WO2015023001A1 - Nouvel organopolysiloxane, agent de traitement de surface le comportant, composition de résine le comportant et son produit gélatineux ou son produit durci - Google Patents

Nouvel organopolysiloxane, agent de traitement de surface le comportant, composition de résine le comportant et son produit gélatineux ou son produit durci Download PDF

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Publication number
WO2015023001A1
WO2015023001A1 PCT/JP2014/071692 JP2014071692W WO2015023001A1 WO 2015023001 A1 WO2015023001 A1 WO 2015023001A1 JP 2014071692 W JP2014071692 W JP 2014071692W WO 2015023001 A1 WO2015023001 A1 WO 2015023001A1
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Prior art keywords
groups
fillers
organopolysiloxane
group
metal
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PCT/JP2014/071692
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English (en)
Inventor
Makoto Iwai
Kosei IWAKAWA
Takuya Ogawa
Tadashi Okawa
Shawn Keith Mealey
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Dow Corning Toray Co., Ltd.
Dow Corning Corporation
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Priority to KR1020167006472A priority Critical patent/KR102263350B1/ko
Priority to JP2016507920A priority patent/JP6159016B2/ja
Priority to CN201480052332.2A priority patent/CN105593234B/zh
Publication of WO2015023001A1 publication Critical patent/WO2015023001A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0896—Compounds with a Si-H linkage
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0834—Compounds having one or more O-Si linkage
    • C07F7/0838—Compounds with one or more Si-O-Si sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/08—Ingredients agglomerated by treatment with a binding agent
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/001—Conductive additives

Definitions

  • Present invention relates to a novel organopolysiloxane, a surface treatment agent comprising the same, and a resin composition comprising the same and particularly suitably relates to a thermally conductive silicone composition.
  • thermally conductive fillers selected from thermally conductive fillers, fluorescent fillers, electrically conductive fillers, dielectric fillers, insulating fillers, light-diffusing fillers, translucent fillers, colorable fillers, and reinforcing fillers are widely used industrially since greases, gels, rubbery cured products, coating agents, phase-change materials, and the like having various functions can be obtained when blended into a resin composition.
  • thermally conductive silicone compositions are used in order to effectively dissipate heat.
  • Thermally conductive silicone greases, thermally conductive silicone gel compositions, thermally conductive silicone rubber compositions, and the like are known as such thermally conductive silicone compositions.
  • thermally conductive silicone compositions examples include thermally conductive silicone compositions using a silicone oil as a primary agent and containing an inorganic filler such as zinc oxide or an alumina powder (see Japanese Unexamined Patent Application Publication No. S50-105573, Japanese Unexamined Patent Application Publication No. S51 -55870, and Japanese Unexamined Patent Application
  • thermoly conductive silicone composition consisting of an organopolysiloxane, an organopolysiloxane having an alkoxy group or an acyloxy group bonded to silicon atoms, a thermally conductive filler, and a curing agent
  • a thermally conductive silicone composition comprising an organopolysiloxane, a curing agent, and a thermally conductive filler that is surface-treated with a silalkylene organosiloxane having an alkoxy group bonded to silicon atoms (see Japanese Unexamined Patent Application Publication No. 2001-139815).
  • Patent Document V Japanese Unexamined Patent Application Publication No.
  • Patent Document 2 Japanese Unexamined Patent Application Publication No. S51-55870
  • Patent Document 3 Japanese Unexamined Patent Application Publication No. S61-157587
  • Patent Document 4 Japanese Unexamined Patent Application Publication No. 2000-256558
  • Patent Document 5 Japanese Unexamined Patent Application Publication No. 2001-139815
  • the components proposed as surface treatment agents are often compounds having hydrolyzable groups such as alkoxysilyl groups. These hydrolyzable groups are effective to a certain degree for metal oxides having hydroxyl groups on the surface such as alumina, but they have no effect on functional fillers that do not have hydroxyl groups on the surface such as boron nitride or graphite, and when these functional fillers - thermally conductive fillers, in particular - are used in high concentrations, the viscosity of the resulting composition increases dramatically, resulting in the problem that the handleability is substantially diminished. Therefore, with a surface treatment agent using a known organopolysiloxane, a resin
  • composition cannot be filled with high concentrations of various functional fillers, so the performance of the resulting composition is insufficient, and there is also the problem that the composition cannot achieve both good handleability and performance.
  • the present invention was conceived in order to solve at least the problems described above, and the present invention provides a novel organopolysiloxane having good handleability or dispersion stability. Problem of increased viscosity or poor dispersion became unlikely to occur, even when a resin composition was filled with various functional fillers, a surface treatment agent comprising the same, and, in particular, a functional resin composition.
  • the inventive concept is embodied in an exemplary novel organopolysiloxane and/or thermally conductive silicone composition with good handleability and high thermal conductivity. Such features may appear even when they comprisee large amounts of thermally conductive fillers.
  • an organopolysiloxane represented by the general formula (1) is provided: [Formula 1]
  • R 1 is a monovalent hydrocarbon group having a plurality of aromatic rings with 10 or more carbon atoms
  • R 2 is a divalent hydrocarbon group which may contain a hetero atom or a direct bond to a silicon (Si) atom;
  • each of R 3 and R 4 is independently selected from a monovalent hydrocarbon group
  • R 5 is a divalent hydrocarbon group which may contain a hetero atom, or an oxygen atom;
  • R 6 is each independently a group selected from alkyl groups, alkenyl groups, aryl groups, and alkoxy groups;
  • n is an integer from 0 to 200;
  • a is an integer from 1 to 3).
  • the present invention relates to a surface treatment agent comprising the organopolysiloxane described above.
  • the surface treatment agent of the present invention can be suitably used for the surface treatment of various functional fillers and, in particular, is used for the surface treatment of one type or two or more types of fillers selected from thermally conductive fillers, fluorescent fillers, electrically conductive fillers, dielectric fillers, insulating fillers, light-diffusing fillers, translucent fillers, colorable fillers, and reinforcing fillers.
