Abstract:
A method for preparing a stable aqueous dispersion of polyurethane modified polyacrylic involving chain extension of polyacrylic with isocyanate and hydroxyl- or amino-functional groups.

Description:
BACKGROUND OF THE INVENTION 
     This invention concerns stable aqueous dispersions of polyurethane-urea modified polyacrylics. Polyether or polyester urethane-urea emulsions are high Mw, thermoplastic type polymer dispersions which give outstanding mechanical properties in various applications. The balance of properties is believed to come from the block structure with rigid urea-urethane semi-crystalline phase in a flexible polyether or polyester matrix. Problems with these disperisons are poor rheology and thermoplastic behavior. 
     Polyether urethane polymers have less than optimum durability, especially in outdoor exposure, and polyester urethanes lack good hydrolysis resistance. 
     Polyurethanes based on aliphatic or cycloaliphatic di- or polyisocyanates are also high priced while those based on aromatic diisocyanates completely lack good outdoor durability due to yellowing on exposure. The typical thermoplastic behavior and poorer rheology is inherent to the technology of making high Mw polyurethane-urea dispersions since the many techniques (see a review article by Dieterich in Progress in Organic Coatings 9(1981 281-340) available for making such aqueous dispersions do not permit easy handling and control of functionality (acid, hydroxyl, amide, etc.) within the polymer architecture needed to give it thermoset behavior and built-in rheology. Acrylic dispersions or emulsions on the other hand prepared via free radical initiated reactions do easily allow the formulator to build in reactive groups to give the polymer the necessary rheological and thermoset behavior. It would therefore be preferable to combine the good rheological and thermoset properties of reactive acrylics with the outstanding mechanical properties of polyurethanes. 
     Both types of polymers, however, are in many cases incompatible due to large solubility parameter differences. Incompatibility does show up in many examples as a phase separation or complete kick-out of the mixed blend polyurethane-urea with acrylic or as a loss in film integrity and physical properties, when applied afterwards. The present invention provides for a method of making a polyurethane-urea modified polyacrylics in which the acrylic has functional groups such as hydroxyl, acid, amine and amide by chain extension of an acrylic dispersion or emulsion having primary or secondary amine groups to form a polyurethane-urea polyacrylic dispersion. 
     DESCRIPTION OF THE PRIOR ART 
     The production of linear or cross-linked aqueous polyurethane-urea dispersions is known as shown in several patents including U.S. Pat. Nos. 3,479,310; 3,870,684; 4,066,591; 4,092,286; 4,203,883; 4,237,264; 4,238,378; 4,408,008, and 4,701,480. The aqueous polyurethane-urea dispersions may be used in a wide range of commercial applications such as adhesives and coatings. 
     The production of functional acrylic dispersions or emulsions has been described in many patent applications as U.S. Pat. Nos. 4,558,092; 4,403,003; 4,322,328; 4,609,690; 4,522,973; 4,733,786; 4,442,257; 4,525,510, and European patent EP 007107. 
     Acrylic emulsions or dispersions are also used in many commercial applications as adhesives and coatings. Polyurethane-urea modified acrylics are described in some patent applications, however, prior art does not allow to produce the dispersions as actually claimed in our invention. 
