Alkoxy-functional silsesquioxane resins and methods of making and using same

Abstract

Provided are an alkoxy functional silsesquioxane resin and a hydrosilylation reaction method for the preparation of the alkoxy functional silsesquioxane resin. The alkoxy-functional silsesquioxane resins are liquid under ambient conditions and are useful in solvent-borne and solvent-free moisture curable compositions, such as coating compositions.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit under 35 USC §119(e) of U.S. Provisional Patent Application Serial No. 63 / 453,261, filed on March 20, 2023. U.S. Provisional Patent Application Serial No. 63 / 453,261 is hereby incorporated by reference. Technical Field

[0003] An alkoxy-functional silsesquioxane resin and a method for preparing the same are provided. The alkoxy-functional silsesquioxane resin can be used in moisture-curable compositions suitable for forming coatings. Background Art

[0004] The coatings industry is under pressure to reduce the use of volatile organic compounds (VOCs) to achieve more environmentally friendly solutions. Therefore, solvent-free liquid products are desirable for leveraging the benefits of silicone resins in high-performance applications. For example, temperature-resistant coatings achieved with solvent-free, moisture-curable compositions are expected to replace less desirable solvent-based options. In addition, since room-temperature curable compositions are preferred for certain applications, moisture curing is desirable.

[0005] Solvent-free liquid silicone resins typically have slower cure times than solvent-based coating compositions due to the need to use inherently lower glass transition resins, which is undesirable for the ultimate desired hardcoat properties.

[0006] Therefore, there is a need in the industry to improve the cure speed of moisture-curable compositions containing silicone resins. Summary of the Invention

[0007] An alkoxy-functional silsesquioxane resin and a method for preparing the same are provided. The alkoxy-functional silsesquioxane resin can be formulated into a moisture-curable composition, such as a coating composition. DETAILED DESCRIPTION

[0008] Alkoxy functional silsesquioxane resins comprise units of the formula:

[0009] (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 ; where each R 2is independently selected from the group consisting of alkyl groups and groups of formula (I);

[0010]

[0011] wherein in formula (I),

[0012] each R 1 is an independently selected alkyl group,

[0013] each D 1 is an independently selected alkylidene group,

[0014] the subscripts a, b, and x are integers whose values are such that

[0015] the subscript a is 1 or 2,

[0016] the subscript b is 0 or 1, and

[0017] the subscript x is 0 or 1;

[0018] with the proviso that on average 5 mol% to 25 mol% of the groups R 2 have formula (I);

[0019] the subscripts c, d, and e represent the mole fraction of each unit in the alkoxy-functional silsesquioxane resin, and the values of the subscripts c, d, and e are such that

[0020] 0 < c < 0.25,

[0021] 0 < d < 0.20,

[0022] 0.55 < e < 1, and

[0023] the quantity (c + d + e) = 1;

[0024] each Z is an independently selected alkyl group; and

[0025] the subscript f represents the molar amount of alkoxy groups in the alkoxy-functional silsesquioxane resin, and the subscript g represents the molar amount of hydroxyl groups in the alkoxy-functional silsesquioxane resin, and the values of the subscripts f and g are such that

[0026] 0.01 < f < 0.70;

[0027] 0 < g < 0.05; and

[0028] 0.02 < (f + g) < 0.75.

[0029] In the above unit formula, subscripts c, d, and e represent the mole fraction of each unit in the alkoxyl-functional silsesquioxane resin. The quantity (c + d + e) = 1. The values of subscripts c, d, and e are such that 0 < c < 0.25, 0 < d < 0.20, and 0.55 < e < 1. Subscript c can be 0, alternatively > 0, alternatively at least 0.100, alternatively at least 0.101, alternatively at least 0.102, alternatively at least 0.110, alternatively at least 0.120, and alternatively at least 0.130; while subscript c can be at most 0.300, alternatively at most 0.250, alternatively at most 0.240, alternatively at most 0.200, and alternatively at most 0.150, alternatively at most 0.110. Alternatively, subscript c can be from 0 to 0.300, alternatively from 0 to 0.250, alternatively from 0.100 to 0.240, and alternatively from 0.102 to 0.240.

[0030] Subscript d can be 0, alternatively > 0, alternatively at least 0.001, alternatively at least 0.002, alternatively at least 0.003, alternatively at least 0.004, alternatively at least 0.005, and alternatively at least 0.006; while subscript d can be at most 0.020, alternatively at most 0.015, alternatively at most 0.010, alternatively at most 0.009, alternatively at most 0.008, alternatively at most 0.007, and alternatively at most 0.006. Alternatively, subscript d can be from 0 to 0.020, alternatively from > 0 to 0.015, and alternatively from 0.006 to 0.010.

[0031] Subscript e is > 0.55 to 1. Alternatively, subscript e can be at least 0.550, alternatively at least 0.600, alternatively at least 0.650, alternatively at least 0.700, alternatively at least 0.750, alternatively at least 0.800; while subscript e can be at most 1, alternatively at most 0.995, alternatively at most 0.991, alternatively at most 0.95, alternatively at most 0.925, alternatively at most 0.920, alternatively at most 0.915, alternatively at most 0.910, alternatively at most 0.905, and alternatively at most 0.0900. Alternatively, subscript e can be from 0.905 to 1, alternatively from 0.910 to 1, alternatively from 0.915 to 1, alternatively from 0.990 to 1, alternatively from 0.991 to 1, alternatively from 0.995 to 1, and alternatively subscript e can be 1.

[0032] In the above unit formula, each Z is an independently selected alkyl group. Suitable alkyl groups can be cyclic or acyclic, branched or unbranched, or combinations thereof. Examples of alkyl groups are, but are not limited to, methyl, ethyl, propyl (e.g., iso-propyl and / or n-propyl), butyl (e.g., iso-butyl, n-butyl, t-butyl, and / or sec-butyl), pentyl (e.g., iso-pentyl, neopentyl, t-pentyl, and / or cyclopentyl), hexyl (e.g., cyclohexyl or n-hexyl), heptyl, octyl, nonyl, and decyl, as well as branched alkyl groups having 6 or more carbon atoms. Alternatively, each Z can be an alkyl group of 1 to 4 carbon atoms, alternatively 1 to 2 carbon atoms. Each Z can be a methyl or ethyl group; alternatively a methyl group.

[0033] Units (HO 1 / 2 ) and (ZO 1 / 2 ) represent hydroxyl and alkoxy groups, respectively, bonded to silicon atoms in the resin (e.g., the hydroxyl and alkoxy groups are bonded to silicon atoms in the resin portion of the alkoxyl-functional silsesquioxane resin that are moieties other than the grafted R 2 groups of Formula (I)). Without wishing to be bound by theory, it is believed that the hydroxyl and / or alkoxy groups can be bonded to any one or more of the silicon atoms in the monofunctional units of Formula (R 2 3SiO 1 / 2 ), the bifunctional units of Formula (R 2 2SiO 2 / 2 ), and the trifunctional units of Formula (R 2 SiO 3 / 2 ) in the alkoxyl-functional silsesquioxane resin.

[0034] In the above unit formula, each alkyl group R 2 is independently selected and can be an alkyl group as described above for Z. Alternatively, each alkyl group of R 2 may be a methyl group. However, at least some of the groups R 2 have Formula (I) (e.g., as a result of the silicon hydride addition reaction in the methods described below). In the unit formula, 5 to 25 mol% of all R 2 groups can have Formula (I), while the remainder of all R 2 groups to 100 mol% are alkyl groups. Alternatively, at least 5 mol%, alternatively at least 6 mol%, alternatively at least 8 mol%, alternatively at least 9 mol%, alternatively at least 10 mol%, alternatively at least 13 mol%, alternatively at least 14 mol%, alternatively at least 15 mol% of all R 2 groups have Formula (I); while the remainder of all R 2at most 25 mol%, alternatively at most 23 mol%, alternatively at most 20 mol%, alternatively at most 15 mol%, alternatively at most 14 mol%, alternatively at most 13 mol%, alternatively at most 12 mol% of the groups have formula (I). Alternatively, R 2 The amount of groups can be 5 mol% to 25 mol%, alternatively 5 mol% to 23 mol%, alternatively 6 mol% to 15 mol%.

