Self-curing silicone resins for non-stick surfaces

Abstract

A polysiloxane resin coating composition can be applied to a surface of a substrate to form a crack and heat resistant coating. The coating composition may include a polysiloxane resin, a surfactant, and a solvent. The polysiloxane resin may be formed from siloxane monomer units. The polysiloxane resin may include less than 80 mol% of T siloxane monomer units, and less than 1 mol% of M and Q siloxane monomer units, based on a total number of moles of siloxane monomer units in the polysiloxane resin. The ratio of the surfactant to the polysiloxane resin may be from 0.01 to 0.09.

Description

[0001] Cross Reference to Related Applications

[0002] This application claims the benefit under 35 U.S.C. § 119(e) of U.S. Provisional Application No. 63 / 501,044, filed May 9, 2023, entitled “SELF-CURABLE SILICONE RESINS FOR BAKEWARE,” and U.S. Provisional Application No. 63 / 516,628, filed July 31, 2023, entitled “SELF-CURABLE SILICONE RESINS FOR NON-STICK SURFACES,” both of which are incorporated by reference in their entirety. TECHNICAL FIELD

[0003] The present disclosure relates to a polysiloxane resin coating composition, a method of making the coating composition, and an article coated with the coating composition. BACKGROUND

[0004] Heat resistant coatings are applied to substrates such as bakeware, bakeware or other cooking utensils to provide functions such as aiding heat transfer, providing a non-stick release surface, and / or providing a decorative color or aesthetic finish. Existing coating compositions can contain fluorine-containing polymers as binders or release agents, which can potentially contain perfluoro / polyfluoroalkyl substances (PFAS). Regulatory environments are increasingly concerned with PFAS, including fluorine-containing polymers. SUMMARY

[0005] The present disclosure provides a curable coating composition comprising a polysiloxane resin formed from a siloxane monomer and a solvent. The siloxane monomer includes [R 1 Si(O) 3 / 2 ] x ; [R 2 R 3 Si(O)] y ; and [R 4 Si(O) 3 / 2 ] z ; wherein: x is any integer from 1 to 50; y is any integer from 1 to 20; z is any integer from 1 to 50; R 1 is a C1-C 30 linear or C3-C 30 cyclic alkyl group; R 2 and R 3 are each independently a C1-C 30 linear or C3-C 30 cyclic alkyl group, or a C6 or C7 aryl group; R 4C6or C7aryl group. The composition comprises less than 5 wt.% of any fluorine containing component, based on the total weight of the composition. The present disclosure further provides an article coated with the aforementioned coating composition.

[0006] The present disclosure provides a method of coating a substrate, the method comprising applying a coating composition to the substrate and curing the coating composition. The coating composition comprises a polysiloxane resin formed from siloxane monomers and a solvent. The siloxane monomers include [R 1 Si(O) 3 / 2 ] x ; [R 2 R 3 Si(O)] y ; and [R 4 Si(O) 3 / 2 ] z ; wherein: x is any integer from 1 to 50; y is any integer from 1 to 20; z is any integer from 1 to 50; R 1 is a C1-C 30 linear or C3-C 30 cyclic alkyl group; R 2 and R 3 are each independently a C1-C 30 linear or C3-C 30 cyclic alkyl group, or a C6or C7aryl group; R 4 is a C6or C7aryl group. The composition comprises less than 5 wt.% of any fluorine containing component, based on the total weight of the composition.

[0007] The present disclosure provides a curable composition comprising a polysiloxane resin formed from siloxane monomer units; a solvent and a surfactant. The polysiloxane resin comprises less than 80 mol % of T siloxane monomer units, based on the total number of moles of siloxane monomer units in the polysiloxane resin. The polysiloxane resin comprises less than 1 mol % of M and Q siloxane monomer units, based on the total number of moles of siloxane monomer units in the polysiloxane resin. The surfactant includes at least one of a surfactant of Formula IIA

[0008]

[0009] wherein x is an ethylene glycol monomer, y is a propylene glycol monomer, and z is an ethylene glycol monomer;

[0010] a surfactant of Formula IIB

[0011]

[0012] wherein x is a propylene glycol monomer, y is an ethylene glycol monomer, and z is a propylene glycol monomer;

[0013] surfactant of Formula III

[0014]

[0015] wherein n = 16-20; and

[0016] a combination of surfactants of Formulas IIA, IIB, and III. The weight ratio of the surfactants to the polysiloxane resin is 0.01 to 0.09, based on the total weight of the composition. The composition comprises less than 1 wt.% of any fluorochemical component, based on the total weight of the composition. The present disclosure further provides an article coated with the curable coating composition described above.

[0017] The present disclosure provides a method of coating a substrate, the method comprising applying a coating composition to the substrate and curing the coating composition. The coating composition comprises a polysiloxane resin formed from siloxane monomer units and having the formula: n SiO((4-n) / 2), wherein R is an alkyl or aryl group; a solvent; and a surfactant. The polysiloxane resin comprises less than 80 mol % of T siloxane monomer units, based on the total number of moles of siloxane monomer units in the polysiloxane resin. The polysiloxane resin comprises less than 1 mol % of M and Q siloxane monomer units, based on the total number of moles of siloxane monomer units in the polysiloxane resin. The surfactant comprises at least one of a surfactant of Formula IIA

[0018]

[0019] wherein x is an ethylene glycol monomer, y is a propylene glycol monomer, and z is an ethylene glycol monomer;

[0020] a surfactant of Formula IIB

[0021]

[0022] wherein x is a propylene glycol monomer, y is an ethylene glycol monomer, and z is a propylene glycol monomer;

[0023] a surfactant of Formula III

[0024]

[0025] wherein n = 16-20; and

[0026] a combination of surfactants of Formulas IIA, IIB, and III. The weight ratio of the surfactants to the polysiloxane resin is 0.01 to 0.09, based on the total weight of the coating composition.

[0027] The present disclosure provides a polysiloxane resin formed from siloxane monomer units: [R 1 Si(O) 3 / 2 ] x ; [R 2 R 3 Si(O)] y ; [R 4 Si(O) 3 / 2 ] z

[0028] wherein: x is any integer from 1 to 50; y is any integer from 1 to 20; z is any integer from 1 to 50; R 1 is a C1-C 30 linear or C3-C 30 cyclic alkyl group; R 2 and R 3 are each independently a C1-C 30 linear or C3-C 30 cyclic alkyl group, or a C6 or C7 aryl group; and R 4 is a C6 or C7 aryl group. The polysiloxane resin comprises less than 80 mol % of T siloxane monomer units, based on the total number of moles of siloxane monomer units in the polysiloxane resin. The polysiloxane resin comprises less than 1 mol % of M and Q siloxane monomer units, based on the total number of moles of siloxane monomer units in the polysiloxane resin. DETAILED DESCRIPTION

[0029] The present disclosure provides a polysiloxane resin coating composition comprising a polysiloxane resin, a solvent, and an additive.

[0030] I. DEFINITIONS

[0031] For the purposes of the following detailed description, it is to be understood that the disclosure can assume various alternative arrangements and step sequences, except where expressly indicated to the contrary, and that the described arrangements and / or sequences can be substituted for other arrangements and sequences, and that any arrangement and sequence that is functionally equivalent is within the scope of the disclosure. Moreover, although specific embodiments have been illustrated and described herein, it should be appreciated that any arrangement calculated to achieve the same purpose can be substituted for the specific embodiments shown. This disclosure is intended to cover any and all adaptations or variations of various embodiments. Therefore, it is intended that the protection granted by letters patent hereon be limited only to the choices explicitly indicated in the following claims.

[0032] Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the disclosure are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements.

[0033] Also, it should be understood that any numerical range recited herein is intended to include all sub-ranges of the same numerical precision subsumed

[0034] The use of a singular term, such as, for example, a or an, includes the plural unless specifically stated otherwise. Also, the use of "or" means "and / or" unless specifically stated otherwise, even though "and / or" can be explicitly used in certain instances.

[0035] As used herein, "wet" coating composition means an uncured coating composition.

[0036] As used herein, "dry" coating composition means a cured coating composition.

[0037] As used herein, "substrate" and "article" mean an object or other item having a surface onto which a coating composition can be applied.

[0038] "Solids" means the non-volatile components present in a composition of volatile and non-volatile components. As used herein, weight percent based on "solids" means the amount of a component based on the total weight of the polysiloxane resin.

[0039] "Resin solids" means the solid components that make up the binder or film-forming component of a composition. As used herein, weight percent based on "resin solids" means the amount of a component based on the total weight of the binder or film-forming component of the composition.

[0040] "Siloxane monomer" means a monomer comprising a silicon atom having one or more Si-0-R linkages, where R is an organic group, that is capable of reacting with other such monomers through hydrolysis and condensation to form a polysiloxane resin having Si-0-Si linkages.

[0041] "Emulsion" means a fine dispersion of one liquid within another liquid. As used herein, "polysiloxane resin coating emulsion" means an emulsion comprising a polysiloxane resin coating composition dispersed in a solvent. As used herein, "emulsion solution" means a dilute emulsion comprising a polysiloxane resin coating composition dispersed in a solvent.

[0042] II. Solvent-borne polysiloxane resin coating compositions

[0043] The present disclosure provides a polysiloxane resin coating composition, which can include a polysiloxane resin, a solvent, and an additive.

[0044] A. Polysiloxane Resin

[0045] The polysiloxane resin can be prepared by hydrolysis and condensation of at least two different types of siloxane monomers, water, a solvent, and a catalyst.

[0046] The polysiloxane resin can include a weight average molecular weight of 1000 g / mol, 1200 g / mol, 1500 g / mol, 1800 g / mol, 2000 g / mol to 4000 g / mol, 6000 g / mol, 8000 g / mol, 10000 g / mol, 20000 g / mol, or any range including any two of the foregoing values as endpoints, such as 1000 g / mol to 20000 g / mol, 1200 g / mol to 10000 g / mol, 1500 g / mol to 8000 g / mol, 1800 g / mol to 6000 g / mol, or 2000 g / mol to 4000 g / mol, as determined by gel permeation chromatography using polystyrene polymer beads for calibration standards.

[0047] The polysiloxane resin can include a molar ratio of aryl groups to silicon of greater than 0.75, greater than 0.80, greater than 0.85, or greater than 0.90, where the molar ratio is based on the total moles of aryl groups to the total moles of silicon in mol % of the monomers that form the polysiloxane resin.

[0048] The polysiloxane resin can include a molar ratio of aryl groups to silicon of greater than 0.90, greater than 0.95, greater than 1.00, greater than 1.10, greater than 1.40, or greater than 1.50, where the molar ratio is based on the total moles of aryl groups to the total moles of silicon in mol % of the monomers that form the polysiloxane resin.

