JP2016534161A - Novel organopolysiloxane, surface treatment agent containing the same, resin composition containing the same, and gel or cured product thereof - Google Patents

Abstract

Formula (1): wherein R1 to R6 are groups as defined in the specification, n is an integer from 0 to 200, and a is an integer from 1 to 3. Organopolysiloxane, its use as a surface treatment agent and a resin composition containing it and a functional filler.

Description

  The present invention relates to a novel organopolysiloxane, a surface treatment agent containing the same, and a resin composition containing the same, and particularly preferably relates to a thermally conductive silicone composition.

  Selected from heat conductive filler, fluorescent filler, conductive filler, dielectric filler, insulating filler, light diffusing filler, translucent filler, coloring filler and reinforcing filler Functional fillers are widely used in industry since they can provide greases, gels, rubber-like cured products, coating agents, phase change materials, and the like having various functions when blended in resin compositions. . In recent years, various types of thermally conductive silicone compositions have been developed to efficiently dissipate heat as printed circuit boards and hybrid ICs equipped with electronic components such as transistors, ICs, and memory devices have become more dense and highly integrated. Is used. As such a heat conductive silicone composition, a heat conductive silicone grease, a heat conductive silicone gel composition, a heat conductive silicone rubber composition, and the like are known.

  As such a heat conductive silicone composition, for example, a heat conductive silicone composition containing silicone oil as a main component and containing an inorganic filler such as zinc oxide or alumina powder (Japanese Patent Laid-Open No. 50-105573, special feature). From JP-A-51-55870 and JP-A-61-157587), an organopolysiloxane, an organopolysiloxane having an alkoxy group or an acyloxy group bonded to a silicon atom, a thermally conductive filler, and a curing agent. A thermally conductive filler that is surface-treated with a thermally conductive silicone composition (see JP 2000-256558 A), an organopolysiloxane, a curing agent, and a silalkylene oligosiloxane having an alkoxy group bonded to a silicon atom. Thermally conductive silicone composition (see JP 2001-139815 A) ) It has been proposed.

JP 50-105573 A JP-A 51-55870 JP-A 61-157487 JP 2000-256558 A JP 2001-139815 A

  However, in a resin composition containing a functional filler, particularly in a thermally conductive silicone composition, the components proposed as the surface treatment agent include many compounds having a hydrolyzable group such as an alkoxysilyl group. . These hydrolyzable groups are effective to some extent for metal oxides having hydroxyl groups on the surface such as alumina, but are ineffective for functional fillers that do not have hydroxyl groups on the surface such as boron nitride and graphite. When trying to fill highly with a functional filler, especially a heat conductive filler, there was a problem that the viscosity of the resulting composition suddenly increased and handling operability was significantly reduced. For this reason, in the surface treatment agent using a known organopolysiloxane, the performance of the resulting composition is insufficient because various functional fillers cannot be highly filled into the resin composition. There was a problem that the performance and performance could not be compatible.

  The present invention has been made to solve the above-mentioned problems, and even if a large amount of various functional fillers are blended in the resin composition, problems such as thickening and poor dispersion are unlikely to occur. It is intended to provide a novel organopolysiloxane that improves the viscosity and a surface treatment agent containing the same, particularly a functional resin composition. In particular, the present invention relates to a novel organopolysiloxane having a high thermal conductivity, even if a large amount of a thermal conductive filler is contained in order to obtain a high thermal conductivity silicone composition, and a high thermal conductivity. It is providing the heat conductive silicone composition containing this.

（式中、
Ｒ^１は、複数の芳香環を有する炭素原子数１０以上の一価の炭化水素基であり、
Ｒ^２は、ヘテロ原子を含んでもよい二価の炭化水素基又はケイ素（Ｓｉ）原子への直接結合であり、
Ｒ^３及びＲ^４は、それぞれ独立して、一価の炭化水素基であり、
Ｒ^５はヘテロ原子を含んでもよい二価の炭化水素基又は酸素原子であり、
Ｒ^６は、それぞれ独立して、アルキル基、アルケニル基、アリール基及びアルコキシ基から選ばれる基であり、
ｎは０から２００の整数であり、
ａは１から３の整数である。）
で表されるオルガノポリシロキサンによって達成される。 As a result of intensive studies on the above problems, the present inventors have reached the present invention. That is, the object of the present invention is the following formula (1):