     U.S. Pat. No. 4,318,833 to M. Guagliarde and EP No. 189,945 to Witco, do not permit having acid, amine or hydroxyl functional monomers in the acrylic since this would react with or terminate the NCO prepolymer. Witco describes formation of the polyurethane isocyanate terminated prepolymer in a monomer blend which obviously should be unreactive versus isocyanate dispersing into water, chain extending and polymerizing the monomer blend. 
     U.S. Pat. No. 4,153,778, Union Carbide, does not mention polyacrylics. They cap isocyanate terminated prepolymer with hydroxyl functional monomer before dispersing in water. Canadian Pat. No. 1,201,244 describes polymer polyurethane acrylate polymer dispersions however different from the present invention, since the acrylic capped polyurethane-urea is dispersed in an inert polymerizable monomer. The end use is in molded articles. Japan Kokai 79/77,795 to Dainippon teaches polymerizing a blend of acrylic monomers in water in the presence of an aqueous urethane dispersion. Japan Kokai 59/157,101-3, Toho, concerns modifications of the above using GMA and HEMA. 
     Ashland Oil U.S. Pat. No. 4,609,690 describes a blend of an hydroxyl functional latex with a dispersible multifunctional isocyanate based crosslinker for structural adhesives in laminates. 
     &#34;Aqueous Dispersions of Crosslinked Polyurethanes&#34; by Terpak and Markusch in Journal of Water Borne Coatings -- Nov. 1, 1986, pages 13-21, teaches the use of polyfunctional amine for crosslinking with dispersed isocyanate prepolymer modified with ethylene oxide and ionic hydrophilic groups. 
     SUMMARY OF THE INVENTION 
     The invention provides a method of preparing a stable aqueous dispersion of polyurethane modified polyacrylic comprising 
     preparing a reaction mixture in the form of an aqueous dispersion or emulsion of amine-functional or amine- and hydroxyl-functional polyacrylic, 
     adding to the reaction mixture prepolymer chain of polyisocyanate or isocyanate-terminated polyurethane, and 
     reacting the resultant mixture to cause chain extension of the ingredients. 
     DETAILED DESCRIPTION OF THE INVENTION 
     A. Acrylic Dispersions 
     Typical acrylic dispersions can be produced in water dilutable solvents or other solvents which are not water soluble. In the latter case, the solvents can be stripped-off after inverting into water. The following exemplary lists are not limiting. 
     Examples of water dilutable solvents: 
     alcohols such as methanol, ethanol, isopropanol, ethylene glycol, butanol and 2-ethylhexanol, 
     glycolethers such as ethylene glycolmonoethylether, diethyleneglycol monobutylether and propylene glycol methyether, 
     ketones such as acetone and methylethylketone, 
     solvents such as N-methylpyrolidone, dimethylformamide and tetrahydrofuran. Examples of solvents partially or non-miscible with water: 
     aromatic such as toluene, xylene, Solvesso 100 from Esso; 
     aliphatics such as heptane and mineral spirits, 
     glycolether acetates such as methylether of propylene glycolacetate. 
     The composition of the acrylic is based on typical unsaturated compounds, and in order to be anionically dispersible the acid value should be at least 25. Preferred is an acid value between 30 and 150 and more preferred between 40 and 100. Typical acid functional monomers are 
     organic types--acrylic acid, methacrylic acid, maleic acid, fumaric acid and itaconic acid, 
     inorganic types--2 acrylamido-2-methylpropanesulfonic acid (AMPS), 2-methacryloxyethyl phosphate (MOP), described in PCT patent publications W088/02381, Apr. 7, 1988 and W088/02382 of the same date, and 2-sulfoethyl methacrylate. 
     Other functional or non-functional monomers can be copolymerized as: 
     