  • a surface treatment agent containing the organopolysiloxane of the present invention can be used for the surface treatment of one type or two or more types of fillers selected from inorganic fillers, organic fillers, nanocrystal structures, and quantum dots, and fillers in which part or all of the surfaces thereof may be covered by a silica layer. These surface treatment agents can be used in the synthesis process of various functional fillers.
  • the present invention relates to a resin composition
  • a resin composition comprising the
  • organopolysiloxane described above and a filler with a surface treated by the
  • organopolysiloxane may be curable resin compositions or thermoplastic resin compositions and may also be non-curing or thickening resin compositions.
  • the resin composition of the present invention can be used for various applications in accordance with the types of functional fillers and resins, but in particular, the resin composition can be used for applications selected from thermally conductive materials, electrically conductive materials, semiconductor sealing materials, optical materials, functional coatings, and cosmetics.
  • the resin composition of the present invention particularly preferably has thickening properties, curability, or phase changeability.
  • Thickening properties refer to properties in which the initial viscosity does not change substantially but the overall viscosity increases by heating under the desired usage conditions or using a thickening agent so as to form a gelatinous or viscous liquid or paste form, and examples include grease compositions or the like.
  • Curability refers to a property in which the composition cures due to heating or the like, and examples include hard coat resin compositions and semiconductor sealing resin compositions as well as resin compositions that can be molded into sheet shapes, resin compositions cured into gelatinous shapes having flexibility, and semicurable resin compositions forming soft rubbers having plasticity.
  • Phase changeability refers to a property in which a heat-softening resin having a softening point such as a wax is filled with a functional filler, wherein the phase changes in accordance with the operating temperature of an exothermic electronic part or the like, and an example is a so-called phase-change material.
  • the present invention relates to a thermally conductive silicone composition
  • a thermally conductive silicone composition comprising (A) the organopolysiloxane of formula (1) described above and (B) a thermally conductive filler.
  • the silicone composition of the present invention may further comprise (C) at least one type of an organopolysiloxane other than the organopolysiloxane of formula (1) described above.
  • the thermally conductive filler (B) described above is preferably at least one or more types of powders and/or fibers selected from a group consisting of pure metals, alloys, metal oxides, metal hydroxides, metal nitrides, metal carbides, metal silicides, carbon, soft magnetic alloys, and ferrite.
  • the pure metal described above is bismuth, lead, tin, antimony, indium, cadmium, zinc, silver, copper, nickel, aluminum, iron, or metal silicon; or
  • the alloy is an alloy consisting of two or more types of metals selected from a group comprising bismuth, lead, tin, antimony, indium, cadmium, zinc, silver, copper, nickel, aluminum, iron, or metal silicon; or
  • the metal oxide is alumina, zinc oxide, silicon oxide, magnesium oxide, beryllium oxide, chromium oxide, or titanium oxide; or
  • the metal hydroxide is magnesium hydroxide, aluminum hydroxide, barium hydroxide, or calcium hydroxide; or
  • the metal nitride is boron nitride, aluminum nitride, or silicon nitride; or
  • the metal carbide is silicon carbide, boron carbide, or titanium carbide; or
  • the metal silicide is magnesium silicide, titanium silicide, zirconium silicide, tantalum silicide, niobium silicide, chromium silicide, tungsten silicide, or molybdenum silicide; or
  • the carbon is diamond, graphite, fullerene, carbon nanotubes, graphene, activated carbon, or amorphous carbon black; or
  • the soft magnetic alloy is an Fe-Si alloy, an Fe-AI alloy, an Fe-Si-AI alloy, an Fe-Si-Cr alloy, an Fe-Ni alloy, an Fe-Ni-Co alloy, an Fe-Ni-Mo alloy, an Fe-Co alloy, an Fe-Si-AI-Cr alloy, an Fe-Si-B alloy, or an Fe-Si-Co-B alloy; or
  • the ferrite is a Mn-Zn ferrite, a n-Mg-Zn ferrite, a Mg-Cu-Zn ferrite, a Ni-Zn ferrite, a Ni-Cu-Zn ferrite, or a Cu-Zn ferrite.
  • the thermally conductive filler (B) described above is particularly preferably (B1) a plate-like boron nitride powder having an average particle size of 0.1 to 30 pm, (B2) a granular boron nitride powder having an average particle size of 0.1 to 50 pm, (B3) a spherical and/or pulverized aluminum oxide powder having an average particle size of 0.01 to 50 pm, (B4) a graphite having an average particle size of 0.01 to 50 pm, or a mixture of two or more types thereof.
  • the content of the component (B) is preferably from 100 to 3,500 parts by mass per total of 100 parts by mass of the component (A) and the component (C).
  • the organopolysiloxane of the component (C) preferably has a hydrolyzable functional group bonded to a silicon atom in the molecule.
  • the component (C) is an organopolysiloxane having a monovalent hydrocarbon group having an aliphatic unsaturated bond with a silicon atom in the molecule and an
  • organopolysiloxane having a hydrogen atom bonded to a silicon atom in the molecule, and the component (C) preferably further contains a catalyst which thickens or cures these
  • organopolysiloxanes as a result of a hydrosilylation reaction.
  • the component (C) is an organopolysiloxane having a hydrolyzable functional group bonded to a silicon atom and having a monovalent hydrocarbon group having an aliphatic unsaturated bond with a silicon atom in the molecule and an organopolysiloxane having a hydrogen atom bonded to a silicon atom in the molecule, and the component (C) preferably further contains a catalyst which thickens or cures these organopolysiloxanes as a result of a hydrosilylation reaction.
  • the present invention relates to a gelatinous product or a cured product formed by thickening or curing the silicone composition described above containing a catalyst which thickens or cures the composition as a result of a hydrosilylation reaction.
  • the novel organopolysiloxane of the present invention is useful as a surface treatment agent for various functional fillers and is advantageous in that various functional fillers can be blended into a resin composition in large quantities without diminishing the handleability or dispersion stability.
  • the novel organopolysiloxane of the present invention is useful for the surface treatment of a thermally conductive filler, and the thermally conductive silicone composition of the present invention demonstrates good handleability without an increased composition viscosity, even when the composition comprises a large amount of a thermally conductive filler in order to obtain a silicone composition with high thermal conductivity.
  • a curable composition there is the feature that a uniform cured product can be obtained.
