Emulsions of alkoxy-functionalized silsesquioxane resins, and processes for their preparation and use.

Abstract

Alkoxy-functionalized silsesquioxane resins and hydrosilylation reaction processes for their preparation are provided. The alkoxy-functionalized silsesquioxane resins are liquid under ambient conditions and are useful in solvent-based, solvent-free, and aqueous curable compositions.

Description

[Technical Field]

[0001] (Cross-reference of related applications) This application claims the interests of U.S. Provisional Patent Application No. 63 / 453,265, filed on March 20, 2023, pursuant to Section 119(e) of the U.S. Patent Act. U.S. Provisional Patent Application No. 63 / 453,265 is incorporated herein by reference.

[0002] (Field of invention) The present invention relates to an emulsion containing an alkoxy-functionalized silsesquioxane resin, and to a process for preparing and using the emulsion. More specifically, the emulsion can be used in coating applications such as paints. [Background technology]

[0003] The coatings and paints industry faces pressure to reduce the use of volatile organic compounds (VOCs) for more environmentally friendly solutions. Therefore, solvent-free liquid products and water-borne (WB) products are desirable to leverage the advantages of silicone resins in high-performance applications. For example, U.S. Patent No. 11,248,119 by DiGiovanni et al. discloses emulsions, compositions containing them, films formed using them, and related methods. While aqueous systems, such as water-borne silicone resin emulsions, are a logical choice for reducing VOC use, aqueous silicone resin emulsions have several significant drawbacks that need to be addressed. Replacing solvent-borne (SB) formulations with WB substitutes is challenging due to the different film-forming processes. For SB products, solvent evaporation and film formation occur efficiently, which explains the relatively fast "curing time" of SB products. In the case of WB dispersions, water evaporation and silicone resin bonding are required before curing, which undesirably increases the curing time and therefore reduces productivity. Subsequent curing occurs by hydrolysis and condensation, similar to SB-type resins. Solvent-free liquid silicone resins typically require the use of glass transition resins that operate at inherently lower temperatures, resulting in slower curing times, which is undesirable for the coating performance of the final product.

[0004] Therefore, there is an industry need to improve the curing of siloxane resins delivered in emulsion form. [Overview of the project]

[0005] The emulsion comprises an alkoxy-functionalized silsesquioxane resin, water, and a surfactant. Processes for preparing and using the emulsion are also provided. This emulsion is suitable for coating applications such as paints. [Modes for carrying out the invention]

[0006] The emulsion introduced above contains a discontinuous phase dispersed in a continuous phase. The emulsion contains a non-aqueous (silicone) phase, which is typically the discontinuous phase of the emulsion (however, it may alternatively be the continuous phase). The non-aqueous phase contains an alkoxy-functionalized silsesquioxane resin. The emulsion further contains an aqueous phase, which is typically the continuous phase of the emulsion (however, it may be the discontinuous phase if the non-aqueous phase is the continuous phase).

[0007] The alkoxy-functionalized silsesquioxane resin has the unit formula: (R 2 3SiO 1 / 2 ) c (R 2 2SiO 2 / 2 ) d (R 2 SiO 3 / 2 ) e (ZO 1 / 2 ) f (HO 1 / 2 ) g and in the formula, each R 2 is independently selected from the group consisting of an alkyl group and a group of formula (I)

[0008]

Chemical formula

[0009] In the above unit formula, the subscripts c, d, and e represent the molar fractions of each unit in the alkoxy-functional silsesquioxane resin. The amount (c + d + e) = 1. The subscripts c, d, and e have values such that 0 ≦ c ≦ 0.25, 0 ≦ d ≦ 0.20, and 0.55 < e ≦ 1. The subscript c may be 0, or may be greater than 0, or at least 0.100, or at least 0.101, or at least 0.102, or at least 0.110, or at least 0.120, or at least 0.130. On the one hand, at the same time, the subscript c may be at most 0.300, or at most 0.250, or at most 0.240, or at most 0.200, or at most 0.150, or at most 0.110. The subscript c may be from 0 to 0.300, or from 0 to 0.250, or from 0.100 to 0.240, or from 0.102 to 0.240.

[0010] The subscript d may be 0, or greater than 0, or at least 0.001, or at least 0.002, or at least 0.003, or at least 0.004, or at least 0.005, or at least 0.006, while at the same time, the subscript d may be up to 0.020, or up to 0.015, or up to 0.010, or up to 0.009, or up to 0.008, or up to 0.007, or up to 0.006. Alternatively, the subscript d may be between 0 and 0.020, or greater than 0 and up to 0.015, or between 0.006 and 0.010.

[0011] The subscript e is greater than 0.55 and up to 1. Alternatively, the subscript e may be at least 0.550, or at least 0.600, or at least 0.650, or at least 0.700, or at least 0.750, or at least 0.800, while at the same time, the subscript e may be at most 1, or at most 0.995, or at most 0.991, or at most 0.95, or at most 0.925, or at most 0.920, or at most 0.915, or at most 0.910, or at most 0.905, or at most 0.0900. Alternatively, the subscript e may be between 0.905 and 1, or between 0.910 and 1, or between 0.915 and 1, or between 0.990 and 1, or between 0.991 and 1, or between 0.995 and 1, or the subscript e may be 1.

[0012] In the above unit formula, each Z is an independently selected alkyl group. Suitable alkyl groups may be cyclic or acyclic, branched or unbranched, or a combination thereof. Examples of alkyl groups, though not limited to them, include methyl, ethyl, propyl (e.g., isopropyl and / or n-propyl), butyl (e.g., isobutyl, n-butyl, tert-butyl, and / or sec-butyl), pentyl (e.g., isopentyl, neopentyl, tert-pentyl, and / or cyclopentyl), hexyl (e.g., cyclohexyl or n-hexyl), heptyl, octyl, nonyl, and decyl, as well as branched alkyl groups with six or more carbon atoms. Alternatively, each Z may be an alkyl group with one to four carbon atoms, or one to two carbon atoms. Each Z may be methyl or ethyl, or it may be methyl.

[0013] Unit (HO 1 / 2 ) and (ZO 1 / 2 ) represent a hydroxyl group and an alkoxy group bonded to a silicon atom in the resin, respectively (for example, the hydroxyl group and the alkoxy group are graft-bonded R in formula (I) 2 (The part of the molecule other than the group, bonded to the silicon atom in the resin portion of the alkoxy-functionalized silsesquioxane resin). Although we do not wish to be bound by theory, the hydroxyl group and / or alkoxy group in the formula (R) of the alkoxy-functionalized silsesquioxane resin. 2 3SiO 1 / 2 ) Monofunctional unit, formula (R 2 2SiO 2 / 2 The two functional units of ) and formula (R 2 SiO 3 / 2 It can bond to one or more silicon atoms in the three functional units of ).

[0014] In the above unit formula, each alkyl group R 2 R is independently selected and may be one of the alkyl groups mentioned above for Z. Alternatively, 2 Each alkyl group may be methyl. However, at least some groups R 2It has formula (I) (for example, the result of a hydrosilylation reaction in the method described below). In the unit formula, all R 2 5 mol% to 25 mol% of the group may have formula (I), while all R 2 The residue up to 100% of the group is alkyl. Or, all R 2 At least 5 mol%, or at least 6 mol%, or at least 8 mol%, or at least 9 mol%, or at least 10 mol%, or at least 13 mol%, or at least 14 mol%, or at least 15 mol%, of the group has formula (I), while at the same time, all R 2 Up to 25 mol%, or up to 23 mol%, or up to 20 mol%, or up to 15 mol%, or up to 14 mol%, or up to 13 mol%, or up to 12 mol%, of the group has formula (I). Or, R having formula (I) 2 The amount of the group may be 5 mol% to 25 mol%, 5 mol% to 23 mol%, or 6 mol% to 15 mol%.

[0015] In the above unit formula, the subscript f represents the molar amount of alkoxy groups in the resin, and the subscript g represents the molar amount of hydroxyl groups in the resin. The subscripts f and g have values ​​such that 0.01 ≤ f ≤ 0.70, 0 ≤ g ≤ 0.05, and 0.02 ≤ (f + g) ≤ 0.75. Alternatively, the subscript f may have a value of at least 0.01, or at least 0.10, or at least 0.20, or at least 0.30, while at the same time having a value of up to 0.70, or up to 0.60, or up to 0.56, or up to 0.52. Alternatively, the subscript f may have a value such that 0.10 ≤ f ≤ 0.60, or 0.30 ≤ f ≤ 0.60, or 0.37 ≤ f ≤ 0.56, or 0.37 ≤ f ≤ 0.44. Alternatively, the subscript g may have a value of at least 0.005, or at least 0.008, or at least 0.01, while at the same time having a value of at most 0.05, or at most 0.049, or at most 0.045, or at most 0.040, or at most 0.035. Alternatively, the subscript g may have a value such that 0.005 ≤ g ≤ 0.05, or 0.006 ≤ g ≤ 0.049, or 0.006 ≤ g ≤ 0.035, or 0.008 ≤ g ≤ 0.05. Alternatively, the quantity (f+g) may be at least 0.02, or at least 0.20, or at least 0.30, or at least 0.40, or at least 0.41, or at least 0.43, or at least 0.45, while at the same time, the quantity (f+g) may be at most 0.57, or at most 0.52, or at most 0.49, or at most 0.47, or at most 0.45. Alternatively, the quantity (f+g) may have a value such that 0.02≦(f+g)≦0.57, or 0.20≦(f+g)≦0.57, or 0.30≦(f+g)≦0.57, or 0.40≦(f+g)≦0.57, or 0.43≦(f+g)≦0.52, or 0.40≦(f+g)≦0.49.

[0016] In the basis of equation (I) above, the subscripts a, b, and x each represent an integer. Subscript a is 1 or 2, or subscript a may be 1. Subscript b is 0 or 1, or subscript b may be 0, or subscript b may be 1. Subscript x is 0 or 1, or subscript x may be 0.

[0017] In the base of formula (I) above, each alkyl group R 1 These are independently selected and may be the alkyl groups described above for Z. Alternatively, each R 1 It may also be methyl.

[0018] Under equation (I) above, each D 1 D is an independently selected alkylene group. 1 This is empirical formula -C h H 2h - may have, and the subscript h is at least 2, or 2-12, or 2-10, or 2-8, or 2-6, or 2-4, or 2-3. Or each D 1 This may be ethylene, propylene, butylene, or hexylene. Alternatively, each D 1 This could be -C2H4-, for example, ethylene.

