VINYL^ACRYLIC^EMULSION^COPOLYMER^AND^USE^THEREOF^IN^ STAIN^RESISTANT^COATING^COMPOSITIONS ^ FIELD^OF^THE^INVENTION^ This^ disclosure^ relates^ generally^ to^ waterborne^ vinyl^ acetate–acrylic,^ “vinyl^ acrylic”^ emulsion^copolymers^which^can^be^used^in^architectural^coati ngs^and^impart^stain^resistance^to^ such^coatings.^The^vinyl^acrylic^emulsion^copolymer^particle s^in^the^emulsion^may^contain^one^ or^more^particle^size^modes,^each^with^a^ respective^narrow^particle^size^distribution.^The^vinyl^ acrylic^emulsion^copolymers^contain^as^a^comonomer^an^ethyle nically^unsaturated^monomer^and^ also^ contain^ a^ hydrolyzable^ silane^ comonomer.^ The^ hydrolyzable^ silane^may^ be^ present^ as^ a^ comonomer^ in^ the^vinyl^acrylic^ copolymer^ and/or^may^be^added^ to^ the^vinyl^ acrylic^emulsion^ copolymer^emulsion^in^the^form^of^a^hydrolyzable^silane^that ^comprises^a^reactive^group^that^is^ capable^of^reacting^with^the^vinyl^acrylic^copolymer.^ ^ BACKGROUND^OF^THE^INVENTION^ Cleansability,^ sometimes^ used^ synonymously^ with^ the^ terms^ “stain^ resistance”^ or^ “washability”,^refers^to^the^ability^of^a^coating^to^res ist^staining^or^to^be^washed^clean^after^being^ stained.^Coatings^that^achieve^good^cleansability^have^utili ty^in^the^areas^of^interior^and^exterior^ architectural/decorative^ coatings.^Waterborne^ coating^ technologies^ that^ occupy^ this^ space^ are^ based^ on^ acrylic,^ vinyl^ acrylic^ (i.e.,^ vinyl^ acetate-acrylic^ copolymers),^ and^ styrene-acrylic^ emulsion^ copolymers,^ for^ example.^ Coatings^ that^ display^ this^ performance^ attribute^ may^ be^ tested^ via^ a^ number^ of^ independent^ entities,^ to^ include^ but^ not^ limited^ to^ ASTM,^ Consumer^ Reports,^and^Master^Painter’s^Institute^(MPI).^ Master^ Painter^s^ Institute^ (MPI)^ is^ an^ independent^ third-party^ organization^ that^ sets^ performance^ standards^ for^ commercially^ available^ paints^ and^ coatings.^Many^ institutional^ and^ high^ performance^ paint^ specifications^ are^ tied^ to^ MPI^ standards.^ Current^ cleansablity^ tests^ evaluate^the^cleansability^of^a^coating^using^hot^coffee,^gr aphite,^and^a^2^wt.^^aqueous^solution^ of^nigrosine.^Cleansability^to^nigrosine^stain^is^considered ^more^difficult^to^pass^than^the^former^ hydrophilic^ stains.^ As^ such,^ meeting^ the^ cleansability^ specification^ according^ to^ the^ MPI^ cleansability^tests^is^highly^desirable^and^a^significant^ch allenge.^^ When^used^as^the^sole^binder^in^an^interior^paint,^many^viny l^acrylic^emulsion^polymers^ do^ not^ meet^ the^ cleansability^ requirement^ for^ MPI^ specifications^ with^ the^ new^ cleansability^ requirements.^However,^ the^cost-effectiveness^of^ vinyl^ acrylic^emulsion^ polymers^makes^ them^ attractive.^ One^approach^to^meeting^the^MPI^specification^related^to^cle ansability^and^still^achieve^a^ cost^target^is^by^blending^acrylic-based^emulsions^into^the^ interior^paints^containing^vinyl^acrylic^ emulsions.^ This^ approach,^ however,^ negatively^ impacts^ other^ properties,^ as^ well^ as^ adds^ additional^cost^to^the^final^coatings^related^to^storage^and ^processing^time^to^blend^the^separate^ emulsions.^Lastly,^acrylic^emulsions^are^not^as^cost-effecti ve^as^vinyl^acrylic^emulsion^polymers.^ Accordingly,^ there^ is^ a^need^ for^a^ cost-effective^vinyl^ acrylic^ emulsion^polymer^ that^ is^ able^to^meet^the^stringent^cleansability^tests,^while^retain ing^cost-effectiveness^and^meeting^other^ critical^performance^standards.^ SUMMARY^OF^THE^INVENTION^ A^first^embodiment^of^an^emulsion^polymer^composition^compri sing^a^population^of^ sizes^of^polymeric^particles^is^provided.^The^polymeric^part icles^comprise^copolymer^ comprising,^in^polymerized^form,^monomers^a),^b)^and^c).^Mon omer^a)^is^present^at^between^40^ weight^percent^and^95^weight^percent,^based^on^the^overall^w eight^of^the^polymeric^particles,^and^ comprises^at^least^one^monomer^comprising^vinyl^acetate.^Mon omer^b)^is^present^at^between^1.0^ weight^percent^and^59.09^weight^percent,^based^on^the^overal l^weight^of^the^polymeric^particles,^ and^comprises^at^least^one^ethylenically^unsaturated^monomer .^Monomer^c)^is^present^at^between^ 0.01^weight^percent^and^4.0^weight^percent,^based^on^the^ove rall^weight^of^the^polymeric^ particles,^and^comprises^at^least^one^monomer^selected^from^ free^radical^polymerizable^ hydrolyzable^silanes.^The^at^least^one^ethylenically^unsatur ated^monomer^b)^is^not^selected^from^ a)^or^c),^and^monomer^a),^monomer^b),^and^monomer^c)^togethe r^total^100^weight^percent.^ Further,^the^population^of^sizes^of^polymeric^particles^in^t he^first^embodiment^comprises^at^least^ one^mode.^Each^mode _i ^comprises^a^respective^weight^average^particle^size^D w _i ^as^measured^by^ disc^centrifuge^photosedimentometry^and^a^respective^number^ average^particle^size^Dn _i ^as^ measured^by^disc^centrifuge^photosedimentometry.^For^each^mo de _i ,^Dw _i /Dn _i ^is^2.0^or^less.^ 2^ ^ Also^provided^is^a^second^embodiment^emulsion^polymer^compos ition^comprising^a^ population^of^sizes^of^polymeric^particles.^The^polymeric^pa rticles^comprise^copolymer^which^ comprises,^in^polymerized^form,^monomer^a)^and^monomer^b).^M onomer^a)^is^present^at^ between^40^weight^percent^and^95^weight^percent,^based^on^th e^overall^weight^of^the^polymeric^ particles.^^Monomer^a)^comprises^at^least^one^monomer^compri sing^vinyl^acetate.^Monomer^b)^is^ present^at^between^5^weight^percent^and^60^weight^percent,^b ased^on^the^overall^weight^of^the^ polymeric^particles.^Monomer^b)^comprises^at^least^one^ethyl enically^unsaturated^monomer.^The^ at^least^one^ethylenically^unsaturated^monomer^b)^is^not^sel ected^from^monomer^a),^and^ monomer^a),^and^monomer^b)^together^total^100^weight^percent .^Further,^the^population^of^sizes^ of^polymeric^particles^in^the^second^embodiment^comprises^at ^least^one^mode.^Each^mode _i ^ comprises^a^respective^weight^average^particle^size^Dw _i ^as^measured^by^disc^centrifuge^ photosedimentometry^and^a^respective^number^average^particle ^size^Dn _i ^as^measured^by^disc^ centrifuge^photosedimentometry.^For^each^mode _i ,^Dw _i /Dn _i ^is^2.0^or^less.^The^second^ embodiment^emulsion^polymer^composition^further^comprises^be tween^0.1^and^5^weight^percent,^ based^on^the^total^dry^weight^of^the^polymeric^particles,^of ^at^least^one^hydrolyzable^silane^ selected^from^trialkoxy^silanes,^tetraalkoxysilanes,^and^mix tures^thereof.^ In^general,^the^process^for^preparing^the^emulsion^polymers^ described^herein^are^known^ to^those^who^practice^the^art;^however,^many^compositions^an d^process^variables^contribute^to^ the^particle^size^distribution^described^above.^For^the^purp ose^of^description,^one^such^process^ for^forming^an^emulsion^polymer^composition^comprising^a^pop ulation^of^sizes^of^polymeric^ particles^is^provided.^The^process^comprises^the^following^s teps:^ Step^i):^^Combining,^in^a^vessel,^water,^an^anionic^surfacta nt,^a^first^monomer^mixture,^ then^a^first^portion^of^free^radical^initiator.^The^first^mo nomer^mixture^comprises^monomers^a),^ b)^and^c).^^Monomer^a)^is^present^at^between^40^weight^perce nt^and^95^weight^percent,^based^on^ the^overall^weight^of^the^first^monomer^mixture.^Monomer^a)^ comprises^at^least^one^monomer^ comprising^vinyl^acetate.^Monomer^b)^is^present^at^between^1 .0^weight^percent^and^59.09^weight^ percent,^based^on^the^overall^weight^of^the^first^monomer^mi xture.^Monomer^b)^comprises^at^ least^one^ethylenically^unsaturated^monomer.^Monomer^c)^is^p resent^at^between^0.01^weight^ percent^and^4.0^weight^percent,^based^on^the^overall^weight^ of^the^first^monomer^mixture.^ 3^ ^

Monomer^c)^comprises^at^least^one^monomer^selected^from^f ree^radical^polymerizable^ hydrolyzable^silanes.^The^at^least^one^ethylenically^unsatur ated^monomer^b)^is^not^selected^from^ a)^or^c),^wherein^monomer^a),^monomer^b),^and^monomer^c)^tog ether^total^100^weight^percent.^^ Step^ii):^Polymerizing^the^first^portion^of^the^monomer^mixt ure^to^form^seed^particles.^ Step^iii):^Combining^in^the^vessel^with^the^seed^particles^a ^second^portion^of^free^radical^ initiator^and^a^second^monomer^mixture.^The^second^monomer^m ixture^comprises^monomers^d),^ e)^and^f).^Monomer^d)^is^present^at^between^40^weight^percen t^and^95^weight^percent,^based^on^ the^overall^weight^of^the^second^monomer^mixture.^Monomer^d) ^comprises^at^least^one^monomer^ comprising^vinyl^acetate.^Monomer^e)^is^present^at^between^1 .0^weight^percent^and^59.09^weight^ percent,^based^on^the^overall^weight^of^the^second^monomer^m ixture.^Monomer^e)^comprises^at^ least^one^ethylenically^unsaturated^monomer.^^Monomer^f)^ is^present^at^between^0.01^weight^ percent^and^4.0^weight^percent,^based^on^the^overall^weight^ of^the^second^monomer^mixture.^ Monomer^f)^comprises^at^least^one^monomer^selected^from^free ^radical^polymerizable^ hydrolyzable^silanes.^The^at^least^one^ethylenically^unsatur ated^monomer^e)^is^not^selected^from^ d)^or^f),^wherein^monomer^d),^monomer^e),^and^monomer^f)^tog ether^total^100^weight^percent.^^ Step^iv):^Polymerizing^on^the^seed^particles^the^second^mono mer^mixture^to^form^the^ population^of^polymeric^particles.^The^population^of^polymer ic^particles^comprises^at^least^one^ mode.^Each^mode _i ^comprises^a^respective^weight^average^particle^size^D w _i ^as^measured^by^disc^ centrifuge^photosedimentometry^and^a^respective^number^avera ge^particle^size^Dn _i ^as^measured^ by^disc^centrifuge^photosedimentometry.^For^each^mode _i ,^Dw _i /Dn _i ^is^2.0^or^less.^ Also^provided^are^coatings^comprising^the^first^emulsion^pol ymer^composition^disclosed^ herein,^as^well^as^coating^comprising^the^second^embodiment^ emulsion^polymer^composition^ disclosed^herein.^The^coatings^are^capable^of^meeting^the^cl eansability^specification^described^in^ MPI^standards^^143-148^and^MPI^^138-141.^ Further^areas^of^applicability^will^become^apparent^from^the ^description^provided^herein.^^ ^ ^ 4^ ^