  • Examples of such a monovalent hydrocarbon group having a plurality of aromatic rings with 10 or more carbon atoms include naphthyl groups, alkyl naphthyl groups, anthracenyl groups, biphenyl groups, phenyl naphthyl groups, phenyl anthracenyl groups, phenyl phenanthrenyl groups, phenyl pyrenyl groups, terphenylene groups, phenyl terphenylene groups, alkyl biphenyl groups, carbonyl biphenyl groups, alkoxy alkyl biphenyl groups, alkoxy naphthyl groups, acyloxy naphthyl groups, alkoxy carbonyl naphthyl groups, alkyl ether naphthyl groups, phenoxy phenyl groups, and phenyl carbonyl oxy phenyl groups.
  • R 2 is a divalent hydrocarbon group which may contain a hetero atom or a direct bond to a silicon (Si) atom, and it may be, for example, a group formed by performing an addition reaction on a silicon-bonded hydrogen atom and a functional group having an unsaturated hydrocarbon group such as an alkenyl group, an acryloxy group, or a methacryloxy group at the terminals, or a group formed by a reaction of a halogen atom, a hydrolyzable functional group such as an alkoxy group or an acyloxy group, and a silanol group.
  • This structure is a divalent linking group represented by the following structural formula or a direct bond to an Si atom.
  • Each of R 3 and R 4 is independently selected from a monovalent hydrocarbon group and preferably a monovalent hydrocarbon group without aliphatic unsaturated bonds with from 1 to 10 carbon atoms.
  • Examples include straight-chain alkyl groups such as methyl groups, ethyl groups, propyl groups, butyl groups, hexyl groups, and decyl groups; branched-chain alkyl groups such as isopropyl groups, tertiary butyl groups, and isobutyl groups; cyclic alkyl groups such as cyclohexyl groups; aryl groups such as phenyl groups, tolyl groups, and xylyl groups; and aralkyl groups such as benzyl groups and phenethyl groups.
  • R 3 and R 4 are preferably alkyl groups or phenyl groups having from 1 to 4 carbon atoms and are particularly preferably methyl groups, ethyl groups or phenyl groups.
  • R 5 is a divalent hydrocarbon group which may contain a hetero atom, or an oxygen atom, and it may contain an oxygen atom or a sulfur atom.
  • R 5 is preferably a divalent hydrocarbon group having from 1 to 20 carbon atoms, an oxygen atom, or a divalent hydrocarbon group containing 1 or 2 oxygen atoms and having from 1 to 20 carbon atoms, and examples include the divalent linking groups represented by the following structural formulas or oxygen atoms (-0-).
  • CO, R 7 , and R 8 are the same groups as those described above. -R 7 - -R 7 -CO- -R 7 -COO-R 8 -
  • R 5 is a group selected from a group comprising methylene groups, ethylene groups, methyl methylene groups, propylene groups, methyl ethylene groups, butylene groups, phenylene groups, methylene phenyl methyl groups, ethylene phenethyl groups, oxygen atoms, methylene ether groups, ethylene ether groups, propylene ether groups, butylene ether groups, phenyl ether groups, phenyl carbonyl groups, carbonyl ether groups, oxycarbonyl groups, methylene carbonyl groups, ethylene carbonyl groups, propylene carbonyl groups, ethylene carboxyl propyl groups, (methyl) ethylene carboxyl propylene groups, and the like.
  • Each R 6 is a group independently selected from alkyl groups, alkenyl groups, aryl groups, and alkoxy groups having from 1 to 20 carbon atoms.
  • R 6 include straight-chain alkyl groups such as methyl groups, ethyl groups, propyl groups, butyl groups, pentyl groups, hexyl groups, heptyl groups, octyl groups, nonyl groups, decyl groups, undecyl groups, dodecyl groups, tridecyl groups, tetradecyl groups, pentadecyl groups, hexadecyl groups, heptadecyl groups, octadecyl groups, nonadecyl groups, and eicodecyl groups; branched-chain alkyl groups such as 2-methy!
  • undecyl groups and -hexyl heptyl groups cyclic alkyl groups such as cyclododecyl groups; aralkyl groups such as 2-(2,4,6-trimethylphenyl)propyl groups;
  • hydrocarbon groups having unsaturated bonds such as vinyl groups, allyl groups, butenyl groups, hexenyl groups, and octenyl groups; aryl groups such as phenyl groups, tolyl groups, and xylyl groups; and aralkyl groups such as benzyl groups and phenethyl groups.
  • n is an integer from 0 to 200
  • a is an integer from 1 to 3
  • p is an integer from 0 to 10.
  • the organopolysiloxane (A) contained as a component of the present invention has a functional group having two or more aromatic rings, so the affinity to fillers having a plate-like structure or polycyclic aromatic fillers is high.
  • a surface treatment agent, a base oil, or the like to produce a composite material such as a grease, a compound, or a gel, the mixability is improved, and it becomes possible to suppress increases in viscosity.
  • the production method of the organopolysiloxane (A) used in the present invention is not particularly limited, but the organopolysiloxane can be produced with the following method.
  • the organopolysiloxane can be obtained by performing an addition reaction by means of a hydrosilylation reaction on (a-1) a silicon-bonded hydrogen atom-containing
  • R 1 , R 2 , R 3 , and R 4 are the same groups as those described above, n, a, and b are the same numbers as those described above.
  • (b-1) a monovalent hydrocarbon compound or an organic silicon compound which has a plurality of aliphatic double bonds in the molecule, may contain an oxygen atom or sulfur atom, and has from 10 to 40 carbon atoms.
