Latex particles and coatings comprising same

Abstract

Elastomeric latex particle emulsions wherein both the core and shell monomers comprise an alkyl diol di(meth)acrylate, coatings comprising the same, layers deposited therefrom, and substrates coated therewith are disclosed.

Description

LATEX PARTICLES AND COATINGS COMPRISING SAMECROSS-REFERENCE TO RELATED APPLICATION

[0001] This application claims the benefit of U.S. Provisional Patent Application No. 63 / 636,429, filed April 19, 2024, which is incorporated herein by reference in its entirety.FIELD OF THE DISCLOSURE

[0002] The present disclosure is directed to emulsions of latex particles wherein both the core monomers and shell monomers comprise an alkyl diol di(meth)acrylate.BACKGROUND OF THE DISCLOSURE

[0003] Coatings used on the exterior of structures, such as houses and other buildings, often have mechanical resistance properties like maximum stress and strain to break values that contribute to low water absorption and / or high-water impermeability. This is particularly relevant in flooding or water ponding conditions. Coatings that exhibit low water absorption and / or high-water impermeability that do not contain substances of concern are desired.SUMMARY OF THE DISCLOSURE

[0004] The present disclosure is directed to an emulsion comprising latex particles comprising a core formed from a core monomer mixture comprising an alkyl diol di(meth)acrylate monomer; a shell formed from a shell monomer mixture comprising an alkyl diol di(meth)acrylate monomer the same as and / or different from the alkyl diol di(meth)acrylate in the core; and a crosslinking monomer component that crosslinks the core and shell upon polymerization, wherein the latex particles are substantially free, essentially free, or completely free of N-methylol acrylamide and residues thereof and benzophenone and residues thereof, and wherein the Tg of the core is higher than the Tg of the shell. Coating compositions, coating layers deposited therefrom, and substrates coated therewith are also within the scope of the disclosure.BRIEF DESCRIPTION OF THE DRAWING

[0005] Fig. 1 is a graph demonstrating strain of films at a constant load in water flooded conditions.DETAILED DESCRIPTION OF THE DISCLOSURE

[0006] The present disclosure is directed to an emulsion comprising latex particles comprising: (a) a core formed from a core monomer mixture comprising an alkyl diol di(meth)acrylate monomer; (b) a shell formed from a shell monomer mixture comprising analkyl diol di(meth)acrylate monomer the same as and / or different from the alkyl diol di(meth)acrylate in the core monomer mixture; (c) a crosslinking monomer component that crosslinks the core and shell upon polymerization. The latex particles are substantially free, essentially free, or completely free of N-methylol acrylamide and residues thereof and benzophenone and residues thereof, and the Tg of the core is higher than the Tg of the shell. The “crosslinking monomer component” refers to the monomer(s) that cause the core and shell to become crosslinked upon polymerization; although the crosslinking monomer component may comprise one or more monomers, it may be referred to herein in the singular as the “crosslinking monomer”. Also, while the crosslinking monomer component is recited as a separate component in the composition, it will be appreciated that it can be added to the core monomer mixture and / or the shell monomer mixture.

[0007] The term “alkyl diol di(meth)acrylate monomer” as used herein refers to a monomer wherein the hydroxy groups of an alkyl diol are each reacted with a (meth)acrylic acid. Any alkyl diol can be reacted with any (meth)acrylic acid to form an alkyl diol di(meth)acrylate used according to the present disclosure. The backbone of the alkyl chain of the alkyl diol can be saturated, in which case the alkyl diol may be an alkane diol, or unsaturated, in which case the alkyl diol may be an alkene or alkyne diol and contain any number of carbon atoms in the backbone. The backbone of the alkyl chain of the alkyl diol may have one to fifteen carbons. As used herein, an alkyl diol having Cl-6 is a “short chain” alkyl diol, and one having C7-15 is a “long chain” alkyl diol. Examples of short chain alkyl diol di(meth)acrylates include ethylene glycol di(meth)acrylate; 1,3 and 1 ,4-butanediol di(meth)acrylate; and 1,6-hexanediol di(meth)acrylate. The backbone may also comprise one or more heteroatoms in addition to carbon atoms, such as O, N, or S, in which case the alkyl diol may, for example, be a polyalkylene glycol. Exemplary long chain alkyl diol di(meth)acrylates include polyethylene glycol di(meth)acrylate and urethane di(meth)acrylate.

[0008] As noted above, both the core monomer and shell monomer mixtures comprise an alkyl diol di(meth)acrylate. These can be the same and / or different. The core may comprise a short chain alkyl diol di(meth)acrylate and the shell may comprise a long chain alkyl diol di(meth)acrylate, a short chain alkyl diol di(meth)acrylate, or both. Particularly suitable latex particles are those in which a short chain alkyl diol di(meth)acrylate, such as 1 ,4-butane diol dimethacrylate, is used in the core monomer mixture and a long chain alkyl dioldi(meth)acrylate, such as polyethylene glycol dimethacrylate, is used in the shell monomer mixture. Different in the “same or different” includes any difference at all, such as the alkyl length, the saturation or unsaturation of the alkyl, use of the methacrylate versus the acrylate, and so on.

[0009] The alkyl diol dimethacrylate monomer, such as a short chain alkyl diol di(meth)acrylate, may be present in the core monomer mixture in an amount 1 wt% to 5 wt%, such as 2 wt% to 3 wt%, based upon the total weight of the core monomer mixture. Similarly, the alkyl diol di(meth)acrylate monomer, such as a long chain alkyl diol di(meth)acrylate alone or in combination with a short chain alkyl diol di(meth)acrylate, may be present in the shell monomer mixture in an amount 1 wt% to 5 wt%, such as 2 wt% to 3 wt%, based upon the total weight of the shell monomer mixture. When both a short and a long chain alkyl diol di(meth)acrylate are used in the shell monomer mixture, the weight ratio of short chain to long chain may be 1:1 to 1:3, such as 1:1.6 or 1: 1.5. The long chain monomer may impart flexibility to the emulsion while the short chain monomer may impart rigidity producing a tightly crosslinked network with increased resistance and impermeability to water.

[0010] A particularly suitable crosslinking monomer according to the present disclosure is a diacetone acrylamide (DAAM) used together with adipic dihydrazide (ADH). These may be present in the core monomer mixture, the shell monomer mixture, and / or may be added at any time during polymerization of the latex particle. DAAM may be present in the shell monomer mixture, for example, in a wt% of 4 wt% to 18 wt%, such as 5 wt% to 16 wt%, such as 5 wt% to 10 wt%, with wt% based on total shell monomer weight. The amount of ADH may be selected so as to give a weight ratio of DAAM: ADH of 1:0.6, 1:0.5, 1:0.4; 1:0.3 or 1:0.2, such as 1:0.6- 0.5. The total amount of crosslinking monomer component may comprise 0.1 wt% to 3 wt%, such as 0.25 wt% to 2 wt%, such as 0.5 wt% to 1.5 wt%, based upon the total weight of the emulsion.

