Patent Publication Number: US-2010112321-A1

Title: Silicone Resin, Silicone Composition, Coated Substrate, and Reinforced Silicone Resin Film

Description:
CROSS-REFERENCE TO RELATED APPLICATIONS 
     None 
     FIELD OF THE INVENTION 
     The present invention relates to a silicone resin and more particularly to silicone resin containing disilyloxane units and siloxane units having the form of particles. The present invention also relates to a silicone composition containing a silicone resin, to a coated substrate comprising a cured product or an oxidized product of a silicone resin, and to a reinforced silicone resin film. 
     BACKGROUND OF THE INVENTION 
     Silicone resins are useful in a variety of applications by virtue of their unique combination of properties, including high thermal stability, good moisture resistance, excellent flexibility, high oxygen resistance, low dielectric constant, and high transparency. For example, silicone resins are widely used as protective or dielectric coatings in the automotive, electronic, construction, appliance, and aerospace industries. 
     Although silicone resin coatings can be used to protect, insulate, or bond a variety of substrates, free standing silicone resin films have limited utility due to low tear strength, high brittleness, low glass transition temperature, and high coefficient of thermal expansion. Consequently, there is a need for free standing silicone resin films having improved mechanical and thermal properties. 
     SUMMARY OF THE INVENTION 
     The present invention is directed to a silicone resin comprising disilyloxane units having the formula O (3-a)/2 R 1   a Si—SiR 1   b O (3-b)/2  (I), and siloxane units having the form of particles, wherein each R 1  is independently —H, hydrocarbyl, or substituted hydrocarbyl; a is 0, 1, or 2; and b is 0, 1, 2 or 3. 
     The present invention is also directed to a silicone composition comprising the aforementioned silicone resin, and an organic solvent. 
     The present invention is further directed to a coated substrate comprising a substrate and a coating on the substrate, wherein the coating is a cured product or an oxidized product of the aforementioned silicone resin. 
     The present invention is still further directed to a reinforced silicone resin film comprising a cured product of the aforementioned silicone resin, and a fiber reinforcement embedded in the cured product. 
     The silicone resin of the present invention is soluble in a variety of organic solvents and is substantially free of gel. Moreover, the silicone resin can be cured to produce coatings exhibiting good adhesion to a variety of substrates. 
     The silicone composition of the present invention can be conveniently formulated as a one-part composition having good shelf-stability. Moreover, the composition can be applied to a substrate by conventional high-speed methods such as spin coating, printing, spraying, graveur coating, and slot die coating. 
     The coating of the coated substrate exhibits very low surface roughness, high resistance to thermally induced cracking, and low tensile strength. 
     The reinforced silicone resin film of the present invention has low coefficient of thermal expansion, high tensile strength, and high modulus compared to an un-reinforced silicone resin film prepared from the same silicone composition. Also, although the reinforced and un-reinforced silicone resin films have comparable glass transition temperatures, the reinforced film exhibits a much smaller change in modulus in the temperature range corresponding to the glass transition. 
     The reinforced silicone resin film of the present invention is useful in applications requiring films having high thermal stability, flexibility, mechanical strength, and transparency. For example, the silicone resin film can be used as an integral component of flexible displays, solar cells, flexible electronic boards, touch screens, fire-resistant wallpaper, and impact-resistant windows. The film is also a suitable substrate for transparent or nontransparent electrodes. 
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
     As used herein, the term “disilyloxane units” refers to organosilicon units having the formula O (3-a)/2 R 1   a Si—SiR 1   b O (3-b)/2  (I), where R 1 , a, and b are defined below. Also, the term “mol % of disilyloxane units” is defined as the ratio of the number of moles of disilyloxane units having the formula (I) in the silicone resin to the sum of the number of moles of siloxane units and disilyloxane units in the resin, multiplied by 100. Further, the term “mol % of siloxane units having the form of particles” is defined as the ratio of the number of moles of siloxane units having the form of particles in the resin to the sum of the number of moles of siloxane units and disilyloxane units in the resin, multiplied by 100. 
     A silicone resin according to the present invention comprises disilyloxane units having the formula O (3-a)/2 R 1   a Si—SiR 1   b O (3-13)/2  ( I ), and siloxane units having the form of particles, wherein each R 1  is independently —H, hydrocarbyl, or substituted hydrocarbyl; a is 0, 1, or 2; and b is 0, 1, 2 or 3. 
     The hydrocarbyl groups represented by R 1  typically have from 1 to 10 carbon atoms, alternatively from 1 to 6 carbon atoms, alternatively from 1 to 4 carbon atoms. Acyclic hydrocarbyl groups containing at least three carbon atoms can have a branched or unbranched structure. Examples of hydrocarbyl groups include, but are not limited to, alkyl, such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 1-ethylpropyl, 2-methylbutyl, 3-methylbutyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, hexyl, heptyl, octyl, nonyl, and decyl; cycloalkyl, such as cyclopentyl, cyclohexyl, and methylcyclohexyl; aryl, such as phenyl and napthyl; alkaryl, such as tolyl and xylyl; arakyl, such as benzyl and phenethyl; alkenyl, such as vinyl, allyl, and propenyl; aralkenyl, such as styryl and cinnamyl; and alkynyl, such as ethynyl and propynyl. 
     The substituted hydrocarbyl groups represented by R 1  can contain one or more of the same or different substituents, provided the substituent does not prevent formation of the alcoholysis product, the hydrolyzate, or the silicone resin. Examples of substituents include, but are not limited to, —F, —Br, —I, —OH, —OR 2 , —OCH 2 CH 2 OR 3 , —CO 2 R 3 , —OC(═O)R 2 , —C(═O)NR 3   2 , wherein R 2  is C 1  to C 8  hydrocarbyl and R 3  is R 2  or —H. 
     The hydrocarbyl groups represented by R 2  typically have from 1 to 8 carbon atoms, alternatively from 3 to 6 carbon atoms. Acyclic hydrocarbyl groups containing at least 3 carbon atoms can have a branched or unbranched structure. Examples of hydrocarbyl include, but are not limited to, unbranched and branched alkyl, such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 1-ethylpropyl, 2-methylbutyl, 3-methylbutyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, hexyl, heptyl, and octyl; cycloalkyl, such as cyclopentyl, cyclohexyl, and methylcyclohexyl; phenyl; alkaryl, such as tolyl and xylyl; aralkyl, such as benzyl and phenethyl; alkenyl, such as vinyl, allyl, and propenyl; arylalkenyl, such as styryl; and alkynyl, such as ethynyl and propynyl. 
     The silicone resin comprises both disilyloxane units having the formula (I) and siloxane units having the form of particles. The silicone resin typically comprises at least 1 mol % of disilyloxane units having the formula (I). For example, the silicone resin typically comprises from 1 to 99 mol %, alternatively from 10 to 70 mol %, alternatively from 20 to 50 mol %, of disilyloxane units having the formula (I). 
     In addition to disilyloxane units having the formula (I), the silicone resin typically comprises up to 99 mol % of siloxane units having the form of particles. For example, the silicone resin typically contains from 0.0001 to 99 mol %, alternatively from 1 to 80 mol %, alternatively from 10 to 50 mol %, of siloxane units having the form of particles. The composition and properties of the particles are described below in the method of preparing the silicone resin. 
