of 5.0 cm./min.
Shear Strength:
The polymer dispersions were coated on steel, acrylonitrile-butadienestyrene (ABS) and glass then dried 24 hours. Like substrates were mated using hand ~les~ e then heat activated at 70~C for 30 minlltes- The samples, which has a bond area of 0.5 x 1.0 inches, were run using ASTM-D-1002 at a crosshead speed of 1.27 cm/min.
Peel Sll . ~h Peel strength was measured as follows. A precut sheet (10.5 x 12.75 inch) of 10 mil thick clear, pressed, polished PVC was cleaned with isopropyl alcohol and placed on a glass or alnminllm plate co~ g a small amount of isopropyl alcohol.
Excess isopropyl alcohol was removed to produce a good seal. The exposed PVC
surface was wiped with isopropyl alcohol. An adhesive film, dispensed from a film applicator set to S mils, was cast over the PVC sheet, according to the method of ASTM
30 specification D323-87. The adhesive was allowed to dry at ambient temperature. A
second sheet of PVC, cleaned similarly to the first sheet, was placed over the first coated W O 98/06768 PCT~US97114386 PVC sheet. The PVC adhesive sandwich was cut into 1 inch strips and allowed to dry over 2 hours.
The strips were placed into a heat sealer with the uncoated PVC in contact with the upper platen, the upper platen having been preheated to 1 90~F and with a 5 ~ c; setting of 50 psi. Following a 30 second dwell time, the temperature at the bond line was 1 60~F. A . " i l ,i,, .. ~ of 6 bonds per strip were heat sealed with a total bond area of 1 inch by 7 inches with 1.5 inches of no bond on both ends.
The bonds were allowed to age at ambient temperature for 1 to 2 hours and 1 week prior to testing. Testing was performed on a Thwing Albert Intellect 500 with a cross head speed of 12 inches per minute, a 1 inch prepeel and 3 inches of recorded peel.
Lap Shear Strength:
The sample was coated on glass and allowed to dry ov~rni~ht The bond area was 0.5xl.0 in2. The lap shear satnple was m~int~ined at 160~F for 30 mimltes Lap shear strength was then measured using ASTM D-1002 with a crosshead speed of 0.5in/mimlte. The measurement was made under an ~llvh~ cnt of 50% relative humidityat a temperature of 23 ~C.

F~s-ml le 1:
This example describes the pl~pdld~ion of a water-based sulfonated polyurethane-vinyl polymer composition. The composition and its pl op~,~ lies are compared to its corresponding polymer components.

Compound lA
Compound lA is an aqueous polyvinyl dispersion prepared with a reactive emulsifying agent which is polyvinyl alcohol/polyvinylamine copolymer (PVOE~-PVAM) from Air Products & Chemicals, Inc. (Allentown, PA3.
(I) Reactor char~e Grams PVOH/PVAM (6% vinyl amine, medium M.W.) 1.50 De-ionized water Acetic acid 350.00 Acetic acid 0.30 CA 022~9364 l998-l2-29 W O 98/06768 PCTrUS97114386 (2) Pre-emulsion Methyl Methacrylate 155.00 N-butyl acrylate 145.00 Methacrylic acid 3.90 Thiolacetic acid 0.10 (3) DelaYed Sllrf~t~nt feed T-Det 0-407 from Harcros 7.50 De-ionized water 30.00 (4) Initiator feed T-butyl hydroperoxide 1.28 De-ionized water 20.00 (5) Reducer feed Sodium formaldehyde sulfoxide 0.92 De-ionized water 20.00 To a reactor equipped with an agitator, thermometer, con~len~r and nitrogen purge was added reactor charge (1). The mi~ul~ was heated to 65~C and it:~te~l for 30 mimltes While m~ g the reaction tel~ d~ule at 65~C, the pre-emulsion (2) and surfactant feed (3) was added over a 3 hour period. The initiator feed (4) and reducer feed (5) were added over a 3.5 hour period. Once all the materials were added, the dispersion was heated an additional 30 minllt~s. The polymer had a solids 25 content of 33.2% and a p~ of 2.65.

