Patent Publication Number: US-5422392-A

Title: Process for producing odor free, air dry, decorative latex paints

Description:
This invention pertains to air dry emulsion paints based on emulsion polymeric binders and more particularly to odor-free, consumer latex .paints free of polluting offensive odoriferous coalescing solvents. This a is a continuation-in-part of application Ser. No. 019,633 filed Feb. 18, 1993, now U.S. Pat. No. 5,326,808. 
    
    
     BACKGROUND OF THE INVENTION 
     Paint coatings are surface protective coatings applied to substrates, dried to form continuous films for decorative purposes as well as to protect the substrate. Consumer paint coatings are air-drying aqueous coatings applied primarily to architectural interior or exterior surfaces, where the coatings are sufficiently fluid to flow out, form a continuous paint film, and dry at ambient temperatures to protect the substrate surface. A paint coating ordinarily comprises an organic polymeric binder, pigments, and various paint additives. In dried paint films, the polymeric binder functions as a binder for the pigments and provides adhesion of the dried paint film to the substrate. The pigments may be organic or inorganic and functionally contribute to opacity and color in addition to durability and hardness, although some paint coatings contain little or no opacifying pigments and are described as clear coatings. The manufacture of paint coatings involves the preparation of a polymeric binder, mixing of component materials, grinding of pigments in a dispersant medium, and thinning to commercial standards. 
     Latex paints for the consumer market ordinarily are based on polymeric binders prepared by emulsion polymerization of ethylenic monomers. A typical consumer latex paint binder contains a vinyl acetate copolymer consisting of polymerized vinyl acetate (80%) and butyl acrylate (20%). The hardness of the latex polymer must be balanced to permit drying and film formation at low application temperatures, which requires soft polymer units, while at the same time the polymer must be hard enough in the final film to provide resistance properties which requires hard polymer units. This is conventionally accomplished by designing a latex polymer with a moderately elevated Tg (glass transition temperature) but then lowering the Tg temporarily with a volatile coalescing solvent. Coalescing solvents function to externally and temporarily plasticize the latex polymer for time sufficient to develop film formation, but then diffuse out of the coalesced film after film formation, which permits film formation and subsequent development of the desired film hardness by the volatilization of the coalescent. Internal plasticization is based on coreaction of soft monomers with hard monomers to form a polymeric copolymer binder, such as 80/20 vinyl acetate/butyl acrylate, to obtain the desired film forming characteristics. If a lower Tg copolymer is used without a coalescing solvent, higher levels of soft comonomer are required leading to lower Tg polymer, and, hence, the final dried film would be undesirably soft, excessively tacky, readily stain, and readily pick up dirt. 
     A significant source of residual odor in latex consumer paints is directly due to the coalescing solvent. Coalescing solvents are typically linear (or slightly branched) glycol ethers and esters of 7 to 12 carbon atoms in length, which have boiling points typically above 200° C., and solubility parameters appropriate for the latex of interest. One typical coalescing solvent ordinarily contained in commercial latex paints is 2,2,4-trimethylpentanediol monoisobutyrate (Texanol® Eastman Chemical Co.). The odor associated with the gradual volatilization of this solvent is considered objectionable by consumers. Quite often the odor lingers for days or weeks after the paint is applied and dried. All useful coalescing solvents are volatile and have similar objectionable characteristics. An additional deficiency in conventional exterior latex paints is the decline in crack resistance of the dried paint film approximately proportional to the evaporation of the coalescing solvent. While better coalescing solvents have a retention time of about one year in dried paint films, cracking starts to progressively appear after one year in dried paint films. Hence, the elimination of coalescing solvents and attendant objectionable odors, along with air pollution caused by volatile organic compounds (VOC), and film cracking deficiencies represent both a technical and marketing advance in the state of the art of consumer latex paints. 
     In polymer technologies unrelated to air-dry vinyl acetate latex paints, preformed polymers have been dispersed into monomers and emulsified in water, whereupon the monomers are then polymerized, such as disclosed in U.S. Pat. No. 4,373,054 pertaining to cathodic electrocoating, or in U.S. Pat. No. 4,313,073 pertaining to alkyd prepolymers; U.S. Pat. No. 4,588,757 pertaining to laminating adhesives, or in U.S. Pat. No. 3,953,386 and U.S. Pat. No. 4,011,388 pertaining to aqueous emulsion blends containing cellulosic ester/acrylic polymers. 
     It now has been found that certain non-volatile softening oligomeric modifiers compatible with an aqueous emulsion addition copolymer binder in a consumer latex paint can be retained in the dried paint film permanently. Softening oligomers of this invention can be incorporated into the paint where the oligomer will be retained permanently in the final paint film. Hence, the paint will not generate an odor while drying nor emit a residual odor from the dried paint film or otherwise emit VOC&#39;s. The softening oligomeric modifiers of this invention externally modify the emulsion copolymer matrix polymer and are not coreacted with the emulsion copolymer polymeric binder. The softening oligomeric modifiers appear to function by a chain-spacing mechanism to soften the matrix copolymers whereby the oligomeric modifiers provide low temperature film formation and tack-free films less prone to soiling at a given hardness and/or flexibility than ordinarily possible. Particularly preferred emulsion copolymer matrix polymers comprising polyvinyl acetate copolymers. A further advantage of this invention enable the use of essentially all hard polymer units of polyvinyl acetate without the need for internal plasticization (coreaction) with soft butyl acrylate polymeric units. 
     The present invention is based on a softening oligomeric modifiers having a low and narrow molecular weight range where the oligomer will not subsequently diffuse out of the matrix polymer when properly dispersed into the polymeric binder phase. Preferred oligomers are non-volatile oligomers having a molecular weight between about 300 and 10,000. Lower molecular weight compounds tend to be volatile and cause excessive plasticizer migration while higher molecular weight polymers lose low temperature film-forming and softening effects, although molecular weights above 10,000 and in some instances up to 20,000 can be used with softer matrix polymers. According to the process of this invention, a compatible organic solution of oligomeric modifier in ethylenic monomer is subjected to high energy shear to prepare a sub-micron size organic phase dispersed into water. Subsequent polymerization of the micronized monomer droplets produces a softened modified latex very different from conventional emulsion or suspension polymerization polymers. The micro suspension polymerization is generally necessary with the oligomeric modifiers to accomplish the required sub-micron aqueous emulsification of the monomer containing the dissolved oligomeric modifier, since the oligomer will not readily diffuse during polymerization from particle to particle across the aqueous phase. 
     The principal advantage of this invention is the elimination of the odor and VOC associated with volatile coalescent solvents which are intentionally volatile and intended to migrate out of the dried paint film. An additional advantage pertains to dried paint films exhibiting superior toughness obtained through the use of a hard polyvinyl acetate matrix polymer balanced with the oligomeric modifier to accommodate softening through the external addition of softening modifier while retaining the desired dried film hardness. A further advantage pertains to lower net cost for both interior and exterior paints since high cost soft monomers can be avoided, volatile coalescing agents can be eliminated and binder volume can be increased by using a permanent non-volatile softening oligomer instead of a volatile coalescent. The resulting dried paint films exhibit a superior balance of hardness and flexibility while maintaining long term flexibility. These and other advantages of this invention will become more apparent by referring to the detailed description and illustrative examples. 
     SUMMARY OF THE INVENTION 
     Briefly, the air-dry emulsion paint of this invention contains an oligomeric modified binder of polymerized ethylenic monomers to provide an aqueous emulsion addition copolymer binder externally modified with a non-reactive, low molecular weight, compatible oligomer selected from a polyester-urethane copolymer, a polyether-urethane copolymer, a polyurethane-urea copolymer, a polyester-amide, or a polyester, where between about 1% and desirably between 3% and 5% by weight of the binder comprises softening oligomer. Preferred emulsion addition copolymers comprise vinyl acetate copolymers. In accordance with the process of this invention, the low molecular weight softening oligomer has a preferred number average molecular weight between 300 and 10,000 and is effectively dissolved in ethylenically unsaturated monomer to form a compatible organic mixture before forming the aqueous emulsion addition matrix polymer. The organic mixture is dispersed into water by high shear, whereupon the ethylenic monomer is polymerized to produce a stabilized latex containing the low molecular weight oligomeric modifier. 
     DETAILED DESCRIPTION OF THE INVENTION 
     The air-dry emulsion paint of this invention comprises an emulsion polymer comprising an aqueous emulsion addition copolymer polymeric binder containing a non-volatile oligomeric modifier. 
     Suitable oligomeric modifiers in accordance with this invention comprise low molecular weight oligomers including urethanes consisting of polyester-urethane copolymers, polyether-urethane copolymers, polyurethane-urea copolymers; polyester polymer comprising polyester-amides and polyester polymers. The foregoing softening oligomeric modifiers function as effective external modifiers for latex emulsion paints, and particularly for the preferred polyvinylacetate binder for interior latex paints. 
     Useful non-volatile oligomeric modifiers have a number average molecular weight range between about 200 and 20,000, preferably between 300 and 10,000 and most preferably between 500 and 5,000. A preferred characterization of the oligomer modifier is in units of degree of polymerization (DP Units) which refers to the repeating monomer units without regard to molecular weight although the molecular weight is maintained relatively low as indicated. DP units defines the approximate chain length of the oligomers without regard to side units. The oligomeric modifier of this invention should have a DP between about 2 and 100, preferably between 2 and 50 and most preferably between 2 and 20 DP units. Useful oligomer modifiers have low Tg&#39;s to sufficiently impart a plasticizing effect on the matrix emulsion copolymer. Useful Tg&#39;s of the oligomeric modifier measured by Differential Scanning Calorimetry (DSC) at 10° C./minute scan rate are less than -20°, preferably less than -40° C. and most preferably below -50°  C. The level of oligomer modifier needed can vary considerably in the final latex. The level required depends on the inherent softening efficiency of the oligomer (estimated by its Tg) and the Tg of the matrix (parent) polymer. The Fox equation is useful for estimating the level needed: 
     