         ______________________________________esters        methyl-, ethyl-, butyl-, isobutyl-,         lauryl-, 2-ethylhexylacrylate and/or         methacrylatehydroxy       hydroxyethyl acrylate and/or         methacrylate, hydroxypropyl acrylate         and/or methacrylatearomatic      styrene, vinyltolueneamide         acrylamide, methacrylamide,         N--methylolacrylamide, butoxy         methylacrylamide or methacrylamide,         methoxy methylacrylamide and/or         methacrylamidesilane        methacryloxyethyltriethoxysilanenitrile       acrylonitrile, methacrylonitrilechloride, acetate         vinylacetate, vinylchloride,         reaction product of monofunctional         epoxies such as, Shell&#39;s Cardura E,         phenylglycidyl ether with acrylic acid,         methacrylic acid.______________________________________ 
    
     The acrylic copolymer can also be acid functionalized via anhydride capping of hydroxy groups or via anhydride copolymerization, e.g., maleic anhydride, itaconic anhydride, capping of hydroxy functional copolymer with succinic anhydride, phthalic anhydride, trimellitic anhydride. 
     The polymer is formed via radical initiated copolymerization using eventually chain transfer agents. 
     Initiators 
     Azo: AIBN azobisisobutylronitrile and the like 
     peroxide: t-butylperoxide, t-butylperacetate, etc. 
     Chain Transfer Agents 
     2-mercaptoethanol, t-dodecylmercaptan, laurylmercaptan, or 
     chlorinated solvents. 
     The acid functional prepolymer can be amine converted by reaction with an imine such as propylene imine, ethyleneimine or hydroxyethylethyleneimine. 
     A certain part of the acid groups are neutralized with tertiary amine so as to make the polymer water dispersible: triethylamine, dimethylethanolamine, etc. 
     The amount of neutralization can be between 20-200% of the free acid groups left after imination reaction, preferably between 70 and 130%. 
     The molecular weight can be between 1500 and 50,000 number average molecular weight, preferably between 3000 and 20,000. The glass transition temperature can be between -80° C. and +130° C. 
     The total composition of the copolymer can vary, preferably it is based on 3-30% of an acid functional monomer, 0.2-15% of amine functional monomer obtained through imination of part of the acid groups after the polymer is formed, 0-40% of hydroxy, silane, alkoxymethylamide, nitrile, amide or other functional monomers. Balance: aromatic, acrylic or methacrylic, vinyl non-functional monomers. 
     The acrylic copolymers can be produced by thermally initiated radical polymerization in the temperature range between 40° and 200° C., preferably between 60° and 180° C., specifically between 60° and 120° C. in case there are more than one different functional groups present that can react with each other that might gel the polymer. When this is not the case, polymerization temperatures can be up to 180° C. The amounts of initiators and chain transfer agents present can be between 0.05 and 10% on monomer weight, preferably between 0.2 and 4%. 
     B. Acrylic Emulsions 
     Typical acrylic emulsions can be produced in water which contains a surfactant and optionally some solvent present. Examples of surfactants can be anionic, nonionic or cationic or blends. 
     Typical examples of nonionics are alkyl phenolethoxylates and alkyl ethoxylates represented by the following chemical structures: ##STR1## with R for instance octyl, isononyl or nonyl. 
     Typical examples of anionic surfactants are salts of alkylsulfates, alkylsulfonates, alkyl phosphates, and sulfated alkylphenolethoxylates. 
     Typical examples of cationic surfactants are alkyltrimethylammonium chloride, and laurylpyridinium chloride. 
     The amount of surfactant used can vary between 0.01 and 20% calculated on monomer but is preferably between 0.2 and 5%. Emulsion polymerization typically uses water soluble initiators such as persulfates but it is not limited to them. One could also use partial soluble or water insoluble initiators as the one mentioned under dispersion polymers. 
     The composition of the copolymer can vary as mentioned under dispersion polymers. 