[0035] In the above unit formula, subscript f represents the molar amount of alkoxy groups in the resin, and subscript g represents the molar amount of hydroxyl groups in the resin. The values of subscripts f and g are such that 0.01 < f < 0.70; 0 < g < 0.05; and 0.02 < (f + g) < 0.75. Alternatively, subscript f can have a value of at least 0.01, alternatively at least 0.10, alternatively at least 0.20, alternatively at least 0.30; while subscript f can have a value of at most 0.70, alternatively at most 0.60, alternatively at most 0.56, alternatively at most 0.52. Alternatively, subscript f can have a value such that 0.10 < f < 0.60, alternatively 0.30 < f < 0.60, alternatively 0.37 < f < 0.56; and alternatively 0.37 < f < 0.44. Alternatively, subscript g can have a value of at least 0.005, alternatively at least 0.008, alternatively at least 0.01; while subscript g can have a value of at most 0.05, alternatively at most 0.049, alternatively at most 0.045, alternatively at most 0.040, alternatively at most 0.035. Alternatively, subscript g can have a value such that 0.005 < g < 0.05, alternatively 0.006 < g < 0.049, alternatively 0.006 < g < 0.035; and alternatively 0.008 < g < 0.05. Alternatively, the amount (f + g) can be at least 0.02, at least 0.20, alternatively at least 0.30, alternatively at least 0.40, alternatively at least 0.41, alternatively at least 0.43, alternatively at least 0.45; while the amount (f + g) can be at most 0.57, alternatively at most 0.52, alternatively at most 0.49, alternatively at most 0.47, and alternatively at most 0.45. Alternatively, the amount (f + g) can have a value such that 0.02 < (f + g) < 0.57; alternatively 0.20 < (f + g) < 0.57; alternatively 0.30 < (f + g) < 0.57; alternatively 0.40 < (f + g) < 0.57; alternatively 0.43 < (f + g) < 0.52; and alternatively 0.40 < (f + g) < 0.49.

[0036] In the groups of the above formula (I), each of the subscripts a, b, and x represents an integer. Subscript a is 1 or 2, alternatively, subscript a can be 1. Subscript b is 0 or 1. Alternatively, subscript b can be 0. Alternatively, subscript b can be 1. Subscript x is 0 or 1. Alternatively, subscript x can be 0.

[0037] In the groups of the above formula (I), each alkyl group R 1 is independently selected and can be an alkyl group as described above for Z. Alternatively, each R 1 may be a methyl group.

[0038] In the groups of the above formula (I), D 1 is an independently selected alkylene group. D 1 may have an empirical formula of -C h H 2h - where subscript h is at least 2, alternatively 2 to 12, alternatively 2 to 10, alternatively 2 to 8, alternatively 2 to 6, alternatively 2 to 4, and alternatively 2 to 3. Alternatively, each D 1 may be an ethylene, propylene, or hexylene group. Alternatively, each D 1 may be -C2H4-, such as an ethylene group.

[0039] The alkoxy-functional silsesquioxane resin can be free or free of tetrafunctional siloxane units of the formula (SiO 4 / 2 ). The alkoxy-functional silsesquioxane resin is liquid at room temperature and ambient pressure (e.g., 101.325 kPa) (e.g., by visual inspection). Alternatively, the alkoxy-functional silsesquioxane resin can have a Mn of 1,300 g / mol to 4,000 g / mol; alternatively 1,400 g / mol to 3,500 g / mol, and alternatively 2,000 g / mol to 2,500 g / mol. Alternatively, the alkoxy-functional silsesquioxane resin can have a Mw of 1,000 g / mol to 50,000 g / mol; alternatively 2,000 g / mol to 50,000 g / mol; alternatively 2,500 g / mol to 40,000 g / mol; alternatively 4,000 g / mol to 10,000 g / mol; and alternatively 1,000 g / mol to 15,000 g / mol; and a PDI of 2 to 4, alternatively 2.3 to 3.9.

[0040] Process for preparing a resin

[0041] The above alkoxy-functional silsesquioxane resins can be prepared via a hydrosilylation reaction process. The process comprises: 1) combining starting materials comprising: A) an alkoxy-functional organosilicon compound and B) a silsesquioxane resin, in the presence of C) a hydrosilylation reaction catalyst, under conditions for effecting a hydrosilylation reaction. Starting material D) is a solvent, which can optionally be used to facilitate mixing and / or delivery of one or more of the starting materials. For example, C) the hydrosilylation reaction catalyst can be dissolved or dispersed in D) the solvent prior to combining with starting materials A) and B). When B) the silsesquioxane resin comprises silicon-bonded aliphatic unsaturation, starting material A) the alkoxy-functional organosilicon compound can comprise silicon-bonded hydrogen atoms. Alternatively, when B) the silsesquioxane resin comprises silicon-bonded hydrogen atoms, A) the alkoxy-functional organosilicon compound can comprise aliphatic unsaturation.

[0042] Starting material C) is a hydrosilylation reaction catalyst. The hydrosilylation reaction catalyst comprises a platinum group metal. The platinum group metal can be selected from the group consisting of platinum, rhodium, ruthenium, palladium, osmium, and iridium. Alternatively, the platinum group metal can be platinum. The hydrosilylation reaction catalyst can be a platinum group metal or a compound or complex of a platinum group metal. For example, the hydrosilylation reaction catalyst can be a compound such as chlorotris(triphenylphosphine)rhodium(I) (Wilkinson's Catalyst), a rhodium diphosphine chelate such as [1,2-bis(diphenylphosphino)ethane]dichlorodirhodium or [1,2-bis(diethylphosphino)ethane]dichlorodirhodium, chloroplatinic acid (Speier's Catalyst), chloroplatinic acid hexahydrate, platinum dichloride, or a complex of such a compound with an alkenyl-functional organopolysiloxane such as a complex of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane with platinum (Karstedt's Catalyst) or Pt(0) complex in tetramethyltetravinylcyclotetrasiloxane (Ashby's Catalyst). Alternatively, the compound or complex can be microencapsulated in a matrix or core-shell structure. Hydrosilylation reaction catalysts are known in the art, for example, as described in Guo et al. PCT Patent Application Publication WO 2021 / 081822 and references cited therein. Hydrosilylation reaction catalysts are commercially available, for example, SYL-OFF TM 4000 Catalyst and SYL-OFF TM2700 is available from Dow. C) The amount of the hydrosilylation reaction catalyst depends on various factors, including the type and amount of starting materials A) and B), and their respective contents of silicon-bonded hydrogen atoms and aliphatic unsaturations, however the amount of C) the hydrosilylation reaction catalyst is sufficient to catalyze the hydrosilylation reaction and can be, for example, an amount sufficient to provide at least 1 ppm of platinum group metal on a combined weight basis of starting materials A), B), and C), while the amount can be sufficient to provide up to 6,000 ppm of platinum group metal on the same basis. Alternatively, the amount of starting material (C) can be sufficient to provide 1 ppm to 1,000 ppm; alternatively 1 ppm to 100 ppm; alternatively 1 ppm to 50 ppm; alternatively 1 ppm to 25 ppm, and alternatively 1 ppm to 15 ppm of platinum group metal on the same basis.

[0043] Starting material D) is an optional solvent that can be used to deliver one or more of the starting materials. A solvent can be added to facilitate the introduction of certain starting materials, such as C) the hydrosilylation reaction catalyst. Solvents that can be used herein are solvents that aid in fluidizing the starting materials but do not substantially react with the starting materials. The solvent can be selected based on the solubility of the starting materials and the volatility of the solvent. Solubility refers to the solvent being sufficient to dissolve and / or disperse the starting materials. Volatility refers to the vapor pressure of the solvent.

[0044] Suitable solvents include polyorganosiloxanes having a suitable vapor pressure, such as hexamethyldisiloxane, octamethyltrisiloxane, hexamethylcyclotrisiloxane, and other oligomeric organosiloxanes, such as polydimethylsiloxanes, for example, DOWSIL TM 200 fluid and DOWSIL TM OS fluid.

[0045] Alternatively, the solvent can include an organic solvent. The organic solvent can 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.

[0046] The amount of D) the solvent will depend on various factors, including the type of solvent selected and the amount and type of other starting materials selected for the composition. However, the amount of the solvent can be in the range of 1 wt% to 99 wt%, alternatively 2 wt% to 90 wt%, based on the combined weight of starting materials A), B), and C).

[0047] The hydrosilylation reaction process can be carried out by any convenient means, such as combining the starting materials A), B), and C), and when present, D). Typically, starting materials A) and B) are combined in a reactor. When the reaction is carried out at an elevated or reduced temperature as described below, the reactor can be heated or cooled in any suitable manner, for example, via a jacket, mantle, exchanger, bath, or coil. Starting materials A), B), and C), and optionally component D), and optionally D), can be fed into the reactor together or separately, or can be arranged in the reactor in any order of addition and in any combination. For example, starting materials A) and C), and optionally D), can be added to the reactor, and starting material B) can be added to it in one aliquot, or alternatively starting material B) can be metered into the reactor in two or more aliquots, either continuously or intermittently. Alternatively, starting materials B) and C), and optionally D), can be added to the reactor, and starting material A) can be added to it in one aliquot, or alternatively starting material A) can be metered into the reactor in two or more aliquots, either continuously or intermittently. The order of addition can depend on various factors, including which starting material has silicon-bonded hydrogen atoms.

