Reinforced silicone resin films

(Cross-reference of related applications) None.

The present invention relates to a reinforced silicone resin film, more specifically, a reinforced silicone resin film containing at least two polymer layers, wherein at least one of the polymer layers is bonded to an average of at least two silicons per molecule. The present invention relates to a reinforced silicone resin film containing a cured product of at least one silicone resin having a hydrogen atom bonded to an alkenyl group or silicon, and at least one of the polymer layers containing a carbon nanomaterial.

Silicone resins are useful in a variety of applications due to their unique combination of properties, including high thermal stability, good moisture resistance, excellent flexibility, high oxidation resistance, low dielectric constant and high transparency. is there. For example, silicone resins are widely used as protective or dielectric coatings in the automotive, electronic, architectural, electrical and aerospace industries.

<p> While silicone resin coatings can be used to protect, insulate or bond various substrates, free-standing silicone resin films have low tear strength, high brittleness, low glass transition temperature and high heat. It has limited usefulness due to its coefficient of expansion. Therefore, there is a need for self-supporting silicone resin films with improved mechanical and thermal properties.</p>

<p> The present invention is essentially With the first polymer layer, With the second polymer layer on the first polymer layer Consisting of, at least one of these polymer layers comprises a cured product of at least one silicone resin having an alkenyl group attached to at least two silicon or a hydrogen atom attached to silicon on average per molecule, and a polymer. At least one of the layers contains a carbon nanomaterial, but if both of the above polymer layers contain a cured product of a silicone resin, then both of the polymer layers are (i) carbon nanomaterials, (ii) fibers. Reinforcing Silicone Resin Films Containing Reinforcing Materials and Reinforcing Materials Selected From Mixtures Containing (iii) (i) and (ii).</p><p> The present invention is also a reinforced silicone resin film. With the first polymer layer, With the second polymer layer on the first polymer layer, With at least one additional polymer layer on the second polymer layer And at least one of these polymer layers comprises a cured product of at least one silicone resin having an alkenyl group bonded to at least two silicon or a hydrogen atom bonded to silicon on average per molecule, and a polymer. At least one of the layers relates to a reinforced silicone resin film containing carbon nanomaterials.</p><p> The reinforced silicone resin film of the present invention has a low coefficient of thermal expansion and high resistance to thermally induced cracks.</p><p> The reinforced silicone resin film of the present invention is useful for applications that require a film with high thermal stability, flexibility, mechanical strength and transparency. For example, this silicone resin film can be used as an integral part of flexible displays, solar cells, flexible electronic circuit boards, touch screens, fire resistant wallpaper and impact resistant windows. This film is also a suitable substrate for transparent or opaque electrodes.</p>

As used herein, the term "aliphatic unsaturated" means that the hydrocarbyl or halogen-substituted hydrocarbyl group does not contain an aliphatic carbon-carbon double bond or carbon-carbon triple bond. To do. Also, the term "group R in silicone resin"²... mol% is alkenyl "is the group R in the silicone resin²It is defined as 100 times the ratio of the number of moles of alkenyl groups bonded to silicon in the resin to the total number of moles of. In addition, the term "group R in organohydrogenpolysiloxane resin"⁴... mol% is organic silylalkyl "is the group R in the organohydrogenpolysiloxane resin.⁴It is defined as 100 times the ratio of the number of moles of organic silylalkyl groups bonded to silicon in the resin to the total number of moles of. Furthermore, the term "group R in silicone resin"⁵"... mol% is hydrogen" is the group R in the silicone resin⁵It is defined as 100 times the ratio of the number of moles of hydrogen atoms bonded to silicon in the resin to the total number of moles of.

The first reinforced silicone resin film according to the present invention is With the first polymer layer, With the second polymer layer on the first polymer layer Essentially from, at least one of these polymer layers contains a cured product of at least one silicone resin having an alkenyl group attached to at least two silicon or a hydrogen atom attached to silicon on average per molecule. , And at least one of the polymer layers contains a carbon nanomaterial, but if both of the above polymer layers contain a cured product of a silicone resin, then both of the polymer layers are (i) carbon nanomaterials, ( ii) Contains fiber reinforcements and reinforcements selected from mixtures containing (iii) (i) and (ii).

The first polymer layer of the first reinforced silicone resin film typically has a thickness of 0.01 to 1000 μm, or 5 to 500 μm, or 10 to 100 μm.

The first polymer layer of the first reinforced silicone resin film can include a thermoplastic polymer or a thermosetting polymer. The thermoplastic or thermosetting polymer may be a homopolymer or a copolymer. Further, the thermoplastic polymer or thermosetting polymer may be a silicone polymer or an organic polymer. As used herein and below, the term "thermoplastic polymer" has the property of changing to a fluid (fluid) state when heated and stiff (non-fluid) when cooled. Refers to the polymer that has. Also, the term "thermosetting polymer" refers to a cured (ie, crosslinked) polymer that does not change to a fluid state upon heating.

Examples of thermoplastic polymers include thermoplastic silicone polymers (eg poly (diphenylsiloxane-co-phenylmethylsiloxane)) and thermoplastic organic polymers (eg polyolefins, polysulfones, polyacrylates and polyetherimides). Not limited to.

Examples of thermosetting polymers include thermosetting silicone polymers (eg, cured silicone elastomers, silicone gels and cured silicone resins), and thermosetting organic polymers (eg, cured epoxy resins, cured amino resins, cured). Examples include, but are not limited to, polyurethanes, cured polyimides, cured phenolic resins, cured cyanate resins, cured bismaleimide resins, cured polyesters and cured acrylic resins.

In addition to the thermoplastic or thermosetting polymer, the first polymer layer of the first reinforced silicone resin film can contain a reinforced material selected from carbon nanomaterials, fiber reinforced materials or mixtures thereof.

The second polymer layer of the first reinforced silicone resin film is as described and illustrated above for the first polymer layer. The first and second polymer layers of this first reinforced silicone resin film have many physical and chemical properties, including thickness, polymer composition, crosslink density and concentration of carbon nanomaterials or other reinforced materials. Different in at least one of them.

At least one of the polymer layers of the first reinforced silicone resin film is a cured product of at least one silicone resin having an average of at least two silicon-bonded alkenyl groups or silicon-bonded hydrogen atoms per molecule. Including. As used herein, the term "cured product of at least one silicone resin" refers to a crosslinked product of at least one silicone resin that has a three-dimensional network structure. The silicone resin, the method for preparing the resin, and the method for preparing the cured product of the silicone resin are described later in the method for preparing the first reinforced silicone resin film of the present invention.

At least one of the polymer layers of the first reinforced silicone resin film contains carbon nanomaterials. The carbon nanomaterial may be any carbon material having at least one physical dimension (eg particle size, fiber diameter, layer thickness) less than about 200 nm. Examples of carbon nanomaterials are carbon nanoparticles with three dimensions less than about 200 nm (eg quantum dots, hollow spheres and graphene), and fibrous carbon nanomaterials with two dimensions less than about 200 nanometers (eg, quantum dots, hollow spheres and graphene). Nanotubes (eg, single-walled nanotubes and multi-walled nanotubes) and nanoparticles (eg, axially aligned platelets, and herringbone or fishbone nanofibers), and 1 less than about 200 nm. Layered carbon nanomaterials having one dimension, such as, but not limited to, carbon nanoplatelets (eg, expanded graphite and graphene sheets), may be conductive or semi-conducting. It may be conductive.

The carbon nanomaterial may be an oxidized carbon nanomaterial prepared by treating the above-mentioned carbon nanomaterial with an oxidizing acid or a mixture of acids at a high temperature. For example, carbon nanomaterials can be obtained by heating the material in a mixture of concentrated nitric acid and concentrated sulfuric acid (1: 3 volume / volume, 25 mL per gram of carbon) at a temperature of 40-150 ° C for 1-3 hours. , Can be oxidized.

The carbon nanomaterial may be a single carbon nanomaterial or a mixture containing at least two different carbon nanomaterials (each as described above).

The concentration of carbon nanomaterial in the first and / or second polymer layers is typically 0.0001 to 99% (weight / weight) or 0.001 to 50% (weight) based on the total weight of the polymer layers. / Weight), or 0.01-25% (weight / weight), or 0.1-10% (weight / weight), or 1-5% (weight / weight).

Methods of preparing carbon nanomaterials are well known in the art. For example, carbon nanoparticles (eg, fullerenes) and fibrous carbon nanomaterials (eg, nanotubes and nanofibers) can be prepared using at least one of the following methods: arc discharge, laser ablation and catalytic. Chemical vapor deposition. In the arc discharge process, the arc discharge between the two graphite rods produces single-walled nanotubes, multi-walled nanotubes and fullerenes, depending on the gas atmosphere. In the laser ablation method, the graphite target carrying the metal catalyst is irradiated by a laser in a tube furnace to produce single-walled and multi-walled nanotubes. In catalytic chemical vapor deposition, a carbon-containing gas or gas mixture is introduced into a tube furnace containing a metal catalyst at a temperature of 500-1000 ° C (and at various pressures) to produce carbon nanotubes and nanofibers. To do. Carbon nanoplatelets can be prepared by graphite intercalation and exfoliation.

If both of the polymer layers of the first reinforced silicone resin film contain a cured product of the silicone resin, both of the polymer layers are (i) carbon nanomaterials, (ii) fiber reinforced materials, and (iii) (i). ) And (ii) containing a reinforcing material selected from the mixture. The carbon nanomaterials are as described and illustrated above. The polymer layer can contain the same or different reinforcements selected from (i), (ii) and (iii), respectively.

The fiber reinforcing material may be any reinforcing material containing fibers as long as the reinforcing material has a high elastic modulus and a high tensile strength. Fiber reinforcements typically have a Young's modulus of at least 3 GPa at 25 ° C. For example, this reinforcement typically has a Young's modulus of 3 to 1,000 GPa, or 3 to 200 GPa, or 10 to 100 GPa at 25 ° C. In addition, the reinforcement typically has a tensile strength of at least 50 MPa at 25 ° C. For example, this reinforcement typically has a tensile strength at 25 ° C of 50-10,000 MPa, or 50-1,000 MPa, or 50-500 MPa.

The fiber reinforcement may be a woven fabric (eg cloth), a non-woven fabric (eg matte or roving), or unbundled (individual) fibers. Reinforcing fiber is typically cylindrical in shape and has a diameter of 1-100 μm, or 1-20 μm, or 1-10 μm. The unbundled fibers may be continuous (this means that the fibers extend over the entire reinforced silicone resin film in a manner that is almost unbreakable) or may be chopped.

Fiber reinforcements are typically heat treated prior to use to remove organic contaminants. For example, fiber reinforced plastics are typically heated in air at high temperatures (eg 575 ° C) for a suitable period of time (eg 2 hours).

Examples of fiber reinforcements include glass fibers, quartz fibers, graphite fibers, nylon fibers, polyester fibers, aramid fibers (eg, Kevlar® and Nomex®, polyethylene fibers, polypropylene fibers, and silicon carbide fibers. Reinforcement materials including, but are not limited to these.

The concentration of fiber reinforcement in the first and / or second polymer layer is typically 0.1-95% (weight / weight), or 5-75% (weight / weight), based on the total weight of the polymer layer. Weight), or 10-40% (weight / weight).

When one or both of the polymer layers of the first reinforced silicone resin film contain a mixture of carbon nanomaterials and fiber reinforced materials, the concentration of the mixture is typically 0.1-96 based on the total weight of the polymer layers. % (Weight / weight), or 5 to 75% (weight / weight), or 10 to 40% (weight / weight).

The first polymer layer and the second polymer layer can be prepared as described later in the method for preparing the first reinforced silicone resin film of the present invention.

The first reinforced silicone resin film is The process of forming the first polymer layer on the release liner, With the step of forming a second polymer layer on top of this first polymer layer At least one of the polymer layers comprises a cured product of at least one silicone resin having an alkenyl group bonded to at least two silicon or a hydrogen atom bonded to silicon on average per molecule. , And at least one of the polymer layers contains a carbon nanomaterial, but if both of the polymer layers contain a cured product of a silicone resin, then both of the polymer layers are (i) carbon nanomaterials. It can be prepared by a method comprising (ii) a fiber reinforcing material and a reinforcing material selected from a mixture containing (iii) (i) and (ii).

In the first step of the method of preparing the first reinforced silicone resin film, the first polymer layer is formed on the release liner.

The release liner may be any rigid or flexible material with a surface that allows the first polymer layer to be removed without damage. Examples of release liners include silicon, quartz, fused quartz, aluminum oxide, ceramics, glass, metal foils, polyolefins (eg polyethylene, polypropylene, polystyrene and polyethylene terephthalates), fluorocarbon polymers (eg polytetrafluoroethylene and polyvinyl fluoride). , Polyethylene (eg, nylon), polyimide, polyester (eg, polymethyl methacrylate), epoxy resins, polyethers, polycarbonates, polysulfones, and polyether sulfones, but are not limited thereto. The release liner may be the material cited above, having a surface treated with a release agent (eg, a silicone release agent).

The first polymer layer can be formed using a variety of methods, depending on the composition of the polymer layer. For example, if the first polymer layer contains a thermoplastic polymer, the layer is (i) coated with a composition containing the thermoplastic polymer in a fluid state, and (ii) the heat of the coated release liner. It can be formed by converting the thermoplastic polymer into a solid state.

In step (i) of the method of forming the first polymer layer described above, the release liner is coated with a composition containing a fluidized thermoplastic polymer.