BRIEF^DESCRIPTION^OF^THE^DRAWINGS^ The^drawings^described^herein^are^for^illustration^purposes^ only.^ Figure^1^illustrates^a^criteria^for^measuring^particle^size^ distribution;^ Figure^2^illustrates^a^criteria^for^measuring^particle^size^ distribution;^ Figure^3^shows^an^exemplary^cleansability^test^panel;^ Figure^4^shows^particle^ size^distributions^for^emulsion^polymers^according^to^Exampl es^ 1-4^and^Comparative^Example^1;^^ Figure^ 5^ shows^ a^ particle^ size^ distribution^ for^ emulsion^ polymers^ according^ to^ Comparative^Example^2;^ Figure^6^shows^a^particle^size^distribution^for^emulsion^pol ymers^according^to^Example^ 5;^and^ Figure^7A^shows^a^bimodal^particle^size^distribution^for^emu lsion^polymers^according^to^ Example^6;^ Figure^7B^shows^the^particle^size^distribution^of^one^of^the ^two^modes^in^Figure^7A;^and^ Figure^7C^shows^the^particle^size^distribution^of^the^other^ of^the^two^modes^in^Figure^7A.^^ ^ DETAILED^DESCRIPTION^ The^ following^ description^ is^merely^ exemplary^ in^ nature^ and^ is^ in^ no^way^ intended^ to^ limit^the^present^disclosure^or^its^application^or^uses.^ In^the^context^of^the^present^disclosure,^“cleansability� �^refers^to^the^ability^of^a^coating^to^ resist^staining^or^to^be^washed^clean^after^being^stained.^ Unless^otherwise^indicated,^all^percentages^herein^are^weigh t^percentages.^^ “Polymer”^as^used^herein,^is^meant^ to^include^organic^molecules^with^a^weight^average^ molecular^weight^higher^than^20,000^g/mol,^preferably^higher ^than^50,000^g/mol,^as^measured^by^ gel^permeation^chromatography.^ 5^ ^

“Hydrolyzable”^ silane^ as^ used^ herein,^ is^ meant^ to^ describe^ a^ molecule^ of^ the^ type^ containing^silicon^atoms^bonded^to^one^or^more^alkoxy^functi onal^groups^that^can^hydrolyze^to^ hydroxyl^functional^groups^under^a^variety^of^aqueous^condit ions.^ Generally,^the^inventors^have^discovered^that^vinyl^acrylic^ emulsion^polymers^containing^ polymer^ particles^ that^ exhibit^ one^ or^ more^ particle^ size^ distributions^ as^ measured^ by^ Disc^ Centrifuge^Photosedimentometer^(“CPS^ Instruments”),^each^with^a^polydispersity^index^of^ less^ than^2.0,^as^expressed^by^the^ratio^of^the^weight^average^pa rticle^size^(D _w )^to^the^number^average^ particle^ size^ (D _n ),^ combined^ with^ a^ low^ level^ of^ a^ hydrolyzable^ silane^ functionality^ in^ the^ polymer^ and/or^ as^ a^ component^ of^ the^ emulsion,^ results^ in^ a^ surprising^ improvement^ in^ cleansability^ of^ a^ coating^ composition^ comprising^ the^ emulsion^ polymer.^ The^ combination^ of^ both^ the^ low^ level^ of^hydrolyzable^ silane,^whether^ included^ as^a^polymerized^monomer^ in^ the^ emulsion^ polymer^ comprising^ the^ particles^and/or^as^ a^ functionalized^hydrolyzable^ silane^ as^a^ separate^component^of^the^emulsion,^and^a^ratio^of^the^weigh t^average^particle^size^to^the^number^ average^particle^ size^of^2.0^ or^ less^ results^ in^better^cleansability^ in^ a^coating^made^ from^ these^ materials^than^either^alone,^ i.e.,^ the^improvement^in^cleansability^is^not^seen^if^both^factors ^are^ not^ present.^ This^ surprising^ discovery^ permits^ the^ use^ of^ coating^ compositions^ comprising^ emulsions^comprising^vinyl^acrylic^emulsion^polymers^without ^ the^need^ to^ separately^blend^ in^ another^separate^emulsion^to^achieve^cleansability^specifica tions.^ In^ a^ first^ embodiment,^ the^ present^ disclosure^ generally^ provides^ an^ emulsion^ polymer^ composition^comprising^polymeric^particles.^The^polymeric^pa rticles^comprise,^in^polymerized^ form,^ three^types^of^monomers.^Monomer^a)^is^at^least^one^monomer^ comprising^vinyl^acetate.^ Monomer^ b)^ may^ be^ at^ least^ one^ ethylenically^ unsaturated^ monomer.^ Monomer^ c)^ may^ be^ selected^from^monomers^containing^hydrolyzable^silane^functi onal^groups^that^are^added^during^ the^ emulsion^ polymerization.^ The^ at^ least^ one^ ethylenically^ unsaturated^ monomer^ b)^ is^ not^ selected^from^a)^vinyl^acetate^or^c)^monomers^containing^hyd rolyzable^silane^functional^groups.^ Together,^the^three^monomers^total^100^weight^percent^on^a^d ry^basis.^ In^a^second^embodiment,^the^present^disclosure^generally^pro vides^an^emulsion^polymer^ composition^comprising^polymeric^particles.^The^polymeric^pa rticles^comprise,^in^polymerized^ form,^ two^ types^of^monomers.^Monomer^a)^ is^at^ least^one^monomer^comprising^vinyl^ acetate.^ 6^ ^

Monomer^ b)^ may^ be^ at^ least^ one^ ethylenically^ unsaturated^ monomer.^ The^ at^ least^ one^ ethylenically^ unsaturated^monomer^ b)^ is^ not^ selected^ from^ a)^ vinyl^ acetate.^ Together,^ the^ two^ monomers^ a)^ and^ b)^ total^ 100^ weight^ percent^ on^ a^ dry^ basis.^ In^ this^ second^ embodiment,^ in^ contrast^ to^ the^ first^ embodiment,^ the^ hydrolyzable^ silane^ functionality^ may^ be^ added^ to^ the^ emulsion^ polymer^ composition^ in^ the^ form^ of^ a^ non-ethylenically^ unsaturated^ hydrolyzable^ silane^additive.^ Throughout^ the^ following^ description,^ the^ difference^ between^ the^ two^ embodiments^ of^ the^emulsion^polymer^composition^is^the^hydrolyzable^silane^ component^of^each^embodiment^as^ described.^ It^ should^ be^ understood^ that^ the^ two^ embodiments^ are^ used^ in^ the^ same^way,^ and^ except^ for^ the^ silane^ component,^ all^ other^ discussion^ herein^ regarding^ coating^ compositions^ made^from^these^embodiments^as^well^as^ their^cleansability^apply^to^each.^Accordingly,^unless^ the^ “first^ embodiment^ emulsion^ polymer^ composition”^ or^ the^ “second^ embodiment^ emulsion^ polymer^composition”^is^expressly^referenced,^the^descript ion^applies^to^each^of^the^first^and^the^ second^emulsion^polymer^composition^embodiments.^ The^ polymeric^ particles^ in^ the^ emulsion^ polymer^ composition^ according^ to^ both^ embodiments^ have^ a^ weight^ average^ particle^ size^ and^ a^ number^ average^ particle^ size,^ both^^ measured^by^disc^centrifuge^photosedimentometry.^Importantly ,^the^ratio^of^the^weight^average^ particle^ size^ to^ the^ number^ average^ particle^ size^ as^ measured^ by^ disc^ centrifuge^ photosedimentometry^is^2.0^or^less.^This^ratio^of^weight^ave rage^particle^size^to^number^average^ particle^size^is^also^referred^to^as^the^size^polydispersity ^index.^ Monomer^a):^vinyl^acetate^ Vinyl^ acetate^ may^ be^ present^ (in^ polymerized^ form)^ in^ the^ polymer^ in^ the^ emulsion^ polymer^composition^at^levels^from^40^weight^percent^to^95^w eight^percent,^based^on^the^overall^ weight^of^the^polymeric^particles,^on^a^dry^basis,^i.e.^excl uding^water.^The^vinyl^acetate^may^be^ present^at^levels^from^40^wt.^^-^90^wt.^,^or^from^45^wt.^^to ^80^wt.^,^or^from^55^wt.^^–^90^ wt.^,^or^60^wt.^^–^85^wt.^,^or^75^wt.^^–^80^wt.^,^or^50^ wt.^^–^80^wt.^,^or^70^wt.^^–^95^ wt.^,^or^75^wt.^^–^85^wt.^,^or^70^wt.^^–^90^wt.^.^ ^ 7^ ^

Monomer^b):^ethylenically^unsaturated^monomer^ Non-limiting^ examples^ of^ suitable^ ethylenically^ unsaturated^ monomers^ that^ may^ be^ included^(in^polymerized^form)^in^the^polymer^comprising^the ^polymeric^particles^include^alkyl^ acrylate^ monomers,^ alkyl^ methacrylate^ monomers,^ vinyl^ ester^ monomers,^ (meth)acrylamide^ monomers,^ and^ mixtures^ thereof.^ Non-limiting^ examples^ include^ such^ monomers^ as^ butyl^ acrylate,^ methyl^ acrylate^ and^ ethyl^ acrylate,^ methyl^ methacrylate,^ ethyl^ methacrylate,^ butyl^ methacrylate,^cyclohexyl^(meth)acrylate,^allyl^methacrylate, ^2-ethylhexyl^acrylate,^styrene^and/or^ its^ derivatives^ such^ as^ alpha-methyl^ styrene.^ Other^ methacrylate,^ acrylate,^ and^ other^ vinyl^ monomers,^ e.g.,^ vinyl^ cyanide^ monomers^ and^ acrylonitriles,^ useful^ in^ the^ monomer^ mixture^ include,^ but^ are^ not^ limited^ to^ iso-octyl^methacrylate,^ iso-octyl^ acrylate,^ lauryl^ acrylate,^ lauryl^ methacrylate,^ stearyl^ acrylate,^ stearyl^ methacrylate,^ isobornyl^ acrylate,^ isobornylmethacrylate,^ methoxy^ ethyl^ acrylate,^ methoxy^ methacrylate,^ 2-ethoxy^ ethyl^ acrylate,^ 2-ethoxy^ ethyl^ methacrylate,^ and^ methacrylate^ monomers,^ styrene^ and^ its^ derivatives,^ acrylamide,^ or^ methacrylamide.^Monoethylenically^unsaturated^monomers^conta ining^acid-functionality^such^as^ monomers^containing^at^least^one^carboxylic^acid^group^inclu ding^acrylic^acid,^methacrylic^acid,^ acryloxypropionic^acid,^(meth)acryloxypropionic^acid,^itacon ic^acid,^aconitic^acid,^maleic^acid^or^ anhydride,^ fumaric^ acid,^ crotonic^ acid,^ monomethyl^ maleate,^ monomethyl^ fumarate,^ monomethyl^ itaconate^and^ the^ like^may^be^used.^Small^ levels^of^multifunctional^monomers^as^ crosslinking^agents^may^also^be^used.^Mixtures^of^any^or^all ^of^these^are^also^suitable.^^ Preferred^ are^ methyl^ acrylate,^ methyl^ methacrylate,^ ethyl^ acrylate,^ ethyl^ methacrylate,^ propyl^ acrylate,^ propyl^ methacrylate,^ n-iso-^ and^ tert-butyl^ acrylate,^ n-iso-^ and^ tert-butyl^ methacrylate,^2-ethylhexyl^acrylate,^and^norbornyl^acrylate. ^^More^preferred^are^n-butyl^acrylate,^ methyl^acrylate,^ethyl^acrylate,^and^2-ethylhexyl^acrylate.^ The^ at^ least^ one^ ethylenically^ unsaturated^ monomer^ may^ be^ present^ in^ the^ polymeric^ particles^ of^ the^ first^ embodiment^ emulsion^ polymer^ composition^ at^ levels^ of^ from^ 1.0^weight^ percent^to^59.09^weight^percent,^based^on^the^overall^weight ^of^the^polymeric^particles,^on^a^dry^ basis.^For^ example,^ the^ at^ least^ one^ ethylenically^ unsaturated^monomer^may^ be^present^ in^ the^ polymeric^particles^of^the^ first^embodiment^ at^ from^2.0^ to^40wt.^,^or^ from^10^ to^30^wt.^,^or^ 8^ ^ from50^to^59wt.^^or^from^15^to^25wt.^,^or^from^20^to^55wt.^, ^or^from^40^to^50wt.^,^based^on^ the^overall^weight^of^the^polymeric^particles,^on^a^dry^basi s.^^ The^ at^ least^ one^ ethylenically^ unsaturated^ monomer^ may^ be^ present^ in^ the^ polymeric^ particles^ of^ the^ second^embodiment^ emulsion^ polymer^ composition^at^ levels^of^ from^5^weight^ percent^ to^60^weight^percent,^ based^on^ the^overall^weight^of^ the^polymeric^particles,^on^ a^dry^ basis.^For^ example,^ the^ at^ least^ one^ ethylenically^ unsaturated^monomer^may^ be^present^ in^ the^ polymeric^particles^of^the^second^embodiment^at^from^2.0^to^ 40wt.^,^or^from^10^to^30^wt.^,^or^ from^50^to^59wt.^^or^from^15^to^25wt.^,^or^from^20^to^55wt.^ ,^or^from^40^to^50wt.^,^based^on^ the^overall^weight^of^the^polymeric^particles,^on^a^dry^basi s.^^ In^ an^ embodiment,^ the^ emulsion^ polymer^ composition^ may^ comprise,^ in^ polymerized^ form,^ acid-containing^monomers,^ selected^ from^but^ not^ limited^ to^ sulfonic^acid-functionalized^ ethylenically^ unsaturated^ monomers^ such^ as^ 2-acrylamido-2-methylpropane^ sulfonic^ acid^ (AMPS),^sodium^vinyl^sulfonate^(SVS),^acrylic^acid,^and^meth acrylic^acid.^These^monomers^can^ be^present^in^polymerized^form^at^a^level^from^0.01^weight^p ercent^and^2.5^weight^percent^based^ on^the^overall^dry^weight^of^the^polymeric^particles.^^ In^ an^ embodiment,^ the^ emulsion^ polymer^ composition^ may^ comprise,^ in^ polymerized^ form,^a^monomer^selected^from^vinyl^versatate^in^an^amount^b etween^0.1^weight^percent^and^10^ weight^ percent.^ Other^ suitable^ monomers^ may^ be^ selected^ from,^ for^ example,^ vinyl^ esters^ of^ tertiary^ substituted^ α-carbon^ carboxylic^ acids^ and^ vinyl^ esters^ of^ C7-C20^ carboxylic^ acids.^ Mixtures^of^any^or^all^of^these^are^suitable^as^well.^ Monomer^ c)^ hydrolyzable^ silane^ monomer^ in^ the^ first^ embodiment^ emulsion^ polymer^ composition^^ Non-limiting^ examples^ of^ suitable^ hydrolyzable^ silane^ co-monomers^ in^ the^ first^ embodiment^emulsion^polymer^composition^include^ethylenicall y^unsaturated^silicon^compounds^ of^the^general^formula^R^SiR _0-2 (OR) _1-3 ,^where^the^number^of^R^and^OR^moieties^is^such^that^t he^ silicon^is^tetravalent.^R^^is^an^organofunctional^substitute d^alkylene,^arylene^or^aralkylene^group,^ which^may^have^from^two^to^thirty^carbon^atoms^and^R^is^an^a lkyl^or^alkoxy-substituted^alkyl,^ aryl,^ or^ aralkyl^ group^ having^ from^ two^ to^ ten^ carbon^ atoms.^ Each^ R^ group^ may^ be^ cyclic,^ 9^ ^