[0019] Alkoxy-functionalized silsesquioxane resins are based on the formula (SiO 4 / 2The alkoxy-functional silsesquioxane resin may or may not contain the tetrafunctional siloxane units. The alkoxy-functional silsesquioxane resin is in a liquid state at RT and ambient pressure (e.g., 101.325 kPa) (e.g., by visual inspection). Alternatively, the alkoxy-functional silsesquioxane resin may have Mn in the range of 1,300 g / mol to 4,000 g / mol, or 1,400 g / mol to 3,500 g / mol, or 2,000 g / mol to 2,500 g / mol. Alternatively, the alkoxy-functionalized silsesquioxane resin may have an Mw of 1,000 g / mol to 50,000 g / mol, or 2,000 g / mol to 50,000 g / mol, or 2,500 g / mol to 40,000 g / mol, or 4,000 to 10,000 g / mol, or 1,000 g / mol to 15,000 g / mol, and a PDI of 2 to 4, or 2.3 to 3.9.

[0020] The alkoxy-functional silsesquioxane resin described above may be prepared by a hydrosilylation reaction process. This process involves 1) combining starting materials, A) an alkoxy-functional organosilicon compound and B) a silsesquioxane resin, under conditions for hydrosilylation, in the presence of C) a hydrosilylation catalyst. A solvent D) may be optionally used to facilitate the mixing and / or transfer of one or more of the starting materials. For example, C) the hydrosilylation catalyst may be dissolved or dispersed in solvent D) before being combined with starting materials A) and B). Starting material A) the alkoxy-functional organosilicon compound may contain silicon-bonded hydrogen atoms if B) the silsesquioxane resin contains silicon-bonded aliphatic unsaturated groups. Alternatively, A) the alkoxy-functional organosilicon compound may contain aliphatic unsaturated groups if B) the silsesquioxane resin contains silicon-bonded hydrogen atoms.

[0021] The starting material C) is a hydrosilylation catalyst. The hydrosilylation catalyst contains a platinum group metal. The platinum group metal may be selected from the group consisting of platinum, rhodium, ruthenium, palladium, osmium, and iridium. Alternatively, the platinum group metal may be platinum. The hydrosilylation catalyst may be a platinum group metal or a compound or complex of a platinum group metal. For example, the hydrosilylation catalyst may be a rhodium diphosphine chelate such as chloride tris(triphenylphosphane)rhodium(I) (Wilkinson catalyst), [1,2-bis(diphenylphosphino)ethane]dichlorodirhodium or [1,2-bis(diethylphosphino)ethane]dichlorodirhodium, chloroplatinic acid (Speier catalyst), chloroplatinic acid hexahydrate, platinum dichloride, or a complex of such a compound with an alkenyl-functional organopolysiloxane, such as a 1,3-diethenyl-1,1,3,3-tetramethyldisiloxane complex with platinum (Karstedt catalyst), or a Pt(0) complex in tetramethyltetravinylcyclotetrasiloxane (Ashby catalyst). Alternatively, the compound or complex may be microencapsulated in a matrix or core-shell structure. Hydrosilylation catalysts are known in the art, for example, as described in International Publication No. 2021 / 081822 to Guo, et al. and the references cited therein. Hydrosilylation catalysts are commercially available, for example, SYL-OFF® 4000 Catalyst and SYL-OFF® 2700 are available from Dow. C) The amount of hydrosilylation catalyst depends on various factors, including the type and amount of starting materials A) and B), and the respective content of silicon-bonded hydrogen atoms and aliphatic unsaturated groups, but C) the amount of hydrosilylation catalyst is sufficient to catalyze the hydrosilylation reaction, for example, to provide at least 1 ppm of platinum group metal based on the combined weight of starting materials A), B), and C), while at the same time, the amount may be sufficient to provide up to 6,000 ppm of platinum group metal on the same basis.Alternatively, the amount of starting material C) may be sufficient to provide platinum group metals in the same range, such as 1 ppm to 1,000 ppm, 1 ppm to 100 ppm, 1 ppm to 50 ppm, 1 ppm to 25 ppm, or 1 ppm to 15 ppm.

[0022] Starting material D) is an optional solvent that can be used to transport one or more of the starting materials. The solvent may be added to facilitate the introduction of certain starting materials, such as C) a hydrosilylation catalyst. The solvents that can be used herein are those that help to fluidize the starting materials but do not react with them in nature. The solvent may be selected based on the solubility of the starting materials and the volatility of the solvent. Solubility means that the solvent is sufficient to dissolve and / or disperse the starting materials. Volatility means the vapor pressure of the solvent.

[0023] Suitable solvents include polyorganosiloxanes with suitable vapor pressures, such as hexamethyldisiloxane, octamethyltrisiloxane, hexamethylcyclotrisiloxane, and other low molecular weight polyorganosiloxanes, such as polydimethylsiloxane, for example, DOWSIL® 200 Fluids and DOWSIL® OS Fluids (commercially available from Dow) with a vapor pressure of 0.5 to 1.5 cSt.

[0024] Alternatively, the solvent may include an organic solvent. The organic solvent may be an alcohol such as methanol, ethanol, isopropanol, butanol, or n-propanol; an aromatic hydrocarbon such as benzene, toluene, ethylbenzene, or xylene; an aliphatic hydrocarbon such as heptane, hexane, or octane; a halogenated hydrocarbon such as dichloromethane, 1,1,1-trichloroethane, or methylene chloride; or a combination thereof.

[0025] D) The amount of solvent varies depending on various factors, including the type of solvent selected, as well as the amount and type of other starting materials selected for the composition. However, the amount of solvent may range from 1% to 99% by weight, or from 2% to 90% by weight, based on the combined weight of starting materials A), B), and C).

[0026] The hydrosilylation reaction process can be carried out by any convenient means, such as combining starting materials A), B), and C), and D) if present. Typically, starting materials A) and B) are combined in a reactor. When the reaction is carried out at high or low temperatures, as described below, the reactor may be heated or cooled in any preferred manner, for example, via a jacket, mantle, exchanger, bath, or coil. Starting materials A), B), and C), and optionally D), may be supplied together or separately in a vessel, or arranged in the vessel in any order of addition and in any combination. For example, starting materials A) and C), and optionally D), may be added to the reactor, and starting material B), may be added to it in one aliquot, or starting material B), may be metered into the reactor continuously or intermittently in two or more aliquots. Alternatively, starting materials B) and C), and optionally D), may be added to the reactor, and starting material A) may be added to it in one aliquot, or starting material A) may be metered into the reactor continuously or intermittently in two or more aliquots. The order of addition may vary depending on various factors, including which starting materials have silicon-bonded hydrogen atoms.

[0027] Alternatively, the starting materials A), B), and optionally D) may first be combined before addition, or added sequentially to the container, after which starting material C) may be added to the container containing starting materials A), B), and optionally D). Generally, the term "reaction mixture" as used herein generally refers to a mixture containing starting materials A), B), and C), and optionally D) (for example, one obtained by combining the starting materials as described above).

[0028] The amounts of starting materials A) and B) are not limited and may be any amount sufficient to provide the content of the group of formula (I) in the alkoxy-functionalized silsesquioxane resin described above.

[0029] Step 1 of the process may further include stirring the reaction mixture. Stirring can enhance the mixing and contact of the starting materials A), B), and C), and D), if present, when combined in the reaction mixture. Such contact can also be carried out independently, with stirring (e.g., in parallel or sequentially), or without stirring (i.e., independently or instead), using other conditions. Other conditions may be adjusted to enhance the contact of starting materials A) and B) for the formation of a reaction product containing an organosilicon compound, and thus enhance the reaction (i.e., isomerization and hydrosilylation).

[0030] Step 1 of the process may further include heating the reaction mixture. The temperature may be between 50°C and 150°C, or between 60°C and 100°C, although this depends on various factors including the vapor pressures of the starting materials A) and B), and D) if present.

[0031] The processes described herein may optionally further include one or more additional steps. For example, the process may further include step 2) purifying the hydrosilylation reaction product to remove and / or recover, for example, unreacted starting materials. Purification may be carried out by any convenient means such as stripping and / or distillation and / or azeotrope with a solvent, filtration, and combinations thereof, while heating and optionally under reduced pressure. Distillation conditions typically include: (i) high temperature; (ii) reduced pressure; or (iii) both high temperature and reduced pressure. High or reduced is in relation to room temperature and atmospheric pressure. Distillation may be continuous or batch and may involve the use of a solvent (e.g., hexane, toluene, or other solvents described herein as starting material D) so that the distillation may be azeotropic distillation.

[0032] As used herein, purification of a hydrosilylation reaction product is typically defined as increasing the relative concentration of the alkoxy-functionalized silsesquioxane resin compared to other compounds combined with it (e.g., in the hydrosilylation reaction product or in its purified form). As understood in the art, purification may include removing other compounds from such combinations (i.e., reducing the amount of impurities and / or unreacted starting materials combined with the alkoxy-functionalized silsesquioxane resin in the hydrosilylation reaction product) and / or removing the alkoxy-functionalized silsesquioxane resin itself from the combination. Any suitable technique and / or protocol for purification may be used. Examples of suitable purification techniques include distillation, stripping / evaporating, extraction, filtration, washing, partitioning, phase separation, adsorption, and chromatography. As understood by those skilled in the art, any of these techniques may be used in combination (e.g., sequentially) with any other technique to purify the hydrosilylation reaction product. Regardless of the specific technique selected, the purification of the hydrosilylation reaction product may be carried out sequentially (i.e., in a line) with the hydrosilylation reaction itself, and therefore may be automated. Alternatively, the purification may be an independent procedure applied to the hydrosilylation reaction product containing the organosilicon compound.

[0033] For example, if A) an alkoxy-functional organosilicon compound has a silicon-bonded hydrogen atom, and B) a silsesquioxane resin has an aliphatic unsaturated group, the process for preparing the above-mentioned alkoxy-functional silsesquioxane resin is as follows: 1) Under conditions for carrying out a hydrosilylation reaction, A1) Formula:

[0034] [ka] Alkoxy-functional organohydrogensiloxane oligomers (wherein R in the formula) 1 , D 1(a and x are as described above) and B1) Unit formula (R 3 3SiO 1 / 2 ) c (R 3 2SiO 2 / 2 ) d (R 3 SiO 3 / 2 ) e (ZO 1 / 2 ) f (HO 1 / 2 Alkenyl-functionalized silsesquioxane resin having )g (wherein Z, c, d, e, f, and g are as described above, and each R 3 However, the group consisting of alkyl groups and alkenyl groups is independently selected, provided that there is at least one R per molecule. 3 However, the process may optionally involve combining a starting material containing an alkenyl group in the presence of the hydrosilylation catalyst (C) described above, and in the presence of the solvent (D) described above. The optional additional steps are as described above.