  • the organopolysiloxane can be obtained by performing an addition reaction by means of a hydrosilylation reaction on (a-2) a silicon-bonded hydrogen atom-containing polysiloxane represented by the general formula:
  • R 3 , R 4 , R 5 , and R 6 are the same groups as those described above, n and a are the same numbers as those described above)
  • Examples of a raw material for (b-2) a hydrocarbon compound or an organic silicon compound having at least one aliphatic double bond in the molecule and having a functional group having a plurality of aromatic rings include vinyl naphthalenes, vinyl anthracenes, vinyl phenanthrenes, vinyl pyrenes, vinyl biphenyls, vinyl terphenyls, vinyl phenyl naphthalenes, vinyl phenyl anthracenes, vinyl phenyl phenanthrenes, vinyl phenyl pyrenes, vinyl phenyl terphenyls, phenoxy styrenes, phenyl carbonyl styrenes, phenyl carboxy styrenes, phenoxy carbonyl styrenes, allyl naphthalenes, allyl anthracenes, allyl phenanthrenes, allyl pyrenes, allyl biphenyls,
  • the molar ratio of component (a-1) and component (b-1) or component (a-2) and component (b-2) is not particularly limited, but it is preferable to perform the reaction with an amount of 0.5 to 1.5 mol of component (b-1) or component (b-2) relative to 1 mol of component (a-1) or component (a-2), and it is particularly preferable to perform the reaction so that the amount is 0.95 to 1.1 mol.
  • an organic solvent is optional in the production method of the present invention.
  • this organic solvent include aromatics such as benzene, toluene, and xylene; aliphatics such as pentane, hexane, heptane, octane, and decane; ethers such as tetrahydrofuran, diethyl ether, and dibutyl ether; ketones such as acetone and methyl ethyl ketone; and esters such as ethyl acetate and butyl acetate.
  • one production method of the organopolysiloxane of the present invention is a method of reacting a siloxane (c) having a hydroxyl group at one terminal and an organic silicon compound (d) having a substituent having a plurality of aromatic functional groups and having a single hydrolyzable group.
  • a siloxane (c) having a hydroxyl group at one terminal and an organic silicon compound (d) having a substituent having a plurality of aromatic functional groups and having a single hydrolyzable group.
  • the following compounds are examples of the siloxane (c) having a hydroxyl group at one terminal:
  • organic silicon compounds can be synthesized in accordance with the method described in the Journal of Organometallic Chemistry (1998), 550 (1-2), 283-300, for example.
  • the organopolysiloxane of the present invention has one or more condensation reactive functional groups (for example, alkoxy groups) or hydrosilylation reactive functional groups (for example, alkenyl groups) in the molecule
  • the organopolysiloxane can be used not only as a surface treatment agent, but also as all or part of the primary agent various functional resin compositions.
  • a curable silicone resin composition can be formed with a method of adding the organopolysiloxane described above having one or more condensation reactive functional groups or hydrosilylation reactive functional groups in the molecule, a reactive silicone serving as a crosslinking agent, and various functional fillers and a curing reaction catalyst described below and then treating the surface of the functional fillers in-situ (integral blending method), and the entire composition can then be cured.
  • the organopolysiloxane described above having one or more condensation reactive functional groups or hydrosilylation reactive functional groups in the molecule
  • a reactive silicone serving as a crosslinking agent
  • various functional fillers and a curing reaction catalyst described below described below
  • the organopolysiloxane of the present invention can be modified so as to have excellent thermal stability and to be provided with the surface hydrophobicity, fine dispersibility, and dispersion stability of microparticles or a fine member having a highly refined structure.
  • the surface treatment of various functional fillers even if the resin composition is filled with high concentrations of the fillers, there is no reduction in handleability such as sudden thickening.
  • the surface treatment agent of the present invention comprises the organopolysiloxane described above and, in particular, preferably comprises at least 50 mass% of the organopolysiloxane described above as the primary agent.
  • the surface treatment agent of the present invention may be used after being diluted in a conventionally known solvent or the like, and other additives such as antioxidants, anti-aging agents, pigments, dyes, other organic silicon compounds, such as silane coupling agents or silylating agents, organic titanate compounds, organic aluminate compounds, organic tin compounds, waxes, fatty acids, fatty acid esters, fatty acid salts, or silanol condensation catalysts such as organic tin compounds may also be added to the surface treatment agent of the present invention within a scope that does not depart from the purpose of the present invention.
  • examples of other surface treatment compounds contained in the surface treatment agent of the present invention include silane compounds such as methyl(trimethoxy)silane, ethyl(trimethoxy)s
  • the present invention may also comprise other reactive silicone compounds within a scope that does not inhibit the effect of the present invention.
  • the surface treatment agent of the present invention is useful as a surface treatment agent for various functional fillers and is able to improve the surface properties of the various functional fillers such as hydrophobicity, agglutination, fluidity, and dispersibility and compounding properties in polymers and in curable resins, in particular.
  • the surface treatment agent of the present invention can be particularly suitably used for the surface treatment of one type or two or more types of fillers selected from thermally conductive fillers, fluorescent fillers, electrically conductive fillers, dielectric fillers, insulating fillers, light-diffusing fillers, translucent fillers, colorable fillers, and reinforcing fillers, and the surface treatment agent has the advantage that even when a resin composition is filled with high concentrations of these fillers, the desired functions can be improved without any diminishment of handleability such as sudden thickening.
  • the shape (spherical, rod shaped, needle shaped, plate shaped, amorphous shape, spindle shaped, cocoon-shaped, or the like), particle size (aerosol form, microparticles, pigment-grade, or the like), and particle structure (crystalline, porous, non-porous, or the like) of the functional fillers are in no way limited, but the average primary particle size is preferably within the range of 1 nm to 100 m.
  • the shapes and average primary particle sizes of the functional fillers can be selected appropriately in accordance with the targeted application and functions, and using functional fillers having a plurality of average primary particle sizes or the like in order to improve the filling ratio is included in the preferred modes of the present invention.
  • Examples of methods for treating the surface of such a functional filler include a method of spraying the surface treatment agent or a solution thereof (including a dispersion in an organic solvent or the like) at room temperature to 200°C while stirring the functional filler with a stirrer and then drying the mixture; a method of mixing the functional filler and the surface treatment agent or a solution thereof in a stirrer (including pulverizers such as a bore mill or a jet mill, ultrasonic dispersion devices, and the like) and then drying the mixture; and a treatment method of blending a treatment agent into a solvent, dispersing the functional filler so as to be adsorbed onto the surface, and then drying and baking the substance.