(Where
R ¹ is a monovalent hydrocarbon group having 10 or more carbon atoms having a plurality of aromatic rings,
R ² is a divalent hydrocarbon group that may contain a hetero atom or a direct bond to a silicon (Si) atom;
R ³ and R ⁴ are each independently 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 an alkyl group, an alkenyl group, an aryl group and an alkoxy group;
n is an integer from 0 to 200;
a is an integer of 1 to 3. )
It is achieved by an organopolysiloxane represented by:

  Moreover, this invention relates also to the surface treating agent containing the said organopolysiloxane.

  The surface treatment agent of the present invention can be suitably used for surface treatment of various functional fillers, and in particular, heat conductive fillers, fluorescent fillers, conductive fillers, dielectric fillers, insulating properties. It is used for the surface treatment of one type or two or more types of fillers selected from fillers, light diffusing fillers, translucent fillers, coloring fillers and reinforcing fillers.

  The surface treatment agent containing the organopolysiloxane of the present invention is selected from inorganic fillers, organic fillers, nanocrystalline structures, quantum dots, and fillers in which part or all of these surfaces are covered with a silica layer. It can be used for the surface treatment of one kind or two or more kinds of fillers. In addition, these surface treating agents can also be used in the synthesis | combination process of various functional fillers.

  The present invention also relates to a resin composition comprising the organopolysiloxane and a filler whose surface is treated with the organopolysiloxane. These resin compositions may be curable resin compositions, thermoplastic resin compositions, or non-curable or thickening resin compositions.

  The resin composition of the present invention can be used in various applications depending on the type of functional filler and resin, and in particular, a heat conductive material, a conductive material, a semiconductor encapsulating material, an optical material, a functional property. It can be used for applications selected from paints and cosmetics.

  The resin composition of the present invention is particularly preferably thickened, curable or phase changeable. Thickening means that the initial viscosity does not change greatly, but the total viscosity increases by heating or using a thickener under the desired use conditions, and a gel-like or viscous liquid or paste The grease composition etc. can be illustrated. Curability is cured by heating or the like, and in addition to a hard coat resin composition and a semiconductor encapsulating resin composition, etc., a resin composition that can be molded into a sheet, and a resin that is cured into a flexible gel. Examples thereof include a composition and a semi-curable resin composition that forms a soft rubber having plasticity. Phase change is exemplified by a so-called phase change material in which a functional filler is filled in a heat softening resin having a softening point, such as wax, and the phase changes according to the operating temperature of an exothermic electronic component, etc. it can.

  In particular, the present invention also relates to a thermally conductive silicone composition comprising (A) an organopolysiloxane of formula (1) and (B) a thermally conductive filler.

  The silicone composition of the present invention can further contain (C) at least one organopolysiloxane other than the organopolysiloxane of the formula (1).

  The (B) thermally conductive filler is selected from the group consisting of pure metal, alloy, metal oxide, metal hydroxide, metal nitride, metal carbide, metal silicide, carbon, soft magnetic alloy and ferrite. It is preferably at least one kind of powder and / or fiber.

The pure metal is bismuth, lead, tin, antimony, indium, cadmium, zinc, silver, copper, nickel, aluminum, iron, or metallic silicon, or
The alloy is an alloy composed of two or more metals selected from the group consisting of bismuth, lead, tin, antimony, indium, cadmium, zinc, silver, copper, nickel, aluminum, iron and metallic 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 nanotube, graphene, activated carbon, or amorphous carbon black, or
The soft magnetic alloy includes Fe-Si alloy, Fe-Al alloy, Fe-Si-Al alloy, Fe-Si-Cr alloy, Fe-Ni alloy, Fe-Ni-Co alloy, Fe-Ni-Mo alloy, Fe -Co alloy, Fe-Si-Al-Cr alloy, Fe-Si-B alloy or Fe-Si-Co-B alloy, or
The ferrite is preferably Mn—Zn ferrite, Mn—Mg—Zn ferrite, Mg—Cu—Zn ferrite, Ni—Zn ferrite, Ni—Cu—Zn ferrite or Cu—Zn ferrite.