     Acid functional monomers need not be present, but they can be present. The presence of acid groups in an emulsion polymer can also vary and can have various purposes such as to provide a reaction site for an imine to make the amine group on the polymer, additionally stabilizing the latex, building in rheology or pigment wetting. 
     The amine group however can also be formed through reaction of an epoxy functional unsaturated monomer with ammonia, mono, di, or polyamines which are primary, secondary and/or blends. 
     Examples of an epoxy functional unsaturated monomers are: glycidylacrylate, glycidylmethacrylate. 
     Examples of mono amines are aliphatic, cycloaliphatic, aromatic such as ethanol amine, alkylamines (methyl, ethyl, propyl, butyl or lauryl), cyclohexylamine, benzylamine and aromatic amines such as aminobenzene. 
     Examples of diamines are aliphatic, cycloaliphatic, aromatic such as ethylenediamine, hexamethylenediamine, isophoronediamine, xylylenediamine or diaminobenzene. 
     Examples of polyether amines are polyethyleneoxidediamines or polypropyleneoxide diamines as known under the tradename Jeffamine from Texaco. 
     Examples of polyamines can be aliphatic, cycloaliphatic or aromatic, diethylene triamine or triethylenetetramine. 
     The amount of ammonia, mono-, di- or polyamines is calculated based on the amount of glycidyl group but can vary and is only limited to the final stability of the amine functional emulsion. 
     If one uses di- or polyamines the emulsion formed can be microgelled. 
     Other bi- or polyfunctional monomers can be used in the emulsion prepolymers to form microgels, e.g., allylmethacrylate, diethyleneglycol dimethacrylate, butanedioldiacrylate, trimethylolpropanetriacrylate, etc. 
     The amounts used of such bi- or polyfunctional monomers can vary and the only limiting factor is the final stability of the emulsion. 
     A typical composition of an emulsion would be 
     0.2-10% of a primary or secondary amine functional monomers that can be obtained (1) through reaction of an acid functional group with an imine and (2) through reaction of ammonia, a mono-, di- or polyamine with an epoxy functional group, in both cases after polymer has been formed; 
     0.30% Of an acid functional unsaturated monomer. 
     0-40% Of a hydroxy, alkoxymethylamide, nitrile, amide, silane or other functional monomers. 0-10% Of poly-unsaturated monomers. Balance aromatic, acrylic or methacrylic vinyl or other non-functional monomers. 
     The emulsion polymer is typically produced between room temperature and 100° C. In case of lower temperature (20°-60° C.) reducing agents as sodium bisulfite can be used to accelerate decomposition of the initiator. The pH of the final emulsion can be adjusted accordingly using amines for anionic emulsions or acids for cationic emulsions. Another way of crosslinking or &#34;chain extending&#34; the emulsion is the use of hydrazides which are known to react with ketones or aldehydes. Examples of such functional unsaturated monomers are acrylein, diacetone acrylamide. The &#34;hydrazide&#34; funtional emulsion can be further reacted with aldehydes as, e.g., formaldehyde. To further modify the emulsion other additives can be added as fungicides, preservative, external crosslinkers, etc. 
     C. Polyurethane Dispersions and Emulsions 
     Isocyanate terminated prepolymers to modify the amine functional dispersions or emulsion. 
     Many patents describe methods of making chain extended polyurethane dispersions using built-in ionic salt groups to stabilize the dispersion or external surfactants. An article by Dieterich in Progress in Organic Coatings 9(1981) 281-340 reviews the various technologies that can be used to make the polyurethane prepolymer before dispersing and chain extending in water. Numerous patents exist in this field. 
     Chain extending the amine or hydrazide functional acrylic dispersion or emulsion can be done by using aliphatic, cycloaliphatic or aromatic polyfunctional isocyanates, preferably bifunctional aliphatic or cycloaliphatic diisocyanates. 