[0011] The monomers used to form the latex particles, the latex particles themselves, as well as the emulsions and coatings prepared from the same, may be substantially free, essentially free, or completely free, of substances of concern or residues thereof. The “monomers used to form the latex particles” refer to the monomers in the core monomer mixture, the shell monomer mixture, and the crosslinking monomer component. A “residue” of a monomer is that portion of the monomer that becomes incorporated into the polymer. Many monomers and compoundspreviously thought safe to humans are now being avoided, if not banned (“substances of concern” or “SOC”). Two SOC often used in latex formation include N-methylol acrylamide and / or benzophenone or residues of either of these. According to the present disclosure, the emulsion can be substantially free, essentially free, or completely free of these. Styrene, which may be a SOC in certain applications, can be used in the present compositions or the composition can be substantially, essentially, and / or completely free of styrene. In reference to these substances of concern, substantially free means the monomer mixtures, emulsion, and coatings prepared therefrom comprise 2 wt% or less of any of these compounds, “essentially free” means 1 wt% or less of any of the compounds, and “completely free” means that only trace amounts of any of these compounds, such as would be present as an impurity in another compound, are present, if at all. DAAM and ADH are not SOC.

[0012] Any other monomers can also be used in the core monomer mixture, the shell monomer mixture, and / or may be added at any time during polymerization of the latex particle; the monomers can be selected to polymerize with the others in the mixture and / or to impart different properties to the emulsion, such as high or low Tg, where “high” means greater than 0°C and “low” means 0°C or lower. Examples include aromatic compounds, such as vinyl aromatic compounds such as styrene and alpha methyl styrene, and alkyl (meth)acrylates such as methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, iso-butyl (meth)acrylate or iso-bornyl (meth)acrylate, butyl (meth)acrylate, and tert-butyl (meth)acrylate.

[0013] The monomers used to form the latex particle may specifically exclude hydroxy functional (meth)acrylic monomers; that is, the monomers used in the formation of the latex particles can be chosen to avoid use of any hydroxy functional (meth)acrylate monomers. Hydroxy functional (meth)acrylic monomers may impart hydrophilicity to a latex emulsion thereby promoting water absorption rather than water resistance. Such hydrophilicity would not be desired in an application where water impermeability is desired. The monomers used to form the latex particle may specifically exclude fluorine containing (meth)acrylic monomers and / or phosphate ester functional monomers; that is, the monomers used in the formation of the latex particles can be chosen to avoid use of any fluorine containing (meth)acrylate monomers, and / or any phosphate ester functional monomers. By “specifically exclude” is meant that these monomers, or other components described herein as being “specifically excluded”, are not intentionally used and any presence of such monomers and / or components is only trace and dueto an impurity, such as 0.3 wt% or less, or 0.1 wt% or less of the latex particles, emulsions, or coatings comprising the same.

[0014] The latex particles of the present disclosure may have a core Tg that is higher than the Tg of the shell. The core Tg may be -8 to 80°C, such as 10 to 80 °C, or 40 to 70 °C and / or the shell Tg may be -25 to -33°C, such as -16 to -25°C, or -25 to -33°C, where Tg is calculated according to the Fox equation. The Tg of the core may be 50°C greater than that of the shell, such as 60°C greater, 70°C greater, 80°C greater, or 90°C greater. To achieve the desired Tg, a combination of low and high Tg monomers may be used. The term “low Tg monomer” as used herein refers generally to a monomer with a Tg of 0°C or lower and a “high Tg monomer” to a monomer with a Tg greater than 0°C, such as one having a Tg of 80°C, 90°C, or 100°C or higher. Examples of low Tg monomers include butyl acrylate, 2-ethylhexyl acrylate, dodecyl methacrylate, trans-butadiene, ethyl acrylate, hexyl acrylate, isobutyl acrylate, isoprene, octyl methacrylate. Examples of high Tg monomers include 2,5-dimethylstyrene, 2,4- dimethylstyrene, tert-butyl methacrylate, cyclohexyl methacrylate, iso-butyl methacrylate or isobornyl methacrylate, phenyl methacrylate, methyl methacrylate, tert-butyl methacrylate.Examples of high Tg monomers that are aromatic monomers having an ethylenically unsaturated group include styrene and alpha methyl styrene. The desired Tg of the core and shell can be achieved by one skilled in the art by using the appropriate monomer(s) in the appropriate amounts.

[0015] Standard methods of core shell polymerization can be used to prepare the latex particle emulsions of the present disclosure. It will be appreciated that each of the core monomer mixture and shell monomer mixture comprise monomers that will react or crosslink with each other during polymerization, such that each of the core and shell comprise a crosslinked network. The presence of the crosslinking monomer also results in crosslinking between the shell and the core. While the latex particles of the present disclosure are described in terms of “comprising a crosslinking monomer” it will be understood that such monomer reacts to crosslink with the shell and the core during particle formation.

[0016] The present emulsions may have a solids content of 20% or higher, such as 40% or higher, such as 50% or higher, such as 20 to 80% or 50 to 60%.

[0017] The latex particles in the present emulsions may have a mean particle size of 250 nm or higher, such as 260 nm or higher, 270 nm or higher, 280 nm or higher, 290 nm or higher,or 300 nm or higher, such as 260 to 310 nm or 280 to 300 nm, as measured by Dynamic Light Scattering (DLS). The latex particles of the present disclosure, as a result of monomer selection and Tg parameters, can be elastomeric, combining rigidity in the core with flexibility in the shell. “Elastomeric particles” are particles having rubber-like properties that can regain their original shape when a load is placed and removed from them. Elastomeric particles have low water absorption and low water permeability with high mechanical resistance; that is, resistance to water ponding may be observed, with mechanical resistance being retained even after extensive water exposure.

[0018] Accordingly, the present disclosure is further directed to a coating composition comprising any of the emulsions of latex particles described above. Coating compositions according to the present disclosure can be formulated using any means known in the art using the emulsions of the present disclosure and one or more standard additives such as water, solvents such as organic solvents, pigments, dyes, fillers such as calcium carbonate, clay, silica, talc and the like, abrasion-resistant particles, anti-oxidants, hindered amine light stabilizers, UV light absorbers and stabilizers, surfactants, flow and surface control agents, thixotropic agents, reactive diluents, driers, catalysts, reaction inhibitors, adhesion promoting components, such as acids and acid derivatives, phosphatized epoxy, and other customary additives known to those skilled in the art. Use of paraffin or other waxes may be specifically excluded from any of the coating compositions of the present disclosure.

[0019] The coating compositions of the present disclosure may further comprise silica or silanes as an adhesion promoting component. The use of these components may promote both wet and dry adhesion between the coatings and a substrate. Examples include colloidal silica and / or epoxy functional silane oligomers, both of which are widely commercially available. The silica and / or silane adhesion promoting component may be present in an amount of 0.1 wt% to 3 wt%, or such as 0.25 wt% to 2 wt%, or such as 0.5 wt% to 1.0 wt%, based upon the total weight of the coating composition.

[0020] Coating compositions as described herein may be applied to a substrate and dried or coalesced. As used herein, the term “cure”, “coalesce”, “harden” or like terms refers to the process by which a coating composition hardens to form a coating or coating layer, the two terms being used interchangeably herein. Coalescing may include the coating composition being cured(e.g. hardening by being crosslinked, either by itself or via a crosslinking agent) or the coating composition being dried.