[0049] The polysiloxane resin can include a molar ratio of alkyl to aryl groups of less than 0.6, less than 0.5, less than 0.4, or less than 0.3, where the molar ratio is based on the total moles of alkyl groups to the total moles of aryl groups in mol % of the monomers that form the polysiloxane resin.

[0050] The polysiloxane resin coating composition can include 50 wt. %, 60 wt. %, 70 wt. % to 75 wt. %, 80 wt. %, 90 wt. %, or any range including any two of the foregoing values as endpoints, such as 50 wt. % to 90 wt. %, 60 wt. % to 80 wt. %, or 70 wt. % to 75 wt. % of the polysiloxane resin, where the weight percent is based on the total weight of the "wet" coating composition.

[0051] The polysiloxane resin coating composition can include 40 wt. %, 50 wt. %, 60 wt. % to 70 wt. %, 80 wt. %, 90 wt. %, or any range including any two of the foregoing values as endpoints, such as 40 wt. % to 90 wt. %, 50 wt. % to 80 wt. %, or 60 wt. % to 70 wt. % of the polysiloxane resin, where the weight percent is based on the total weight of the "dry" coating composition.

[0052] i. Siloxane Monomer

[0053] The polysiloxane resin can be formed as a reaction product of a plurality of siloxane monomers, for example, three siloxane monomer units.

[0054] The polysiloxane resin can include 65 wt. %, 70 wt. %, 75 wt. % to 80 wt. %, 90 wt. %, 95 wt. %, or any range including any two of the foregoing values as endpoints, such as 65 wt. % to 95 wt. %, 70 wt. % to 90 wt. %, or 75 wt. % to 80 wt. % of the siloxane monomer, where the weight percent is based on the total solids weight of the polysiloxane resin.

[0055] The siloxane monomer can be described in terms of oxygen substitution or functionality on the central silicon.

[0056] Table 1: Siloxane Monomer Types

[0057]

[0058] “Linear” organopolysiloxanes typically contain primarily D siloxane monomer units, which yield polydiorganosiloxanes as fluids of varying viscosities depending on the “degree of polymerization” or DP, as indicated by the number of D units in the polydiorganosiloxane. When organopolysiloxanes are prepared primarily using T siloxy units, the resulting organosiloxanes are often referred to as “silsesquioxane resins.” When organopolysiloxanes are prepared primarily using M and Q siloxy units, the resulting organosiloxanes are often referred to as “MQ resins.” MQ resins are non-linear resins, more like cages, with a high degree of cross-linking.

[0059] The polysiloxane resins of the present disclosure can be linear and comprise D and T siloxane monomer units.

[0060] Suitable tri-functional siloxane monomers for producing the polysiloxane resins can include methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, ethyltriethoxysilane, octyltriethoxysilane, and propyltriethoxysilane.

[0061] Suitable di-functional siloxane monomers for producing the polysiloxane resins can include dimethyldimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane, dimethyldiethoxysilane, diphenyldiethoxysilane, and methylphenyldiethoxysilane.

[0062] In the synthesis of the polysiloxane resins, 50 wt. %, 55 wt. %, 60 wt. % to 65 wt. %, 70 wt. %, 75 wt. %, or any range including any two of the foregoing values as endpoints, such as 50 wt. % to 75 wt. %, 55 wt. % to 70 wt. %, or 60 wt. % to 65 wt. %, of the Si-OR within the siloxane monomers can be converted to Si-OH or Si-O-Si.

[0063] The polysiloxane resins can comprise a residual Si-OR, Si-OH, or combination of Si-OH and Si-OR groups in a weight percentage of 5 wt. %, 6 wt. %, 8 wt. % to 10 wt. %, 12 wt. %, 15 wt. %, or any range including any two of the foregoing values as endpoints, such as 5 wt. % to 15 wt. %, 6 wt. % to 12 wt. %, or 8 wt. % to 10 wt. %, wherein the weight percentage is based on the total solids weight of the polysiloxane resin.

[0064] The polysiloxane resins can comprise:

[0065] (i) [R 1 Si(O)3 / 2]x;

[0066] (ii) [R 2 R 3 Si(O)]y; and

[0067] (iii) [R 4 Si(O)3 / 2]z,

[0068] wherein:

[0069] x is any integer from 1 to 50 (including all integers such as 1, 2, 3, 4, 5,..., up to and including 50, or any range including a lower integer as the endpoint as any two of the foregoing);

[0070] y is any integer from 1 to 20 (including all integers such as 1, 2, 3, 4, 5,..., up to and including 20, or any range including a lower integer as the endpoint as any two of the foregoing);

[0071] z is any integer from 1 to 50 (including all integers such as 1, 2, 3, 4, 5,..., up to and including 50, or any range including a lower integer as the endpoint as any two of the foregoing);

[0072] [R 1 Si(O)3 / 2]x is a T unit, R 1 is a C1-C30 (including all integers such as 1, 2, 3, 4, 5,..., up to and including 30, or any range including a lower integer as the endpoint as any two of the foregoing) linear or cyclic alkyl group;

[0073] [R 2 R 3 Si(O)]y is a D unit, R 2 and R 3 are each independently a C1-C30 (including all integers such as 1, 2, 3, 4, 5,..., up to and including 30, or any range including a lower integer as the endpoint as any two of the foregoing) linear or cyclic alkyl group, or a C6 or C7 aryl group; and

[0074] [R 4 Si(O)3 / 2]z is a T unit, R 4 is a C6 or C7 aryl group.

[0075] The polysiloxane resin can comprise [R 1 Si(O)3 / 2]x, wherein the mole percentages are based on the total molar mass of the polysiloxane resin.

[0076] The polysiloxane resin can comprise [R 2 R 3 Si(O)]y, wherein the mole percentages are based on the total molar mass of the polysiloxane resin.

[0077] The polysiloxane resin can comprise [R 4 Si(O)3 / 2]z, wherein the mole percentages are based on the total molar mass of the polysiloxane resin.

[0078] The polysiloxane resin can preferably comprise a total amount of T siloxane monomer units of less than 80 mol %, less than 70 mol %, less than 65 mol %, less than 60 mol %, less than 55 mol %, or less than 50 mol %, based on the total number of moles of siloxane monomer units in the polysiloxane resin.

[0079] The polysiloxane resin can comprise a total amount of D siloxane monomer units of greater than 20 mol %, greater than 30 mol %, greater than 35 mol %, greater than 40 mol %, greater than 45 mol %, or greater than 50 mol %, based on the total number of moles of siloxane monomer units in the polysiloxane resin.

[0080] Suitable commercially available polysiloxane resins can include the resins summarized in Table 2 below.

[0081] Table 2: Structural properties of commercially available polysiloxane resins

[0082]

[0083] 1 a sheet-type polysiloxane resin.

[0084] 2 a polysiloxane resin in a solvent

[0085] The polysiloxane resin can be substantially free, essentially free, or completely free of M and Q siloxane monomer units. Substantially free of M and Q units means that the polysiloxane resin can contain less than 5 mol % of M and Q units, based on the total moles of siloxane units in the polysiloxane resin. Essentially free of M and Q units means that the polysiloxane resin can contain less than 1 mol % of M and Q units, based on the total moles of siloxane units in the polysiloxane resin. Completely free of M and Q units means that the polysiloxane resin can contain less than 0.1 mol % of M and Q units, based on the total moles of siloxane units in the polysiloxane resin.

[0086] The polysiloxane resins of the present disclosure having less than 80 mol % of T siloxane monomer units / greater than 20 mol % of D units can have higher flexibility than coating compositions comprising MQ polysiloxane resins. Silsesquioxane resins having greater than 80 mole % of T units and over-crosslinked MQ resins can lack flexibility, which is important to match the thermal expansion of metal substrates. Coating compositions lacking flexibility can have reduced heat resistance and crack upon exposure to heat.

[0087] ii. solvent

[0088] The polysiloxane resin can comprise a solvent, such as an organic solvent, in an amount of 5 wt. %, 10 wt. %, 15 wt. % to 20 wt. %, 25 wt. % to 35 wt. %, or any range using any two of the foregoing values as endpoints, such as 5 wt. % to 35 wt. %, 10 wt. % to 25 wt. %, or 15 wt. % to 20 wt. %, based on the total weight of the polysiloxane resin.

[0089] Inclusion of a solvent in the polysiloxane resin can form a resin solution that allows for a low weight ratio of surfactant (discussed further below) to polysiloxane resin for successful emulsification of the low-fluorine component coating. In the polysiloxane coating composition comprising a surfactant, the weight ratio of surfactant to polysiloxane resin can be 0.01, 0.02, 0.03 to 0.05, 0.07 to 0.09, or any range using any two of the foregoing values as endpoints, for example, 0.01 to 0.09, 0.02 to 0.07, or 0.03 to 0.05, based on the total weight of the coating composition.

[0090] Increasing the amount of solvent beyond the ranges described above can inhibit emulsion formation. In addition, using too little solvent can prevent emulsification. Compositions with too little solvent can require excessive amounts of surfactant. High surfactant loadings are not preferred because they can yellow at high temperatures and leach from the coating.

[0091] B. Condensation Catalyst

[0092] The polysiloxane resin coating composition can include a condensation catalyst. The condensation catalyst can be an acid catalyst or a base catalyst.

[0093] Suitable acid catalysts can include organic acids such as p-toluenesulfonic acid, n-butylphosphoric acid, and the like, or metal salts such as tin naphthenate, tin benzoate, tin octoate, tin butyrate, tin 2-ethylhexanoate, dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin diacetate, iron stearate, lead octoate, and the like.

[0094] Suitable base catalysts can include aqueous ammonia, ammonium hydroxide, tetraalkylammonium hydroxide, alkali metal hydroxides (e.g., NaOH, KOH), alkaline earth metal oxides (e.g., CaO, MgO), organic amines (e.g., R3N, R2NH, RNH2), alcohol amines (e.g., ethanolamine), or aminosilanes (e.g., NH2(CH2)3Si(OR)3, NH2(CH2)2NH(CH2)3Si(OR)3).

[0095] The polysiloxane resin coating composition can include any of the foregoing catalysts in a weight percent of 0.01 wt. %, 0.02 wt. %, 0.05 wt. %, 0.10 wt. % to 1 wt. %, 2 wt. %, 5 wt. %, 10 wt. %, or any range including any two of the foregoing values as endpoints, such as 0.01 wt. % to 10 wt. %, 0.02 wt. % to 5 wt. %, 0.05 wt. % to 2 wt. %, or 0.10 wt. % to 1 wt. %, wherein the weight percent is based on the total weight of the “wet” coating composition.