     In addition to units having formulae (I) and siloxane units having the form of particles, the silicone resin may contain up to 98.9 mol %, alternatively up to 90 mol %, alternatively up to 60 mol %, of other siloxane units (i.e., siloxane units not having the form of particles). Examples of other siloxane units include, but are not limited to, units having formulae selected from: R 1   3 SiO 1/2 , R 1   2 SiO 2/2 , R 1 SiO 3/2 , and SiO 4/2 , wherein R 1  is as described and exemplified above. 
     The silicone resin typically has a number-average molecular weight of from 200 to 500,000, alternatively from 500 to 150,000, alternatively from 1,000 to 75,000, alternatively from 2,000 to 12,000, wherein the molecular weight is determined by gel permeation chromatography using a refractive index detector and polystyrene standards. 
     The silicone resin typically contains from 1 to 50% (w/w), alternatively from 5 to 50% (w/w), alternatively from 5 to 35% (w/w), alternatively from 10% to 35% (w/w), alternatively from 10 to 20% (w/w), of silicon-bonded hydroxy groups based on the total weight of the resin, as determined by  29 Si NMR. 
     Examples of silicone resins include, but are not limited to, resins having the following formulae: (O 2/2 MeSiSiO 3/2 )0.1(PhSiO 3/2 ) 0.9 , (O 2/2 MeSiSiMeO 2/2 ) 0.2 (Me 2 SiO 2/2 ) 0.1 (PhSiO 3/2 ) 0.7 , (O 2/2 MeSiSiO 3/2 ) 0.1 (O 2/2 MeSiSiMeO 2/2 ) 0.15 (Me 2 SiO 2/2 ) 0.1 (MeSiO 3/2 ) 0.65 , (O 1/2 Me 2 SiSiO 3/2 ) 0.25 (SiO 4/2 ) 0.5 (MePhSiO 2/2 ) 0.25 , (O 2/2 EtSiSiEt 2 O 1/2 ) 0.1 (O 2/2 MeSiSiO 3/2 ) 0.15 (Me 3 SiO 1/2 ) 0.5 (PhSiO 3/2 ) 0.5 (SiO 4/2 ) 0.2 , (O 2/2 MeSiSiO 3/2 ) 0.3 (PhSiO 3/2 ) 0.7 , (O 2/2 MeSiSiO 3/2 ) 3/2 ) 0.4 (MeSiO 3/2 ) 0.6 , (O 3/2 SiSiMeO 2/2 ) 0.5 (Me 2 SiO 2/2 ) 0.5 , (O 3/2 SiSiMeO 2/2 ) 0.6 (Me 2 SiO 2/2 ) 0.4 , (O 3/2 SiSiMeO 2/2 ) 0.7 (Me 2 SiO 2/2 ) 0.3 , (O 3/2 SiSiMe 2 O 1/2 ) 0.75 (PhSiO 3/2 ) 0.25 , (O 3/2 SiSiMeO 2/2 ) 0.75 (SiO 4/2 ) 0.25 , (O 2/2 MeSiSiMe 2 O 1/2 )MeSiSiO 3/2 ) 0.3 (PhSiO 3/2 ) 0.2 , (O 2/2 EtSiSiMeO 2/2 ) 0.8 (MeSiO 3/2 ) 0.05 (SiO 4/2 ) 0.15 , (O 2/2 MeSiSiO 3/2 ) 0.8 (Me 3 SiO 1/2 ) 0.05 (Me 2 SiO 2/2 ) 0.1 (SiO 4/2 ) 0.5 , (O 2/2 MeSiSiEtO 2/2 ) 0.25 (O 3/2 SiSiMeO 2/2 ) 0.6 (MeSiO 3/2 ) 0.1 (SiO 4/2 ) 0.05 , (O 1/2 Me 2 SiSiMeO 2/2 ) 0.75 (O 2/2 MeSiSiMeO 2/2 ) 0.25 , (O 1/2 Et 2 SiSiEtO 2/2 ) 0.5 (O 2/2 EtSiSiEtO 2/2 ) 0.5 , (O 1/2 Et 2 SiSiEtO 2/2 ) 0.2 (O 2/2 MeSiSiMeO 2/2 ) 0.8 , and (O 1/2 Me 2 SiSiMeO 2/2 ) 0.6 (O 2/2 EtSiSiEtO 2/2 ) 0.4 , where Me is methyl, Et is ethyl, Ph is phenyl, the resin contains siloxane units in the form of particles, and the numerical subscripts outside the parenthesis denote mole fractions. Also, in the preceding formulae, the sequence of units is unspecified. 
     The silicone resin can be prepared by (i) reacting at least one halodisilane having the formula Z 3-a R 1   a Si—SiR 1   b Z 3-b  and, optionally, at least one halosilane having the formula R 1   b SiZ 4-b  with at least one alcohol having the formula R 4 OH in the presence of an organic solvent to produce an alcoholysis product, wherein each R 1  is independently —H, hydrocarbyl, or substituted hydrocarbyl, R 4  is alkyl or cycloalkyl, Z is halo, a=0, 1, or 2, and b=0, 1, 2 or 3; (ii) reacting the alcoholysis product with water in the presence of siloxane particles at a temperature of from 0 to 40° C. to produce a hydrolyzate; and (iii) heating the hydrolyzate to produce the resin. 
     In step (i) of the method of preparing the silicone resin at least one halodisilane having the formula Z 3-a R 1   a Si—SiR 1   b Z 3-b  and, optionally, at least one halosilane having the formula R 1   b SiZ 4-b  are reacted with at least one alcohol having the formula R 4 OH in the presence of an organic solvent to produce an alcoholysis product, wherein each R 1  is independently —H, hydrocarbyl, or substituted hydrocarbyl, R 4  is alkyl or cycloalkyl, Z is halo, a=0, 1, or 2, and b=0, 1, 2 or 3. As used herein, the term “alcoholysis product” refers to a product formed by replacement of the silicon-bonded halogen atom(s) in the halodisilane and, when present, the halosilane with the group —OR 4 , wherein R 4  is as described and exemplified below. 
     The halodisilane is at least one halodisilane having the formula Z 3-a R 1   a Si—SiR 1   b Z 3-b , wherein R 1 , a, and b are as described and exemplified above for the silicone resin, and Z is halo. Examples of halo atoms represented by Z include —F, —Cl, —Br, and —I. 
     Examples of halodisilanes include, but are not limited to, disilanes having the formulae: Cl 2 MeSiSiMeCl 2 , Cl 2 MeSiSiMe 2 Cl, Cl 3 SiSiMeCl 2 , Cl 2 EtSiSiEtCl 2 , Cl 2 EtSiSiEt 2 Cl, Cl 3 SiSiEtCl 2 , Cl 3 SiSiCl 3 , Br 2 MeSiSiMeBr 2 , Br 2 MeSiSiMe 2 Br, Br 3 SiSiMeBr 2 , Br 2 EtSiSiEtBr 2 , Br 2 EtSiSiEt 2 Br, Br 3 SiSiEtBr 2 , Br 3 SiSiBr 3 , I 2 MeSiSiMeI 2 , I 2 MeSiSiMe 2 I, I 3 SiSiMeI 2 , I 2 EtSiSiEtI 2 , I 2 EtSiSiEt 2 I, I 3 SiSiEtI 2 , and I 3 SiSiI 3 , where Me is methyl and Et is ethyl. 
     The halodisilane can be a single halodisilane or a mixture comprising two or more different halodisilanes, each having the formula Z 3-a R 1   a Si—SiR 1   b Z 3-b , wherein R 1 , Z, a, and b are as described and exemplified above. 
     Methods of preparing halodisilanes are well known in the art; many of these compounds are commercially available. Also, the halodisilane can be obtained from the residue having a boiling point greater than 70° C. produced in the Direct Process for making methylchlorosilanes, as taught in WO 03/099828. Fractional distillation of the Direct Process residue gives a methylchlorodisilane stream containing a mixture of chlorodisilanes. 
     The optional halosilane is at least one halosilane having the formula R 1   b SiZ 4-b , wherein each R 1  is independently —H, hydrocarbyl, or substituted hydrocarbyl, Z is halo, and b=0, 1, 2 or 3. 
     Examples of halosilanes include, but are not limited to, silanes having the formulae: SiCl 4 , SiBr 4 , HSiCl 3 , HSiBr 3 , MeSiCl 3 , EtSiCl 3 , MeSiBr 3 , EtSiBr 3 , Me 2 SiCl 2 , Et 2 SiCl 2 , Me 2 SiBr 2 , Et 2 SiBr 2 , Me 3 SiCl, Et 3 SiCl, and Me 3 SiBr, Et 3 SiBr, where Me is methyl and Et is ethyl. 
     The halosilane can be a single halosilane or a mixture comprising two or more different halosilanes, each having the formula R 1   b SiZ 4-b , wherein R 1 , Z, and b are as described and exemplified above. Further, methods of preparing halosilanes are well known in the art; many of these compounds are commercially available. 
     The alcohol is at least one alcohol having the formula R 4 OH, wherein R 4  is alkyl or cycloalkyl. The structure of the alcohol can be linear or branched. Also, the hydroxy group in the alcohol may be attached to a primary, secondary or tertiary carbon atom. 
     The alkyl groups represented by R 4  typically have from 1 to 8 carbon atoms, alternatively from 1 to 6 carbon atoms, alternatively from 1 to 4 carbon atoms. Alkyl groups containing at least 3 carbon atoms can have a branched or unbranched structure. Examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 1-ethylpropyl, 2-methylbutyl, 3-methylbutyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, hexyl, heptyl, and octyl. 
     The cycloalkyl groups represented by R 2  typically have from 3 to 12 carbon atoms, alternatively from 4 to 10 carbon atoms, alternatively from 5 to 8 carbon atoms. Examples of cycloalkyl groups include, but are not limited to, cyclopentyl, cyclohexyl, and methylcyclohexyl. 
     Examples of alcohols include, but are not limited to, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-butanol, 1,1-dimethyl-1-ethanol, pentanol, hexanol, cyclohexanol, heptanol, and octanol. The alcohol can be a single alcohol or a mixture comprising two or more different alcohols, each as described and exemplified above. 