[0021] The coating compositions of the present disclosure may be one component compositions. As used herein, the term “one component” or “IK” refers to a composition in which all of the ingredients may be premixed and stored and wherein the reactive components do not readily react until exposed to air at ambient or slightly thermal conditions: that is, the coating compositions of the present disclosure can cure or coalesce without the use of a separate crosslinker.

[0022] The coating compositions of the present disclosure may comprise a dispersion component that promotes resistance to waterlogging, the dispersion component comprising an aliphatic polyurethane based on a poly ether diol, in an amount selected from 0.1 wt% to 3 wt%, or from 0.25 wt% to 2 wt%, or from 0.5 wt% to 1.0 wt%, based upon the total weight of the coating composition.

[0023] The present disclosure is further directed to a method for using any of the coating compositions described above to coat at least a portion of a substrate comprising depositing a coating or coating layer (which may be used interchangeably herein) onto the substrate.

[0024] The compositions of the present disclosure can be deposited onto the surface of a substrate in any number of different ways, such as brushes, rollers, films, trowels, spatulas, dips, spray guns, sprays or applicator guns. Upon application, the coating layer can be dried or cured by any suitable means known to those skilled in the art. Examples include ambient curing, baking in a thermal oven, induction heating, infrared heating, exposure to actinic radiation, and / or combinations thereof. For example, the coating may be cured or coalesced at ambient conditions, or at moderately elevated conditions such as at a temperature up to 60°C. “Ambient” conditions generally refer to room temperature and humidity conditions, such as and may be 20°C + / - 5°C and 20% relative humidity to 80% relative humidity, while slightly thermal conditions are just above ambient temperature (e.g., above 30°C).

[0025] Hardened or cured coating layers deposited from the present coating compositions, after 14 days ambient temperature and exposure, may have a maximum stress (psi) and Strain @ Break (%) according to ASTM D2370-16, Standard Test Method for Tensile Properties of Organic Coatings, that meets or exceeds NMX-C-450-ONNCCE-2019, which specifies that a coating have a minimum stress of 200 lb. / in2and a minimum Strain @ Break of100%. NMX-C-450-ONNCCE-2019 is the Mexican Standard related to specifications and testing methods for liquid elastomeric waterproofing materials. Hardened or cured coating layers deposited from the present coating compositions after 14 days ambient temperature and exposure and 100 hours of QUV exposure, Lamp UV-A of 340 nm, UV at 60°C for 4 Hrs., condensation at 50°C for 8 Hrs., and irradiance of 0.77 W / m2 / nm, may have a maximum stress of 300 psi or greater, such as 310 psi or greater, such as 320 psi or greater, such as 330 psi or greater, such as 300 to 340 psi, as measured by ASTM D2370-16. Hardened or cured coating layers deposited from the present coating compositions after 14 days ambient temperature and exposure and 21 days immersed in water according to ASTM D471-16a may have a maximum stress of 70 psi or greater, such as 80 psi or greater, and a Strain @ Break of 500% or greater, such as 600% or greater, such as 700% or greater, such as 800% or greater, such as 900% or greater, such as 600 to 900 % as measured by ASTM D2370-16.

[0026] The coating compositions may be applied to any substrates known in the art, for example, architectural components, such as roofs, walls, bricks, vinyl siding, concrete, cement, cement board, MDF (medium density fiberboard) and particle board, gypsum board, wood, wood composite, veneer, stone, metal, plastics, wallpaper and textile, etc., which may be pre -primed by waterborne or solvent borne primers. The architectural component may be an interior or exterior component, such as a wall and / or roof of a building or residence. An “exterior” component is one that is exposed to the elements. “Architectural component” as used herein refers to any of those listed above or otherwise known to those skilled in the art to be used in the building of structures.

[0027] Automotive substrates, marine substrates, industrial substrates, packaging substrates, wood flooring and furniture, apparel, electronics including housings and circuit boards and including consumer electronics such as housings for computers, notebooks, smartphones, tablets, televisions, gaming equipment, computer equipment, computer accessories, MP3 players, glass and transparencies, sports equipment including golf balls, and the like are also suitable substrates.

[0028] Substrates can be, for example, metallic or non - metallic. Metallic substrates include tin, steel, tin -plated steel, chromium passivated steel, galvanized steel, aluminum, aluminum foil. Metal sheet as used herein refers to flat metal sheet and coiled metal sheet, which is coiled, uncoiled for coating, and then re-coiled for shipment to a manufacturer. Non-metallic substrates include polymeric, plastic, polyester, polyolefin, polyamide, cellulosic, polystyrene, polyacrylic, poly (ethylene naphthalate), polypropylene, polyethylene, nylon, EVOH, polylactic acid, other “green” polymeric substrates, poly(ethyleneterephthalate) (“PET”), polycarbonate, polycarbonate acrylobutadiene styrene (“PC / ABS”), polyamide, glass, paper, cardboard, textiles, leather both synthetic and natural, and those non-metallic substrates listed above as architectural components.

[0029] Accordingly, the present disclosure is further directed to a substrate comprising a coating layer deposited from any of the coating compositions described herein.

[0030] Any numerical range recited herein is intended to include all sub-ranges subsumed therein. Singular encompasses plural and vice versa. For example, although reference is made herein to “an” emulsion, “a” long chain alkyl diol, “a” short chain alkyl diol, “a” crosslinking monomer, “an” architectural component and the like, one or more of each of these and any other components can be used. Also, as used herein, the term “polymer” refers to prepolymers, oligomers and both homopolymers and copolymers; the prefix “poly” refers to two or more. When ranges are given, any endpoints of those ranges and / or numbers within those ranges can be combined with the scope of the present disclosure. “Including”, “such as”, “for example” and like terms means “including / such as / for example but not limited to”. The terms “(meth)acrylic”, “(meth)acrylate” and the like refer to both acrylate and methacrylate and include acrylic acids, anhydrides, and derivatives thereof, lower alkyl-substituted acrylic acids, e.g., C1-C2 substituted acrylic acids, such as methacrylic acid, methacrylic acid, etc., and their Ci-Ce alkyl esters and hydroxyalkyl esters, unless clearly indicated otherwise.ASPECTS

[0031] Aspect 1. An emulsion comprising latex particles comprising a. a core formed from a core monomer mixture comprising an alkyl diol di(meth)acrylate monomer; b. a shell formed from a shell monomer mixture comprising an alkyl diol di(meth)acrylate monomer that is the same as and / or different from the alkyl diol di(meth)acrylate in the core; c. a crosslinking monomer component that crosslinks with the core and shell upon polymerization;wherein the latex particles are substantially free, essentially free, or completely free of N-methylol acrylamide and residues thereof and benzophenone and residues thereof; and wherein the Tg of the core is higher than the Tg of the shell.

[0032] Aspect 2. The emulsion of aspect 1 , wherein the core monomer mixture comprises a short chain alkyl diol di(meth)acrylate and the shell monomer mixture comprises a long chain alkyl diol di(meth)acrylate and / or a short chain alkyl diol di(me th) acrylate; and wherein when both a short chain and long chain alkyl diol di(meth)acrylate are used in the shell monomer mixture the weight ratio of short: long is 1: 1 to 1:3.