         1/Tg(mix)=(W.sub.p /T.sub.g,p)+(W.sub.m /T.sub.g,m) 
    
     where 
     Tg (mix)=glass transition temperature of the modified polymer (which is a mixture); 
     W p , W m  =weight fraction of the parent (matrix) polymer and oligomeric modifier, respectively; 
     T g ,p ; T g ,m =glass transition temperature of the parent (matrix) polymer and the oligomeric modifier, respectively. 
     Thus, the level of oligomeric modifier required is directly related to the Tg of the parent matrix polymer, and inversely related to the Tg of the oligomer. Hence, the lower oligomer Tg will more efficiently soften the emulsion addition matrix polymer provided the oligomer and matrix polymer are compatible. Compatibility of a polymeric mixture is commonly said to exist when the mixture remains substantially optically clear, which indicates the two components are mutually soluble. In this invention, compatibility is intended to mean that the oligomeric modifier is soluble in the matrix polymer in the solid state. Complete compatibility is believed to exist when these conditions are met: in the solid state the mixture has a Tg (DSC, DMA) intermediate between the Tg&#39;s of the two components; the absence of component Tg transitions; the mixture Tg is smoothly dependent on level of modifier; and the mixture Tg follows a mixing rule such as the Fox equation. Tg&#39;s of mixtures depend on the Tg&#39;s of the two components, concentrations of the two components, and compatibility of the two components. The present invention pertains to substantially compatible components. 
     In accordance with this invention, low molecular weight polyurethane oligomers such as polyester-urethanes, polyether-urethanes, polyether urethane-urea copolymers, and polyester polymers including polyester-amide copolymers can be utilized as external Softening oligomers in the polyvinyl acetate binder matrix polymers. Useful polyurethane copolymers typically contain urethane groups in the polymer backbone and are produced by reacting excess equivalents of diol or polyol with lesser equivalents of di- or polyisocyanate. The polyisocyanates can be di- or triisocyanates such as for example 2,4- and 2,6-toluene diisocyanate, phenylene diisocyanate; hexamethylene or tetramethylene diisocyanate, 1,5-naphthalene diisocyanate, ethylene or propylene diisocyanate, trimethylene or triphenyl or triphenylsulfone triisocyanate, and similar di- or triisocyanates. The polyisocyanate can be generally selected from the group of aliphatic, cyclo-aliphatic and aromatic polyisocyanates such as for example hexamethylene 1,6-diisocyanate, isophorone diisocyanate, diisocyanate, 1,4-dimethyl cyclohexane, diphenylmethane diisocyanate 2,4-toluene diisocyanate, 2,6-toluene diisocyanate and mixtures thereof, polymethylene polyphenyl polyisocyanate. 
     Polyester-urethanes can be produced from diols comprising hydroxyl functional polyester polymer prepared by conventional esterification polymerization techniques from the common dicarboxylic acids and dihydroxyl functional reactants. Suitable carboxylic acids include adipic acid, succinic acid and anhydride, azelaic acid, maleic acid and anhydride, and other aliphatic carboxylic acids. Aromatic dicarboxylic acids include isophthalic acid, phthalic acid and anhydride, terephthalic acid, trimelitic anhydride and the like. Lesser amounts of mono-functional acids can be included, such as benzoic acid, 2-ethylhexanoic acid, if desired. Suitable dihydroxy functional materials include ethylene and propylene glycol, dipropylene glycol, diethylene glycol, neopentyl glycol, trimethylol propane, and lesser amounts of mono-functional alcohols such as benzyl alcohol and hexanol, if desired. Polyester prepolymers are generally prepared with excess hydroxyl functionality at molecular weights ranging from about 100 to 10,000 preferably about 200 to 2,000. Polyester prepolymers can be used alone or in combination with polyethers as hydroxyl functional prepolymers. Suitable hydroxyl functional polyether prepolymers include polyethylene oxide, polypropylene oxide, polybutylene oxide, and tetramethylene oxide where the polyether prepolymers have a molecular weight between about 100 and 10,000. 
     The polyesters and/or polyether prepolymers are then reacted with diisocyanate to advance the prepolymers to a molecular weight of about 200 to 20,000 and preferably between 300 and 10,000 to form polyester or polyether urethane oligomers of this invention. Diisocyanates are used preferably at an equivalent ratio of about 1 isocyanate group to 1.1 to 10 hydroxyl groups. Ratios of about 1.5 to 3 hydroxyl groups per isocyanate group are preferred. Preferred diisocyanates include toluene diisocyanate, isophorone diisocyanate, 1,6-hexane diisocyanate, diphenylmethane diisocyanate, and the like. Catalysts such as dibutyltindilaurate, tin oxide and the like can be used to increase the isocyanate reaction rate with the hydroxyl polyester or polyether prepolymer at temperatures of about 30° to 120° C. and preferably at about 70° to 100° C. 
     The polyester or polyether urethane copolymers can be further extended with diamine or polyamine, if desired, to produce polyurethane-urea copolymer useful as a softening oligomer modifier in polyvinyl acetate binder matrix polymers in accordance with this invention. In this regard, primary diamine or polyamine can be added to an isocyanate terminated polyurethane intermediate containing unreacted pendant or terminal isocyanate groups obtained by reacting excess equivalents of isocyanate relative to hydroxyl equivalents in the polyester or polyether prepolymers. The primary diamines readily react with the isocyanate functional intermediate to chain extend the polyurethane to a polyurethane-urea of a higher molecular weight. Alternatively amine can be prereacted with the diisocyanate prior to reacting with polyol. Suitable primary amines for chain extension include hexamethylene diamine, 2-methyl-pentanediamine and similar aliphatic diamines. Polyester and polyether urethane copolymers or polyurethanes extended with diamine to form polyurethane-ureas exhibit excellent compatibility with vinyl acetate monomers as well as the resulting polyvinylacetate polymers. Polyurethane intermediate molecular weights before chain extension can be between 400 and 10,000 while after chain extension with the diamine the final molecular weight of the polyurethane-urea can be between about 800 and 20,000. 
     In accordance with this invention, the polyurethane copolymers can be synthesized, dissolved in ethylenically unsaturated monomer such as vinyl acetate monomer, subsequently suspended in water, followed by polymerization of the ethylenic monomers. Polyurethane oligomers can be dissolved in the ethylenically unsaturated monomers to form a fluid organic solution containing above 1% and desirably between about 3% and 50% and preferably between 10% and 25% by weight oligomer based on the weight of the organic monomer solution. This organic mixture of oligomer and monomer is then suspended in water with high shear mixing to form a coarse suspension using the common latex surfactants as stabilizers, such as the sulfosuccinates, the sulfates, various ethoxylated phenols, and the like. The coarse suspension is then micronized to very fine particle size emulsion droplets of average size of less than 5 microns, preferably less than 1 micron, and most preferably less than 0.7 micron. High mechanical shear and/or ultrasound can be used to form the microemulsion. Typical additional ingredients include buffers, acrylic acid, sodium salt of acrylamido methyl propane sulfonic acid (NaAMPS) ordinarily added at 0.1% to 5% by weight levels based on solids. Initiators such as persulfate, peroxide, and azo initiators can be added before or after suspension of the organic mixture in water. Redox catalysts can be added if desired. Polymerization can be accomplished by simply raising the suspension temperature to about 70° C. to 80° C. using persulfate initiators. Initial reflux of vinyl acetate will be at 67° C., but the temperature will rise with monomer polymerization conversion. Additional ethylenic monomer can be added, preferably after the preformed suspended addition copolymer emulsion and other monomer have polymerized. 