     The organic solvent can be any aprotic or dipolar aprotic organic solvent that does not react with the halodisilane, the halosilane, or the silicone resin product under the conditions of the present method, and is miscible with the halodisilane, the halosilane, and the silicone resin. The organic solvent can be immiscible or miscible with water. As used herein, the term “immiscible” means that the solubility of water in the solvent is less than about 0.1 g/100 g of solvent at 25° C. The organic solvent can also be the alcohol having the formula R 4 OH, wherein R 4  is as described and exemplified above, that is reacted with the halodisilane and, optionally, the halosilane. 
     Examples of organic solvents include, but are not limited to, saturated aliphatic hydrocarbons such as n-pentane, hexane, n-heptane, isooctane and dodecane; cycloaliphatic hydrocarbons such as cyclopentane and cyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene; cyclic ethers such as tetrahydrofuran (THF) and dioxane; ketones such as methyl isobutyl ketone (MIBK); halogenated alkanes such as trichloroethane; halogenated aromatic hydrocarbons such as bromobenzene and chlorobenzene; and alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-butanol, 1,1-dimethyl-1-ethanol, pentanol, hexanol, cyclohexanol, hepatanol, and octanol. 
     The organic solvent can be a single organic solvent or a mixture comprising two or more different organic solvents, each as described and exemplified above. 
     The reaction of the halodisilane and the optional halosilane with the alcohol to produce the alcoholysis product can be carried out in any standard reactor suitable for contacting, for example, halosilanes with alcohol. Suitable reactors include glass and Teflon-lined glass reactors. Preferably, the reactor is equipped with a means of agitation, such as stirring. 
     The halodisilane, the optional halosilane, the alcohol, and the organic solvent can be combined in any order. Typically, the halodisilane and optional halosilane are combined with the alcohol in the presence of the organic solvent by adding the alcohol to a mixture of the halodisilane, optional halosilane, and organic solvent. Reverse addition, i.e., addition of the silane(s) to the alcohol is also possible. The hydrogen halide gas (e.g., HCl) produced as a by-product in the reaction is typically allowed to pass from the reaction vessel into an acid neutralization trap. 
     The rate of addition of the alcohol to the halodisilane and the optional halosilane is typically from 5 mL/min. to 50 mL/min. for a 1000-mL reaction vessel equipped with an efficient means of stirring. When the rate of addition is too slow, the reaction time is unnecessarily prolonged. When the rate of addition is too fast, the violent evolution of hydrogen halide gas may be hazardous. 
     The reaction of the halodisilane and the optional halosilane with the alcohol is typically carried out at room temperature (˜23±2° C.). However, the reaction can be carried out at lower or higher temperatures. For example, the reaction can be carried out at a temperature of from 10° C. to 60° C. 
     The reaction time depends on several factors, including the structures of the halodisilane and the optional halosilane, and the temperature. The reaction is typically carried out for an amount of time sufficient to complete alcoholysis of the halodisilane and the optional halosilane. As used herein, the term “to complete alcoholysis” means that at least 85 mol % of the silicon-bonded halogen atoms originally present in the halodisilane and the optional halosilane combined are replaced with the group —OR 2 . For example, the reaction time is typically from 5 to 180 min., alternatively from 10 to 60 min., alternatively from 15 to 25 min., at a temperature of from 10 to 60° C. The optimum reaction time can be determined by routine experimentation using the methods set forth in the Examples section below. 
     The concentration of the halodisilane in the reaction mixture is typically from 5 to 95% (w/w), alternatively from 20 to 70% (w/w), alternatively from 40 to 60% (w/w), based on the total weight of the reaction mixture. 
     The mole ratio of the halosilane to the halodisilane is typically from 0 to 99, alternatively from 0.5 to 80, alternatively from 0.5 to 60, alternatively from 0.5 to 40, alternatively from 0.5 to 20, alternatively from 0.5 to 2. 
     The mole ratio of the alcohol to the silicon-bonded halogen atoms in the halodisilane and the halosilane combined is typically from 0.5 to 10, alternatively from 1 to 5, alternatively from 1 to 2. 
     The concentration of the organic solvent is typically from 0.01 to 95% (w/w), alternatively from 5 to 88% (w/w), alternatively from 30 to 50% (w/w), based on the total weight of the reaction mixture. 
     In step (ii) of the method, the alcoholysis product is reacted with water in the presence of siloxane particles at a temperature of from 0 to 40° C. to produce a hydrolyzate. 
     The siloxane particles of the present method can be any particles comprising siloxane units. The siloxane units may be represented by the following formulae: R 1   2 SiO 1/2  units (M units), R 1   2 SiO 2/2  units (D units), R 1 SiO 3/2  units (T units), and SiO 4/2  units (Q units), where R 1  is as described and exemplified above. 
     The siloxane particles typically have a median particle size (based on mass) of from 0.001 to 500 μm, alternatively from 0.01 to 100 μm. 
     Although the shape of the siloxane particles is not critical, particles having a spherical shape are preferred because they generally impart a smaller increase in viscosity to the silicone composition than particles having other shapes. 
     Examples of siloxane particles include, but are not limited to, silica particles comprising SiO 4/2  units, such as colloidial silica, dispersed pyrogenic (fumed) silica, precipitated silica, and coacervated silica; silicone resin particles comprising R 1 SiO 3/2  units, such as particles comprising MeSiO 3/2  units, particles comprising MeSiO 3/2  units and PhSiO 3/2  units, and particles comprising MeSiO 3/2  units and Me 2 SiO 2/2  units; and silicone elastomer particles comprising R 1   2 SiO 2/2  units, such as particles comprising a cross-linked product of a poly(dimethylsiloxane/methylvinylsiloxane) and a poly(hydrogenmethylsiloxane/dimethylsiloxane); and wherein R 1  is a described and exemplified above. 
     The siloxane particles can also be a metal polysilicate having the formula (M +a O a/2 ) x (SiO 4/2 ) y , where M is a metal cation having the charge +a, where a is an integer from 1 to 7, x has a value of from greater than zero to 0.01, y has a value of from 0.99 to less than 1, and the sum x+y=1. Examples of metals include, but are not limited to, alkali metals such as sodium and potassium; alkaline earth metals such as beryllium, magnesium, and calcium; transition metals such as iron, zinc, chromium, and zirconium; and aluminum. Examples of metal polysilicates include a polysilicate having the formula (Na 2 O) 0.01 (SiO 2 ) 0.99 . 
     The siloxane particles can also be treated siloxane particles prepared by treating the surfaces of the aforementioned particles with an organosilicon compound. The organosilicon compound can be any of the organosilicon compounds typically used to treat silica fillers. Examples of organosilicon compounds include, but are not limited to, organochlorosilanes such as methyltrichlorosilane, dimethyldichlorosilane, and trimethyl monochlorosilane; organosiloxanes such as hydroxy-endblocked dimethylsiloxane oligomer, hexamethyldisiloxane, and tetramethyldivinyldisiloxane; organosilazanes such as hexamethyldisilazane, hexamethylcyclotrisilazane; and organoalkoxysilanes such as methyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-methacryloxypropyltrimethoxysilane. 
     The siloxane particles of the present method can comprise a single type of siloxane particles or two or more different types of siloxane particles that differ in at least one of the following properties: composition, surface area, surface treatment, particle size, and particle shape. 