[0033] Aspect 3. The emulsion of aspect 2, wherein the weight ratio of shortdong is1:2.

[0034] Aspect 4. The emulsion of aspect 2, wherein the weight ratio of shortdong is1: 1.6.

[0035] Aspect 5. The emulsion of aspect 2, wherein the weight ratio of shortdong is1: 1.5.

[0036] Aspect 6. The emulsion of any preceding aspect, wherein the core monomer mixture, the shell monomer mixture, or both comprise a short chain alkyl diol (di)meth acrylate.

[0037] Aspect 7. The emulsion of aspect 6, wherein the short chain alkyl diol (di)meth acrylate comprises 1 ,4-butanediol di(meth)acrylate.

[0038] Aspect 8. The emulsion of any of aspects 6-7, wherein the short chain alkyl diol (di)meth acrylate comprises 1,6-hexanediol di(meth)acrylate.

[0039] Aspect 9. The emulsion of any of aspects 6-8, wherein the short chain alkyl diol (di)meth acrylate comprises ethylene glycol di(meth)acrylate.

[0040] Aspect 10. The emulsion of any of aspects 6-9, wherein the short chain alkyl diol (di)meth acrylate comprises 1,3 -butanediol di(meth)acrylate.

[0041] Aspect 11. The emulsion of any preceding aspect, wherein the core monomer mixture, the shell monomer mixture, or both comprise a long chain alkyl diol (di)meth acrylate.

[0042] Aspect 12. The emulsion of aspect 11, wherein the long chain alkyl diol di(meth) acrylate comprises polyethylene glycol di(meth)acrylate.

[0043] Aspect 13. The emulsion of any of aspects 11-12, wherein the long chain alkyl diol di(meth) acrylate comprises urethane di(meth)acrylate.

[0044] Aspect 14. The emulsion of any preceding aspect, wherein the crosslinking monomer component comprises diacetone acrylamide (DAAM) in combination with adipic dihydrazide (ADH).

[0045] Aspect 15. The emulsion of aspect 14, wherein the ratio of DAAM:ADH is 1:0.6.

[0046] Aspect 16. The emulsion of aspect 14, wherein the ratio of DAAM:ADH is 1:0.5.

[0047] Aspect 17. The emulsion of aspect 14, wherein the ratio of DAAM:ADH is 1:0.4.

[0048] Aspect 18. The emulsion of aspect 14, wherein the ratio of DAAM:ADH is 1:0.3.

[0049] Aspect 19. The emulsion of aspect 14, wherein the ratio of DAAM:ADH is 1:0.2.

[0050] Aspect 20. The emulsion of aspect 14, wherein the ratio of DAAM:ADH isL0.6-0.5.

[0051] Aspect 21. The emulsion of any preceding aspect, wherein the alkyl diol di(meth)acrylate monomer comprises 1 to 5 wt%, of the core monomer mixture, based upon the total weight of the core monomers.

[0052] Aspect 22. The emulsion of any preceding aspect, wherein the alkyl diol di(meth)acrylate monomer comprises 2 to 3 wt%, of the core monomer mixture, based upon the total weight of the core monomers.

[0053] Aspect 23. The emulsion of any preceding aspect, wherein the alkyl diol di(meth)acrylate monomer comprises 1 to 5 wt%, of the shell monomer mixture, based upon the total weight of the shell monomers.

[0054] Aspect 24. The emulsion of any preceding aspect, wherein the alkyl diol di(meth)acrylate monomer comprises 2 to 3 wt%, of the shell monomer mixture, based upon the total weight of the shell monomers.

[0055] Aspect 25. The emulsion of any preceding aspect, wherein the crosslinking monomer component comprises 0.1 to 3.0 wt% based on the total weight of the emulsion.

[0056] Aspect 26. The emulsion of any preceding aspect, wherein the crosslinking monomer component comprises 0.25 to 2.0 wt% based on the total weight of the emulsion.

[0057] Aspect 27. The emulsion of any preceding aspect, wherein the crosslinking monomer component comprises 0.5 to 1.5 wt% based on the total weight of the emulsion.

[0058] Aspect 28. The emulsion of any preceding aspect, wherein the crosslinking monomer component comprises 4.0 to 18.0 wt% based on the total weight of the shell monomer mixture weight.

[0059] Aspect 29. The emulsion of any preceding aspect, wherein the crosslinking monomer component comprises 5.0 to 16.0 wt% based on the total weight of the shell monomer mixture weight.

[0060] Aspect 30. The emulsion of any preceding aspect, wherein the crosslinking monomer component comprises 5.0 to 10.0 wt% based on the total weight of the shell monomer mixture weight.

[0061] Aspect 31. The emulsion of any preceding aspect, wherein the core monomer mixture further comprises styrene.

[0062] Aspect 32. The emulsion of any preceding aspect, wherein the core monomer mixture further comprises 2,5-dimethylstyrene.

[0063] Aspect 33. The emulsion of any preceding aspect, wherein the core monomer mixture further comprises 2,4-dimethylstyrene.

[0064] Aspect 34. The emulsion of any preceding aspect, wherein the core monomer mixture further comprises tert-butyl methacrylate.

[0065] Aspect 35. The emulsion of any preceding aspect, wherein the core monomer mixture further comprises cyclohexyl methacrylate.

[0066] Aspect 36. The emulsion of any preceding aspect, wherein the core monomer mixture further comprises iso-butyl methacrylate.

[0067] Aspect 37. The emulsion of any preceding aspect, wherein the core monomer mixture further comprises iso-bornyl methacrylate.

[0068] Aspect 38. The emulsion of any preceding aspect, wherein the core monomer mixture further comprises phenyl methacrylate.

[0069] Aspect 39. The emulsion of any preceding aspect, wherein the core monomer mixture further comprises methyl methacrylate.

[0070] Aspect 40. The emulsion of any preceding aspect, wherein the core monomer mixture further comprises alpha methyl styrene.

[0071] Aspect 41. The emulsion of any preceding aspect, wherein the shell monomer mixture further comprises styrene.

[0072] Aspect 42. The emulsion of any preceding aspect, wherein the shell monomer mixture further comprises 2,5-dimethylstyrene.

[0073] Aspect 43. The emulsion of any preceding aspect, wherein the shell monomer mixture further comprises 2,4-dimethylstyrene.

[0074] Aspect 44. The emulsion of any preceding aspect, wherein the shell monomer mixture further comprises tert-butyl methacrylate.

[0075] Aspect 45. The emulsion of any preceding aspect, wherein the shell monomer mixture further comprises cyclohexyl methacrylate.

[0076] Aspect 46. The emulsion of any preceding aspect, wherein the shell monomer mixture further comprises iso-butyl methacrylate.

[0077] Aspect 47. The emulsion of any preceding aspect, wherein the shell monomer mixture further comprises iso-bornyl methacrylate.

[0078] Aspect 48. The emulsion of any preceding aspect, wherein the shell monomer mixture further comprises phenyl methacrylate.

[0079] Aspect 49. The emulsion of any preceding aspect, wherein the shell monomer mixture further comprises methyl methacrylate.