     A further desirable non-reactive oligomer useful as a softening oligomer modifier in this invention comprises a polyester polymer. In accordance with this invention, a low molecular weight ester or polyester can be dissolved in the ethylenically unsaturated monomer, suspended in water, and the aqueous suspension micronized prior to polymerization of the monomers. Useful polyester oligomers comprise esterification reaction products of diols with dicarboxylic acids or a functional equivalent with minor amounts of polyol or polyacid if desired, to produce a low acid number polyester polymer. Suitable esters and polyesters for blending have molecular weights between about 200 and 20,000 and include the linear and branched esters and polyesters formed from saturated dicarboxylic acids such as adipic acid, glutaric acid, succinic acid, and other such linear aliphatic acids, acid anhydrides, and lower alkyl esters thereof; phthalic acid, isophthalic acid, trimellitic anhydride, and other aromatic acids, acid anhydrides, and lower alkyl esters thereof; monoacids such as benzoic acid, 2-ethylhexanoic acid and other aromatic and aliphatic acids, which if desired, may be used in minor amounts to end cap and limit molecular weight. Minor amounts of unsaturated dicarboxylic acids such as fumaric or maleic acid can be included, if desired, to enhance grafting with polymerized ethylenic monomers, which promotes compatibility and permanence of the oligomer in the matrix polyvinyl acetate polymer. 
     Diol functional materials include diethylene glycol, neopentyl glycol, 2-methyl pentane diol, ethylene glycol, butylene glycol, propylene glycol, dipropylene glycol and the like; or mono-functional glycol ether groups, such as butylcellosolve, butyl carbitol, and the like; as well as hydroxy acids such as lactic acid, and lesser amounts of triols and polyols, such as trimethylol propane and ethane, and pentaerythritol. Acids can be used in carboxyl form, anhydride form, or an ester form, such as the methyl ester form, with the above diols to form linear and branched polyesters desirably having an Acid No. below about 20, and a molecular weight between 200 and 20,000, desirably between 300 and 10,000, and preferably between about 500 and 5,000. Polyesters of diethylene or dipropylene glycol with adipic acid are preferred. The low molecular weight esters and polyesters lower the Tg of the blend and can eliminate the need for expensive comonomers such as butyl acrylate. Thus, low molecular weight esters and polyesters can be effectively used to provide excellent, non-tacky, paint films without the inclusion of coalescing solvents. 
     Ester and polyester oligomeric modifiers described above can be easily dissolved in ethylenic monomers to form a fluid organic solution above about 1% and desirably between 3% and 50% by weight and preferably 10% to 25% oligomer, based on the weight of the organic solution. The organic solution of oligomer and monomer can be suspended in a surfactant treated aqueous medium by high speed prop stirring to form a coarse suspension, followed by ultrasonification or very high shear to produce a micronized suspension and reduce the particle size of the organic phase to about 5 microns or less, preferably less than 1 micron. Suitable surfactants are used at about 0.1 to 5% by weight (based on solids) and include the nonionic surfactants such as various ethoxylated phenols, block copolymers of ethylene oxide and propylene oxide, anionic surfactants such as sulfosuccinates, sulfates, and sulfonates, and the like (sulfosuccinates such as hexyl, octyl, and hexadecyl sulfosuccinate are preferred). Part of the ethylenic monomer can be polymerized followed by further polymerization of the remaining monomer if desired. Common initiators are used, such as the persulfates, azos, hydroperoxides, and peroxides, at typical initiator levels and polymerization temperatures as previously described for emulsion polymerization. 
     Polyester amide oligomeric modifiers are formed by the reaction of diols and diamines with dicarboxylic acids or esters. In a preferred process, methyl esters of adipic, glutaric, isophthalic or other common dicarboxylic acids are transesterified with diols and diamines at about 150° C. to 250° C. in the presence of common esterification catalysts such as butylstanoic acid. Typically greater amounts of diols, such as diethylene and dipropylene glycol, neopentyl glycol and the like are used with lesser amounts of diamines, such as 1,6-hexanediamine, 2-methyl pentanediamine, or the longer chain amines (e.g. Jeffamine-Texaco). Lesser amounts of monoacids, monoesters, alcohols and amines, or polyacid, polyols, or polyamines can be added, if desired. 
     In accordance with this invention, the oligomers are solubilized in ethylenic monomer, then dispersed into water and micronized into a microemulsion. The ethylenic monomer is polymerized to produce a polymeric binder comprising emulsion polymerized ethylenic monomer. The preferred ethylenic monomer is vinyl acetate. Other ethylenic monomers can be copolymerized with the vinyl acetate monomer to produce a preferred copolymer containing by weight less than 60% and preferably less than 30% and most preferably less than 20% other ethylenic monomer. Polymerizable ethylenically unsaturated monomers contain carbon-to-carbon unsaturation and include vinyl monomers, acrylic monomers, allylic monomers, acrylamide monomers, and mono- and dicarboxylic unsaturated acids. Vinyl esters include vinyl propionate, vinyl laurate, vinyl decanoate, vinyl butyrates, vinyl benzoates, vinyl isopropyl acetates and similar vinyl esters; vinyl aliphatic hydrocarbon monomers include vinyl chloride and vinylidene chloride as well as alpha olefins such as ethylene, propylene, isobutylene, as well as conjugated dienes such as 1,3 butadiene, methyl-2-butadiene, 1,3-piperylene, 2,3-dimethyl butadiene, isoprene, cyclohexane, cyclopentadiene, and dicyclopentadiene; and vinyl alkyl ethers include methyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, and isobutyl vinyl ether. Acrylic monomers include lower alkyl esters of acrylic or methacrylic acid having an alkyl ester portion containing between 1 to 12 carbon atoms as well as aromatic derivatives of acrylic and methacrylic acid. Useful acrylic monomers include, for example, acrylic and methacrylic acid, methyl acrylate and methacrylate, ethyl acrylate and methacrylate, butyl acrylate and methacrylate, propyl acrylate and methacrylate, 2-ethyl hexyl acrylate and methacrylate, cyclohexyl acrylate and methacrylate, decyl acrylate and methacrylate, isodecyl acrylate and methacrylate, benzyl acrylate and methacrylate, and various reaction products such as butyl, phenyl, and cresyl glycidyl ethers reacted with acrylic and methacrylic acids, hydroxyl alkyl acrylates and methacrylates such as hydroxyethyl and hydroxypropyl acrylates and methacrylates, amino acrylates, methacrylates as well as acrylic acids such as acrylic and methacrylic acid, ethacrylic acid, alpha-chloroacrylic acid, alpha-cycanoacrylic acid, crotonic acid, beta-acryloxy propionic acid, and beta-styrl acrylic acid. Particularly preferred comonomers include acrylates such as methyl, ethyl, propyl, butyl (linear and branched), 2-ethyl hexyl; methacrylates such as methyl, ethyl, propyl, butyl (linear and branched), 2-ethyl hexyl; vinyl esters such as acetate, proprionate, butyrate, pentanoate (neo 5), nonanoate (neo 9), 2-ethyl hexanoate, decanoate (neo 10); and other ethylenic monomers such as ethylene, vinyl chloride, vinylidene chloride and butadiene. For exterior latex paints, the matrix copolymer ordinarily comprises copolymerized acrylic monomers where the acrylic copolymer content can be between about 40% and 100% by weight of the copolymer. 