     Methods of preparing silicone resin particles and silicone elastomer particles are well known in the art. For example, silicone resin particles can be prepared by the hydrolysis-condensation of alkoxysilane(s) in an aqueous alkaline medium, as exemplified in U.S. Pat. No. 5,801,262 and U.S. Pat. No. 6,376,078. Silicone elastomer particles can be prepared by spray drying and curing a curable organopolysiloxane composition, as described in Japanese Patent Application No. 59096122; spray-drying an aqueous emulsion of a curable organopolysiloxane composition, as disclosed in U.S. Pat. No. 4,761,454; curing an emulsion of a liquid silicone rubber microsuspension, as disclosed in U.S. Pat. No. 5,371,139; or pulverizing cross-linked silicone rubber elastomer. 
     The alcoholysis product is typically combined with water by adding the alcoholysis product to a mixture of the water and siloxane particles. Reverse addition, i.e., addition of water to the alcoholysis product is also possible. However, reverse addition may result in formation of predominantly gels. 
     The rate of addition of the alcoholysis product to the mixture of water and siloxane particles is typically from 2 mL/min. to 100 mL/min. for a 1000-mL reaction vessel equipped with an efficient means of stirring. When the rate of addition is too slow, the reaction time is unnecessarily prolonged. When the rate of addition is too fast, the reaction mixture may form a gel. 
     The reaction of step (ii) is typically carried out at a temperature of from 0 to 40° C., alternatively from 0 to 20° C., alternatively from 0 to 5° C. When the temperature is less than 0° C., the rate of the reaction is typically very slow. When the temperature is greater than 40° C., the reaction mixture may form a gel. 
     The reaction time depends on several factors, including the structure of the alcoholysis product and the temperature. The reaction is typically carried out for an amount of time sufficient to complete hydrolysis of the alcoholysis product. As used herein, the term “to complete hydrolysis” means that at least 85 mol % of the silicon-bonded groups —OR 4  originally present in the alcoholysis product are replaced with hydroxy groups. For example, the reaction time is typically from 0.5 min. to 5 h, alternatively from 1 min. to 3 h, alternatively from 5 min. to 1 h at a temperature of from 0 to 40° C. The optimum reaction time can be determined by routine experimentation using the methods set forth in the Examples section below. 
     The concentration of water in the reaction mixture is typically sufficient to effect hydrolysis of the alcoholysis product. For example, the concentration of water is typically from 1 mole to 50 moles, alternatively from 5 moles to 20 moles, alternatively from 8 moles to 15 moles, per mole of the silicon-bonded groups —OR 4  in the alcoholysis product. 
     The concentration of the siloxane particles in the reaction mixture is typically from 0.0001 to 99% (w/w), alternatively from 1 to 80% (w/w), alternatively from 10 to 50% (w/w), based on the total weight of the reaction mixture. 
     In step (iii) of the method of preparing the silicone resin, the hydrolyzate is heated to produce the silicone resin. The hydrolyzate is typically heated at a temperature of from 40 to 100° C., alternatively from 50 to 85° C., alternatively from 55 to 70° C. The hydrolyzate is typically heated for a period of time sufficient to produce a silicone resin having a number-average molecular weight of from 200 to 500,000. For example, the hydrolyzate is typically heated for a period of from 1 h to 2 h, at a temperature of from 55° C. to 70° C. 
     The method can further comprise recovering the silicone resin. When the mixture of step (iii) contains a water-immiscible organic solvent, such as tetrahydrofuran, the silicone resin can be recovered from the reaction mixture by separating the organic phase containing the resin from the aqueous phase. The separation can be carried out by discontinuing agitation of the mixture, allowing the mixture to separate into two layers, and removing the aqueous or organic phase. The organic phase is typically washed with water. The water can further comprise a neutral inorganic salt, such as sodium chloride, to minimize formation of an emulsion between the water and organic phase during washing. The concentration of the neutral inorganic salt in the water can be up to saturation. The organic phase can be washed by mixing it with water, allowing the mixture to separate into two layers, and removing the aqueous layer. The organic phase is typically washed from 1 to 5 times with separate portions of water. The volume of water per wash is typically from 0.5 to 2 times the volume of the organic phase. The mixing can be carried out by conventional methods, such as stirring or shaking. The silicone resin can be used without further isolation or purification or the resin can be separated from most of the solvent by conventional methods of evaporation. 
     When the mixture of step (iii) contains a water-miscible organic solvent (e.g., methanol), the silicone resin can be recovered from the reaction mixture by separating the resin from the aqueous solution. For example, the separation can be carried out by distilling the mixture at atmospheric or subatmospheric pressure. The distillation is typically carried out at a temperature of from 40 to 60° C., alternatively from 60 to 80° C., at a pressure of 0.5 kPa. 
     Alternatively, the silicone resin can be separated from the aqueous solution by extracting the mixture containing the resin with a water immiscible organic solvent, such as methyl isobutyl ketone. The silicone resin can be used without further isolation or purification or the resin can be separated from most of the solvent by conventional methods of evaporation. 
     A silicone composition according to the present invention comprises: 
     (A) at least one silicone resin comprising disilyloxane units having the formula O (3-a)2 R 1   a Si—SiR 1   b O (3-b)/2  (I), and siloxane units having the form of particles, wherein each R 1  is independently —H, hydrocarbyl, or substituted hydrocarbyl; a is 0, 1, or 2; and b is 0, 1, 2 or 3; and 
     (B) an organic solvent. 
     Component (A) is the silicone resin of the present invention, described and exemplified above. Component (A) can be a single silicone resin or a mixture comprising two or more different silicone resins, each as described above. 
     Component (B) of the silicone composition is at least one organic solvent. The organic solvent can be any protic, aprotic, or dipolar aprotic organic solvent that does not react with the silicone resin or any optional ingredients (e.g., a crosslinking agent) and is miscible with the silicone resin. 
     Examples of organic solvents include, but are not limited to, alcohols, such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-butanol, 1-pentanol, and cyclohexanol; saturated aliphatic hydrocarbons such as n-pentane, hexane, n-heptane, isooctane and dodecane; cycloaliphatic hydrocarbons such as cyclopentane and cyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene; cyclic ethers such as tetrahydrofuran (THF) and dioxane; ketones such as methyl isobutyl ketone (MIBK); halogenated alkanes such as trichloroethane; and halogenated aromatic hydrocarbons such as bromobenzene and chlorobenzene. The organic solvent can be a single organic solvent or a mixture comprising two or more different organic solvents, each as defined above. 
     The concentration of the organic solvent is typically from 0.01% to 99.5% by weight, alternatively from 40 to 95% by weight, alternatively from 60% to 90% by weight, based on the total weight of the silicone composition. 
     The silicone composition can comprise additional ingredients, provided the ingredient does not prevent the silicone resin from forming a cured product or an oxidized product, as described below. Examples of additional ingredients include, but are not limited to, adhesion promoters; dyes; pigments; anti-oxidants; heat stabilizers; UV stabilizers, flame retardants, flow control additives, cross-linking agents, and condensation catalysts. 