branched^or^linear^and^contains^no^unsaturation.^Preferab ly,^the^ethylenically^unsaturated^silane^ compound^ is^ selected^ from^ the^group^consisting^of^vinyltrimethoxysilane,^vinyltriethox ysilane,^ methacryloxypropyl^ trimethoxysilane,^ methacryloxypropyl^ triethoxysilane,^ and^ methacryloxypropyl^tripropoxysilane.^ The^ hydrolyzable^ silane^ co-monomers^ in^ the^ first^ embodiment^ emulsion^ polymer^ composition^may^comprise^from^0.01^weight^percent^to^4.0^wei ght^percent,^based^on^the^overall^ dry^ solids^ weight^ of^ the^ polymeric^ particles^ in^ the^ first^ embodiment^ emulsion^ polymer^ composition,^ of^ the^ hydrolyzable^ silane^ monomer.^ For^ example,^ the^ hydrolyzable^ silane^ comonomer^may^be^present^at^from^0.05^to^1.0^wt.^,^based^on^ the^overall^dry^solids^weight^of^ the^polymeric^particles^in^the^first^embodiment^emulsion^pol ymer^composition.^The^hydrolysable^ silane^may^be^present^in^the^first^embodiment^at^from^0.05^t o^0.5wt.^,^or^from^0.8^to^1.0^wt.^^or^ from^1.0^to^3.0wt.^^or^from^2.0^to^3.5wt.^,^or^from^0.06^to^ 0.9wt.^,^based^on^the^overall^dry^ solids^weight^of^the^polymeric^particles^in^the^first^embodi ment^emulsion^polymer^composition.^^ Monomer^ c)^ hydrolyzable^ silane^ in^ the^ second^ embodiment^ emulsion^ polymer^ composition^^ Non-limiting^ examples^ of^ suitable^ hydrolyzable^ silane^ compounds^ in^ the^ second^ embodiment^ emulsion^polymer^composition^ include^ silicon^compounds^of^ the^ general^ formula^ R^SiR _0-2 (OR) _1-3 ,^where^the^number^of^R^and^OR^moieties^is^such^that^t he^silicon^is^tetravalent.^R^^ is^an^organofunctional^substituted^alkylene,^arylene^or^aral kylene^group,^which^may^have^from^ two^ to^ thirty^ carbon^ atoms^ and^ may^ contain^ heteroatoms^ such^ as^ oxygen^ or^ sulfur.^ The^ R^^ functional^group^may^contain^ functional^groups^that^are^reactive^ toward^heteroatoms^contained^ in^the^vinyl^acrylic^emulsion^polymer^composition,^such^as^h eteroatom-terminating^monomers^in^ polymerized^ form^ in^ the^ emulsion^ polymer^ composition.^ R^ is^ an^ alkyl^ or^ alkoxy-substituted^ alkyl,^aryl,^or^aralkyl^group^having^from^two^to^ten^carbon^ atoms.^Each^R^group^may^be^cyclic,^ branched^or^linear^and^contains^no^unsaturation.^Preferably, ^the^hydrolysable^silane^compound^in^ the^ second^ embodiment^ is^ selected^ from^ the^ group^ consisting^ of^ trialkoxy^ silanes,^ tetraalkoxysilanes,^epoxy^functionalized^trialkoxy^silanes.^ The^hydrolysable^silane^in^the^second^ embodiment^emulsion^polymer^composition^may^comprise^glycidy lpropyl^trimethoxysilane.^The^ hydrolyzable^ silicon^ compound^ may^ be^ selected^ from^ the^ group^ consisting^ of^ hydrolyzable^ 10^ ^

epoxy^silanes,^hydrolyzable^amino^silanes,^hydrolyzable^m ercapto^silanes,^hydrolyzable^alkoxy^ silane^compounds^having^the^formula^(R ⁶ )n—Si—(OR ⁷ ) _4-n ,^wherein^n^is^0,^1,^2^or^3,^and^R ⁶ ^and^ R ⁷ ^are^each^independently^a^straight-chain^or^branched^C 1-C16^alkyl,^and^mixtures^thereof.^ Suitable^ hydrolyzable^ epoxy^ silanes^ may^ comprise,^ for^ example,^ 3-glycidoxypropyl^ trimethoxysilane^ and^ 3-glycidoxypropyl^ triethoxysilane.^ Further^ suitable^ hydrolyzable^ epoxy^ silanes^include^silane^oligomers^comprising,^for^example,^ep oxy^functionalities.^ Suitable^ hydrolyzable^ amino^ silanes^ may^ comprise,^ for^ example,^ 3-(2- aminoethylamino)propyl^ trimethoxysilane,^ and^ 3-(2-aminoethylamino)propyl^ methyldimethoxysilane.^ Suitable^hydrolyzable^mercapto^ silanes^may^ comprise,^ for^ example,^mercaptosilanes^of^ the^general^formula^HS—(CR ⁴ 2)1-3—SiR ⁵ 3,^where^R ⁴ ^is^identical^or^different^and^is^H^or^a^C1^to^ C6^alkyl^ group,^R ⁵ ^is^ identical^ or^different^and^ is^ a^C1^ to^C6^alkyl^group^or^C1^ to^C6^alkoxy^ group,^at^least^one^of^the^radicals^R ⁵ ^being^an^alkoxy^group.^The^hydrolyzable^mercapto^sila nes^ may^ be^ selected^ from^ the^ group^ consisting^ of^ 3-mercaptopropyl^ triethoxysilane,^ 3- mercaptopropyl^trimethoxysilane,^and^3-mercaptopropyl^methyl dimethoxysilane.^ Suitable^ hydrolyzable^ alkoxy^ silane^ compounds^ include,^ for^ example,^ silanes^ of^ the^ formula^(R ⁶ ) _n —Si—(OR ⁷ ) _4-n ,^wherein^n^is^0,^1,^2^or^3,^and^R ⁶ ^and^R ⁷ ^are^each^independently^a^ straight-chain^ or^ branched^ C1-C16^ alkyl.^ The^ hydrolyzable^ silane^ compound^may^ be^ selected^ from^ the^ group^ consisting^ of^ tetramethoxysilane,^ tetraethoxysilane,^ methyltrimethoxysilane,^ ethyltrimethoxysilane,^ propyltrimethoxysilane,^ butyltrimethoxysilane,^ pentyltrimethoxysilane,^ hexyltrimethoxysilane,^ methyltriethoxysilane,^ ethyltriethoxysilane,^ propyltriethoxysilane,^ butyltriethoxysilane,^ pentyltriethoxysilane^ and^ hexyltriethoxysilane.^ Particularly^ preferred^ hydrolyzable^ silicon^ compounds^ are^ 3-glycidoxypropyl^ trimethoxysilane,^ 3-glycidoxypropyl^ triethoxysilane,^ 3-(2-aminoethylamino)propyl^ trimethoxysilane,^ 3-mercaptopropyl^ trimethoxysilane,^ tetraethoxysilane,^ methyltriethoxysilane,^ hexyltriethoxysilane,^ and^ mixture^ thereof.^ The^hydrolyzable^silane^ in^ the^second^embodiment^emulsion^polymer^composition^may^ comprise^from^0.01^weight^percent^to^4.0^weight^percent,^bas ed^on^the^overall^dry^solids^weight^ 11^ ^

of^ the^ polymeric^ particles^ in^ the^ second^ embodiment^ emulsion^ polymer^ composition,^ of^ the^ hydrolyzable^silane^monomer.^For^example,^ the^hydrolyzable^silane^may^be^present^at^from^0.5^ to^2.0wt.^^or^from^1.0^to^3.0wt.^,^For^example,^the^hydrolyz able^silane^may^be^present^at^from^ 0.05^to^1.0^wt.^,^based^on^the^overall^dry^solids^weight^of^ the^polymeric^particles^in^the^second^ embodiment^ emulsion^ polymer^ composition.^ The^ hydrolysable^ silane^ comonomer^ may^ be^ present^in^the^first^embodiment^at^from^0.05^to^0.5wt.^,^or^ from^0.8^to^1.0^wt.^^or^from^1.0^to^ 3.0wt.^^or^from^2.0^to^3.5wt.^,^or^from^0.06^to^0.9wt.^,^bas ed^on^the^overall^dry^solids^weight^ of^the^polymeric^particles^in^the^second^embodiment^emulsion ^polymer^composition.^^ Particle^Size^Distribution^and^Number^of^Modes^in^Population ^of^Particles^Sizes:^ As^is^known^in^the^art,^emulsion^polymerization^forms^a^popu lation^of^varying^sizes^of^ the^polymeric^particles^that^comprise^the^emulsion^polymer.^ This^population^thus^has^a^particle^ size^distribution,^which^may^be^ characterized^by^a^weight^average^particle^ size^Dw,^a^number^ average^ particle^ size^ Dn,^ and^ the^ ratio^ between^ them,^ Dw/Dn.^ Typically,^ the^ particle^ size^ distribution^has^at^least^one^mode,^which^is^seen^as^a^peak^ on^a^chart^showing^the^number^(or^the^ weight)^ of^ particles^ having^ a^certain^ size.^According^ to^ some^embodiments,^ the^ population^of^ particle^ sizes^ disclosed^ herein^ may^ have^more^ than^ one^mode,^ i.e.^ more^ than^ one^ such^ peak.^ These^modes^ are^ referred^ to^herein^as^mode _i ,^ and^each^mode _i ^has^a^ respective^weight^average^ particle^ size^Dw _i ^ and^ a^ respective^ number^ average^ particle^ size^Dn _i .^ For^ example,^ if^ i=1,^ the^ distribution^of^particle^sizes^in^ the^population^of^particles^ is^monomodal^and^ the^population^of^ particle^ sizes^ thus^ has^one^Dw ₁ ^and^ one^Dn ₁ ^and^ a^corresponding^ single^Dw ₁ /Dn ₁ .^ If^ i=2,^ the^ distribution^of^particle^sizes^in^the^population^of^particle s^is^bimodal^and^the^population^thus^has^ two^weight^average^particle^sizes:^Dw ₁ ,^^Dw ₂ ;^^two^number^average^particle^sizes:^Dn ₁ ,^^Dn ₂ ;^and^ two^ ratios^ thereof:^ Dw ₁ /Dn ₁ ^ and^ ^ Dw ₂ /Dn ₂ .^Additional^ embodiments^ corresponding^ to^ higher^ multi-modal^particle^size^distributions,^i.e.,^i=3,^i=4,^i=5 ,^and^higher^can^be^envisioned^by^those^ having^ordinary^skill^in^the^art^and^are^encompassed^by^the^ present^disclosure.^ Weight^average^particle^size:^ The^weight^average^particle^size,^also^referred^to^in^the^ar t^as^the^“weight^mean^diameter”^ or^“Dw”,^or^“weight^mean^particle^size”^of^the^polym eric^particles^in^the^emulsion^is^measured^ 12^ ^