[0080] Aspect 50. The emulsion of any preceding aspect, wherein the shell monomer mixture further comprises alpha methyl styrene.

[0081] Aspect 51. The emulsion of any preceding aspect, wherein the monomers used to form the latex particle specifically exclude hydroxy functional (meth)acrylic monomers.

[0082] Aspect 52. The emulsion of any preceding aspect, wherein the monomers used to form the latex particle specifically exclude fluorine containing (meth)acrylic monomers.

[0083] Aspect 53. The emulsion of any preceding aspect, wherein the monomers used to form the latex particle specifically exclude phosphate ester functional monomers.

[0084] Aspect 54. The emulsion of any preceding aspect, wherein the monomers used to form the latex particle are substantially free of N-methylol acrylamide monomers and residues thereof.

[0085] Aspect 55. The emulsion of any preceding aspect, wherein the monomers used to form the latex particle are essentially free of N-methylol acrylamide monomers and residues thereof.

[0086] Aspect 56. The emulsion of any preceding aspect, wherein the monomers used to form the latex particle are completely free of N-methylol acrylamide monomers and residues thereof.

[0087] Aspect 57. The emulsion of any preceding aspect, wherein the monomers used to form the latex particle are substantially free of benzophenone and residues thereof.

[0088] Aspect 58. The emulsion of any preceding aspect, wherein the monomers used to form the latex particle are essentially free of benzophenone and residues thereof.

[0089] Aspect 59. The emulsion of any preceding aspect, wherein the monomers used to form the latex particle are completely free of benzophenone and residues thereof.

[0090] Aspect 60. The emulsion of any preceding aspect, wherein the Tg of the core is -8 to 80°C, wherein Tg is calculated according to the Fox equation.

[0091] Aspect 61. The emulsion of any preceding aspect, wherein the Tg of the core is 40 to 70°C, wherein Tg is calculated according to the Fox equation.

[0092] Aspect 62. The emulsion of any preceding aspect, wherein the Tg of the shell is -25 to -33°C, wherein Tg is calculated according to the Fox equation.

[0093] Aspect 63. The emulsion of any preceding aspect, wherein the Tg of the shell is -16 to -25°C, wherein Tg is calculated according to the Fox equation.

[0094] Aspect 64. The emulsion of any preceding aspect, wherein the Tg of the core is more than 50°C higher than the Tg of the shell, wherein Tg is calculated according to the Fox equation.

[0095] Aspect 65. The emulsion of any preceding aspect, wherein the Tg of the core is more than 60°C higher than the Tg of the shell, wherein Tg is calculated according to the Fox equation.

[0096] Aspect 66. The emulsion of any preceding aspect, wherein the Tg of the core is more than 70°C higher than the Tg of the shell, wherein Tg is calculated according to the Fox equation.

[0097] Aspect 67. The emulsion of any preceding aspect, wherein the Tg of the core is more than 80°C higher than the Tg of the shell, wherein Tg is calculated according to the Fox equation.

[0098] Aspect 68. The emulsion of any preceding aspect, wherein the Tg of the core is more than 90°C higher than the Tg of the shell, wherein Tg is calculated according to the Fox equation.

[0099] Aspect 69. The emulsion of any preceding aspect, wherein the solids content of the emulsion is 20% or higher.

[0100] Aspect 70. The emulsion of any preceding aspect, wherein the solids content of the emulsion is 40% or higher.

[0101] Aspect 71. The emulsion of any preceding aspect, wherein the solids content of the emulsion is 50% or higher.

[0102] Aspect 72. The emulsion of any preceding aspect, wherein the solids content of the emulsion is 20% to 80%.

[0103] Aspect 73. The emulsion of any preceding aspect, wherein the latex particles have a mean particle size of 250 nm or higher, as measured by DLS.

[0104] Aspect 74. The emulsion of any preceding aspect, wherein the latex particles have a mean particle size of 260 nm or higher.

[0105] Aspect 75. The emulsion of any preceding aspect, wherein the latex particles have a mean particle size of 270 nm or higher, as measured by DLS.

[0106] Aspect 76. The emulsion of any preceding aspect, wherein the latex particles have a mean particle size of 280 nm or higher, as measured by DLS.

[0107] Aspect 77. The emulsion of any preceding aspect, wherein the latex particles have a mean particle size of 290 nm or higher, as measured by DLS.

[0108] Aspect 78. The emulsion of any preceding aspect, wherein the latex particles have a mean particle size of 300 nm or higher, as measured by DLS.

[0109] Aspect 79. The emulsion of any preceding aspect, wherein the latex particles have a mean particle size of 260 nm to 310 nm, as measured by DLS.

[0110] Aspect 80. The emulsion of any preceding aspect, wherein the latex particles have a mean particle size of 280 nm to 310 nm, as measured by DLS.

[0111] Aspect 81. A coating composition comprising the emulsion of any preceding aspect.

[0112] Aspect 82. The coating composition of aspect 81, wherein the composition does not comprise a crosslinker.

[0113] Aspect 83. The coating composition of any of aspects 81-82, wherein the composition does not comprise a wax.

[0114] Aspect 84. The coating composition of any of aspects 81-83, wherein the composition further comprises an adhesion promoter.

[0115] Aspect 85. The coating composition of aspect 84, wherein the adhesion promoter comprises silica.

[0116] Aspect 86. The coating composition of aspect 85, wherein the silica comprises colloidal silica.

[0117] Aspect 87. The coating composition of any of aspects 84-86, wherein the adhesion promoter comprises silane.

[0118] Aspect 88. The coating composition of aspect 87, wherein the silane comprises epoxy functional silane.

[0119] Aspect 89. The coating composition of any of aspects 84-88, wherein the adhesion promoter is used in an amount of 0.1 wt% to 3.0 wt%, based on the total weight of the coating composition.

[0120] Aspect 90. The coating composition of any of aspects 84-89, wherein the adhesion promoter is used in an amount of 0.25 wt% to 2.0 wt%, based on the total weight of the coating composition.

[0121] Aspect 91. The coating composition of any of aspects 84-89, wherein the adhesion promoter is used in an amount of 0.5 wt% to 1.0 wt%, based on the total weight of the coating composition.

[0122] Aspect 92. The coating composition of any of aspects 81-91, wherein the coating further comprises an aliphatic polyurethane based on a polyether diol.

[0123] Aspect 93. A method for using the coating composition of any of aspects 81- 92 to coat at least a portion of a substrate, comprising depositing a coating layer from the coating composition onto the substrate.

[0124] Aspect 94. The coating layer deposited according to the method of aspect 93.

[0125] Aspect 95. The coating layer of aspect 94, wherein the coating layer, after deposition and 14 days of ambient temperature and exposure, has a maximum stress(psi) andStrain @ Break (%) according to ASTM D2370-16, Standard Test Method for Tensile Properties of Organic Coatings that meets a minimum of 200 lb. / in2and a minimum Strain @ Break of100% according to NMX-C-450-ONNCCE-2019.

[0126] Aspect 96. The coating layer of any of aspects 94-95, wherein the coating layer, after deposition and 14 days of ambient temperature and exposure and 100 hours of QUV exposure (QUV Accelerated Weathering Tester Q-Lab), has a maximum stress of 300 psi or greater, as measured by ASTM D2370-16.