[0048] Alternatively, starting materials A), B), and optionally D), can be first combined before addition, or can be added sequentially to a vessel, and thereafter starting material C) can be added to the vessel containing starting materials A) and B), and optionally D). Generally, references herein to a “reaction mixture” generally refer to a mixture comprising starting materials A), B), and C), and optionally D) (e.g., obtained by combining such starting materials, as described above).

[0049] The amounts of starting materials A) and B) are not limited and can be any amount sufficient to provide the group content of formula (I) in the alkoxy-functional silsesquioxane resin described above.

[0050] Step 1) of the process can further include stirring the reaction mixture. Stirring can enhance the mixing and contacting of starting materials A), B), and C), and when present, D), together when, for example, combined in their reaction mixture. Such contacting can independently be with other conditions, with stirring (e.g., simultaneously or sequentially) or without stirring (i.e., independently of, or alternatively to, stirring). The other conditions can be regulated to enhance the contacting of starting materials A) and B), thereby enhancing the reaction (i.e., isomerization and hydrosilylation) to form the reaction product comprising organosilicon compounds.

[0051] Step 1) of the process can further include heating the reaction mixture. The temperature depends on various factors, including the vapor pressure of starting materials A) and B), and when present, D), however the temperature can be from 50 °C to 150 °C, alternatively from 60 °C to 100 °C.

[0052] The methods described herein can optionally further include one or more additional steps. For example, the method can further include step 2) purifying the hydrosilylation reaction product, for example to remove and / or recover unreacted starting materials. Purification can be carried out by any convenient means, such as stripping and / or heated distillation and optionally under reduced pressure and / or with azeotroping with a solvent, filtration, and combinations thereof. Distillation conditions typically include: (i) high temperature; (ii) reduced pressure; or (iii) both high temperature and reduced pressure. Elevated or reduced means compared to room temperature and atmospheric pressure. Distillation can be continuous or batch, and can include the use of a solvent (e.g., hexane, or toluene, or other solvents described herein as starting material D) such that the distillation can be an azeotropic distillation.

[0053] As used herein, purifying the hydrosilylation reaction product is generally defined as increasing the relative concentration of the alkoxy-functional silsesquioxane resin compared to other compounds with which it is combined (e.g., in the hydrosilylation reaction product or a purified version thereof). As understood in the art, purification can include removing other compounds from such a combination (i.e., reducing the amount of impurities and / or unreacted starting materials mixed with the alkoxy-functional silsesquioxane resin in the hydrosilylation reaction product) and / or removing the alkoxy-functional silsesquioxane resin itself from the combination. Any suitable purification technique and / or protocol can be used. Examples of suitable purification techniques include distillation, stripping, evaporation, extraction, filtration, washing, partitioning, phase separation, adsorption, and chromatography. As will be appreciated by one of skill in the art, any of these techniques can be used in combination (e.g., sequentially) with any other technique to purify the hydrosilylation reaction product. Regardless of the particular technique(s) selected, purifying the hydrosilylation reaction product can be carried out sequentially (i.e., in order) with the hydrosilylation reaction itself, and thus can be automated. Alternatively, purification can be a separate procedure to which the hydrosilylation reaction product comprising organosilicon compounds is subjected.

[0054] For example, when A) the alkoxy-functional organosilicon compound has silicon-bonded hydrogen atoms, and B) the silsesquioxane resin has aliphatically unsaturated groups, the method for making the alkoxy-functional silsesquioxane resin described above can include:

[0055] 1) combining starting materials comprising:

[0056] A1) an alkoxy-functional organohydrogensiloxane oligomer having the following formula:

[0057] wherein R 1 , D 1 , a, and x are as described above; and

[0058] B1) an alkenyl-functional silsesquioxane resin having the following unit formula:

[0059] (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 )g, wherein Z, c, d, e, f, and g are as described above, and

[0060] each R 3 is independently selected from the group consisting of alkyl groups and alkenyl groups,

[0061] with the proviso that at least one R 3 per molecule is an alkenyl group;

[0062] optionally D) a solvent as described above; and

[0063] in the presence of C) a hydrosilylation reaction catalyst as described above. Optional additional steps are as described above.

[0064] The starting material A1) is an alkoxy-functional organohydrogensiloxane oligomer of the formula:

[0065] wherein R 1 , D 1 , a, and x are as described above. Alternatively, the alkoxy-functional organohydrogensiloxane oligomer can have subscript a = 1 and subscript x = 0. Alternatively, in the formula for the A1) alkoxy-functional organohydrogensiloxane oligomer, each R 1 = methyl, and each D 1 may have the empirical formula -C2H4-. Alternatively, the alkoxy-functional organohydrogensiloxane oligomer can be trimethoxysilyl ethyl-1,1,3,3,5,5-hexamethyltrisiloxane; trimethoxysilyl ethyl-1,1,3,3-tetramethyldisiloxane; or combinations thereof. The alkoxy-functional organohydrogensiloxane oligomers of the formula shown above are known in the art and can be prepared by known methods, such as those described in the following patents: Gohndrone et al. U.S. Patent 10,968,317; Gohndrone et al. U.S. Patent 11,098,163;

[0066] U.S. Patent Nos. 11,161,939 to Zhou et al.; 11,168,181 to Zhou et al.; and 11,492,448 to Gohndrone et al.; and JP 2007077136 to Uehara et al.

[0067] The starting material B1) is a silsesquioxane resin that is a unit formula (R 3 3SiO 1 / 2 ) c (R 3 2SiO 2 / 2 ) d (R 3 SiO 3 / 2 ) e (ZO 1 / 2 ) f wherein Z, c, d, e, and f are as described above, and each R 3 is independently selected from the group consisting of alkyl groups and alkenyl groups capable of undergoing a hydrosilylation reaction, with the proviso that at least one R 3 is an alkenyl group per molecule. Examples of suitable alkenyl groups can have 2 to 12, alternatively 2 to 10, alternatively 2 to 8, and alternatively 2 to 6 carbon atoms. The alkenyl groups are capable of undergoing a hydrosilylation reaction with silicon-bonded hydrogen atoms. Examples of alkenyl groups suitable for R 3 are vinyl, allyl, and hexenyl; alternatively vinyl and hexenyl; and alternatively vinyl.

[0068] The starting material B1) can be prepared by known methods, such as a co-hydrolyzable organosilane having three silicon atom-bonded hydrolyzable moieties (columns such as halogen or alkoxy) per molecule. For example, the starting material B1) can be prepared by the method described in U.S. Patent No. 11,248,119 by varying the starting materials and their amounts. The starting material B1) can be obtained, for example, by co-hydrolysis of methyltrimethoxysilane and vinyltrimethoxysilane, optionally with additional silanes such as octyltriethoxysilane and octyltrimethoxysilane. Alkoxy silanes having two alkoxy groups per molecule or having 1 alkoxy group per molecule, such as dimethyldimethoxysilane or trimethylmethoxysilane, can be included to add di- and / or mono-functional siloxane units to the silsesquioxane resin, respectively. Acid catalysts, such as triflic acid, water, and / or alcohol can be used to facilitate the co-hydrolysis.

[0069] Alternatively, when A) the alkoxy-functional organosilicon compound has an aliphatically unsaturated group and B) the silsesquioxane resin has silicon-bonded hydrogen atoms, the above-described method of making an alkoxy-functional silsesquioxane resin can include:

[0070] 1) combining starting materials comprising:

[0071] A2) an alkoxy-functional organosilicon compound of the formula R 1 x R 5 Si(OR 1 ) 3-x wherein R 1 and x are as described above, and R 5 is an alkenyl group capable of undergoing a hydrosilylation reaction; and

[0072] B2) a hydride-functional silsesquioxane resin having the following unit formula:

[0073] (R 4 3SiO 1 / 2 ) c (R 4 2SiO 2 / 2 ) d (R 4 SiO 3 / 2 ) e (ZO 1 / 2 ) f ; wherein 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, with the proviso that at least one R 4 per molecule is H;

[0074] optionally D) a solvent as described above, and

[0075] in the presence of C) a hydrosilylation reaction catalyst as described above.