The composition containing the thermoplastic polymer may be any composition containing the thermoplastic polymer in a fluid (ie, liquid) state. As used herein, the term "fluid thermoplastic polymer" means that the polymer is in a molten state or is dissolved in an organic solvent. For example, the composition is the melting point of the polymer (T_m) Or glass transition temperature (T_g) Can be included, or the composition can include a thermoplastic polymer and an organic solvent.

The thermoplastic polymer of the above composition is as described and exemplified above for the first reinforced silicone resin film. The thermoplastic polymer may be a single thermoplastic polymer or a mixture (ie, a blend) containing two or more different thermoplastic polymers. For example, the thermoplastic polymer may be a polyolefin blend.

The organic solvent may be any protic, aprotic, or bipolar aprotic organic solvent that does not react with the thermoplastic polymer and is miscible with the polymer. Examples of organic solvents include saturated aliphatic hydrocarbons (eg n-pentane, hexane, n-heptane, isooctane and dodecane), alicyclic hydrocarbons (eg cyclopentane and cyclohexane), aromatic hydrocarbons (eg benzene, etc.). Toluene, xylene and mesitylene), cyclic ethers (eg tetrahydrofuran (THF) and dioxane), ketones (eg methylisobutylketone (MIBK)), halogenated alcohols (eg trichloroethane), halogenated aromatic hydrocarbons (eg bromobenzene and chlorobenzene) ), And alcohols (eg methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-butanol, 1,1-dimethyl-1-ethanol, pentanol, hydrocarbons, cyclos. (Hexanol, heptanol and octanol), but not limited to these.

The organic solvent may be a single organic solvent or a mixture containing two or more different organic solvents, each as described and exemplified above.

Compositions comprising thermoplastic polymers can further comprise the carbon nanomaterials described and exemplified above.

The release liner may be coated with a composition comprising a fluidized thermoplastic polymer using conventional coating techniques such as spin coating, dipping, spraying, brushing, extrusion or screen printing. The amount of composition is sufficient to form a first polymer layer with a thickness of 0.01-1000 μm.

In step (ii) of the method described above, the thermoplastic polymer of the coated release liner is converted to a solid state. If the composition used to coat the release liner contains a molten thermoplastic polymer, the thermoplastic polymer will have a liquid-solid transition temperature (T)._gOr T_m) It can be converted to a solid state by allowing the polymer to cool to a lower temperature, eg room temperature. If the composition used to coat the release liner comprises a thermoplastic polymer and an organic solvent, the thermoplastic polymer can be converted to a solid state by removing at least a portion of the solvent. The organic solvent can be removed by vaporizing the solvent at room temperature or by heating the coating to a moderate temperature, for example below the solid-liquid transition temperature of the polymer.

The method of forming the first polymer layer containing the thermoplastic polymer is to apply a second release liner to the coated release liner of the first step after step (i) and before step (ii). The steps of forming the assembly and compressing the assembly can be further included. This assembly can be compressed to remove excess composition and / or invading air and reduce the thickness of the coating. The assembly can be compressed using conventional equipment (eg stainless steel rollers, hydraulic presses, rubber rollers or laminated roll sets). The assembly is typically compressed at a pressure of 1,000 Pa-10 MPa and at a temperature of room temperature (about 23 ± 2 ° C) to 200 ° C.

If the same composition is used in each coating step, the method of forming the first polymer layer containing the thermoplastic polymer is a step of repeating steps (i) and (ii) to further increase the thickness of the polymer layer. Can include.

If the first polymer layer contains a thermosetting (ie, crosslinked) polymer, the layer will (i) coat the release liner with a curable composition containing the thermosetting polymer and (ii) coat the release liner. It can be formed by curing the thermosetting polymer of.

In step (i) of the method immediately prior to forming the first polymer layer, the release liner is coated with a curable composition comprising a thermosetting polymer.

The curable composition containing a thermosetting polymer may be any curable composition containing a thermosetting polymer. As used herein and below, the term "thermosetting polymer" refers to a polymer that has the property of being persistently rigid (immobilized) when cured (ie, crosslinked). The curable composition typically comprises a thermosetting polymer and additional components such as an organic solvent, a cross-linking agent and / or a catalyst.

Examples of curable compositions containing thermosetting polymers include curable silicone compositions (eg, hydrosilylated curable silicone compositions, condensation curable silicone compositions and peroxide curable silicone compositions), curable silicones. Compositions (eg, silicone and polypropylene compositions), curable polyamide compositions, curable epoxy resin compositions, curable amino resin compositions, curable polyurethane compositions, curable polyimide compositions, curable polyester compositions, and Curable acrylic resin compositions include, but are not limited to.

The curable composition containing the thermosetting polymer may be a hydrosilylation-curable silicone composition containing a silicone resin having an alkenyl group bonded to at least two silicons or a hydrogen atom bonded to silicon on average per molecule. ..

The hydrosilylation-curable silicone composition may be any hydrosilylation-curable silicone composition comprising an alkenyl group bonded to at least two silicons per molecule or a silicone resin having a hydrogen atom bonded to silicon. Typically, the hydrosilylation-curable silicone composition is the silicone resin described above and an organosilicon compound in an amount sufficient to cure the silicone resin, with an average of at least two silicone resins per molecule. Includes an organosilicon compound having a silicon-bonded alkenyl group or a silicon-bonded hydrogen atom capable of reacting with a silicon-bonded hydrogen atom or a silicon-bonded alkenyl group, and a catalytic amount of a hydrosilylation catalyst.

Silicone resins in hydrosilylation curable silicone compositions are typically copolymers containing T units, T and Q units or T and / or Qsiloxane units in combination with M and / or Dsiloxane units. Further, the silicone resin may be a rubber-modified silicone resin, which will be described later in the fifth and sixth embodiments of the hydrosilylation-curable silicone composition.

According to the first embodiment, the hydrosilylation-curable silicone composition is of formula (A) (R).¹R²₂SiO_1/2)_w(R²₂SiO_2/2)_x(R²SiO_3/2)_y(SiO_4/2)_zSilicone resin having (I) (in the formula, R¹Is C₁~ C₁₀Hydrocarbyl or C₁~ C₁₀Halogen-substituted hydrocarbyls, both of which are free of aliphatic unsaturated and R²Is R¹Or alkenyl, w is 0 to 0.95, x is 0 to 0.95, y is 0 to 1, z is 0 to 0.95, w + x + y + z = 1, y + Z is 0.05 to 1 and w + x is 0 to 0.95, but this silicone resin has an average of at least two silicon-bonded alkenyl groups per molecule), and (B) the above silicone resin. It contains an organosilicon compound having an average of at least two silicon-bonded hydrogen atoms per molecule, in an amount sufficient to cure the silicon, and (C) a catalytic amount of a hydrosilylation catalyst.

Ingredient (A) is the formula (R)¹R²₂SiO_1/2)_w(R²₂SiO_2/2)_x(R²SiO_3/2)_y(SiO_4/2)_zAt least one silicone resin having (I) (in the formula, R¹Is C₁~ C₁₀Hydrocarbyl or C₁~ C₁₀Halogen-substituted hydrocarbyls, both of which are free of aliphatic unsaturated and R²Is R¹Or alkenyl, w is 0 ~ 0.95, x is 0 ~ 0.95, y is 0 ~ 1, z is 0 ~ 0.95, w + x + y + z = 1, y + z is 0.05 to 1 and w + x is 0 to 0.95, where y is 0, w + x is 0.05 to 0.8, and this silicone resin averages at least two silicons per molecule. Has an alkenyl group attached to).

R¹The hydrocarbyl and halogen-substituted hydrocarbyl groups represented by are free of aliphatic unsaturateds and typically have 1-10 carbon atoms, or 1-6 carbon atoms. Acyclic hydrocarbyls containing at least 3 carbon atoms and halogen-substituted hydrocarbyl groups can have a branched or non-branched structure. R¹Examples of hydrocarbyl groups represented by are alkyl (eg, 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 (eg cyclopentyl, cyclohexyl and methylcyclohexyl), Examples include, but are not limited to, aryl (eg, phenyl and naphthyl), alkalinel (eg, trill and xsilyl), and aralkyl (eg, benzyl and phenethyl). R¹Examples of halogen-substituted hydrocarbyl groups represented by are 3,3,3-trifluoropropyl, 3-chloropropyl, chlorophenyl, dichlorophenyl, 2,2,2-trifluoroethyl, 2,2,3, Examples include, but are not limited to, 3-tetrafluoropropyl and 2,2,3,3,4,4,5,5-octafluoropentyl.

R²The alkenyl group represented by (which may be the same or different) typically has 2 to about 10 carbon atoms, or 2 to 6 carbon atoms, eg. Examples include, but are not limited to, vinyl, allyl, butenyl, hexenyl and octenyl.

In the above silicone resin formula (I), the subscripts w, x, y and z are mole fractions. The subscript w typically has a value of 0 to 0.95, or 0.02 to 0.75, or 0.05 to 0.3, and the subscript x typically has a value of 0 to 0.95, or 0 to 0.7, or 0 to 0.25. Has a value, the subscript y typically has a value of 0 to 1, 0.25 to 0.8, or 0.5 to 0.8, and the subscript z typically has a value of 0 to 0.95, or 0 to 0.7. , Or has a value of 0 to 0.15. The sum y + z is typically 0.05 to 1, 0.5 to 0.95, or 0.65 to 0.9. Further, the sum w + x is typically 0 to 0.95, or 0.05 to 0.5, or 0.1 to 0.35.

Typically, the group R in the silicone resin²At least 50 mol%, or at least 65 mol%, or at least 80 mol% of is alkenyl.

Silicone resins typically have a number average molecular weight (M) of 500-50,000, or 500-10,000, or 1,000-3,000._n), Where this molecular weight is measured by gel transmission chromatography using a small angle laser light scattering detector, or a refractive index detector and a silicone resin (MQ) standard.

The viscosity of the silicone resin at 25 ° C is typically 0.01 to 100,000 Pa · s, 0.1 to 10,000 Pa · s, or 1 to 100 Pa · s.

Silicone resin is²⁹When measured by Si NMR, it typically contains less than 10% (weight / weight), or less than 5% (weight / weight), or less than 2% (weight / weight) of silicon-bonded hydroxy groups.

The above silicone resin is R¹R²₂SiO_1/2Units (ie M units) and / or R²₂SiO_2/2In combination with the unit (ie D unit), R²SiO_3/2Unit (ie T unit), R²SiO_3/2Units (ie T units) and SiO_4/2Unit (ie Q unit), or R²SiO_3/2Units (ie T units) and / or SiO_4/2Including units (ie Q units), R¹And R²Is as described and illustrated above. For example, the silicone resin can be a T resin, a TQ resin, a DT resin, an MT resin, an MDT resin, an MQ resin, a DQ resin, an MDQ resin, an MTQ resin, a DTQ resin or an MDTQ resin.

Examples of the above silicone resins include, but are not limited to, resins having the following formulas: (Vi).₂MeSiO_1/2)_0.25(PhSiO_3/2)_0.75、(ViMe₂SiO_1/2)_0.25(PhSiO_3/2)_0.75, (ViMe₂SiO_1/2)_0.25(MeSiO_3/2)_0.25(PhSiO_3/2)_0.50, (ViMe₂SiO_1/2)_0.15(PhSiO_3/2)_0.75(SiO_4/2)_0.1, And (Vi₂MeSiO_1/2)_0.15(ViMe₂SiO_1/2)_0.1(PhSiO_3/2)_0.75(In the formula, Me is methyl, Vi is vinyl, Ph is phenyl, and the subscript of the number outside the parentheses means mole fraction). Moreover, in the above-mentioned formula, the array of units is not specified.

Ingredient (A) may be a single silicone resin or a mixture containing two or more different silicone resins (each as described above).

Methods for preparing silicone resins are well known in the art and many of these resins are commercially available. Silicone resins are typically prepared by co-hydrolyzing a suitable mixture of chlorosilane precursors in an organic solvent (eg, toluene). For example, essentially R¹R²₂SiO_1/2Unit and R²SiO_3/2The silicone resin consisting of the unit is the formula R¹R²₂Compounds with SiCl and formula R²SiCl₃Can be prepared by co-hydrolyzing a compound with (in the formula, R).¹And R²Is as defined and illustrated above). The hydrochloric acid and silicone hydrolyzate are separated, the hydrolyzate is washed with water to remove residual acid, heated in the presence of a mild condensation catalyst, and the resin is "thickened" to the required viscosity. (body) ". If desired, the resin can be further treated with a condensation catalyst in an organic solvent to reduce the content of hydroxy groups attached to silicon. Alternatively, hydrolyzable groups other than chloro (-Br, -I, -OCH₃, -OC (O) CH₃, -N (CH)₃)₂, NHCOCH₃, And -SCH₃Silanes containing) can be used as a starting material for simultaneous hydrolysis reactions. The properties of the resin product depend on the type of silane, the molar ratio of silane, the degree of condensation and the treatment conditions.

Component (B) is at least one organosilicon compound having an average of at least two silicon-bonded hydrogen atoms per molecule in an amount sufficient to cure the silicone resin of component (A).

This organosilicon compound has an average of at least two silicon-bonded hydrogen atoms per molecule, or at least three silicon-bonded hydrogen atoms per molecule. Crosslinks can occur when the sum of the average number of alkenyl groups per molecule in component (A) and the average number of hydrogen atoms attached to silicon per molecule in component (B) is greater than 4. Generally understood.

The organosilicon compound may be organohydrogensilane or organohydrogensiloxane. The organohydrogensilane may be monosilane, disilane, trisilane or polysilane. Similarly, the organohydrogensiloxane may be disiloxane, trisiloxane or polysiloxane. The structure of the organosilicon compound may be linear, branched, cyclic, or resinous. Cyclosilanes and cyclosiloxanes typically have 3-12 silicon atoms, or 3-10 silicon atoms, or 3-4 silicon atoms. In acyclic polysilanes and polysiloxanes, hydrogen atoms bonded to silicon may be present at the terminal, pendant, or both terminal and pendant positions.