     The silicone composition can further comprises a cross-linking agent and/or a condensation catalyst. The cross-linking agent can have the formula R 3   q SiX 4-q , wherein R 3  is C 1  to C 8  hydrocarbyl, X is a hydrolysable group, and q is 0 or 1. The hydrocarbyl groups represented by R 3  are as described and exemplified above. 
     As used herein the term “hydrolysable group” means the silicon-bonded group reacts with water in the absence of a catalyst at any temperature from room temperature (˜23±2° C.) to 100° C. within several minutes, for example thirty minutes, to form a silanol (Si—OH) group. Examples of hydrolysable groups represented by X include, but are not limited to, —Cl, —Br, —OR 3 , —OCH 2 CH 2 OR 4 , CH 3 C(═O)O—, Et(Me)C═N—O—, CH 3 C(═O)N(CH 3 )—, and —ONH 2 , wherein R 3  and R 4  are as described and exemplified above. 
     Examples of cross-linking agents include, but are not limited to, alkoxy silanes such as MeSi(OCH 3 ) 3 , CH 3 Si(OCH 2 CH 3 ) 3 , CH 3 Si(OCH 2 CH 2 CH 3 ) 3 , CH 3 Si[O(CH 2 ) 3 CH 3 ] 3 , CH 3 CH 2 Si(OCH 2 CH 3 ) 3 , C 6 H 5 Si(OCH 3 ) 3 , C 6 H 5 CH 2 Si(OCH 3 ) 3 , C 6 H 5 Si(OCH 2 CH 3 ) 3 , CH 2 ═CHSi(OCH 3 ) 3 , CH 2 ═CHCH 2 Si(OCH 3 ) 3 , CF 3 CH 2 CH 2 Si(OCH 3 ) 3 , CH 3 Si(OCH 2 CH 2 OCH 3 ) 3 , CF 3 CH 2 CH 2 Si(OCH 2 CH 2 OCH 3 ) 3 , CH 2 ═CHSi(OCH 2 CH 2 OCH 3 ) 3 , CH 2 ═CHCH 2 Si(OCH 2 CH 2 OCH 3 ) 3 , C 6 H 5 Si(OCH 2 CH 2 OCH 3 ) 3 , Si(OCH 3 ) 4,  Si(OC 2 H 5 ) 4 , and Si(OC 3 H 7 ) 4 ; organoacetoxysilanes such as CH 3 Si(OCOCH 3 ) 3 , CH 3 CH 2 Si(OCOCH 3 ) 3 , and CH 2 ═CHSi(OCOCH 3 ) 3 ; organoiminooxysilanes such as CH 3 Si[O—N═C(CH 3 )CH 2 CH 3 ] 3 , Si[O—N═C(CH 3 )CH 2 CH 3 ] 4 , and CH 2 ═CHSi[O—N═C(CH 3 )CH 2 CH 3 ] 3 ; organoacetamidosilanes such as CH 3 Si[NHC(═O)CH 3 ] 3  and C 6 H 5 Si[NHC(═O)CH 3 ] 3 ; amino silanes such as CH 3 Si[NH(s-C 4 H 9 )] 3  and CH 3 Si(NHC 6 H 11 ) 3 ; and organoaminooxysilanes. 
     The cross-linking agent can be a single silane or a mixture of two or more different silanes, each as described above. Also, methods of preparing tri- and tetra-functional silanes are well known in the art; many of these silanes are commercially available. 
     When present, the concentration of the cross-linking agent in the silicone composition is sufficient to cure (cross-link) the silicone resin. The exact amount of the cross-linking agent depends on the desired extent of cure, which generally increases as the ratio of the number of moles of silicon-bonded hydrolysable groups in the cross-linking agent to the number of moles of silicon-bonded hydroxy groups in the silicone resin increases. Typically, the concentration of the cross-linking agent is sufficient to provide from 0.2 to 4 moles of silicon-bonded hydrolysable groups per mole of silicon-bonded hydroxy groups in the silicone resin. The optimum amount of the cross-linking agent can be readily determined by routine experimentation. 
     As stated above, the silicone composition can further comprise at least one condensation catalyst. The condensation catalyst can be any condensation catalyst typically used to promote condensation of silicon-bonded hydroxy (silanol) groups to form Si—O—Si linkages. Examples of condensation catalysts include, but are not limited to, amines; and complexes of lead, tin, zinc, and iron with carboxylic acids. In particular, the condensation catalyst can be selected from tin(II) and tin(IV) compounds such as tin dilaurate, tin dioctoate, and tetrabutyl tin; and titanium compounds such as titanium tetrabutoxide. 
     The concentration of the condensation catalyst is typically from 0.1 to 10% (w/w), alternatively from 0.5 to 5% (w/w), alternatively from 1 to 3% (w/w), based on the total weight of the silicone resin. 
     When the silicone composition described above contains a condensation catalyst, the composition is typically a two-part composition where the silicone resin and condensation catalyst are in separate parts. 
     A coated substrate according to the present invention comprises: 
     a substrate; and 
     a coating on the substrate, wherein the coating is a cured product or an oxidized product of a silicone resin comprising disilyloxane units having the formula O (3-a)/2 R 1   a Si—SiR 1   b O (3-b)/2  (I), and siloxane units having the form of particles, wherein each R 1  is independently —H, hydrocarbyl, or substituted hydrocarbyl; a is 0, 1, or 2; and b is 0, 1, 2 or 3. 
     The substrate can be any rigid or flexible material having a planar, complex, or irregular contour. The substrate can be transparent or nontransparent to light in the visible region (˜400 to ˜700 nm) of the electromagnetic spectrum. Also, the substrate can be an electrical conductor, semiconductor, or nonconductor. Examples of substrates include, but are not limited to, semiconductors such as silicon, silicon having a surface layer of silicon dioxide, silicon carbide, indium phosphide, and gallium arsenide; quartz; fused quartz; aluminum oxide; ceramics; glass; metal foils; polyolefins such as polyethylene, polypropylene, polystyrene, polyethylene terephthalate (PET), and polyethylene naphthalate; fluorocarbon polymers such as polytetrafluoroethylene and polyvinylfluoride; polyamides such as Nylon; polyimides; polyesters such as poly(methyl methacrylate); epoxy resins; polyethers; polycarbonates; polysulfones; and polyether sulfones. 
     The coating of the coated substrate typically has a thickness of from 0.010 μm to 20 μm, alternatively from 0.050 μm to 10 μm, alternatively from 0.100 μm to 5 μm. The coating levels the irregular surfaces of various substrates and has excellent thermal crack resistance as well as dielectric and adhesion properties. 
     The coated substrate, wherein the coating is a cured product of a silicone resin can be prepared by applying the silicone resin or a silicone composition, each as described above, on a substrate to form a film and curing the silicone resin of the film. The silicone resin or silicone composition can be applied to the substrate using conventional methods such as spin coating, dip coating, spray coating, flow coating, screen printing, and roll coating. When present, the solvent is typically allowed to evaporate from the coated substrate before the film is heated. Any suitable means for evaporation may be used such as simple air drying, applying a vacuum, or heating (up to 50° C.). 
     The silicone resin can be cured (i.e., crosslinked) by heating the film. For example, the silicone resin is typically cured by heating the film at a temperature of from 50 to 260° C., alternatively from 50 to 250° C., alternatively from 100 to 200° C. When the silicone composition comprises a condensation catalyst, the silicone resin can typically be cured at a lower temperature, e.g., from room temperature (˜23±2° C.) to 200° C. The time of heating, which depends on the structure of the silicone resin, is typically from 1 to 50 h, alternatively from 1 to 10 h, alternatively from 1 to 5 h. The film can be heated using convention methods such as a quartz tube furnace, a convection oven, or radiant or microwave energy. 
     The coated substrate, wherein the coating is an oxidized product of a silicone resin, can be prepared by applying a silicone resin or a silicone composition, each as described above, on a substrate to form a film and oxidizing the silicone resin of the film. 
     The silicone resin or silicone composition can be applied on the substrate as described above. The silicone resin can be oxidized by heating the film, or exposing the film to UV radiation in the presence of an oxidizing agent. For example, the silicone resin can be oxidized by heating the film in air at a temperature of from 300 to 600° C. The film is typically heated for a period of time such that the mass of the oxidized coating is from 1 to 3% (w/w) greater than the mass of the coating prepared by curing the silicone resin of the film. For example, the film is typically heated for a period of from 0.01 to 1 h, alternatively from 0.01 to 0.2 h. Alternatively, the silicone resin can be oxidized by curing the silicone resin of the film, as described above, and then heating the cured silicone resin at a temperature of from 300 to 600° C. 