using^Disc^Centrifugation^Photosedimentometry^(“CPS^ Instruments”).^Dynamic^light^scattering^ methods^generally^are^not^preferred,^as^that^technique^may^n ot^resolve^particle^size^distributions^ within^ the^ particle^ size^ ranges^ generated^ in^ the^ emulsion^ polymerization.^ The^weight^ average^ particle^ size^ may^ range^ from^ 0.05^ µm^ to^ 2.0^ µm,^ dependent^ upon^ the^ capabilities^ of^ the^ instrument.^The^weight^average^particle^size^may^be^less^tha n^2.0^µm,^or^less^than^0.8^µm,^or^less^ than^0.5^µm,^or^less^than^0.25^µm,^or^less^than^0.2^µm,^o r^less^than^0.1^µm.^The^smallest^suitable^ weight^average^particle^size^is^0.05^µm.^ Number^average^particle^size:^ The^ number^ average^ particle^ size,^ also^ referred^ to^ in^ the^ art^ as^ the^ “number^ mean^ diameter”^or^“Dn”,^or^“number^mean^particle^size”^ of^the^polymeric^particles^in^the^emulsion^is^ measured^ using^ Disc^ Centrifugation^ Photosedimentometry^ (“CPS^ Instruments”).^ The^ number^ average^particle^size^may^range^from^0.05^µm^to^2.0^µm,^de pendent^upon^the^capabilities^of^the^ instrument.^The^number^average^particle^size^may^be^less^tha n^2.0^µm,^or^less^than^0.8^µm,^or^ less^than^0.5^µm,^or^less^than^0.25^µm,^or^less^than^0.2^� �m,^or^less^than^0.1^µm.^^ Ratio^of^weight^average^particle^size^Dw^to^number^average^p article^size^Dn:^ As^is^known^in^the^art,^emulsions^are^formed^ from^a^population^of^varying^sizes^of^the^ polymeric^particles^that^comprise^the^emulsion.^As^described ^above,^ this^population^thus^has^at^ least^ one^ mode^ and^ each^ mode _i ^ has^ a^ respective^ particle^ size^ distribution,^ which^ may^ be^ characterized^ by^ a^ respective^ weight^ average^ particle^ size^ Dw _i ,^ a^ respective^ number^ average^ particle^size^Dn _i ,^and^a^respective^ratio^between^them,^Dw _i /Dn _i .^^ As^described^in^more^detail^below,^the^particle^size^distrib ution^of^the^emulsion^polymer^ compositions^ disclosed^ herein^ are^ defined^ as^ those^ measured^ using^ disc^ centrifuge^ photosedimentometry.^Accordingly,^ the^population^of^ sizes^of^polymeric^particles^comprises^at^ least^ one^ mode,^ and^ each^ mode _i ^ comprises^ a^ respective^ weight^ average^ particle^ size^ Dw _i ^ as^ measured^by^disc^centrifuge^photosedimentometry^and^a^respec tive^number^average^particle^size^ Dn _i ^as^measured^by^disc^centrifuge^photosedimentometry.^A s^discussed^above,^the^population^of^ sizes^of^polymeric^particles^comprises^at^least^one^mode,^an d^each^mode _i ^comprises^a^respective^ weight^ average^ particle^ size^ Dw _i ^ as^ measured^ by^ disc^ centrifuge^ photosedimentometry^ and^ a^ 13^ ^

respective^number^average^particle^size^Dn _i ^as^measured^by^disc^centrifuge^photosedimentometry^ and^wherein^for^each^mode _i ,^^Dw _i /Dn _i ^is^2.0^or^less.^ Disc^Centrifuge^Photosedimentometry:^ The^ Dwi,^ and^ Dni^ of^ each^ mode^ of^ the^ population^ of^ the^ polymer^ particles^ disclosed^ herein^are^measured^using^disc^centrifuge^photosedimentometr y.^Polymer^particles^are^separated^ using^disc^centrifuge^photosedimentometry^and^an^integral^cu rve^is^generated^that^corresponds^to^ the^ relative^ amount^ of^ polymer^ particles^ eluting^ from^ the^ disc^ as^ a^ function^ of^ time,^ which^ corresponds^to^different^particle^sizes.^This^integral^curve ^is^converted^to^the^differential^scans^of^ the^type^shown^in^Figures^4-7.^For^mono-modal^particle^size^ distributions,^a^peak^can^be^defined^ by^ the^ increase^ and^ the^ decrease^ relative^ to^ the^ baseline.^ For^ multi-modal^ polymer^ particle^ distributions,^a^particle^size^distribution^is^defined^based ^on^the^following^criteria.^These^criteria^ are^illustrated^in^Figure^1^and^Figure^2.^ a)^ As^illustrated^in^Figure^1,^a^peak^is^considered^resolved,^i .e.^is^a^separate^mode^of^the^ polymer^particle^size^distribution^if^ the^valley^between^two^peaks^has^a^peak^height^ that^is^less^than^50^^of^the^peak^height^of^the^distribution ^of^the^lowest^height;^and^^ b)^ A^peak^is^considered^a^mode _i ^if^it^satisfies^criteria^a)^and,^as^shown^in^Figure^2 ,^also^ contributes^to^>5^^by^area^of^the^total^area^in^the^scan^ of^the^population^of^particle^ sizes.^ The^ratio^of^weight^average^particle^size,^or^Dw,^to^number^ average^particle^size,^or^Dn;^ Dw/Dn,^also^referred^to^as^the^polydispersity^index^(PDI)^of ^the^particle^sizes,^provides^a^way^to^ express^the^range^of^sizes^that^are^present^in^the^emulsion^ polymer^composition.^Without^wishing^ to^be^bound^by^theory,^the^inventors^have^found^that^when^th e^Dw _i /Dn _i ^(PDI)^of^each^mode _i ^in^a^ particle^size^population^of^the^vinyl^acrylic^emulsion^discl osed^herein^is^2^or^less,^and^the^vinyl^ acrylic^ emulsion^ further^comprises^a^hydrolysable^silane,^ the^cleansability^ of^ a^coating^ formed^ form^this^elution,^as^measured^according^to^the^MPI^cleansab ility^tests^described^in^at^ least^one^ of^MPI^138-141^and^143-148,^is^much^better^than^if^only^one^ of^these^criteria^are^met.^^^ 14^ ^

In^ the^ embodiments^ of^ the^ invention^ disclosed^ herein,^ Disc^ Centrifuge^ Photosedimentometry^ is^ used^ to^ analyze^ the^ particle^ size^ and^ particle^ size^ distribution^ of^ a^ population^ of^polymeric^ emulsion^polymers^with^high^ resolution.^This^ technique^ separates^ the^ distributions^ of^ particles^ via^ centrifugation^ and^ sedimentation.^ The^ ratio^ of^ weight^ average^ particle^ size,^ or^Dw,^ to^ number^ average^ particle^ size,^ or^Dn,^ (Dw/Dn)^ also^ referred^ to^ as^ the^ polydispersity^index^(PDI)^of^the^particle^sizes,^provides^a ^way^to^express^the^range^of^sizes^that^ are^present^in^the^population^of^polymeric^particles^in^the^ emulsion.^^ ^Figure^ 4^ illustrates^ a^ representative^ disc^ centrifuge^ particle^ size^ measurement^ of^ an^ emulsion^ polymer^ with^ a^mono-modal^ particle^ size^ distribution^ prepared^ through^methods^ by^ disclosed^herein.^Analysis^shows^the^single^particle^size^po pulation^with^a^Dw^of^0.245,^a^Dn^of^ 0.232,^and^a^PDI^(Dw/Dn)^of^1.06.^Figure^6^ illustrates^a^representative^disc^centrifuge^particle^ size^measurement^of^an^emulsion^polymer^with^a^broader^mono- modal^particle^size^distribution^ prepared^ through^methods^ by^ those^ skilled^ in^ the^ art.^ Analysis^ shows^ the^ single^ particle^ size^ population^with^a^Dw^of^0.358,^a^Dn^of^0.213,^and^a^PDI^of^1 .68.^^ Figures^ 7A,^ 7B,^ and^ 7C^ illustrate^ a^ representative^ disc^ centrifuge^ particle^ size^ measurement^ of^ an^ emulsion^ polymer^ with^ a^ multi-modal^ particle^ size^ distribution^ prepared^ through^methods^disclosed^herein.^Figure^7A^illustrates^both ^modes^of^the^population^on^a^single^ plot.^Each^of^the^two^particle^size^modes^in^the^population^ is^measured^separately^and^analysis^ and^are^illustrated^separately^in^Figures^7B^and^7C.^Figure^ 7C^shows^the^smaller^mode^has^a^Dw^ of^ 0.132,^ a^Dn^ of^0.114,^ and^ a^ PDI^ of^ 1.158.^ Figure^ 7B^ shows^ the^ larger^mode^ has^ a^Dw^ of^ 0.346,^a^Dn^of^0.320,^and^a^PDI^of^1.08.^^ Figure^ 5^ illustrates^ a^ representative^ disc^ centrifuge^ particle^ size^ measurement^ of^ a^ comparative^ emulsion^ polymer^ with^ a^ population^ of^ polymer^ particles^ having^ a^ particle^ size^ distribution,^as^measured^by^the^ratio^Dw/Dn,^of^greater^tha n^2.0.^^ According^to^embodiments^of^the^ invention,^the^ ratio^of^weight^average^particle^size^to^ number^ average^ particle^ size^ for^ each^mode _i ^may^ range^ from^ 1.0^ to^ 2.0.^The^ ratio^ of^weight^ average^particle^size^to^number^average^particle^size^for^ea ch^mode _i ^may^range^from^1.1^to^1.95,^ or^from^1.1^to^1.9,^or^from^1.1^to^1.85,^or^from^1.1^to^1.8, ^or^from^1.1^to^1.75,^or^from^1.1^to^1.7,^ 15^ ^

or^from^1.1^to^1.65,^or^from^1.1^to^1.6^or^from^1.1^to^1. 55,^or^from^1.1^to^1.5,^or^from^1.1^to^1.45,^ or^from^1.1^to^1.4,^or^from^1.1^to^1.35,^or^from^1.1^to^1.3, ^or^from^1.1^to^1.25,^or^from^1.1^to^1.2,^ or^from^1.1^to^1.15.^ Glass^transition^temperatures^of^the^emulsion^polymer^compos ition:^ The^vinyl^acrylic^emulsion^polymer^composition^ that^comprises^ the^polymeric^particles^ as^ described^ herein^ are^ composed^ of^ co-monomers^ so^ as^ to^ generate^ polymers^ with^ a^ glass^ transition^temperature^(Tg)^in^the^range^of^-10˚C^and^40˚C ,^as^measured^by^differential^scanning^ calorimetry^(DSC).^^Preferred^glass^transition^temperatures^ are^in^the^range^of^-10˚C^and^20˚C,^ with^more^preferred^ranges^from^0˚C^and^15˚C.^ Protective^colloid^stabilizers:^^ In^ an^ embodiment,^ the^ emulsion^ polymer^ composition^ that^ comprises^ the^ polymeric^ particles^ as^described^herein^may^optionally^ further^comprise^ from^0.01^weight^ percent^ to^2.0^ weight^ percent^ based^ on^ the^ total^ weight^ of^ the^ polymeric^ particles^ of^ a^ protective^ colloid^ stabilizer^that^is^partially^or^completely^grafted^to^the^em ulsion^polymer.^In^an^embodiment,^the^ colloidal^ stabilizer^ may^ be^ hydroxyethyl^ cellulose.^ Preferred^ levels^ for^ protective^ colloidal^ stabilizers^ are^0.05^weight^percent^ to^0.75^weight^percent^based^on^ the^total^dry^weight^of^ the^ polymeric^particles.^ Coating^compositions:^ In^ an^ embodiment,^ the^ emulsion^ polymer^ composition^ that^ comprises^ the^ polymeric^ particles^ as^ described^ herein,^ may^ be^ formulated^ into^ a^ coating^ composition^ comprising^ an^ aqueous^medium.^The^coating^composition^comprising^ the^emulsion^polymer^composition^may^ comprise^other^further^components.^The^further^component^may ^comprise^at^least^one^pigment.^ The^ further^ component^ may^ comprise^ for^ example,^ at^ least^ one^ additive^ such^ as^ dispersants,^ surfactants,^ defoamers,^ pH^ adjusters,^ extenders,^ opacifiers,^ rheology^ modifiers,^ coalescent^ agents,^ colorants,^ tints,^ pigments,^ dyes,^ titanium^ dioxide,^ fillers,^ brightness^ enhancers,^ thickeners,^ freeze-thaw^ and/or^ open^ time^ additives,^ antioxidants,^UV^ stabilizers,^ and^mixtures^ thereof.^ 16^ ^