[0127] Aspect 97. The coating layer of aspect 96, wherein the maximum stress is 310 psi or greater.

[0128] Aspect 98. The coating layer of aspect 96, wherein the maximum stress is 320 psi or greater.

[0129] Aspect 99. The coating layer of aspect 96, wherein the maximum stress is 300 to 340 psi.

[0130] Aspect 100. The coating layer of any of aspects 94-99, wherein the coating layer, after deposition and 14 days of ambient temperature and exposure and 21 days immersed in water according to ASTM D 4798 aging test; ASTM D2379 elongation; and ASTM D2370 tension, has a maximum stress of 70 psi or greater, and a Strain @ Break of 500% or greater, as measured by ASTM D2370-16.

[0131] Aspect 101. The coating layer of aspect 100, wherein the maximum stress is600% or greater.

[0132] Aspect 102. The coating layer of aspect 100, wherein the maximum stress is700% or greater.

[0133] Aspect 103. The coating layer of aspect 100, wherein the maximum stress is800% or greater.

[0134] Aspect 104. The coating layer of aspect 100, wherein the maximum stress is900% or greater.

[0135] Aspect 105. The coating layer of aspect 100, wherein the maximum stress is600% to 900%.

[0136] Aspect 106. A substrate comprising the coating layer of any of aspects 93-105.

[0137] Aspect 107. The substrate of aspect 106, wherein the substrate is metallic.

[0138] Aspect 108. The substrate of aspect 106, wherein the substrate is non-metallic.

[0139] Aspect 109. The substrate of aspect 108, wherein the substrate comprises concrete and / or cement.

[0140] Aspect 110. The substrate of any of aspects 108-109, wherein the substrate comprises wood, wood composite and / or particle board.

[0141] Aspect 111. The substrate of any of aspects 108-110, wherein the substrate comprises gypsum board.

[0142] Aspect 112. The substrate of aspect 106, wherein the substrate comprises an architectural component.

[0143] Aspect 113. The substrate of aspect 112, wherein the architectural component comprises a roof.

[0144] Aspect 114. The substrate of aspect 112, wherein the architectural component comprises a wall.

[0145] Aspect 115. The substrate of aspect 112, wherein the architectural component comprises an exterior component.EXAMPLES

[0146] The following examples are intended to illustrate the disclosure and should not be construed as limiting the disclosure in any way.Emulsion Formation

[0147] Emulsions comprising core shell latex particles according to the present disclosure were prepared using standard emulsion polymerization techniques as indicated below.

[0148] A 2-liter kettle reactor equipped with a four blade 45° impeller stirrer, thermocouple, reflux condenser and dosing pumps were used. A quantity of 500.71 grams of deionized water was added to the reactor and heated to 85°C. Core monomer mixtures and shell monomer mixtures contained the ingredients and amounts shown in Tables 1 and 2. The final Tg of the core and the shell, determined using the Fox Equation, are also shown in these tables.Table 1Core Monomer MixturesAmounts given in grams fatty alcohol ether sulphate, sodium salt emulsifier commercially available from BASF Lauryl Alcohol alkoxylated surfactant commercially available from OxitenoTable 2Shell Monomer MixturesPolyethylene glycol 200-dimethacrylate commercially available from Evonik

[0149] With the reactor internal temperature at 82°C, the following ingredients were added to the reactor: the core monomer mixture and a mixture of 2.29 grams of ammonium persulfate in 10.00 grams of deionized water. The temperature of reaction was raised to 85°C and the reaction mixture was stirred for 20 minutes at 85°C.

[0150] The shell monomer mixture and a mixture of 3.41 grams of ammonium persulfate dissolved in 30.00 grams of deionized water were then fed to the reactor simultaneously over a four-hour period at 85°C. After the completion of the monomer and initiator feed, 30.00 grams of deionized water was used to rinse the ME2 emulsion tank and the reaction mixture was held at 85°C for half an hour, and then cooled to 54 - 56°C.

[0151] A mixture of 1.44 grams of t-butylhydroperoxide in 10.00 grams of deionized water were fed into reactor and the reaction mixture was held at 54-56°C for 5 minutes, afterwards 0.96 grams of Sodium Formaldehyde Sulfoxylate (BRUGOGOLITE E-01 commercially available from Briiggemann) in 10.00 grams of deionized water were added to the reactor. The reaction mixture was held for 15 minutes at 56-58°C and cooled to 25 - 30°C, then 9.47 of ammonia solution (28%) in 30.00 grams of deionized water and 2.80 grams of adipic dihydrazide (for Examples 1-6; 5.60 g for Example 7; 8.34 g for Example 8) in 30.00 grams of deionized water were added to the reactor. The reaction mixture was filtered to remove grit.The final latex had a solids content and a mean particle size as measured by DLS as indicated in Table 3.Table 3Comparative Examples

[0152] Certain additives and surfactants were used in the comparative examples to maintain the stability of the emulsion. Such additives were not needed in the inventive examples.Comparative EXAMPLE 1

[0153] A 2-liter, kettle reactor equipped with a four blade 45° impeller stirrer, thermocouple, reflux condenser and dosing pumps were used. A quantity of 523.37 grams of deionized water was added to the reactor and heated to 85°C.

[0154] A first monomer emulsion for core formation was prepared by mixing 12.37 grams of deionized water, 0.28 grams of DISPONIL FES 32, 0.12 grams of RHODACAL DSB (commercially available from Rhodia), 1.57 grams of butyl acrylate, 9.63 grams of methyl methacrylate, and 0.34 grams of 1 ,4-butanediol dimethacrylate (EVONIK).

[0155] A second monomer emulsion for shell formation was prepared in an emulsion glass tank by mixing 222.00 grams of deionized water, 34.81 grams of DISPONIL FES 32, 11.94 grams of RHODACAL DSB, 0.88 grams of ethoxylated lauric alcohol (SURFACPOL EL- 10 (commercially available from Polaquimia, 850.71 grams of butyl acrylate, 221.40 grams of styrene and 16.87 grams of methacrylic acid.

[0156] With the reactor internal temperature at 82°C, the following ingredients were added to the reactor: all the first monomer emulsion for core formation prepared previously and a mixture of 0.45 grams of ammonium persulfate in 10.00 grams of deionized water. The temperature of reaction was raised to 85 °C and the reaction mixture was stirred for 20 minutes at 85°C.

[0157] The second monomer emulsion for the shell and a mixture of 3.45 grams of ammonium persulfate dissolved in 45.50 grams of deionized water were then fed to the reactor simultaneously over a four-hour period at 85 °C. After the completion of the monomer and initiator feed, 12.86 grams of deionized water was used to rinse the monomer emulsion tank and the reaction mixture was held at 85 °C for half an hour, and then cooled to 54 - 56°C.