[0076] Starting material A2) is an alkoxy-functional organosilicon compound having at least one alkenyl group per molecule. The alkoxy-functional organosilicon compound can be an alkoxy-functional silane of the formula R 1 x R 5 Si(OR 1 ) 3-x wherein 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 can have 2 to 12, alternatively 2 to 10, alternatively 2 to 8, and alternatively 2 to 6 carbon atoms. The alkenyl group is capable of undergoing a hydrosilylation reaction with a silicon-bonded hydrogen atom. Suitable R 5Examples of alkenyl groups are vinyl, allyl, and hexenyl; alternatively vinyl and hexenyl; and alternatively vinyl. Alkoxy-functional silanes suitable 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 vinyltri(methoxyethoxy)silane; alkenyl-functional dialkoxysilanes such as vinylphenyldiethoxysilane, vinylmethyldimethoxysilane, and vinylmethyldiethoxysilane; alkenyl-functional monoalkoxysilanes such as trivinylmethoxysilane are available from Gelest, Inc. of Morrisville, Pennsylvania, USA.

[0077] Starting material B2) is 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 wherein Z, c, d, e, and f are as described above, and each R 4 is independently selected from the group consisting of alkyl groups and H, with the proviso that at least one R 4 per molecule is H. Starting material B2) can be prepared by known methods, such as those described above for starting material B1), by substituting an alkenyl-functional alkoxy silane with an appropriate starting material, such as a hydrogen-functional alkoxy silane. For example, starting material B2) can be prepared by the methods described in U.S. Patent 11,248,119 by changing the starting materials and their amounts.

[0078] The product of these methods is the alkoxy-functional silsesquioxane resin described above. The alkoxy-functional silsesquioxane resin can be used in a curable composition, such as a coating composition, for example a conformal coating composition.

[0079] Moisture-curable composition

[0080] The alkoxy-functional silsesquioxane resins prepared as described above can be used in moisture-curable compositions, such as coating compositions. For example, the alkoxy-functional silsesquioxane resins described herein can be used in moisture-curable (polyorganosiloxane) compositions for electrical / electronic devices, such as described in U.S. Patent Application Publication 2021 / 0238444, wherein the alkoxy-functional silsesquioxane resins described herein are used with or in place of the resins described in U.S. Patent Application Publication 2021 / 0238444.

[0081] The moisture-curable composition can comprise: I) the alkoxy-functional silsesquioxane resin described above, and II) a condensation reaction catalyst.

[0082] The starting material II) is a condensation reaction catalyst. Examples of II) condensation reaction catalysts include, but are not limited to: tin compounds such as dimethyltin dineodecanoate and stannous octoate; titanium compounds such as titanium tetraisopropoxide; titanium tetra(n-butoxide); and titanium tetra(t-butoxide); and organotitanium chelates such as titanium di(isopropoxide)bis(ethyl acetoacetate); titanium di(isopropoxide)bis(methyl acetoacetate); titanium di(isopropoxide)bis(acetylacetone); and bis(ethylacetoacetato-O1',O3")bis(propan-2-olato) titanium. Condensation reaction catalysts are known in the art and are commercially available. For example, organotitanates and zirconates are available under the trade designation TYZOR TM Available commercially from Dorf Ketal.

[0083] The content of the starting material II) is not limited, provided that it is in an amount that imparts sufficient curability to the moisture-curable composition. For example, the content of the starting material II) can be 0.01 to 20 parts by weight, alternatively 0.01 to 15 parts by weight, alternatively 0.01 to 10 parts by weight, alternatively 0.01 to 5 parts by weight, alternatively 0.01 to 1 parts by weight, alternatively 0.05 to 10 parts by weight, or alternatively 0.05 to 5 parts by weight, relative to 100 parts by weight of the combined starting materials I) and II). Without wishing to be bound by theory, it is believed that when the content of II) condensation reaction catalyst is greater than or equal to the lower limit of the above range, the resulting composition is sufficiently cured by moisture in air, and when the content is less than or equal to the upper limit of the above range, the surface curing rate of the resulting composition can be improved.

[0084] The moisture-curable composition can optionally further comprise one or more additional starting materials (i.e., in addition to the above I) alkoxyl-functional silsesquioxane resin and II) condensation reaction catalyst). For example, the composition can further comprise at least one of III) a solvent, IV) an alkoxysilane, V) a fluorescent brightening agent and / or UV indicator, VI) a corrosion inhibitor, VII) a chelating agent, VIII) an adhesion promoter, and IX) a combination of two or more of III) through VIII).

[0085] Starting material III) is a solvent, which can be a solvent as described above for starting material D). Alternatively, examples of suitable solvents for use in the moisture- curable composition include, but are not limited to, aliphatic hydrocarbon solvents such as heptane, octane, nonane, decane, and undecane; and siloxane-type solvents such as linear dimethylsiloxane oligomers (described above), cyclic dimethylsiloxane oligomers, and tetra(trimethylsiloxy)silane.

[0086] The content of III) solvent is not limited, provided that it is in an amount to improve the coating properties of the resulting moisture-curable composition. When present, the content of III) solvent can be 0.1 parts by weight to 50 parts by weight, alternatively 0.1 parts by weight to 30 parts by weight, alternatively 0.1 parts by weight to 20 parts by weight, alternatively 0.1 parts by weight to 15 parts by weight, or alternatively 0.1 parts by weight to 10 parts by weight, relative to the content of 100 parts by weight of the combined starting materials I) and II) of the composition. Alternatively, the moisture-curable composition can be essentially free of organic solvent. As used herein, “essentially free of organic solvent” means that organic solvent is not intentionally added to the moisture-curable composition, however, this does not exclude residual solvent present in one or more other starting materials used in the moisture-curable composition. For example, the moisture-curable composition can be free of organic solvent. Alternatively, the moisture-curable composition can contain an undetectable amount of organic solvent by gas chromatography. Alternatively, the moisture-curable composition can contain up to 100 ppm of organic solvent, which is residual in the starting materials used to make the moisture-curable composition.

[0087] Starting material IV) is an alkoxysilane, which can be represented by the general formula: 6 i Si(OR 7 ) (4-i) wherein R 6 is a monovalent hydrocarbon group, R 7 is an alkyl group, and the subscript i is an integer. In the formula of the alkoxysilane, R 6is a monovalent hydrocarbon group. Examples of such groups include, but are not limited to: alkyl groups such as those described above for Z; alkenyl groups such as ethenyl, allyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, and octadecenyl; aryl groups such as phenyl, tolyl, xylyl, naphthyl, benzyl, phenethyl, and phenylpropyl. Alternatively, each R 6 may be independently selected from an alkyl group or an alkenyl group. Alternatively, each R 6 may be independently selected from methyl and ethenyl. Each R 7 is an independently selected alkyl group. Examples of such groups include the alkyl groups described above for Z. Alternatively, each R 7 may be independently selected from methyl or ethyl. The subscript i is an integer having a value of 0 to 2, alternatively 1 or 2.

[0088] IV) Examples of alkoxysilanes include, but are not limited to: dimethyldimethoxysilane, methyltrimethoxysilane, methylphenyldimethoxysilane, and dimethyldiethoxysilane. The starting material IV) can be one of these alkoxysilanes, or a combination of two or more. Alternatively, the starting material IV) can comprise or can be dimethyldimethoxysilane and / or methyltrimethoxysilane. Alkoxysilanes such as these are known in the art and are commercially available as described above for starting materials B1) and B2). Alternatively, the alkoxysilane and the condensation reaction catalyst can be supplied as a moisture cure package, such as under the trade designation TYZOR AC 2930® available from Dorf Ketal. TM is commercially available from Dorf Ketal.

[0089] The content of IV) alkoxysilane is not limited provided that it is in an amount that imparts sufficient shelf life to the resulting composition. Alternatively, the content of IV) alkoxysilane can be 0.5 parts by weight to 20 parts by weight, alternatively 1 part by weight to 20 parts by weight, alternatively 1 part by weight to 15 parts by weight, or alternatively 0.5 parts by weight to 10 parts by weight, relative to 100 parts by weight of the combined starting materials I) and II) of the composition. Without wishing to be bound by theory, it is believed that when the content of IV) alkoxysilane is greater than or equal to the lower limit of the above range, the resulting moisture-curable composition is rapidly cured in air by moisture, and when the content is less than or equal to the upper limit of the above range, the curability of the resulting moisture-curable composition is sufficient and the shelf life of the composition under moisture block is improved.

[0090] The starting material V) is a fluorescent whitening agent and / or UV indicator, which can be a molecule that fluoresces under irradiation with 365 nm and / or 405 nm light. Examples of fluorescent whitening agents include, but are not limited to: benzoxazol derivatives, such as 2,5-bis(benzo[d]oxazol-2-yl)thiophene derivatives, such as 2,5-bis(5-(tert-butyl)benzo[d]oxazol-2-yl)thiophene, which is commercially available under the trade name TINOPAL OB from BASF; diaminostilbene-sulfonic acid derivatives, such as 4,4'-bis-(2-morpholino-4-phenylamino-s-triazine-6-ylamino)stilbene disulfonic acid disodium salt, which is commercially available under the trade name Tinopal DMS from Ciba-Geigy AG; and bisphenyl-stilbenyl derivatives, such as 2,2'-bis-(phenyl-stilbenyl) disulfonic acid disodium salt, which is commercially available under the trade name Tinopal CBS from Ciba-Geigy AG; and diarylpyrazoline derivatives. Exemplary 2,5-bis(benzo[d]oxazol-2-yl)thiophene derivatives can have the general formula:

[0091] wherein each R 8 is independently selected from the group consisting of H and an alkyl group of 1 to 30 carbon atoms.