[0035] The starting material A1) is an alkoxy-functional organohydrogensiloxane oligomer (A1) of the following formula:

[0036] [ka] It is an alkoxy-functional organohydrogensiloxane oligomer) in which R 1 , D 1 , a, and x are as described above. Alternatively, the alkoxy-functional organohydrogensiloxane oligomer may have subscripts a=1 and x=0. Alternatively, in the formula of A1) alkoxy-functional organohydrogensiloxane oligomer, each R 1 =methyl, each D 1It may have the empirical formula -C2H4-. Alternatively, the alkoxy-functional organohydrogensiloxane oligomer may be trimethoxysilylethyl-1,1,3,3,5,5-hexamethyltrisiloxane, trimethoxysilylethyl-1,1,3,3-tetramethyldisiloxane, or a combination thereof. The alkoxy-functional organohydrogensiloxane oligomers of the above formulas are known in the art and can be prepared by known methods, such as those described in U.S. Patent No. 10,968,317 for Gohndrone, et al., No. 11,098,163 for Gohndrone, et al., No. 11,161,939 for Zhou, et al., No. 11,168,181 for Zhou, et al., and No. 11,492,448 for Gohndrone, et al., and Japanese Patent Application Publication No. 2007077136 for Uehara, et al.

[0037] Starting material B1) has the unit formula (R 3 3SiO 1 / 2 ) c (R 3 2SiO 2 / 2 ) d (R 3 SiO 3 / 2 ) e (ZO 1 / 2 ) f The silsesquioxane resin is an alkenyl-functionalized silsesquioxane resin, where Z, c, d, e, and f are as described above, and each R 3 However, the group consisting of alkyl groups and alkenyl groups capable of undergoing hydrosilylation reactions is independently selected, provided that at least one R is present per molecule. 3 However, it is an alkenyl group. Suitable examples of alkenyl groups may have 2 to 12, 2 to 10, 2 to 8, or 2 to 6 carbon atoms. The alkenyl group can undergo hydrosilylation reactions with silicon-bonded hydrogen atoms. 3 Suitable alkenyl groups include vinyl, allyl, and hexenyl, or vinyl and hexenyl, or vinyl.

[0038] The starting material B1) can be prepared by known methods, for example, by co-hydrolyzing an organosilane having three hydrolyzable moieties (e.g., halogen or alkoxy) per molecule bonded to a silicon atom. For example, starting material B1) can be prepared by the process described in U.S. Patent No. 11,248,119 by varying the starting materials and their amounts. Starting material B1) can be obtained, for example, by co-hydrolyzing methyltrimethoxysilane and vinyltrimethoxysilane, optionally together with additional silanes such as octyltriethoxysilane and octyltrimethoxysilane. Alkoxysilanes having two alkoxy groups per molecule or one alkoxy group per molecule, such as dimethyldimethoxysilane or trimethylmethoxysilane, may be included to add bifunctional and / or monofunctional siloxane units to the silsesquioxane resin. An acid catalyst such as triflic acid, water, and / or alcohol can be used to promote the co-hydrolysis.

[0039] Alternatively, when A) the alkoxy-functional organic silicon compound has an aliphatic unsaturated group and B) the silsesquioxane resin has a silicon-bonded hydrogen atom, the process for preparing the above-mentioned alkoxy-functional silsesquioxane resin is as follows: 1) Under the conditions for performing the hydrosilylation reaction, A2) an alkoxy-functional organic silicon compound of the formula R 1 x R 5 Si(OR 1 ) 3-x (where R 1 and x are as described above, and R 5 is an alkenyl group capable of undergoing a hydrosilylation reaction) and B2) a unit formula (R 4 3SiO 1 / 2 ) c (R 4 2SiO 2 / 2 ) d (R 4 SiO 3 / 2 ) e (ZO 1 / 2 ) fThe hydride-functional silsesquioxane resin (where Z, c, d, e, and f are as described above, and each R 4 is independently selected from the group consisting of an alkyl group and H, provided that at least one R 4 per molecule is H) may be included in the combination of a starting material in the presence of the above-mentioned C) hydrosilylation reaction catalyst, optionally in the presence of the above-mentioned D) solvent.

[0040] Starting material A2) is an alkoxy-functional organic silicon compound and has at least one alkenyl group per molecule. The alkoxy-functional organic silicon compound may be an alkoxysilane of the formula R 1 x R 5 Si(OR 1 ) 3-x , where R 1 and x are as described above, and R 5 is an alkenyl group capable of undergoing a hydrosilylation reaction. Examples of suitable alkenyl groups may have 2 to 12, or 2 to 10, or 2 to 8, or 2 to 6 carbon atoms. The alkenyl group can undergo a hydrosilylation reaction with a silicon-bonded hydrogen atom. Suitable alkenyl groups for R 5 are exemplified by vinyl, allyl, and hexenyl, or by vinyl and hexenyl, or by vinyl. Suitable alkoxysilanes for starting material A2) are known in the art and are commercially available. For example, alkenyl-functional trialkoxysilanes such as allyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, and vinyltris(methoxyethoxy)silane; alkenyl-functional dialkoxysilanes such as vinylphenyldiethoxysilane, vinylmethyldimethoxysilane, and vinylmethyldiethoxysilane; alkenyl-functional monoalkoxysilanes such as trivinylmethoxysilane are all available from Gelest, Inc., Morrisville, Pennsylvania, USA.

[0041] Starting material B2) has the unit formula (R 4 3SiO 1 / 2 ) c (R 4 2SiO 2 / 2 ) d (R 4 SiO 3 / 2 ) e (ZO 1 / 2 ) f The hydride-functionalized silsesquioxane resin, in which Z, c, d, e, and f are as described above, and each R 4 However, selected independently from the group consisting of alkyl groups and H, provided that at least one R is present per molecule. 4 However, it is H. Starting material B2) can be prepared by known methods such as those described above for starting material B1) by substituting an alkenyl-functionalized alkoxysilane with a suitable starting material such as a hydride-functionalized alkoxysilane. For example, starting material B2) can be prepared by changing the starting material and its amount by the process described in U.S. Patent No. 11,248,119.

[0042] The products of these processes are the alkoxy-functionalized silsesquioxane resins described above. These alkoxy-functionalized silsesquioxane resins are useful, for example, in emulsions for paint applications.

[0043] The non-aqueous phase of the emulsion contains the alkoxy-functionalized silsesquioxane resin described above. The non-aqueous phase may contain the alkoxy-functionalized silsesquioxane resin in amounts of 50-100, 60-100, 70-100, 80-100, 90-100, 95-100, 96-100, 97-100, 98-100, 99-100, or 100% by weight, based on the total weight of the non-aqueous phase.

[0044] The aqueous phase contains water. The water may be from any source and may optionally be purified by, for example, filtration, distillation, deionization, and / or reverse osmosis. The aqueous phase may contain water or may consist of water. As used herein, “essentially consisting of water” means that the aqueous phase contains water, and optionally a surfactant and any optional additional starting materials described below. In particular, the aqueous phase may contain water in amounts of 50–100, or 60–100, or 70–100, or 80–100, or 90–100, or 95–100, or 96–100, or 97–100, or 98–100, or 99–100, or 100 percent by weight of the total weight of the aqueous phase.

[0045] The emulsion further comprises a surfactant, which may also be called an emulsifier, and generally works to emulsify discontinuous phases within the continuum of the emulsion. The surfactant may be any surfactant suitable for preparing emulsions having a non-aqueous phase and an aqueous phase.

[0046] For example, surfactants may include one or more anionic, cationic, nonionic, and / or amphoteric surfactants, organically modified silicones such as dimethicone copolyol, oxyethylene and / or oxypropylene ethers of glycerol, oxyethylene and / or oxypropylene ethers of aliphatic alcohols such as ceteareth-30 and C12-15 pareth-7, fatty acid esters of polyethylene glycol such as PEG-50 stearate and PEG-40 monostearate, sugar esters and ethers such as sucrose stearate, sucrose cocoate and sorbitan stearate, and mixtures thereof, phosphate esters such as DEA oleth-10 phosphate and salts thereof, sulfosuccinates such as disodium PEG-5 citrate lauryl sulfosuccinate and disodium ricinolamide MEA sulfosuccinate, alkyl ether sulfates such as sodium lauryl ether sulfate, isethionates, betaine derivatives, and mixtures thereof.

[0047] Examples of anionic surfactants include (i) alkyl or aralkyl (e.g., alkylnaphthalene or alkyldiphenyl ether) sulfonic acids having at least six carbon atoms in the alkyl substituent, and their salt derivatives (e.g., dodecylbenzenesulfonic acid and its sodium salt or amine salt), (ii) alkyl sulfates having at least six carbon atoms in the alkyl substituent (e.g., sodium lauryl sulfate), (iii) sulfate esters of polyoxyethylene monoalkyl ethers, and (iv) long-chain carboxylic acid (e.g., lauric acid, stearic acid, oleic acid) surfactants and their alkali metal and amine salts. Some other examples of anionic surfactants include alkali metal sulfosuccinates; sulfonated glyceryl esters of fatty acids (e.g., sulfonated monoglycerides of coconut oil); monovalent sulfonated alcohol ester salts (e.g., sodium oleyl isocyanate); aminosulfonic acid amides (e.g., sodium salt of oleyl methyl taurid); sulfonated products of fatty acid nitriles (e.g., palmitonitrile sulfonate); sulfonated aromatic hydrocarbons (e.g., sodium α-naphthalene monosulfonate); condensation products of naphthalene sulfonic acid with formaldehyde; sodium octahydroanthracene sulfonate; alkali metal alkyl sulfates; ether sulfates having alkyl groups of 8 or more carbon atoms (e.g., sodium lauryl ether sulfate); and alkylaryl sulfonates having one or more alkyl groups of 8 or more carbon atoms (e.g., hexadecylbenzenesulfonic acid, and C 20 It is a neutral salt of alkylbenzenesulfonic acid.

[0048] Available commercial anionic surfactants include sodium dodecylbenzenesulfonic acid, sold by Alcolac Inc. of Baltimore, Maryland, USA under the trade name SIPONATE® DS-10; sodium alkyl alkoxylate sulfate, sold by Dow under the trade name DOWFAX® AS-801; sodium n-hexadecyldiphenyl oxide disulfonate, sold by Dow under the trade name DOWFAX® 8390; sodium secondary alkanesulfonate, sold by Clariant Corporation of Charlotte, North Carolina, USA under the trade name HOSTAPUR® SAS 60; N-acyl taurates such as sodium N-lauroyl methyl taurate, sold by Nikko Chemicals Company, Ltd. of Tokyo, Japan under the trade name NIKKOL LMT®; and Stepan, Northfield, Illinois, USA. One example is linear alkylbenzene sulfonic acid, sold by the Company under the trade name BIO-SOFT(trademark) S-100. Other suitable surfactants include sodium alkyl sulfonates such as HOSTAPUR(trademark) SAS-30 and triethanolamine dodecylbenzenesulfonate such as BIO-SOFT(trademark) N 300.