  • a method of spraying the surface treatment agent or a solution thereof including a dispersion in an organic solvent or the like
  • a method of mixing the functional filler and the surface treatment agent or a solution thereof in a stirrer including pulverizers such as a bore mill or a jet mill, ultrasonic dis
  • Another example is a method of adding the functional filler and the surface treatment agent to the resin into which the functional filler is to be blended and then treating the mixture in-situ (integral blending method).
  • the amount of surface treatment agent added when treating the surface of the functional filler is preferably from 0.1 to 50 parts by mass and particularly preferably from 0.1 to 25 parts by mass per 100 parts by mass of the functional filler.
  • the filler to be suitably treated by the surface treatment agent of the present invention is one type or two or more types of fillers selected from inorganic fillers, organic fillers, nanocrystal structures, quantum dots, and fillers in which part or all of the surfaces thereof is covered by a silica layer.
  • these are well known as raw materials for thermally conductive materials, electrically conductive materials, semiconductor sealing materials, optical materials, functional coatings, cosmetics, and the like, and the surface treatment agent of the present invention is suitable for the surface treatment of these fillers.
  • the surface treatment agent of the present invention is suitable for the surface treatment of these fillers.
  • microparticles in which part or all of the surfaces thereof are covered by a silica layer it is possible to dramatically improve the fine dispersibility and dispersion stability in hydrophobic curable resins and in silicone resins, in particular, which yields the advantage that the
  • the nanocrystals may also have a core-shell structure.
  • the average particle size of the nanocrystal structures used in a light-emitting semiconductor - quantum dots, in particular - is within the range of approximately 0.1 nm to several 10s of nm and is selected in accordance with the light emission wavelength.
  • a dielectric filler is a ferroelectric filler, a paraelectric filler, or a combination of these two, and the filler is able to provide a relatively high dielectric constant so that the composition can store a charge.
  • these dielectric fillers include lead zirconate titanate, barium titanate, calcium metaniobate, bismuth metaniobate, iron metaniobate, lanthanum metaniobate, strontium metaniobate, lead metaniobate, lead metatantalate, strontium barium titanate, sodium barium niobate, potassium barium niobate, rubidium barium niobate, titanium oxide, tantalum oxide, hafnium oxide, niobium oxide, aluminum oxide, and stearite.
  • treatment with barium titanate and titanium oxide is suitable from the perspective of improving the dielectric constant, but the present invention is not limited to this case.
  • An insulating filler provides the composition with electrical insulation, and in addition to the thermally conductive fillers described below, fumed silica, precipitated silica, molten silica, or the like can be used. Some or all of these are components that also function as reinforcing fillers.
  • Translucent fillers consist of microparticles with a high refractive index and negligibly small light scattering, and these fillers can provide the composition with a high refractive index and high transparency.
  • the surface treatment agent of the present invention can be suitably used in the surface treatment of metal oxide microparticles used in optical materials.
  • the average particle size of the metal oxide microparticles used as translucent fillers is in a range of 1 to 500 nm and particularly preferably from 1 to 100 nm, and the range of 1 to 20 nm is even more preferable from the perspective of the transparency of the optical material containing the microparticles.
  • these metal oxide microparticles may be - and are preferably - nanocrystalline particles with a crystal diameter of 10 to 100 nm.
  • the translucent filler treated by the surface treatment agent of the present invention also has excellent heat resistance when used in an optical semiconductor element or the like, which yields the advantage that the element is resistant to yellowing, discoloration, and the like.
  • zirconium oxide has a relatively high refractive index (refractive index: 2.2) and is therefore useful for optical material applications which require a high refractive index and high transparency.
  • barium titanate has a high dielectric constant and refractive index and is useful for imparting optical and electromagnetic performance to organic materials.
  • the surface treatment agent of the present invention makes it possible to finely and stably disperse metal oxide microparticles into a hydrophobic curable resin as a result of surface treatment with metal oxide microparticles such as barium titanate, which makes it possible to compound large quantities more stably than untreated microparticles. This results in the advantage that the optical properties (in particular, the high refractive index) and electromagnetic properties of the resulting resin composition can be dramatically improved.
  • a reinforcing filler is a component for providing the required high mechanical strength in accordance with the application of the composition.
  • a reinforcing filler include fumed silica, precipitated silica, molten silica, and aerosol titanium oxide.
  • These reinforcing fillers may have a surface that is hydrophobized with a polyorganosiloxane other than the organopolysiloxane of the present invention, a hexamethyl disiloxane, or the like.
  • the surface treatment agent of the present invention is a conventionally known reinforcing filler and can be used in the treatment of a substrate used in a functional resin composition.
  • examples include talc, clay, mica powders, glass powders (glass beads), glass frits, glass cloths, glass tapes, glass mats, or substances in which the surfaces thereof are partially or completely covered by a silica layer.
  • the surface treatment agent of the present invention has the advantage that, when used in the surface treatment of swelling layered clay materials - in particular, nanoclay materials - blended into the composition for the purpose of improving the mechanical characteristics, the gas permeability, or steam permeability of the functional resin composition, in particular, the mechanical characteristics, the gas permeability, or steam permeability of the functional resin composition can be improved without diminishing the compounding ratios or dispersion stability of other functional fillers.
  • a “nanoclay” refers to a natural or synthetic, modified or unmodified ionic phyllosilicate primarily having a layered structure, and examples include smectite clay minerals such as, for example, montmorillonite - sodium montmorillonite, in particular - bentonite; hectorite; saponite; stevensite; and smectite and hectorite clays containing phyllosilicates such as beidellite.
  • the layered structure of the nanoclay has spread in only the one-dimensional direction in the range of nanometers, so interlayer peeling or swelling tends to occur easily, and which allows them to be separated from one another when incorporated into the resin composition.
  • Each peeled layer preferably has a thickness of less than 25 A
  • the surface treatment of the present invention may also be used in the synthesis of a functional filler produced by a liquid-phase method.
  • the surface treatment agent of the present invention is used in a liquid-phase synthesis method, the particle surface of the resulting functional filler is partially or completely covered by the organopolysiloxane of the present invention in the particle formation process. Therefore, there is not only the advantage that it is possible to finely and uniformly disperse the substance in the re-dispersion step, but also the advantage that the surface characteristics of the resulting fine member can be designed as desired by selecting the refractive index of the organic silicon compound or the types of the reactive functional groups used.