In^another^embodiment,^a^method^of^coating^a^substrate^wi th^the^coating^composition^is^ disclosed.^The^method^of^coating^a^substrate^may^comprise^a^ step^of^applying^a^layer^comprising^ the^coating^composition^comprising^ the^emulsion^polymer^composition^onto^ the^surface^of^ the^ substrate^and^a^step^of^drying^the^layer^of^coating^composit ion^to^obtain^a^film,^wherein^the^film^ passes^a^cleansability^test^according^to^at^least^one^of^MPI ^^143-148^and^MPI^^138-141.^ The^coating^composition^may^be^applied^by^conventional^techn iques,^ such^as^brushing,^ rolling,^or^spraying^the^coating^composition^onto^a^variety^ of^substrate^surfaces.^The^substrates^ may^ include^ without^ limitation,^ wood,^ fabricated^ wood,^ paper,^ cardboard,^ textiles,^ synthetic^ resins,^ceramics,^ferrous^metals,^non-ferrous^metals,^stone, ^concrete,^plaster,^and^the^like.^ Process^for^forming^the^first^embodiment^emulsion^polymer^co mposition:^^ One^ suitable^ process^ for^ forming^ the^ first^ embodiment^ emulsion^ polymer^ composition^ comprising^polymeric^particles^is^disclosed.^The^process^com prises^the^following^steps:^ First,^water,^surfactant,^and^a^portion^of^a^first^monomer^m ixture^are^combined^in^a^vessel^ and^ heated.^ The^ first^monomer^mixture^ comprises:^ a)^ at^ least^ one^monomer^ comprising^ vinyl^ acetate;^b)^at^least^one^ethylenically^unsaturated^monomer;^ and^c)^at^least^one^monomer^selected^ from^the^group^of^hydrolyzable^silanes.^The^at^least^one^eth ylenically^unsaturated^monomer^b)^is^ not^selected^from^a)^or^c).^Monomer^a),^monomer^b),^and^mono mer^c)^together^total^100^weight^ percent.^ The^ first^ monomer^mixture^ is^ then^ polymerized^ through^ the^ addition^ of^ free^ radical^ initiator^to^form^seed^particles^as^the^second^step.^ Third,^a^second^portion^of^free^radical^initiator^and^a^seco nd^monomer^mixture^are^added^ separately^ to^ the^ seed^particles^ in^ the^vessel^over^a^period^of^1-5^hours.^The^second^monomer^ mixture^ may^ comprise:^ d)^ at^ least^ one^ monomer^ comprising^ vinyl^ acetate;^ e)^ at^ least^ one^ ethylenically^ unsaturated^ monomer;^ and^ f)^ at^ least^ one^monomer^ selected^ from^ the^ group^ of^ hydrolyzable^silanes.^The^at^least^one^ethylenically^unsatur ated^monomer^e)^is^not^selected^from^ d)^at^least^one^monomer^comprising^vinyl^acetate^or^f)^at^ least^one^monomer^selected^from^the^ group^ of^ hydrolyzable^ silanes.^Monomer^ d),^ monomer^ e),^ and^monomer^ f)^ together^ total^ 100^ weight^ percent.^ The^ second^ monomer^ mixture^ may^ have^ the^ same^ composition^ as^ the^ first^ monomer^mixture,^ or^ the^ second^ monomer^ mixture^ may^ have^ a^ composition^ that^ is^ different^ 17^ ^

from^that^of^the^ first^monomer^mixture.^The^fourth^ step^is^polymerizing,^on^ the^seed^particles,^ the^ second^monomer^mixture^ to^ form^ the^ polymeric^ particles.^ The^ polymeric^ particles^ have^ a^ weight^ average^ particle^ size^ and^ a^ number^ average^ particle^ size^ as^ measured^ by^ disc^ centrifugation^photosedimentometry.^The^ratio^of^the^weight^ average^particle^size^to^the^number^ average^particle^ size^(D _w /D _n )^as^measured^by^disc^centrifugation^photosedimentomet ry^may^be^ 2.0^or^less.^ Process^for^forming^the^second^embodiment^emulsion^polymer^c omposition:^^ One^suitable^process^for^forming^the^second^embodiment^emuls ion^polymer^composition^ comprising^ polymeric^ particles^ is^ also^ disclosed.^As^with^ the^ difference^ between^ the^ first^ and^ second^ emulsion^ polymer^ compositions,^ the^difference^between^ these^ first^ and^ second^ process^ embodiments^is^the^presence^or^absence,^respectively,^of^the ^hydrolyzable^silane^in^the^monomer^ mixtures.^The^process^comprises^the^following^steps:^ First,^water,^surfactant,^and^a^portion^of^a^first^monomer^m ixture^are^combined^in^a^vessel^ and^ heated.^ The^ first^monomer^mixture^ comprises:^ a)^ at^ least^ one^monomer^ comprising^ vinyl^ acetate;^ and^ b)^ at^ least^ one^ ethylenically^ unsaturated^monomer.^ The^ at^ least^ one^ ethylenically^ unsaturated^monomer^b)^is^not^selected^from^a).^Monomer^a),^ and^monomer^b)^together^total^100^ weight^ percent.^ The^ first^ monomer^ mixture^ is^ then^ polymerized^ through^ the^ addition^ of^ free^ radical^initiator^to^form^seed^particles^as^the^second^step. ^ Third,^a^second^portion^of^free^radical^initiator^and^a^seco nd^monomer^mixture^are^added^ separately^ to^ the^ seed^particles^ in^ the^vessel^over^a^period^of^1-5^hours.^The^second^monomer^ mixture^(which^may^be^the^same^as^or^different^from^the^firs t^monomer^mixture)^may^comprise:^ d)^at^ least^one^monomer^comprising^vinyl^ acetate;^and^e)^at^least^one^ethylenically^unsaturated^ monomer.^The^at^least^one^ethylenically^unsaturated^monomer^ e)^is^not^selected^from^d)^at^least^ one^monomer^comprising^vinyl^acetate.^Monomer^d)^and^monomer ^e)^together^total^100^weight^ percent.^The^fourth^step^is^polymerizing,^on^the^seed^partic les,^the^second^monomer^mixture^to^ form^the^polymeric^particles.^The^polymeric^particles^have^a ^weight^average^particle^size^and^a^ number^average^particle^size^as^measured^by^disc^centrifugat ion^photosedimentometry.^The^ratio^ 18^ ^

of^the^weight^average^particle^size^to^the^number^average ^particle^size^(D _w /D _n )^as^measured^by^ disc^centrifugation^photosedimentometry^may^be^2.0^or^less.^ For^ both^ of^ these^ first^ and^ second^ embodiment^ processes,^ the^ polymeric^ particles^may^ comprise^ from^ 3^ weight^ percent^ to^ 20^ weight^ percent^ of^ the^ first^ monomer^ mixture^ (in^ polymerized^ form).^ The^ polymeric^ particles^ may^ comprise^ from^ 5^ –^ 10^ wt.^,^ or^ from^ 4^ –^ 9^ wt.^,^ or^ from^5^–^ 8^wt.^^or^ from^ 6^–^ 9^wt.^^ or^ from^6.6^–^7.5^wt.^^^of^ the^ first^monomer^ mixture^(in^polymerized^form).^^ Anionic^surfactant:^ In^ both^ of^ these^ first^ or^ second^ embodiment^ processes,^ the^ anionic^ surfactant^ may^ comprise,^ for^ example,^ sodium^ sulfonate,^ sodium^ lauryl^ sulfate,^ sodium^ dodecylbenzenesulfonate,^ potassium^ stearate,^ sodium^ dioctyl^ sulfosuccinate,^ sodium^ dodecyldiphenyloxide^ disulfonate,^ onylphenoxyethylpolyethoxyethyl^ sulfate^ ammonium^ salt,^ sodium^ styrene^ sulfonate,^ sodium^ dodecyl^ allyl^ sulfosuccinate,^ sodium^or^ ammonium^ salts^ of^ phosphate^ esters^ of^ ethoxylated^ nonylphenol,^ sodium^ octoxynol-3-sulfonate,^ sodium^ cocoyl^ sarcocinate,^ sodium^ 1-alkoxy-2-hydroxypropyl^ sulfonate,^ sodium^ α-olefin^ (C14-C16)sulfonate,^ sulfates^of^hydroxyalkanols,^ tetrasodium^N-(1,2-dicarboxy^ethyl)-N-octadecylsulfosuccinam ate,^ disodium^ N-octadecylsulfosuccinamate,^ disodium^ alkylamido^ polyethoxy^ sulfosuccinate,^ disodium^ ethoxylated^ nonylphenol^half^ ester^ of^ sulfosuccinic^acid^ and^ the^ sodium^ salt^ of^ tert- octylphenoxyethoxypolyethoxyethyl^ sulfate^ and^ combinations^ thereof.^ Suitable^ amounts^ are^ from^0.1-10^wt.^^or^from^0.1-5wt.^^of^the^reaction^mixture.^ ^ Nonionic^surfactant:^ Non-limiting^ examples^ of^ suitable^ nonionic^ emulsifiers^ include^ acyl,^ alkyl,^ oleyl,^ and^ alkylaryl^ ethoxylates.^ These^ products^ are^ commercially^ available,^ for^ example,^ under^ the^ tradename^Genapol™,^Lutenso™^or^Emuan™.^They^ include,^ for^example,^ethoxylated^mono-,^ di-,^ and^ tri-alkylphenols^ (EO^ degree:^ 3^ to^ 80,^ alkyl^ substituent^ radical:^ C4^ to^ C12)^ and^ also^ ethoxylated^ fatty^ alcohols^ (EO^degree:^3^ to^80;^alkyl^ radical:^C8^ to^C36),^ especially^C10-C14^ fatty^alcohol^(EO^3-80)^ethoxylates,^C11-C15^oxo-process^alc ohol^(EO^3-80)^ethoxylates,^C16- C18^fatty^alcohol^ (EO^3-80)^ethoxylates,^C11^oxo-process^alcohol^(EO^3-80)^eth oxylates,^C13^ 19^ ^