[0096] The polysiloxane resin coating composition can include any of the foregoing catalysts in a weight percent of 0.01 wt. %, 0.02 wt. %, 0.05 wt. %, 0.10 wt. % to 1 wt. %, 5 wt. %, 10 wt. %, 20 wt. %, or any range including any two of the foregoing values as endpoints, such as 0.01 wt. % to 20 wt. %, 0.02 wt. % to 10 wt. %, 0.05 wt. % to 5 wt. %, or 0.10 wt. % to 1 wt. %, wherein the weight percent is based on the total weight of the “dry” coating composition.

[0097] C. Solvents

[0098] The polysiloxane resin coating composition can include a solvent.

[0099] Suitable solvents can include xylene, butanol, toluene, methyl ethyl ketone, methyl isobutyl ketone, acetone, butyl acetate, dipropylene glycol monomethyl ether, methoxypropoxy propanol, methoxypropyl acetate, and methyl soyate. Additionally, the solvent can include water alone, or one or more of the foregoing solvents in combination with water.

[0100] The coating composition can include a solvent in a weight percent of 10 wt. %, 20 wt. %, 40 wt. % to 60 wt. %, 80 wt. %, 90 wt. %, or any range including any two of the foregoing values as endpoints, such as 10 wt. % to 90 wt. %, 20 wt. % to 80 wt. %, or 40 wt. % to 60 wt. %, where the weight percent is based on the total weight of the “wet” coating composition.

[0101] The coating composition can include a solvent in a weight percent of 0.30 wt. %, 0.50 wt. %, 0.70 wt. % to 0.90 wt. %, 1.10 wt. %, 1.30 wt. %, or any range including any two of the foregoing values as endpoints, such as 0.30 wt. % to 1.30 wt. %, 0.50 wt. % to 1.10 wt. %, or 0.70 wt. % to 0.90 wt. %, where the weight percent is based on the total weight of the “dry” coating composition.

[0102] D. Additives

[0103] The polysiloxane resin coating composition can include additives, such as catalysts, surface agents, surfactants, pigments, fillers, linear siloxane fluids / silicone oils, and wetting agents as described above.

[0104] The coating composition can include additives in a total weight percent of 0.1 wt. %, 0.5 wt. %, 1 wt. % to 5 wt. %, 10 wt. %, 15 wt. %, or any range including any two of the foregoing values as endpoints, such as 0.1 wt. % to 15 wt. %, 0.5 wt. % to 10 wt. %, or 1 wt. % to 5 wt. %, where the weight percent is based on the total weight of the “wet” coating composition.

[0105] The coating composition can include a total weight percentage of 0.50 wt. %, 1 wt. %, 5 wt. % to 10 wt. %, 20 wt. %, 30 wt. %, or any range including any two of the foregoing values as endpoints, such as 0.50 wt. % to 30 wt. %, 1 wt. % to 20 wt. %, or 5 wt. % to 10 wt. %, where the weight percentage is based on the total weight of the "dry" coating composition.

[0106] i. Surfactant

[0107] A surfactant can be added to the coating composition to enable combination with an emulsifier. Suitable surfactants can include, but are not limited to, the following: alkyl sulfates (e.g., sodium dodecyl sulfate); ether sulfates; phosphate esters; sulfonates; and various alkali, ammonium, amine salts thereof; fatty alcohol ethoxylates; alkyl phenol ethoxylates (e.g., nonylphenol polyether); salts and / or combinations thereof.

[0108] The surfactant in the coating composition can include a non-ionic triblock copolymer. As used herein, the structural unit of the non-ionic surfactant based on the triblock copolymer refers to a compound of the following Formula II.

[0109]

[0110] Formula IIA

[0111] wherein x is an ethylene glycol monomer, y is a propylene glycol monomer, and z is an ethylene glycol monomer.

[0112]

[0113] Formula IIB

[0114] wherein x is a propylene glycol monomer, y is an ethylene glycol monomer, and z is a propylene glycol monomer.

[0115] The surfactant of Formula IIA or IIB can be used alone or in combination with other surfactants, such as a second triblock copolymer of Formula IIA, where the ratio of x to y or z to y of the second triblock copolymer is 0.1 : 1 to 3 : 1.

[0116] The surfactants of Formula II A and II B can have a hydrophilic-lipophilic balance (HLB) value of greater than 10, greater than 15, greater than 20, greater than 22, greater than 24, greater than 26, greater than 28, greater than 30, or any range of HLB values using any two of the foregoing values as endpoints, as determined by using the Griffin method or Davies method as described in National Journal of Pharmaceutical Sciences 2021; 1(2): 23-24.

[0117] The surfactants of Formula II A can have an average molecular weight of 8000 g / mol, 10000 g / mol, 12000 g / mol to 14000 g / mol, 14600 g / mol, 15000 g / mol, or any range including any two of the foregoing values as endpoints, such as 8000 g / mol to 15000 g / mol, 10000 g / mol to 14600 g / mol, or 12000 g / mol to 14000 g / mol, as determined by gel permeation chromatography using polystyrene polymer beads for calibration standards.

[0118] The surfactants of Formula II B can have an average molecular weight of 2000 g / mol, 2500 g / mol, 3000 g / mol to 3500 g / mol, 3700 g / mol, 4000 g / mol, or any range including any two of the foregoing values as endpoints, such as 2000 g / mol to 4000 g / mol, 2500 g / mol to 3700 g / mol, or 3000 g / mol to 3500 g / mol, as determined by gel permeation chromatography using polystyrene polymer beads for calibration standards.

[0119] The structural unit of the non-ionic surfactant based on fatty alcohol ethoxylate can be referenced to the compound of Formula III below.

[0120]

[0121] Formula III

[0122] wherein the alkyl chain is a C11 to C14 branched or linear alkyl group, wherein n = 16-18, having an HLB value of greater than 5, greater than 10, greater than 15, or greater than 20, or any range of HLB values using any two of the foregoing values as endpoints, the HLB value being determined by using the Griffin method or Davies method as described in National Journal of Pharmaceutical Sciences 2021; 1(2): 23-24.

[0123] The surfactant of Formula III can be used alone or in combination with other surfactants. The coating composition can comprise the surfactant of Formula III in an amount of 1 wt. %, 2 wt. %, 2.5 wt. % to 3 wt. %, 4 wt. %, 5 wt. %, or any range including any two of the foregoing values as endpoints, such as 1 wt. % to 5 wt. %, 2 wt. % to 4 wt. %, or 2.5 wt. % to 3 wt. %, where wt. % is based on the total weight of surfactant incorporated per 100 g of emulsion (including 37 g to 40 g of polysiloxane resin dispersed therein).

[0124] The coating composition can comprise the surfactant in a weight percent of 0.01 wt. %, 0.05 wt. %, 0.1 wt. % to 1 wt. %, 5 wt. %, 10 wt. %, or any range including any two of the foregoing values as endpoints, such as 0.01 wt. % to 10 wt. %, 0.05 wt. % to 5 wt. %, or 0.1 wt. % to 1 wt. %, where the weight percent is based on the total weight of the “wet” coating composition.

[0125] ii. Silicone oil / silicone fluid

[0126] The silicone oil or silicone fluid can be used as a release agent in the coating composition. The coating composition can comprise one or more silicone oils or fluids of low molecular weight, medium molecular weight, high molecular weight, or a combination thereof.

[0127] The low molecular weight silicone oil can have a molecular weight of less than 8000 g / mol, less than 7000 g / mol, less than 6000 g / mol, less than 5000 g / mol, less than 4000 g / mol, or less than 3000 g / mol, or any value or range encompassed by the foregoing.

[0128] The medium molecular weight silicone oil can have a molecular weight of 12,000 g / mol or greater, 12,500 g / mol or greater, 13,000 g / mol or greater, 13,500 g / mol or less, 14,000 g / mol or less, 14,500 g / mol or less, 15,000 g / mol or less, or any value or range of values encompassed by the foregoing.

[0129] The high molecular weight silicone oil can have a molecular weight of 90,000 g / mol or greater, 92,000 g / mol or greater, 94,000 g / mol or greater, 96,000 g / mol or less, 98,000 g / mol or less, 100,000 g / mol or less, or any value or range of values encompassed by the foregoing.

[0130] The coating composition can include silicone oil / siloxane fluid in a weight percent of 0.1 wt. %, 1 wt. %, 5 wt. % to 10 wt. %, 15 wt. %, 20 wt. %, or any range including any two of the foregoing values as endpoints, such as 0.1 wt. % to 20 wt. %, 1 wt. % to 15 wt. %, or 5 wt. % to 10 wt. %, where the weight percent is based on the total weight of the “wet” coating composition.

[0131] iii. Pigments and Fillers

[0132] The coating composition can include pigments. Suitable pigments and / or pigment compositions can include iron oxides, aluminum oxides, mixed metal spinels, carbazole dioxazine crude pigments, azo, monoazo, disazo, naphthol AS, salt type (lakes), benzimidazolone, condensed, metal complex, isoindolinone, isoindoline and polynuclear phthalocyanine, quinacridone, perylene, perinone, diketopyrrolo pyrrole, thioindigo, anthraquinone, indanthrone, anthrapyrimidine, flavanthrone, pyranthrone, anthraquinone, dioxazine, triarylcarbonium, quinophthalone pigments, diketopyrrolo pyrrole red (“DPPBO red”), titanium dioxide, carbon black, carbon fibers, graphite, other conductive pigments and / or fillers, and mixtures thereof.

[0133] Further, the composition can include a surfactant. Suitable fillers can include calcium silicate, potassium titanate, aluminum oxide, silicon carbide, kaolin, silica, mica, talc, clay, and inorganic minerals.

[0134] The coating composition can include 0.1 wt. %, 1 wt. %, 5 wt. % to 10 wt. %, 15 wt. %, 20 wt. %, or any range including any two of the foregoing values as endpoints, such as 0.1 wt. % to 20 wt. %, 1 wt. % to 15 wt. %, or 5 wt. % to 10 wt. % of pigments and fillers, where the weight percent is based on the total weight of the “wet” coating composition.

[0135] E. Application and curing of the polysiloxane resin coating composition

[0136] The polysililoxane resin coating composition can be applied to the substrate / article using a variety of application methods.

[0137] Suitable substrates and articles can include metal, die cast aluminum, enamel frit, ceramic, or plastic substrates / articles. Further, the coated substrate / article can be a suitable substrate for application of the coating composition of the present disclosure.

[0138] The coating can be applied to the substrate using vapor deposition, spray, roll, air knife, or any other suitable coating method. Once applied, the coating composition can be cured at a temperature of 100 °C, 200 °C, 250 °C to 350 °C, 400 °C, 450 °C, or any range including any two of the foregoing values as endpoints, such as 100 °C to 450 °C, 200 °C to 400 °C, or 250 °C to 350 °C.