Examples of organohydrogensilanes are diphenylsilane, 2-chloroethylsilane, bis [(p-dimethylsilyl) phenyl] ether, 1,4-dimethyldisilylethane, 1,3,5-tris (dimethylsilyl). Examples include, but are not limited to, benzene, 1,3,5-trimethyl-1,3,5-trisilane, poly (methylcilylene) phenylene and poly (methylsilylene) methylene.

Organohydrogensilane is the formula HR¹₂Si-R³-SiR¹₂May have H (in the formula, R¹Is C₁~ C₁₀Hydrocarbyl or C₁~ C₁₀Halogen-substituted hydrocarbyls, both of which are free of aliphatic unsaturated and R³Is an aliphatic unsaturated hydrocarbylene group having a formula selected from:<chemistry num="1"><img file="JP2010519086A_D0001.tif" /></chemistry>(In the formula, g is 1 to 6)). R¹The hydrocarbyl and halogen-substituted hydrocarbyl groups represented by are as defined and exemplified for the silicone resin of component (A).

Expression HR¹₂Si-R³-SiR¹₂H (in the formula, R¹And R³Examples of organohydrogensilanes having (as described and exemplified above) include, but are not limited to, silanes having the following formulas.<chemistry num="2"><img file="JP2010519086A_D0002.tif" /></chemistry>

Examples of organohydrogensiloxanes are 1,1,3,3-tetramethyldisiloxane, 1,1,3,3-tetraphenyldisiloxane, phenyltris (dimethylsiloxy) silane, 1,3,5-trimethyl. Cyclotrisiloxane, trimethylsiloxy-terminated poly (methylhydrogensiloxane), trimethylsiloxy-terminated poly (dimethylsiloxane / methylhydrogensiloxane), dimethylhydrogensiloxy-terminated poly (methylhydrogensiloxane), and essentially HMe₂SiO_1/2Unit, Me₃SiO_1/2Unit and SiO_4/2Examples include, but are not limited to, resins consisting of units (Me is methyl in the formula).

Organohydrogensiloxane is expressed by the formula (R)¹R⁴₂SiO_1/2)_w(R⁴₂SiO_2/2)_x(R¹SiO_3/2)_y(SiO_4/2)_zIt may be an organohydrogenpolysiloxane resin having (II) (in the formula, R).¹Is C₁~ C₁₀Hydrocarbyl or C₁~ C₁₀Halogen-substituted hydrocarbyls, both of which are free of aliphatic unsaturated and R⁴Is R¹Or an organic silylalkyl group with a hydrogen atom attached to at least one silicon, w is 0 to 0.8, x is 0 to 0.6, y is 0 to 0.99, z is 0 to 0.35. , W + x + y + z = 1, y + z is 0.2 ~ 0.99, and w + x is 0.01 ~ 0.8, but the base R⁴At least 50 mol% of is organic silylalkyl).

R¹The hydrocarbyl and halogen-substituted hydrocarbyl groups represented by are as described and exemplified above for the silicone resin of component (A). R⁴Examples of organic silylalkyl groups represented by are, but are not limited to, groups having the following formulas:<chemistry num="3"><img file="JP2010519086A_D0003.tif" /></chemistry>(In the formula, Me is methyl, Ph is phenyl, and the subscript n has a value between 2 and 10).

In formula (II) of the organohydrogenpolysiloxane resin, the subscripts w, x, y and z are mole fractions. The subscript w typically has a value of 0 to 0.8, or 0.02 to 0.75, or 0.05 to 0.3, and the subscript x typically has a value of 0 to 0.6, or 0 to 0.45, or 0 to 0.25. Has a value, the subscript y typically has a value of 0 to 0.99, or 0.25 to 0.8, or 0.5 to 0.8, and the subscript z typically has a value of 0 to 0.35, or 0 to 0.25, or It has a value of 0 to 0.15. The sum y + z is typically 0.2 to 0.99, 0.5 to 0.95, or 0.65 to 0.9. Further, the sum w + x is typically 0.01 to 0.80, or 0.05 to 0.5, or 0.1 to 0.35.

Typically, the group R in the organohydrogenpolysiloxane resin⁴At least 50 mol%, or at least 65 mol%, or at least 80 mol% of is an organic silylalkyl group having a hydrogen atom attached to at least one silicon.

Organohydrogen polysiloxane resins typically have a number average molecular weight (M) of 500-50,000, 500-10,000, or 1,000-3,000._n), And this molecular weight is measured by gel transmission chromatography using a small angle laser light scattering detector or a refractive index detector and a silicone resin (MQ) standard.

Organohydrogen polysiloxane resins are typically²⁹When measured by Si NMR, it contains less than 10% (weight / weight), or less than 5% (weight / weight), or less than 2% (weight / weight) of silicon-bonded hydroxy groups.

Organohydrogen polysiloxane resin is R¹R⁴₂SiO_1/2Units (ie M units) and / or R⁴₂SiO_2/2In combination with the unit (ie D unit), R¹SiO_3/2Units (ie T units) and / or SiO_4/2Includes units (ie Q units) (in equation, R¹And R⁴Is as described and illustrated above). For example, the organohydrogenpolysiloxane resin may be a DT resin, an MT resin, an MDT resin, a DTQ resin and an MTQ resin, and an MDTQ resin, a DQ resin, an MQ resin, a DTQ resin, an MTQ resin or an MDQ resin.

Examples of organohydrogenpolysiloxane resins include, but are not limited to, resins having the following formulas: ((HMe₂SiC₆H₄SiMe₂CH₂CH₂)₂MeSiO_1/2)_0.12(PhSiO_3/2)_0.88, ((HMe₂SiC₆H₄SiMe₂CH₂CH₂)₂MeSiO_1/2)_0.17(PhSiO_3/2)_0.83, ((HMe₂SiC₆H₄SiMe₂CH₂CH₂)₂MeSiO_1/2)_0.17(MeSiO_3/2)_0.17(PhSiO_3/2)_0.66, ((HMe₂SiC₆H₄SiMe₂CH₂CH₂)₂MeSiO_1/2)_0.15(PhSiO_3/2)_0.75(SiO_4/2)_0.10,and ((HMe₂SiC₆H₄SiMe₂CH₂CH₂)₂MeSiO_1/2)_0.08(HMe₂SiC₆H₄SiMe₂CH₂CH₂) Me₂SiO_1/2)_0.06(PhSiO_3/2)_0.86(In the formula, Me is methyl, Ph is phenyl, and C₆H₄Represents a poly-phenylene group, and the subscript of the number outside the parentheses means mole fraction). Moreover, in the above-mentioned formula, the array of units is not specified.

Ingredient (B) may be a single organosilicon compound or a mixture containing two or more different organosilicon compounds, each as described above. For example, component (B) is a single organohydrogensilane, a mixture of two different organohydrogensilanes, a single organohydrogensiloxane, a mixture of two different organohydrogensiloxanes, or an organohydrogensilane and an organo. It may be a mixture of hydrogen siloxane. In particular, component (B) is of formula at least 0.5% (weight / weight), or at least 50% (weight / weight), or at least 75% (weight / weight), based on the total weight of component (B). It may be a mixture containing an organohydrogenpolysiloxane resin having (II) and an organohydrogensilane and / or an organohydrogensiloxane (this organohydrogensiloxane is different from the organohydrogenpolysiloxane resin).

The concentration of the component (B) is sufficient to cure (crosslink) the silicone resin of the component (A). The exact amount of component (B) depends on the desired degree of curing, which increases the ratio of the number of moles of hydrogen atoms bonded to silicon in component (B) to the number of moles of alkenyl groups in component (A). Generally, it increases as it is used. The concentration of component (B) is typically 0.4 to 2 mol of hydrogen atoms bonded to silicon, or 0.8 to 1.5 mol of hydrogen atoms bonded to silicon, or 0.8 to 1.5 mol of hydrogen atoms per mole of alkenyl group of component (A). The concentration is sufficient to provide 0.9-1.1 mol of hydrogen atoms bound to silicon.

Methods for preparing organosilicon compounds containing hydrogen atoms bonded to silicon are well known in the art. For example, organohydrogensilanes can be prepared by reacting Grignard reagents with alkyl halides or aryl halides. In particular, the formula HR¹₂Si-R³-SiR¹₂The organohydrogensilane having H is given by the formula R.³X₂The aryldihalide with is treated with magnesium in ether to produce the corresponding Grignard reagent, which is then expressed in formula HR.¹₂It can be prepared by treating with chlorosilane having SiCl (in the formula, R).¹And R³Is as described and illustrated above).

Methods for preparing organohydrogensiloxanes (eg, hydrolysis and condensation of organic halosilanes) are also well known in the art.

In addition, the organohydrogenpolysiloxane resin having the formula (II) is the formula (a) (R).¹R²₂SiO_1/2)_w(R²₂SiO_2/2)_x(R¹SiO_3/2)_y(SiO_4/2)_z(B) Organosilicon compounds having hydrogen atoms bonded to an average of 2 to 4 silicons per molecule and having a molecular weight of less than 1,000, and (c) a hydrosilylation catalyst, and optionally, (d) Can be prepared by reacting in the presence of an organic solvent (both in the formula do not contain aliphatic unsaturateds (in the formula, R).¹Is C₁~ C₁₀Hydrocarbyl or C₁~ C₁₀Halogen-substituted hydrocarbyls, both of which are free of aliphatic unsaturated and R²Is R¹Or alkenyl, w is 0 ~ 0.8, x is 0 ~ 0.6, y is 0 ~ 0.99, z is 0 ~ 0.35, w + x + y + z = 1, y + Z is 0.2 to 0.99 and w + x is 0.01 to 0.8, where the silicone resin (a) has an average of at least two silicon-bonded alkenyl groups per molecule and in (a). The molar ratio of the hydrogen atom bonded to silicon in (b) to the alkenyl group of is 1.5 to 5).

The organosilicon compound (b) is at least one organosilicon compound having an average of 2 to 4 hydrogen atoms bonded to silicon per molecule. Alternatively, this organosilicon compound has an average of 2-3 hydrogen atoms bonded to silicon per molecule. This organosilicon compound typically has a molecular weight of less than 1,000, or less than 750, or less than 500. The organic group bonded to silicon in this organosilicon compound is R of the formula of the silicone resin of the component (A).¹Are selected from the hydrocarbyl and halogen-substituted hydrocarbyl groups described and exemplified above, both of which do not contain aliphatic unsaturateds.

The organosilicon compound (b) may be organohydrogensilane or organohydrogensiloxane. The organohydrogensilane may be monosilane, disilane, trisilane or polysilane. Similarly, the organohydrogensiloxane may be disiloxane, trisiloxane or polysiloxane. The structure of the organosilicon compound may be linear, branched, or cyclic. Cyclosilanes and cyclosiloxanes typically have 3-12 silicon atoms, or 3-10 silicon atoms, or 3-4 silicon atoms. In acyclic polysilanes and polysiloxanes, hydrogen atoms bonded to silicon may be present at the terminal, pendant, or both terminal and pendant positions.

Examples of organohydrogensilanes are diphenylsilane, 2-chloroethylsilane, bis [(p-dimethylsilyl) phenyl] ether, 1,4-dimethyldisilylethane, 1,3,5-tris (dimethylsilyl). Examples include, but are not limited to, benzene and 1,3,5-trimethyl-1,3,5-trisilane. Organohydrogensilane is the formula HR¹₂Si-R³-SiR¹₂Can also have H (in the formula, R¹And R³Is as described and illustrated above).

Examples of organohydrogensiloxanes are 1,1,3,3-tetramethyldisiloxane, 1,1,3,3-tetraphenyldisiloxane, phenyltris (dimethylsiloxy) silane and 1,3,5-trimethyl. Cyclotrisiloxane, but is not limited to these.

The organosilicon compound (b) may be a single organosilicon compound or a mixture containing two or more different organosilicon compounds (each as described above). For example, component (B) is a single organohydrogensilane, a mixture of two different organohydrogensilanes, a single organohydrogensiloxane, a mixture of two different organohydrogensiloxanes, or an organohydrogensilane and an organo. It may be a mixture of hydrogen siloxane.

Methods for preparing organohydrogensilanes, such as the reaction of the Grignard reagents with alkyl halides or aryl halides, are well known in the art. Similarly, methods for preparing organohydrogensiloxanes, such as hydrolysis and condensation of organic halosilanes, are well known in the art.

The hydrosilylation catalyst (c) may be either a platinum group metal (ie, platinum, rhodium, ruthenium, palladium, osmium and iridium) or a well-known hydrosilylation catalyst containing a compound containing a platinum group metal. Preferably, the platinum group metal is platinum based on its high activity of the hydrosilylation reaction.

Hydrosilylation catalysts include complexes of chloroplatinic acid and certain vinyl-containing organosiloxanes disclosed by Willing in US Pat. No. 3,419,593. This U.S. patent is hereby incorporated by reference. This type of catalyst is the reaction product of chloroplatinic acid and 1,3-diethenyl-1,1,3,3-tetramethyldisiloxane.

The hydrosilylation catalyst may also be a supported hydrosilylation catalyst containing a solid support having a platinum group metal on its surface. The supported catalyst can be easily separated from the organohydrogenpolysiloxane resin product, for example, by filtering the reaction mixture. Examples of supported catalysts include, but are limited to, platinum-carbon, palladium-carbon, ruthenium-carbon, rhodium-carbon, platinum-silica, palladium-silica, platinum-alumina, palladium-alumina and ruthenium-alumina. Not done.