oxo-process^ alcohol^ (EO^ 3-80)^ ethoxylates,^ polyoxyethylenesorbitan^ monooleate^ with^ 20^ ethylene^ oxide^ groups,^ copolymers^of^ethylene^oxide^ and^ propylene^ oxide^ having^ a^minimum^ ethylene^ oxide^ content^ of^ 10^^ by^ weight,^ the^ polyethylene^ oxide^ (EO^ 3-80)^ ethers^ of^ oleyl^ alcohol,^and^the^polyethene^oxide^(EO^3-80)^ethers^of^nonylp henol.^Particularly^suitable^are^the^ polyethylene^oxide^(EO^3-80)^ethers^of^fatty^alcohols,^more^ particularly^of^oleyl^alcohol,^stearyl^ alcohol^or^C11^alkyl^alcohols.^Suitable^amounts^are^from^0.1 -10^wt.^^or^from^0.1-5wt.^^of^the^ reaction^mixture.^ Free^radical^initiators:^^ The^ free^ radical^ initiators^ suitable^ for^ the^ polymerization^ of^ the^ monomers^ used^ to^ prepare^the^emulsion^polymer^particles^as^described^herein^f or^both^the^first^embodiment^and^the^ second^embodiment^processes^may^be^any^water^soluble^or^wate r^insoluble^initiator^suitable^for^ aqueous^ emulsion^ polymerization.^ Examples^ of^ free^ radical^ initiators^ used^ in^ both^ the^ first^ embodiment^and^the^second^embodiment^processes^to^prepare^th e^emulsion^polymer^particles^of^ the^ present^ application^ include,^ but^ are^ not^ limited^ to,^ hydrogen^ peroxide,^ tert-butyl^ peroxide,^ alkali^metal^persulfates^such^as^sodium,^potassium,^and^lith ium^persulfate,^ammonium^persulfate,^ and^ mixtures^ of^ such^ initiators^ with^ a^ reducing^ agent.^ The^ amount^ of^ initiator^ may^ be,^ for^ example,^from^0.01^to^3^wt.^,^or^from^0.01-1wt.^^based^on^th e^total^weight^of^monomer.^ In^ some^embodiments,^ a^ redox^ polymerization^ initiator^system^ is^used.^ In^ a^ redox^ free^ radical^initiation^system,^a^reducing^agent^may^be^used^in^c onjunction^with^an^oxidant.^Reducing^ agents^ suitable^ for^ the^ aqueous^ emulsion^ polymerization^ include^ sulfites^ (e.g.,^ alkali^ metal^ metabisulfite,^ hydrosulfite,^ and^ hyposulfite).^ In^ some^ embodiments,^ ascorbic^ acid^ derivatives,^ such^ as^ ascorbic^ acid,^ isoascorbic^ acid,^ or^ an^ alkali^metal^ (iso)ascorbate^ salt,^might^ also^ be^ a^ suitable^reducing^agent^for^the^aqueous^emulsion^polymerizat ion.^In^a^redox^system,^the^amount^ of^ reducing^ agent^ may^ be,^ for^ example,^ from^0.01^ to^ 3^ percent^ by^weight^ based^ on^ the^ total^ amount^of^monomer.^ Oxidizing^ agents^ (oxidants)^ include,^ for^ example,^ for^ example,^ hydrogen^ peroxide^ and^ ammonium^or^alkali^metal^persulfates,^perborates,^peracetate s,^peroxides,^and^percarbonates^and^ a^water-insoluble^oxidizing^agent^such^as,^for^example,^benz oyl^peroxide,^lauryl^peroxide,^t-butyl^ 20^ ^

peroxide,^ t-butyl^ hydroperoxide,^ 2,2^-azobisisobutyronitrile,^ t-amyl^ hydroperoxide,^ t-butyl^ peroxyneodecanoate,^ and^ t-butyl^ peroxypivalate.^ The^ amount^ of^ oxidizing^ agent^ may^ be,^ for^ example,^from^0.01^to^3^percent^by^weight,^based^on^the^tota l^amount^of^monomer.^^ The^ free^ radical^polymerization^ temperature^ typically^ is^ in^ the^ range^of^ about^10º^C^ to^ 100º^C.^In^the^case^of^the^persulfate^systems,^the^temperat ure^may^be^in^the^range^of^about^60º^C^ to^about^100º^C.^In^the^redox^system,^the^temperature^may^b e^in^the^range^of^about^30º^C^to^about^ 100º^C,^in^the^range^of^about^30º^C^to^about^60º^C,^or^in ^the^range^of^about^30º^C^to^about^45º^C.^ ^ Test^procedures:^ Particle^size^measurement:^ Disc^ Centrifuge^ Photosedimentometry^ is^ a^ high^ resolution^ analytical^ method^ used^ to^ analyze^ the^ particle^ size^ and^ particle^ size^ distribution^ of^ the^ polymeric^ emulsion^ polymers^ disclosed^herein.^A^CPS^Disc^Centrifuge^Model^DC24000^UHR^fr om^CPS^Instruments^was^used^ to^conduct^ the^ separation^and^data^ collection^and^analyzed^ using^CPSV95^ software^ from^CPS^ Instruments.^^ In^ disc^ centrifuge^ photosedimentometry,^ particles^ are^ separated^ by^ centrifugal^ sedimentation^in^a^ring^of^liquid^medium^that^has^a^slight^d ensity^gradient^different^from^that^of^ the^particle.^This^ ring^of^ liquid^medium^is^ formed^within^a^clear^ rotation^disc^ that^ spins^up^ to^ 24,000^ rpm.^A^ dilute^ sample^of^ latex^ is^ administered^ into^ this^ ring^ of^ liquid^ and^ the^ particles^ sediment^at^a^rate^depending^on^their^size^to^the^edge^of^th e^fluid^ring.^A^detector^monitors^the^ scatter^and^reduction^of^light^intensity^from^the^particle^i nterference.^The^time^versus^the^detector^ beam^intensity^is^ converted^to^a^size^distribution^using^a^modified^version^of ^Stokes’^Law^and^ Mie^theory^light^scattering^calculations.^ The^emulsion^polymer^ samples^were^analyzed^by^ first^preparing^ an^aqueous^dispersion^ by^ adding^ 1-2^ drops^ of^ emulsion^ polymer^ (~55^wt^^ emulsion^ polymer)^ into^ 10-20^milliliters^ (mL)^ of^ deionized^ water.^ For^ the^ emulsion^ polymer,^ the^ monomer^ composition^ was^ used^ to^ calculate^a^refractive^index^of^1.465^and^a^particle^density ^of^1.142^g/mL.^Next,^0.1^mL^of^ the^ diluted^ sample^was^injected^into^the^spinning^disc^filled^with^a^suc rose^gradient.^Samples^were^ 21^ ^

analyzed^ relative^ to^ a^ 303^ ±^ 6^ nanometer^ (nm)^ Nanosphere™^ polystyrene^ standard^ (ThermoFisher^Scientific),^which^have^a^density^of^1.052^g/m L.^To^prepare^the^sucrose^gradient,^ 2^wt^^and^8^wt^^sucrose^solutions^in^HPLC-grade^water^were^p repared^and^the^auto-gradient^ pump^generates^a^ sucrose^gradient^on^the^disc^ from^2^wt^^to^8^wt^.^This^gradient^has^a^fluid^ density^ of^ 1.012^ g/mL,^ a^ refractive^ index^ of^ 1.325,^ and^ a^ fluid^ viscosity^ of^ 1.1^ centipoise^ (cPs).This^ is^ followed^ by^ a^ 1mL^ dodecane^ cap^ to^ prevent^ evaporation^ of^ the^water^ from^ the^ sucrose^gradient.^For^these^analyses,^a^standard^disc^was^ut ilized^at^a^disc^speed^of^24,000^rpm^ operating^ at^ ambient^ temperature.^ Single^ measurements^ were^ taken^ for^ the^ analyses^ reported^ herein.^ Temperature^of^measurement:^ambient;^20°Cto^25°C.^ Particles^were^assumed^to^be^spherical.^ Light^absorption^of^particles^was^assumed^to^be^0.^ Any^other^details^of^analysis^that^are^important^for^replica tion?^NO^ Cleansability:^^ Cleansability^was^measured^according^to^MPI^standards^issued ^May^4,^2016^for^interior^ latex^wall^paints,^i.e.^the^cleansability^test^in^MPI^standa rds^^143-148^and^MPI^^138-141.^These^ tests^ comprise^ the^ steps^ of^ applying^ a^ coating^ to^ be^ tested^ to^ a^ white^ plastic^ scrub^ panel^ and^ allowing^it^dry^under^specified^conditions.^After^the^approp riate^dry^time,^three^stains^are^applied^ to^the^coating^(graphite,^hot^coffee,^and^a^standard^aqueous ^solution^of^nigrosine),^and^allowed^to^ remain^on^the^coating^for^10^minutes^before^rinsing^off^the^ excess^stains.^The^resulting^stains^are^ then^ subjected^ to^ mechanical^ scrubbing^ with^ a^ cellulosic^ sponge^ using^ an^ aqueous^ cleaning^ media.^After^scrubbing,^the^residual^soap^solution^is^gently ^rinsed^off^and^the^panels^are^allowed^ to^dry^overnight.^o^ The^ staining^ of^ the^ coating^ is^ measured^ using^ the^ International^ Commission^on^Illumination^(CIE)^L*a*b^color^space^ΔE^color ^differences.^The^reference^is^the^ unstained^ surface.^ The^ reference^ for^ the^ color^ readings^ is^ the^ unstained^ surface^ along^ the^ scrubbing^ path^ on^ the^ panel.^ By^ definition,^ smaller^ ΔE^ color^ differences^ indicate^ better^ cleansability,^ since^ they^ indicate^ that^ the^ stained^ and^ the^ scrubbed^ surfaces^ are^more^ alike^ in^ terms^of^color.^ 22^ ^

Figure^ 3^ shows^ an^ exemplary^ schematic^ representation^ of^ a^ typical^ test^ panel^ for^ the^ cleansability^test.^According^to^the^MPI^standards,^the^coat ing^composition^passes^the^test^if^the^ ΔE^color^differences^are^less^ than^1.5^for^the^graphite,^less^than^2.0^for^the^hot^coffee, ^and^less^ than^1.0^for^the^nigrosine.^Smaller^ΔE^color^differences^in dicate^better^cleansability,^since^they^ indicate^that^the^stained^and^the^scrubbed^surfaces^are^more ^alike^in^terms^of^color^differences.^^ Non-limiting^aspects^of^the^invention^may^be^summarized^as^f ollows:^^ Aspect^1:^An^emulsion^polymer^composition^comprising^a^popul ation^of^sizes^of^ polymeric^particles,^wherein^the^polymeric^particles^compris e^copolymer^which^comprises,^in^ polymerized^form:^ a)^ between^40^weight^percent^and^95^weight^percent,^based^on^th e^overall^weight^of^ the^polymeric^particles,^of^at^least^one^monomer^comprising^ vinyl^acetate;^ b)^ between^1.0^weight^percent^and^59.09^weight^percent,^based^o n^the^overall^weight^ of^the^polymeric^particles,^of^at^least^one^ethylenically^un saturated^monomer;^and^ c)^ between^0.01^weight^percent^and^4.0^weight^percent,^based^on ^the^overall^weight^ of^the^polymeric^particles,^of^at^least^one^monomer^selected ^from^free^radical^polymerizable^ hydrolyzable^silanes,^wherein^the^at^least^one^ethylenically ^unsaturated^monomer^b)^is^not^ selected^from^a)^or^c),^wherein^monomer^a),^monomer^b),^and^ monomer^c)^together^total^100^ weight^percent;^^ and^wherein^the^population^of^sizes^of^polymeric^particles^c omprises^at^least^one^mode,^ and^wherein^each^mode _i ^comprises^a^respective^weight^average^particle^size^D w _i ^as^measured^by^ disc^centrifuge^photosedimentometry^and^a^respective^number^ average^particle^size^Dn _i ^as^ measured^by^disc^centrifuge^photosedimentometry^and^wherein^ for^each^mode _i ,^^Dw _i /Dn _i ^is^2.0^ or^less.^ Aspect^2:^The^emulsion^polymer^composition^according^to^Aspe ct^1,^wherein^the^at^least^ one^ethylenically^unsaturated^monomer^b)^is^selected^from^th e^group^consisting^of^ alkyl(meth)acrylate^monomers,^(meth)acrylamide^monomers,^and ^mixtures^thereof.^ 23^ ^