[0049] Cationic surfactants useful in this specification include compounds containing a quaternary ammonium hydrophilic moiety within a positively charged molecule, for example, R 8 R 9 R 10 R 11 N + X" - (In the formula, R 8 ~R 11Examples include quaternary ammonium salts represented by an alkyl group containing 1 to 30 carbon atoms, or an alkyl group derived from tallow, coconut oil, or soybeans, where X'' is a halogen, such as chlorine or bromine. Alternatively, the quaternary ammonium compound may be alkyltrimethylammonium and dialkyldimethylammonium halides, acetates, or hydroxides, each alkyl substituent having at least 8 carbon atoms. Dialkyldimethylammonium salts can be used, and such salts are R 12 R 13 N + (CH3)2X” - It is expressed by, in the formula, R 12 and R 13 However, it is an alkyl group containing 12 to 30 carbon atoms, or an alkyl group derived from tallow, coconut oil, or soybeans, where X'' is the halogen mentioned above. Monoalkyltrimethylammonium salts can be used, and such salts are R 14 N+(CH3)3X' - It is expressed by, in the formula, R 14 However, X' is an alkyl group containing 12 to 30 carbon atoms, or an alkyl group derived from tallow, coconut oil, or soybeans, where X' is a halogen, acetate, or hydroxide.

[0050] Exemplary quaternary ammonium halide salts include dodecyltrimethylammonium chloride / lauryltrimethylammonium chloride (LTAC), cetyltrimethylammonium chloride (CTAC), didodecyldimethylammonium bromide, dihexadecyldimethylammonium chloride, dihexadecyldimethylammonium bromide, dioctadecyldimethylammonium chloride, dieicosyldimethylammonium chloride, and didocosyldimethylammonium chloride. These quaternary ammonium salts are marketed under trade names such as ADOGEN® and VARIQUAT® from Evonik in Essen, Germany, and ARQUAD® from Nouryon.

[0051] Other suitable cationic surfactants that can be used include fatty acid amines and amides, as well as their salts and derivatives, such as aliphatic fatty amines and their derivatives. AMMONYX® by Stepan Company.

[0052] Some suitable nonionic surfactants that can be used include polyoxyethylene alkyl ethers (e.g., lauryl, cetyl, stearyl, or octyl), polyoxyethylene alkylphenol ethers, alkyl glycosides, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitan monooleate, polyoxyethylene alkyl esters, polyoxyethylene sorbitan alkyl esters, polyethylene glycol (e.g., polyethylene glycol having 23 ethylene oxide units), polypropylene glycol, diethylene glycol, ethoxylated trimethylnonanol, tristyrylphenol ether (TSP), distyryl phenol ether (DSP), and polyoxyalkylene glycol-modified polysiloxane surfactants.

[0053] Examples of commercially available nonionic surfactants include (i) 2,6,8-trimethyl-4-nonyloxypolyethyleneoxyethanol (6EO) and (10EO), sold under the names TERGITOL™ TMN-6 and TERGITOL™ TMN-10; (ii) C 11~15 Secondary alkyl polyoxyethylene ethers (for example, C, which have an HL value of 15.4 and are sold under the names TERGITOL® 15-S-7, TERGITOL® 15-S-9, and TERGITOL® 15-S-15) 11~15Secondary alcohol ethoxylates (7EO, 9EO, and 15EO), other C20s sold by Dow under the trade names ECOSURF® EH-40 and TERGITOL® 15-S-12, TERGITOL® 15-S-30, and TERGITOL® 15-S-40. 11~15(iii) Octylphenyl polyoxyethylene (40) ether sold by Dow under the name TRITON(trademark) X405; (iii) Nonylphenyl polyoxyethylene (10) ether sold by Stepan Company under the name MAKON(trademark) 10; (iv) Ethoxylated alcohol sold by Henkel Corp. / Emery Group of Cincinnati, Ohio, USA under the name Trycol 5953; (v) Ethoxylated alcohol sold by Croda Inc. of Edison, New Jersey, USA under the names BRIJ(trademark) L23 (with HLB value 16.9) and BRIJ(trademark) L4 (with HLB value 9.7); (vi) Polyoxyethylene 23 lauryl ether (Laureth-23) marketed by ICI Surfactants of Wilmington, Delaware, USA under the trade name BRIJ(trademark) 23; and RENEX(trademark) 30 (ICI (vii) Alkyl-oxo alcohol polyglycol ethers such as polyoxyethylene ether alcohol sold by Surfactants; (viii) Alkyl polyethylene glycol ethers based on C10-Guerbet alcohol and ethylene oxide, such as LUTENSOL XP 79; and (ix) Alkyl polyglycosides such as decyl glucoside, lauryl glucoside, and coco glucoside, sold by BASF under the trade name Glucopon® and by Dow under the trade name EcoSense®. Other commercially available nonionic surfactants include TERGITOL™ 15-S-5 (also manufactured by Dow, with an HLB value of 10.5); Lutensol XP 50 with an HLB value of 10; and Lutensol XP 140 with an HLB value of 16.

[0054] Nonionic surfactants may also be silicone polyethers (SPEs). An SPE as a surfactant may have a rake-shaped structure in which polyoxyethylene or polyoxyethylene-polyoxypropylene copolymer units are grafted onto a siloxane backbone, or it may have an ABA block copolymer structure, where A represents the polyether portion of the ABA structure and B represents the siloxane portion of the ABA structure. Alternatively, an SPE may have a resin structure, such as a polyorganosilicate resin having polyether groups bonded to silicon atoms. A preferred SPE is DOWSIL® OFX-5329 Fluid from Dow. Alternatively, nonionic surfactants may be selected from polyoxyalkylene-substituted silicones, silicone alkanolamides, silicone esters, and silicone glycosides. Such silicone surfactants may be used to form such aqueous emulsions, which are known in the art and are described, for example, in U.S. Patent No. 4,122,029 to Gee et al., U.S. Patent No. 5,387,417 to Rentsch, and U.S. Patent No. 5,811,487 to Schulz et al. Other silicone polyether surfactants are also known in the art and are commercially available, for example, DOWSIL® 502W and DOWSIL® 67 Additive, which are commercially available from Dow.

[0055] Alternatively, the nonionic surfactant may include a polyvinyl alcohol compound. Polyvinyl alcohol compounds are known in the art and are disclosed, for example, in paragraphs

[0172] and

[0173] of U.S. Patent Application Publication 2007 / 0099007. The polyvinyl alcohol compound may be prepared by saponification of polyvinyl acetate, so that up to 15% of polyvinyl acetate may remain in the polyvinyl alcohol compound used herein. Alternatively, the polyvinyl alcohol compound may be 88% to 92% polyvinyl alcohol (with a residue of 12% to 8% polyvinyl acetate). The polyvinyl alcohol compound may have a minimum viscosity of 5 cP in a 4% aqueous solution at 20°C.

[0056] Examples of amphoteric surfactants include amino acid surfactants, betaines (e.g., lauryl betaine, bis-(2-hydroxy-ethyl) talobetaine, cocamidopropyl betaine, N-alkylamide betaine, and their derivatives), proteins and their derivatives, glycinates (glycine derivatives such as cocampu glycinate, cocampocarboxyglycinate, and cocampodipropionate), sultaines (e.g., lauryl sultaine and cocamidopropyl hydroxysultaine), alkylaminopropionates, alkyl polyaminocarboxylates, and alkylamphoacetates, lecithins and hydrogenated lecithins, and combinations thereof. These surfactants may also be available from other suppliers under different trade names. For example, REWOTERIC® AM TEG is produced by Evonik in Essen, Germany. AMPHOSOL® CG is available from Stepan Company.

[0057] Surfactants can be included in the emulsion at concentrations effective for emulsifying the non-aqueous phase in the aqueous phase (or vice versa). Such concentrations range from 0% to 10% by weight, or from 0.3% to 7.0% by weight, based on the total weight of the emulsion. Surfactants, or combinations of surfactants, can be present in the aqueous phase of the emulsion, the non-aqueous phase of the emulsion, the interface between the aqueous and non-aqueous phases, or in combinations thereof.

[0058] One or more additional starting materials may be optionally combined with the emulsion. For example, the emulsion may further include a catalyst, such as a condensation catalyst. The condensation catalyst can be selected from any catalyst known in the art to bring about condensation curing of the condensation-curable composition. The catalyst may be included in the emulsion immediately before its optional end use, for example, as a two-component (2k) system, to prevent premature curing of the components in the emulsion.

[0059] The condensation catalyst used in the emulsion and / or composition may be any chemical entity or molecule, which may be used to promote the condensation reaction of silicon-bonded hydroxy(silanol) groups and / or silicon-bonded alkoxy groups to form Si-O-Si bonds (and by-product water and / or alcohol molecules) to obtain a condensation-cured product. Examples of suitable condensation catalysts include nitrogen-containing bases (e.g., nitrogen-containing superstrong bases) described herein, as well as complexes of lead, tin, titanium, zinc, and iron, such as various tin catalysts or titanium catalysts.Other examples include other basic compounds, e.g., trimethylbenzylammonium hydroxide, tetramethylammonium hydroxide, and metal-containing compounds, e.g., tetraethyl titanate, tetrapropyl titanate (e.g., tetraisopropyl orthotitanate), tetrabutyl titanate, titanium tetraisooctylate, titanium isopropyl tristearoyate, titanium triisopropyl stearoyate, titanium diisopropyl distearoyate, tetra(isopropoxy)titanium; tetra(n-butoxy)titanium and tetra(t-butoxy)titanium; organotitanium chelates such as di(isopropoxy)bis(ethylacetate)titanium; di(isopropoxy)bis(methylacetate)titanium; di(isopropoxy)bis(acetylacetonate)titanium; and bis(ethylacetate-O1',O3")bis(propane-2-olate)titanium; Examples include zirconium tetrapropylate, zirconium tetraisopropylate, zirconium tetrabutyrate, titanium acetylacetonate, aluminum triisobutoxide, aluminum triisopropoxide, zirconium tetra(acetylacetonate), zirconium tetrabutyrate, cobalt octylate, cobalt acetylacetonate, iron acetylacetonate, tin acetylacetonate, dibutyltin octylate, dibutyltin laurate, zinc octylate, zinc benzoate, zinc p-tert-butylbenzoate, zinc laurate, zinc stearate, aluminum phosphate, and aluminum triisopropoxide; organoaluminum chelates, such as aluminum trisacetylacetonate and aluminum bis-ethylacetoacetate monoacetylacetonate; and tin compounds, such as dimethyltin dineodecanoate and tin octoate.