     A reinforced silicone resin film according to the present invention comprises: 
     a cured product of at least one silicone resin comprising disilyloxane units having the formula O (3-a)/2 R 1   a Si—SiR 1   b O (3-b)/2  (I), and siloxane units having the form of particles, wherein each R 1  is independently —H, hydrocarbyl, or substituted hydrocarbyl; a is 0, 1, or 2; and b is 0, 1, 2 or 3; and 
     a fiber reinforcement embedded in the cured product. 
     The reinforced silicone resin film comprises a cured product of at least one silicone resin, where the silicone resin is as described and exemplified above. As used herein, the term “cured product of a silicone resin” refers to a cross-linked silicone resin having a three-dimensional network structure 
     The cured product of the silicone resin can be prepared as described below in the method of preparing the reinforced silicone resin film of the present invention. 
     The reinforced silicone resin film also comprises a fiber reinforcement embedded in the cured product of the silicone resin. The fiber reinforcement can be any reinforcement comprising fibers, provided the reinforcement has a high modulus and high tensile strength. The fiber reinforcement typically has a Young&#39;s modulus at 25° C. of at least 3 GPa. For example, the reinforcement typically has a Young&#39;s modulus at 25° C. of from 3 to 1,000 GPa, alternatively from 3 to 200 GPa, alternatively from 10 to 100 GPa. Moreover, the reinforcement typically has a tensile strength at 25° C. of at least 50 MPa. For example, the reinforcement typically has a tensile strength at 25° C. of from 50 to 10,000 MPa, alternatively from 50 to 1,000 MPa, alternatively from 50 to 500 MPa. 
     The fiber reinforcement can be a woven fabric, e.g., a cloth; a nonwoven fabric, e.g., a mat or roving; or loose (individual) fibers. The fibers in the reinforcement are typically cylindrical in shape and have a diameter of from 1 to 100 μm, alternatively from 1 to 20 μm, alternatively form 1 to 10 μm. Loose fibers may be continuous, meaning the fibers extend throughout the reinforced silicone resin film in a generally unbroken manner, or chopped. 
     The fiber reinforcement is typically heat-treated prior to use to remove organic contaminants. For example, the fiber reinforcement is typically heated in air at an elevated temperature, for example, 575° C., for a suitable period of time, for example 2 h. 
     Examples of fiber reinforcements include, but are not limited to reinforcements comprising glass fibers; quartz fibers; graphite fibers; nylon fibers; polyester fibers; aramid fibers, such as Kevlar® and Nomex®; polyethylene fibers; polypropylene fibers; and silicon carbide fibers. 
     The reinforced silicone resin film of the present invention typically comprises from 10 to 99% (w/w), alternatively from 30 to 95% (w/w), alternatively from 60 to 95% (w/w), alternatively from 80 to 95% (w/w), of the cured silicone resin. Also, the reinforced silicone resin film typically has a thickness of from 10 to 3,000 pm, alternatively 15 to 500 μm, alternatively from 15 to 300 μm, alternatively from 20 to 150 μm, alternatively from 30 to 125 μm. 
     The reinforced silicone resin film typically has a flexibility such that the film can be bent over a cylindrical steel mandrel having a diameter less than or equal to 3.2 mm without cracking, where the flexibility is determined as described in ASTM Standard D522-93a, Method B. 
     The reinforced silicone resin film has low coefficient of linear thermal expansion (CTE), high tensile strength, and high modulus. For example the film typically has a CTE of from 0 to 80 μm/m° C., alternatively from 0 to 20 μm/m° C., alternatively from 2 to 10 μm/m° C., at temperature of from room temperature (˜23±2° C.) to 200° C. Also, the film typically has a tensile strength at 25° C. of from 50 to 200 MPa, alternatively from 80 to 200 MPa, alternatively from 100 to 200 MPa. Further, the reinforced silicone resin film typically has a Young&#39;s modulus at 25° C. of from 2 to 10 GPa, alternatively from 2 to 6 GPa, alternatively from 3 to 5 GPa. 
     The transparency of the reinforced silicone resin film depends on a number of factors, such as the composition of the cured silicone resin, the thickness of the film, and the refractive index of the fiber reinforcement. The reinforced silicone resin film typically has a transparency (% transmittance) of at least 10%, alternatively at least 60%, alternatively at least 75%, alternatively at least 85%, in the visible region of the electromagnetic spectrum. 
     A method of preparing a reinforced silicone resin film according to the present invention comprises the steps of: 
     impregnating a fiber reinforcement in a silicone composition comprising (A) a silicone resin comprising disilyloxane units having the formula O (3-a)/2 R 1   a Si—SiR 1   b O (3-b)/2  (I), and siloxane units having the form of particles, wherein each R 1  is independently —H, hydrocarbyl, or substituted hydrocarbyl, a is 0, 1, or 2, and b is 0, 1, 2 or 3, and (B) an organic solvent; and 
     curing the silicone resin of the impregnated fiber reinforcement. 
     In the first step of the method of preparing a reinforced silicone resin film, a fiber reinforcement is impregnated in a silicone composition comprising (A) a silicone resin comprising disilyloxane units having the formula O (3-a)/2 R 1   a Si—SiR 1   b O (3-b)/2  (I), and siloxane units having the form of particles, wherein each R 1  is independently —H, hydrocarbyl, or substituted hydrocarbyl, a is 0, 1, or 2, and b is 0, 1, 2 or 3, and (B) an organic solvent. 
     The silicone composition and the fiber reinforcement in the method of preparing the reinforced silicone resin film are each as described and exemplified above. 
     The fiber reinforcement can be impregnated in the silicone composition using a variety of methods. For example, according to a first method, the fiber reinforcement can be impregnated by (i) applying a silicone composition, described above, to a release liner to form a silicone film; (ii) embedding a fiber reinforcement in the film; (iii) degassing the embedded fiber reinforcement; and (iv) applying the silicone composition to the degassed embedded fiber reinforcement to form an impregnated fiber reinforcement. 
     In step (i), a silicone composition, described above, is applied to a release liner to form a silicone film. The release liner can be any rigid or flexible material having a surface from which the reinforced silicone resin film can be removed without damage by delamination after the silicone resin is cured, as described below. Examples of release liners include, but are not limited to, Nylon, polyethyleneterephthalate, and polyimide. 
     The silicone composition can be applied to the release liner using conventional coating techniques, such as spin coating, dipping, spraying, brushing, or screen-printing. The silicone composition is applied in an amount sufficient to embed the fiber reinforcement in step (ii), below. 
     In step (ii), a fiber reinforcement is embedded in the silicone film. The fiber reinforcement can be embedded in the silicone film by simply placing the reinforcement on the film and allowing the silicone composition of the film to saturate the reinforcement. 
     In step (iii), the embedded fiber reinforcement is degassed. The embedded fiber reinforcement can be degassed by subjecting it to a vacuum at a temperature of from room temperature (˜23±2° C.) to 60° C., for a period of time sufficient to remove entrapped air in the embedded reinforcement. For example, the embedded fiber reinforcement can typically be degassed by subjecting it to a pressure of from 1,000 to 20,000 Pa for 5 to 60 min. at room temperature. 
     In step (iv), the silicone composition is applied to the degassed embedded fiber reinforcement to form an impregnated fiber reinforcement. The silicone composition can be applied to the degassed embedded fiber reinforcement using conventional methods, as describe above for step (i). 