     The preferred matrix copolymer comprises emulsion polymerized vinyl acetate monomer to produce a matrix polymeric binder of polymerized vinyl acetate where the most preferred polymeric binders comprise homopolymers of vinyl acetate. On a weight basis, the preferred polymeric binders comprise between 40% and 100% polymerized vinyl acetate with the balance being other ethylenic monomers. Preferred polymeric binders contain at least 70% by weight polymerized vinyl acetate and most preferred 80% to 100% vinyl acetate. The number average molecular weight of the polymeric vinyl acetate binders should be between about 30,000 and 10,000,000 and preferably between 50,000 and 1,000,000 as measured by GPC (gel permeation chromatography) according to ASTM D3016-78, D3536-76, and D3593-80. The Tg or softening point of the modified polymeric binder particles should be less than 20° C. as measured by differential scanning calorimetry, preferably less than 10° C., most preferably &lt;5° C. The MFT (minimum film formation temperature) is an alternative measure of polymer film formation determined on the neat latex on a temperature gradient temperature bar, and is typically a few degrees higher than the Tg of the latex. MFT should be less than 20° C., preferably less than 15° C., most preferred less than 10° C. The LTFF (low temperature film formation) is a film forming test run on the fully formulated paint. LTFF typically is reported as the lowest temperature at which no cracking is observed, or alternatively, the amount of coalescent or oligomer needed to achieve 40° F. failure-free coatings. LTFF should be less than 50° F. (10° C.), preferably less than 40° F. (5° C.). The distinction with LTFF is that other paint ingredients may have either an elevating influence (fillers, pigments) or depressing (surfactants, incidental solvents in additives) effect on LTFF relative to the MFT, which is measured on the latex alone. In turn, the MFT is measured from the wet state, and therefore includes the plasticizing effect of water, while the Tg is measured on an anhydrous sample of latex film, which does not include the water plasticizing effect. Latex paints are formulated to achieve LTFF of less than 50° F. (10° C.), preferably less than 40° C. (5° C.). It is also necessary for the final dried films to not be tacky at normal use temperatures (60°-110° F.). The polymeric binder contains between about 5% and 45% by weight softening oligomer with the balance being copolymer matrix polymer. 
     In accordance with the process of this invention, the preformed softening oligomer modifier is dissolved in the ethylenic monomer prior to polymerization to produce a compatible organic mixture of oligomer and monomer. The organic mixture may further contain a free radical initiator and is then suspended in water containing surfactant using high shear or ultrasound to produce an emulsified mixture of less than 5 microns and preferably less than 1 micron emulsion phase droplet comprising an organic phase dispersed into water. Thereafter the ethylenic monomer is polymerized in an aqueous polymerization medium by adding other emulsion polymerization ingredients. Initiators can include for example, typical free radical and redox types such as hydrogen peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, benzoyl peroxide, benzoyl hydroperoxide, 2,4-dichlorobenzoyl peroxide, t-butyl peracetate, azobisisobutyronitrile, ammonium persulfate, sodium persulfate, potassium persulfate, sodium perphosphate, potassium perphosphate, isopropyl peroxycarbonate, and redox initiators such as sodium persulfate-sodium formaldehyde sulfoxylate, cumene hydroperoxide-sodium metabisulfite, potassium persulfate-sodium bisulfite, cumene hydroperoxide-iron (II) sulfate. Redox systems consist of oxidants and reductants, which can be mixed in any pair. Transition metals such as iron can be used as accelerators for initiators for redox couples. The polymerization initiators are usually added in amounts between about 0.1 to 2 weight percent based on the monomer additions. 
     Suitable anionic surfactants include for example, salts of fatty acids such as sodium and potassium salts of stearic, palmetic, oleic, lauric, and tall oil acids, salts of sulfated fatty alcohols, salts of phosphoric acid esters of polyethylated long chain alcohols and phenols. Preferred anionic surfactants include for example, alkylbenzene sulfonate salts such as sodium dodecylbenzene sulfonate and salts of hexyl, octyl, and higher alkyl diesters of 2-sulfosuccinic acid. Suitable non-ionic surfactants include polyoxyethylene glycols reacted with a lyophilic compound, ethylene oxide condensation products reacted with t-octylphenol or nonylphenol and known as &#34;Triton&#34; surfactants, polymerized oxyethylene (IgepalCA), ethylene oxide reacted with organic acids (Emulfor), or organic acid reacted with polyoxyamylene ether of stearic or oleic acid esters (Tweens). 
     The preferred process involves pre-suspension by mechanical shear followed by rotor-stator shear or ultrasonification to less than about 1 micron. Suitable surfactants include the various sulfosuccinates such as hexyl, octyl, and hexadecyl sulfosuccinate, the various alkyl and alkyl-aromatic sulfates and sulfonates, as well as the various nonionic ethylene oxide surfactants. The aqueous suspension can be generally formed at about 10% to 60% by weight total solids. The suspension can be heated to polymerize the ethylenic monomer while initiator is added if not already present in the pre-emulsion mixture. Suitable initiators include the common persulfates, peroxides, and hydroperoxides, along with redox initiator systems if desired. Additional vinyl acetate monomer can be added at any time during the polymerization to increase the particle size and raise the total solids of the system and help control the polymerization exotherm. The resulting addition copolymer suspensions containing softening oligomer can be used directly in place of the common copolymer latices in interior or exterior consumer air-dry paints. 
     A paint coating composition can be produced by combining the externally modified emulsion polymer of this invention with pigments and other paint additives in a dispersing mill such as a Cowles disperser. A pigment dispersion can be preformed consisting of a dispersant and pigments on a disperser mill, a sand mill, a pebble mill, a roller mill, a ball mill or similar conventional grinding mill for milling the mineral pigments into the dispersion medium. The premix can then be combined under low shear with the polymeric binder of this invention and other paint additives as desired. Useful mineral pigments ordinarily include opacifying pigments such as titanium dioxide, zinc oxide, titanium calcium, as well as tinting pigments such as carbon black, yellow oxides, brown oxides, tan oxides, raw and burnt sienna or umber, chromium oxide green, phthalocyanine green, phthalonitrile blue, ultramarine blue, cadmium pigments, chromium pigments, and the like. Filler pigments such as clay, silica, talc, mica, wollastonite, wood flower, barium sulfate, calcium carbonate and the like can be added. 
     Historically, prior art paints achieved a balance of properties by making the latex slightly too hard for LTFF to achieve the tack-free character, and then temporarily softening the binder polymer with a coalescing solvent to achieve the desired LTFF. This solvent then evaporates from the film over a period of days, which allows the restoration of tack-free character. If a binder copolymer containing an internal plasticizer is formulated to pass the LTFF test directly, the paint will be so tacky as to be unacceptable as a paint. However, by using non-volatile, external softening oligomers in accordance with this invention, the historical relationship between Tg (or MFT) and LTFF in the final paint has changed such that both film formation and tack free character are simultaneously obtained without the need for a volatile coalescing solvent. The softening oligomer is permanent by design and will not volatilize out of the paint film. 
    