[0060] Additional examples of condensation catalysts include, but are not limited to, aluminum alkoxides, antimony alkoxides, barium alkoxides, boron alkoxides, calcium alkoxides, cerium alkoxides, erbium alkoxides, gallium alkoxides, silicon alkoxides, germanium alkoxides, hafnium alkoxides, indium alkoxides, iron alkoxides, lanthanum alkoxides, magnesium alkoxides, neodymium alkoxides, samarium alkoxides, strontium alkoxides, tantalum alkoxides, titanium alkoxides, tin alkoxides, vanadium alkoxide oxides, yttrium alkoxides, zinc alkoxides, zirconium alkoxides, titanium or zirconium compounds, particularly titanium and zirconium alkoxides, as well as chelates (e.g., alkylacetylacetonate, ethanolamine, ammonium salts of lactic acid), oligocondensates and polycondensates, dialkyltin diacetates, tin(II) octoates, dialkyltin diacylates, dialkyltin oxides, and bimetallic alkoxides. Bimetallic alkoxides are alkoxides containing two different metals in a specific ratio. Condensation catalysts are commercially available; for example, organic titanates and zirconates are available from Dorf Ketal under the trade name TYZOR®.

[0061] The amount of catalyst in the emulsion, if present, may be changed and is not limited. For example, the amount of catalyst may be catalytically effective in promoting (enhancing) the hydrolysis and / or condensation reaction or curing between the alkoxy-functionalized silsesquioxane resin and / or with other starting materials used in the emulsion. However, the amount of catalyst contained in the emulsion, if present, may be between 0 ppm and 1,000 ppm, or between 1 ppm and 500 ppm, or between 10 ppm and 100 ppm, or between 10 ppm and 50 ppm, or between 5 ppm and 30 ppm, or between 5 ppm and 25 ppm, relative to the weight of the emulsion. Alternatively, the amount of catalyst may be between 0 and 10% by weight of the emulsion, or between 0% and 10% by weight.

[0062] The emulsion may further contain one or more various optional starting materials (additives), such as coupling agents, antistatic agents (e.g., in amounts of 0 to 10% by weight of the emulsion), UV absorbers, plasticizers, leveling agents, preservatives, surfactants (surfactants or detergents or emulsifiers), foaming accelerators, deposition agents, thickeners, aqueous phase stabilizers, fillers, preservatives (e.g., in amounts of 0 to 1% by weight of the emulsion), suspending agents, biocides, freeze / thaw additives, antifreeze agents, various thickeners, viscosity modifiers, foam control agents, dyes (e.g., pigments or other colorants), binders, and combinations thereof. Examples of these optional additives and their amounts are exemplified by those disclosed in U.S. Patent No. 11,248,119.

[0063] Alternatively, or in addition to the above, the emulsion may further contain various additive compounds to improve the properties of the film formed therefrom. Examples of additive compounds include silanes, such as tetrakis(dimethylamine)silane, tetraethyl orthosilicate, glycidoxypropyltrimethoxysilane, triethylsilane, and isobutyltrimethoxysilane, and siloxanes, such as 1,1,1,3,5,5,5-heptamethyltrisiloxane and 1,1,3,3-tetramethyldisiloxane.

[0064] Alternatively, the emulsion may further contain dyes. The dyes may be selected from powder dyes (such as pigments and nacre) and water-soluble dyes. The term "pigment" means any form of mineral or organic particles, white or colored, which are insoluble in the physiological medium and intended to color the emulsion. The term "nacre" means any form of pearly particles, particularly those produced within the shells of certain mollusks or otherwise synthesized.

[0065] Pigments may be white or colored, and may be minerals and / or organic. Examples of mineral pigments include titanium dioxide, optionally surface-treated zirconium oxide or cerium oxide, zinc oxide, iron oxide (black, yellow, or red), chromium oxide, manganese violet, ultramarine blue, chromium hydrate, ferric blue, and metal powders, such as aluminum powder or copper powder. Examples of organic pigments include carbon black, D&C type pigments, lakes based on cochineal carmine, or lakes based on barium, strontium, calcium, or aluminum.

[0066] The pigment may also have the effect of particles containing natural or synthetic organic or mineral substrates such as glass, acrylic resin, polyester, polyurethane, polyethylene terephthalate, ceramic, or alumina, the substrate being either uncoated or coated with metallic substances such as aluminum, gold, silver, platinum, copper, or bronze, or with metal oxides such as titanium dioxide, iron oxide, or chromium oxide, or combinations thereof.

[0067] The pearlescent layer may be selected from white pearlescent pigments such as mica coated with titanium or bismuth oxychloride, colored pearlescent pigments such as titanium mica coated with iron oxide, titanium mica coated with ferric blue or chromium oxide, titanium mica coated with the above-mentioned types of organic pigments, and further from pearlescent pigments based on bismuth oxychloride. Alternatively, interference pigments such as liquid crystals or multilayer interference pigments may be used.

[0068] If a dye is present in the emulsion, it may be included in any appropriate amount depending on the desired end-use characteristics of the emulsion. For example, in certain embodiments, the emulsion may contain the dye in an amount of 1 to 60, or 5 to 40, or 10 to 30% by weight, based on the total weight of the emulsion.

[0069] Suitable fillers for use in emulsions may be minerals or organic materials in any form, such as plate-like, spherical, or elliptical, regardless of their crystalline form (e.g., layered, cubic, hexagonal, or orthorhombic). Examples include talc, mica, silica, kaolin, polyamide, poly-β-alanine powder and polyethylene powder, tetrafluoroethylene polymer powder, starch, boron nitride, hollow polymer microspheres, acrylic acid copolymers, solid silicone resin microbeads, elastomer polyorganosiloxane particles, precipitated calcium carbonate, magnesium carbonate, magnesium bicarbonate, hydroxyapatite, hollow silica microspheres, glass and ceramic microcapsules, metal soaps such as zinc stearate, magnesium stearate, lithium stearate, zinc laurate and magnesium myristate, and poly(methyl methacrylate) powder, as well as mixtures of two or more of these. Alternatively, the filler may be polyurethane powder. Fillers are commercially available. For example, SILLITIN V85 is available from Hoffman Mineral.

[0070] If a filler is present in the emulsion, it may be included in any suitable amount depending on the desired end-use characteristics of the emulsion. For example, in certain embodiments, the emulsion may contain the filler in amounts of 0 to 50% by weight, or 2.5% to 40% by weight, or 5% to 30% by weight, based on the total weight of the emulsion.

[0071] Thickening agents (also called viscosity modifiers or rheology modifiers) may also be included in the emulsion, for example, to achieve desired viscosity and flow properties. Thickening agents such as cellulose derivatives including hydroxyethylcellulose, methylcellulose, and carboxymethylcellulose, or polyurethane thickening agents can be used. The thickening agent is optional and may not be present. Alternatively, the amount of thickening agent may be 0-10% by weight of the emulsion, or more than 0% by weight up to 5% by weight. Commercially available thickening agents include ACRYSOL® RM-2020E Rheology Modifier.

[0072] The emulsion may optionally further contain an antifoaming agent. The antifoaming agent may be any suitable chemical additive that reduces and suppresses foam formation in the emulsion, or a composition prepared therefrom. Antifoaming agents are known in the art and are typically selected based on other components present in the composition. Antifoaming agents are commercially available. For example, DOWSIL® 8590 Additive is available from Dow. The antifoaming agent is optional and may not be present. Alternatively, the amount of antifoaming agent may be 0 to 2% by weight, or 0.5% to 2% by weight, based on the weight of the emulsion.

[0073] If the emulsion contains a compatibilizer, the compatibilizer may be any compound or component that alters or improves the wetting of the components in the emulsion. Examples of such compatibilizers include titanium alcoholates, phosphate esters, phosphite esters, phosphonic acid esters, and silicate esters, metal salts and esters of aliphatic, aromatic, and alicyclic acids, ethylene / acrylic acid or methacrylic acid, ethylene / acrylic acid or methacrylic acid esters, ethylene / vinyl acetate resin, styrene / maleic anhydride resin or its esters, acrylonitrile butadiene styrene resin, methacrylate / butadiene styrene resin (MBS), styrene acrylonitrile resin (SAN), and butadiene acrylonitrile copolymer. Alternatively, or in addition, the compatibilizer may include silanes, such as hydrocarbonoxysilanes, such as alkoxysilanes, combinations of alkoxysilanes and hydroxy-functional polyorganosiloxanes, amino-functional silanes, or combinations thereof. The silane may contain any functional group, which may be an adhesion-promoting group such as an amino group, epoxy group, mercapto group, and / or acrylate group. Combinations of functional groups may be used; for example, the compatibilizer may contain an epoxy-functionalized alkoxysilane. Suitable epoxy-functionalized organic groups are exemplified by 3-glycidoxypropyl and (epoxycyclohexyl)ethyl. Unsaturated organic groups are exemplified by 3-methacryloyloxypropyl, 3-acryloyloxypropyl, and unsaturated monovalent hydrocarbon groups such as vinyl, allyl, hexenyl, and undecylenyl. Examples of suitable epoxy-functionalized alkoxysilanes include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, (epoxycyclohexyl)ethyldimethoxysilane, (epoxycyclohexyl)ethyldiethoxysilane, and combinations thereof.Suitable examples of unsaturated alkoxysilanes include vinyltrimethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, hexenyltrimethoxysilane, undecylenyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltriethoxysilane, and combinations thereof. Amino-functional silanes, such as amino-functional alkoxysilanes, may have a variety of amino groups, as understood in the art. Other examples of compatibilizers include modified polyethylene and modified polypropylene obtained by modifying polyethylene and polypropylene, respectively, using reactive groups containing polar monomers such as maleic anhydride or esters, acrylic acid or methacrylic acid or esters, vinyl acetate, acrylonitrile, and styrene.

[0074] Specific examples of UV stabilizers include branched and linear 2-(2H-benzotriazol-2-yl)-6-dodecyl-4-methylphenol (TINUVIN® 571). Further examples of suitable UV stabilizers include bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, methyl 1,2,2,6,6-pentamethyl-4-piperidyl / sebacate, and combinations thereof (TINUVIN® 272). These and other TINUVIN® additives (e.g., TINUVIN® 765) are commercially available from Ciba Specialty Chemicals in Tarrytown, NY, USA. Other UV and light stabilizers are commercially available and are exemplified by LowLite from Chemtura, OnCap from PolyOne, and Light Stabilizer 210 from EIdu Pont de Nemours and Company in Delaware, USA. An example of an oligomeric antioxidant stabilizer (particularly a hindered amine light stabilizer (HALS)) is Ciba TINUVIN® 622, which is a dimethyl ester of butanediic acid copolymerized with 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol.