The organic solvent (d) is at least one organic solvent. The organic solvent does not react with the silicone resin (a), organosilicon compound (b) or organohydrogenpolysiloxane resin under the conditions of the method of the present invention, and the components (a), (b) and organohydrogenpoly It may be any aprotic or bipolar aprotic organic solvent that is compatible with the siloxane resin.

Examples of organic solvents include saturated aliphatic hydrocarbons (eg n-pentane, hexane, n-heptane, isooctane and dodecane), alicyclic hydrocarbons (eg cyclopentane and cyclohexane), aromatic hydrocarbons (eg benzene, etc.). Toluene, xylene and mesitylene), cyclic ethers (eg tetrahydrofuran (THF) and dioxane), ketones (eg methylisobutylketone (MIBK)), alkane halides (eg trichloroethane), and halogenated aromatic hydrocarbons (eg bromobenzene and bromobenzene). Chlorobenzene), but is not limited to these. The organic solvent (d) may be a single organic solvent or a mixture containing two or more different organic solvents (each as described above).

The reaction can be carried out in any standard reactor suitable for the hydrosilylation reaction. Suitable reactors include glass reactors and glass reactors lined with Teflon®. Preferably, the reactor is provided with a means of stirring (eg, stirring). Also preferably, the reaction is carried out in the absence of moisture in an inert atmosphere (eg nitrogen or argon).

The silicone resin, the organosilicon compound, the hydrosilylation catalyst and optionally the organic solvent can be mixed in any order. Typically, the organosilicon compound (b) and the hydrosilylation catalyst (c) are mixed prior to the introduction of the silicone resin (a) and optionally the organic solvent (d).

The reaction is typically carried out at a temperature of 0 to 150 ° C, or room temperature (about 23 ± 2 ° C) to 115 ° C. If the temperature is below 0 ° C, the reaction rate is typically very slow.

The reaction time depends on several factors, such as the structure and temperature of the silicone resin and organosilicon compound. The reaction time is typically 1 to 24 hours at room temperature (about 23 ± 2 ° C) to 150 ° C. Optimal reaction times can be determined in routine tests using the methods described in the Examples section below.

The molar ratio of hydrogen atoms bonded to silicon in the organosilicon compound (b) to the alkenyl group in the silicone resin (a) is typically 1.5 to 5, 1.75 to 3, or 2 to 2.5.

The concentration of the hydrosilylation catalyst (c) is sufficient to catalyze the addition reaction between the silicone resin (a) and the organosilicon compound (b). Typically, the concentration of the hydrosilylation catalyst (c) is 0.1-1000 ppm platinum group metal, or 1-500 ppm platinum group, based on the combined weight of the silicone resin (a) and organosilicon compound (b). The concentration is sufficient to provide a metal, or a platinum group metal of 5 to 150 ppm. The reaction rate is very slow under platinum group metals below 0.1 ppm. The use of platinum group metals greater than 1000 ppm does not result in a significant increase in reaction rate and is therefore uneconomical.

The concentration of organic solvent (d) is typically 0-99% (weight / weight), or 30-80% (weight / weight), or 45-60% (weight / weight), based on the total weight of the reaction mixture. Weight / weight).

The organohydrogen polysiloxane resin can be used without isolation or purification in the first embodiment of the hydrosilylation curable silicone composition, or the resin can be used as a solvent by conventional vaporization methods. Can be separated from most. For example, the reaction mixture may be heated under reduced pressure. In addition, if the hydrosilylation catalyst used to prepare the organohydrogenpolysiloxane resin is a supported catalyst as described above, the resin should be immediately separated from the hydrosilylation catalyst by filtering the reaction mixture. Can be done. However, if the organohydrogenpolysiloxane resin is not separated from the hydrosilylation catalyst used to prepare the resin, the catalyst will be used as component (C) of the first embodiment of the hydrosilylation curable silicone composition. It can be used.

The component (C) of the hydrosilylation-curable silicone composition is at least one hydrosilylation catalyst that promotes the addition reaction between the component (A) and the component (B). The hydrosilylation catalyst may be any of a well-known hydrosilylation catalyst containing a platinum group metal, a compound containing a platinum group metal, or a microencapsulated platinum group metal-containing catalyst. Examples of the platinum group metal include platinum, rhodium, ruthenium, palladium, osmium and iridium. Preferably, the platinum group metal is platinum based on its high activity of the hydrosilylation reaction.

Suitable hydrosilylation catalysts include complexes of chloroplatinic acid and certain vinyl-containing organosiloxanes disclosed by Willing in US Pat. No. 3,419,593. This U.S. patent is hereby incorporated by reference. Suitable catalysts of this type are reaction products of chloroplatinic acid and 1,3-diethenyl-1,1,3,3-tetramethyldisiloxane.

The hydrosilylation catalyst may also be a microencapsulated platinum group metal-containing catalyst containing a platinum group metal encapsulated in a thermoplastic resin. Compositions containing microencapsulated hydrosilylation catalysts are stable at normal temperature and pressure for long periods of time (typically several months or longer), but still above the melting point or softening point of the thermoplastic. Cure relatively quickly. Microencapsulated hydrosilylation catalysts and methods for preparing them are well known in the art, as illustrated in US Pat. No. 4,766,176 and references therein, as well as US Pat. No. 5,017,654.

Component (C) comprises a single hydrosilylation catalyst, or two or more different catalysts that differ in at least one property (eg, structure, morphology, platinum group metals, complex-forming ligands and thermoplastics). It may be a mixture.

The concentration of the component (C) is sufficient to catalyze the addition reaction between the component (A) and the component (B). Typically, the concentration of component (C) is 0.1-1000 ppm platinum group metal, preferably 1-500 ppm platinum group metal, more preferably 1-500 ppm platinum group metal, based on the combined weight of component (A) and component (B). Is a concentration sufficient to provide a platinum group metal of 5 to 150 ppm. The curing rate is very slow under platinum group metals below 0.1 ppm. The use of platinum group metals greater than 1000 ppm does not result in a significant increase in reaction rate and is therefore uneconomical.

According to the second embodiment, the hydrosilylation-curable silicone composition is of formula (A') (R).¹R⁵₂SiO_1/2)_w(R⁵₂SiO_2/2)_x(R⁵SiO_3/2)_y(SiO_4/2)_z(III) (In the formula, R¹Is C₁~ C₁₀Hydrocarbyl or C₁~ C₁₀Halogen-substituted hydrocarbyls, both of which are free of aliphatic unsaturated and R⁵Is R¹Or -H, w is 0 to 0.95, x is 0 to 0.95, y is 0 to 1, z is 0 to 0.95, w + x + y + z = 1. y + z is 0.05 to 1 and w + x is 0 to 0.95, but this silicone resin has an average of at least two silicon-bonded hydrogen atoms per molecule), and ( B') contains an organosilicon compound having an average of at least two silicon-bonded alkenyl groups per molecule, sufficient to cure the silicone resin, and (C) a catalytic amount of a hydrosilylation catalyst.

Ingredient (A') is the formula (R¹R⁵₂SiO_1/2)_w(R⁵₂SiO_2/2)_x(R⁵SiO_3/2)_y(SiO_4/2)_z(III) (In the formula, R¹Is C₁~ C₁₀Hydrocarbyl or C₁~ C₁₀Halogen-substituted hydrocarbyls, both of which are free of aliphatic unsaturated and R⁵Is R¹Or -H, w is 0 to 0.95, x is 0 to 0.95, y is 0 to 1, z is 0 to 0.95, w + x + y + z = 1. y + z is 0.05 to 1 and w + x is 0 to 0.95, but this silicone resin has at least one silicone resin with an average of at least two silicon-bonded hydrogen atoms per molecule). Is. In equation (III), R¹, W, x, y, z, y + z and w + x are as described and exemplified above for silicone resins having formula (I).

Typically, the group R in the silicone resin⁵At least 50 mol%, or at least 65 mol%, or at least 80 mol% of hydrogen is hydrogen.

This silicone resin typically has a number average molecular weight (M) of 500-50,000, 500-10,000, or 1,000-3,000._n), Where the molecular weight is measured by gel transmission chromatography using a small angle laser light scattering detector, or a refractive index detector and a silicone resin (MQ) standard.

The viscosity of the silicone resin at 25 ° C is typically 0.01 to 100,000 Pa · s, 0.1 to 10,000 Pa · s, or 1 to 100 Pa · s.

The above silicone resin is²⁹When measured by Si NMR, it typically contains less than 10% (weight / weight), or less than 5% (weight / weight), or less than 2% (weight / weight) of silicon-bonded hydroxy groups. ..

The above silicone resin is R¹R⁵₂SiO_1/2Units (ie M units) and / or R⁵₂SiO_2/2In combination with the unit (ie D unit), R⁵SiO_3/2Unit (ie T unit), R⁵SiO_3/2Units (ie T units) and SiO_4/2Unit (ie Q unit), or R⁵SiO_3/2Units (ie T units) and / or SiO_4/2Includes units (ie Q units). For example, this silicone resin may be T resin, TQ resin, DT resin, MT resin, MDT resin, MQ resin, DQ resin, MDQ resin, MTQ resin, DTQ resin or MDTQ resin.

Examples of silicone resins suitable for use as component (A') include, but are not limited to, resins having the following formula: (HMe₂SiO_1/2)_0.25(PhSiO_3/2)_0.75, (HMeSiO_2/2)_0.3(PhSiO_3/2)_0.6(MeSiO_3/2)_0.1,and (Me₃SiO_1/2)_0.1(H₂SiO_2/2)_0.1(MeSiO_3/2)_0.4(PhSiO_3/2)_0.4(In the formula, Me is methyl, Ph is phenyl, and the subscript of the number outside the parentheses means mole fraction). Moreover, in the above-mentioned formula, the array of units is not specified.

The component (A') may be a single silicone resin or a mixture containing two or more different silicone resins (each as described above).

Methods for preparing silicone resins containing hydrogen atoms bonded to silicon are well known in the art and many of these resins are commercially available. Silicone resins are typically prepared by co-hydrolyzing a suitable mixture of chlorosilane precursors in an organic solvent (eg, toluene). For example, essentially R¹R⁵₂SiO_1/2Unit and R⁵SiO_3/2The silicone resin consisting of the unit is the formula R¹R⁵₂Compounds with SiCl and formula R⁵SiCl₃Can be prepared by co-hydrolyzing a compound with (in the formula, R).¹And R⁵Is as described and illustrated above). The hydrochloric acid and silicone hydrolyzate are separated, the hydrolyzate is washed with water to remove residual acid, heated in the presence of a mild non-basic condensation catalyst, and the resin "increases" to the required viscosity. Be sticky (body) ". If desired, the resin can be further treated with a non-basic condensation catalyst in an organic solvent to reduce the content of hydroxy groups attached to silicon. Alternatively, hydrolyzable groups other than chloro, such as -Br, -I, -OCH₃, -OC (O) CH₃, -N (CH)₃)₂, NHCOCH₃, And -SCH₃Silanes containing the above can be used as a starting material for the simultaneous hydrolysis reaction. The properties of the resin product depend on the type of silane, the molar ratio of silane, the degree of condensation and the treatment conditions.

Component (B') is at least one organosilicon compound having an average of at least two silicon-bonded alkenyl groups per molecule, sufficient to cure the silicone resin of component (A').

This organosilicon compound contains an alkenyl group bonded to at least two silicons on average per molecule, or an alkenyl group bonded to at least three silicons per molecule. Crosslinks when the sum of the average number of hydrogen atoms bonded to silicon per molecule in component (A') and the average number of alkenyl groups bonded to silicon per molecule in component (B') is greater than 4. Is usually understood when

The organosilicon compound may be an organosilane or an organosiloxane. The organic silane may be monosilane, disilane, trisilane or polysilane. Similarly, the organosiloxane may be disiloxane, trisiloxane or polysiloxane. The structure of the organosilicon compound may be linear, branched, cyclic, or resinous. Cyclosilanes and cyclosiloxanes typically have 3-12 silicon atoms, or 3-10 silicon atoms, or 3-4 silicon atoms. In acyclic polysilanes and polysiloxanes, silicon-bonded alkenyl groups may be present at the terminal, pendant, or both terminal and pendant positions.

Examples of organic silanes suitable for use as component (B') include, but are not limited to, silanes having the following formulas: Vi₄Si, PhSiVi₃, MeSiVi₃, PhMeSiVi₂, Ph₂SiVi₂And PhSi (CH₂CH = CH₂)₃(In the formula, Me is methyl, Ph is phenyl, and Vi is vinyl).

Examples of organosiloxanes suitable for use as component (B') include, but are not limited to, siloxanes having the following formula: PhSi (OSiMe).₂Vi)₃, Si (OSiMe₂Vi)₄, MeSi (OSiMe₂Vi)₃And Ph₂Si (OSiMe₂Vi)₂(In the formula, Me is methyl, Ph is phenyl, and Vi is vinyl).

The component (B') may be a single organosilicon compound or a mixture containing two or more different organosilicon compounds (each as described above). For example, component (B') may be a single organic silane, a mixture of two different organic silanes, a single organosiloxane, a mixture of two different organosiloxanes or a mixture of organic silanes and an organosiloxane.