     Examples of such diisocyanates are hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, bis (4-isocyanatocyclohexyl)-methane such as Desmodur W from Bayer, xylylene diisocyanate, tetramethyl xylene diisocyanate. 
     Examples of aromatic and polyfunctional isocyanates are: toluene diisocyanate, diphenylmethane diisocyanate, Bayer&#39;s Desmodur N (trifunctional biuret of hexamethylene diisocyanate), or Desmodur N3390 (cyclotrimer of hexamethylene diisocyanate). 
     Chain extension can also be done by a polyester, polyether-urethane which has an isocyanate as terminal groups. 
     The polyester can be linear or branched and is typically based on aliphatic, aromatic, mono-, di- or polyacids and mono-, di- or polyfunctional alcohols. 
     Preferably the isocyanate terminated prepolymer is linear and based on difunctional reactants with the diisocyanate in excess. Bifunctional polyesters which are hydroxy terminated are made by reacting dialcohols with diacids, stripping off water in the temperature range of 150°-250° C., then using esterification catalysts such as tin salts or strong acids, e.g., dibutyltindioxide or p-toluene-sulfonic acid can be used. Polyesters are characterized by the OH value and/or the number average molecular weight which can vary between OH value 10-300 with MW of 150-11000. Typical examples of diacids or anhydrides are phthalic anhydride, isophthalic acid, terephthalic acid, adipic acid, succinic acid, maleic anhydride fand fumaric acid. Typical examples of dialcohols are propane diol -1,2 or -1,3 ethylene glycol, dimethyl 2,2-propanediol, butanediol (1,2 or 1,3 or 1,4), hexanediol (1,2 or 1,6), dimethylol 1,4 cyclohexane, etc. The polyurethane prepolymer can contain water soluble or ionic groups which will after dispersion in water additionally stabilize the polyolefin polyurethane dispersions. 
     An example of a cationic group is diethanolmonomethylamine in its amine salt. An example of an anionic group is dimethylol-propionic acid in its salt form. An example of non-ionic stabilizing group is a hydroxyl functional polyethyleneoxide chain. In the case of anionically stabilizing groups the acid function can be neutralized with a base which can be metal (such as potassium) or a tertiary amine. In case of cationically stabilized disperisons, the amine group can be stabilized with a mono acid (e.g., acetic acid). The polyester prepolymer can also be formed using chain extension of a lactone on a diol (e.g., capa linear polycaprolactones available from Interox). Linear polyethers are available from many companies and are based on, e.g., ethylene-, propylene- and or butyleneoxide. The prepolymer might also contain ether difunctional polymers such as hydroxy fifunctional acrylics, polycarbonates or polyubtadienes. 
     The urethane prepolymer is formed at 100% active ingredients or in an inert solvent. An inert solvent means a chemical compound which does not have an active hydrogen atom according to the Zerewitinoff test, J. Amer. Chem. Soc. 49, 3181 (1927). 
     The molecular weight of the various difunctional reaction partners can vary between 200 and 6000. The temperature of forming the prepolymer can vary up to 160° C. but typically is run to avoid side reactions of the diisocyanate at 60°-100° C. Suitable catalysts such as amines or metal salts can be used to accelerate the reaction. The end point is typically determined by running the NCO content. 
     Chain extending the amine functional dispersion or emulsion with the isocyanate or polyurethane prepolymer can be done at any temperatures below reflux of the water/solvent blend. The ratio of equivalent isocyanate in the prepolymer to equivalent amine in the dispersion/emulsion can also vary between 1/5 and 5/1 and is mainly determined by getting sufficient cross reaction to make both polymers fully compatible. Additional additives can be used in the chain extension step. Part or a whole of the isocyanate groups might also be blocked with labile blocking agents such as methylethyl ketoxime or caprolactam. 
     The polymers are typically used for further crosslinking in case they still have functional groups. Crosslinkers can be water soluble or dispersible melamine, urea or benzoguanamine resins. 
    