Compound lB
Compound 1 B is a water-based sulfonated polyurethane-urea polymer.
A reactor was charged with 4.5 grams (0.099 hydroxyl equivalence) 2-methyl-1,3-propanediol and 95.4 grams (0.093 hydroxyl equivalents) molten Rucoflex~).
XS-5570-55 which is a sulfonated polyol from Ruco Polymer Corporation based on 5-sulfoisophthalic acid monosodium salt (4% by weight), adipic acid and diethyleneglycol. The ll~ ul~ was charged with 39.96 grams isophorone diisocyanate, eye drop of dibutyl tin dilaurate and heated to 80~C for 2 hours to produce an isocyanate-termin~te~l polyurethane prepolymer.

CA 02259364 l998-l2-29 The reslllting isocyanate-t~rmin~tecl polyurethane prepolyrner was dispersed in 247.0 grams de-ionized water at 70~C, using mild agitation, and heated an additional 2 hours at 65~C.
Compound lC
Compound lC is a water-based sulfonated polyurethane-vinyl polymer.
139.86 grams of a isocyanate-t~orrninsit---l polyurethane prepolymer, (prepared in the manner of compound lB), which had a temperature of 80~C, was dispersed in 139.86 grarns de-ionized water and ~gihted for 5 i"i"~ The dispersed prepolymer was charged with 341.5 grams of an amine and hydroxyl functional polyvinyl dispersion 10 (Compound lA). The mi~ t; was agitated and heated to 65~C for 2 hours. The water-based sulfonated polyurethane-vinyl polymer had a solids content of 40.2% and a pH of 6.4.
The compounds were tested for tensile strength, elongation and shear strength on glass, steel and acrylonitrile-butadiene-styrene copolymers (ABS). The 15 results are provided in Table I below:

Table 1. Tensile Strenth, clc gS~tiq and shear strength Compound Tensile ~i~n~ptif~n ShearSti-ength (Kgs./cu.cm.) Strength (~/0) (Kgs./cu.cm) Steel/Steel Glass/Glass ABS/ABS
Compo-ln~l lA 117.40 1,020 20.38 18.98 40.07 Compound lB 60.45 3,810 18.98 21.79 26.71 Compound lC 75.92 1,680 33.04 40.07 39.36 Compound IA 44.29 1,130 21.79 26.71 37.26 and lB (50/50 Blend~

The data shows the sulfonated polyurethane-vinyl polymer (Compound CA 022~9364 1998-12-29 W 098/06768 PCT~US97114386 lC) has enhanced mechanical ~lupel~ies compared to the blend of Compound lA and lB. The data also shows Compound lC has enh~n-e~l adhesion properties compared to Compound lA, Compound lB and their 50/50 blend, thus showing the utility ofthe invention.
s F~s-ml~le 2:
This exarnple describes the ~l~d~ion of a water-based sulfonated polyurethane-vinyl polymer using vinyl acetate. The inventive polymer properties are compared to its corresponding polymer components.
Compound 2A
Compound 2A is an aqueous polyvinyl acetate dispersion using a reactive emulsifying agent, which is polyvinyl alcohol-polyvinylamine copolymer (PVOH-PVAM), from Air Products & Chemicals, Inc. (Allentown, PA).
The polymer was pl~_~alcd as described in Example 1 (Compound lA) with the exception that the pre-emulsion contained 265.0 grams vinyl acetate, 35.0 grams n-butyl acrylate, 3.9 grams methacrylic acid and ~).10 grams thiolacetic acid. The reslllting polymer dispersion had a solid content of 33.6% and a p~I of 2.5.

Compound 2B
Compound 2B is a sulfonated polyurethane prepolymer.
The polymer was prepared exactly as described in Example 1 (Compound lB).