  • the organopolysiloxane of the present invention and a filler that is surface-treated by the organopolysiloxane have the advantage that, when blended into various resin compositions, it is possible to blend large amounts of various functional fillers into the resin compositions without diminishing the handleability or dispersion stability of the various functional fillers, and resin compositions stably filled with high concentrations of these functional fillers can be obtained. These resin compositions will be described hereinafter.
  • thickening properties refer to properties in which the initial viscosity does not change substantially but the overall viscosity increases by heating under the desired usage conditions or using a thickening agent so as to form a gelatinous or viscous liquid or paste form, and examples include grease compositions or the like.
  • compositions as well as resin compositions that can be molded into sheet shapes, resin compositions cured into gelatinous state having flexibility, and semicurable resin compositions forming soft rubbers having plasticity.
  • Phase changeability refers to a property in which a heat-softening resin having a softening point such as a wax is filled with a functional filler, wherein the phase changes in accordance with the operating temperature of an exothermic electronic part or the like, and an example is a so-called phase change material.
  • AAS acrylonitrile-acrylate-styrene
  • ACS acrylonitrile-polyethylene chloride-styrene
  • ionomers and polyacetals with linear structures engineering plastic
  • polyamides nylon
  • polycarbonates polyphenylene oxides
  • polyethylene terephthalates polybutylene
  • the resin used in the present invention is preferably a resin composition comprising at least one type of resin selected from a group comprising heat-softening resins such as waxes, epoxy resins, phenol resins, silicone resins, melamin resins, urea resins, unsaturated polyester resins, diallyl terephthalate resins, polyphenylene oxide resins, polyimide resins, polyamide resins, (meth)acrylic acid ester resins, benzocyclobutene resins, fluorine resins, polyurethane resins, polycarbonate resins, norbornene resins, polyolefin resins, and polystyrene resins.
  • the resin composition of the present invention is particularly preferably a silicone composition.
  • These resin compositions may be curable resin compositions or thermoplastic resin compositions and may also be non-curing or thickening resin compositions.
  • the resin when it is a heat-softening resin, it can be a phase-change material.
  • the resin composition of the present invention can be used for various applications in accordance with the types of functional fillers and resins, but in particular, the resin composition can be used for applications selected from thermally conductive materials, electrically conductive materials, semiconductor sealing materials, optical materials, functional coatings, and cosmetics.
  • the organic silicon compound of the present invention and a filler that is surface-treated by the organic silicon compound are preferably blended into a silicone composition.
  • the handleability remains good without any increases in the viscosity of the composition, even when the composition is filled with high concentrations of thermally conductive fillers in order to realize high thermal conductivity.
  • a curable composition there is the feature that a uniform cured product can be obtained.
  • the thermally conductive silicone composition of the present invention comprises (A) the organic silicon compound described above and (B) a thermally conductive filler, and the surface treatment of the thermally conductive filler using the organic silicon compound (A) is as described for the surface treatment of functional fillers above.
  • Component (B) is a thermally conductive filler for providing the composition of the present invention with thermal conductivity and is preferably at least one type of powder and/or fiber selected from a group comprising pure metals, alloys, metal oxides, metal hydroxides, metal nitrides, metal carbides, metal silicides, carbon, soft magnetic alloys, and ferrite.
  • the component particularly preferably does not contain a hydroxyl group on the surface and contains a carbon system expected to interact with aromatic groups or a thermally conductive material having a flat plate-like appearance.
  • the powders and/or fibers that are used may be treated with various surface treatment agents known as coupling agents.
  • Examples of pure metals include bismuth, lead, tin, antimony, indium, cadmium, zinc, silver, copper, nickel, aluminum, iron, and metal silicon.
  • Examples of alloys include alloys consisting of two or more types of metals selected from a group comprising bismuth, lead, tin, antimony, indium, cadmium, zinc, silver, aluminum, iron, and metal silicon.
  • Examples of metal oxides include alumina, zinc oxide, silicon oxide, magnesium oxide, berilium oxide, chromium oxide, and titanium oxide.
  • Examples of metal hydroxides include magnesium hydroxide, aluminum hydroxide, barium hydroxide, and calcium hydroxide.
  • metal nitrides include boron nitride, aluminum nitride, and silicon nitride.
  • metal carbides include silicon carbide, boron carbide, and titanium carbide.
  • metal silicides include magnesium silicide, titanium silicide, zirconium silicide, tantalum silicide, niobium silicide, chromium silicide, tungsten silicide, and molybdenum silicide.
  • carbon include diamond, graphite, fullerene, carbon nanotubes, graphene, activated carbon, and amorphous carbon black.
  • soft magnetic alloys include Fe-Si alloys, Fe-AI alloys, Fe-Si-AI alloys, Fe-Si-Cr alloys, Fe-Ni alloys, Fe-Ni-Co alloys, Fe-Ni-Mo alloys, Fe-Co alloys, Fe-Si-AI-Cr alloys, Fe-Si-B alloys, and Fe-Si-Co-B alloys.
  • ferrite include Mn-Zn ferrite, Mn-Mg-Zn ferrite, Mg-Cu-Zn ferrite, Ni-Zn ferrite, Ni-Cu-Zn ferrite, and Cu-Zn ferrite.
  • Component (B) is preferably at least one type of powder and/or fiber selected from these components.
  • the thermally conductive filler (B) described above is particularly preferably (B1) a plate-like boron nitride powder having an average particle size of 0.1 to 30 ⁇ , (B2) a granular boron nitride powder having an average particle size of 0.1 to 50 ⁇ , (B3) a spherical and/or pulverized aluminum oxide powder having an average particle size of 0.01 to 50 ⁇ , (B4) a spherical and/or pulverized graphite having an average particle size of 0.01 to 50 ⁇ , or a mixture of two or more types thereof.
  • Examples of the shape of component (B) include a spherical shape, a needle shape, a disc shape, a rod shape, a flat shape, an amorphous shape, and a fiber shape.
  • Examples of the surface treatment agent for treating the powder and/or fiber of component (B) include surfactants, silane coupling agents, aluminum coupling agents, and silicone surface treatment agents.