The concentration of the component (B') is sufficient to cure (crosslink) the silicone resin of the component (A'). The exact amount of component (B') depends on the desired degree of curing, which is bound to silicon in component (B') relative to the number of moles of hydrogen atoms bonded to silicon in component (A'). It generally increases as the ratio of the number of moles of alkenyl groups increases. The concentration of component (B') is typically to 0.4 to 2 moles of silicon-bonded alkenyl group or 0.8 to 1.5 moles of silicon per mole of hydrogen atom bonded to silicon of component (A'). Concentration sufficient to provide bound alkenyl groups, or 0.9-1.1 mol of silicon bound alkenyl groups.

Methods for preparing organic silanes and organosiloxanes containing silicon-bonded alkenyl groups are well known in the art and many of these compounds are commercially available.

The component (C) of the second embodiment of the present silicone composition is as described and illustrated above for the component (C) of the first embodiment.

According to the third embodiment, the present hydrosilylation-curable silicone composition has the formula (A) (R).¹R²₂SiO_1/2)_w(R²₂SiO_2/2)_x(R²SiO_3/2)_y(SiO_4/2)_zA silicone resin having (I), (B) an organosilicon compound having an average of at least two silicon-bonded hydrogen atoms per molecule in an amount sufficient to cure the silicone resin, and (C) a catalyst. Amount of hydrosilylation catalyst and equation (D) (i) R¹R²₂SiO (R²₂SiO)_aSiR²₂R¹(IV) and (ii) R⁵R¹₂SiO (R¹R⁵SiO)_{b b}SiR¹₂R⁵Silicone rubber having the formula selected from (V) (in the formula, R¹Is C₁~ C₁₀Hydrocarbyl or C₁~ C₁₀Halogen-substituted hydrocarbyls, both of which are free of aliphatic unsaturated and R²Is R¹Or alkenyl, R⁵Is R¹Or -H, the subscripts a and b each have a value of 1 to 4, w is 0 to 0.95, x is 0 to 0.95, y is 0 to 1, and z is 0 to. 0.95, w + x + y + z = 1, y + z is 0.05 ~ 1, w + x is 0 ~ 0.95, but the above silicone resin and silicone rubber (D) (i) Each has an alkenyl group bonded to at least two silicons on average per molecule, and silicone rubbers (D) (ii) have hydrogen atoms bonded to at least two silicons on average per molecule, and a silicone resin. The molar ratio of the alkenyl group bonded to silicon or the hydrogen atom bonded to silicon in the silicone rubber (D) to the alkenyl group bonded to silicon in (A) is 0.01 to 0.5).

The components (A), (B) and (C) of the third embodiment of the silicone composition are as described and exemplified above for the first embodiment.

The concentration of the component (B) is sufficient to cure (crosslink) the silicone resin of the component (A). When component (D) is (D) (i), the concentration of component (B) is the component relative to the total number of moles of alkenyl groups attached to silicon in component (A) and component (D) (i). The concentration is such that the ratio of the number of moles of hydrogen atoms bonded to silicon in (B) is typically 0.4 to 2, 0.8 to 1.5, or 0.9 to 1.1. Further, when the component (D) is (D) (ii), the concentration of the component (B) is the component (B) and the component (D) with respect to the number of moles of the alkenyl group bonded to silicon in the component (A). The concentration is such that the ratio of the total number of moles of hydrogen atoms bonded to silicon in (ii) is typically 0.4 to 2, 0.8 to 1.5, or 0.9 to 1.1.

Ingredient (D) is (i) R¹R²₂SiO (R²₂SiO)_aSiR²₂R¹(IV) and (ii) R⁵R¹₂SiO (R¹R⁵SiO)_{b b}SiR¹₂R⁵Silicone rubber having the formula selected from (V) (in the formula, R¹Is C₁~ C₁₀Hydrocarbyl or C₁~ C₁₀Halogen-substituted hydrocarbyls, both of which are free of aliphatic unsaturated and R²Is R¹Or alkenyl, R⁵Is R¹Or -H, and the subscripts a and b each have a value of 1 to 4, except that the silicone rubbers (D) and (i) have an average of at least two silicon-bonded alkenyl groups per molecule. And silicone rubber (D) (ii) has an average of at least two silicon-bonded hydrogen atoms per molecule).

The components (D) and (i) are given by the formula R¹R²₂SiO (R²₂SiO)_aSiR²₂R¹At least one silicone rubber having (IV) (in the formula, R¹And R²Is described and exemplified above, where subscript a has a value of 1 to 4, but silicone rubber (D) (i) has an average of at least two silicon-bonded alkenyl groups per molecule. ). Alternatively, the subscript a has 2 to 4 or 2 to 3 values.

Examples of silicone rubbers suitable for use as Ingredients (D) (i) include, but are not limited to, silicone rubbers having the following formulas: ViMe₂SiO (Me₂SiO)_aSiMe₂Vi, ViMe₂SiO (Ph₂SiO)_aSiMe₂Vi, and ViMe₂SiO (PhMeSiO)_aSiMe₂Vi (in the formula, Me is methyl, Ph is phenyl, Vi is vinyl, and the subscript a has a value of 1-4).

Ingredients (D) and (i) may be a single silicone rubber or a mixture containing two or more different silicone rubbers, each of which has the formula (IV).

Ingredients (D) and (ii) are given by equation R⁵R¹₂SiO (R¹R⁵SiO)_{b b}SiR¹₂R⁵At least one silicone rubber with (V) (in the formula, R¹And R⁵Is as described and illustrated above, with subscripts b having values from 1 to 4, but silicone rubber (D) (ii) has an average of at least two silicon-bonded hydrogen atoms per molecule. ). Alternatively, the subscript b has a value of 2 to 4, or 2 to 3.

Examples of silicone rubbers suitable for use as Ingredients (D) (ii) include, but are not limited to, silicone rubbers having the following formulas: HMe₂SiO (Me₂SiO)_{b b}SiMe₂H, HMe₂SiO (Ph₂SiO)_{b b}SiMe₂H, HMe₂SiO (PhMeSiO)_{b b}SiMe₂H, and HMe₂SiO (Ph₂SiO)₂(Me₂SiO)₂SiMe₂H (in the formula, Me is methyl, Ph is phenyl, and the subscript b has a value of 1-4).

Ingredients (D) and (ii) may be a single silicone rubber or a mixture containing two or more different silicone rubbers, each of which has the formula (V).

The molar ratio of the alkenyl group bonded to silicon or the hydrogen atom bonded to silicon in the silicone rubber (D) to the alkenyl group bonded to silicon in the silicone resin (A) is typically 0.01 to 0.5 or 0.05 to 0.05 to It is 0.4 or 0.1 to 0.3.

Methods for preparing silicone rubbers containing silicon-bonded alkenyl groups or silicon-bonded hydrogen atoms are well known in the art and many of these compounds are commercially available.

According to the fourth embodiment, the hydrosilylation-curable silicone composition is of formula (A') (R).¹R⁵₂SiO_1/2)_w(R⁵₂SiO_2/2)_x(R⁵SiO_3/2)_y(SiO_4/2)_zA silicone resin having (III), an organosilicon compound having (B') an organosilicon compound having an average of at least two silicon-bonded alkenyl groups per molecule in an amount sufficient to cure this silicone resin, and (C) a catalyst. Amount of hydrosilylation catalyst and (D) (i) R¹R²₂SiO (R²₂SiO)_aSiR²₂R¹(IV) and (ii) R⁵R¹₂SiO (R¹R⁵SiO)_{b b}SiR¹₂R⁵Silicone rubber having the formula selected from (V) (in the formula, R¹Is C₁~ C₁₀Hydrocarbyl or C₁~ C₁₀Halogen-substituted hydrocarbyls, both of which are free of aliphatic unsaturated and R²Is R¹Or alkenyl, R⁵Is R¹Or -H, the subscripts a and b each have a value of 1 to 4, w is 0 to 0.95, x is 0 to 0.95, y is 0 to 1, and z is 0 to 0. 0.95, w + x + y + z = 1, y + z is 0.05 to 1, and w + x is 0 to 0.95, but the above silicone resin and silicone rubber (D) (ii). ) Have an average of at least two silicon-bonded hydrogen atoms per molecule, and silicone rubbers (D) and (i) each have an average of at least two silicon-bonded alkenyl groups per molecule, and the silicone resin (A). The molar ratio of the alkenyl group bonded to silicon or the hydrogen atom bonded to silicon in the silicone rubber (D) to the hydrogen atom bonded to silicon in') is 0.01 to 0.5).

The components (A') (B') and (C) of the fourth embodiment of the silicone composition are as described and exemplified above for the second embodiment, and the components of the fourth embodiment ( D) is as described and illustrated above for the third embodiment.

The concentration of the component (B') is sufficient to cure (crosslink) the silicone resin of the component (A'). When the component (D) is (D) (i), the concentration of the component (B') is the component (B') and the component (D') with respect to the number of moles of hydrogen atoms bonded to silicon in the component (A'). ) The concentration is such that the ratio of the total number of moles of alkenyl groups bonded to silicon in (i) is typically 0.4 to 2, 0.8 to 1.5, or 0.9 to 1.1. Further, when the component (D) is (D) (ii), the concentration of the component (B') is the number of moles of hydrogen atoms bonded to silicon in the component (A') and the components (D) (ii). The ratio of the number of moles of the alkenyl group bonded to silicon of the component (B') to the total of is typically 0.4 to 2, 0.8 to 1.5, or 0.9 to 1.1.

The molar ratio of alkenyl groups bonded to silicon or hydrogen atoms bonded to silicon in silicone rubber (D) to hydrogen atoms bonded to silicon in silicone resin (A') is typically up to 0.01 to 0.5. Alternatively, it is 0.05 to 0.4, or 0.1 to 0.3.

According to the fifth embodiment, the present hydrosilylation-curable silicone composition is of the formula (A ) (R).¹R²₂SiO_1/2)_w(R²₂SiO_2/2)_x(R²SiO_3/2)_y(SiO_4/2)_zSilicone resin with (I) and formula R⁵R¹₂SiO (R¹R⁵SiO)_cSiR¹₂R⁵A rubber-modified silicone resin prepared by reacting a silicone rubber with (VI) in the presence of a hydrosilylation catalyst and optionally an organic solvent to form a soluble reaction product (in the formula, R).¹Is C₁~ C₁₀Hydrocarbyl or C₁~ C₁₀Halogen-substituted hydrocarbyls, both of which are free of aliphatic unsaturated and R²Is R¹Or alkenyl, R⁵Is R¹Or -H, c has a value of ~ 1,000 greater than 4, w is 0 ~ 0.95, x is 0 ~ 0.95, y is 0 ~ 1, z is 0 ~ 0.95. , W + x + y + z = 1, y + z is 0.05 to 1, and w + x is 0 to 0.95, but silicone resin (I) averages at least two silicons per molecule. Silicone rubber (VI) has an average of at least two silicon-bonded hydrogen atoms per molecule and is a silicone rubber for the silicon-bonded alkenyl group in the silicone resin (I). (VI) The molar ratio of hydrogen atoms bonded to silicon in silicon is 0.01-0.5) and (B) an amount sufficient to cure this rubber-modified silicone resin, at least on average per molecule. It contains an organic silicon compound having a hydrogen atom bonded to two silicons and (C) a catalytic amount of a hydrosilylation catalyst.

The components (B) and (C) of the fifth embodiment of the silicone composition are as described and exemplified for the first embodiment.

The concentration of the component (B) is a concentration sufficient to cure (crosslink) the silicone resin modified with the rubber. The concentration of component (B) is the ratio of the total number of moles of hydrogen atoms bonded to silicon in the component (B) and silicon rubber (VI) to the number of moles of alkenyl groups bonded to silicon in the silicone resin (I). However, the concentration is typically 0.4 to 2, 0.8 to 1.5, or 0.9 to 1.1.

Ingredient (A ) is the formula (R¹R²₂SiO_1/2)_w(R²₂SiO_2/2)_x(R²SiO_3/2)_y(SiO_4/2)_zAt least one silicone resin with (I) and formula R⁵R¹₂SiO (R¹R⁵SiO)_cSiR¹₂R⁵A rubber-modified silicone resin prepared by reacting at least one silicone rubber with (VI) in the presence of a hydrosilylation catalyst and optionally an organic solvent to form a soluble reaction product. (In the formula, R¹, R², R⁵, W, x, y, z, y + z and w + x are as described and exemplified above, and the subscript c has a value greater than 4 to ~ 1,000).

The silicone resin having formula (I) is as described and exemplified above for the first embodiment of the silicone composition. Further, the hydrosilylation catalyst and the organic solvent are as described and exemplified above in the method for preparing an organohydrogenpolysiloxane resin having the formula (II). As used herein, the term "soluble reaction product" means that in the presence of an organic solvent, the reaction product for preparing component (A ") is miscible with that organic solvent. It means that it does not form a precipitate or suspension.

In the silicone rubber formula (VI), R¹And R⁵Is as described and illustrated above, and the subscript c typically has a value greater than 4 to ~ 1,000, or 10 to 500, or 10 to 50.

Examples of silicone rubbers having formula (VI) include, but are not limited to, silicone rubbers having the following formulas: HMe.₂SiO (Me₂SiO)₅₀SiMe₂H, HMe₂SiO (Me₂SiO)₁₀SiMe₂H, HMe₂SiO (PhMeSiO)₂₅SiMe₂H, and Me₃SiO (MeHSiO)₁₀SiMe₃(In the formula, Me is methyl, Ph is phenyl, and the subscripts indicate the number of siloxane units of each type).

The silicone rubber having the formula (VI) may be a single silicone rubber or a mixture containing two or more different silicone rubbers each having the formula (VI).

Methods for preparing silicone rubbers containing hydrogen atoms bonded to silicon are well known in the art and many of these compounds are commercially available.