Compound 2C
Compound 2C is a water-based sulfonated polyurethane-vinyl acetate polymer.
139.86 grams of an isocyanate-termin~tefl polyurethane prepolymer prepared in the manner of compound lB but before dispersion, which had a temperature of 80~C, was dispersed in 247 grarns de-ionized water (70~C) and ~git~t~l for approximately 10 minlltes. The dispersed prepolymer was charged with 341.5 grams of the amine and W 098/06768 PCT~US97/14386 hydroxyl functional polyvinyl dispersion described as Compound 2A. The mixture was mildly ~3~it~e-1 and heated to 65~C for 2 hours. The resulting water-based sulfonated polyul~Lllalle-vinyl acetate polymer composition had a solids content of 35.5% and a pH
of 6.5.
The compounds were tested for tensile strength, elongation and shear strength on glass, steel and acrylonitrile-b~lt~1iene-styrene copolymers (ABS). The results are provided in Table 2:

Table 2. Tensile Strenth, elongation and shear strength - Compound Tensile Elongation ShearStrength (Kgs./eu.cm.) Strength (~/0) ~Kgs./cu.cm) Steel/Steel Glass/Glass ABS/ABS
Compound2A 131.46 330 9.14 3.51 16.17 Compound 2B 60.45 3810 21.79 21.79 26.71 Compound 2C 120.91 1,190 26.71 32.33 34.45 Compo~md 71.00 920 18.28 33.74 47.10 2Aand 2B
(50/50 Blend) The data shows the sulfonated polyurethane-vinyl acetate polymer (Compound 2C) has enhanced m~ch~nical pl~lpCL ~ies compared to the blend of Compounds 2A and 2B. The data also shows Compound 2C has enh~nc~ecl adhesion properties compared to Compound 2A and Compound 2B thus showing the utility of the 1 5 invention.

Example 3:
This example describes the plcpalc~Lion of a water-based sulfonated polyurethane-vinyl polymer wherein the amine functional polyvinyl dispersion is formed W O 98/06768 PCTrUS97/14386 using Vinamer EF monomer which is N-ethenylformamide from Air Products &
Chemicals, Inc. (Allentown, PA).
-Compound 3A
S Compound 3A is an arnine functional polyvinyl dispersion using N-ethenylform~mi~le (1) Reactor Char~e Grams De-ionized water 295.0 Potassium persulfate 0.42 De-ionized water 20.0 (2) Pre-emulsion Grams De-ionized water 80.0 T-Det 0-407 (Hacros) 8.86 Fo~ t~r 111 0.325 Potassium persulfate 0.55 Methyl methacrylate 155.0 N-butyl acrylate 155.0 Methacrylic acid O.S
10 (3) Initiator feed Grams De-ionized water 20.0 Potassium persulfate 0.42 (4) Monomer feed Grams - Vinamer EF 3.1 The pre-emulsion (2) was ~l~al~,d using the following procedure. The W 098/06768 ~CT~US97/14386 water, s~lrf~f~ntJ defoamer and initi~tor were combined and ~it~tçfl for 15 minl~t~s.
The monomers were added to this mixture over a 30 minute period, using agitation, to form a milky white pre-emulsion.
To a reactor equipped with an agitator, thermometer, condenser and S nitrogen purge was added the reactor charge (1). The m~t.?ri~l~ were heated to approxin~Rtely 80~C and charged with 2% of the total pre-emulsion (2) then stirred an additional 15 minlltt~ While Ill~ A;II;II~ a reaction lelllpc~dlul~ of 80~C, the pre-emulsion (2) was added over a 3 hour period. The monomer feed (4) was added approxim~ly 1.5 hours after the pre-emulsions initial feed. Once all the m~tf.ri~l~ were 10 added, the reaction mixture was heated an additional 30 minutes. To the dispersion was charged 3.1 grams Igepal C0-710, which is a surfactant from Rhone-Poulenc, and the reaction mixture was heated an additional hour to allow the complete free radical polymerization of said mon~mer~ The incorporated Vinamer EF monomer was then hydrolyzed to a primary amine. This was accomp!i~hed by adding 17.5 grams of a 5%
15 sodium hy~o~side solution and heating an additional 2 hours at 80~C.