    
     EXAMPLES 
     In the following examples, parts, proportions and percentages are by weight (such as in grams) except where indicated otherwise. Instead of butanol, other solvents such as xylene can be used and later stripped off after dispersing into water. 
     EXAMPLE 1 
     Polyacrylic-amine Functional Dispersion 
     The following ingredients were fed from feed tanks into a reactor equipped with a stirrer and a condenser and temperature control unit. 
     
         ______________________________________n-Butanol (B)               600Heat at reflux - 120° C. in reactorStyrene (S)                 600Methylmethacrylate (MMA)    600Butylacrylate (BA)           1200Hydroxyethylacrylate (HEA)  360Acrylic acid (AA)           240Tert-butylperoxy-2-ethylhexanoate 60 (Trigonox21S from Akzo) (tBPEH)B                           60Feed over 3 hours at refluxB                           40Rinsing step for feed tank - Add to reactor -Hold 15 minutestBPEH                       4add to reactor from feed tankB                           16Rinsing - Hold 30 minutes at 120° C. refluxRepeat 4 times - additional 4 parts tBPEH forrinsingCool to 70° C. - Test prepolymer______________________________________ 
    
     Test results on prepolymer diluted to 60% theoretical solids with B 
     
         ______________________________________Solids                     60.4%Visc. Gardner Holtz Z4AN (Acid Number)           58.7Continue the reaction by iminating the acidfunctional prepolymer to form an aminefunctional dispersionPropylene imine (PI)       96Add to reactorB                          64Rinsing - Hold till AN = 30 by reaction at 70° C.Triethylamine (TEA)        125.6Add neutralizerDeionized water (DW)       6194.4DisperseTest results:Solids                     30%pH                         9.5MN                         8800MW                         95,200AN after imination         30.9Amine value                27.8______________________________________ 
    
     EXAMPLE 2 
     Polyurethane Prepolymer 
     This example describes the formation of an isocyanate terminated polyester-urethane prepolymer. 
     
         ______________________________________(based on neopentylglycol (NPG), hexanediol (HD),                         606.9adipic acid (ADA) - MN = 546, OH ≠ 205)Dibutyltindilaurate catalyst  0.1(DBTDL)Heat 70-75° C. under nitrogen purge in a reactorequipped with condensor, addition funnel andtemperature control unit.Isophoronediisocyanate (IPDI) 444Add slowly over 45 minutesNMP                           49Rinsing - Hold 3 hours at 95° C.______________________________________ 
    
     EXAMPLE 3 
     Polyurethane Modified Acrylic Dispersion 
     This example describes chain extension of the isocyanate terminated prepolymer of Example 2 with the amine functional acrylic dispersion of Example 1. 
     
         ______________________________________Example 1                   1580DW                          516Mix with high shear mixerExample 2                   212.1Add over 30 minutes and stir till NCO in IR hasdisappearedTest results:solids                      29.3pH                          8.4MN                          5,500MW                          362,500______________________________________ (Biomodal MW distribution  showing chain extension). 
    
     EXAMPLE 4 
     Polyacrylic-amine Functional Dispersion 
     Formula see Example 1 but instead of 96, PI, 64 PI was used 
     
         ______________________________________  Test results______________________________________  solids   29.2  pH       8.2______________________________________ 
    
     EXAMPLE 5 
     A, B, D Urea Modified Acrylics 
     These examples describe chain extension of an amine functional acrylic dispersion with diisocyanate. 
     
         ______________________________________                       C       A       B       (control)                                D______________________________________Example 4     255.3     255.3   255.3  255.3DW            77.6      77.6    51.06  77.6Mix until homogeneousunder high shearIPDI                    3.12           6.24m-xylylenediisocyanate         3.55solids        24.7      24.4    24.2   26.9pH            8.6       8.4     8.6    8.4______________________________________ Control had MN = 10,100 MW = 125,700 
    
     All other samples were insoluble (microgelled) in THF for GPC run, showing chain extension. 
     EXAMPLE 6 
     Polyacrylic-amine Functional Emulsion 
     This example describes formation of an amine functional acrylic emulsion. 
     