The silicone resin (I), silicone rubber (VI), hydrosilylation catalyst and organic solvent may be mixed in any order. Typically, the silicone resin, silicone rubber and organic solvent are mixed prior to the introduction of the hydrosilylation catalyst.

The reaction is typically carried out at room temperature (about 23 ± 2 ° C) to 150 ° C, or room temperature to 100 ° C.

The reaction time depends on several factors including the structure of the silicone resin and the silicone rubber and the temperature. The components are typically reacted for a period sufficient to complete the hydrosilylation reaction. This is typically when measured by FTIR spectroscopy, where at least 95 mol%, or at least 98 mol%, or at least 99 mol% of the hydrogen atoms initially present in the silicone rubber are hydrosilylated. It means that the ingredients are reacted until they are consumed in. The reaction time is typically 0.5 to 24 hours at room temperature (about 23 ± 2 ° C) to 100 ° C. Optimal reaction times can be determined in routine tests using the methods described in the Examples section below.

The molar ratio of hydrogen atoms bonded to silicon in silicone rubber (VI) to the alkenyl group bonded to silicon in silicone resin (I) is typically 0.01 to 0.5, or 0.05 to 0.4, or 0.1 to 0.3. is there.

The concentration of the hydrosilylation catalyst is sufficient to catalyze the addition reaction between the silicone resin (I) and the silicone rubber (VI). Typically, the concentration of the hydrosilylation catalyst is sufficient to provide 0.1-1000 ppm platinum group metal, based on the combined weight of resin and rubber.

The concentration of the organic solvent is typically 0-95% (weight / weight), or 10-75% (weight / weight), or 40-60% (weight / weight), based on the total weight of the reaction mixture. ).

The rubber-modified silicone resin can also be used without isolation or purification in the fifth embodiment of the hydrosilylation curable silicone composition, or the resin will be the majority of the solvent by conventional vaporization methods. Can also be separated from. For example, the reaction mixture may be heated under reduced pressure. Furthermore, when the hydrosilylation catalyst is a supported catalyst as described above, the rubber-modified silicone resin can be immediately separated from the hydrosilylation catalyst by filtering the reaction mixture. However, if the rubber-modified silicone resin is not separated from the hydrosilylation catalyst used to prepare the resin, the catalyst should be used as component (C) of the fifth embodiment of the hydrosilylation curable silicone composition. Is possible.

According to a sixth embodiment, the hydrosilylation-curable silicone composition is in the presence of a (A ') hydrosilylation catalyst and optionally an organic solvent of formula (R).¹R⁵₂SiO_1/2)_w(R⁵₂SiO_2/2)_x(R⁵SiO_3/2)_y(SiO_4/2)_zSilicone resin with (III) and formula R¹R²₂SiO (R²₂SiO)_dSiR²₂R¹A rubber-modified silicone resin prepared by reacting a silicone rubber having (VII) to form a soluble reaction product (in the formula, R).¹Is C₁~ C₁₀Hydrocarbyl or C₁~ C₁₀Halogen-substituted hydrocarbyls, both of which are free of aliphatic unsaturated and R²Is R¹Or alkenyl, R⁵Is R¹Or -H, the subscript d has a value of ~ 1,000 greater than 4, w is 0 ~ 0.95, x is 0 ~ 0.95, y is 0 ~ 1, z is 0 ~ 0.95. , W + x + y + z = 1, y + z is 0.05 to 1, and w + x is 0 to 0.95, but silicone resin (III) averages at least 2 per molecule. Silicone rubber (VII) has an alkenyl group bonded to at least two silicons on average per molecule, and has a hydrogen atom bonded to one silicon. Silicone rubber to the hydrogen atom bonded to silicon in the silicone resin (III). The molar ratio of alkenyl groups bound to silicon in (VII) is 0.01-0.5) and (B') an amount sufficient to cure this rubber-modified silicone resin, at least on average per molecule. It contains an organic silicon compound having an alkenyl group bonded to two silicons and (C) a catalytic amount of a hydrosilylation catalyst.

The components (B') and (C) of the sixth embodiment of the silicone composition are as described and exemplified for the second embodiment.

The concentration of the component (B') is a concentration sufficient to cure (crosslink) the silicone resin modified with the rubber. The concentration of the component (B') is the sum of the number of moles of the component (B') and the number of moles of the alkenyl group bonded to silicon in the silicone rubber (VII) with respect to the number of moles of hydrogen atoms bonded to silicon in the silicone resin (III). The ratio of is typically 0.4 to 2, 0.8 to 1.5, or 0.9 to 1.1.

The component (A ') is the formula (R)¹R⁵₂SiO_1/2)_w(R⁵₂SiO_2/2)_x(R⁵SiO_3/2)_y(SiO_4/2)_zAt least one silicone resin with (III) and formula R¹R²₂SiO (R²₂SiO)_dSiR²₂R¹A rubber-modified silicone resin prepared by reacting a silicone rubber having (VII) and at least one silicone rubber in the presence of a hydrosilylation catalyst and an organic solvent to form a soluble reaction product ((VII). In the formula, R¹, R², R⁵, W, x, y, z, y + z and w + x are as described and exemplified above, and the subscript d has a value greater than 4 to ~ 1,000).

The silicone resin having formula (III) is as described and exemplified above for the second embodiment of the hydrosilylation curable silicone composition. Further, the hydrosilylation catalyst and the organic solvent are as described and exemplified above in the method for preparing an organohydrogenpolysiloxane resin having the formula (II). As in previous embodiments of the silicone composition, the term "soluble reaction product" is the organic of the reaction product for preparing the component (A "') in the presence of an organic solvent. It is miscible with the solvent and means that it does not form a precipitate or suspension.

In the silicone rubber equation (VII), R¹And R²Is as described and illustrated above, and the subscript d typically has a value of 4 to 1,000, or 10 to 500, or 10 to 50.

Examples of silicone rubber having the formula (VII) include, for example, silicone rubber having the following formula: ViMe₂SiO (Me₂SiO)₅₀SiMe₂Vi, ViMe₂SiO (Me₂SiO)₁₀SiMe₂Vi, ViMe₂SiO (PhMeSiO)₂₅SiMe₂Vi, and Vi₂MeSiO (PhMeSiO)₂₅SiMe₂Vi (In the formula, Me is methyl, Ph is phenyl, Vi is vinyl, and the subscript of the number indicates the number or type of siloxane unit).

The silicone rubber having the formula (VII) may be a single silicone rubber or a mixture containing two or more different silicone rubbers each having the formula (VII).

Methods for preparing silicone rubbers containing alkenyl groups bonded to silicon are well known in the art and many of these compounds are commercially available.

In the reaction for preparing the component (A '), the silicone resin having the formula (I) and the silicone rubber having the formula (VI) were combined with the resin having the formula (III) and the rubber having the formula (VII), respectively. Except for being replaced, it can be carried out by the method described above to prepare the component (A ") of the fifth embodiment of the silicone composition. The molar ratio of the alkenyl group bonded to silicon in the silicone rubber (VII) to the hydrogen atom bonded to silicon in the silicone resin (III) is 0.01 to 0.5, 0.05 to 0.4, or 0.1 to 0.3. In addition, the silicone resin and silicone rubber are typically reacted for a sufficient amount of time to complete the hydrosilylation reaction. This is because, when measured by FTIR spectroscopy, at least 95 mol%, or at least 98 mol%, or at least 99 mol% of the silicon-bonded alkenyl groups originally present in the rubber are consumed in the hydrosilylation reaction. It means that the above components are reacted until they are processed.

The hydrosilylation-curable silicone composition of the method of the present invention may contain additional components, which allow the silicone composition to cure to a low coefficient of thermal expansion, high tensile strength and high modulus as described below. Only when the component does not interfere with the formation of the cured silicone resin to have. Examples of additional components are hydrosilylation catalytic inhibitors (eg 3-methyl-3-penten-1-in, 3,5-dimethyl-3-hexen-1-in, 3,5-dimethyl-1-hexin-). Teached in 3-ol, 1-ethynyl-1-cyclohexanol, 2-phenyl-3-butin-2-ol, vinylcyclosiloxane and triphenylphosphine, adhesion promoters (US Pat. Nos. 4,087,585 and 5,194,649). Adhesion promoters, etc.), dyes, dyes, antioxidants, heat stabilizers, UV stabilizers, flame retardants, fluidity adjusting additives, and diluents (eg, organic solvents and reactive diluents). However, it is not limited to these.

For example, the present hydrosilylation-curable silicone composition is (E) (i) an organosiloxane having an average of at least two silicon-bonded alkenyl groups per molecule and 0.001 to 2 Pa · s at 25 ° C. The viscosity of i) is 20% or less of the viscosity of the silicone resin of the above silicone composition (for example, the components (A), (A'), (A ") (A"')), and this organosiloxane is composed of. Equation (R¹R²₂SiO_1/2)_m(R²₂SiO_2/2)_n(R¹SiO_3/2)_p(SiO_4/2)_q(In the formula, R¹Is C₁~ C₁₀Hydrocarbyl or C₁~ C₁₀Halogen-substituted hydrocarbyls, both of which are free of aliphatic unsaturated and R²Is R¹Or alkenyl, m is 0 to 0.8, n = 0 to 1, p = 0 to 0.25, q = 0 to 0.2, m + n + p + q = 1, and m + n is not equal to 0, but when p + q = 0, n is not equal to 0 and not all of the alkenyl groups are terminal)), (ii) ( E) On average at least two silicons per molecule, sufficient to provide 0.5-3 mol of hydrogen atoms attached to silicon in (E) (ii) per mol of alkenyl groups in (i). Organohydrogensiloxane with bonded hydrogen atoms and a viscosity of 0.001 to 2 Pa · s at 25 ° C (this organohydrogensiloxane is of formula (HR)¹₂SiO_1/2)_s(R¹SiO_3/2)_t(SiO_4/2)_vHas (in the formula, R¹Is C₁~ C₁₀Hydrocarbyl or C₁~ C₁₀Halogen-substituted hydrocarbyls, both of which are free of aliphatic unsaturated s, s is 0.25 to 0.8, t is 0 to 0.5, v is 0 to 0.3, s + t + v = 1 And t + v is not equal to 0)) and can include reactive diluents.

Ingredients (E) and (i) are at least one organosiloxane having an average of at least two alkenyl groups per molecule and a viscosity of 0.001 to 2 Pa · s at 25 ° C (the viscosity of (E) (i) is The viscosity of the silicone resin of the above silicone composition is 20% or less, and this organosiloxane is of the formula (R).¹R²₂SiO_1/2)_m(R²₂SiO_2/2)_n(R¹SiO_3/2)_p(SiO_4/2)_q(In the formula, R¹Is C₁~ C₁₀Hydrocarbyl or C₁~ C₁₀Halogen-substituted hydrocarbyls, both of which are free of aliphatic unsaturated and R²Is R¹Or alkenyl, m is 0 to 0.8, n = 0 to 1, p = 0 to 0.25, q = 0 to 0.2, m + n + p + q = 1, and m + n is not equal to 0, but when p + q = 0, n is not equal to 0 and not all of the alkenyl groups are terminal (ie, the alkenyl groups in the organosiloxane). All of R¹R²₂SiO_1/2It is not in the unit))). In addition, the organosiloxanes (E) (i) can have a linear, branched or cyclic structure. For example, if the subscripts m, p, and q in the equations for organosiloxanes (E) and (i) are each equal to 0, then the organosiloxane is an organic cyclosiloxane.

The viscosity of the organosiloxane (E) (i) at 25 ° C is typically 0.001 to 2 Pa · s, 0.001 to 0.1 Pa · s, or 0.001 to 0.05 Pa · s. In addition, the viscosity of the organosiloxanes (E) (i) at 25 ° C is typically 20% or less, 10% or less, or 1% of the viscosity of the silicone resin in the hydrosilylation curable silicone composition. It is as follows.

Examples of organosiloxanes suitable for use as organosiloxanes (E) (i) include, but are not limited to, organosiloxanes having the following formula: (ViMeSiO)₃, (ViMeSiO)₄, (ViMeSiO)₅, (ViMeSiO)₆, (ViPhSiO)₃, (ViPhSiO)₄, (ViPhSiO)₅, (ViPhSiO)₆, ViMe₂SiO (ViMeSiO)_nSiMe₂Vi, Me₃SiO (ViMeSiO)_nSiMe₃, And (ViMe₂SiO)₄Si (Me is methyl, Ph is phenyl, Vi is vinyl, and the subscript n has a value such that this organosiloxane has a viscosity of 0.001 to 2 Pa · s at 25 ° C. ).

Ingredients (E) and (i) may be a single organosiloxane or a mixture containing two or more different organosiloxanes (each as described above). Methods for making alkenyl-functional organosiloxanes are well known in the art.

Ingredients (E) and (ii) are in sufficient quantity to provide 0.5 to 3 mol of hydrogen atom bonded to silicon in (E) and (ii) per mol of alkenyl group in (E) and (i). Organohydrogensiloxane with an average of at least two silicon-bonded hydrogen atoms per molecule and a viscosity of 0.001 to 2 Pa · s at 25 ° C (this organohydrogensiloxane is of formula (HR)¹₂SiO_1/2)_s(R¹SiO_3/2)_t(SiO_4/2)_vHas (in the formula, R¹Is C₁~ C₁₀Hydrocarbyl or C₁~ C₁₀Halogen-substituted hydrocarbyls, both of which do not contain aliphatic unsaturateds, s is 0.25 to 0.8, t is 0 to 0.5, v is 0 to 0.3, and s + t + v = And t + v is not equal to 0)).

The viscosity of organohydrogensiloxane (E) (ii) at 25 ° C is typically 0.001 to 2 Pa · s, 0.001 to 0.1, or 0.001 to 0.05 Pa · s.