[0139] F. Properties of the polysiloxane resin coating

[0140] The polysiloxane resin coating composition can have improved crack resistance and heat resistance compared to traditional coating compositions.

[0141] i. Fluorine-containing polymers

[0142] The coating of the present disclosure can also be substantially free, essentially free, or completely free of fluorine-containing components.

[0143] The fluorine-containing components can include perfluoro / polyfluoroalkyl substances (PFAS), such as fluorine-containing polymers, fluorine-containing oligomers, and / or fluorine-containing small molecules.

[0144] Substantially free of fluorine-containing polymers means that the coating composition can include less than 5 wt. % of fluorine-containing polymers, based on the total weight of the “wet” coating composition. Essentially free of fluorine-containing polymers means that the coating composition can include less than 1 wt. % of fluorine-containing polymers, based on the total weight of the “wet” coating composition. Completely free of fluorine-containing polymers means that the coating composition can include less than 0.01 wt. % of fluorine-containing polymers, based on the total weight of the “wet” coating composition.

[0145] ii. VOC

[0146] Environmental standards exist in many places to limit the level of VOCs that can be present in coating compositions. VOCs are compounds with high vapor pressure (typically 10 Pa or greater at 20 °C) and low water solubility.

[0147] The polysiloxane resin coating composition 100a of the present disclosure can contain minimal VOCs, for example, less than the threshold of the U.S. Environmental Protection Agency (U.S. EPA) of 3.5 lbs / gal or less and / or the European standard of 420 g / liter. The polysiloxane resin coating composition 100a can contain an amount of VOCs of less than 200 g / liter, less than 150 g / liter, less than 100 g / liter, less than 50 g / liter, less than 10 g / liter, or less than 5 g / liter, or within any range including any two of the foregoing values as endpoints, such as 5 g / liter to 200 g / liter, 10 g / liter to 150 g / liter, or 50 g / liter to 100 g / liter.

[0148] The polysiloxane resin coating composition can contain VOC levels that comply with VOC restrictions of certain states. The polysiloxane resin coating composition can contain an amount of VOCs of less than 370 g / liter, less than 300 g / liter, less than 250 g / liter, less than 200 g / liter, less than 150 g / liter, or less than 100 g / liter, or within any range including any two of the foregoing values as endpoints, such as 100 g / liter to 370 g / liter, 150 g / liter to 300 g / liter, or 200 g / liter to 250 g / liter.

[0149] iii. Initial cracking

[0150] The cured coating can be measured for initial film cracking on a scale of 1 to 10, as shown in Table 3 below. The cured coating film can be visually inspected for cracks. The amount of cracking is correlated to a numerical value of 1 to 10, where a rating of 10 has no cracks visible to the naked eye and a rating of 1 is completely disintegrated and detached from the substrate.

[0151] The amount of cracking can vary with film thickness. If the coating film has the same film thickness, the coating film can experience less cracking. The coating composition can have a thickness of 10 µm, 15 µm, 20 µm to 30 µm, 40 µm, 50 µm, or any range including any two of the foregoing values as endpoints, such as 10 µm to 50 µm, 15 µm to 40 µm, or 20 µm to 30 µm. The coating composition of the present disclosure can experience an initial cracking rating of greater than 7, greater than 8, greater than 9, or 10.

[0152] Table 3: Initial Cracking Rating

[0153]

[0154] iv. Number of thermal cycles to failure

[0155] The durability of the coating can be tested by a thermal cycling test. The coating composition can be subjected to thermal cycling by heating the coating to 300°C for one hour and then immediately cooling the coating to 20°C by immersing the coating in water. Once the coating has cooled, the coating can be dried and inspected for cracks. If no cracks are present, the coating can be heated and cooled again. The number of cycles of heating and cooling that the coating composition can withstand before it cracks can be recorded as the number of thermal cycles to failure.

[0156] Failure occurs when the coating exhibits a cracking rating of 7 or below, the cracking rating being according to the initial crack rating described in Table 3 above.

[0157] The polysiloxane resin coating of the present disclosure can exhibit a number of thermal cycles to failure of 6, 7, 8 to 9, 10, 11, or any range including any of the foregoing values as endpoints, such as 6 to 11, 7 to 19, or 8 to 9.

[0158] III. Aqueous polysiloxane resin coating emulsion

[0159] The coating composition emulsion can be formulated by dissolving the above polysiloxane resin, co-solvent, and above surfactant or combination of surfactants into water. The “co-solvent” can be an aromatic solvent such as xylene or toluene; glycol ethers such as Dowanol PM and Downanol DPM; and miscible with water such as NMP and triethyl phosphate.

[0160] The components can be mixed or agitated as appropriate, such as using a serrated blade or other suitable mixing method, at 1000 revolutions per minute (RPM). The solid polysiloxane resin can be dissolved in the solvent first, followed by the addition of the surfactant.

[0161] The emulsion can be agitated at a first speed for a first duration, such as 30 minutes, and then agitated at an elevated speed, such as 2000 RPM, for a second duration, the water stabilized at different pH (pH of 2-9). The water can be stabilized at lower pH using acids (e.g., acetic acid, HNO3, HC1, H3PO4) and at higher pH using organic and inorganic bases (e.g., triethylamine, dimethylethanolamine, triethanolamine, ammonia, NaOH, KOH, and mixtures thereof). Once the pH stabilized water is added, the emulsion can be agitated for an additional 5 minutes and checked for water dilution as described below.

[0162] A. Water dilution test

[0163] To test the degree of dilution of the emulsion in water, a water dilution test can be performed using the following method. A 1 wt. % polysiloxane resin coating emulsion solution can be prepared by mixing 1 g of the polysiloxane resin coating emulsion into 99 g of deionized water. The emulsion solution can be shaken to ensure the coating composition is incorporated into the water. The quality of the solution can be evaluated according to the ratings described in Table A below. The emulsions of the present disclosure have a solution quality evaluation rating of 3 or 4.

[0164] Table A: Emulsion Solution Quality Evaluation Ratings

[0165]

[0166] B. Application and Curing of the Polysiloxane Resin Emulsion

[0167] The emulsion can be allowed to sit overnight and then applied to a substrate / article by a variety of coating application methods.

[0168] Suitable substrates and articles can include metal, die cast aluminum, enamel frit, ceramic, or plastic substrates / articles. Further, the coated substrates / articles can be suitable substrates for application of the coating compositions of the present disclosure.

[0169] The coating can be applied to the substrate using spray coating, knife coating, vapor deposition, roll coating, air knife coating, or any other suitable coating method. Once applied to the substrate, the emulsion can be cured.

[0170] The coated substrate can be placed in a low temperature oven and baked at a temperature of 100 °C, 110 °C, 120 °C to 130 °C, 140 °C, 150 °C, or any range including any of the foregoing as endpoints, such as 100 °C to 150 °C, 110 °C to 140 °C, or 120 °C to 130 °C. The emulsion can be baked for a period of 1 minute (min), 2 min, 4 min to 6 min, 8 min, 10 min, or any range including any of the foregoing as endpoints, such as 1 to 10 min, 2 to 8 min, or 4 to 6 min. The coated substrate can then be transferred to a higher temperature oven for a period of time. The high temperature oven can be at a temperature of 200 °C, 250 °C, 280 °C to 300 °C, 350 °C, 400 °C, or any range including any of the foregoing as endpoints, such as 200 °C to 400 °C, 250 °C to 250 °C, or 280 °C to 300 °C. The coated substrate can be baked in the high temperature oven for a period of 10 min, 15 min, 20 min to 25 min, 30 min, 35 min, or any range including any of the foregoing as endpoints, such as 10 to 35 min, 15 to 30 min, or 20 to 25 min. The coated substrate can then be allowed to cool to room temperature (20-25 °C).

[0171] The cured emulsion can have a film thickness on a substrate of 15 pm, 30 pm, 50 pm to 60 pm, 80 pm, 100 pm, or any range including any of the foregoing values as endpoints, for example, 15 pm to 100 pm, 30 pm to 80 pm, or 50 pm to 60 pm.

[0172] C. Properties of the polysiloxane resin emulsion coating

[0173] The shelf life of a polysiloxane resin coating emulsion can be evaluated by aging a portion of the emulsion at an elevated temperature for a period of time. The stability of the coating composition emulsion can be further tested for phase separation after 24 hours at 50 °C, shear stability after 1 month, and viscosity at the phase inversion point. Properties of the polysiloxane resin emulsion and emulsion solutions can be found in Table F. To measure shear stability, a small portion of the emulsion (about 0.5 g) that has been aged at 50 °C for 1 month is placed on the stage of a rheometer (Anton Paar MCR302e) with a cone and plate o rheometer with a cone angle of 0.995

[0174] i. Shear stability

[0175] Shear stability testing shows the stability of the polysiloxane resin within the emulsion under stress. Poor shear stability can result in uneven build-up of the polysiloxane resin particles in the emulsion across the coated surface.

[0176] To test shear stability, the emulsion can be subjected to elevated temperature and force, such as a viscometer.

[0177] According to the shear stability ratings described in Table B, the polysiloxane resin emulsion can have a shear stability of greater than 1, greater than 2, or greater than 3 at 50 °C.

[0178] Table B: Shear stability ratings of emulsions

[0179]

[0180] According to the shear stability ratings described in Table C, the polysiloxane resin emulsion solution can have a shear stability of 3 or 4.

[0181] Table C: Shear stability ratings of emulsion solutions

[0182]

[0183] ii. Phase separation

[0184] Phase separation of the coating composition emulsion can be measured at 50°C to determine the amount of solvent separated from the emulsion after 24 hours. The amount of phase separation can be evaluated according to the ratings described in Table D below. The emulsions of this disclosure may have a phase separation of 3 or 4.

[0185] Table D: Phase Separation Rating

[0186]

[0187] iii. Viscosity at the phase inversion point

[0188] The phase inversion point of an emulsion is the point at which an emulsion changes from one type of emulsion to another (i.e., from a continuous phase to a dispersed phase). Phase inversion can usually be detected by an increase in the emulsion's viscosity.

[0189] To test the viscosity of the emulsion during phase inversion, a small portion (approximately 0.5 g) of the emulsion at the stage when 40% of the total water was added to the resin was placed on the platform of a rheometer (Anton Paar MCR 302e) with a cone angle of 03.995°. o A conical rotor was used. Subsequently, a shear rate of 100 s⁻¹ was applied to the sample and the viscosity was measured.

[0190] Using a cone angle of 0.995 o The viscosity of an emulsion during phase inversion was measured using an Anton Paar MCR 302e with a conical rotor at a shear rate of 100 s⁻¹.