Aspect^3:^The^emulsion^polymer^composition^according^to^e ither^of^Aspect^1^or^Aspect^ 2,^wherein^the^at^least^one^ethylenically^unsaturated^monome r^b)^is^selected^from^the^group^ consisting^of^ethyl(meth)acrylate,^butyl^acrylate^and^mixtur es^thereof.^^ Aspect^4:^The^emulsion^polymer^composition^according^to^any^ of^Aspects^1^–^3,^wherein^ the^copolymer^further^comprises,^in^polymerized^form,^at^lea st^one^monomer^selected^from^the^ group^consisting^of^2-acrylamido-2-methylpropane^sulfonic^ac id^(AMPS),^sodium^vinyl^ sulfonate^(SVS),^acrylic^acid,^methacrylic^acid,^and^mixture s^thereof^in^an^amount^between^0.01^ weight^percent^and^2.5^weight^percent,^based^on^the^overall^ dry^weight^of^the^polymeric^ particles.^ Aspect^5:^The^emulsion^polymer^composition^according^to^any^ of^Aspects^1^–^4,^wherein^ the^copolymer^further^comprises,^in^polymerized^form,^at^lea st^one^monomer^selected^from^the^ group^consisting^of^vinyl^versatate,^vinyl^esters^of^tertiar y^substituted^α-carbon^carboxylic^acids,^ vinyl^esters^of^C7-C20^carboxylic^acids,^and^mixtures^thereo f,^in^an^amount^between^0.4^weight^ percent^and^4^weight^percent,^based^on^the^overall^dry^weigh t^of^the^polymeric^particles.^^ Aspect^6:^The^emulsion^polymer^composition^according^to^any^ of^Aspects^1^–^5,^further^ comprising^from^0.01^weight^percent^to^1^weight^percent^base d^on^the^total^dry^weight^of^the^ polymeric^particles,^of^hydroxyethyl^cellulose^in^copolymeri zed^form.^^ Aspect^7:^A^coating^composition^comprising^an^emulsion^polym er^composition^according^ to^any^of^Aspects^1^–^6^and^at^least^one^further^component ^dispersed^in^an^aqueous^medium.^ Aspect^8:^The^coating^composition^according^to^Aspect^7,^the ^at^least^one^further^ component^comprising^at^least^one^pigment.^ Aspect^9:^The^coating^composition^according^to^either^Aspect ^7^or^Aspect^8,^further^ comprising^at^least^one^additive^selected^from^the^group^con sisting^of^dispersants,^surfactants,^ defoamers,^pH^adjusters,^extenders,^opacifiers,^rheology^mod ifiers,^coalescent^agents,^colorants,^ and^mixtures^thereof.^ Aspect^10:^A^method^of^coating^a^substrate^wherein^the^metho d^comprises^a^step^of^ applying^a^layer^comprising^the^coating^composition^accordin g^to^any^of^Aspects^7^–^9^on^a^ 24^ ^

surface^of^the^substrate^and^a^step^of^drying^the^layer^o f^coating^composition^to^obtain^a^film,^ wherein^the^film^passes^a^cleansability^test^in^at^least^one ^of^MPI^^143-148^and^MPI^^138-141.^ Aspect^11:^An^emulsion^polymer^composition^comprising^a^popu lation^of^sizes^of^ polymeric^particles,^wherein^the^polymeric^particles^compris e^copolymer^which^comprises,^in^ polymerized^form:^ a)^ between^40^weight^percent^and^95^weight^percent,^based^on^th e^overall^weight^of^ the^polymeric^particles,^of^at^least^one^monomer^comprising^ of^vinyl^acetate;^and^ b)^ between^5^weight^percent^and^60^weight^percent,^based^on^the ^overall^weight^of^ the^polymeric^particles,^of^at^least^one^ethylenically^unsat urated^monomer,^wherein^the^at^least^ one^ethylenically^unsaturated^monomer^b)^is^not^selected^fro m^monomer^a),^wherein^monomer^ a),^and^monomer^b)^together^total^100^weight^percent;^ and^wherein^the^population^of^sizes^of^polymeric^particles^c omprises^at^least^one^mode,^ and^wherein^each^mode _i ^comprises^a^respective^weight^average^particle^size^D w _i ^as^measured^by^ disc^centrifuge^photosedimentometry^and^a^respective^number^ average^particle^size^Dn _i ^as^ measured^by^disc^centrifuge^photosedimentometry^and^wherein^ for^each^mode _i ,^^Dw _i /Dn _i ^is^2.0^ or^less;^and^ wherein^the^emulsion^polymer^composition^further^comprises^b etween^0.1^and^5^weight^ percent,^based^on^the^total^dry^weight^of^the^polymeric^part icles,^of^at^least^one^hydrolyzable^ silane^selected^from^trialkoxy^silanes,^tetraalkoxysilanes,^ and^mixtures^thereof.^^ Aspect^ 12:^ The^ emulsion^ polymer^ composition^ according^ to^ Aspect^ 11,^ wherein^ the^ hydrolyzable^silane^is^selected^from^epoxy^functionalized^tr ialkoxy^silanes.^ Aspect^ 13:^ The^ emulsion^ polymer^ composition^ according^ to^ either^ of^ Aspect^ 11^ or^ Aspect^12,^wherein^ the^ at^ least^one^ethylenically^unsaturated^monomer^b)^ is^ selected^ from^ the^ group^ consisting^ of^alkyl(meth)acrylate^monomers,^ (meth)acrylamide^monomers,^and^mixtures^ thereof.^ 25^ ^

Aspect^ 14:^ The^ emulsion^ polymer^ composition^ according^ to^ any^ of^ Aspects^ 11^ –^ 13,^ wherein^ the^ at^ least^ one^ ethylenically^ unsaturated^ monomer^ b)^ is^ selected^ from^ the^ group^ consisting^of^alkyl(meth)acrylate^monomers,^and^mixtures^the reof.^^ Aspect^ 15:^ The^ emulsion^ polymer^ composition^ according^ to^ any^ of^ Aspects^ 11^ –^ 14,^ wherein^ the^ at^ least^ one^ ethylenically^ unsaturated^ monomer^ b)^ is^ selected^ from^ the^ group^ consisting^of^ethyl(meth)acrylate,^butyl^acrylate,^and^mixtu res^thereof.^ Aspect^ 16:^ The^ emulsion^ polymer^ composition^ according^ to^ any^ of^ Aspects^ 11^ –^ 15,^ wherein^the^copolymer^further^comprises,^in^polymerized^form ,^between^0.01^weight^percent^and^ 1.5^weight^ percent,^ based^ on^ the^ overall^ dry^weight^ of^ the^polymeric^particles,^ of^at^ least^one^ monomer^ selected^ from^ the^ group^ consisting^ of^ 2-acrylamido-2-methylpropane^ sulfonic^ acid^ (AMPS),^sodium^vinyl^sulfonate^(SVS),^acrylic^acid,^and^meth acrylic^acid,^and^mixtures^thereof.^^ Aspect^ 17:^ The^ emulsion^ polymer^ composition^ according^ to^ any^ of^ Aspects^ 11^ –^ 16,^ wherein^ the^ copolymer^ comprises,^ in^ polymerized^ form,^ between^ 0.4^ weight^ percent^ and^ 4^ weight^ percent,^ based^ on^ the^ overall^ dry^ weight^ of^ the^ polymeric^ particles,^ of^ a^ monomer^ selected^from^the^group^consisting^of^vinyl^versatate,^vinyl ^esters^of^tertiary^substituted^α-carbon^ carboxylic^acids,^vinyl^esters^of^C7-C20^carboxylic^acids,^a nd^mixtures^thereof.^^ Aspect^ 18:^ The^ emulsion^ polymer^ composition^ according^ to^ any^ of^ Aspects^ 11^ –^ 17,^ further^comprising^from^0.01^weight^percent^to^1^weight^perc ent^based^on^the^total^dry^weight^of^ the^ polymeric^ particles^ of^ a^ colloidal^ stabilizer,^ selected^ from^ hydroxyethyl^ cellulose^ in^ copolymerized^form.^^ Aspect^19:^A^coating^composition^comprising^an^emulsion^poly mer^composition^ according^to^any^of^Aspects^11^–^18^and^at^least^one^furth er^component^dispersed^in^an^aqueous^ medium.^ Aspect^20:^The^coating^composition^according^to^Aspect^19,^t he^at^least^one^further^ component^comprising^at^least^one^pigment.^ Aspect^21:^The^coating^composition^according^to^either^of^As pect^19^or^Aspect^20,^ further^comprising^at^least^one^additive^selected^from^the^g roup^consisting^of^dispersants,^ 26^ ^

surfactants,^defoamers,^pH^adjusters,^extenders,^opacifie rs,^rheology^modifiers,^coalescent^ agents,^colorants^and^mixtures^thereof.^ Aspect^22:^A^method^of^coating^a^substrate^wherein^the^metho d^comprises^a^step^of^ applying^a^layer^comprising^the^coating^composition^accordin g^to^any^of^Aspects^19^–^21^on^a^ surface^of^the^substrate^and^a^step^of^drying^the^layer^of^c oating^composition^to^obtain^a^film,^ wherein^the^film^passes^a^cleansability^test^in^at^least^one ^of^MPI^^143-148^and^MPI^^138-141.^^ ^ EXAMPLES^ The^compositions^shown^in^Table^1^were^prepared^according^to ^the^procedures^outlined^ in^Examples^1-6^and^Comparative^Examples^1-2.^The^compositio ns^according^ to^ the^invention^ were^ prepared^ as^ described^ in^ Examples^ 1-6.^ The^ comparative^ examples^ 1-2^ were^ prepared^ according^ to^ the^ emulsion^polymer^procedures^ shown,^ and^ represent^ the^ prior^art.^The^weight^ average^and^number^average^particle^sizes,^as^well^as^the^ra tio^of^the^weight^average^and^number^ average^particle^sizes^were^measured^using^disc^centrifuge^p hotosedimentometry.^ In^ the^tables,^ the^following^abbreviations^are^used:^ VA^ =^ vinyl^ acetate;^ BA^ =^ butyl^ acrylate;^ VTMS^ =^ vinyl^ trimethoxy^ silane^ as^ a^ comonomer;^ GP-TMS^ =^ glycidylpropyl^ trimethoxysilane^ added^ after^ polymerization;^ Dw^ =^ weight^average^particle^size^in^µm;^Dn^=^number^average^par ticle^size^in^µm;^Dw/Dn^=^ratio^of^ weight^ average^ particle^ size^ to^ number^average^ particle^ size.^All^monomers^ and^ additives^ are^ shown^as^weight^percent,^based^on^the^total^dry^weight^of^th e^polymeric^particles.^ Example^1:^Preparation^of^emulsion^polymer^composition^with^ 0.1^weight^percent^ hydrolyzable^silane^monomer^and^narrow^particle^size^distrib ution^ In^a^three-liter^jacketed^glass^reactor^equipped^with^dual^i mpellers,^a^reflux^condenser,^a^ stainless^steel^feed^line,^and^a^stainless^steel^thermocoupl e^is^added:^2.33g^sodium^acetate,^0.6g^ anionic^ surfactant,^4.7g^ anionic^ surfactant,^1.94g^nonionic^ surfactant,^ 1.94g^of^ a^ 25^^solution^ sodium^vinyl^sulfonate,^and^0.5g^hydroxyethyl^cellulose^as^c olloidal^stabilizer,^and^552g^water.^ The^reactor^was^then^heated^to^65°C.^^ 27^ ^

A^ monomer^ mixture^ was^ prepared^ by^ combining^ 675.9g^ vinyl^ acetate,^ 19.36g^ vinyl^ versatate,^272.61g^butyl^acrylate,^and^1.0g^vinyl^trimethoxy silane^(VTMS).^ A^third^stream^feed^was^prepared^by^combining^25g^water,^18. 5g^nonionic^surfactant,^16g^ anionic^surfactant,^and^4.8g^2-arylamido-2-methylpropane^sul fonic^acid,^aqueous^sodium^salt.^ The^reactor^was^charged^with^7.0^^by^weight^of^the^monomer^m ixture,^followed^by^the^ addition^of^0.2g^sodium^persulfate^in^5g^water,^then^0.2g^so dium^metabisulfite^in^5g^water.^The^ contents^ were^ allowed^ to^ exotherm^ and^ then^ held^ for^ 15^ minutes^ to^ form^ the^ seed^ polymer^ particles.^ The^ temperature^was^ then^ raised^ to^75°C^for^ the^ remainder^of^ the^polymerization.^The^ remaining^monomer^mixture^was^added^to^the^reactor^over^a^pe riod^of^205^minutes,^concurrently^ with^the^third^stream^feed.^Additionally,^1.8g^sodium^persul fate^in^20g^water^was^added^over^220^ minutes.^The^final^mixture^was^held^at^75°C^for^an^addition al^30^minutes^after^the^initiator^feed^ was^completed.^ The^reactor^was^then^cooled^to^70-75°C^and^solutions^of^1.4 4g^t-butyl^hydroperoxide^in^ 20g^water^and^1.0g^ sodium^metabisulfite^in^20g^water^were^added^via^separate^fe ed^streams^to^ the^reactor^over^60^minutes.^The^reactor^is^then^cooled^to^& lt;40°C^and^the^ reactor^contents^were^ transferred.^Example^1^has^a^total^solids^content^of^56.6^^b ased^on^the^weight^of^the^emulsion^ polymer,^a^pH^of^4.5,^and^a^viscosity^of^400^cPs.^ Example^2:^Preparation^of^emulsion^polymer^composition^with^ 0.26^weight^percent^ hydrolyzable^silane^monomer^and^narrow^particle^size^distrib ution^ Example^2^was^prepared^under^the^same^procedure^as^that^show n^in^Example^1,^except^ that^2.6g^of^the^hydrolyzable^silane^monomer,^vinyltrimethox y^silane^in^that^example,^was^added^ to^the^monomer^mixture.^Example^2^had^a^total^solids^content ^of^56.6^^based^on^the^weight^of^ the^emulsion^polymer,^a^pH^of^4.6,^and^a^viscosity^of^300^cP s.^ Example^3:^Preparation^of^emulsion^polymer^composition^with^ 0.51^weight^percent^ hydrolyzable^silane^monomer^and^narrow^particle^size^distrib ution^ 28^ ^