Compound 3B
Compound 3B is a water-based sulfonated polyurethane-vinyl polymer.
To a reaction flask was charged 95.4 grams (0.093 hydroxyl equivalents) 20 Rucoflex(~ XS-5570-55 and 4.5 grams 2-methyl-1,3-propanediol. The m~teri~ls were heated to 50~C and then charged with 39.96 grams isophorone diisocyanate and 1 drop of dibutyl tin dilaurate. The mixture was heated an additional 2 llours at 80~C. The rçs~llting isocyanate-tt;, .";ll~ 7 polyurethane prepolymer was dispersed in a solution cont~ining 315 grams of an arnine functional polyvinyl polymer (Compound 3A) and25 244 grams de-ionized water. The dispersion was stirred for 2 hours at 60~C.
The compounds mechanical and adhesion ~ 3p~ ~ies are provided in Table 3:
Table 3. Tensile Strenth, elongation and shear strength W O 98/06768 PCTrUS97/14386 Compound T~nsile F.lnn~linn Shear Strength (Kgs./cu.cm.) Strength (%) (Kgs./cu.cm) Steel/Steel Glass/Glass ABS/ABS
Compound 3A 55.46 1,987 10.89 14.34 23.90 Compound 3B 48.36 2,118 19.47 17.78 27.27 Example 4:
Exarnple 4 describes the p~ dlion of water-based polymer compositions wherein isocyanate-terrnin~tcd sulfonated polyulc;llldlle prepolymers are S dispersed in hydroxy functional water-based polyacrylic dispersions.

Compound 4A
Compound 4A is a hydroxyl functional polyacrylic dispersion wherein the hydroxyl groups are within the latex particle.
(1) Reactor Char~e Grams De-ionized water 275.0 Methacrylic acid 1.0 (2) Pre-emulsion Grams De-ionized water 80.0 T-Det 0-407 (Hacros) 8.86 Methyl methacrylate 155.0 N-butyl acrylate 155.0 Hydroxyl ethyl acrylate 10.85 N-dodecyl mc~.;~l~l 0.31 (3) Initiator fee Grams De-ionized water 20.0 W O 98/06768 PCT~US971143~6 T-butyl hydroperoxide 1.37 (4) Reducer feed rams De-ionized water 20.0 Sodium forrnaldehyde sulfoxide 0.97 To a reactor equipped with an agitator, thermometer, condenser and nitrogen purge was added the reactor charge (1). The water was heated to approximately 5 65~C and then charged with 3% of the total pre-emulsion. While m~ a reaction temperature of 65~C, the pre-emulsion (2), was added over a 3 hour period while the initiator feed (3) and reducer feed (4) were added over a 4 hour period. The reaction mixture was charged with 10.85 grams hydroxyl ethyl acrylate after addition of approximately 75% of the pre-emulsion. Once all the m~t.o.ri~s were added, the reaction 10 lni~ulG was heated an additional hour. The dispersion had a solids content of 45.2%, a pH of 2.65 and a number average particle size diameter of 443 nanometers.
Compound 4B
Compound 4B is a hydroxyl functional polyacrylic dispersion wll~ lGi,l a portion of the hydroxyl groups are distributed on the surface of the particle.
(1) Reactor Char~e Grams De-ionized water 275.0 Methacrylic acid 1.0 (2) Pre-emulsion Grams De-ionized water 80.0 T-Det 0-407 (Hacros) 8.86 Methyl methacrylate 155.0 N-butyl acrylate 155.0 N-dodecyl mGrc~l~l 0.31 CA 022~9364 1998-12-29 W O 98/06768 PCT~US97114386 (3) Initiator fee Grams De-ionized water 20.0 T-butyl hy-llopwoxide 1.37 (4) Reducer feed Grams De-ionized water 20.0 Sodium form~ hyde sulfoxide 0.97 To a reactor equipped with an agitator, thermometer, con(len~r, and nitrogen purge was added the reactor charge (1). The water was heated to approximately 65~C and then charged with 3% ofthe total pre-emulsion (2). While mz~ g a reaction temperature of 65~C, the pre-emulsion (2) was added over a 3 hour period while the initiator feed (3) and reducer feed (4) were added over a 4 hour period. The reaction mixture was charged with 10.85 grams of hydroxyl ethyl acrylate after addition of approximately 75% of the pre-emulsion. Once all the m~t~ri~l~ were added, the reaction ll~i~l~u~ was heated an additional hour. The dispersion had a solids content of 45.2%, a pH of 2.65 and a number average particle size diameter of 443 nanometers.
Compound 4C
Compound 4C is a sulfonated polyurethane prepolymer.
A reactor was charged with 4.5 grams (0.099 hydroxyl equivalents) 2--methyl-1,3-propanediol and 95.4 grams (0.093 hydroxyl equivalence) molten Rucoflex(~
XS-5570-SS which is a sulfonated polyol from RUCO Polymer Corporation based on 5-sulfoisophthalic acid monosodium salt (4% by weight), adipic acid and diethyleneglycol. The mixture was charged with 39.96 grams isophorone diisocyanate, 1 drop of dibutyl tin dilaurate and heated to 80~C for 2 hours.
Compound 4D
Compound 4D is a water-based sulfonated polyurethane-urea polymer.
139.86 grams of the prepolymer (80~C) described as Compound 4C was charged with 629.3 grams de-ionized water (65~C) and stirred for 2 hours keeping the CA 02259364 l998-l2-29 W O 98/06768 PCT~US97/14386 Lt~ dLult; below 65~C.
Compound 4E
Compound 4E is of a water-based sulfonated polyurethane-acrylic polymer composition.
139.86 grams ofthe prepolymer (80~C) described as Compound 4C was dispersed in 309.4 grams of a hydroxyl functional polyacrylic dispersion (65~C) described as Compound 4A. The dispersion mixture was stirred for 5 ll~il~uLt~S and then charged with 250.0 grams of de-ionized water ~65~C). The m~tf~ were heated an additional 2 hours at 65~C to generate a polymer composition having a solids content of 10 40.2% and a pH of 6.5.
Compound 4F
Compound 4F was ~ d as simil~riy described as Compound 4E with the exception that 312.2 grams of the hydroxyl functional polyacrylic dispersiondescribed as Compound 4B was used. The polymer composition had a solids content of 15 40% and a pH of 6.5.
The compounds mech~niç:~l properties are diagramed below in Table 4:

Table 4. Tensile Strenth and elongation CompoundTensile StrengthElongation(S) (Kgs./cu.cm.) Compound 4A 71.8 1,484 Compound 4B 94.3 1,648 Compound 4C 60.7 3,807 Compound 4D 120.8 2,205 Compound 4E 117.0 2,437 Compound 4A and 4C61.0 2,620 (50/50 Blend) Compound 4B and 4C68.3 2,537 (50/50 Blend) The data shows the inventive polymer compositions ~Compounds 4E and W O 98/067C8 PCTrUS97/14386 4F) have enhanced tensile strength compared to Compound 4A, Compound 4B, Compound 4D, the S0/S0 blend of Compound 4A and 4D and the S0/S0 blend of Compound 4B and 4D.
Example 5:
S This example describes the ~ lion of a water-based sulfonated polyurethane-urea/polyvinyl polymer and its ~ lies culllp~ed to its corresponding polymer components.
Compound SA
Compound S~ describes the ~ lion of a polyvinyl dispersion which is free of active hydrogen atoms.
(1) Reactor Charge Grams De-ionized water 290.0 (2) Pre-emulsion Grams De-ionized water 90.0 T-Det 0-407 (Hacros) lS.0 Methyl methacrylate 170.0 N-butyl acrylate 180.0 Methacrylic acid 7.0 N-dodecyl m~ L~l 7.0 (3) Initiator fee Grams De-ionized water 30.0 T-butyl hydr~,pe~o2~ide 2.15 lS (4) Reducer feed ~ams W 098/06768 PCTrUS97/14386 De-ionized water 30.0 Sodium formaldehyde sulfoxide 2.10 To a reactor equipped with an agitator, thermometer, con~1en~Pr and nitrogen purge was added (1) the reactor charge. The water was heated to approxirnately 65~C and then charged with 3% by weight of the total pre-em~ ion (2). While ~; m~ g a reaction Le~ dL Ire of 65~C, the pre-emulsion (2), initi~tor feed (3), reducer feed (4) were added over a 3 hour period. Once all the mz~teri?ll~ were added, the dispersion was heated an additional hour.
Compound SB
Compound SB is a water-based sulfonated polyurethane-urea polymer.
To a reaction vessel was charged 95.4 grams (0.093 hydroxyl equivalents) Rucoflex(l~) XS-5570-SS and 4.5 grams 2-methyl-1,3-propanediol. The mixture was heated to 50~C then charged with 39.96 grams isophorone diisocyanate and 1 drop of dibutyl tin dilaurate. The lllixLult; was heated to 80~C for approximately 2 hours using mild agitation. The isocyanate-t~ . . " i. ~ cl polyu~lal e prepolymer was then dispersed in 339.4 grams de-ionized water and charged with a solution cu~ llg 2.88 grams ethylene ~ mine, 1.09 grams diethylene triamine and 20 grams de-ionized water.
ComPound 5C
Compound SC is a water-based sulfonated polyurethane-urea/polyvinyl dispersion.
To a reaction vessel was charged 95.4 grams (0.093 hydroxyl equivalents) Rucoflex~ XS-5570-SS and 4.5 grams 2-methyl-1,3-propanediol. The mixture was heated to 50~C then charged with 39.96 grams isophorone diisocyanate and 1 drop of dibutyl tin t~ lnqte The mixture was heated to 80~C for approximately 2 hours using mild agitation to give an isocyanate-terrnin~e~i polyurethane prepolymer. The isocyanate te~min~te~l polyurethane prepolymer was then dispersed in a mixture CO~ g 339.4 grams de-ionized water and 969.3 grams of the polyacrylic dispersion, compound SA, which mixture had been adjusted to a pH of 9.3, using 10% sodium hydroxide/water mixture, before the dispersion process. The resulting isocyanate-termin~d polyurethane prepolymer/polyvinyl dispersion was charged with a solution W 098/06768 PCTrUS97114386 co~ 2.88 grarns ethylene ~i~min~, 1.09 grams diethylene tri~mine and 20 grams de-ionized water. The resulting water-based sulfonated polyur,ll,~le-urea/polyvinyl polymer had a solids content of 35% and a pH of 9Ø
The compounds described above were tested for shear strength on glass, 5 steel and acrylonitrile-butadiene-styrene copolymers (ABS). The results are provided in Table 5 below:
Table 5. Shear ~
Shea~ Strength Shea~ Strength (Kgs./cu.cm.) (Kgs./cu.cm.) GlassMlass SteeVSteel ABS/ABS
Compound SA 41.6 55.95 19.19 Compound 5B 20.87 11.17 25.94 Compound 5C 75.71 59.82 31.21 Compound SA and 23.48 23.97 23.12 5B (50/50 Blend) The data shows the inv~ ive; polymer (Compound 5C) has increased 10 shear strength compared to Compound SA, Compound SB and the 50/50 blend of Compound 5A and 5B showing the utility of the invention.
Examples 6 and 7 relate to the formation of water based sulfonated polymer compositions in which a polyurethane dispersion is used as a seed to polymerize (meth)acrylic monomers. The reslllting water based sulfonated polymer composition 15 may be used for fiberglass sizing. As used herein, acrylic denotes acrylate, methacrylic acid, and acrylamide.