    
     The merits of this invention are further supported by the following illustrative examples. 
     EXAMPLES 
     Polyesters with a range of molecular weights and structures can function as effective non-volatile plasticizing and coalescing agents for emulsion addition copolymers. Polymer alloys (polymer blends) of the polyesters with emulsion addition polymers particularly vinyl acetate copolymers, form good clear films at room temperature and can be formulated into good air dry paints. Comonomer is not needed with vinyl acetate polymer and coalescing aid is not required for good film formation. This unique approach to avoiding the use of coalescing solvents is possible because the higher molecular weight polyesters are dissolved in polyvinyl acetate monomer and then dispersed into water by high shear and/or ultrasound prior to polymerization of the polyvinyl acetate as illustrated in the following examples. 
     EXAMPLE 1 
     An adipate polyester oligomer was prepared as follows: 
     
         ______________________________________                                    
               Grams                                                      
______________________________________                                    
Adipic acid      438.6                                                    
Diethylene glycol                                                         
                 382                                                      
Butylstanoic acid                                                         
                 0.5                                                      
______________________________________                                    
 
    
     The above raw materials were heated in a 2 liter flask under a nitrogen blanket with mechanical stirring to 170° C. while using the head temperature above a column packed with glass beads to regulate the esterification reaction. With a head temperature of 98° C., the reaction temperature increased slowly to 220° C., where the temperature was held for 2 hours and then cooled. 
     An aqueous suspension of vinyl acetate monomer and the above adipate polyester was prepared from the following materials. 
     
         ______________________________________                                    
                   Grams                                                  
______________________________________                                    
a)      deionized water  2000                                             
        MM-80, Mona Chemical.sup.1                                        
                         11.2                                             
        (NH.sub.4) HCO.sub.3                                              
                         2.5                                              
        NaAMPS, Lubrizol Corp.                                            
                         2.5                                              
        vinyl acetate monomer                                             
                         625                                              
b)      polyester from above                                              
                         312                                              
        MT-70, Mona Chemical.sup.2                                        
                         5.6                                              
c)      (NH.sub.4).sub.2 S.sub.2 O.sub.8                                  
                         5.0                                              
d)      vinyl acetate monomer                                             
                         625                                              
        MT-70.sup.3      5.6                                              
______________________________________                                    
 .sup.1 MM80 = sodium dihexyl sulfosuccinate                              
 .sup.2 NaAMPS = sodium acrylamide methyl propane sulfonate               
 .sup.3 MT70 sodium ditridecyl sulfosuccinate                             
 
    
     Organic solution (a) was dispersed in aqueous solution (b) with a prop stirrer at about 5000 rpm for 20 seconds and passed through the flow through cell of a Sonics Corp. model VC-600 ultrasonic device at 85% power. The resulting aqueous emulsion was heated with stirring under a nitrogen blanket to 65° C. Component (c) was added and 65° C. was held for 1.5 hours. Monomer mixture (d) was added over 3 hours at 72° C., held 1 hour, and then cooled. 
     EXAMPLE 2 
     In a manner similar to Example 1, a phthalate polyester oligomer was prepared, mixed with vinyl acetate monomer, micronized into water by high shear, and polymerized. The phthalate polyester was as follows: 
     
         ______________________________________                                    
                Grams                                                     
______________________________________                                    
phthalic anhydride                                                        
                  593                                                     
diethylene glycol 318.3                                                   
butyl cellosolve  236.4                                                   
______________________________________                                    
 
    
     The raw materials were heated under nitrogen to 200° C., then slowly raised to 220° C. over 2 hours while keeping the head temperature of the packed distillation column at 98° C. Total distillate was 73 g. A suspension of the above phthalate polyester was prepared as follows: 
     
         ______________________________________                                    
                   Grams                                                  
______________________________________                                    
a)       deionized water 800                                              
         MM-80           3.0                                              
         NaHCO.sub.3     2.0                                              
b)       vinyl acetate monomer                                            
                         250                                              
         polyester (Ex. 2 above)                                          
                         80                                               
c)       K.sub.2 S.sub.2 O.sub.8                                          
                         2.0                                              
d)       vinyl acetate monomer                                            
                         250                                              
         MT-70           3.0                                              
______________________________________                                    
 
    
     The procedure for polymerizing the ethylenic monomers was the same as described in Example 1. 
     EXAMPLE 3 
     In a manner similar to Example 2, a polymer was prepared from the raw material in Example 4 except that the amount of phthalate polyester was increased from 80 grams to 150 grams. 
     EXAMPLE 4 
     In a manner similar to Example 2, a polymer was prepared using the following components using a commercial polyester believed to be a polyether-phthalate-polyester capped with benzoic acid (Hercoflex 900, Hercules Corp.). 
     
         ______________________________________                                    
                  Grams                                                   
______________________________________                                    
a)      deionized water 2000                                              
        MM-80           15                                                
        NaHCO.sub.3     2.5                                               
        NaHCO.sub.3     7.5                                               
        NaAMPS          2.5                                               
b)      vinyl acetate monomer                                             
                        625                                               
        Hercoflex 900, (Hercules                                          
        Corp.)          250                                               
c)      K.sub.2 S.sub.2 O.sub.8                                           
                        5.0                                               
d)      vinyl acetate monomer                                             
                        625                                               
        MT-70           7.5                                               
______________________________________                                    
 
    
     The procedure from Example 1 was used to produce a latex polymer. 
     EXAMPLE 5 
     In a manner similar to Example 1, a polyester triester was prepared from the following reactants: 
     
         ______________________________________                                    
                   Grams                                                  
______________________________________                                    
Ektasolve DB, Eastman Chem.                                               
                     365                                                  
(diethylene glycol butyl ether)                                           
trimelitic anhydride 145                                                  
butylstanoic acid    0.1                                                  
______________________________________                                    
 
    
     The water of reaction distilled off was 29 grams. 
     A polymer was prepared according to the polymerization process described in Example 3 but from the following components: 
     
         ______________________________________                                    
                   Grams                                                  
______________________________________                                    
a)       deionized water 800                                              
         MM-80           3.0                                              
         NaHCO.sub.3     2.0                                              
b)       vinyl acetate monomer                                            
                         250                                              
         triester from Ex. 4                                              
                         50                                               
         MT-70           1.0                                              
c)       K.sub.2 S.sub.2 O.sub.8                                          
                         2.0                                              
         vinyl acetate monomer                                            
                         250                                              
         MT-70           3.0                                              
______________________________________                                    
 
    
     EXAMPLE 6 
     Clear unpigmented films were prepared from the polymers prepared in Examples 1-5. Physical properties of latex and air dried clear paint films were as follows: 
     
         ______________________________________                                    
        Min. Film Temp.                                                   
                       Min. Film Temp.                                    
Suspension                                                                
        Crack Point    Knife Point  Tack                                  
______________________________________                                    
Ex. 3   &lt;3             &lt;3           None                                  
Ex. 4    12            24           None                                  
Ex. 5    3              9           None                                  
Ex. 6   &lt;3              6           None                                  
Ex. 7    4             15           None                                  
Control*                                                                  
         10            12           None                                  
______________________________________                                    
 *Control was an unmodified commercial latex typically used in consumer   
 airdry paints and comprising 80/20 weight ratio of vinyl acetate         
 polymerized with butyl acrylate.                                         
 
    
     EXAMPLE 7 
     White semi-gloss latex paints were prepared from any one of the foregoing emulsion polymers described in Examples 1-5 from the following ingredients: Pigment Grind: 
     
         ______________________________________                                    
Group       Ingredient     Grams                                          
______________________________________                                    
A           Water          151.68                                         
A           Thickener      .50                                            
A           Ammonia (28%)  .01                                            
B           Surfactant     5.00                                           
C           Defoamer       2.00                                           
C           Surfactant     2.00                                           
D           TiO.sub.2 pigment                                             
                           145.00                                         
D           Clay extender pigment                                         
                           50.00                                          
______________________________________                                    
 
    
     Group A ingredients were added to Cowles dispersing equipment and mixed for 5 minutes. Group B and then C ingredients were added with continued mixing under slow agitation. Group D ingredients were added under high speed agitation and grind for 15 minutes or until a Hegman 5.5 was attained. The foregoing is the grind portion of the paint. 
     