     The first method can further comprise the steps of (v) degassing the impregnated fiber reinforcement; (vi) applying a second release liner to the degassed impregnated fiber reinforcement to form an assembly; and (vii) compressing the assembly. 
     The assembly can be compressed to remove excess silicone composition and/or entrapped air, and to reduce the thickness of the impregnated fiber reinforcement. The assembly can be compressed using conventional equipment such as a stainless steel roller, hydraulic press, rubber roller, or laminating roll set. The assembly is typically compressed at a pressure of from 1,000 Pa to 10 MPa and at a temperature of from room temperature (˜23±2° C.) to 50° C. 
     Alternatively, according to a second method, the fiber reinforcement can be impregnated in a silicone composition by (i) depositing a fiber reinforcement on a release liner; (ii) embedding the fiber reinforcement in a silicone composition, described above; (iii) degassing the embedded fiber reinforcement; and (iv) applying the silicone composition to the degassed embedded fiber reinforcement to form an impregnated fiber reinforcement. The second method can further comprise the steps of (v) degassing the impregnated fiber reinforcement; (vi) applying a second release liner to the degassed impregnated fiber reinforcement to form an assembly; and (vii) compressing the assembly. In the second method, steps (iii) to (vii) are as described above for the first method of impregnating a fiber reinforcement in a silicone composition. 
     In step (ii), the fiber reinforcement is embedded in a silicone composition, described above. The reinforcement can be embedded in the silicone composition by simply covering the reinforcement with the composition and allowing the composition to saturate the reinforcement. 
     Furthermore, when the fiber reinforcement is a woven or nonwoven fabric, the reinforcement can be impregnated in a silicone composition by passing it through the composition. The fabric is typically passed through the silicone composition at a rate of from 1 to 1,000 cm/s at room temperature (˜23±2° C.). 
     In the second step of the method of preparing a reinforced silicone resin film, the silicone resin of the impregnated fiber reinforcement is cured. The silicone resin can be cured by heating the impregnated fiber reinforcement at a temperature of from 50 to 250° C., for a period of from 1 to 50 h. When the silicone composition comprises a condensation catalyst, the silicone resin can typically be cured at a lower temperature, e.g., from room temperature (˜23±2° C.) to 200° C. 
     The silicone resin of the impregnated fiber reinforcement can be cured at atmospheric or subatmospheric pressure, depending on the method, described above, employed to impregnate the fiber reinforcement in the condensation-curable silicone composition. For example, when the impregnated fiber reinforcement is not enclosed between a first and second release liner, the silicone resin is typically cured at atmospheric pressure in air. Alternatively, when the impregnated fiber reinforcement is enclosed between a first and second release liner, the silicone resin is typically cured under reduced pressure. For example, the silicone resin can be heated under a pressure of from 1,000 to 20,000 Pa, alternatively from 1,000 to 5,000 Pa. The silicone resin can be cured under reduced pressure using a conventional vacuum bagging process. In a typically process, a bleeder (e.g., polyester) is applied over the impregnated fiber reinforcement, a breather (e.g, Nylon, polyester) is applied over the bleeder, a vacuum bagging film (e.g., Nylon) equipped with a vacuum nozzle is applied over the breather, the assembly is sealed with tape, a vacuum (e.g., 1,000 Pa) is applied to the sealed assembly and, if necessary, the evacuated assembly is heated as described above. 
     The method of preparing the reinforced silicone resin film can further comprise the step of separating the cured silicone resin from the release liner(s). The cured silicone resin can be separated from the release liner by mechanically peeling the film away from the release liner. 
     The silicone resins of the present invention are soluble in a variety of organic solvents. For example, the solubility of the silicone resins in an organic solvent, which depends on the structure, molecular weight, and content of silicon-bonded hydroxy groups, is typically at least 2 g/mL, alternatively at least 1 g/mL, at room temperature (˜23±2° C.). In particular, the solubility of the silicone resins in methyl isobutyl ketone is typically from 0.1 to 2 g/mL, alternatively from 0.2 to 1 g/mL, at room temperature (˜23±2° C.). 
     The silicone resins are also substantially free of gel as determined by visible light spectrometry. For example, a solution containing 16% (w/w) of the first or second silicone resin in an organic solvent typically has a percent transmittance of at least 60%, alternatively at least 80%, alternatively at least 90%, for light in the visible region (˜400 to ˜700 nm) of the electromagnetic spectrum, as measured using a cell having a path length of 2.54 cm. 
     The silicone composition of the present invention can be conveniently formulated as a one-part composition having good shelf-stability. Moreover, the composition can be applied to a substrate by conventional high-speed methods such as spin coating, printing, and spraying. 
     The coating of the coated substrate exhibits very low surface roughness, high resistance to thermally induced cracking, and low tensile strength. 
     The reinforced silicone resin film of the present invention has low coefficient of thermal expansion, high tensile strength, and high modulus compared to an un-reinforced silicone resin film prepared from the same silicone composition. Also, although the reinforced and un-reinforced silicone resin films have comparable glass transition temperatures, the reinforced film exhibits a much smaller change in modulus in the temperature range corresponding to the glass transition. 
     The reinforced silicone resin film of the present invention is useful in applications requiring films having high thermal stability, flexibility, mechanical strength, and transparency. For example, the silicone resin film can be used as an integral component of flexible displays, solar cells, flexible electronic boards, touch screens, fire-resistant wallpaper, and impact-resistant windows. The film is also a suitable substrate for transparent or nontransparent electrodes. 
     Examples 
     The following examples are presented to better illustrate the silicone resin, silicone composition, and reinforced silicone resin film of the present invention, but are not to be considered as limiting the invention, which is delineated in the appended claims. Unless otherwise noted, all parts and percentages reported in the examples are by weight. The following methods and materials were employed in the examples: 
     Measurement of Mechanical Properties 
     Young&#39;s modulus, tensile strength, and tensile strain at break were measured using an MTS Alliance RT/5 testing frame, equipped with a 100-N load cell. Young&#39;s modulus, tensile strength, and tensile strain were determined at room temperature (˜23±2° C.) for the test specimens of Examples 2. 
     The test specimen was loaded into two pneumatic grips spaced apart 25 mm and pulled at a crosshead speed of 1 mm/min. Load and displacement data were continuously collected. The steepest slope in the initial section of the load-displacement curve was taken as the Young&#39;s modulus. Reported values for Young&#39;s modulus (GPa), tensile strength (MPa), and tensile strain (%) each represent the average of three measurements made on different dumbbell-shaped test specimens from the same silicone resin film. 
     The highest point on the load-displacement curve was used to calculate the tensile strength according to the equation: 
       σ= F /( wb ), 
     where:
     σ=tensile strength, MPa,   F=highest force, N,   w=width of the test specimen, mm, and   b=thickness of the test specimen, mm.   