[0075] When used, the antioxidant may be any antioxidant known in the art. Specific examples include phenolic antioxidants and combinations of phenolic antioxidants with stabilizers. Phenolic antioxidants include fully sterically hindered phenols and partially sterically hindered phenols; as well as sterically hindered amines such as tetramethyl-piperidine derivatives. Suitable phenolic antioxidants include vitamin E and IRGANOX® 1010 from Ciba Specialty Chemicals (USA). IRGANOX® 1010 contains pentaerythritol tetrakis(3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate). Examples of additional antioxidants are described in U.S. Patent Nos. 11,248,119.

[0076] Biocides may be exemplified by fungicides, herbicides, insecticides, antimicrobial agents, or combinations thereof, as appropriate examples are, for example, set forth in U.S. Patent No. 11,248,119.

[0077] Examples of suitable flame retardants are disclosed, for example, in U.S. Patent No. 11,248,119, and include carbon black, aluminum hydroxide hydrate, and silicates (e.g., wollastonite). Alternatively, if a flame retardant is used, it may be selected from halogenated flame retardants. Alternatively, if a flame retardant is used, it may be selected from phosphorus-based flame retardants. Other suitable flame retardants include tetraalkyl lead compounds, iron pentacarbonyl, methylcyclopentadienylmanganet tricarbonyl, melamine and its derivatives (e.g., melamine salts), guanidine, dicyandiamide, ammonium sulfamate, alumina trihydrate, and magnesium hydroxide and alumina trihydrate.

[0078] Those skilled in the art will recognize that suitable additional starting materials can be selected for use in the emulsion, and that certain types of additional starting materials may have more than one function. For example, carbon black may be a filler, a pigment, and / or a flame retardant. The additional starting materials may be selected to be different from each other. The emulsion may, for example, contain 50% to 80% by weight of the above-mentioned I) alkoxy-functionalized silsesquioxane resin, more than 0% to 10% by weight, or 2% to 10% by weight of a surfactant (such as the anionic surfactant described above), and 15% to 40% by weight of water, each based on the combined weight of all the starting materials in the emulsion. The alkoxy-functionalized silsesquioxane resin may be present in the discontinuous phase of this emulsion, and the water may be present in the continuous phase. Alternatively, the emulsion may be further defined as a composition such as a paint composition further comprising one or more of the above-mentioned additional starting materials. For example, a paint composition may be prepared by combining one or more of the above-mentioned additional starting materials with an emulsion of an alkoxy-functional silsesquioxane resin, a surfactant, and water. For example, a paint composition may be prepared by combining an emulsion of an alkoxy-functional silsesquioxane resin, a surfactant, and water, and the emulsion may contain a dye such as a pigment in an amount of 30% to 50% by weight of the paint composition (for example, 40% to 60% by weight of the paint composition), an antifoaming agent (for example, 0.5% to 2% by weight of the paint composition), and a filler (for example, 4.5% to 10% by weight of the paint composition).

[0079] Emulsions can be prepared by methods comprising shearing or mixing selected starting materials. Shearing or mixing can be achieved by any method known in the art for resulting in the mixing of high-viscosity materials. Mixing can be carried out as a batch, semi-continuous, or continuous method. Mixing may be carried out using equipment such as batch mixing apparatus with medium / low shear, including, for example, change can mixers, double planetary mixers, conical screw mixers, ribbon blenders, double arm, or sigma blade mixers; batch apparatus with high-shear high-speed dispensers, including those manufactured by Charles Ross & Sons (NY) and Hockmeyer Equipment Corp. (NJ); batch mixing equipment (e.g., those sold under the trade name Speedmixer®); and batch equipment performing high-shear action, including Banbury type (CW Brabender Instruments Inc., NJ) and Henschel type (Henschel mixers America, TX). Examples of continuous mixers / compounders include single-screw, twin-screw, and multi-screw extruders, co-rotating extruders, twin-screw counter-rotating extruders, two-stage extruders, twin-screw rotary continuous mixers, dynamic and static mixers, and combinations thereof, manufactured by companies such as Krupp Werner & Pfleiderer Corp (Ramsey, NJ) and Leistritz (NJ).

[0080] The combination of emulsion starting materials can be carried out in a single-step or multi-step process. Therefore, all starting materials may be combined and then mixed by any of the techniques described herein. Alternatively, only some of the starting materials may be combined and mixed first, and then additional amounts of any starting materials may be added and further mixed. Typically, when forming an emulsion, water is added gradually until sufficient gradually increasing water is added to form the emulsion. Furthermore, the emulsion (of alkoxy-functionalized silsesquioxane resin, surfactant, and water) may be prepared first and then combined with other starting materials or other compositions or emulsions; for example, the emulsion itself may be a component of another composition.

[0081] A method for preparing a film using an emulsion is provided. The method for preparing a film includes applying the emulsion to a substrate. The method further includes forming a film on the substrate.

[0082] There may be various methods for applying the emulsion to the substrate. For example, the step of applying the emulsion to the substrate may use a wet coating method. Specific examples of wet coating methods suitable for this method include dip coating, spin coating, flow coating, spray coating, roll coating, gravure coating, sputtering, slot coating, inkjet printing, and combinations thereof.

[0083] The substrate is not limited and may be any material, may be continuous or discontinuous, and may have any size, shape, dimensions, and surface roughness. In certain embodiments, the substrate includes plastic, which may be thermosetting and / or thermoplastic. However, the substrate may also be glass, metal, paper, wood, silicone, or other materials, or a combination thereof.

[0084] Specific examples of suitable plastic substrates include polyamide (PA); polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PET), polytrimethylene terephthalate (PTT), polyethylene naphthalate (PEN), and liquid crystal polyester; polyolefins such as polyethylene (PE), polypropylene (PP), and polybutylene; styrene resin; polyoxymethylene (POM); polycarbonate (PC); polymethylene methacrylate (PMMA); polyvinyl chloride (PVC); polyphenylene sulfide (PPS); and polyphenylene ether (polyphenylene ether (PPE); polyimide (PI); polyamideimide (PAI); polyetherimide (PEI); polysulfone (PSU); polyethersulfone; polyketone (PK); polyetherketone (PEK); polyvinyl alcohol (PVA); polyetheretherketone (PEEK); polyetherketoneketone (PEKK); polyarylate (PAR); polyethernitrile (PEN); phenolic resins; phenoxy resins; cellulose such as triacetylcellulose and diacetylcellulose, and cellophane fluorinated resins such as polytetrafluoroethylene;Examples include thermoplastic elastomers such as polystyrene, polyolefin, polyurethane, polyester, polyamide, polybutadiene, polyisoprene, and fluorotype; as well as copolymers thereof and combinations thereof.

[0085] Typically, applying an emulsion to a substrate brings forth a wet film on the substrate, and forming a wet film on the substrate includes drying the wet film on the substrate to form a film. For example, drying the wet film may include (i) evaporating water from the wet film, (ii) exposing the wet film to a high temperature to expel water from it, (iii) curing the wet film, or (iv) any combination of (i) to (iii). Forming a film from a wet film may also result in chemical reactions beyond mere physical drying of the wet film. For example, alkoxy groups from an alkoxy-functionalized silsesquioxane resin may react (e.g., cure) such that the film is a reaction product of the alkoxy-functionalized silsesquioxane resin and optionally one or more additional starting materials in the emulsion.

[0086] The film may be separable from the substrate (e.g., peelable) or may be physically and / or chemically bonded to the substrate. The substrate may be subjected to a single-piece hot plate or a single-piece or separate furnace for drying / curing the deposit. The substrate may optionally have a continuous or discontinuous shape, size, dimensions, surface roughness, and other properties. Alternatively, the substrate may have a high softening point temperature. However, the emulsion and method are not so limited.

[0087] Typically, film formation involves exposing a wet film to a high temperature for a certain period of time. The high temperature is typically 50°C to 250°C, or 100°C to 200°C, or 110°C to 190°C, or 120°C to 180°C, or 130°C to 170°C, or 140°C to 160°C, or 145°C to 155°C. This time is typically sufficient to allow the alkoxy-functionalized silsesquioxane resin to dry and / or cure, or at least cure (e.g., crosslink). This time may be greater than 0 hours and up to 10 hours, or greater than 0 hours and up to 5 hours, or greater than 0 hours and up to 2 hours. This time may be divided into drying / curing cycles (e.g., first curing and post-curing), where the first curing is, for example, 1 hour, and the post-curing is, for example, 1 hour. The high temperature may be independently selected in such cycles, or may be the same in each cycle. Alternatively, the film can be formed by simply exposing the wet film to ambient conditions, that is, by drying it in RT under conditions where there is atmospheric moisture and no high temperatures.

[0088] The film may also be formed by a repeating process, depending on the film thickness and other dimensions. For example, a first deposit may be formed and optionally exposed to a first high temperature for a first time to obtain a partially dried and / or hardened deposit. Then, a second deposit may be placed on top of the first deposit, or the deposit may be partially dried and / or hardened and optionally exposed to a second high temperature for a second time to obtain a second partially dried and / or hardened deposit. This process may be repeated, for example, 1 to 50 times to construct the film as desired. Each high temperature and time may be selected independently, may be the same as or different from each other. The repeating process may be wet-on-wet. Alternatively, the repeating process may be wet-on-dry, depending on the drying / hardening state of the partially dried and / or hardened deposits.

[0089] The film may have a variety of thicknesses depending on its end application. Typically, the film may have a thickness greater than 0 μm and up to 4,000 μm, or greater than 0 μm and up to 3,000 μm, or greater than 0 μm and up to 2,000 μm, or greater than 0 μm and up to 1,000 μm, or greater than 0 μm and up to 500 μm, or greater than 0 μm and up to 250 μm, or greater than 0 μm and up to 100 μm, or 1 to 50 μm, or 20 to 30 μm. However, other thicknesses, such as 0.1 to 200 μm, are also expected. For example, the film thickness may be any one of the following: 0.2-175 μm; 0.5-150 μm; 0.75-100 μm; 1-75 μm; 2-60 μm; 3-50 μm; 4-40 μm; or 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, 40, 45, 50, 60, 70, 75, 80, 90, 100, 150, 175, and 200 μm.

[0090] Regardless of the method by which the film is formed, once the film is formed on a substrate from an emulsion and / or composition, the film may undergo further post-treatment such as heating, humidification, catalytic post-treatment, light irradiation, or electron beam irradiation.