         ______________________________________                                    
Letdown     Ingredient     Grams                                          
______________________________________                                    
E           Water          33.00                                          
F           Water          33.00                                          
F           Thickener      3.50                                           
F           Ammonia Hydroxide                                             
                           .01                                            
G           Preservative   1.00                                           
H           Defoamer       5.00                                           
H           Propylene glycol                                              
                           40.00                                          
H           Surfactant     4.50                                           
H           Rheology Modifier                                             
                           9.00                                           
H           Surfactant     3.00                                           
I           Latex          393.00                                         
I           Opacifier latex                                               
                           105.00                                         
______________________________________                                    
 
    
     Group E ingredients were added in separate vessel, followed by Premix F added to E ingredients with slow speed agitation. Group G ingredients were added at slow speed. Premix H ingredients were then added to vessel. Premix I ingredients were mixed for 30 minutes and then added to vessel. The final composition was mixed for 1 hour. The foregoing is the letdown portion of the paint. 
     Latex Paint 
     The letdown above was added to the pigment grind above under slow speed agitation and allowed to mix for 2 hours. 
     EXAMPLE 8 
     Benzoic Acid Capped Polyester Oligomer Modifier 
     
         ______________________________________                                    
Ingredient       Grams                                                    
______________________________________                                    
adipic acid      731                                                      
diethylene glycol                                                         
                 637                                                      
butylstanoic acid                                                         
                 0.5                                                      
benzoic acid     244                                                      
______________________________________                                    
 
    
     Heat the above components gradually with adequate stirring under a nitrogen atmosphere to 220° C. (Water will begin to distill at about 170° C., and about 3 hours will be required to move the batch from 170° C. to 220° C.). Using a packed column, maintain the head temperature at 99° C. throughout this portion of the synthesis. When the head temperature drops below 80° C., remove the column and replace with a Dean-Stark trap. Fill the trap with xylene, and then add just enough additional xylene to give a constant reflux. Allow xylene reflux to azeotrophe water out of the batch, and reduce acid number to about 10 mg KOH/g resin. Remove xylene under a vacuum (25 inches Hg). Cool. 
     EXAMPLE 9 
     Benzoic Acid Capped Polyester Urethane Oligomer Modifier 
     As in Example 8, but use only 122 g benzoic acid, then cool batch to 60° C. at the end of the synthesis, and add 111 g isophorone diisocyanate. Allow the exotherm to carry the temperature (with gentle heating) to 90° C., and hold for 2 hours. Cool. 
     EXAMPLE 10 
     Polyester Urethane Oligomeric External Modifier 
     
         ______________________________________                                    
Ingredient       Grams                                                    
______________________________________                                    
adipic acid      731                                                      
diethylene glycol                                                         
                 636                                                      
butylstanoic acid                                                         
                 0.5                                                      
______________________________________                                    
 
    
     Synthesize a polyester from the above ingredients in the same manner as in Example 8, and then add 111 g isophorone diisocyanate to form a polyester urethane as in Example 9. 
     EXAMPLE 11 
     Polyester Urethane External Modifier 
     
         ______________________________________                                    
Ingredient        Grams                                                   
______________________________________                                    
adipic acid       366                                                     
dipropylene glycol                                                        
                  403                                                     
butylstanoic acid 0.2                                                     
______________________________________                                    
 
    
     Form a polyester from the above ingredients as in Example 8, and then add 56 g isophorone diisocyanate to form a urethane as in Example 9. 
     EXAMPLE 12 
     Polyester Urethane Urea Oligomeric External Modifier 
     
         ______________________________________                                    
Ingredient        Grams                                                   
______________________________________                                    
adipic acid       731                                                     
dipropylene glycol                                                        
                  805                                                     
butylstanoic acid 0.5                                                     
______________________________________                                    
 
    
     Synthesize a polyester from the above as in Example 8, and place 300 g of the product in a separate flask at 20° C. Add 29 g isophorone diisocyanate and 30 g Jeffamine ED-2001 polyethylene oxide diamine, 2000 mol. wt. no. ave.--Texaco. The Jeffamine is predissolved in 30 g vinyl acetate to enhance miscibility. Slowly warm to 40° C. to allow amine reaction with isocyanate, hold 1 hour, and then heat to 90° C. Hold 2 hours, and then cool. 
     EXAMPLE 13 
     Polyester Amide External Oligomer Modifier 
     
         ______________________________________                                    
Ingredient          Grams                                                 
______________________________________                                    
DBE-5 (dimethyl ester of                                                  
                    481                                                   
glutaric acid, DuPont)                                                    
dipropylene glycol  268                                                   
Dytek A (2-methylpentane                                                  
                    58                                                    
diamine)                                                                  
butylstanoic acid   0.2                                                   
______________________________________                                    
 
    
     Warm with good agitation under nitrogen to about 190° C. and distill off methanol with a good packed column. Keep column head temperature at 64° C., and gradually warm batch to 210° C. Cool after 160 g of methanol is removed. 
     EXAMPLE 14 
     Polyester Amide External Oligomer Modifier 
     
         ______________________________________                                    
Ingredient           Grams                                                
______________________________________                                    
DBE-5                481                                                  
dipropylene glycol   268                                                  
Jeffamine D-230      115                                                  
(polypropylene oxide diamine)                                             
butylstanoic acid    0.5                                                  
______________________________________                                    
 
    
     Synthesized by same procedure as in Example 13. 
     EXAMPLE 15 
     Polyester External Oligomer Modifier 
     
         ______________________________________                                    
Ingredient        Grams                                                   
______________________________________                                    
dipropylene glycol                                                        
                  4717                                                    
adipic acid       4283                                                    
triphenyl phosphine                                                       
                  1.2                                                     
butylstanoic acid 3.0                                                     
______________________________________                                    
 
    
     Synthesize as in Example 8, but do not use xylene. When column head temperature drops to 80° C. acid number is about 20 mg KOH/g resin. Pull a vacuum of about 10 inches of Hg, and then gradually increase vacuum to pull off remaining water. Final acid number is 3 mg KOH/g resin. 
     EXAMPLE 16 
     Latexes were prepared with the following generalized formula and synthesized as described below. 
     
         ______________________________________                                    
a)   2122   g     deionized water                                         
     8.5    g     MA-80 (dihexyl sulfosuccinate, Mona Chem.)              
     5.4    g     ammonium acetate                                        
     8.1    g     Na AMPS, 48% (Lubrizol Chemical)                        
     10.5   g     A246L (Na olefin sulfonate, Rhone Poulenc)              
b)   7.4    g     Na formaldehyde sulfoxylate                             
     10     ml    FESO.sub.4 aqueous solution, 1000 ppm                   
c)   869    g     vinyl acetate                                           
     370    g     modifier as above from Examples 8 to 16                 
     3.1    g     acrylic acid                                            
d)   6.3    g     ammonium persulfate                                     
     14     g     A246L                                                   
     159    g     deionized water                                         
e)   874    g     vinyl acetate                                           
     3.1    g     acrylic acid                                            
f)   2.0    g     ammonium persulfate                                     
     27     g     deionized water                                         
______________________________________                                    
 
    
     Weigh and mix thoroughly groups (a) and (c). Combine groups (a) and (c), stir with a spatula to disperse, and then emulsify for 5 minutes at 10,000 rpm in a Ross ME 100L emulsifier. Add (b) ingredients to the emulsion, and warm in a 5 liter Morton flask to 50° C. with good agitation under nitrogen. Pump in 40 ml of (d) over 2.5 hours, adjusting pumping rate to give a reaction temperature of about 55° C. Pump in the rest of (d) and all of (e) over 3 hours. Pump in (f) over 1 hour. Cool. 
     EXAMPLES 17-24 
     Latexes approximately equivalent were prepared as in Example 16 and mixed with modifiers identified in Examples 8-15 as indicated in Table 2. 
     