  The (B) thermally conductive filler is (B1) plate-like boron nitride powder having an average particle size of 0.1 to 30 μm, and (B2) granular nitriding having an average particle size of 0.1 to 50 μm. Boron powder, (B3) spherical and / or crushed aluminum oxide powder having an average particle size of 0.01 to 50 μm, or (B4) graphite having an average particle size of 0.01 to 50 μm, or these two types A mixture of the above is particularly preferred.

  It is preferable that content of the said (B) component is 100-3,500 mass parts with respect to a total of 100 mass parts of the said (A) component and the said (C) component.

  The organopolysiloxane of component (C) preferably has a hydrolyzable functional group bonded to a silicon atom in the molecule.

  The component (C) includes an organopolysiloxane having a monovalent hydrocarbon group having an aliphatic unsaturated bond bonded to a silicon atom in the molecule, and an organopolysiloxane having a hydrogen atom bonded to a silicon atom in the molecule. It is preferably a siloxane and further contains a catalyst for thickening or curing these organopolysiloxanes by a hydrosilylation reaction.

  In addition, the component (C) is an organopolysiloxane having a hydrolyzable functional group bonded to a silicon atom in the molecule and a monovalent hydrocarbon group having an aliphatic unsaturated bond bonded to a silicon atom. It is preferable to include a siloxane and an organopolysiloxane having a hydrogen atom bonded to a silicon atom in the molecule, and further a catalyst for thickening or curing the organopolysiloxane by a hydrosilylation reaction.

  The present invention also relates to a gel or cured product obtained by thickening or curing the silicone composition containing a catalyst for thickening or curing by a hydrosilylation reaction.

  The novel organopolysiloxane according to the present invention is useful as a surface treatment agent for various functional fillers, and a large amount of various functional fillers are blended into a resin composition without impairing handling workability and dispersion stability. There are advantages you can do. In particular, the novel organopolysiloxane according to the present invention is useful for surface treatment of a thermally conductive filler, and the thermally conductive silicone composition of the present invention is thermally conductive to obtain a highly thermally conductive silicone composition. Even when the filler is contained in a large amount, the viscosity of the composition is not increased and the handling workability is good. In the case of a curable composition, a uniform cured product can be obtained.

  First, the novel organopolysiloxane according to the present invention will be described in detail. In the composition, the organopolysiloxane is treated as “component (A)”.

で表されるオルガノポリシロキサンである。 The organopolysiloxane of the present invention has the formula (1):

It is organopolysiloxane represented by these.

R ¹ is a monovalent hydrocarbon group having 10 or more carbon atoms having a plurality of aromatic rings, and may contain an oxygen atom or a sulfur atom. In addition, a plurality of aromatic rings may be condensed and preferably condensed. More preferably, R ¹ is a monovalent hydrocarbon group having 10 to 40 carbon atoms having a plurality of aromatic rings. Examples of the monovalent hydrocarbon group having 10 or more carbon atoms having a plurality of aromatic rings include a naphthyl group, an alkylnaphthyl group, an anthracenyl group, a biphenyl group, a phenylnaphthyl group, a phenylanthracenyl group, and a phenyl group. Phenanthrenyl group, phenylpyrenyl group, terphenylene group, phenylterphenylene group, alkylbiphenyl group, carbonylbiphenyl group, alkoxyalkylbiphenyl group, alkoxynaphthyl group, acyloxynaphthyl group, alkoxycarbonylnaphthyl group, alkyl ether naphthyl group A phenoxyphenyl group, a phenylcarbonyloxyphenyl group, and the like. Preferably, R ¹ is 1-naphthyl group, 2-naphthyl group, o-biphenyl group, m-biphenyl group, p-biphenyl group, p-biphenyl ether group, p-methylnaphthyl group and p-ethylnaphthyl group. is there. Particularly preferably, R ¹ is a 1-naphthyl group or a 2-naphthyl group.