[0191] According to the rating levels described in Table E, polysiloxane resin coating emulsions may have a phase inversion point viscosity of 3 or 4.

[0192] Table E: Phase Inversion Viscosity Rating

[0193]

[0194] Table F: Properties of Polysiloxane Resin Coating Emulsions

[0195]

[0196] Examples

[0197] The aspects of this disclosure will be further illustrated with reference to the following examples. It will be apparent to those skilled in the art that many modifications can be made to the materials and methods without departing from the scope of this disclosure.

[0198] Example 1: Formation of a polysiloxane resin

[0199] The polysiloxane resins of the present invention (invention example) and comparative (comparative example) were prepared according to Table 4 and the following steps.

[0200] Synthesis of the present invention and comparative resins 1-10: acid catalysis

[0201] Into a 500 mL four necked flask, fitted with an overhead stirrer, condenser, N2inlet and thermocouple, was added 199.5 g phenyltriethoxysilane, 22.5 g phenylmethyldimethoxysilane, 43.5 g methyltriethoxysilane, 6.8 g diphenyldiethoxysilane and 15 g ethanol. The contents were mixed at room temperature (20-25 °C) and then 0.92 g HC1 (37%) was added. 33 g of distilled water was added over a period of 30 minutes.

[0202] The temperature of the reaction mixture was raised to 50 °C and held for 1 hour. After which the temperature was raised to 70 °C and held for 2 hours while mixing the contents. The reaction was then cooled to about 30 °C and 4.8 g of NaHC03was added and the contents were stirred for 2 hours. The solid residue was then filtered. To the filtrate was added 90 g of xylene. The light fraction was distilled from the filtrate at 80-120 °C. The resin was isolated as a 65-85 wt. % solution in xylene.

[0203] Synthesis of the present invention resins 11-14: base catalysis

[0204] Into a 250 mL four necked flask, fitted with an overhead stirrer, condenser, N2inlet and thermocouple, was added 100.0 g phenyltrimethoxysilane, 14.0 g phenylmethyldimethoxysilane, 20.0 g methyltrimethoxysilane, 4.0 g diphenyldiethoxysilane and 10 g ethanol. The contents were mixed at room temperature and then 1.15 g ammonium hydroxide (30%) was added. 20.1 g of distilled water was added over a period of 30 minutes.

[0205] The temperature of the reaction mixture was raised to 50 °C and held for 1 hour. After which the temperature was raised to 70 °C and held for 4 hours while mixing the contents. 45 g of xylene was added. The light fraction was distilled from the filtrate at 80-120 °C. The resin was isolated as a 65-85 wt. % solution in xylene.

[0206] Comparative resins were synthesized using similar procedures.

[0207] Table 4: Polysiloxane resins

[0208]

[0209] Example 2: Preparation of a solvent-based polysiloxane coating composition

[0210] Example (Examples) solventborne coating compositions of the present disclosure and comparative (comparative example) coating compositions were prepared according to Tables 5 and 6.

[0211] Solvent-based coatings were formulated by adding materials in the order listed with moderate agitation using a serrated blade. The polysiloxane resin solution was added, followed by a 2% solution of tin (II) 2-ethylhexanoate (condensation catalyst). Next, BYK-333 was added as a wetting agent, and additional xylene was optionally added to adjust solids.

[0212] The fully formulated solution was stirred for 5-10 minutes, then applied to a 3003 series aluminum available from Q-Lab (Q412) by draw down using a wire-wound rod (#8). The coating was placed in a 120 °C oven for 10 minutes, then transferred to a 300 °C oven and heated for 20 minutes. The coating was allowed to cool at room temperature, and the film thickness was 15 - 30 µm.

[0213] All coating compositions listed in Table 5 contain the same wt. % of dry polysiloxane resin. Solvent was added to Examples 1-4 and Comparative Examples 5-6 to maintain the same wt. % solids as Comparative Examples 1-4, where the resin contains more solvent.

[0214] Table 5: Coating compositions with acid-catalyzed resins

[0215]

[0216] Table 6: Coating compositions with base-catalyzed resins

[0217]

[0218] Example 3: Preparation of an aqueous polysiloxane resin coating emulsion

[0219] Example (Example) polysiloxane resin coating emulsions of the present disclosure were prepared according to Tables 7 and 8.

[0220] The polysiloxane resin coating emulsions were prepared by adding the resin solution, any additional co-solvent, and surfactant or combination of surfactants under agitation with a serrated blade at 1000 RPM. If the resin was a solid, it was first dissolved in solvent prior to adding the surfactant. Agitation was continued for 30 minutes. After 30 minutes, agitation was increased to 2000 RPM and a 0.23% solution of ammonia in water was added in portions of about 3 g. Each portion was added quickly in a single shot. Once all of the aqueous base was added, the emulsion was stirred for an additional 5 minutes and checked for water dilution.

[0221] One gram of the polysiloxane resin coating emulsion was added to a 20 mL jar, followed by 6 g of deionized water. The dilution was shaken to ensure incorporation. The formulation was acceptable if the product was a free-flowing white dispersion throughout the dilution process. The formulation was unacceptable if the white emulsion did not incorporate into the water, but existed as a separate phase.

[0222] The formulation was left to stand overnight, and then applied to 3003 series aluminum plates (Q412) available from Q-Lab by spraying or scraping. The coating was placed in a 120°C oven for 1–10 minutes, and then transferred to a 300°C oven for 20 minutes. The coating was cooled to room temperature, and the film thickness was 15–30 μm.

[0223] Table 7: Coating composition emulsions with acid-catalyzed resins

[0224]

[0225] Table 8: Coating composition emulsions with base-catalyzed resins

[0226]

[0227] Example 4: Polysiloxane resin emulsion with Pluronic F108

[0228] Prepare polysiloxane resin emulsions according to Table 9.

[0229] The following commercially available resins were used to produce the emulsion: Silres 604, Dowanol RSN 0233, Dowanol RSN 0220, and Dowanol RSN 0431.

[0230] The nonionic surfactant (Pluoronic F108; CAS No.: 691397-13-4) and solvent (Dowanol DPM) were mixed together using high-shear dispersing blades (1-inch diameter x 1 / 4-inch center-hole Type A 316 SS dispersing blades) until a homogeneous solution was obtained. Then, a separate aqueous solution containing dissolved ammonia (0.75 g of 30% ammonium hydroxide in 100 g of deionized water), stabilized at pH 10, was gradually incorporated into the resin solution. Water was added in 10 portions (3 g each; 10% of the total water volume), with a one-minute interval between each addition. After all water was added, the emulsion was stirred for an additional 15 minutes.

[0231] Table 9: Coating emulsions

[0232]

[0233] 1 For Silres 604, Dowsil RSN 0233, and Dowsil RSN 0220, the polysiloxane resin is a solvent-free solid flake powder.

[0234] 2 For Dowsil RSN 0431, the polysiloxane resin is a mixture of solvent (20%) and resin (80%) dissolved in the solvent.

[0235] Example 5: Properties of coating compositions

[0236] The properties of the cured coating compositions of the present disclosure and comparative coating compositions were recorded, as shown in Table 10.

[0237] Once cured, the initial film cracking of the coating compositions was measured by visual rating on a scale of 10 - 1. It was found that cracking varied with film thickness, and it was important to maintain an equal film thickness.

[0238] The coatings that were rated a 10 for initial cracking were further tested for durability to thermal cycling. The coatings were placed in a 300°C oven for 1 hour, and then immediately cooled by immersion in water. The coatings were then dried and inspected for cracks. If no cracks appeared, they were placed back in the oven for another cycle. The number of cycles at which cracks appeared was used as a measure of performance, with a higher number indicating better performance.

[0239] Table 10: Properties of Coating Compositions

[0240]

[0241] a Silres 604, available from Wacker Chemie; b Dowsil RSN-0233, available from Dow Silicones; c Dowsil RSN-0220, available from Dow Silicones; d Dowsil RSN-0431, available from Dow Silicones; e Information from Technical Data Sheet

[0242] The example coating compositions of the present disclosure (Examples 1-4) and comparative coating compositions (Comparative Examples 1-4) show a range of performance in initial crack rating and number of thermal cycles to failure, despite all coatings having an alkyl / silicon atom ratio of 1 - 1.2. The mixed performance demonstrates that this range is known in the art and does not represent the heat resistance of the present invention as described herein.

[0243] Examples 1-3 coating compositions contain resins with 10 mole% PhMeSiO monomer, a Ph / silicone mole ratio of greater than 0.8, a methyl / phenyl mole ratio of less than 0.4, and 50 - 75 % SiOR conversion to SiOH or SiOSi during synthesis. Example 4 is similar to the Example 1-3 compositions, except that Example 4 has 5 mole% PhMeSiO monomer.

[0244] The coating compositions of the present disclosure all (Examples 1-4) have excellent crack resistance as shown by the initial crack rating. In addition, coating composition Example 1 and Example 2 survived 9 heat cycles, coating composition Example 3 survived 5 heat cycles, and coating composition Example 4 survived 7 heat cycles. All of the coating compositions of the present disclosure survived an increased number of heat cycles compared to Comparative Coating 4 (Comparative Example 4) which only survived 3 heat cycles before failing.

[0245] Comparative Coating 1 (Comparative Example 1) shows the importance of the PhMeSiO monomer. Without at least 5% of this monomer, the coating fails the initial crack test.

[0246] Comparative Coating 2 (Comparative Example 2) shows the additive effect of SiOR conversion with the PhMeSiO monomer. Comparative Example 2 did not achieve an initial crack rating of 10 and had even worse initial cracking than Comparative Example 1.

[0247] Comparative Coating 3 (Comparative Example 3) shows the additive effect of the PhMeSiO monomer, the Ph / Silicone mole ratio, the methyl / phenyl mole ratio, and the SiOR conversion. While Comparative Examples 1-3 all have initial crack ratings that are outside the scope of the present invention (10), Comparative Example 3 has the worst initial crack rating.

[0248] Comparative Coating 4 (Comparative Example 4) shows that a coating with a Ph / Silicone mole ratio and an alkyl / silicone mole ratio within the scope of the present invention, but a methyl / phenyl mole ratio greater than the scope of the present invention, passes the initial crack rating but has poor performance in the heat cycle test.

[0249] The coating composition examples 5-7 of the present disclosure show that base catalyzed resins perform similarly to acid catalyzed resins if the resin structure is within the scope of the present invention. Example 8 shows that acid catalyzed resins can form water dilutable coating compositions with heat durability after application if the resin is within the scope of the present invention.