Example 6. Synthcsis of pol~ ~r~lhane dispersion aclylic hybrid latex Example 6 describes the prepalation of a water based sulfonated polymer 20 composition by seed emulsion polymerization and its p,~ . Lies compared to the blend of its coll~s~onding polymer components.
Compound 6A
Compound 6A is a polyacrylate pre-em~ n (l) Reactor char~e Grams Deionized water 90.8 Pluronic L64 (a sl~ t~nt, BASF) 9.08 (2) MonomerMixture Methyl methacrylate (ICI) 159.6 N-butyl acrylate (Hoechst Ce1~n~osc) 163.5 Hydroxyl ethyl methacrylate (Rohrn & Haas) 6.49 Reactor charge (1) was added to a kettle with an agitator and mixed for 10 minllt~s at a temperature of 25~C. Monomer mixture (2) was then added over a period of 30 mimltes under agitation to the kettle. The mixture was mixed for an additional 10 minutes at a temperature of 25~C. The r~slllting pre-emulsion was transferred to a feed 15 tank.
Compound 6B
Compound 6B is a polyurethane dispersion for use in the preparation of the inventive compositions.
(1) Reactor char~e Grams Deionized water, 181.7 Thiolactic acid (Evans) 0.065 Hydrosulfite AWC (Henkel) 0.065 Hamp-O 14.5 % Iron (H~llp~ G) 0.039 Reactor charge ~1) was added to a j~ eted clean reaction kettle equipped with agitator, thermometer, condenser and nitrogen purge and mixed well. 332.3 Grams of NP-4062-M (a polyul~Ll~e dispersion, H.B. Fuller Company) was added to the e. The reactor, under nitrogen purge, was ~g1tZ~tefl and the ten-~G~ re raised to 65~C.
Compound 6C
Compound 6C is a water based sulfonated polymer composition prepared by seed emulsion polymerization.
Over a period of 4.5 hours, the polyacrylate pre-emulsion ~Compound 6A), an initiator solution co~ i . .g 1.95 grams of t-butyl hydrogen peroxide (Akzo) and 19.5 grams of deionized water, a reducer solution COl ~1~; l l i l ~g 0.91 grams of hydrosulfite AWC (Henkel) and l9.5 grams of deionized water, were fed to a jacketed clean reaction W 098/06768 PCTrUS97114386 kettle equipped with agitator, therrnometer, contl~n~er and nitrogen purge CO~ the polyurethane dispersion llliXIWC (Compound 6B). Following completion of the feeds, the 111i2~Ul~; was held at constant temperature for another hour to allow the full Col~ ion of monomers. The reactor was then cooled to ambient temperature and theresulting latex filtered through 200 mesh filter. A stable latex with 45% solids, pH 7.35 and viscosity of 316 cps was obtained.
Additional compounds were prel)~ed similarly to compound 6C varying the amount of compound 6B res-llting in a water based sulfonated polymer composition with dir~Lclll pol~ lane /polyacrylate (PU/PA) ratios. Compound 6C, and similarly 10 prepared compounds with different polyurethane/polyacrylic ratios, and blends of compounds 6A and 6B, (absent the initisltor and reducer solutions) were tested for tensile strength and elongation, peel strength (using a clear and a white PVC sheet as ~ub~lldlcs) and lap shear strength. The results are provided in Tables 6-9. Note that the polyurethane to polyacrylate ratio is based on solids content of the polyurethane and the 15 polyacrylate. Thus a PU/PA ratio of 75/25 inrlic~f.os that there are 3 parts polyurethane solids for every part of polyacrylate solids. Also note that the "hybrid" referred to in Table 9 is ~ ucd as in Compound 6C with a PU/PA ratio of 25/75. The blend in Table 9 has a PU/PA ratio of 25/75.