                       TABLE 2                                                     
______________________________________                                    
Ex.  Modifier DSC Tg   Knife Point MFFT                                   
                                   Dry Film Tack                          
______________________________________                                    
17   Ex. 8     0       8.2         None                                   
18   Ex. 9    11       8.8         None                                   
19   Ex. 10   11       12.5        None                                   
20   Ex. 11   10       13.7        None                                   
21   Ex. 12   13       19.5        None                                   
22   Ex. 13    6       7.6         None                                   
23   Ex. 14   -5       10.0        Tacky                                  
24   Ex. 15   --       16.5        None                                   
______________________________________                                    
 *DSC Tg&#39;s in degrees C. (single, distinct transitions are noted). MFFT = 
 minimum film formation temperature in degree C. (knife point). Tack and  
 MFFT were measured for dry latex films (only DSC Tg was measured for     
 modifiers).                                                              
 
    
     The film from Example 23 is tacky at room temperature, while the other latexes form good, tack free films. The tack in Example 8 may be due to its very low Tg (-5° C.). Generally, Tg&#39;s in the 5°-10° C. range are preferred. MFFT&#39;s of 20° C. or less are preferred, indicating that good ambient and low temperature film formation will occur. Example 23 was marginally tacky due to low Tg of the film. 
     EXAMPLE 25 
     A polyester oligomer modifier was prepared from the following ingredients synthesized by the procedure in Example 8. Mn=910 and Mw=1770. 
     
         ______________________________________                                    
Ingredient      Grams                                                     
______________________________________                                    
adipic acid     2303                                                      
diethylene glycol                                                         
                2006                                                      
butylstanoic acid                                                         
                2.0                                                       
______________________________________                                    
 
    
     EXAMPLE 26 
     A polyester modifier higher molecular weight was synthesized as in Example 1 to acid number 7, mg KOH/g resin. Mn=2570, Mw=5010. 
     
         ______________________________________                                    
Ingredient       Grams                                                    
______________________________________                                    
adipic acid      330                                                      
diethylene glycol                                                         
                 450                                                      
butylstanoic acid                                                         
                 0.2                                                      
______________________________________                                    
 
    
     EXAMPLE 27 
     A polyester modifier of high molecular weight was synthesized as in Example 1, add 4 g additional diethylene glycol (to correct for glycol loss) and advance to higher molecular weight. Mn=8810, Mw=29,600 
     
         ______________________________________                                    
Ingredient       Grams                                                    
______________________________________                                    
diethylene glycol                                                         
                 326.6                                                    
adipic acid      450                                                      
butylstanoic acid                                                         
                 0.2                                                      
______________________________________                                    
 
    
     EXAMPLES 28-32 
     Latex paints were made from the latex of Example 15 mixed with the modifiers in Examples 25-27. 
     
         ______________________________________                                    
Example       Modifier                                                    
______________________________________                                    
28            Ex. 25                                                      
29            Ex. 26                                                      
30            Ex. 27                                                      
31            DER 333N (190 epoxy eqv. wt.,                               
              Dow Chemical)                                               
32            Poly THF 1000                                               
              (polytetramethylene oxide 1000                              
              m. wt.)                                                     
______________________________________                                    
 
    
     EXAMPLE 33 
     A latex was made from the following ingredients and synthesized as described below. 
     
         ______________________________________                                    
a-1)    760    g       deionized water                                    
        3.0    g       MA-80                                              
        3.7    g       A246L                                              
        1.9    g       ammonium acetate                                   
        3.1    g       Na AMPS                                            
a-2)    312    g       vinyl acetate                                      
        1.1    g       acrylic acid                                       
        116    g       modifier (as above)                                
b)      2.6    g       Na formaldehyde sulfoxylate                        
c)      3.7    ml      FESO.sub.4 aqueous solution, 1000 ppm              
d)      0.61   g       ammonium persulfate                                
        1.3    g       A246L                                              
        31     g       deionized water                                    
e)      1.7    g       ammonium persulfate                                
        5.6    g       A246L                                              
        42     g       deionized water                                    
f)      330    g       vinyl acetate                                      
        1.1    g       acrylic acid                                       
g)      0.71   g       ammonium acetate                                   
        9.6    g       deionized water                                    
______________________________________                                    
 
    
     Prepare mix a-1) and a-2), combine, and emulsify in an IKA works lab emulsifier, model SD-50, at the finest setting for 5 minutes. Place emulsion in a 2 liter Morton flask, and heat to 55° C. under nitrogen. Add (b) and (c), and then pump in (d) over 2.5 hours, controlling the exotherm at 55° C. Feed in mix (e) and (f) simultaneously over 2 hours, and then feed in (g) over 1 additional hour. Cool. 
     EXAMPLE 34 
     A vinyl acetate/butyl acrylate latex with polyester modifier was prepared as in Example 33 above, but instead mix (a-2) below and mix (f) below were used as follows: 
     
         ______________________________________                                    
a-2)    280    g      vinyl acetate                                       
        1.1    g      acrylic acid                                        
        38.6   g      polyester modifier from Example 18                  
        70     g      butyl acrylate                                      
f)      296    g      vinyl acetate                                       
        74     g      butyl acrylate                                      
        1.1    g      acrylic acid                                        
______________________________________                                    
 
    
     EXAMPLE 35 
     A vinyl acetate/butyl acrylate latex with modifier was prepared as in Example 33 above but instead mix (a-2) and mix (f) below were used as follows: 
     
         ______________________________________                                    
a-2)    265    g      vinyl acetate                                       
        1.1    g      acrylic acid                                        
        77.3   g      polyester modifier from Example 18                  
        66     g      butyl acrylate                                      
f)      280    g      vinyl acetate                                       
        70     g      butyl acrylate                                      
        1.1    g      acrylic acid                                        
______________________________________                                    
 
    
     The following is Table 3 listing properties for latex Examples 28-34. 
     
                       TABLE 3                                                     
______________________________________                                    
Example   Knife Point MFFT                                                
                        Ambient Film Tack                                 
______________________________________                                    
28        16° C. None                                              
29        19° C. None                                              
30        28° C. None                                              
31        &gt;29° C.                                                  
                        None                                              
32        &gt;29° C.                                                  
                        None                                              
33        17.4° C.                                                 
                        None                                              
34        16.3° C.                                                 
                        None                                              
______________________________________                                    
 
    
     The series of Examples 28, 29, and 30 illustrate the importance of modifier molecular weight. In moving from a polyester modifier with 2120 Mn (Example 28) to a polyester modifier with 8810 Mn (Example 30), MFFT moves from 16° C., which is normal for a latex with good low temperature film formation properties, to 28° C., which is too high for acceptable ambient and low temperature film formation. Increased amounts of the high molecular weight modifier will lower the MFT to an acceptable level. Examples 38 and 39 are unsatisfactory due to the composition and incompatibility of modifier. 
     EXAMPLE 36 
     A low molecular weight butyl carbitol diethylene glycol butyl ether/trimelitic anhydride triester modifier was prepared from the following ingredients and synthesized as described below. 
     
         ______________________________________                                    
Ingredient          Grams                                                 
______________________________________                                    
diethylene glycol butyl ether                                             
                    1095                                                  
trimelitic anhydride                                                      
                    435                                                   
butylstanoic acid   0.5                                                   
______________________________________                                    
 
    
     Stir under nitrogen in a 2 liter flask, and reflux off water with a good packed column, keeping head temperatures at 95° C. Cook at 190°-220° C., cool after 6.5 hours. 
     EXAMPLES 37-42 
     Several latexes were made according to the recipe below containing the triester modifier in Example 36 at triester levels indicated in each example 37-42 hereafter. 
     
         ______________________________________                                    
Example Number  Triester Level                                            
______________________________________                                    
37              0                                                         
38              25           g                                            
39              75           g                                            
40              100          g                                            
41              125          g                                            
42              150          g                                            
______________________________________                                    
 
    
     The above levels of triester were used in the following latex to form a latex paint containing the triester modifier. 
     