[0250] The coating emulsion examples 9-11 of the present disclosure show that base catalyzed resins can form water dilutable coating compositions with heat durability after application if the resin is within the scope of the present invention.

[0251] The example coating emulsions 11, 12, and 13 show that surfactants of Formula II and Formula III can be used alone or in combination without affecting the water swellability or the heat performance of the final coating.

[0252] Examples coating emulsions 14 and 15 in Table 11 describe the quality of emulsions made from commercially available polysiloxane resins and the thermal cycling performance rating of the coatings obtained from the emulsions. The rating correlation to heat resistance is described above in Table 3. All resins showed water swellability, but it was observed that the emulsion made with Dowsil 0431 (Example 15d) achieved the maximum resistance to thermal shock, which was found to be 22 thermal cycle exposures.

[0253] Where specific examples of the application have been described in the foregoing for purposes of illustration, it will be evident to those skilled in the art that numerous variations in the details of the application can be made without departing from the application as defined in the appended claims. Accordingly, the application is intended to embrace all variations, uses, or adaptations of the application which are obvious in light of the disclosure. Further, the application is intended to embrace such departures from the present disclosure as come within the known or customary practice in the art to which the disclosure pertains and fall within the limits of the appended claims.

[0254] Aspects

[0255] Aspect 1 is a curable coating composition comprising: a polysiloxane resin formed from siloxane monomers: [R 1 Si(O) 3 / 2 ] x ; [R 2 R 3 Si(O)] y ; and [R 4 Si(O) 3 / 2 ] z ; wherein: x is any integer from 1 to 50; y is any integer from 1 to 20; z is any integer from 1 to 50; R 1 is a C1-C 30 linear or C3-C 30 cyclic alkyl group; R 2 and R 3 are each independently a C1-C 30 linear or C3-C 30 cyclic alkyl group, or a C6 or C7 aryl group; R 4 is a C6 or C7 aryl group; and a solvent; wherein the composition comprises less than 5 wt.% of any fluorine-containing component, based on the total weight of the composition.

[0256] Aspect 2 is the composition of Aspect 1, further comprising a condensation catalyst.

[0257] Aspect 3 is the composition of any one of Aspect 1 or Aspect 2, wherein the polysiloxane resin comprises aryl groups and includes a molar ratio of aryl groups to silicon atoms of 0.8 or greater, based on the total moles of aryl groups in mol % of the monomers that form the polysiloxane resin divided by the total moles of silicon atoms.

[0258] Aspect 4 is the composition of any one of Aspects 1 to 3, wherein the polysiloxane resin comprises phenyl groups and includes a molar ratio of phenyl groups to silicon atoms of 0.8 or greater, based on the total moles of phenyl groups in mol % of the monomers that form the polysiloxane resin divided by the total moles of silicon atoms.

[0259] Aspect 5 is the composition of any one of Aspects 1 to 4, wherein the polysiloxane resin comprises phenyl groups, and further wherein: the molar amount of the component [R 4 Si(O) 3 / 2 ] z is greater than 60 mol % based on the total moles of the monomers that form the polysiloxane resin; and the molar amount of the component [R 2 R 3 Si(O)] y is from 5 mol % to 30 mol % based on the total moles of the polysiloxane resin.

[0260] Aspect 6 is the composition of any one of Aspects 1 to 5, wherein the polysiloxane resin comprises phenyl groups, and further wherein: the molar amount of the component [R 4 Si(O) 3 / 2 ] z is greater than 65 % based on the total moles of the polysiloxane resin; and the molar amount of the component [R 2 R 3 Si(O)] y is from 5 % to 10 % based on the total moles of the polysiloxane resin.

[0261] Aspect 7 is the composition of any one of Aspects 1 to 6, wherein the polysiloxane resin comprises alkyl groups and aryl groups and includes a molar ratio of alkyl groups to aryl groups of 0.45 or less, based on the total moles of alkyl groups in mol % of the monomers that form the polysiloxane resin divided by the total moles of aryl atoms.

[0262] Aspect 8 is the composition of any one of aspects 1 to 7, wherein the polysiloxane resin comprises methyl groups and phenyl groups, and comprises a molar ratio of methyl groups to phenyl groups of 0.45 or less, based on the total moles of methyl groups divided by the total moles of phenyl atoms in mol % of the monomers that form the polysiloxane resin.

[0263] Aspect 9 is the composition of any one of aspects 1 to 8, wherein the polysiloxane resin comprises monomeric residues of each of the following siloxane monomers: phenyl trialkoxysilane; phenyl methyl dialkoxysilane; methyl trialkoxysilane; and diphenyl dialkoxysilane.

[0264] Aspect 10 is an article coated with the coating composition of any one of aspects 1-9.

[0265] Aspect 11 is the article of aspect 10, wherein the article is at least one of a metal, a die cast aluminum, a porcelain enamel frit, a ceramic, a plastic, and a pre-coated article.

[0266] Aspect 12 is a method of coating a substrate, the method comprising: applying a coating composition to a substrate, the coating composition comprising: a polysiloxane resin formed from siloxane monomers: [R 1 Si(O) 3 / 2 ] x ; [R 2 R 3 Si(O)] y ; and [R 4 Si(O) 3 / 2 ] z ; wherein: x is any integer from 1 to 50; y is any integer from 1 to 20; z is any integer from 1 to 50; R 1 is a C1-C 30 linear or C3-C 30 cyclic alkyl group; R 2 and R 3 are each independently a C1-C 30 linear or C3-C 30 cyclic alkyl group, or a C6 or C7 aryl group; R 4 is a C6 or C7 aryl group; and a solvent; wherein the composition comprises less than 5 wt. % of any fluorine-containing component, based on the total weight of the composition; and curing the coating composition.

[0267] Aspect 13 is the method of aspect 12, wherein the coating composition further comprises a condensation catalyst.

[0268] Aspect 14 is the method of claim 12 or claim 13, wherein the polysiloxane resin comprises aryl groups and includes a molar ratio of aryl groups to silicon atoms of 0.8 or greater, the molar ratio being based on the total moles of aryl groups to the total moles of silicon atoms in mol % of the monomers that form the polysiloxane resin.

[0269] Aspect 15 is the method of any one of aspects 12 to 14, wherein the polysiloxane resin comprises phenyl groups and includes a molar ratio of phenyl groups to silicon atoms of 0.8 or greater, the molar ratio being based on the total moles of phenyl groups to the total moles of silicon atoms in mol % of the monomers that form the polysiloxane resin.

[0270] Aspect 16 is the method of any one of aspects 12 to 15, wherein the polysiloxane resin comprises phenyl groups, and further wherein: the molar amount of component [R 4 Si(O) 3 / 2 ] z is greater than 60 mol % based on the total molar mass of the polysiloxane resin; and the molar amount of component [R 2 R 3 Si(O)] y is from 5 mol % to 10 mol % based on the total molar mass of the polysiloxane resin.

[0271] Aspect 17 is the method of any one of aspects 12 to 16, wherein the polysiloxane resin comprises phenyl groups, and further wherein: the molar amount of component [R 4 Si(O) 3 / 2 ] z is greater than 65 % based on the total molar mass of the polysiloxane resin; and the molar amount of component [R 2 R 3 Si(O)] y is from 5 % to 10 % based on the total molar mass of the polysiloxane resin.

[0272] Aspect 18 is the method of any one of aspects 12 to 17, wherein the polysiloxane resin comprises alkyl groups and aryl groups and includes a molar ratio of alkyl groups to aryl groups of 0.45 or less, the molar ratio being based on the total moles of alkyl groups to the total moles of aryl atoms in mol % of the monomers that form the polysiloxane resin.

[0273] Aspect 19 is the method of any one of aspects 12 to 18, wherein the polysiloxane resin comprises methyl groups and phenyl groups, and comprises a molar ratio of methyl groups to phenyl groups of 0.45 or less, the molar ratio being based on the total moles of methyl groups divided by the total moles of phenyl atoms in mol % of the monomers that form the polysiloxane resin.

[0274] Aspect 20 is the method of any one of aspects 12 to 19, wherein the polysiloxane resin comprises monomer residues of each of the following siloxane monomers: phenyl trialkoxysilane; phenyl methyl dialkoxysilane; methyl trialkoxysilane; and diphenyl dialkoxysilane.

[0275] Aspect 21 is the method of any one of aspects 12 to 20, wherein the substrate is at least one of a metal, a die cast aluminum, a porcelain enamel frit, a ceramic, a plastic, and a pre-coated substrate.

[0276] Aspect 22 is a curable composition comprising: a polysiloxane resin formed from siloxane monomer units; wherein the polysiloxane resin comprises less than 80 mol % of T siloxane monomer units based on the total moles of siloxane monomer units in the polysiloxane resin; wherein the polysiloxane resin comprises less than 1 mol % of M and Q siloxane monomer units based on the total moles of siloxane monomer units in the polysiloxane resin; a solvent; and a surfactant; wherein the surfactant comprises at least one of the following: a surfactant of Formula IIA

[0277]

[0278] wherein x is an ethylene glycol monomer, y is a propylene glycol monomer, and z is an ethylene glycol monomer; a surfactant of Formula IIB

[0279]

[0280] wherein x is a propylene glycol monomer, y is an ethylene glycol monomer, and z is a propylene glycol monomer; a surfactant of Formula III

[0281]

[0282] wherein n = 16-20; and a combination of the surfactants of Formulas IIA, IIB, and III; and wherein the weight ratio of the surfactant to the polysiloxane resin is 0.01 to 0.09 based on the total weight of the composition; and wherein the composition comprises less than 1 wt. % of any fluoro component based on the total weight of the composition.

[0283] Aspect 23 is the curable composition of aspect 22, further comprising a condensation catalyst.

[0284] Aspect 24 is the curable composition of either Aspect 22 or Aspect 23, wherein the polysiloxane resin comprises alkyl groups and aryl groups and comprises a molar ratio of alkyl groups to aryl groups of 1 or less, the molar ratio being based on the total moles of alkyl groups divided by the total moles of aryl atoms in mol % of the monomers that form the polysiloxane resin.

[0285] Aspect 25 is the curable composition of any one of claims 22 to 24, wherein the surfactant of Formula IIA is capable of having an average molecular weight of 8000 g / mol to 15,000 g / mol.

[0286] Aspect 26 is the curable composition of any one of claims 22 to 25, wherein the surfactant has a hydrophilic-lipophilic balance (HLB) of 15-27, as determined using the Griffin method or the Davies method.

[0287] Aspect 27 is the curable composition of any one of claims 22 to 26, wherein the solvent comprises a first solvent comprising at least one of xylene, butanol, toluene, methyl ethyl ketone, methyl isobutyl ketone, acetone, butyl acetate, dipropylene glycol monomethyl ether, and a second solvent comprising water.