[0092] The content of starting material V) in the moisture-curable composition is not limited, provided that it is in an amount that improves the visibility under UV light exposure of a coating prepared with the moisture-curable composition compared to a coating made with the same moisture-curable composition except that starting material V) is omitted. For example, the content of starting material V) can be 0.001 parts by weight to 0.1 parts by weight, alternatively 0.005 parts by weight to 0.1 parts by weight, or alternatively 0.005 parts by weight to 0.05 parts by weight, relative to the content of the combined starting materials I) and II) of 100 parts by weight.

[0093] The starting material VI) is a corrosion inhibitor. Examples of corrosion inhibitors include, but are not limited to: 1H-1,2,3-triazole, 2H-1,2,3-triazole, 1H-1,2,4-triazole, 4H-1,2,4-triazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 1H-1,2,3-triazole, 2H-1,2,3-triazole, 1H-1,2,4-triazole, 4H-1,2,4-triazole, benzotriazole, tolyltriazole, carboxybenzotriazole, carboxylic acid 1H-benzotriazole-5-methyl ester, 3-amino-1,2,4-triazole, 4-amino-1,2,4-triazole, 5-amino-1,2,4-triazole, 3-mercapto-1,2,4-triazole, chlorobenzotriazole, nitrobenzotriazole, aminobenzotriazole, cyclohexanone[1,2-d]triazole, 4,5,6,7-tetrahydroxytolyltriazole, 1-hydroxybenzotriazole, ethylbenzotriazole, naphtholtriazole, 1-N,N-bis(2-ethylhexyl)-[(1,2,4-triazol-1-yl)methyl]amine, 1-[N,N-bis(2- ethylhexyl)aminomethyl]benzotriazole, 1-[N,N-bis(2-ethylhexyl)aminomethyl]tolyltriazole, 1- [N,N-bis(2-ethylhexyl)aminomethyl]carboxybenzotriazole, 1-[N,N-bis(2-hydroxyethyl)- aminomethyl]benzotriazole, 1-[N,N-bis(2-hydroxyethyl)-aminomethyl]tolyltriazole, 1- [N,N-bis(2-hydroxyethyl)-aminomethyl]carboxybenzotriazole, 1-[N,N-bis(2-hydroxypropyl)- aminomethyl]carboxybenzotriazole, 1-[N,N-bis(1-butyl)aminomethyl]carboxybenzotriazole, 1- [N,N-bis(1-octyl)aminomethyl]carboxybenzotriazole, 1-(2',3'-di-hydroxypropyl)benzotriazole, 1-(2',3'-di-carboxyethyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-dimethylphenyl)benzotriazole, 2-(2'-hydroxy-4'- octyloxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-butylphenyl)benzotriazole, 1- hydroxybenzotriazole-6-carboxylic acid, 1-oleoylbenzotriazole, 1,2,4-triazole-3-ol, 5-amino-3-mercapto-1,2,4-triazole, 5-amino-1,2,4-triazole-3-carboxylic acid, 1,2,4-triazole-3- carboxamide, 4-amino urazole, and 1,2,4-triazole-5-one.

[0094] The amount of corrosion inhibitor is not limited provided it is in an amount that can inhibit corrosion of a substrate covered with the cured product of the resulting moisture-curable composition. The amount of corrosion inhibitor can be from 0.01 ppm to about 3 wt% of the composition.

[0095] The starting material VII) is a chelating agent. Examples of chelating agents include, but are not limited to, a-acetylated acetic acid esters such as methyl acetoacetate, ethyl acetoacetate. The content of the chelating agent is not limited provided that it is in an amount that can impart sufficient stability to the resulting moisture-curable composition. For example, the content of the chelating agent can be 0.01 to 20 parts by mass, alternatively 0.01 to 15 parts by mass, relative to 100 parts by mass of the total amount of the starting materials I) and II).

[0096] The starting material VIII) is an adhesion promoter. Examples of adhesion promoters include, but are not limited to, epoxy group-containing alkoxysilanes such as 3-glycidyloxytrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and 4-oxysilylbutyltrimethoxysilane; acrylic group-containing alkoxysilanes such as 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, and 3-acryloyloxypropyltrimethoxysilane; amino group-containing alkoxysilanes such as 3- aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3- aminopropyltrimethoxysilane, and N-phenyl-3-aminopropyltrimethoxysilane; and reaction mixtures of the above-mentioned epoxy group-containing alkoxysilanes and the above-mentioned amino group-containing alkoxysilanes. Alternatively, the adhesion promoter comprises, or is, a reaction mixture selected from the above-mentioned epoxy group-containing alkoxysilanes and the above-mentioned amino group-containing alkoxysilanes. Adhesion promoters are known in the art and are commercially available, such as DOWSIL TM Z-6011 silane, DOWSIL TM Z-6121 silane, DOWSIL TM Z-6137 silane, XIAMETER TM OFS-6011 silane, and XIAMETER TM OFS-6610 silane, all of which are available from Dow.

[0097] The content of the adhesion promoter in the moisture-curable composition is not limited provided that it is in an amount that can impart sufficient adhesion to various substrates contacted during curing of the composition. For example, the content of the adhesion promoter can be 0.01 to 10 parts by weight, or alternatively 0.01 to 5 parts by weight, relative to 100 parts by weight of the combined starting materials I) and II).

[0098] The moisture-curable composition can be prepared by any convenient means, such as mixing the starting materials comprising I) an alkoxy-functional silsesquioxane resin and II) a condensation reaction catalyst, and any optional additional starting materials, in the amounts as described above, at room temperature. The starting materials can be combined and mixed in any order. In a one-part composition, the starting materials can be mixed under anhydrous conditions. Alternatively, the moisture-curable composition can be prepared in a multi-part kit, such as a two-part kit. For example, the two-part kit can include a base part and a curative part, and optionally instructions to mix the base part and the curative part prior to use. The base part can comprise one or more of I) an alkoxy-functional silsesquioxane resin and additional starting materials. The curative part can comprise one or more of II) a condensation reaction catalyst and additional starting materials, such as IV) an alkoxysilane. The base part and the curative part can each be prepared by any convenient means under anhydrous or ambient conditions. The base part and the curative part can be combined by any convenient means, such as mixing, just prior to use. The base part and the curative part can be combined in relative amounts of base:curative in the range of 1 : 1 to 10: 1.

[0099] The equipment used to mix the starting materials for the moisture-curable composition is not particularly limited. Examples of suitable mixing equipment can be selected depending on the type and amount of each starting material selected. For example, a stirred batch kettle can be used for relatively low viscosity compositions. Alternatively, a continuous compounding device, such as an extruder, such as a twin screw extruder, can be used for more viscous compositions. Exemplary methods that can be used to prepare the moisture-curable compositions described herein include, for example, those disclosed in U.S. Patent Application Publication Nos. US 2009 / 0291238 and US 2008 / 0300358.

[0100] A method of making a moisture-curable film is provided. The method of making the film includes applying a moisture-curable composition on a substrate. The method further includes forming the film on the substrate.

[0101] The method by which the moisture-curable composition is applied on the substrate can vary. For example, the step of applying the moisture-curable composition on the substrate can use a wet coating application method. Particular examples of wet coating application methods suitable for use in the method include dip coating, spin coating, flow coating, spray coating, roll coating, gravure coating, sputtering, slot coating, inkjet printing, and combinations thereof.

[0102] The substrate is not limited and can be any material, and can be continuous or discontinuous, and can have any size, shape, dimension, and surface roughness. In certain embodiments, the substrate comprises a plastic, which can be thermoset and / or thermoplastic. However, alternatively, the substrate can be glass, metal, paper, wood, silicone, or other materials, or combinations thereof. Alternatively, the substrate can be all or a portion of an electrical / electronic device.