Example^3^was^prepared^under^the^same^procedure^as^that^s hown^in^Example^1,^except^ that^5.1g^of^the^hydrolyzable^silane^monomer,^vinyltrimethox y^silane^in^that^example,^was^added^ to^the^monomer^mixture.^Example^3^had^a^total^solids^content ^of^56.7^^based^on^the^weight^of^ the^emulsion^polymer,^a^pH^of^4.5,^and^a^viscosity^of^560^cP s.^ Comparative^ Example^ 1:^ Preparation^ of^ emulsion^ polymer^ composition^ with^ 0^ weight^percent^hydrolyzable^silane^monomer^and^narrow^partic le^size^distribution^ Comparative^ example^ 1^ was^ prepared^ under^ the^ same^ procedure^ as^ that^ shown^ in^ Example^1,^except^that^the^hydrolyzable^silane^monomer,^viny ltrimethoxy^silane^in^that^example,^ was^not^included^in^the^monomer^composition.^Comparative^Exa mple^1^had^a^total^solids^content^ of^56.7^^based^on^the^weight^of^the^emulsion^polymer,^a^pH^o f^4.5,^and^a^viscosity^of^480^cPs.^ Example^4:^Preparation^of^polymer^composition^comprising^Com parative^Example^ 2^with^hydrolyzable^silane^added^to^final^emulsion^polymer^ Example^4^was^prepared^by^the^slow^addition^under^agitation^ of^10.0g^of^glycidylpropyl^ trimethoxysilane^ (GP-TMS)^ to^ the^ Comparative^ example^ 1.^ The^ physical^ properties^ of^ this^ emulsion^polymer^composition^was^not^affected^by^the^additio n^of^GP-TMS.^ Comparative^ Example^ 2:^ Preparation^ of^ emulsion^ polymer^ composition^ with^ hydrolyzable^silane^monomer^and^broad^particle^size^distribu tion^(PDI^>2.0)^ In^a^three-liter^jacketed^glass^reactor^equipped^with^dual^i mpellers,^a^reflux^condenser,^a^ stainless^steel^feed^line,^and^a^stainless^steel^thermocoupl e^is^added:^2.55g^sodium^acetate,^9.2g^ anionic^surfactant,^65.6g^of^a^nonionic^surfactant,^2.3g^of^ a^25^^solution^sodium^vinyl^sulfonate,^ and^ 1.66g^ hydroxyethyl^ cellulose^ as^ colloidal^ stabilizer,^ and^ 575g^water.^ The^ reactor^ is^ then^ heated^to^69°C.^^ A^ monomer^ mixture^ was^ prepared^ by^ combining^ 890.5g^ vinyl^ acetate,^ 256.2g^ butyl^ acrylate,^and^1.09g^vinyl^trimethoxysilane^(VTMS).^ An^oxidizer^solution^was^prepared^by^the^addition^of^0.81g^T BHP^to^81.3g^water^and^a^ reducer^solution^was^prepared^by^the^addition^of^0.81g^SMBS^ to^88g^water^with^2.18g^anionic^ 29^ ^

surfactant.^A^third^stream^solution^of^HEC^was^prepared^b y^the^addition^of^1.25g^HEC^to^41.4g^ water.^ To^the^reactor^contents^at^65°C^was^fed^the^monomer^mixture ,^ the^oxidizer^solution,^the^ reducer^solution,^and^the^HEC^solution^over^210^minutes,^mai ntaining^a^temperature^of^65-73˚C.^ The^ final^ mixture^ was^ held^ at^ 75°C^ for^ an^ additional^ 30^minutes^ after^ the^ initiator^ feed^ was^ completed.^ With^ the^ reactor^ contents^ at^ 65-73˚C,^ solutions^ of^ 1.33g^ t-butyl^ hydroperoxide^ in^ 20g^ water^and^0.69g^sodium^metabisulfite^in^20g^water^were^added ^via^separate^feed^streams^to^the^ reactor^ over^ 60^ minutes.^ The^ reactor^ is^ then^ cooled^ to^ <40C^ and^ the^ reactor^ contents^ were^ transferred.^Comparative^Example^2^had^a^total^solids^conten t^of^59.6^^based^on^the^weight^of^ the^emulsion^polymer,^a^pH^of^4.8,^and^a^viscosity^of^600^cP s.^ Example^5:^Preparation^of^emulsion^polymer^composition^with^ hydrolyzable^silane^ monomer^and^broad^particle^size^distribution^(PDI^<2.0)^ Example^5^was^prepared^under^the^same^procedure^as^that^show n^in^Example^1,^except^ that^the^amount^of^HEC^in^the^initial^reactor^charge^was^inc reased^to^2.0g.^Example^5^had^a^total^ solids^ content^ of^ 56.7^^ based^ on^ the^ weight^ of^ the^ emulsion^ polymer,^ a^ pH^ of^ 4.5,^ and^ a^ viscosity^of^210^cPs.^ Example^6:^Preparation^of^emulsion^polymer^composition^with^ hydrolyzable^silane^ monomer^ and^ multimodal^ particle^ size^ distribution^ (PDI^ <2.0^ for^ each^ particle^ size^ population)^ Example^6^was^prepared^under^the^same^procedure^as^that^show n^in^Example^1,^except^ that^the^anionic^surfactant^was^removed^from^the^initial^rea ctor^charge.^Comparative^Example^1^ had^a^total^solids^content^of^56.0^^based^on^the^weight^of^t he^emulsion^polymer,^a^pH^of^4.4,^ and^a^viscosity^of^60^cPs.^ ^ 30^ ^

^ ^ Preparation^ of^ coating^ compositions^ with^ vinyl^ acrylic^ emulsion^ polymer^ of^ the^ Example^and^Comparative^Example^polymer^compositions^ Coating^compositions^incorporating^the^polymer^emulsions^sho wn^ in^Examples^1-6^and^ Comparative^Examples^1-2^were^prepared^according^to^the^coat ing^formulation^shown^in^Table^ 2.^The^coating^composition^was^ prepared^ in^accordance^ to^ procedures^ and^practices^known^ to^ those^skilled^in^the^art.^ ^ 31^ ^

^ Cleansability^ evaluation^ of^ the^ coating^ compositions^ containing^ the^ vinyl^ acrylic^ emulsion^polymer^of^the^Example^and^Comparative^Example^poly mer^compositions^ The^coatings^prepared^according^to^Table^2^were^tested^ for^MPI^cleansability^using^the^ procedure^outlined^ in^the^“Cleansability”^section.^Graphite^and^coffee^clea nsability^will^not^be^ discuss,^as^these^specifications^are^easily^obtained^in^viny l^acrylic^emulsion^polymer^of^the^type^ described^ in^ the^ Examples^ and^ Comparative^ Examples^ in^ Table^ 1.^ The^ cleansability^ of^ the^ coatings^to^nigrosin^were^measured^and^these^ΔE^values^are^ shown^in^Table^3,^ along^with^the^ ratio^of^weight^average^particle^size^to^number^average^part icle^and^the^amount^of^hydrolyzable^ silane^in^each^polymer^emulsion^composition.^ 32^ ^

^ Figures^ 2-5^ represent^ the^ particle^ size^ distributions^ analyzed^ for^ Examples^ 1-6^ and^ Comparative^Examples^1-2^as^measured^by^disc^centrifuge^phot osedimentometry,^though^other^ high^resolution^particle^size^techniques^can^be^used^to^eval uate^weight^average^particle^size^and^ number^average^particle^size.^ First,^ the^ emulsion^ polymer^ compositions^ of^ the^ current^ invention^ are^ represented^ by^ Examples^1-6^in^Table^3.^Disc^centrifuge^data^for^Examples^1 -4^and^Comparative^Example^1^are^ shown^ in^ Figure^ 2.^ In^ accordance^ with^ the^ first^ embodiment^ of^ this^ invention,^ Example^ 1^ contains^a^low^level^of^VTMS,^with^Examples^2^and^3^having^i ncreasing^levels^of^VTMS.^All^ three^ examples^ have^ a^ narrow^ PDI,^ represented^ by^ D _w /D _n .^ ^With^ the^ inclusion^ of^ 0.1^ weight^ percent^ VTMS,^ nigrosin^ cleansability^ is^ ΔE^ 0.55,^ where^ increasing^ levels^ result^ in^ improved^ nigrosin^cleansability;^ΔE^0.47^with^0.26^weight^percent^VT MS^and^ΔE^0.37^with^0.51^weight^ percent^ VTMS.^ Comparative^ Example^ 1,^ on^ the^ other^ hand,^ demonstrates^ that^ without^ hydrolyzable^silane^in^the^emulsion^polymer^composition,^eve n^with^a^narrow^PDI,^the^nigrosin^ cleansability^is^poor,^with^a^ΔE^of^2.1.^In^accordance^with ^the^second^embodiment^of^the^current^ invention,^ Example^ 4^ contains^ no^ hydrolyzable^ silane^ introduced^ during^ the^ emulsion^ polymerization,^ though^ benefits^ from^ the^ addition^ of^ 1.0^ weight^ percent^ of^ glycidylpropyl^ trimethoxysilane^ (GP-TMS).^ This^ further^ broadens^ the^ utility^ of^ this^ technology^ to^ a^ post- addition^scenario,^in^which^nigrosin^cleansability^is^ΔE^2. 10^without^GP-TMS^and^ΔE^1.51^after^ the^addition^of^GP-TMS.^ Comparative^Example^2^represents^an^emulsion^polymer^that^is ^prepared^in^such^a^way^at^ the^generate^a^broad^particle^size^distribution^with^PDI^> ;2.0,^as^represented^by^the^ratio^of^D _w ^to^ D _n ^in^Figure^3.^While^ this^emulsion^polymer^composition^contains^0.1^weight^percen t^VTMS,^ the^broad^particle^size^distribution^results^in^poor^nigrosi n^cleansability.^ The^emulsion^polymer^compositions^of^Examples^5^and^6,^as^sh own^in^Figures^4^and^5,^ are^ broader^ than^ those^ in^ Examples^ 1-3,^ though^ the^ nigrosin^ cleansability^ is^ excellent.^ In^ Example^5,^the^amount^of^VTMS^in^the^emulsion^polymer^compos ition^is^0.1^weight^percent^and^ the^PDI^is^<2.0.^In^Example^6^the^amount^of^VTMS^in^the^e mulsion^polymer^composition^is^0.1^ 33^ ^

weight^percent^and^the^PDI^for^each^emulsion^polymer^part icle^population^is^<2.0,^wherein^the^ individual^emulsion^polymer^particle^populations^are^integra ted^separately,^as^shown^in^the^scans^ in^Figure^5. _^ Within^ this^ specification^ embodiments^ have^ been^ described^ in^ a^ way^which^ enables^ a^ clear^ and^ concise^ specification^ to^ be^ written,^ but^ it^ is^ intended^ and^ will^ be^ appreciated^ that^ embodiments^may^be^variously^combined^or^separated^without^d eparting^from^the^invention.^For^ example,^ it^will^be^appreciated^ that^ all^preferred^features^described^herein^are^applicable^to^al l^ aspects^of^the^invention^described^herein.^^ The^ foregoing^ description^ of^ various^ forms^ of^ the^ invention^ has^ been^ presented^ for^ purposes^ of^ illustration^ and^ description.^ It^ is^ not^ intended^ to^ be^ exhaustive^ or^ to^ limit^ the^ invention^ to^ the^precise^ forms^disclosed.^Numerous^modifications^or^variations^are^po ssible^ in^ light^of^the^above^teachings.^The^forms^discussed^were^chose n^and^described^to^provide^the^best^ illustration^of^the^principles^of^the^invention^and^its^prac tical^application^to^thereby^enable^one^of^ ordinary^skill^in^the^art^to^utilize^the^invention^in^variou s^forms^and^with^various^modifications^as^ are^suited^to^the^particular^use^contemplated.^All^such^modi fications^and^variations^are^within^the^ scope^ of^ the^ invention^ as^ determined^ by^ the^ appended^ claims^when^ interpreted^ in^ accordance^ with^the^breadth^to^which^they^are^fairly,^legally,^and^equi tably^entitled.^^ 34^ ^