         ______________________________________DW                          504Fenopon CO436 (F) from GAF  29(ammonium salt of sulfated alkylphenolethoxylate)Heat at 60° C. under N.sub.2 purge in a reactor equippedwith condensor, addition funnel and temperaturecontrol.Ammoniumpersulfate (AP)     0.8DW                          19.2Add to reactor. Start next feedMMA                         160BA                          160Hydroxypropylmethacrylate (HPMA)                       60Clycidylmethacrylate (GMA)  20Add 10%. Hold 20 minutes. Feed rest over 3 hours at60° C.DW                          10Rinsing - Heat 90° C.Ammonia solution (25% in DW)                       9.5DWAdd to reactor. Hold 45 minutes at 90° C.DW                          22Thin downSolids                      41.3%pH                          10Total ammonia               0.48%Total ammonia bound to polymer                       0.15%______________________________________ 
    
     Equipment and processes equal to previous examples was used to prepare examples 7-18. 
     EXAMPLE 7 
     Polyurethane Prepolymer 
     
         ______________________________________Polyester based on butanediol-adipic acid                       400.02000 MN and OH = 56Dimethylolpropionic acid (DMPA)                       53.6NMP                         156TEA                         38.4Heat till 80-85° C. till dissolved. Cool 55° C. undernitrogen purge.IPDI                        199.8Add over 20 minutes at 65° C. max reactor temperatureNMP                         85.6Rinsing - hold for NCO % = 1.8%.______________________________________ 
    
     EXAMPLE 8 
     A, B, Polyurethane Modified Acrylic Emulsion 
     
         ______________________________________                  A         B______________________________________Example 6              1000      1000DW                     334.1     334.1Dimethylethanolamine   5         5Antorox CO730 from GAF           25(Nonylphenolpolyethyleneoxide)Heat to 50° C. while stirringExample 7              334.1     334.1Add over 20-30 minutes while stirringSolids                 43.7      43.5pH                     6.5       6.6Control Test 1 - Polyurethane-urea DispersionDW                   933.4High shear mixingExample 7            933.4Add slowly while dispersingEthylenediamine      9.6DW                   100Add over 20&#39;DW                   68.4Rinsing - Hold 1 hourSolids               33.2%pH                   6.8______________________________________ 
    
     To prove the advantages of chain extending the polyurethane in presence of the amine functional acrylic emulsion following test was run: 
     
         ______________________________________Control A: Blend of acrylic (amine functional) andpolyurethane-urea.Example 6                     100Example 9                     77Control B: Chain extended acrylic (amine functional)with polyurethane.Example 8A                    100DW                            40______________________________________ 
    
     Both control A and B contain the same solids and ratio of acrylic/urethane. Control A resulted in a strong viscosity increase on blending while Control B was fluid and low in viscosity. A draw-down on glass was made of both A and B and baked 20 minutes at 120° C. Control A gave a slightly cloudy structured film with low hardness (80&#34; Persoz) while B resulted in a smooth transparent hard film (209&#34; Persoz). This show incompatability in Control A compared to Control B which represents the invention. 
     EXAMPLE 9 
     Polyacrylic-amine Functional Dispersion 
     This dispersion contains no cosolvent. 
     
         ______________________________________Cardura E (Shell)            294Dimethylmaleate              147Heat at 170° C.Butylmethacrylate (BMA)      l96S                            147AA                           196Ditertiarybutylperoxide      20Feed over 6 hours at 165-170° C. Hold 30 minutes.Cool to 120° C.Dimethylethanolamine (DMEA)  119.4Add and cool to 105° C.DW                           2505.6Add over 30&#39; and disperse. Heat 65-70° C.Propyleneimine               13Add to reactorDW                           414Rinsing - add to reactor and hold 90&#39;  at 70-75° C.Solids                       24.7%pH                           8MN                           3000MW                           13,400______________________________________ 
    
     EXAMPLE 10 
     Polyurethane-urea Modified Acrylic Dispersion 
     
         ______________________________________Example 9               1200Mix under high shearExample 7               160.2Add slowly while dispersing. Mix 1 hour.Solids                  30.4pH                      7.6______________________________________ 
    
     EXAMPLE 11 
     Polyacrylic-amine Functional and Crosslinked (Microgel) 
     