[0103] Generally, applying the moisture-curable composition on a substrate results in a wet film on the substrate, and forming a film on the substrate includes drying the wet film on the substrate to form the film. For example, drying the wet film can include: optionally (i) evaporating solvent from the wet film (when solvent is present); optionally (ii) exposing the wet film to elevated temperature to drive solvent (when solvent is present) therefrom; and (iii) curing the wet film. Curing the wet film can occur via exposure to atmospheric moisture. Without wishing to be bound by theory, it is believed that the alkoxy groups from the alkoxy-functional silsesquioxane resin can react (e.g., cure) such that the film is a reaction product of the alkoxy-functional silsesquioxane resin and optionally one or more additional starting materials in the moisture-curable composition.

[0104] The film can be separable from the substrate (e.g., peelable), or can be adhered to the substrate physically and / or chemically. The substrate can have an integrated hot plate or integrated or independent oven for drying / curing the deposit. The substrate can optionally have continuous or discontinuous shape, size, dimension, surface roughness, and other characteristics. Alternatively, the substrate has a softening point temperature at elevated temperature. However, the moisture-curable composition and method are not so limited.

[0105] Generally, forming the film includes exposing the wet film to elevated temperature for a period of time. The elevated temperature is generally 50 °C to 250 °C, alternatively 100 °C to 200 °C, alternatively 110 °C to 190 °C, alternatively 120 °C to 180 °C, alternatively 130 °C to 170 °C, alternatively 140 °C to 160 °C, alternatively 145 °C to 155 °C. The period of time is generally sufficient to achieve drying and / or curing, or at least curing (e.g., crosslinking) of the alkoxy-functional silsesquioxane resin. The period of time can be > 0 hours to 10 hours, alternatively > 0 hours to 5 hours, alternatively > 0 hours to 2 hours. The period of time can be broken up into drying / curing iterations, e.g., a first cure and a post-cure, the first cure being, for example, one hour, and the post-cure being, for example, one hour. The elevated temperature can be independently selected in such iterations, and can be the same in each iteration. Alternatively, the film can be formed by merely exposing the wet film to ambient conditions, i.e., drying at room temperature in the presence of atmospheric moisture without any elevated temperature.

[0106] The film can also be formed via an iterative process, depending on the thickness and other dimensions of the film. For example, a first deposit can be formed and optionally subjected to a first elevated temperature for a first period of time to result in a partially dried and / or cured deposit. A second deposit can then be disposed on the first deposit or partially dried and / or cured deposit and optionally subjected to a second elevated temperature for a second period of time to result in a second partially dried and / or cured deposit. This process can be repeated, for example, 1 to 50 times, to manufacture the film as desired. Each elevated temperature and period of time can be independently selected and can be the same or different from one another. The iterative process can be wet-on-wet. Alternatively, the iterative process can be wet-on-dry, depending on the dried / cured state of the partially dried and / or cured deposit.

[0107] The thickness of the film can vary depending on its end-use application. Generally, the thickness of the film is > 0 pm to 4,000 pm, alternatively > 0 pm to 3,000 pm, alternatively > 0 pm to 2,000 pm, alternatively > 0 pm to 1,000 pm, alternatively > 0 pm to 500 pm, alternatively > 0 pm to 250 pm, alternatively > 0 pm to 100 pm, alternatively 1 pm to 50 pm, alternatively 20 pm to 30 pm. However, other thicknesses are contemplated, for example, 0.1 pm to 200 pm. For example, the thickness of the film can be 0.2 pm to 175 pm; or 0.5 pm to 150 pm; alternatively 0.75 pm to 100 pm; alternatively 1 pm to 75 pm; alternatively 2 pm to 60 pm; alternatively 3 pm to 50 pm; alternatively 4 pm to 40 pm; or any of 1 pm, 2 pm, 3 pm, 4 pm, 5 pm, 6 pm, 7 pm, 8 pm, 9 pm, 10 pm, 15 pm, 20 pm, 25 pm, 30 pm, 35 pm, 40 pm, 45 pm, 50 pm, 60 pm, 70 pm, 75 pm, 80 pm, 90 pm, 100 pm, 150 pm, 175 pm, and 200 pm.

[0108] Regardless of the method of forming the film, once the film is formed on the substrate from the emulsion and / or composition, the film can further undergo post-treatment, such as heating, humidification, catalytic post-treatment, light irradiation, or electron beam irradiation.

[0109] If desired, the film can be subjected to further processing depending on the end use application of the film. For example, the film can be subjected to oxidation deposition (e.g., SiO2deposition), resist deposition, and patterning, etching, chemical or plasma stripping, metallization or metal deposition processing. Such further processing techniques are generally known. Such deposition can be chemical vapor deposition (including low pressure chemical vapor deposition, plasma enhanced chemical vapor deposition, and plasma assisted chemical vapor deposition), physical vapor deposition, or other vacuum deposition techniques. Many such further processing techniques involve elevated temperatures, particularly vacuum deposition, for which the film is well suited given its excellent thermal stability. However, depending on the end use of the film, the film can be used without such further processing.

[0110] Alternatively, the substrate can include an electrical / electronic device. By using the above-described moisture-curable composition, a coated electrical / electronic device can be obtained. The electrical / electronic device is not particularly limited, but examples are electrical / electronic devices including a circuit and / or an electrode. It is considered that such a coated electrical / electronic device has good to excellent reliability due to good to excellent adhesion to a contacted substrate and / or good to excellent thermal shock stability during curing of the moisture-curable composition.

[0111] Examples

[0112] The following examples are provided to illustrate the application to one of ordinary skill in the art and should not be interpreted as limiting the scope of the application set forth in the claims. The starting materials used in these examples are shown in Table 1 below.

[0113] Table 1 - Starting materials

[0114]

[0115] In this Reference Example 1, a sample of a vinyl-functional silsesquioxane resin was prepared as follows: A 1000 mL 3-necked flask was equipped with a magnetic stir bar, a water-cooled condenser, a thermocouple, and a nitrogen blanket. The following starting materials were charged to the flask: 1) the indicated amount of methoxysilane shown in Table 2 below was added, followed by the indicated amount of triflic acid shown in Table 2 below. The indicated amount of DI water shown in Table 2 below was added slowly to the flask, starting at room temperature. An exotherm to 64 °C was observed. The contents of the flask were then heated at 65 °C for 2 h. Some methanol was distilled off using a Dean Stark apparatus. The contents of the flask were cooled to 50 °C, and CaCO3was added to neutralize the triflic acid. The contents of the flask were mixed overnight at room temperature. The resulting product was stripped on a rotary evaporator heated with an oil bath at 80 °C under reduced pressure of 4 mm Hg. The contents of the flask were then cooled to room temperature and pressure filtered through a 47 mm diameter Magna, Nylon, Supported, Plain 0.45 μιη filter. A vinyl-functional silsesquioxane resin was prepared.

[0116] In this Reference Example 2, a sample of a vinyl-functional MDT resin was prepared as described in Reference Example 1 above, except that octyltriethoxysilane and tetramethyldisiloxane were added. Samples CE2 and CE4 were prepared by this method. These samples are summarized in Table 3 below.

[0117] In this Reference Example 3, a sample of a hydrogen-functional silsesquioxane resin was prepared as follows: A 1 L 3-necked flask was equipped with a thermocouple, a Teflon stir paddle attached to a glass stir bar, a Dean Stark apparatus attached to a water-cooled condenser, and a nitrogen blanket. The following starting materials were charged to the flask: the indicated amount of methoxysilane shown in Table 2 below was added, followed by the indicated amount of triflic acid shown in Table 2 below. The indicated amount of DI water shown in Table 2 below was added slowly to the flask, starting at room temperature. An exotherm to 58 °C was observed. The contents of the flask were then heated at 65 °C for 30 min. Some methanol was distilled off using a Dean Stark apparatus. Tetramethyldisiloxane was added to the flask, followed by the addition of DI water to the flask in the amounts shown in Table 4 below. The contents of the flask were heated at 55 °C for 3 h. Methanol was then distilled off at a temperature of 70 °C in the flask. The amount removed was 77 g. CaCO3was added to neutralize the triflic acid. The contents of the flask were mixed overnight at room temperature. The resulting product was stripped on a rotary evaporator heated with an oil bath at 80 °C under reduced pressure of 3 mm Hg. The contents of the flask were then cooled to room temperature and pressure filtered through a 47 mm diameter Magna, Nylon, Supported, Plain 0.45 μιη filter. A vinyl-functional silsesquioxane resin was prepared. Samples CE5 and CE6 were prepared using this method. CE6 used different proportions of starting materials than CE5. These samples are summarized in Table 4 below.