[0158] A mixture of 1.06 grams of t-butylhydroperoxide in 10.00 grams of deionized water were fed into reactor and the reaction mixture was held at 54-56°C for 5 minutes, after which 0.78 grams of BRUGGOLITE E-01 in 10.00 grams of deionized water were added to the reactor. The reaction mixture was held for 15 minutes at 56-58°C and cooled to 25 - 30°C, then 9.75 of ammonia solution (28%) in 10.00 grams of deionized water were added to the reactor. The reaction mixture was filtered to remove grit. The final latex had a solids content of 55.45 % and a particle size was measured by DLS to be 294 nm.Comparative EXAMPLE 2

[0159] A 2-liter, kettle reactor equipped with a four blade 45° impeller stirrer, thermocouple, reflux condenser and dosing pumps were used. A quantity of 505.98 grams of deionized water, 0.92 grams of sodium carbonate and 0.78 grams of sodium bicarbonate were added and dissolved into the reactor, then a mixture of 1.65 grams of fatty alcohol ether sulphate, sodium salt (DISPONIL FES 32) and 0.16 grams of lauryl alcohol alkoxylated (OXITIVE 7254) dissolved in 30.00 grams of deionized water were added to the reactor.

[0160] 35.88 grams of a first monomer emulsion for core formation used in ComparativeExample 1 was added to the reactor, some properties of the acrylic latex for seeding include nonvolatile content of 25%, 65 nm of particle size measured by DLS, Tg <0°C calculated by the Fox Equation. The mixture in the reactor was heated to 85°C.

[0161] A monomer emulsion for the shell was prepared by mixing 169.40 grams of deionized water, 29.33 grams of fatty alcohol ether sulphate, sodium salt (DISPONIL FES 32), 2.94 grams of lauryl alcohol alkoxylated (OXITIVE 7254), 844.58 grams of butyl acrylate, 219.80 grams of styrene and 16.21 grams of methacrylic acid.

[0162] When the internal temperature of the reactor reached 85 °C, 2.71 grams of ammonium persulfate dissolved in 10.00 grams of deionized water were added to the reactor and immediately after this dissolution shot, both the monomer emulsion prepared for shell and a mixture of 3.36 grams of ammonium persulfate dissolved in 35.00 grams of deionized water were fed to the reactor over a four-hour period at 85°C. After the completion of the monomer and initiator feed, 30.00 grams of deionized water was used to rinse the monomer emulsion tank and the reaction mixture was held at 85°C for half an hour, and then cooled to 54 - 56°C.

[0163] A mixture of 1.03 grams of t-butylhydroperoxide in 10.00 grams of deionized water were fed into reactor and the reaction mixture was held at 54-56°C for 5 minutes, afterwards 0.76 grams of sodium formaldehyde sulfoxylate (BRUGGOLITE E-01) in 10.00 grams of deionized water were added to the reactor. The reaction mixture was held for 15 minutes at 56-58°C and cooled to 25 - 30°C, then 9.51 grams of ammonia solution (28%) in 30.00 grams of deionized water were added to the reactor. The reaction mixture was filtered to remove grit. The final latex had a solids content of 54.52 % and a particle size was measured by DLS to be 243 nm.Comparative EXAMPLE 3

[0164] A 2-liter, kettle reactor equipped with a four blade 45° impeller stirrer, thermocouple, reflux condenser and dosing pumps were used. A quantity of 576.40 grams of deionized water, 0.91 grams of sodium carbonate and 0.77 grams of sodium bicarbonate were added and dissolved into the reactor, then a mixture of 1.64 grams of fatty alcohol ether sulphate, sodium salt (DISPONIL FES 32) and 0.14 grams of lauryl alcohol alkoxylated (OXITIVE 7254) were added to the reactor.

[0165] 35.77 grams of the latex seed for core formation used in Comparative Example 1 was added to the reactor, some properties of the acrylic latex for seeding include non-volatile content of 25%, 65 nm of particle size measured by DLS, Tg <0°C calculated by the Fox Equation. The mixture in the reactor was heated to 85°C.

[0166] A monomer emulsion for the shell was prepared by mixing 151.20 grams of deionized water, 14.63 grams of fatty alcohol ether sulphate, sodium salt (DISPONIL FES 32), 1.30 grams of lauryl alcohol alkoxylated (OXITIVE 7254), 824.60 grams of butyl acrylate, 214.00 grams of styrene, 26.88 grams of N-methylolacrylamide (FLOCRYL NMA) monomer (48%) and 16.40 grams of methacrylic acid. When the internal temperature of the reactor reach 85°C, 2.69 grams of ammonium persulfate dissolved in 9.60 grams of deionized water was added to the reactor and immediately after this dissolution shot, both the EMS-Emulsion for Shell and a mixture of 3.36 grams of ammonium persulfate dissolved in 45.40 grams of deionized water were fed to the reactor over a four-hour period at 85°C. After 3.5 hours, 5.6 grams of vinyltrimethoxy silane (SILQUEST A- 171) were added to the remaining monomer emulsion.

[0167] After the completion of the monomer and initiator feed, 11.86 grams of deionized water were used to rinse the monomer emulsion tank and the reaction mixture was held at 85 °C for half hour, and then cooled to 54 - 56°C. A mixture of 1.03 grams of t-butylhydroperoxide in 12.40 grams of deionized water were fed into reactor and the reaction mixture was held at 54- 56°C for 5 minutes, afterwards 0.75 grams of sodium formaldehyde sulfoxylate (BRUGGOLITE E-01) in 12.40 grams of deionized water were added to the reactor. The reaction mixture was held for 15 minutes at 56-58°C and cooled to 25 - 30°C, then 9.49 grams of ammonia solution (28%) in 12.60 grams of deionized water were added to the reactor. Afterwards, a mixture of 2.69 grams of benzophenone in 2.69 grams of xylene was added to the reactor. The reactionmixture was filtered to remove grit. The final latex had a solids content of 53.67 % and a particle size was measured by DLS to be 295 nm.TESTING

[0168] Coatings were formulated using the emulsion latices prepared above including water, additives, and fillers. The coatings were applied to asbestos cement and tested for maximum stress(psi) and Strain at Break (%) according to ASTM D2370-16, Standard Test Method for Tensile Properties of Organic Coatings. Testing was conducted after the coating layer had been allowed to air dry for 14 days. Non-volatile content was measured according to ASTM DI 644-01 Standard Test Method for Nonvolatile Content of Varnishes.

[0169] Coatings made with the latex emulsion of Examples 1-7 all contained PEG200DMA in the shell monomer mixture and diacetone acrylamide / adipic dihydrazide as the crosslinking monomer. An increase in the maximum stress for all examples and an increased strain at break for examples 1, 3, and 5-7 were observed as compared to comparative example 1, which did not contain any of these components. The coatings made with the emulsion of examples 6 and 7 showed better overall mechanical properties as compared to comparative example 3, which used benzophenone — a substance of concern - as a crosslinking monomer.Table 4Mechanical properties of coating films

[0170] Coatings made using the emulsions of Examples 6 and 7 and comparative examples 1 and 3 were prepared and tested as described above, but in addition to the 14 days drying time were also subjected to 100 hours of QUV exposure in the QUV Accelerated Weathering Tester Q-Lab.