         ______________________________________                                    
a)  800    g     deionized water                                          
    6.0    g     MM-80                                                    
    1.0    g     NAHCO                                                    
    1.0    g     NaAMPS.sup.3                                             
b)  250    g     vinyl acetate                                            
    2.0    g     WAM (wet adhesion ureidal? monomer, Alcolac              
                 Chem.)                                                   
    (Z)    g     triester level as above                                  
c)  2.0    g     ammonium persulfate                                      
d)  250    g     vinyl acetate                                            
    6.0    g     MT-70 (ditridecyl sulfosuccinate, Mona                   
                 Chemical)                                                
______________________________________                                    
 
    
     Blend mix (b) into mix (a) with a lab turbine at about 1000 rpm. Pass through the flow through cell of an ultrasound unit at 85% (Sonics &amp; Materials, VC-600). Heat to 67° C., hold 30 minutes, add (c) and hold 1.5 hours. Pump in (d) over 3 hours, and cool. 
     
                       TABLE 4                                                     
______________________________________                                    
To determine the effect of modifier level on degree of                    
plasticizer, a variety of VA homopolymer latexes were                     
synthesized, as described in examples 45-50 which contain                 
concentrations of triester ranging from 0 to 30% of the latex             
solids as noted in Examples 45-50. Glass transition                       
temperature were determined by DSC, as described in the                   
specification, with results of two DSC runs as follows:                   
Ex.    Pct. Triester Tg DSC(1) Tg DSC(2)                                  
______________________________________                                    
45      0            38        36                                         
46      5            13        30                                         
47     15             6        13                                         
48     20             0         6                                         
49     25            -4         2                                         
50     30            -12       -5                                         
______________________________________                                    
 
    
     Run 1 involves cooling to -100° C., and scanning to 150° C. Run 2 immediately follows run 1, and involves the same cooling and heating processes. It is commonly accepted in the field of thermal analysis that the more reliable and practically-significant result is the one for run 2. 
     This demonstrates the dependence of the Tg of the polymer-modifier mixture on the concentration of the plasticizing modifier. It also demonstrates the compatibility of the mixture, in that only single transitions are observed. 
     EXAMPLES 43 AND 44 
     Vinyl acetate homopolymer (Ex. 43) and vinyl acetate/butyl acrylate copolymer (Ex. 44) were produced from the following ingredients. 
     
         ______________________________________                                    
            Ex. 44                                                        
Ex. 43      (control)                                                     
______________________________________                                    
a)     2022   g     2022   g    deionized water                           
       7.2    g     7.2    g    MM-80                                     
       4.3    g     4.3    g    ammonium acetate                          
       5.4    g     --          SAM 181 surfactants                       
                                (PPG Chemical)                            
       --           5.4    g    A246L                                     
b)     35     g     28     g    vinyl acetate                             
       --           7.0    g    butyl acrylate                            
       0.7    g     0.7    g    ammonium persulfate                       
c)     1700   g     1034   g    vinyl acetate                             
       --           677    g    butyl acrylate                            
       2.4    g     2.4    g    acrylic acid                              
d)     5.4    g     5.4    g    ammonium persulfate                       
       21     g     21     g    A246L                                     
       135    g     135    g    deionized water                           
       12     g     --          SAM 181                                   
       --           15     g    NaAMPS                                    
e)     20     g     --          Triton X-100                              
                                (Rohm and Haas)                           
______________________________________                                    
 
    
     Warm (a) to 71° C. under nitrogen with good stirring. Add (b) and allow exotherm to die (about 15 minutes). Pump in (c) and (d) in parallel over 5 hours. Hold 1 hour and add (e) dropwise over 5 minutes. Mix 20 minutes and cool. 
     EXAMPLE 45 
     Comparison of Soft Copolymer, Coalesced Hard Copolymer (Prior Art) with Current Invention 
     Prior art. Conventionally, the balance of low temperature film formation and absence of tack at ambient temperature is achieved by utilizing a latex composition with an elevated Tg, to achieve absence of tack, and then temporarily reducing its Tg with a volatile coalescing solvent such as Texanol, to achieve low temperature film formation. While this works well, it also involves the emission of the coalescing solvent into the atmosphere, which contributes odor and air pollution. Example 43 describes the synthesis of such a typical copolymer composition. For this experiment, coalescing solvent Texanol at the level of 6% was added to the latex of Example 43 to achieve a KMFT of 10° C. A film cast with this coalesced latex is non-tacky at room temperature, but emits volatile solvent to the atmosphere. 
     Conversely, if one makes a copolymer with a low enough Tg to achieve low temperature film formation (60/40 VA/BA), it forms a film which is excessively tacky at ambient use temperature. While this would involve no emissions to the atmosphere, it involves a commercially unacceptable balance of properties. Example 44 describes the synthesis of a typical soft copolymer which achieves a KMFT of 10° C. on its own. A film cast from this latex is extremely tacky at room temperature, but emits no solvents to the atmosphere. 
     Present Invention. In the present invention, the use of a non-volatile external plasticizer accomplishes all three goals simultaneously: low temperature film formation, tack-free behavior at ambient temperatures, and no volatile organic emissions to the atmosphere. Using the formula in Example 43, a vinyl acetate homopolymer was synthesized containing 18% oligomeric modifier, which achieved a KMFT (knife MFT) of 10° C. on its own. A film cast from this latex is non-tacky at room temperature, and emits no solvents to the atmosphere. The results are summarized as follows: 
     
         ______________________________________                                    
                                   Organic                                
Approach     LTFF?    Ambient Tack (?)                                    
                                   Emissions?                             
______________________________________                                    
Coalesced hard latex                                                      
             yes      no           yes                                    
Soft copolymer                                                            
             yes      yes          no                                     
Present invention                                                         
             yes      no           no                                     
______________________________________                                    
 
    
     EXAMPLE 46 
     Demonstration of Non-volatile and Non-migrating Behavior of Modifier 
     A VA/BA 80/20 copolymer latex was compared to a vinyl acetate homopolymer latex coalesced conventionally with dibutyl phthalate (DBP); to one coalesced conventionally with Texanol; and to an example of this invention (example 24) which was a VA homopolymer containing a polyester external modifier. The Tg of films of the four latexes was monitored by DSC for up to 8 weeks, while the films were aged at 140° F, to simulate accelerated aging of the films, and results are reported on Table 5. 
     
                       TABLE 5                                                     
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Latex       Initial Tg Tg (8 wks)                                         
                                 Change in Tg                             
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hard copolymer                                                            
            17         17         0                                       
VA/DBP      12         31        19                                       
VA/Texanol  10         32        22                                       
Ex. 24       4          6         2                                       
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     As expected, the untreated copolymer showed no change in Tg, since there were no volatiles to be lost in the system. Also as expected, the conventionally coalesced latexes showed a substantial increase in Tg, due to the loss of the volatile coalescing solvent. However, example 24 of this invention showed a negligible change, indicating that the modifier is essentially non-volatile. 
     An examination of the films showed that block resistance increased for the coalesced samples over time, while it remained constant for the untreated copolymer and for the example of this invention. This indicates that the modifier is also essentially non-migrating in nature. 
     EXAMPLE 47 
     Demonstration of Compatibility of Modifier in Matrix Polymer 
     The Tg&#39;s of the latex samples described in Table 4 were determined by both DSC and DMA. In both cases, the samples exhibited single Tg&#39;s, which were intermediate between the Tg&#39;s of the components. Additionally, there was no evidence of Tg transitions characteristic of either of the individual components. This is strong evidence of the compatibility the mixture of the modifier and the matrix polymer. 
     In addition, the Tg&#39;s of these same latex samples were compared to those calculated by the Fox relationship as described in the text. The component Tg&#39;s were -72° C. for the triester modifier, and 36° C. for VA homopolymer parent polymer, as determined by DSC. Results are reported in the following Table 6. 
     
                       TABLE 6                                                     
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Pct. Modifier                                                             
           Meas. Tg    Calc. Tg Difference                                
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 0         36          --       --                                        
 5         30          28       2                                         
15         13          13       0                                         
20          6           6       0                                         
25          2           0       2                                         
30         -5          -7       2                                         
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     This correlation between measured and calculated Tg&#39;s and the strong dependence of the Tg on the level of modifier, are strong evidence of the compatibility of the triester with the VA homopolymer.