[0118] In this reference example 4, a sample of an octyl functional DT resin was prepared as follows: the same apparatus as reference example 1 was used. Methyltrimethoxysilane (355 g), octyltriethoxysilane (41 g) and D4 cyclotene® (18 g) were added to the flask. Then triflic acid (0.21 g) was added and then the slow addition of DI water (71 g) was started at room temperature. An exotherm to 64 °C was observed and then the contents of the flask were heated at 65 °C for 2 h. Some alcohol (methanol and ethanol) was distilled off using a Dean stark apparatus. The amount removed was 213 g. Next, n-heptane (144 g) was added and then calcium carbonate (0.83 g) was added to neutralise the triflic acid. The contents of the flask were mixed for 1 h while cooling. The volatiles were distilled off until a vapour temperature of 98 °C. The amount removed was 91 g. The resulting product was filtered through a 47 mm diameter Magna, Nylon, Supported, Plain 0.45 μιη filter. The resulting resin was stripped using a rotary evaporator heated with an oil bath at 80 °C at 1 mmHg - 2 mmHg. CE8 and CE9 were prepared using this method. These samples are summarised in Table 4 below.

[0119] Table 2 - Starting materials used in Comparative Examples (amounts in grams)

[0120] Examples / Starting materials CE1 CE3 CE7 MeSi(OMe)3 355 354.9 354.9 ViSi(OMe)3 68 68.0 68.0 Triflic acid 0.21 0.21 0.21 DI water 68 71.8 71.8 Methanol removal 190 204.0 207.1 CaCO3 0.84 0.84 0.84 Heptane 0 59.9 90.0 Unit formula of the produced resin T Me 0.843 T Vi 0.148 ]]> T Me 0.856 T Vi 0.144 ]]> T Me 0.853 T Vi 0.147 ]]> Preparation process Reference Example 1 Reference Example 1 Reference Example 1

[0121] Table 3 - Starting materials used in Comparative Examples (amounts in grams)

[0122]

[0123] Table 4 - Starting materials used in Comparative Examples (amounts in grams)

[0124]

[0125] In this reference example 5, an ETM converted DT resin was prepared as follows:

[0126] A 250 mL flask was fitted with a thermocouple, magnetic stir bar and water cooled condenser. The DT resin with unit formula D Me2 0.009 T Me 0.843 T Vi 0.148A 500 mL 3 -neck flask was equipped with a thermocouple, magnetic stir bar, and water cooled condenser. The flask was charged with a vinyl functional resin (50 g), ETM transfer agent (26 g), and toluene (76 g). A nitrogen blanket was applied. The contents of the flask were heated to 70 °C and a Karstedt’s catalyst was added in an amount sufficient to provide 10 ppm Pt based on the combined weight of the resin and ETM. The contents of the flask were heated at 100 °C for 21 h. The SiH content, which was an indicator of reaction product, was monitored using FTIR. The resulting product was stripped to dryness using a rotary evaporator heated by an oil bath at 80 °C at 0.5 mm Hg to 1 mm Hg. 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. The amounts in Table 5 below are in grams unless otherwise specified.

[0127] In this reference example 6, ETM-converted DT resins were prepared according to the method of reference example 5, except that the resin of CE2 was used as the vinyl functional resin starting material for sample IE4 and the resin of CE4 was used as the vinyl functional resin starting material for sample IE6. These samples are summarized in Table 6 below. The amounts in Table 6 below are in grams unless otherwise specified.

[0128] In this reference example 7, samples IE7 and IE8 were prepared as follows: A 500 mL 3 -neck flask was equipped with a thermocouple, magnetic stir bar, and water cooled condenser. The flask was charged with a vinyl functional resin (50 g), ETM transfer agent (26 g), and toluene (76 g). A nitrogen blanket was applied. The contents of the flask were heated to 70 °C and a Karstedt’s catalyst was added in an amount sufficient to provide 10 ppm Pt based on the combined weight of the resin and ETM. The contents of the flask were heated at 100 °C for 21 h. The SiH content, which was an indicator of reaction product, was monitored using FTIR. The resulting product was stripped to dryness using a rotary evaporator heated by an oil bath at 80 °C at 0.5 mm Hg to 1 mm Hg. 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. The amounts in Table 5 below are in grams unless otherwise specified. H 0.102 T Me 0.892 A resin of a resin (sample CE5) or M H 0.102 T Me 0.892 A resin of a resin (sample CE6) and heptane. A nitrogen blanket was applied. The contents of the flask were heated to 80 °C. A Karstedt’s Pt catalyst was added in an amount equal to 5 ppm Pt based on the resin. Vinyltrimethoxysilane was added slowly with an addition funnel. The exotherm was to 94 °C. The contents of the flask were heated at about 100 °C for 3 h. FTIR was used to verify the reaction was complete. The product was stripped to dryness using a rotary evaporator heated by an oil bath at 80 °C at 1 mm Hg to 2 mm Hg. These samples are summarized in Table 7 below. The amounts in Table 7 below are in grams unless otherwise specified.

[0129] In this reference example 8, sample IE9 was prepared as follows: A 500 mL 3 -neck flask was equipped with a thermocouple, magnetic stir bar, and water cooled condenser. The flask was charged with a resin of a resin (50 g), ETM transfer agent (26 g), and toluene (76 g). A nitrogen blanket was applied. The contents of the flask were heated to 70 °C and a Karstedt’s catalyst was added in an amount sufficient to provide 10 ppm Pt based on the combined weight of the resin and ETM. The contents of the flask were heated at 100 °C for 21 h. The SiH content, which was an indicator of reaction product, was monitored using FTIR. The resulting product was stripped to dryness using a rotary evaporator heated by an oil bath at 80 °C at 0.5 mm Hg to 1 mm Hg. 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. The amounts in Table 5 below are in grams unless otherwise specified. Me 0.853 T Vi 0.147Resin (150 g), sample CE7, and heptane (81 g). A nitrogen blanket was applied. The contents of the flask were heated to 50 °C and then an amount of Karstedt’s Pt catalyst was added that resulted in 5 ppm Pt based on resin + MeHSi(OMe)2. MeHSi(OMe)2(30 g) was slowly added to the flask using an addition funnel. The contents of the flask were heated at 60 °C for a total of 23 h. At the 5 h mark, additional Karstedt’s Pt catalyst was added sufficient to increase the Pt concentration to 10 ppm, and then at the 22 h mark, additional Karstedt’s Pt catalyst was added sufficient to increase the Pt concentration to 15 ppm. The progress of the reaction was monitored by FTIR. The resulting product was stripped to dryness using a rotary evaporator heated with an oil bath at 80 °C at 1 mmHg - 2 mmHg. This sample is summarized in Table 8 below.

[0130] Table 5 - Starting materials for working examples (amounts in grams, unless otherwise indicated)

[0131]

[0132] Table 6 - Starting materials for working examples IE4 and IE6

[0133]

[0134] Table 7 - Starting materials for working examples IE7 and IE8

[0135]

[0136] Note: The resin of CE5 was used to make IE7, and the resin of CE6 was used to make IE8.

[0137] Table 8 - Starting materials for working example IE9

[0138] Examples / Starting materials IE9 T Me 0.853 T Vi 0.147 resin 150 Heptane 81 MeHSi(OMe)2 30 Kast catalyst 15 ppm based on the weight of the reactants Unit formula of the produced resin T Me 0.853 T DM 0.147 ]]> Preparation process Reference Example 8

[0139] Table 9 - Properties of the resins prepared as described above

[0140]

[0141] Table 9 - Properties of the resins prepared as described above (continued)

[0142]

[0143] Table 9 - Properties of the resins prepared as described above (continued)

[0144]

[0145] Table 9 - Properties of the resins prepared as described above (continued)

[0146]

[0147] In this reference example 9, 99 parts by weight of resin and 1 part by weight of wet cure package (TYZOR TM The curability of some resins prepared as described above was tested by mixing 99 parts by weight of resin and 1 part by weight of wet cure package (TYZOR

[0148] A Zehntner automatic applicator with vacuum panel (ZAA2300) was used to apply each composition to an A-36 aluminum Q-panel with a 10 mil drawdown square (5 cm wide) at a speed of 25 mm / sec. The tack of the surface of each resulting coating was tested every 60 seconds after application of each composition until the tack free time was reached. The tack free time was recorded where the finger was released without wet coating adhering to the nitrile glove after lightly pressing the coating surface and immediately releasing.

[0149] The following Tables 10 and 11 show that only for resins containing alkoxy functionality grafted onto the resin after the presence of vinyl or SiH moieties on the resin can tack free times of less than 30 min be achieved. This provides for the first time a route to rapidly curing alkoxy functional siloxane resins where the alkoxy groups on the resin are not simply those left over from synthesis but are intentionally introduced at the desired concentration and away from the resin core.

[0150] Table 10 - Comparative Examples for testing the tack-free time

[0151] Tested property Standard CE CE1 CE2 CE4 CE6 Tack-free time (min) < 30 minutes 30.5 >60 240 >30 >60

[0152] Note: In Table 10, the samples labeled CE are DOWSIL TM 2405 resin, which is commercially available from Dow.