[0288] Aspect 28 is the curable composition of any one of claims 22 to 27, wherein the curable composition is dilutable in water.

[0289] Aspect 29 is the curable composition of any one of claims 22 to 28, wherein the polysiloxane resin further comprises: a molar ratio of the sum of alkyl and aryl groups to Si of 1.1 to 1.4; a molar ratio of methyl to phenyl groups of 0.4 to 1.

[0290] Aspect 30 is the curable composition of any one of claims 22 to 29, further comprising a second surfactant of Formula IIA, wherein at least one of the ratio of x to y or z to y of the second surfactant is 0.1:1 to 3:1.

[0291] Aspect 31 is an article coated with the coating composition of any one of Aspects 22 to 30.

[0292] Aspect 32 is the article of Aspect 31, wherein the article is at least one of a metal, a die cast aluminum, a porcelain enamel frit, a ceramic, a plastic, and a pre-coated article.

[0293] Aspect 33 is a method of coating a substrate, the method comprising: applying a coating composition to a substrate, the coating composition comprising: a polysiloxane resin formed from siloxane monomer units and having the following formula: R n SiO((4-n) / 2), wherein R is an alkyl or aryl group; wherein the polysiloxane resin comprises less than 80 mol % of T siloxane monomer units based on the total moles of siloxane monomer units in the polysiloxane resin; wherein the polysiloxane resin comprises less than 1 mol % of M and Q siloxane monomer units based on the total moles of siloxane monomer units in the polysiloxane resin; a solvent; and a surfactant; wherein the surfactant comprises at least one of: a surfactant of Formula IIA

[0294]

[0295] wherein x is an ethylene glycol monomer, y is a propylene glycol monomer, and z is an ethylene glycol monomer; a surfactant of Formula IIB

[0296]

[0297] wherein x is a propylene glycol monomer, y is an ethylene glycol monomer, and z is a propylene glycol monomer; a surfactant of Formula III

[0298]

[0299] wherein n = 16-20; and a combination of surfactants of Formulas IIA, IIB, and III; and wherein, based on the total weight of the coating composition, the weight ratio of the surfactant to the polysiloxane resin is 0.01 to 0.09; and curing the coating composition.

[0300] Aspect 34 is the method of Aspect 33, wherein the coating composition further comprises a condensation catalyst.

[0301] Aspect 35 is the method of Aspect 33 or Aspect 34, wherein the coating composition is diluted with water prior to applying the coating composition to the substrate.

[0302] Aspect 36 is the method of any one of Aspects 33-35, wherein the surfactant has an average molecular weight of 8000 g / mol to 15,000 g / mol and a hydrophilic-lipophilic balance (HLB) of greater than 10 as determined using the Griffin method or the Davies method.

[0303] Aspect 37 is the method of any one of aspects 33-36, wherein the polysiloxane resin further comprises: a ratio of alkyl groups to Si of 1.1 to 1.4; a ratio of methyl groups to phenyl groups of 0.4 to 1.

[0304] Aspect 38 is the method of any one of aspects 33-37, wherein the substrate is at least one of a metal, a die cast aluminum, an enamel frit, a ceramic, a plastic, or a pre-coated substrate.

[0305] Aspect 39 is a polysiloxane resin formed from siloxane monomer units: [R 1 Si(O) 3 / 2 ] x ; [R 2 R 3 Si(O)] y ; [R 4 Si(O) 3 / 2 ] z ; wherein: x is any integer from 1 to 50; y is any integer from 1 to 20; z is any integer from 1 to 50; R 1 is a C1-C 30 linear or C3-C 30 cyclic alkyl group; R 2 and R 3 are each independently a C1-C 30 linear or C3-C 30 cyclic alkyl group, or a C6 or C7 aryl group; and R 4 is a C6 or C7 aryl group; wherein the polysiloxane resin comprises less than 80 mol % of T siloxane monomer units based on the total moles of siloxane monomer units in the polysiloxane resin; wherein the polysiloxane resin comprises less than 1 mol % of M and Q siloxane monomer units based on the total moles of siloxane monomer units in the polysiloxane resin.

[0306] Aspect 40 is the polysiloxane resin of aspect 39, wherein the polysiloxane resin comprises aryl groups and includes a molar ratio of aryl groups to silicon atoms of 0.8 or greater, the molar ratio based on the total moles of aryl groups in mol % of the monomers forming the polysiloxane resin divided by the total moles of silicon atoms.

[0307] Aspect 41 is the polysiloxane resin of aspect 39 or aspect 40, wherein the polysiloxane resin comprises phenyl groups and includes a molar ratio of phenyl groups to silicon atoms of 0.8 or greater, the molar ratio based on the total moles of phenyl groups in mol % of the monomers forming the polysiloxane resin divided by the total moles of silicon atoms.

[0308] Aspect 42 is the polysiloxane resin of any one of Aspects 39-41, wherein the polysiloxane resin comprises phenyl groups, and further wherein: the molar amount of component [R 4 Si(O)3 / 2]z is greater than 60 mol %; and the molar amount of component [R 2 Si(O)]y is 5 mol % to 30 mol %. 3 Si(O)]y is 5 mol % to 30 mol %.

[0309] Aspect 43 is the polysiloxane resin of any one of Aspects 39 to 42, wherein the polysiloxane resin comprises phenyl groups, and further wherein: the molar amount of component [R 4 Si(O)3 / 2]z is greater than 65 %; and the molar amount of component [R 2 Si(O)]y is 5 % to 10 %. 3 Si(O)]y is 5 % to 10 %.

[0310] Aspect 44 is the polysiloxane resin of any one of Aspects 39 to 43, wherein the polysiloxane resin comprises alkyl groups and aryl groups and comprises a molar ratio of alkyl groups to aryl groups of 0.45 or less, the molar ratio being based on the total moles of alkyl groups divided by the total moles of aryl atoms in mol % of monomers forming the polysiloxane resin.

[0311] Aspect 45 is the polysiloxane resin of any one of Aspects 39 to 44, wherein the polysiloxane resin comprises methyl groups and phenyl groups and comprises a molar ratio of methyl groups to phenyl groups of 0.45 or less, the molar ratio being based on the total moles of methyl groups divided by the total moles of phenyl atoms in mol % of monomers forming the polysiloxane resin.

[0312] Aspect 46 is the polysiloxane resin of any one of Aspects 39 to 45, wherein the polysiloxane resin comprises monomer residues of each of the following siloxane monomers: a phenyl trialkoxysilane; a phenyl methyl dialkoxysilane; a methyl trialkoxysilane; and a diphenyl dialkoxysilane.

[0313] Aspect 47 is the polysiloxane resin of any one of Aspects 39 to 46, wherein the polysiloxane resin further comprises a solvent in an amount of 5-35 wt. % based on the total weight of the polysiloxane resin.

Claims

1. A curable coating composition comprising: a polysiloxane resin formed from siloxane monomers: [R 1 Si(O) 3 / 2 ] x ; [R 2 R 3 Si(O)] y ; and [R 4 Si(O) 3 / 2 ] z ; wherein: x is any integer from 1 to 50; y is any integer from 1 to 20; z is any integer from 1 to 50; R 1 is C1-C 30 linear or C3-C 30 cyclic alkyl group; R 2 and R 3 each independently is a C1-C 30 linear or C3-C 30 cyclic alkyl group, or a C6or C7aryl group; R 4 is a C6or C7aryl group; and a solvent; wherein the composition comprises less than 5 wt.% of any fluorine-containing component, based on the total weight of the composition.

2. The composition of claim 1, further comprising a condensation catalyst.

3. The composition of claim 1 or claim 2, wherein the polysiloxane resin comprises aryl groups and includes a molar ratio of aryl groups to silicon atoms of 0.8 or greater, the molar ratio being based on the total moles of aryl groups in mol % of the monomers forming the polysiloxane resin divided by the total moles of silicon atoms.

4. The composition of any one of claims 1 to 3, wherein the polysiloxane resin comprises phenyl groups and includes a molar ratio of phenyl groups to silicon atoms of 0.8 or greater, the molar ratio being based on the total moles of phenyl groups in mol % of the monomers forming the polysiloxane resin divided by the total moles of silicon atoms.

5. The composition of any one of claims 1 to 4, wherein the polysiloxane resin comprises phenyl groups, and further wherein: based on the mol % of the monomers forming the polysiloxane resin, the monomer [R 4 Si(O) 3 / 2 ] z is greater than 60 mol%; and component [R] is present in an amount of 5 to 30 mol% based on the total molar mass of the polysiloxane resin. 2 R 3 Si(O)] y 5 to 30 mol%.

6. The composition of any one of claims 1 to 5, wherein the polysiloxane resin comprises phenyl groups, and further wherein: based on the total molar mass of the polysiloxane resin, component [R 4 Si(O) 3 / 2 ] z is greater than 65 %; and component [R] is present in an amount of 5 % to 10 % based on the total molar mass of the polysiloxane resin. 2 R 3 Si(O)] y 5 % to 10 %.

7. The composition of any one of claims 1 to 6, wherein the polysiloxane resin comprises alkyl groups and aryl groups and includes a molar ratio of alkyl groups to aryl groups of 0.45 or less, the molar ratio being based on the total moles of alkyl groups in mol % of the monomers forming the polysiloxane resin divided by the total moles of aryl atoms.

8. The composition of any one of claims 1 to 7, wherein the polysiloxane resin comprises methyl groups and phenyl groups and includes a molar ratio of methyl groups to phenyl groups of 0.45 or less, the molar ratio being based on the total moles of methyl groups in mol % of the monomers forming the polysiloxane resin divided by the total moles of phenyl atoms.

9. The composition of any one of claims 1 to 8, wherein the polysiloxane resin comprises monomeric residues of each of the following siloxane monomers: phenyl trialkoxysilane; phenyl methyl dialkoxysilane; methyl trialkoxysilane; and diphenyl dialkoxysilane.

10. An article coated with the coating composition of any one of claims 1 to 9.

11. The article of claim 10, wherein the article is at least one of a metal, a die cast aluminum, a porcelain enamel frit, a ceramic, a plastic, and a pre-coated article.

12. A method of coating a substrate, the method comprising: applying a coating composition to a substrate, the coating composition comprising: a polysiloxane resin formed from siloxane monomers: [R 1 Si(O) 3 / 2 ] x ; [R 2 R 3 Si(O)] y ; and [R 4 Si(O) 3 / 2 ] z ; wherein: x is any integer from 1 to 50; y is any integer from 1 to 20; z is any integer from 1 to 50; R 1 is C1-C 30 linear or C3-C 30 cyclic alkyl group; R 2 and R 3 each independently is a C1-C 30 linear or C3-C 30 cyclic alkyl group, or a C6or C7aryl group; R 4 is a C6or C7aryl group; and a solvent; wherein the composition comprises less than 5 wt. % of any fluoro-containing component, based on the total weight of the composition; and curing the coating composition.