Table 6. Tensile Strenth and elo t~
Tensile Streng~ (PSI) Tensile Elongation (%) PU/PA Ratio Blend Hybrid Blend Hybrid W 098/~6768 PCT~US97/14386 Table 7. Peel Strength, Clear PVC Film Green strength (PSI) 7 Day Strength (PSI) PU/PA Ratio Blend Hybrid Blend Hybrid 100/0 5.6 - 3.2 75/25 5.4 6.1 5.1 6.8 50/50 4.3 5.9 1.7 6.g 25/75 2.0 6.3 0.6 5.4 0/100 2 5 - 0.8 Table 8. Peel Strength, White PVC Film: ~Hybrid prepared with Example 6) Green streng~ 7 Day Strength (PSI) (PSI~
PU/PA Ratio Blend Hybrid Blend Hybrid 100/0 2.6 - 2.0 75/25 4.6 4.4 4.2 3.7 50/50 5.4 5.3 4.6 5.1 25/75 4.6 5.4 1.1 4.4 0/100 4.3 - 2.2 Table 9. Lap Shear Sl, ~..~,11,: (glass to glass) Material Lap Shear Strength (PSI) ~IP-4062 54 Hybrid 393 Blend 210 Acrylic 60 E2cample 7. Synthesis of Wate~Chain-Extended Water Based Sulfonated Polymer Composition With the sample process of Example 6, another water based sulfonated 10 polymer composition was p~ aLed in ~e manner of Example 6C except that the W 098/06768 PCTtUS97tl4386 31 polyul~,lh~le dispersion NP-4062 used to prepare compound 6B was replaced by NP-4073 (a sulfonated polyurethane dispersion, H.B. Fuller Co.llpa~ly).
Capillary Hydrodynamic Fractionation was used to monitor the latex particle growth in Exarnples 6 and 7. Figures 1 and 2 present the seed polyurethane S particle si~e distribution (dotted line) as a function of the final hybrid latex particle distribution (solid line), for the latex (water based sulfonated polymer composition) prepared in Examples 6 and 7. Both figures demonstrate that no new population ofacrylic particles was generated, implying that a polyurethane-core-polyacrylic-shell hybrid structure was formed. The unique hybrid morphology of the water based 10 sulfonated polymer composition latex in this disclosure leads to superior physical properties compared to the corresponding blend or comrnon alloy.