[0153] Table 11 - Working examples for testing the tack-free time

[0154] Tested property Standard IE1 IE3 IE4 IE6 IE8 Tack-free time (min) < 30 minutes 25 19 13 8 19

[0155] Definitions and usage of terms

[0156] All amounts, ratios, and percentages herein 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 forms "a", "an" and "the" include plural referents unless the context of the specification clearly dictates otherwise. The summary of the application and the abstract herein are hereby incorporated by reference. The transitional phrases "comprising", "consisting essentially of, and "consisting of are used in accordance with the Ninth Edition of the Patent Examining Procedure, Revision 08.2017, last revised January 2018, Chapters §2111.03 I., II., and III. Any feature or aspect of the present application can be used in combination with any other feature or aspect described herein. Abbreviations used herein have the definitions in Table 12.

[0157] Table 12 - Abbreviations

[0158]

[0159] Test methods

[0160] An example of a test method for determining the hydrolyzable group content of a silsesquioxane resin is as follows. The hydrolyzable group content is determined by 29 Si and 13 C NMR analysis in deuterated benzene. The total hydrolyzable content is determined from 29 Si NMR analysis and reported as a mole fraction based on Si units. The amount of methoxy groups in the hydrolyzable group content is determined from 13 C NMR analysis (1,4-dioxane used as an internal standard). The difference between the total hydrolyzable group content and the amount of methoxy groups is the amount of OH groups present.

[0161] GPC samples were prepared at a concentration of 1% w / w in qualified THF, filtered with a 0.45 μιη PTFE syringe filter, and analyzed relative to polystyrene standards. The relative calibration (third order fit) for molecular weight determinations was based on twelve polystyrene standards ranging in molecular weight from 580 Daltons to 1,735,000 Daltons. The chromatographic separation apparatus consisted of a Viscotek GPCmax VE2001 solvent / sample module equipped with a vacuum degasser, a Viscotek VE3580 RI monitor, and two (300 mm x 7.5 mm) Polymer Laboratories Mixed C columns (molecular weight separation range 200 to 3,000,000) preceded by a guard column. Separations were performed using qualified THF flowing at 1.0 mL / min, the injection volume was set to 100 μί and the columns and detector were heated to 35 °C. Data collection was for 30 minutes and processed with OmniSEC software.

Claims

1. An alkoxy-functionalized silsesquioxane resin, the alkoxy-functionalized silsesquioxane resin comprising 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 ;in Each R 2 independently selected from the group consisting of alkyl groups and groups of formula (I), Wherein in formula (I), Each R 1 are independently selected alkyl groups, Each D 1 are independently selected alkylene groups, The subscripts a, b, and x are integers, the values of which are such that Subscript a is 1 or 2; Subscript b is 0 or 1, and Subscript x is 0 or 1; The prerequisite is that an average of 5 mol% to 25 mol% of R 2 Having formula (I); Subscripts c, d, and e represent the molar fractions of each unit in the alkoxy-functionalized silsesquioxane resin, and the values of subscripts c, d, and e are such that 0≤c≤0.25， 0≤d≤0.20， 0.55 < e ≤ 1, and The quantity (c + d + e) = 1; Each Z is an independently selected alkyl group; and Subscript f represents the molar amount of alkoxy groups in the resin, and subscript g represents the molar amount of hydroxyl groups in the resin, and the values of subscripts f and g are such that 0.01≤f≤0.70； 0 ≤ g ≤ 0.05; and 0.02 ≤ (f + g) ≤ 0.75; Where the alkoxy-functionalized silsesquioxane resin is liquid at 23 °C ± 3 °C and 101.325 kPa.

2. The silsesquioxane resin according to claim 1, wherein Subscript a = 1, Subscript b = 1, Each D 1 With the empirical formula -C2H4-, Each R 1 is methyl, Each R that is not a group of formula (I) 2 is a methyl group, and Each Z is independently selected from the group consisting of methyl and ethyl.

3. The alkoxy-functionalized silsesquioxane resin according to claim 1, wherein Subscript b = 0, Each D 1 With the empirical formula -C2H4-, Each R 1 is methyl, Each R that is not a group of formula (I) 2 is a methyl group, and Each Z is independently selected from the group consisting of methyl and ethyl.

4. The alkoxy-functional silsesquioxane resin according to any one of claims 1 to 3, wherein R 2 In each molecular unit (R 2 SiO 3 / 2 ) has the formula (I) in at least one case.

5. The alkoxy-functionalized silsesquioxane resin 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 measured by gel permeation chromatography.

6. A method for preparing the alkoxy-functionalized silsesquioxane resin according to any one of claims 1 to 5, wherein the method comprises: 1) Combining starting materials comprising the following under conditions for effecting a hydrosilylation reaction: A) An alkoxy-functionalized organosilicon compound, and B) A silsesquioxane resin, Provided that one of A) the alkoxy-functionalized organosilicon compound and B) the silsesquioxane resin has a silicon-bonded hydrogen atom, and the other of A) the alkoxy-functionalized organosilicon compound and B) the silsesquioxane resin has an aliphatic unsaturated group capable of undergoing a hydrosilylation reaction, Optional D) A solvent, and In the presence of C) A hydrosilylation reaction catalyst, Thereby forming a hydrosilylation reaction product comprising the alkoxy-functionalized silsesquioxane resin, and Optionally 2) Purifying the hydrosilylation reaction product.

7. A method for preparing the alkoxy-functionalized silsesquioxane resin according to any one of claims 1 to 6, the method comprising: 1) Combining starting materials comprising the following under conditions for effecting a hydrosilylation reaction: A) An alkoxy-functionalized organosilicon compound, and B) A silsesquioxane resin, Optional D) A solvent; and In the presence of C) A hydrosilylation reaction catalyst; Provided that one of A) the alkoxy-functionalized organosilicon compound and B) the silsesquioxane resin contains a silicon-bonded hydrogen atom, and the other of B) the silsesquioxane resin and A) the alkoxy-functionalized organosilicon compound contains an aliphatic unsaturated group.

8. A method for preparing the alkoxy-functional silsesquioxane resin according to claim 1 or claim 2, the method comprising: 1) Combining starting materials comprising the following under conditions for achieving a hydrosilylation reaction: A) an alkoxy-functional organohydrogensiloxane oligomer having the formula: where R 1 、D 1 , a and x are as described above; and B) an alkenyl functional silsesquioxane resin having 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 (HO 1 / 2 ) g , wherein Z, c, d, e, f and g are as described above, and Each R 3 independently selected from the group consisting of alkyl groups and alkenyl groups, The prerequisite is that at least one R in each molecule 3 is an alkenyl group; optionally D) a solvent; and In the presence of C) a hydrosilylation catalyst.

9. A method for preparing the alkoxy-functional silsesquioxane resin according to claim 1 or claim 3, the method comprising: 1) Combining starting materials comprising the following under conditions for achieving a hydrosilylation reaction: A) Formula R 1 x R 5 Si(OR 1 ) 3-x An alkoxy-functional organosilicon compound, wherein R 1 and x as above, and R 5 is an alkenyl group; and B) a hydrogenated functional silsesquioxane resin having 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 (HO 1 / 2 ) g ; wherein Z, c, d, e, f and g are as described above, and Each R 4 are independently selected from the group consisting of alkyl groups and H, The prerequisite is that at least one R in each molecule 4 It is H; optionally D) a solvent; and In the presence of C) a hydrosilylation catalyst.

10. A moisture-curable composition comprising: 1) an alkoxy-functional silsesquioxane resin according to any one of claims 1 to 6; and II) Condensation reaction catalyst.

11. The composition of claim 10, further comprising an additional starting material selected from the group consisting of: III) a solvent, IV) an alkoxysilane, V) a fluorescent brightener, a UV indicator, or both, VI) a corrosion inhibitor, VII) a chelating agent, VIII) an adhesion promoter, and IX) a combination of two or more thereof.

12. A composition according to claim 10 or claim 11, wherein the composition is substantially free of organic solvents.

13. A method for preparing a membrane, wherein the method comprises: 1) applying the moisture-curable composition according to any one of claims 10 to 12 to a substrate; 2) forming the film on the substrate from the moisture-curable composition.

14. The method of claim 13, wherein forming the film on the substrate comprises forming a wet film on the substrate, and Drying the wet film on the substrate to form the film, wherein drying the wet film comprises optionally (i) evaporating a solvent from the wet film when one is present, optionally (ii) when a solvent is present, exposing the wet film to an elevated temperature to drive the solvent therefrom, (iii) curing the wet film, or (iv) Any combination of (i) to (iii).

15. A membrane produced by the method according to claim 13 or claim 14.

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