Examples of organohydrogensiloxanes suitable for use as organohydrogensiloxanes (E) (ii) include, but are not limited to, organohydrogensiloxanes having the formula: PhSi (OSiMe₂H)₃, Si (OSiMe₂H)₄, MeSi (OSiMe₂H)₃, (HMe₂SiO)₃SiOSi (OSiMe₂H)₃And (HMe₂SiO)₃SiOSi (Ph) (OSiMe₂H)₂(In the formula, Me is methyl and Ph is phenyl).

Ingredients (E) (ii) may be a single organohydrogensiloxane or a mixture containing two or more different organohydrogensiloxanes (each as described above). Methods for making organohydrogensiloxanes are well known in the art.

The concentration of the components (E) and (ii) is determined by the hydrogen atom bonded to 0.5 to 3 mol of silicon, the hydrogen atom bonded to 0.6 to 2 mol of silicon, or the hydrogen atom bonded to 0.5 to 2 mol of silicon per mole of the alkenyl group in the component (E) (i). The concentration is sufficient to provide 0.9-1.5 mol of hydrogen atoms bound to silicon.

The concentration of the reactive diluent (E) (combined components (E) (i) and (E) (ii)) of the hydrosilylation-curable silicone composition is typically the silicone resin in the above embodiments. 0-90% (weight / weight), based on the combined weight of the (component (A), (A'), or (A ")) and organosilicon compound (component (B) or (B')), Alternatively, it is 0 to 50% (weight / weight), 0 to 20% (weight / weight), or 0 to 10% (weight / weight).

Curable compositions comprising thermosetting polymers may further comprise carbon nanomaterials, which are described and exemplified above. If present, the carbon nanomaterial is typically 0.0001 to 99% (weight / weight), or 0.001 to 50% (weight / weight), or 0.01 to 0.01, based on the total weight of the thermosetting polymer. It has a concentration of 25% (weight / weight), or 0.1-10% (weight / weight), or 1-5% (weight / weight).

The release liner may be coated with a curable composition comprising a thermosetting polymer using conventional coating techniques such as spin coating, dipping, spraying, brushing, extrusion or screen printing. The amount of the composition is sufficient to form a first polymer layer having a thickness of 0.01-1000 μm after the polymer has been cured in step (ii) of the method described below.

In step (ii) of the method immediately prior to forming the first polymer layer, the thermosetting polymer of the coated release liner is cured. This thermosetting polymer can be cured using a variety of methods, depending on the type of curable composition used to coat the release liner, the polymer at room temperature, high temperature, moisture or Including exposure to radiation.

A hydrosilylation-curable silicone composition in which the curable composition used to coat the release liner comprises at least one silicone resin having an alkenyl group bonded to at least two silicons per molecule or a hydrogen atom bonded to silicon on average. In some cases, the silicone resin of the release liner can be cured by heating the coating at a temperature sufficient to cure the silicone resin. The coating can be heated at atmospheric pressure, below atmospheric pressure, or above atmospheric pressure. The coating is typically heated at atmospheric pressure at room temperature (about 23 ± 2 ° C) to 250 ° C, or room temperature to 200 ° C, or room temperature to 150 ° C. The coating liner is heated for a time sufficient to cure (crosslink) the silicone resin. For example, the coating is typically heated at a temperature of 150-200 ° C for 0.1-3 hours.

Alternatively, a hydrosilylation-curable silicone composition in which the curable composition used to coat the release liner comprises at least one silicone resin having an alkenyl group bonded to at least two silicons or a hydrogen atom bonded to silicon on average per molecule. In the case of objects, the coated silicone resin of the release liner can be cured by heating the coating in vacuum for 0.5 to 3 hours at a temperature of 100 to 200 ° C and a pressure of 1,000 to 20,000 Pa. The coating is a traditional vacuum bagging process. Can be cured in vacuum using process). In a typical process, a bleeder (eg polyester) is applied over a coated release liner and a breather (eg nylon, polyester) is applied over this bleeder for a vacuum bag with a vacuum nozzle. A film (eg nylon) is applied over the breather, the assembly is tape sealed, a vacuum (eg 1,000 Pa) is applied to the sealed assembly, and the evacuated bag is heated as described above.

The method of forming the first polymer layer containing the thermosetting polymer is to apply a second release liner to the coated release liner of the first step after step (i) and before step (ii). The steps of forming the assembly and compressing the assembly can be further included. This assembly can be compressed to remove excess composition and / or invading air and reduce the thickness of the coating. This assembly can be compressed using conventional equipment (eg stainless steel rollers, hydraulic presses, rubber rollers or laminated roll sets). This assembly is typically compressed at a pressure of 1,000 Pa to 10 MPa and at a temperature of room temperature (about 23 ± 2 ° C) to 50 ° C.

If the same curable composition is used in each coating step, the method of forming a first polymer layer containing a thermosetting polymer repeats steps (i) and (ii) to increase the thickness of the polymer layer. Further steps can be included.

If the first polymer layer contains a thermoplastic polymer and a fiber reinforced material, the polymer layer is (a) impregnated with the fiber reinforced material in a composition containing the thermoplastic polymer in a fluid state, and (b) impregnated. It can be formed by the step of converting the thermoplastic polymer of the fiber reinforced material into a solid state.

In step (a) of the method immediately prior to forming the first polymer layer, the fiber reinforced material is impregnated in a composition comprising a fluidized thermoplastic polymer.

The fiber reinforced material can be impregnated in a composition comprising a fluidized thermoplastic polymer using various methods. For example, according to the first method, the fiber reinforced plastic is formed by (i) applying a composition containing a thermoplastic polymer in a fluid state to a release liner to form a film, and (ii) applying the fiber reinforced plastic to the film. It can be impregnated by embedding and (iii) applying the above composition to the embedded fiber reinforcing material to form an impregnated fiber reinforcing material.

In step (i) of the method immediately prior to impregnating the fiber reinforced material, the composition containing the thermoplastic polymer in the fluid state is applied to a release liner to form a film. The release liner and composition are as described and exemplified above. The composition can be applied to the release liner using conventional coating techniques such as spin coating, dipping, spraying, brushing, extrusion or screen printing. The composition is applied in an amount sufficient to embed the fiber reinforced plastic in the following step (ii).

In step (ii), the fiber reinforced material is embedded in the film. The fiber reinforcing material is as described and illustrated above. The fiber reinforced material can be embedded in the film by simply arranging the reinforcing material on the film and saturating the reinforcing material in the composition of the film.

In step (iii), the composition comprising the fluidized thermoplastic polymer is applied to the embedded fiber reinforced material to form an impregnated fiber reinforced plastic. The composition can be applied to the embedded fiber reinforcement using conventional methods, as described above for step (i).

The first method of impregnating the fiber reinforced material further comprises (iv) applying a second release liner to the impregnated fiber reinforced material to form an assembly, and (v) compressing the assembly. be able to. The first method is to remove gas from the embedded fiber reinforced plastic after step (ii) and before step (iii), and / or after step (iii) and step (iii). Before iv), a step of removing gas from the impregnated fiber reinforced plastic can be further included.

This assembly can be compressed to remove excess composition and / or invading air and reduce the thickness of the impregnated fiber reinforced plastic. The assembly can be compressed using conventional equipment (eg stainless steel rollers, hydraulic presses, rubber rollers or laminated roll sets). The assembly is typically compressed at a pressure of 1,000 Pa-10 MPa and at a temperature of room temperature (about 23 ± 2 ° C) to 200 ° C.

The embedded or impregnated fiber reinforced material can be degassed by exposing it to vacuum at a temperature sufficient to maintain the fluid state of the thermoplastic polymer.

Alternatively, according to the second method, the fiber reinforced plastic is obtained by (i) placing the fiber reinforced plastic on a release liner and (ii) embedding the fiber reinforced plastic in a composition containing a thermoplastic polymer in a fluid state. iii) By applying the composition to the embedded fiber reinforcing material to form the impregnated fiber reinforcing material, it can be impregnated into the composition containing the thermoplastic polymer in the fluid state. The second method can further include (iv) applying a second release liner to the impregnated fiber reinforced material to form an assembly, and (v) compressing the assembly. In the second method, steps (iii)-(v) are as described above for the first method of impregnating the composition containing the fluidized thermoplastic polymer with the fiber reinforcement. The second method is to remove the gas from the embedded fiber reinforced plastic after the step (ii) and before the step (iii), and / or after the step (iii) and the step. Prior to (iv), a step of removing gas from the impregnated fiber reinforced plastic can be further included.

Impregnating a fiber reinforcement in step (ii) of the process of the immediately preceding Ru, fiber reinforcement is embedded in a composition comprising a thermoplastic polymer in a fluid state. The reinforcing material can be embedded in the composition by simply covering the reinforcing material with the composition and saturating the reinforcing material in the composition.

Further, if the fiber reinforcement is a woven or non-woven fabric, the reinforcement can be impregnated into the composition by passing it through a composition containing a fluidized thermoplastic polymer. The cloth typically passes through this composition at a rate of 1-1,000 cm / sec.

In step (b) of the method described above for forming the first polymer layer, the thermoplastic polymer of the impregnated fiber reinforced material is converted into a solid state. If the composition used to coat the release liner contains a molten thermoplastic polymer, the thermoplastic polymer will have a liquid-solid transition temperature (T)._gOr T_m) It can be converted to a solid state by allowing the polymer to cool to a lower temperature, eg room temperature. If the composition used to coat the release liner comprises a thermoplastic polymer and an organic solvent, the thermoplastic polymer can be converted to a solid state by removing at least a portion of the solvent. The organic solvent can be removed by vaporizing the solvent at room temperature or by heating the coating to a moderate temperature, eg, below the solid-liquid transition temperature of the polymer.

The method of forming the first polymer layer containing the composition containing the thermoplastic resin in the fluid state and the fiber reinforcing material repeats steps (a) and (b) when the same composition is used for each impregnation. The step of increasing the thickness of the polymer layer can be further included.

If the first polymer layer contains a thermosetting polymer and a fiber reinforced plastic, the polymer layer is (a') impregnated with the fiber reinforced plastic in a curable composition containing a thermosetting polymer and (b'). It can be formed by curing the thermosetting polymer of the impregnated fiber reinforced material.

In step (a') of the method immediately before forming the first polymer layer, the fiber reinforced material is impregnated into the curable composition containing the thermosetting polymer. The fiber reinforced materials and compositions are as described and illustrated above. The fiber reinforced material can be impregnated into the curable composition using the above method for impregnating the fiber reinforced material into the composition containing the thermoplastic polymer.

In the step (b') of the method immediately before forming the first polymer layer, the thermosetting polymer of the impregnated fiber reinforced material is cured. Thermosetting polymers vary from room temperature to high temperature, including exposure to moisture or radiation, depending on the type of curable composition used to impregnate the fiber reinforced plastic. It can be cured using the method.

For example, a hydrosilylation-curable silicone containing at least one silicone resin having an alkenyl group bonded to at least two silicons or a hydrogen atom bonded to silicon on average in the curable composition used for impregnating the fiber reinforcing material. In the case of a composition, the silicone resin can be cured by heating a fibrous reinforcing material impregnated with atmospheric pressure, below atmospheric pressure, and above atmospheric pressure. The impregnated fiber reinforced plastic is typically heated at atmospheric pressure at room temperature (about 23 ± 2 ° C) to 250 ° C, room temperature to 200 ° C, or room temperature to 150 ° C. The reinforcing material is heated for a time sufficient to cure (crosslink) the silicone resin. For example, the impregnated fiber reinforced plastic is typically heated at a temperature of 150-200 ° C for 0.1-3 hours.

Alternatively, the curable composition used for impregnating the fiber reinforcing material is a hydrosilylation-curable silicone composition containing at least one silicone resin having an alkenyl group bonded to at least two silicons or a hydrogen atom bonded to silicon on average per molecule. In the case of a silicone resin, the silicone resin can be cured by heating the impregnated fiber reinforcing material in vacuum at a temperature of 100 to 200 ° C. and a pressure of 1,000 to 20,000 Pa for 0.5 to 3 hours. The impregnated fiber reinforcement can be cured in vacuum using a conventional vacuum bag pressurization process. In a typical process, a bleeder (eg polyester) is applied over the impregnated fiber reinforced plastic and a breather (eg nylon, polyester) is applied over the bleeder and a vacuum bag film (eg nylon) with a vacuum nozzle. ) Is applied over the breather, the assembly is tape-sealed, a vacuum (eg 1,000 Pa) is applied to the sealed assembly, and the evacuated bag is heated as described above.

If the same curable composition is used for each impregnation, the method of preparing a first polymer layer containing a thermosetting polymer and a fiber reinforced material is to repeat steps (a') and (b') to make the polymer layer. It is possible to further include a step of increasing the thickness of the.

In the second step of the method of preparing the first reinforced silicone resin film, the second polymer layer described above is formed on the first polymer layer. This second polymer layer is as described above in the method of forming the first polymer layer, except that the second polymer layer is formed on top of the first polymer layer rather than the release liner. Can be formed.

The method of preparing the first reinforced silicone resin film can further include the step of separating the first polymer layer from the release liner. The first polymer layer can be separated from the release liner either before or after the second polymer layer is formed. Further, the first polymer layer can be separated from the release liner by mechanically stripping the layer from the release liner.

The second reinforced silicone resin film according to the present invention is With the first polymer layer, With the second polymer layer on the first polymer layer, With at least one additional polymer layer on at least one of the first and second polymers And at least one of these polymer layers contains a cured product of at least one silicone resin having an alkenyl group bonded to at least two silicon or a hydrogen atom bonded to silicon on average per molecule. At least one of the polymer layers contains carbon nanomaterials.