13. The method of claim 12, wherein the coating composition further comprises a condensation catalyst.

14. The method of claim 12 or claim 13, wherein the polysiloxane resin comprises aryl groups and comprises a molar ratio of aryl groups to silicon atoms of 0.8 or greater, the molar ratio being based on the total moles of aryl groups to the total moles of silicon atoms in mol % of the monomers forming the polysiloxane resin.

15. The method of any one of claims 12 to 14, wherein the polysiloxane resin comprises phenyl groups and comprises a molar ratio of phenyl groups to silicon atoms of 0.8 or greater, the molar ratio being based on the total moles of phenyl groups to the total moles of silicon atoms in mol % of the monomers forming the polysiloxane resin.

16. The method of any one of claims 12 to 15, wherein the polysiloxane resin comprises phenyl groups, and further wherein: based on the total molar mass of the polysiloxane resin, component [R 4 Si(O) 3 / 2 ] z is greater than 60 mol %; and component [R 2 R 3 Si(O)] y 5 mol % to 10 mol % based on the total molar mass of the polysiloxane resin.

17. The method of any one of claims 12 to 16, wherein the polysiloxane resin comprises phenyl groups, and further wherein: component [R 4 Si(O) 3 / 2 ] z of greater than 65 %; and component [R] is present in an amount of 5 to 10 % by mole, based on the total molar mass of the polysiloxane resin. 2 R 3 Si(O)] y 5 to 10 % by mole.

18. The method of any one of claims 12 to 19, wherein the polysiloxane resin comprises alkyl groups and aryl groups and comprises a molar ratio of alkyl groups to aryl groups of 0.45 or less, the molar ratio being based on the total moles of alkyl groups to the total moles of aryl atoms in mol % of the monomers forming the polysiloxane resin.

19. The method of any one of claims 12 to 18, wherein the polysiloxane resin comprises methyl groups and phenyl groups and comprises a molar ratio of methyl groups to phenyl groups of 0.45 or less, the molar ratio being based on the total moles of methyl groups to the total moles of phenyl atoms in mol % of the monomers forming the polysiloxane resin.

20. The method of any one of claims 12 to 19, wherein the polysiloxane resin comprises a monomeric residue of each of the following siloxane monomers: phenyl trialkoxysilane; phenyl methyl dialkoxysilane; methyl trialkoxysilane; and diphenyl dialkoxysilane.

21. The method of any one of claims 12 to 20, wherein the substrate is at least one of a metal, a die cast aluminum, a porcelain enamel frit, a ceramic, a plastic, and a pre-coated substrate.

22. A curable composition comprising: a polysiloxane resin formed from siloxane monomer units; wherein the polysiloxane resin comprises less than 80 mol % of T siloxane monomer units, based on the total moles of siloxane monomer units in the polysiloxane resin; wherein the polysiloxane resin comprises less than 1 mol % of M and Q siloxane monomer units, based on the total moles of siloxane monomer units in the polysiloxane resin; a solvent; and a surfactant; wherein the surfactant comprises at least one of: a surfactant of Formula IIA wherein x is an ethylene glycol monomer, y is a propylene glycol monomer, and z is an ethylene glycol monomer; a surfactant of Formula IIB wherein x is a propylene glycol monomer, y is an ethylene glycol monomer, and z is a propylene glycol monomer; a surfactant of Formula III wherein n = 16-20; and a combination of surfactants of Formulas IIA, IIB, and III; and wherein the weight ratio of the surfactant to the polysiloxane resin is 0.01 to 0.09 based on the total weight of the composition; and wherein the composition comprises less than 1 wt.% of any fluorochemical component based on the total weight of the composition.

23. The curable composition of claim 22, further comprising a condensation catalyst.

24. The curable composition of claim 22 or claim 23, wherein the polysiloxane resin comprises alkyl groups and aryl groups and comprises a molar ratio of alkyl groups to aryl groups of 1 or less, the molar ratio being based on the total moles of alkyl groups divided by the total moles of aryl atoms in mol % of the monomers that form the polysiloxane resin.

25. The curable composition of any one of claims 22 to 24, wherein the surfactant of Formula IIA can have an average molecular weight of 8000 g / mol to 15,000 g / mol.

26. The curable composition of any one of claims 22 to 25, wherein the surfactant has a hydrophilic-lipophilic balance (HLB) of 15 to 27 as determined using the Griffin method or the Davies method.

27. The curable composition of any one of claims 22 to 26, wherein the solvent comprises a first solvent comprising at least one of xylene, butanol, toluene, methyl ethyl ketone, methyl isobutyl ketone, acetone, butyl acetate, dipropylene glycol monomethyl ether, and a second solvent comprising water.

28. The curable composition of any one of claims 22 to 27, wherein the curable composition is dilutable in water.

29. The curable composition of any one of claims 22 to 28, wherein the polysiloxane resin further comprises:

30. The curable composition of any one of claims 22 to 29, further comprising a second surfactant of Formula IIA, wherein at least one of the ratio of x to y or z to y of the second surfactant is 0.1:1 to 3:

1.

31. An article coated with a coating composition of any one of claims 22 to 30.

32. The article of claim 31, wherein the article is at least one of a metal, a die cast aluminum, a porcelain enamel frit, a ceramic, a plastic, and a pre-coated article.

33. A method of coating a substrate, the method comprising: applying a coating composition to a substrate, the coating composition comprising: polysiloxane resins formed from siloxane monomer units and having the following formula: R n SiO((4-n) / 2), wherein R is an alkyl or aryl group; wherein the polysiloxane resin comprises less than 80 mol % of T siloxane monomer units based on the total moles of siloxane monomer units in the polysiloxane resin; and wherein the polysiloxane resin comprises less than 1 mol % of M and Q siloxane monomer units based on the total moles of siloxane monomer units in the polysiloxane resin; a solvent; and a surfactant; wherein the surfactant comprises at least one of: a surfactant of Formula IIA wherein x is an ethylene glycol monomer, y is a propylene glycol monomer, and z is an ethylene glycol monomer; a surfactant of Formula IIB wherein x is a propylene glycol monomer, y is an ethylene glycol monomer, and z is a propylene glycol monomer; a surfactant of Formula III wherein n = 16-20; and a combination of surfactants of Formulas IIA, IIB, and III; and wherein the weight ratio of the surfactant to the polysiloxane resin is 0.01 to 0.09 based on the total weight of the coating composition; and curing the coating composition.

34. The method of claim 33, wherein the coating composition further comprises a condensation catalyst.

35. The method of claim 33 or claim 34, wherein the coating composition is diluted with water prior to applying the coating composition to the substrate.

36. The method of any one of claims 33 to 35, wherein the surfactant has an average molecular weight of 8000 g / mol to 15,000 g / mol and a hydrophilic-lipophilic balance (HLB) of greater than 10 as determined using the Griffin method or the Davies method.

37. The method of any one of claims 33 to 36, wherein the polysiloxane resin further comprises:

38. The method of any one of claims 33 to 37, wherein the substrate is at least one of a metal, a die cast aluminum, a porcelain enamel frit, a ceramic, a plastic, or a pre-coated substrate.

39. A polysiloxane resin formed from siloxane monomer units: [R 1 Si(O) 3 / 2 ] x ; [R 2 R 3 Si(O)] y ; [R 4 Si(O) 3 / 2 ] z ; wherein: x is any integer from 1 to 50; y is any integer from 1 to 20; z is any integer from 1 to 50; R 1 is C1-C 30 linear or C3-C 30 cyclic alkyl group; R 2 and R 3 each independently is a C1-C 30 linear or C3-C 30 cyclic alkyl group, or a C6or C7aryl group; and R 4 is a C6or C7aryl group; wherein the polysiloxane resin comprises less than 80 mol % of T siloxane monomer units based on the total moles of siloxane monomer units in the polysiloxane resin; wherein the polysiloxane resin comprises less than 1 mol % of M and Q siloxane monomer units based on the total moles of siloxane monomer units in the polysiloxane resin.

40. The polysiloxane resin of claim 39, wherein the polysiloxane resin comprises aryl groups and comprises a molar ratio of aryl groups to silicon atoms of 0.8 or greater, based on the total moles of aryl groups in mol % of the monomers forming the polysiloxane resin divided by the total moles of silicon atoms.

41. The polysiloxane resin of claim 39 or claim 40, wherein the polysiloxane resin comprises phenyl groups and comprises a molar ratio of phenyl groups to silicon atoms of 0.8 or greater, based on the total moles of phenyl groups in mol % of the monomers forming the polysiloxane resin divided by the total moles of silicon atoms.

42. The polysiloxane resin of any one of claims 39 to 41, wherein the polysiloxane resin comprises phenyl groups, and further wherein: the molar amount of monomers [R 4 Si(O)3 / 2]z is greater than 60 mol %; and component [R 2 R 3 a molar amount of 5 mol % to 30 mol % of Si(O)]y.

43. The polysiloxane resin of any one of claims 39 to 42, wherein the polysiloxane resin comprises phenyl groups, and further wherein: component [R 4 a molar amount of Si(O)3 / 2]z greater than 65 %; and component [R] is present in an amount of 5 to 10 % by moles based on the total moles of the polysiloxane resin. 2 R 3 the molar amount of Si(O)]y is 5 % to 10 %.

44. The polysiloxane resin of any one of claims 39 to 43, wherein the polysiloxane resin comprises alkyl groups and aryl groups, and comprises a molar ratio of alkyl groups to aryl groups of 0.45 or less, the molar ratio being based on the total moles of alkyl groups to the total moles of aryl atoms in mol % of the monomers forming the polysiloxane resin.

45. The polysiloxane resin of any one of claims 39 to 44, wherein the polysiloxane resin comprises methyl groups and phenyl groups, and comprises a molar ratio of methyl groups to phenyl groups of 0.45 or less, the molar ratio being based on the total moles of methyl groups to the total moles of phenyl atoms in mol % of the monomers forming the polysiloxane resin.

46. The polysiloxane resin of any one of claims 39 to 45, wherein the polysiloxane resin comprises a monomeric residue of each of the following siloxane monomers: phenyl trialkoxysilane; phenyl methyl dialkoxysilane; methyl trialkoxysilane; and diphenyl dialkoxysilane.

47. The polysiloxane resin of any one of claims 39 to 46, wherein the polysiloxane resin further comprises a solvent in an amount of 5 to 35 wt. %, based on the total weight of the polysiloxane resin.

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