         ______________________________________DW                         504Disponil SUS87 from GAF (Sulfo                      29succinic acid semi ester-disodium salt)Heat to 60° C. under nitrogen purge.AP                         0.8DW                         19.2Add to reactor. Start next feed.MMA                        156BA                         120Polypropylene glycol monomethacrylate                      60(Bisomer PPM5) from BPGMA                        48Methacrylic acid MAA       16Add 10%. Hold 20 minutes. Feed rest over 3 hours.DW                         10Rinsing - Heat 90° C.Ammonia solution (25% in DW)                      35Add to reactorDW                         2Rinsing - Hold 45 minutes at 90° C.Solids                     40.6%pH                         10.2______________________________________ 
    
     EXAMPLE 12 
     Polyurethane Prepolymer 
     
         ______________________________________Polyester based on neopentylglycol and                      1028adipic acid MN = 1028 OH = 110DMPA                       93.8TEA                        35.35NMP                        130.60Heat at 100° C. till dissolved. Cool 80° C. undernitrogen purgeIPDI                       599.4NMP                        15Add over 20 minutes - Temperature maximum 95° C.NMP                        16.5Rinsing - hold for NCO = 3.2NMP                        106.3Thin down.______________________________________ 
    
     EXAMPLE 13 
     Polyurethane-urea Modified Acrylic Emulsion 
     
         ______________________________________Example 11             1000DW                     29.7DMEA                   9Heat at 70° C.Example 13             497Add slowly while dispersing. Hold 90&#39;Solids                 47%pH                     7.1______________________________________ 
    
     EXAMPLE 14 
     Polyacrylic-hydrazide Functional Emulsion 
     
         ______________________________________DW                            351.9Fenopon CO436 from GAF        2.6Heat 81° C. under N.sub.2Fenopon CO436                 3.7MMA                           136.9BA                            152.1Diacetoneacrylamide           10DW                            258Preemulsifying monomer blend. Add 5% to reactor.AP                            1DW                            25.4Add to reactor. Hold 20 minutes. Feed rest of freeemulsion over 60 minute at 85-86° C.DW                            13.8RinsingAdipic dihydrazide            5.2DW                            19.4Add - hold 60 minutes at 86-88° C.DW                            20Rinsing______________________________________ 
    
     EXAMPLE 15 
     Polyurethane Prepolymer 
     
         ______________________________________Polyester based on butanediol and adipicacid MN2000 OH = 56 400 gmDMPA                      53.6NMP                       156Heat 70° C. till dissolved under nitrogen purgeIPDI                      199.8Add over 20-25 minutesNMP                       65.6Rinsing - hold till NCO = 1.1%TEA                       38.4Add - neutralizeNMP 20Rinsing______________________________________ 
    
     EXAMPLE 16 
     Polyurethane-urea Modified Acrylic Emulsion 
     
         ______________________________________Example 14                1000DMEA                      5DW                        120Heat 50° C.Prepolymer Example 16     94Add slowly while dispersing. Hold 60 minutes.______________________________________ 
    
     EXAMPLE 17 
     Polyacrylic-amine Functional Emulsion 
     
         ______________________________________DW                         504Fenopon CO436              2.4Heat 60° C. under N.sub.2AP                         0.8H508                       19.2Add to reactorMMA                        176BA                         176HPMA                       40GMA                        8Feed 10% - hold 20 minutes - feed rest over 3 hours.DW                         10Rinsing - heat 90° C.Ethylenediamine            2DW                         13Add to reactor - hold 60 minutes at 90° C.DW                         27Rinsing 1000Test results:Solids                     40.9%pH                         9.8______________________________________ 
    
     EXAMPLE 18 
     Polyurethane-urea Modified Acrylic Emulsion 
     
         ______________________________________Example 17       1000DW               140High shear mixingExample 7        140Add - stir for 1 hourDMEA             6.3AddTest results:Solids           39.6%pH               7.8.______________________________________ 
    
     All polyurethane-urea modified acrylic emulsions or dispersions were stable.