[0171] The coating layers formulated according to the present disclosure had improved resistance to the ageing in QUV at lOOh showing higher levels of maximum stress and strain atbreak than a coating formulated with a latex without the crosslinking monomer (comparative example 1) and a coating formulated with a latex having a substance of concern (comparative example 3); this is shown in Table 5.Table 5

[0172] Maximum stress and Strain @ Break generally correlate with a rigid core and flexible shell in which water impermeability would be expected to be high. The nature of the monomers in both the core and shell provides a density in the network that supports high stresses and high elongation, which results in coatings being less susceptible to alteration by water absorption. To confirm, coatings formulated according to the present disclosure and coatings prepared with the comparative emulsions were tested for maximum water absorption at 7 days according to ASTM D471-16a Water Swelling and wet adhesion to a cementitious substrate as tested according to ASTM D903-98. As shown in Table 6, the coatings prepared according to the present disclosure showed much lower water absorption and much higher wet adhesion than the comparative coatings.Table 6Coating Film properties in water flooded conditions.

[0173] A coating prepared using the emulsion of example 8 and a coating prepared using the emulsion of comparative example 3 were tested in the following manner. Two coats wereapplied to a fluorinated ethylene -propylene (FEP) sheet substrate (see Test Method D 2370) for a minimum of a 4h drying period between coats to give a total dry film thickness of 20 ± 2 mils (0.50 ± 0.05 mm). The film was allowed to thoroughly dry at 73.4 ± 3.6°F (23 ± 2°C) and 50 ± 10% relative humidity for 336 ± 12 h. The film was removed from the release paper and turned over after the first 168 h to allow for complete drying. The coating of the present disclosure showed less strain during the first 10 days than that made with comparative example 3, as illustrated in Figure 1. Furthermore, the coating of the present disclosure resisted break after more than 60 days under load in a water environment as compared to the coating film of comparative example 3, which broke after 9 days. In addition, the strain of the coating film in water flooded conditions shows that the coating film formulated with example 8 had better retention of the mechanical properties expressed as both higher max. stress and strain in function of time versus the coating film formulated with comparative example 3, as shown in Table 7.Table 7Tensile properties of coating films at different days in flooded conditions without load

[0174] Coatings prepared using the emulsion of example 7 were formulated with and without an adhesion promoter as shown in Table 8 and tested for maximum water absorption and wet adhesion according to the test methods described above and as further indicated in the table. The examples with the adhesion promoter had both lower water absorption and better adhesion as compared to the example without.Table 81COATOSIL MP 200, commercially available from Momentive Performance Materials

[0175] Whereas particular examples of this disclosure have been described above for purposes of illustration, it will be evident to those skilled in the art that numerous variations of the details of the present disclosure may be made without departing from what is defined in the appended claims.

Claims

What is claimed is:

1. An emulsion comprising latex particles comprising: a. a core formed from a core monomer mixture comprising an alkyl diol di(meth)acrylate monomer; b. a shell formed from a shell monomer mixture comprising an alkyl diol di(meth)acrylate monomer that is the same as and / or different from the alkyl diol di(meth)acrylate in the core; c. a crosslinking monomer component that crosslinks with the core and shell upon polymerization; wherein the latex particles are substantially free, essentially free, or completely free of N-methylol acrylamide and residues thereof and benzophenone and residues thereof; and wherein the Tg of the core is higher than the Tg of the shell.

2. The emulsion of Claim 1 , wherein the core monomer mixture comprises a short chain alkyl diol di(meth)acrylate and the shell monomer mixture comprises a long chain alkyl diol di(meth)acrylate and / or a short chain alkyl diol di(meth)acrylate; and wherein when both a short chain and long chain alkyl diol di(meth)acrylate are used in the shell monomer mixture the weight ratio of shortdong is 1: 1 to 1:3.

3. The emulsion of any preceding claim, wherein the short chain alkyl diol (di)meth acrylate comprises 1 ,4-butanediol di(meth)acrylate and / or 1,6-hexanediol di(meth)acrylate.

4. The emulsion of any preceding claim, wherein the long chain alkyl diol di(meth) acrylate comprises polyethylene glycol di(meth)acrylate.

5. The emulsion of any preceding claim, wherein the crosslinking monomer component comprises diacetone acrylamide in combination with adipic dihydrazide.

6. The emulsion of any preceding claim, wherein the alkyl diol di(meth)acrylate monomer comprises 1 to 5 wt% of the core monomer mixture, based upon the total weight of the core monomers.

7. The emulsion of any preceding claim, wherein the alkyl diol di(meth)acrylate monomer comprises 1 to 5 wt% of the shell monomer mixture, based upon the total weight of the shell monomers.

8. The emulsion of any preceding claim, wherein the crosslinking monomer component comprises 0.1 wt% to 3.0 wt%, based upon the total weight of the emulsion.

9. The emulsion of any preceding claim, wherein the core monomer mixture, the shell monomer mixture or both further comprise styrene, 2,5-dimethylstyrene, 2,4-dimethylstyrene, tert-butyl methacrylate, cyclohexyl methacrylate, iso-butyl methacrylate or iso-bornyl methacrylate, phenyl methacrylate, methyl methacrylate, and / or alpha methyl styrene.

10. The emulsion of any preceding claim, wherein the monomers used to form the latex particle specifically exclude hydroxy functional (meth)acrylic monomers; and / or specifically exclude fluorine containing (meth)acrylic monomers; and / or specifically exclude phosphate ester functional monomers.

11. The emulsion of any preceding claim, wherein the Tg of the core is -8 to 80°C, and / or the Tg of the shell is -25 to -33°C, wherein Tg is calculated according to the Fox equation.

12. The emulsion of any preceding claim, wherein the Tg of the core is more than 50°C higher than the Tg of the shell, wherein Tg is calculated according to the Fox equation.

13. A coating composition comprising the emulsion of any preceding claim.

14. The coating composition of Claim 13, wherein the coating composition does not comprise a crosslinker other than the crosslinking monomer of the latex particle and / or does not comprise a wax.

15. The coating composition of any of Claims 13-14, wherein the composition further comprises an adhesion promoter component comprising a silica and / or a silane.

16. A method for using the coating composition of any of Claims 13-16 to coat at least a portion of a substrate, comprising depositing a coating layer from the coating composition onto the substrate.

17. The coating layer deposited according to the method of Claim 16.

18. The coating layer of Claim 17, wherein after deposition and 14 days ambient temperature and exposure, has a maximum stress(psi) and Strain @ Break (%) according to ASTM D2370- 16, Standard Test Method for Tensile Properties of Organic Coatings that meets a minimum of 200 lb. / in2and a minimum Strain @ Break of 100% according to NMX-C-450-ONNCCE-2019; and / or after 14 days ambient temperature and exposure and 100 hours of QUV exposure (QUV Accelerated Weathering Tester Q-Lab) has a maximum stress of 300 psi or greater, as measured by ASTM D2370-16; and / or after 14 days ambient temperature and exposure and 21 days immersed in water according to ASTM D 4798 aging test; D2370 elongation; and D2370 tension, has a maximum stress of 70 psi or greater, and a Strain @ Break of 500% or greater, as measured by ASTM D2370-16.

19. A substrate comprising the coating layer of any of Claims 17-18.

20. The substrate of Claim 19, wherein the substrate is metallic.

21. The substrate of Claim 19, wherein the substrate is non-metallic.

22. The substrate of any of Claims 19-21, wherein the substrate comprises an architectural component.

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