  • the content of component (B) is not particularly limited, but in order to form a silicone composition having good thermal conductivity, the content is preferably at least 30 volume% in the composition, more preferably within the range of from 30 to 90 volume%, even more preferably within the range of from 60 to 90 volume%, and particularly preferably within the range of from 80 to 90 volume%.
  • the content of component (B) is preferably at least 50 mass% in the composition, more preferably within the range of from 70 to 98 mass%, and particularly preferably within the range of from 90 to 97 mass%.
  • the content of component (B) is preferably within the range of from 100 to 3,500 parts by mass, more preferably within the range of from 100 to 2,500 parts by mass, and particularly preferably within the range of from 00 to 2,500 parts by mass relative to a total of 100 parts by mass of component (A) and component (C).
  • the content of component (B) is less than the lower limit of the range described above, the thermal conductivity of the resulting silicone composition tends to be insufficient, whereas when the content exceeds the upper limit of the range described above, the viscosity of the resulting silicone composition becomes too high, which tends to make it impossible to uniformly disperse component (B) into the resulting silicone composition or to dramatically diminish the handleability thereof.
  • the organopolysiloxane of component (C) is not particularly limited, but an
  • organopolysiloxane having a hydrolyzable group bonded to a silicon atom in the molecule such as an alkoxy group, an alkoxyalkoxy group, an alkenoxy group, an acyloxy group, or a trialkoxy silyl alkyl group, for example, can be used.
  • the organopolysiloxane of component (C) is an organopolysiloxane having monovalent hydrocarbon group having an aliphatic unsaturated bond with a silicon atom in the molecule and an organopolysiloxane having a hydrogen atom bonded to a silicon atom in the molecule, and an organopolysiloxane having a hydrolyzable group bonded to a silicon atom in the molecule may further be used.
  • the monovalent hydrocarbon group having an aliphatic unsaturated bond is preferably a straight-chain alkenyl group and is particularly preferably a vinyl group, an allyl group, or a hexenyl group.
  • An example of a group bonding to silicon atom bonds other than the monovalent hydrocarbon group having an aliphatic unsaturated bond is a monovalent hydrocarbon group not having an aliphatic unsaturated bond, and this group is preferably an alkyl group or an aryl group, more preferably an alkyl group having from 1 to 4 carbon atoms, and particularly preferably a methyl group or an ethyl group.
  • the viscosity of this organopolysiloxane at 25°C is not particularly limited, but is preferably within the range of from 20 to 100,000 mPa-s, more preferably within the range of from 50 to 100,000 mPa-s, even more preferably within the range of from 50 to 50,000 mPa-s, and particularly preferably within the range of from 10o to 50,000 mPa-s.
  • the molecular structure of this organopolysiloxane is not particularly limited and may be, for example, straight chain, branched chain, straight chain having some branches, cyclic or dendritic (dendrimer-like). Examples of this organopolysiloxane include single polymers having these molecular structures, copolymers consisting of these molecular structures, or mixtures thereof.
  • organopolysiloxane examples include dimethylpolysiloxanes capped at both molecular terminals with dimethylvinylsiloxy groups, dimethylpolysiloxanes capped at both molecular terminals with methylphenylvinylsiloxy groups, dimethylsiloxane-methylphenylsiloxane copolymers capped at both molecular terminals with dimethylvinylsiloxy groups,
  • dimethylsiloxane-methylvinylsiloxane copolymers capped at both molecular terminals with dimethylvinylsiloxy groups dimethylsiloxane-methylvinylsiloxane copolymers capped at both molecular terminals with trimethylsiloxy groups, methyl(3,3,3-trifluoropropyl)polysiloxanes capped at both molecular terminals with dimethylvinylsiloxy groups,
  • dimethylsiloxane-methylvinylsiloxane copolymers capped at both molecular terminals with silanol groups dimethylsiloxane-methylvinylsiloxane-methylphenylsiloxane copolymers capped at both molecular terminals with silanol groups, organosiloxane copolymers consisting of a siloxane unit represented by the formula: (CH 3 ) 3 SiOi / 2, a siloxane unit represented by the formula:
  • siloxane unit represented by the formula CH 3 Si0 3 /2 and a siloxane unit represented by the formula: (CH 3 ) 2 Si0 2/ 2, dimethylpolysiloxanes capped at both molecular terminals with silanol groups, dimethylsiloxane-methylphenylsiloxane copolymers capped at both molecular terminals with silanol groups, dimethylpolysiloxanes capped at both molecular terminals with trimethoxysiloxy groups, dimethylsiloxane-methylphenylsiloxane copolymers capped at both molecular terminals with trimethoxysilyl groups, dimethylpolysiloxanes capped at both molecular terminals with methyldimethoxysiloxy groups, dimethylpolysiloxanes capped at both molecular terminals with trimethoxysilylethyl groups, and mixtures of two or more types of these components.
  • an example of a group bonding to a silicon atom bond other than a hydrogen atom is a monovalent hydrocarbon group not having the aliphatic unsaturated bond described above, and this group is preferably an alkyl group or an aryl group, more preferably an alkyl group having from 1 to 4 carbon atoms, and particularly preferably a methyl group or an ethyl group.
  • the viscosity of this organopolysiloxane at 25°C is not particularly limited, but is preferably within the range of from 1 to 100,000 mPa-s and particularly preferably within the range of from 1 to 5,000 mPa-s.
  • the molecular structure of this organopolysiloxane is not particularly limited and may be, for example, straight chain, branched chain, straight chain having some branches, cyclic or dendritic (dendrimer-like). Examples of this organopolysiloxane include single polymers having these molecular structures, copolymers consisting of these molecular structures, and mixtures thereof.
  • the hydrolyzable group is preferably an alkoxy group, an alkoxyalkoxy group, an alkenoxy group, an acyloxy group, a silanol group, or a trialkoxy silyl alkyl group.