式中「ＣＯ」は-Ｃ（＝Ｏ）−で示されるカルボニル基であり、Ｒ^７は、それぞれ独立に、置換若しくは非置換の、直鎖状若しくは分岐鎖状の、炭素原子数２〜２２のアルキレン基若しくはアルケニレン基、又は、炭素原子数６〜２２のアリーレン基を表す。また、Ｒ^８は、Ｒ^７と同様の基又は下記式で示される二価基から選択される基である。

R ² is a divalent hydrocarbon group which may contain a hetero atom or a direct bond to a silicon (Si) atom, for example, a silicon-bonded hydrogen atom and an unsaturated hydrocarbon such as an alkenyl group, an acryloxy group or a methacryloxy group A group formed by the addition reaction of a functional group having a terminal group, or a group formed by the reaction of a silanol group with a hydrolyzable functional group such as a halogen atom, an alkoxy group and an acyloxy group; it can. The structure is, for example, a divalent linking group represented by the following structural formula or a direct bond to a Si atom.

In the formula, “CO” is a carbonyl group represented by —C (═O) —, and each R ⁷ is independently a substituted or unsubstituted, linear or branched chain having 2 to 22 carbon atoms. An alkylene group or an alkenylene group, or an arylene group having 6 to 22 carbon atoms. R ⁸ is a group selected from the same group as R ⁷ or a divalent group represented by the following formula.

Specifically, R ² is methylene group, ethylene group, methylmethylene group, propylene group, methylethylene group, butylene group, phenylene group, methylenephenylmethyl group, ethylenephenethyl group, oxygen atom, methylene ether group, ethylene group. It is a group selected from a real group, a propylene ether group, a butylene ether group, a phenyl ether group, a phenylcarbonyl group, a carbonyl ether group, an oxycarbonyl group, a methylenecarbonyl group, an ethylenecarbonyl group and a propylenecarbonyl group. R ² is particularly preferably a methylene group, an ethylene group, a methylmethylene group, a propylene group, a methylethylene group, an oxygen atom, an oxymethylene group or an oxyethylene group in view of the availability of raw materials and the ease of synthesis.

R ³ and R ⁴ are each independently a monovalent hydrocarbon group, preferably a monovalent hydrocarbon group having 1 to 10 carbon atoms that does not have an aliphatic unsaturated bond. For example, linear alkyl groups such as methyl, ethyl, propyl, butyl, hexyl and decyl groups; branched alkyl groups such as isopropyl, tertiary butyl and isobutyl groups; cyclic such as cyclohexyl groups Alkyl groups; aryl groups such as phenyl, tolyl and xylyl; and aralkyl groups such as benzyl and phenethyl. R ³ and R ⁴ are preferably an alkyl group having 1 to 4 carbon atoms or a phenyl group, and particularly preferably a methyl group, an ethyl group or a phenyl group.

R ⁵ is a divalent hydrocarbon group or an oxygen atom which may contain a hetero atom, and may contain an oxygen atom or a sulfur atom. Preferably, R ⁵ is a divalent hydrocarbon group having 1 to 20 carbon atoms or an oxygen atom, or a divalent hydrocarbon group having 1 to 20 carbon atoms containing 1 to 2 oxygen atoms, For example, the bivalent coupling group or oxygen atom (-O-) shown by the following structural formula is mentioned. In the formula, CO, R ⁷ and R ⁸ are the same groups as described above.

Specifically, R ⁵ is a methylene group, ethylene group, methylmethylene group, propylene group, methylethylene group, butylene group, phenylene group, methylenephenylmethyl group, ethylenephenethyl group, oxygen atom, methylene ether group, ethylene ether. Group, propylene ether group, butylene ether group, phenyl ether group, phenylcarbonyl group, carbonyl ether group, oxycarbonyl group, methylenecarbonyl group, ethylenecarbonyl group, propylenecarbonyl group, ethylenecarboxylpropyl group and (methyl) ethylenecarboxylpropylene group It is a group selected from Particularly preferably, R ⁵ is a methylene group, an ethylene group, a methylmethylene group, a propylene group, a methylethylene group, an oxygen atom, an oxymethylene group, an oxyethylene group, or an ethylene carboxyl group because of the availability of raw materials or the ease of synthesis. A propyl group or a (methyl) ethylenecarboxylpropylene group.