[0091] If desired, the film may be subjected to further processing depending on its end use. For example, the film may be subjected to oxide deposition (e.g., SiO2 deposition), resist deposition and patterning, etching, chemical stripping or plasma stripping, metal coating, or metal deposition. Such further processing techniques are generally known. Such deposition may be chemical vapor deposition (low-pressure chemical vapor deposition, plasma-enhanced chemical vapor deposition, and plasma-assisted chemical vapor deposition, etc.), physical vapor deposition, or other vacuum vapor deposition techniques. Many such further processing techniques involve high temperatures, especially vacuum vapor deposition, and given the excellent thermal stability, the film is well suited to these. However, depending on the end use of the film, it may be used without such further processing. [Examples]

[0092] The following examples are provided to illustrate the present invention to those skilled in the art and should not be construed as limiting the scope of the invention as defined in the claims. The starting materials used in these examples are shown in Table 1 below.

[0093] [Table 1]

[0094] In this Reference Example 1, a sample of vinyl-functionalized silsesquioxane resin was prepared as follows: A 1000 mL three-necked flask was fitted with a magnetic stirring rod, a water-cooled condenser, a thermocouple, and a nitrogen blanket. The following starting materials were placed in the flask: 1) Methoxysilane in the amounts shown in Table 2 below, followed by triflic acid in the amounts shown in Table 2 below. The amount of DI water shown in Table 2 below was slowly added to the flask, starting with RT. Exothermic reaction up to 64°C was observed. The contents of the flask were then heated at 65°C for 2 hours. A certain amount of methanol was removed by distillation using a Dean-Stark apparatus. The contents of the flask were cooled to 50°C, and triflic acid was neutralized by adding CaCO3. The contents of the flask were mixed overnight in RT. The resulting product was stripped using a rotary evaporator heated in an oil bath at 80°C under reduced pressure of 4 mmHg. Next, the flask contents were cooled to RT and pressure filtered through a 47 mm diameter Magna nylon-supported plain 0.45 μm filter. Vinyl-functionalized silsesquioxane resin was produced.

[0095] In this Reference Example 2, samples of vinyl-functionalized MDT resin were prepared as described above in Reference Example 1, except that octyltriethoxysilane and tetramethyldisiloxane were added. Samples CE2 and CE4 were prepared by this method. These samples are summarized in Table 3 below.

[0096] In this Reference Example 3, a sample of hydride-functionalized silsesquioxane resin was prepared as follows. A thermocouple, a Teflon stirring paddle attached to a glass stirring rod, a Dean Stark apparatus attached to a water-cooled condenser, and a nitrogen blanket were attached to a 1 L three-necked flask. The following starting materials were placed in the flask. Methoxysilane in the amounts shown in Table 2 was added, followed by triflic acid in the amounts shown in Table 2. The amount of DI water shown in Table 2 was slowly added to the flask, starting at RT. Exothermic reaction was observed up to 58°C. The contents of the flask were then heated at 65°C for 30 minutes. A certain amount of methanol was removed using the Dean Stark apparatus. Tetramethyldisiloxane was added to the flask, followed by DI water in the amounts shown in Table 4. The contents of the flask were heated at 55°C for 3 hours. The temperature inside the flask was then raised to 70°C and methanol was removed by distillation. The amount removed was 77 g. Triflic acid was neutralized by adding CaCO3. The flask contents were mixed overnight in RT. The resulting product was stripped under reduced pressure of 3 mmHg using a rotary evaporator heated in an oil bath at 80°C. The flask contents were then cooled to RT and pressure filtered through a 47 mm diameter Magna nylon-supported plain 0.45 μm filter. Vinyl-functionalized silsesquioxane resins were prepared. CE5 and CE6 were prepared using this process. CE6 used different ratios of starting materials than CE5. These samples are summarized in Table 4 below.

[0097] In this Reference Example 4, a sample of octyl-functionalized DT resin was prepared as follows. The same apparatus as in Reference Example 1 was used. Methyltrimethoxysilane (355 g), octyltriethoxysilane (41 g), and D4 cyclic compound (18 g) were added to the flask. Triflic acid (0.21 g) was then added, followed by the slow addition of DI water (71 g), starting at room temperature. Exothermic reaction was observed up to 64°C, after which the flask contents were heated at 65°C for 2 hours. Some alcohol (methanol and ethanol) was removed using a Dean-Stark apparatus. The amount removed was 213 g. Next, n-heptane (144 g) was added, followed by calcium carbonate (0.83 g) to neutralize the triflic acid. The flask contents were mixed for 1 hour while cooling. The volatile matter was removed by distillation to a vapor temperature of 98°C. The amount removed was 91 g. The obtained product was filtered through a 47 mm diameter Magna nylon-supported plain 0.45 μm filter. The resulting resin was stripped at 1–2 mmHg using a rotary evaporator heated in an oil bath at 80°C. CE8 and CE9 were prepared using this process. These samples are summarized in Table 4 below.

[0098] [Table 2]

[0099] [Table 3]

[0100] [Table 4]

[0101] In this reference example 5, the ETM-converted DT resin was prepared as follows. The 250 mL flask was equipped with a thermocouple, a magnetic stirring rod, and a water-cooled condenser. Unit formula D from Comparative Example 3 Me2 0.009 T Me 0.843T Vi 0.148 A vinyl functionalized resin (50 g), an ETM converter (26 g), and toluene (76 g) were placed in a flask. A nitrogen blanket was applied. The contents of the flask were heated to 70°C, and Karstedt catalyst (an amount sufficient to provide 10 ppm of Pt based on the combined weight of the resin and ETM) was added. The contents of the flask were heated at 100°C for 21 hours. The SiH content as an indicator of the reaction product was monitored using FTIR. The resulting product was stripped using a rotary evaporator heated in an oil bath at 80°C until dry at 0.5–1 mmHg. Samples IE2, IE3, and IE5 were prepared by this procedure by varying the amount of starting material. These samples are summarized in Table 5 below. In Table 5 below, quantities are in grams unless otherwise specified.

[0102] In this Reference Example 6, the ETM-converted DT resin was prepared according to the method of Reference Example 5, except that the CE2 resin was used as the vinyl-functionalized resin starting material for sample IE4, and the CE4 resin was used as the vinyl-functionalized resin starting material for sample IE6. These samples are summarized in Table 6 below. In Table 6 below, quantities are in grams unless otherwise specified.

[0103] In this reference example 7, samples IE7 and IE8 were prepared as follows: A thermocouple, magnetic stirring rod, and water-cooled condenser were attached to a 500 mL three-necked flask. Formula M was then added to this flask. H 0.102 T Me 0.892 Resin (sample CE5) or M H 0.102 T Me 0.892The resin (sample CE6) and heptane were added. A nitrogen blanket was applied. The contents of the flask were heated to 80°C. Karstedt's Pt catalyst was added in an amount equal to 5 ppm Pt based on the resin. Vinyltrimethoxysilane was slowly added using a dropping funnel. The temperature was heated to 94°C. The contents of the flask were heated to approximately 100°C for 3 hours. FTIR was used to confirm that the reaction was complete. The product was stripped to dry at 1-2 mmHg using a rotary evaporator heated in an oil bath at 80°C. These samples are summarized in Table 7 below. In Table 7 below, quantities are in grams unless otherwise specified.

[0104] In this reference example 8, sample IE9 was prepared as follows: A thermocouple, magnetic stirring rod, and water-cooled condenser were attached to a 500 mL three-necked flask. The flask was then filled with T prepared as described above. Me 0.853 T Vi 0.147 Resin (150g), sample CE7, and heptane (81g) were placed in the flask. A nitrogen blanket was applied. The flask contents were heated to 50°C, and then Karstedt's Pt catalyst was added in an amount that yielded 5 ppm of Pt based on the resin + MeHSi(OMe)2. MeHSi(OMe)2 (30g) was slowly added to the flask using a dropping funnel. The flask contents were heated at 60°C for a total of 23 hours. At 5 hours, enough additional Karstedt's Pt catalyst was added to increase the Pt concentration to 10 ppm, and then at 22 hours, enough additional Karstedt's Pt catalyst was added to increase the Pt concentration to 15 ppm. The progress of the reaction was monitored by FTIR. The resulting product was stripped to dry at 1-2 mmHg using a rotary evaporator heated in an oil bath at 80°C. This sample is summarized in Table 8 below.

[0105] [Table 5]

[0106] [Table 6]

[0107] [Table 7]

[0108] Note: IE7 was prepared using CE5 resin, and IE8 was prepared using CE6 resin.

[0109] [Table 8]

[0110] [Table 9]

[0111] [Table 10]

[0112] [Table 11]

[0113] [Table 12]

[0114] In this Reference Example 9, several of the resins prepared as described above were incorporated into an emulsion composition. Each sample was prepared by combining 66.6 parts by weight of resin and 6.66 parts by weight of anionic surfactant by blending them in a dental mixer at 3600 rpm for 30 seconds. An emulsion was then produced by adding 26.74 parts by weight of water.

[0115] In this Reference Example 10, each emulsion prepared as described in Reference Example 9 was tested as a binder in a paint composition by combining the emulsion with a colored paste, then mixing it with a Speedmixer at 2000 rpm for 1 minute, stabilizing it in a can for 24 hours, and remixing it before application. The colored paste composition contained the starting materials in the amounts shown in Table 10 below.

[0116] [Table 13]

[0117] The colored paste composition was prepared as follows: Using a blade, an antifoaming agent was added to the pigment dispersion and stirred for 10 minutes. A filler was added to this blend and stirred again for 10 minutes. The resulting colored paste had an NVC of 72.57%.

[0118] A paint composition was obtained by blending 60% of the previously colored paste with 40% of the emulsion prepared as described in Reference Example 9. After completion, a condensation catalyst (TYZOR® TAA from Dorf Ketal) was added. The sample paint compositions were each applied by drawdown onto CRS metal substrates that had been washed with isopropanol before application (wet film thickness = 150 μm).

[0119] The performance of the samples prepared as described above was evaluated as follows. "Dry touch performance" was developed from "Set-to-Touch Time" (see U.S. Patent No. 5,922,398). This test is similar to ASTM D1640, a test for drying organic coatings at RT. The coating composition was applied to a non-porous substrate (metal panel) to a specific film thickness by appropriate means. Measurements were taken at 2 hours and 4 hours by touching the wet coating film with the tip of a clean thumb. The ASTM method was modified so that the "Set-to-Touch" time in these examples is defined not only by the time when no coating adheres to the fingertip and no fingerprints are left on the panel after a light touch, but also by the time it takes for the wet coating to become non-sticky. A mark of 1 was assigned to a completely dry coating, 3 to a dry but soft coating, and 5 to a wet coating.