Claims (10)

Claims What is claimed is:

1. A water-based sulfonated polymer composition comprising a sulfonated polyurethane-vinyl polymer comprising the reaction product of:
A) at least one polymer comprising the reaction product of;
1) at least one polyisocyanate; and 2) at least one sulfonated polyester polyol wherein the sulfo groups are present in the form of alkali metal salts; and B) at least one polyvinyl dispersion comprising the free radically polymerized product of;
1) at least one ethylenically unsaturated monomer; and 2) optionally, at least one protective colloid comprising active hydrogen atoms.

2. A water-based sulfonated polymer composition comprising:
A) at least one polymer comprising the reaction product of;
1) at least one polyisocyanate; and 2) at least one sulfonated polyester polyol wherein the sulfo groups are present in the form of alkali metal salts;
B) at least one polyvinyl dispersion comprising the free radically polymerized product of;
1) at least one ethylenically unsaturated monomer; and 2) optionally, at least one protective colloid comprising active hydrogen atoms; and C) a polyurethane-vinyl polymer comprising the reaction product of;
1) at least one isocyanate-terminated sulfonated polyurethane prepolymer comprising the reaction product of;
a) at least one polyisocyanate; and b) at least one sulfonated polyester polyol wherein the sulfo groups are present in the form of alkali metal salts; with 2) at least one polyvinyl dispersion comprising the reaction product of;

a) at least one ethylenically unsaturated monomer; and b) optionally, at least one protective colloid comprising active hydrogen atoms.

3. A method for the preparation of water-based sulfonated polymer compositions comprising the steps of:
A). forming a water dispersible isocyanate-terminated prepolymer by reacting;
1) at least one polyisocyanate; and 2) at least one sulfonated polyester polyol wherein the sulfo groups are present in the form of alkali metal salts;
B) providing a polyvinyl dispersion comprising the free radically polymerized product of;
1 ) at least one ethylenically unsaturated monomer; and 2) optionally, at least one protective colloid having active hydrogen atoms; then C) combining A) and B).

4. A method for the preparation of water-based sulfonated polymer compositions by seed emulsion polymerization comprising the steps of:
A) providing at least one free radical initiator;
B) forming at least one pre-emulsion comprising;
1) at least one ethylenically unsaturated monomer;
2) water; and 3) optionally, at least one surfactant;
C) providing a water-based polyurethane comprising the reaction product of;
1) at least one polyisocyanate; and 2) at least one sulfonated polyester polyol wherein the sulfo groups are present in the form of alkali metal salts; then D) adding A) and B) to C) then initiating the free radical polymerization using heat, the polyurethane serving as the seed.

5. A water-based sulfonated polymer composition comprising the reaction product of:

A) at least one free radical initiator;
B) at least one pre-emulsion comprising;
1) at least one ethylenically unsaturated monomer;
2) water; and 3) optionally, at least one surfactant; and C) at least one water-based polyurethane dispersion comprising the reaction product of;
1) at least one polyisocyanate; and 2) at least one sulfonated polyester polyol wherein the sulfo groups are present in the form of alkali metal salts;
wherein said dispersion is used as a seed during the free radical polymerization of said emulsion.

6. The composition as described in any of the previous Claims having particles, the particles comprising polymers selected from the group consisting of sulfonated polyurethane polymers, polyvinyl polymers, sulfonated polyurethane-vinyl polymers and mixtures thereof.

7. The composition as described in any of the previous Claims having particles, the particles comprising a core and a surface wherein the core and surface comprise polymers selected from the group consisting of sulfonated polyurethane polymers, polyvinyl polymers and sulfonated polyurethane-vinyl polymers.

8. An article comprising a substrate, said substrate having a dried polymer layer on at least one portion thereof, wherein the polymer comprises the composition described in any of previous claims.

9. An adhesive, coating, binder and primer comprising the composition described in any of the previous claims.

10. A fiberglass sizing composition comprising the composition described in any of the previous claims.