     The tensile strain at break was approximated by dividing the difference in grip separation before and after testing by the initial separation according to the equation: 
       ε=100( l   2   −l   1 ) l   1 , 
     where:
     ε=tensile strain at break, %,   l 2 =final separation of the grips, mm, and   l 1 =initial separation of the grips, mm.   

     Disilane Composition A is a chlorodisilane stream obtained by fractional distillation of the residue produced in the direct process for manufacturing methylchlorosilanes. The composition contains C 4 H 9 SiMeCl 2 , 7.1%, Me 3 Cl 3 Si 2 O, 0.3%, Me 4 Cl 2 Si 2 , 8.6%, Me 2 Cl 4 Si 2 O, 1.9%, C 10  hydrocarbon, 1.9%, Me 3 Cl 3 Si 2 , 25.8%, and Me 2 Cl 4 Si 2 , 52.8%, based on total weight. 
     Disilane Composition B is a chlorodisilane stream obtained by fractional distillation of the residue produced in the direct process for manufacturing methylchlorosilanes. The composition contains Me 4 Cl 2 Si 2 , 0.1%, Me 3 Cl 3 Si 2 , 30.9%, and Me 2 Cl 4 Si 2 , 66.2%, based on total weight. 
     ORGANOSILICASOL™ IPA-ST, obtained from Nisan Chemical (Houston, Tex.), is a dispersion of colloidal silica in isopropyl alcohol, where the colloidal silica has a particle size of 10-15 nm. The dispersion contains 30% (w/w) of SiO 2 , and has a pH of 2-4 and a specific gravity of 0.96-1.02. 
     Glass Fabric, which is available from JPS Glass (Slater, SC), is an untreated style 106 electrical glass fabric having a plain weave and a thickness of 37.5 μm. 
     Example 1 
     Disilane Composition A (30 g), was mixed with 120 g of methyl isobutyl ketone (MIBK) and 38.4 g of anhydrous methanol. The HCl produced from the reaction was allowed to escape from the open mouth of the flask. The liquid mixture was placed in a sealed bottle, chilled in an ice water bath, and then transferred to an addition funnel mounted on top of a three necked round bottom flask equipped with a stirrer and a thermometer. A mixture containing 120 g of deionized water and 51.8 g of ORGANOSILICASOL™ IPA-ST was placed in the flask and cooled with an external ice water bath to 2 to 4° C. The mixture in the addition funnel was continuously added to the chilled mixture of deionized water/colloidal silica over a period of 10 min., during which time the temperature of the mixture increased by 3 to 5° C. After completion of the addition, the mixture was stirred in the ice bath for 1 h. The flask was then heated to 50 to 75° C. with a water bath and held at that temperature for 1 h. The mixture was allowed to cool to room temperature and then washed with a solution of 10 g of NaCl in 200 mL of water, four times. After each wash the aqueous phase was discarded. The organic phase was isolated and concentrated at 60° C. and a pressure of 2.7 kPa to produce a solution containing 22.4% (w/w) of the silicone resin in MIBK. The mole ratio of SiO 4/2  units to disilyloxane units in the resin is 4.4, as determined by  29 Si NMR. 
     Example 2 
     Glass fabric (38.1 cm×8.9 cm) was impregnated with the silicone composition of Example 1 by passing the fabric through the composition at a rate of about 5 cm/s. The impregnated fabric was then hung vertically in an air-circulating oven and the silicone resin was cured by heating the impregnated fabric from room temperature to 150° C. at 5° C/min. and then holding the temperature at 150° C. for 10 min. The oven was turned off and the reinforced silicone resin film was allowed to cool to room temperature. The steps of impregnating, curing, and cooling were repeated two additional times, except the silicone resin was cured by heating the impregnated fabric from room temperature to 200° C. at 5° C/min. and holding the temperature at 200° C. for 1 hour. The mechanical properties of the reinforced silicone resin film are shown in Table 1. 
     
       
         
           
               
               
               
               
               
             
               
                   
                 TABLE 1 
               
             
            
               
                   
                   
               
               
                   
                 Thickness 
                 Tensile Strength (MPa) 
                 Young&#39;s Modulus (GPa) 
                 Strain at Break (%) 
               
            
           
           
               
               
               
               
               
               
               
               
            
               
                 Ex. 
                 (μm) 
                 Warp 
                 Fill 
                 Warp 
                 Fill 
                 Warp 
                 Fill 
               
               
                   
               
               
                 2 
                 40 
                 49.4 ± 19.7 
                 117.5 ± 14.9 
                 3.30 ± 0.46 
                 4.12 ± 0.49 
                 2.0 ± 0.6 
                 4.7 ± 2.0