[0120] After curing at room temperature for 24 hours, ■Pendulum hardness (Persoz) was evaluated. Pendulum hardness corresponds to the frequency required for the pendulum amplitude to decrease from 12° to 4°, measured on a dry film. The harder the coating, the higher the frequency. ■High-temperature resistance was evaluated after exposing the coated plate to heat on a hot plate, following the protocol below. ● The oven temperature was raised from room temperature to 500°C in 1 hour, and then maintained at a constant temperature of 500°C for 1 hour. Next, the cooling process was initiated over several hours. ●The evaluation of discoloration of the coating is done using the so-called CIELAB color coordinate a * , b * , and L * When performed using and combined to identify, the color of the object was described (under given or known observational conditions), and then the color deviation was measured according to ASTM D2244-21. ●The adhesion of the coating on the substrate was evaluated according to the DIN 2409 test method. Adhesion was reported in terms of material loss percentage. The degree of cohesive failure was reported based on the amount of material loss on the adhesive tape (in photographic form). ● Chalking was evaluated by rubbing the coating nine times with a finger. If chalking occurred, some dense dust appeared on the finger and it was reported as "present".

[0121] The results are shown in Table 11 below.

[0122] [Table 14]

[0123] [Table 15]

[0124] All tested work examples showed better coating performance than commercially available resins DOWSIL® US-CF-2403 and DOWSIL® CF-2405. Specifically, the better (lower) dry hardness after 2 hours indicates that the alkoxy-functionalized silsesquioxane resin has a faster curing time. Samples CE2 and IE4 showed improved coating performance when the vinyl groups on the resin of CE2 were reacted with an ETM converter, alkoxy groups were grafted using spacers, and they were positioned away from the resin core. Specifically, under the tested conditions, IE4 showed a decrease in dry touch value, an increase in hardness, a decrease in discoloration value, and almost no significant change in adhesion value before and after heat treatment compared to CE2. Samples CE3 and IE5 showed improved coating performance when the vinyl groups on the resin of CE3 were reacted with an ETM converter, alkoxy groups were grafted using spacers, and they were positioned away from the resin core. Specifically, under the tested conditions, the dry touch value and discoloration value decreased. A decrease in the dry touch value is an indicator of a reduction in curing time (faster curing of alkoxy-functionalized silsesquioxane resin), which is frequently desired by customers. While we do not wish to be bound by theory, it is thought that emulsions with lower dry touch values ​​cure faster, resulting in faster processing speeds as desired by customers. Furthermore, customers also desire higher hardness of the cured film. While we do not wish to be bound by theory, the inventors of this invention have surprisingly found that silsesquioxane resin, which is in a liquid state under ambient conditions, can be easily emulsified into an aqueous silicone-type emulsion. Moreover, this liquid resin cures at a good curing rate to form a solid film. Furthermore, these advantages can be achieved without adding organic solvents to the emulsion.

[0125] In this reference example 11 (samples IE11 and IE12), the emulsions were prepared as follows. An alkoxy-functionalized silsesquioxane resin was prepared by repeating IE7. The emulsion was prepared by combining 66.6 parts by weight of alkoxy-functionalized silsesquioxane resin (prepared as described above for IE7) and 6.66 parts by weight of anionic surfactant, blended at 3600 rpm for 30 seconds using a dental mixer. Water was then sequentially added in amounts of 25.74 parts by weight to produce an emulsion, which was sample IE11. Sample IE12 was prepared in the same manner, but 1 part by weight of Acrysol RM-2020 was added to the emulsion. The film had a good and smooth appearance. Each emulsion was formulated as a paint.

[0126] The performance was evaluated as described herein and is shown in Table 12 below.

[0127] [Table 16]

[0128] Definitions and Use of Terms All quantities, ratios, and percentages in this specification are by weight unless otherwise indicated by the context of the specification. The articles “a,” “an,” and “the” each refer to one or more unless otherwise indicated by the context of the specification. The singular form includes the plural form unless otherwise indicated by the context of the specification. The “Summary of the Invention” and “Abstract” are incorporated herein by reference. The transitional phrases “comprising,” “consisting essentially of,” and “consisting of” are used as described in the Manual of Patent Examining Procedure Ninth Edition, Revision 08.2017, Last Revised January 2018 at section §2111.03 I, II, and III. Any feature or aspect of the Invention may be used in combination with any other feature or aspect enumerated herein. Abbreviations used herein have their definitions in Table 13.

[0129] [Table 17]

[0130] Test method An example of a test method for determining the hydrolyzable group content of silsesquioxane resin is as follows: The hydrolyzable group content is determined in deuterated benzene, 29 Si and 13 It is analyzed by 13C NMR. The total hydrolyzable content is: 29 The amount of this hydrolyzable group, which is methoxy, is measured by Si NMR analysis and reported as a mole fraction based on Si units. 13 This is determined by 13C NMR analysis (using 1,4-dioxane as an internal standard). The difference between the total hydrolyzable group content and the amount of methoxy was the amount of OH groups present.

[0131] GPC samples were prepared at a 1% (weight / weight) concentration in certified THF, filtered through a 0.45 μm PTFE syringe filter, and analyzed by comparison with polystyrene standards. The relative calibration curve (tertiary fit) used for molecular weight determination was based on 12 polystyrene standards with a molecular weight range of 580–1,735,000 Daltons. The chromatography apparatus consisted of a vacuum degasser, a Viscotek VE3580 RI detector, and a Viscotek GPCmax VE2001 Solvent / Sample Module fitted with two (300 mm × 7.5 mm) Polymer Laboratories Mixed C columns (molecular weight separation range 200–3,000,000), with a guard column mounted in front of them. Separation was performed using certified grade THF programmed to flow at 1.0 mL / min, with the injection volume set to 100 μL, and the columns and detector heated to 35°C. Data collection took 30 minutes, and processing was performed using OmniSEC software.

[0132] The evaluation of discoloration of the coating is done using the so-called CIELAB color coordinate a * , b * , and L * When performed using and combined to identify, the color of the object was described (under given or known observational conditions), and then the color deviation was measured according to ASTM D2244-21.

Claims

1. It is an emulsion, I) A) A non-aqueous phase containing an alkoxy-functionalized silsesquioxane resin, II) The aqueous phase containing water, III) containing a surfactant, The alkoxy-functionalized silsesquioxane resin has the following unit formula: (R ２ ３ SiO １／２ ) ｃ (R ２ ２ SiO ２／２ ) ｄ (R ２ SiO ３／２ ) ｅ (ZO １／２ ) ｆ (HO １／２ ) ｇ comprising, wherein, Each R ２ However, alkyl groups and the base of formula (I) 【Chemistry 1】 Independently selected from the group consisting of, In equation (I), Each R １ However, it is an alkyl group that is selected independently. Each D １ However, it is an alkylene group that is selected independently. The subscripts a, b, and x are, The subscript 'a' is 1 or 2, The subscript b is 0 or 1, An integer whose subscript x is either 0 or 1, However, R is present in an average of 5 mol% to 25 mol% per molecule. ２ However, it has formula (I), The subscripts c, d, and e represent the mole fractions of each unit in the alkoxy-functionalized silsesquioxane resin, and the subscripts c, d, and e are, 0 ≤ c ≤ 0.25, 0 ≤ d ≤ 0.20, 0.55 < e ≤ 1, and The quantity (c + d + e) ​​has a value such that it equals 1. Each Z is an independently selected alkyl group. The subscript f represents the molar amount of alkoxy groups in the resin, and the subscript g represents the molar amount of hydroxyl groups in the resin. The subscripts f and g are, 0.01 ≤ f ≤ 0.70, 0 ≤ g ≤ 0.05, and The value has such that 0.02 ≤ (f + g) ≤ 0.75, An emulsion in which the alkoxy-functionalized silsesquioxane resin is in a liquid state at 23°C ± 3°C and 101.325 kPa.

2. A) In the alkoxy-functionalized silsesquioxane resin, The subscript a = 1, The subscript b = 1, Each D １ However, experimental formula C ２ H ４ - has, Each R １ However, it is methyl, Each R that is not a base of equation (I) ２ However, it is methyl, The emulsion according to claim 1, wherein each Z is independently selected from the group consisting of methyl and ethyl.

3. A) In the alkoxy-functionalized silsesquioxane resin, The subscript b = 0, Each D １ However, experimental formula C ２ H ４ - has, Each R １ However, it is methyl, Each R that is not a base of equation (I) ２ However, it is methyl, The emulsion according to claim 1, wherein each Z is independently selected from the group consisting of methyl and ethyl.

4. A) In the alkoxy-functionalized silsesquioxane resin, R ２ However, per molecule, unit (R ２ SiO ３／２ The emulsion according to claim 1, having formula (I) in at least one of the cases of ).

5. The emulsion according to any one of claims 1 to 4, wherein the alkoxy-functionalized silsesquioxane resin has a weight-average molecular weight of 1,000 g / mol to 15,000 g / mol as measured by gel permeation chromatography.

6. III) The emulsion according to any one of claims 1 to 5, wherein the surfactant includes an anionic surfactant.

7. III) The emulsion according to claim 6, wherein the surfactant comprises sodium lauryl sulfate.

8. The emulsion described above, I) 50% to 80% by weight of the alkoxy-functionalized silsesquioxane resin, II) Water in a concentration of 15% to 40% by weight, The surfactant is contained in an amount of 2% to 10% by weight of III), An emulsion according to any one of claims 1 to 7, each based on the combined weight of all the starting materials in the emulsion.

9. The emulsion according to any one of claims 1 to 8, wherein the composition is substantially free of organic solvents.

10. An emulsion according to any one of claims 1 to 9, further comprising additional starting materials selected from the group consisting of condensation reaction catalysts, coupling agents, antistatic agents, ultraviolet (UV) stabilizers, plasticizers, leveling agents, preservatives, foam enhancers, adhesives, thickeners, aqueous phase stabilizers, fillers, suspending agents, biocides, freeze / thaw additives, antifreeze agents, viscosity modifiers, defoaming agents, compatibilizers, dyes, binders, antioxidants, flame retardants, and two or more combinations thereof.

11. The emulsion according to any one of claims 1 to 9, further defined as a paint composition, further comprising additional starting materials selected from the group consisting of dyes, defoamers, fillers, and combinations of two or more thereof.

12. A method for preparing an emulsion, wherein the method is The combination is obtained by combining the alkoxy-functionalized silsesquioxane resin, water, and the surfactant as starting materials. A method for preparing an emulsion according to any one of claims 1 to 11, comprising shearing the combination to prepare the emulsion.

13. A method for preparing a film, wherein the method is 1) Applying the emulsion according to any one of claims 1 to 11 to a substrate, 2) A method comprising forming the film on the substrate from the emulsion.

14. Forming the film on the substrate is Forming a wet film on the aforementioned substrate, The process includes drying the wet film on the substrate to form the film, and drying the wet film is (i) Evaporating water from the wet film, (ii) Exposing the wet film to a high temperature to expel water from it, (iii) curing the wet film, or The method according to claim 13, comprising any combination of (iv)(i) to (iii).

15. A membrane prepared by the method of claim 13 or 14.

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