The first polymer layer of this second reinforced silicone resin film typically has a thickness of 0.01 to 1000 μm, or 5 to 500 μm, or 10 to 100 μm.

The first polymer layer of the second reinforced silicone resin film can include a thermoplastic polymer or a thermosetting polymer. The thermoplastic polymer and the thermosetting polymer are as described and exemplified above for the first reinforced silicone resin film.

In addition to the thermoplastic or thermosetting polymer, the first polymer layer of this second reinforced silicone resin film is a carbon nanomaterial, a fiber reinforced material or a mixture thereof (as illustrated and exemplified above, respectively). Can include reinforcing materials selected from).

The second polymer layer and the additional polymer layer of the second reinforced silicone resin film are as described and exemplified above for the first polymer layer. Adjacent layers of the second reinforced silicone resin film differ in at least one of many physical and chemical properties, including thickness, polymer composition, crosslink density, concentration of carbon nanomaterials or concentration of additional components.

The second reinforced silicone resin film typically comprises 1-100 additional polymer layers, or 1-10 additional polymer layers, or 2-5 additional polymer layers.

At least one of the polymer layers of the second reinforced silicone resin film contains an average of at least two silicon-bonded alkenyl groups per molecule or a cured product of at least one silicone resin with silicon-bonded hydrogen atoms. Including. The silicone resin, the method for preparing the resin, and the method for preparing the cured product of the silicone resin are as described above in the method for preparing the first reinforced silicone resin film of the present invention.

At least one of the polymer layers of the second reinforced silicone resin film contains carbon nanomaterials. The carbon nanomaterial, the concentration of the carbon nanomaterial and the method for preparing the carbon nanomaterial are as described and exemplified above for the first reinforced silicone resin film.

The first polymer layer, the second polymer layer and the additional polymer layer can be prepared as described later in the method for preparing the second reinforced silicone resin film of the present invention.

The second reinforced silicone resin film is The process of forming the first polymer layer on the release liner, The process of forming the second polymer layer on top of the first polymer layer, With the step of forming at least one additional polymer layer on at least one of the first and second polymer layers At least one of these polymer layers contains a cured product of at least one silicone resin having an average of at least two silicon-bonded alkenyl groups or silicon-bonded hydrogen atoms per molecule. Including, at least one of the polymer layers can be prepared by methods comprising carbon nanomaterials.

The first polymer layer, the second polymer layer and the additional polymer layer can be formed as described above in the method of preparing the first reinforced silicone resin film.

The reinforced silicone resin films of the present invention typically have 1-99% (weight / weight), or 1-95% (weight / weight), or 30-95% (weight / weight), or 50-95%. Contains (weight / weight) cured silicone resin. The reinforced silicone resin film typically has a thickness of 1 to 3000 μm, or 15 to 500 μm, or 15 to 300 μm, or 20 to 150 μm, or 30 to 125 μm.

Reinforced silicone resin films are typically placed on a cylindrical steel mandrel whose flexibility is measured as described in ASTM Standard D522-93a, Method B, where the film has a diameter of 3.2 mm or less. It has flexibility so that it can be bent without cracking.

The reinforced silicone resin film has a low linear coefficient of thermal expansion (CTE), high tensile strength, high modulus of elasticity, and high resistance to thermally induced cracks. For example, this film typically has 0-80 μm / m ° C, or 0-20 μm / m ° C, or 2-10 μm / m ° at room temperature (approximately 23 ± 2 ° C) to 200 ° C. Has a CTE of C. The film also has a tensile strength of typically 5 to 200 MPa, or 20 to 200 MPa, or 50 to 200 MPa at 25 ° C. In addition, this reinforced silicone resin film typically has a Young's modulus of 0.5-10 GPa, or 1-6 GPa, or 3-5 GPa at 25 ° C.

The transparency of this reinforced silicone resin film depends on many factors (eg, the composition of the cured silicone resin, the thickness of the film and the type and concentration of the reinforcing material). The reinforced silicone resin film typically has at least 5%, or at least 10%, or at least 15%, or at least 20% transparency (% transmittance) in the visible region of the electromagnetic spectrum.

The reinforced silicone resin film of the present invention has a low coefficient of thermal expansion and exhibits high resistance to thermally induced cracks.

The reinforced silicone resin film of the present invention is useful for applications that require a film with high thermal stability, flexibility, mechanical strength and transparency. For example, this silicone resin film can be used as an integral part of flexible displays, solar cells, flexible electronic circuit boards, touch screens, fire resistant wallpaper and impact resistant windows. This film is also a suitable substrate for transparent or opaque electrodes.

<p> The following examples are shown to better illustrate the reinforced silicone resin films and methods of the invention, but these should be considered limiting the invention as described in detail in the appended claims. is not it. Unless otherwise stated, all copies and percentages reported in the Examples are by weight. The following methods and materials were used in the examples.</p><p> (Measurement of mechanical properties) Young's modulus, tensile strength and tensile strain at break were measured using the MTS Alliance RT / 5 test frame with 100-N load cells. Young's modulus, tensile strength and tensile strain were measured at room temperature (about 23 ± 2 ° C) for the test pieces of Example 6 and Example 7.</p><p> Specimens were set on two pneumatic grips 25 mm apart and pulled at a crosshead speed of 1 mm / min. Load and displacement data were collected continuously. The steepest slope in the initial section of the load-displacement curve was adopted as Young's modulus. The reported values for Young's modulus (MPa), tensile strength (MPa) and tensile strain (%) each represent the average of three measurements made on different dumbbell-shaped specimens from the same silicone resin film. ..</p><p> Tensile strength was calculated according to the following equation using the highest position of the load-displacement curve: σ = F / (Wb) (During the ceremony, σ = tensile strength (MPa), F = maximum force (N), w = Specimen width (mm), and b = Test piece thickness (mm)).</p><p> The tensile strain at rupture was approximated by dividing the difference in grip distance before and after the test by the initial grip distance according to the equation below: ε = 100 (l₂-l₁) / l₁(During the ceremony, ε = tensile strain of fracture (%) l₂= The final distance (mm) of the grip, and l₁= Initial distance of the grip (mm)).</p><p> Pyrograf®-III Grade HHT-19 Carbon Nanofibers, commercially available from Pyrograf Products, Inc. (Cedarville, Ohio), are 100-200 nanometers in diameter. And heat-treated (up to 3000 ° C) carbon nanofibers with a length of 30,000 to 100,000 nanometers.</p><p> Silicone Base A: Formula (PhSiO) with a weight average molecular weight of about 1700, a number average molecular weight of about 1440, and a hydroxy group attached to about 1 mol% silicon._3/2)_0.75(ViMe₂SiO_1/2)_0.25A mixture containing 82% silicone resin and 18% 1,-4-bis (dimethylsilyl) benzene.²⁹Si NMR and¹³The molar ratio of 1- and 4-bis (dimethylsilyl) benzene-bonded hydrogen atoms to silicon-bonded vinyl groups in the silicone resin as measured by C NMR is 1.1: 1.</p><p> Silicone Base B: Formula (PhSiO) with a weight average molecular weight of about 1700, a number average molecular weight of about 1440, and a hydroxy group attached to about 1 mol% silicon._3/2)_0.75(ViMe₂SiO_1/2)_0.25A mixture containing 76% silicone resin, 9.5% phenyltris (dimethylsiloxy) silane, and 14.5% 1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane.²⁹Si NMR and¹³When measured by C NMR, the hydrogen atom of phenyltris (dimethylsiloxy) silane for the vinyl group bonded to silicon of the silicone resin, and the 1,1,5,5-tetra for the vinyl group bonded to silicon. The molar ratio of hydrogen atoms bonded to silicon in methyl-3,3-diphenyltrisiloxane is 0.55: 1, respectively.</p><p> Commercially available from SDC Technologies, Inc. (Anaheim, CA), SDC MP101 Crystal Coat Resin contains methanol, 2-propanol, water and acetic acid (approximately 1-2%). ) In essentially MeSiO_3/2Unit and SiO_4/2A solution containing 31% (weight / weight) of a silicone resin consisting of units.</p><p> Sold by DuPont Teijin Films (Hopewell, VA), Melinex® 516 is a 125 μm thick polyethylene terephthalate that is slippery and pretreated on one side with a release agent. (PET) film.</p><p> Glass Fabric is a heat-treated glass fabric prepared by heating a style 106 electric glass fabric with a plain weave and a thickness of 37.5 μm at 575 ° C for 6 hours. The untreated glass cloth was obtained from JPS Glass (Slater, South Carolina).</p><p> (Example 1) This example shows the preparation of chemically oxidized carbon nanofibers. Pyrograph®-III carbon nanofibers (2.0 g), 12.5 mL concentrated nitric acid and 37.5 mL concentrated sulfuric acid, cooler, thermometer, Teflon® coated magnetic stir bar and temperature controller Sequentially mixed in a 500 mL three-necked flask provided. The mixture was heated to 80 ° C and kept at this temperature for 3 hours. The mixture was then cooled by placing the flask on a layer of dry ice in a 1 gallon bucket. The mixture was poured into a Büchner funnel containing a nylon membrane (0.8 μm) and carbon nanofibers were collected by vacuum filtration. The nanofibers remaining on the membrane were washed several times with deionized water until the pH of the filtrate was equal to the pH of the wash water. After the final wash, the carbon nanofibers were kept in the funnel for an additional 15 minutes with subsequent application of vacuum. The nanofibers supported on the filter membrane were then placed in the oven at 100 ° C. for 1 hour. The carbon nanofibers were removed from the filter membrane and stored in a dry, sealed glass jar.</p><p> (Example 2) The oxidized carbon nanofibers (0.1 g) of Example 1 were mixed with silicone base A (9.9 g) in a glass vial, then 4.0 g of heptane was added. The vial was placed in an ultrasonic bath for 115 minutes. The mixture was then centrifuged at 1500 rpm for 30 minutes. The supernatant was transferred to a clean vial and kept under vacuum (45 mmHg (about 6 kPa)) at 50 ° C for 90 minutes to remove most of the heptane.</p><p> (Example 3) The oxidized carbon nanofibers (0.04 g) of Example 1 were mixed with silicone base B (20.0 g) in a glass vial, then 8.0 g heptane was added. The vial was placed in an ultrasonic bath for 115 minutes. The mixture was then centrifuged at 1500 rpm for 30 minutes. The supernatant was transferred to a clean vial and kept under vacuum (45 mmHg (about 6 kPa)) at 50 ° C for 90 minutes to remove most of the heptane.</p><p> (Example 4) A catalyst in which the silicone composition (4.0 g) of Example 2 is composed of a platinum (0) complex of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane in toluene and contains 1000 ppm of platinum. Mixed with 0.05 g. The resulting composition (2.0 g) was added to Melinex® 516. It was applied to the release agent-treated surface of PET film (8 inches x 11 inches (about 20 cm x about 28 cm)). A glass cloth having the same dimensions as the PET film was carefully placed on this silicone film to allow the composition to completely wet the fabric for a sufficient period of time. The silicone composition of Example 2 was then uniformly applied to the embedded fabric. The same PET film was placed on top of the coating with the release agent side in contact with the silicone composition. The stack was then passed between two stainless steel rods separated by a distance of 300 μm. The laminate was heated in an oven according to the following cycle: room temperature to 80 ° C at 2 ° C / min, 30 minutes at 80 ° C, 80 ° C to 160 ° C at 2 ° C / min, 60 ° C for 60 minutes, 2 ° C / min from 160 ° C to 200 ° C, 200 ° C for 60 minutes. The oven was switched off and the laminate was allowed to cool to room temperature in the oven. The upper PET film was separated (peeled) from the reinforced silicone resin film, and then the silicone resin film was separated from the lower PET film.</p><p> (Example 5) Reinforced silicone resin films were prepared according to the method of Example 4, except that the silicone composition of Example 3 was used instead of the silicone composition of Example 2.</p><p> (Example 6) The reinforced silicone resin prepared according to the method of Example 4 was passed through a silicone composition prepared by diluting MP101 Crystal Coat Resin with an equal amount of 1-butanol at a rate of about 5 cm / sec. .. The coated film was hung vertically in a ventilation hood at room temperature to dry and then cured in an air circulation oven according to the following cycle: 1 ° C / min from room temperature to 75 ° C, 75 ° C 1 Hours, 1 ° C / min from 75 ° C to 100 ° C, 100 ° C for 1 hour, 1 ° C / min from 100 ° C to 125 ° C, 125 ° C for 1 hour. This three-layer reinforced silicone resin film contains a central layer having a thickness of about 40 μm and two outer layers each having a thickness of about 1.5 μm. Table 1 shows the mechanical properties of this reinforced silicone resin film.</p><p> (Example 7) The reinforced silicone resin prepared according to the method of Example 5 was passed through a silicone composition prepared by diluting MP101 crystal coated resin with an equal amount of 1-butanol at a rate of about 5 cm / sec. The coated film was hung vertically in a ventilation hood at room temperature to dry and then cured in an air circulation oven according to the following cycle: 1 ° C / min from room temperature to 75 ° C, 75 ° C 1 Hours, 1 ° C / min from 75 ° C to 100 ° C, 100 ° C for 1 hour, 1 ° C / min from 100 ° C to 125 ° C, 125 ° C for 1 hour. This three-layer reinforced silicone resin film contains a central layer having a thickness of about 40 μm and two outer layers each having a thickness of about 1.5 μm. Table 1 shows the mechanical properties of this reinforced silicone resin film. table 1<tables num="1"><img file="JP2010519086A_D0004.tif" /></tables></p>