  • Examples of such an organopolysiloxane include dimethylpolysiloxanes capped at one molecular terminal with a trimethoxysiloxy group (trimethylsiloxy group), dimethylpolysiloxanes capped at one molecular terminal with a trimethoxysiloxy group (dimethylvinylsiloxy group), dimethylsiloxane-methylphenylsiloxane copolymers capped at one molecular terminal with a trimethoxysiloxy group (dimethylvinylsiloxy group), dimethylpolysiloxanes capped at one molecular terminal with a trimethoxysiloxy group (dimethylvinylsiloxy group),
  • dimethylpolysiloxanes capped at both molecular terminals with trimethoxysiloxy groups dimethylsiloxane-methylmethoxysiloxane copolymers capped at both molecular terminals with trimethylsiloxy groups, dimethylsiloxane-methylethoxysiloxane copolymers capped at both molecular terminals with trimethylsiloxy groups, methyl(3-trimethoxysilylpropyl)-dimethylsiloxane copolymers capped at both molecular terminals with trimethoxysiloxy groups,
  • trimethoxysilylethyl groups and mixtures of two or more types of these components.
  • preparation method [1] wherein the component (A) is mixed with the component (B), the component (C) is added in small amounts thereto, and the resulting composition is mixed may be used or, alternatively, preparation method [2] wherein the component (A) is premixed with the component (C), and the component (B) is added in small amounts thereto may be used.
  • preparation method [1] is particularly preferable.
  • Various devices can be used as the mixing device, but a rotation/revolution mixing device (commercially available products including the Awatori Neritaro series manufactured by Thinky Corp., UM-118 manufactured by UNIX Corp., the UFO series manufactured by EME Corp., speed mixers manufactured by House-Child Corp., and the like) is preferable from the perspective of mixing efficiency.
  • reaction mixture was left to stand, and the upper layer was subjected to mixing/washing liquid separation 3 times with 100 milliliters of ion exchange water, 2 times with 100 milliliters of a saturated sodium hydrogen carbonate aqueous solution, and 3 times with 100 milliliters of a saturated sodium chloride aqueous solution.
  • the mixture was dehydrated with anhydrous sodium sulfide, and 62 g of a fraction of 61 to 65°C/1 hPa (yield: 65%) was obtained by distillation under reduced pressure.
  • the reaction mixture was heated under reduced pressure to 90°C/1 hPa so as to remove solvents, low-boiling-point non-reaction products, and the like, and 28.9 g of a reaction product (yield: 96%) was obtained.
  • this fraction was analyzed by NMR and IR, it was ascertained that the fraction is a, -trimethylsilyl((2-naphthyl)ethyl)-polydimethylsiloxane (degree of polymerization: 25).
  • thermally conductive silicone composition of the present invention will be described in detail hereinafter.
  • viscosity and the thermal conductivity of the thermally conductive silicone composition were measured as follows.
  • the viscosity of the thermally conductive silicone composition at 25°C was measured using a rheometer (AR550) manufactured by TA Instruments. For the geometry, a parallel plate having a diameter of 20 mm was used. The gap was 200 pm, and the shear rate was 10.0 (1 /s). A small viscosity value means that the viscosity of the thermally conductive silicone composition is smaller, thus indicating superior handleability.
  • the heat resistance at 25°C of a thermally conductive silicone grease composition with an area of 1 cm x 1 cm and a thickness of 200 pm and 500 ⁇ was measured with a C-Therm TCi thermal conductivity measurement device manufactured by C-Therm Corp., and the thermal conductivity was determined from this value.
  • Thermally conductive silicone compositions were prepared using the same method as in
  • Example 1 as an organopolysiloxane and switching to the compositions indicated in Table 1.
  • Thermally conductive silicone compositions were prepared using the same method as in Working Example 5 with the exception of using the organopolysiloxane indicated in Table 2 instead of the substance obtained in Working Example 1 as an organopolysiloxane and switching to the compositions indicated in Table 2.
  • the viscosities (shear rate: 10.0 (1/s)) and thermal conductivities of these thermally conductive silicone compositions are shown in Table 2.
  • the organopolysiloxanes of these Comparative Examples were used, the resulting compositions did not form uniform pastes, and it was not possible to measure the thermal conductivity thereof.
  • CH 2 CH(CH 2 ) 2 SiO((CH 3 )2SiO) n Si(CH 3 ) 2
  • 25.6 parts by mass of boron nitride having an average particle size of 20 pm, 0.09 parts by mass of tetravinyl tetramethyl cyclotetrasiloxane, and 0.9 parts by mass of a platinum complex of 1 ,3-divinyltetramethyldisiloxane having a platinum content of 0.5 mass% were loaded into a 100 milliliter vessel.
  • This composition was heated for 15 minutes at 150°C so as to perform a hydrosilylation reaction, and a thermally conductive silicone cured product (thickness: 1 mm and 2 mm) was thereby prepared.
  • the thermal conductivity of this thermally conductive cured product was 5.5 W/m ⁇ K.
  • a thermally conductive silicone cured product was prepared with the same method as in Working Example 12 with the exception of using instead of
  • the viscosity (shear rate: 10.0 (1/s)) of this composition prior to curing was 350, and it was difficult to obtain a uniform cured product since the viscosity was too high.

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Abstract

L'invention concerne un organopolysiloxane représenté par la formule : R6 3Si-R5-[SiR4 2 O]n-Si R3 (3-a)-[R2-R1]a (dans laquelle R1 représente un groupe hydrocarboné monovalent ayant une pluralité de noyaux aromatiques ayant au moins 10 atomes de carbone; R2 représente un groupe hydrocarboné divalent qui peut contenir un hétéroatome ou une liaison directe à un atome de silicium (Si); chacun parmi R3 et R4 représente indépendamment un groupe hydrocarboné monovalent; R5 représente un groupe hydrocarboné divalent qui peut contenir un hétéroatome ou un atome d'oxygène; chaque R6 représente un groupe indépendamment choisi parmi des groupes alkyle, des groupes alcényle, des groupes aryle et des groupes alkoxy, n est un entier de 0 à 200; et a est un entier de 1 à 3); son utilisation en tant qu'agent de traitement de surface et une composition de résine comportant l'organopolysiloxane et une charge fonctionnelle.
PCT/JP2014/071692 2013-08-14 2014-08-13 Nouvel organopolysiloxane, agent de traitement de surface le comportant, composition de résine le comportant et son produit gélatineux ou son produit durci WO2015023001A1 (fr)

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