R ⁶ is each independently a group selected from an alkyl group having 1 to 20 carbon atoms, an alkenyl group, an aryl group, and an alkoxy group. Examples of R ⁶ include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl Linear alkyl groups such as a group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group and eicosyl group; branched alkyl groups such as 2-methylundecyl group and 1-hexylheptyl group; cyclic such as cyclododecyl group An alkyl group; an aralkyl group such as 2- (2,4,6-trimethylphenyl) propyl group; a hydrocarbon group having an unsaturated bond such as a vinyl group, an allyl group, a butenyl group, a hexenyl group, and an octenyl group; a phenyl group; Aryl groups such as tolyl and xylyl groups; and aralkyl groups such as benzyl and phenethyl groups; And so on.

  n is an integer from 0 to 200, a is an integer from 1 to 3, and p is an integer from 0 to 10.

  Since the organopolysiloxane (A) contained as a component of the present invention has a functional group having two or more aromatic rings, it has an affinity for a filler having a plate-like structure or consisting of polycyclic aromatics. When a composite material such as grease, compound, or gel is used for a surface treatment agent or base oil, the miscibility is improved and the viscosity can be suppressed from increasing.

Examples of such organopolysiloxane include the following compounds. However, Me denotes a CH ₃ group.

  Although the manufacturing method of organopolysiloxane (A) used for this invention is not specifically limited, It is possible to manufacture with the following method.

（ただし、Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４は、前記同様の基であり。ｎ、ａ及びｂは前記同様の数である。）
で表されるケイ素原子結合水素原子含有オルガノポリシロキサンと、
（ｂ−１）一分子中に脂肪族二重結合を複数有する、酸素原子又は硫黄原子を含んでいてもよい炭素原子数１０から４０の一価の炭化水素化合物又は有機ケイ素化合物と
をヒドロシリル化反応により付加反応させることにより得ることが可能である。 (A-1) General formula:

(However, R ¹ , R ² , R ³ and R ⁴ are the same groups as described above. N, a and b are the same numbers as described above.)
A silicon-bonded hydrogen atom-containing organopolysiloxane represented by:
(B-1) Hydrosilylation of a monovalent hydrocarbon compound or organosilicon compound having 10 to 40 carbon atoms, which may contain an oxygen atom or a sulfur atom, having a plurality of aliphatic double bonds in one molecule It can be obtained by addition reaction.

（式中、Ｒ^３Ｒ^４、Ｒ^５及びＲ^６は前記同様の基である。ｎ及びａは前記同様の数である。）
で表されるケイ素原子結合水素原子含有ポリシロキサンと、
（ｂ−２）一分子中に脂肪族二重結合を一個以上有し、且つ、複数の芳香環を有する官能基を含有する、酸素原子又は硫黄原子を含んでいてもよい炭素原子数１０以上の一価の炭化水素化合物又は有機ケイ素化合物と
をヒドロシリル化反応により付加反応させることにより得ることが可能である。 Or
(A-2) General formula:

(In the formula, R ³ R ⁴ , R ⁵ and R ⁶ are the same groups as described above. N and a are the same numbers as described above.)
A silicon-bonded hydrogen atom-containing polysiloxane represented by:
(B-2) 10 or more carbon atoms that contain one or more aliphatic double bonds in one molecule and contain a functional group having a plurality of aromatic rings, and may contain an oxygen atom or a sulfur atom Can be obtained by addition reaction of a monovalent hydrocarbon compound or organosilicon compound with a hydrosilylation reaction.

（式中、Ｒ^３、Ｒ^４、Ｒ^５及びＲ^６は前記同様の基である。ｎ及びａは前記同様の数である。）
で表されるケイ素原子結合水酸基含有オルガノポリシロキサンと、
Ｒ_ｂＳｉＸ_{（４−ｂ）}
（式中、Ｒは、複数の芳香環を有する官能基を含有する、炭素原子数１０以上の一価の炭化水素基であり、Ｘはハロゲン原子、アルコキシ基及びアシロキシ基等の加水分解性を有する官能基であり、ｂは１から４の整数である）
で表される有機ケイ素化合物と
を置換反応させることにより得ることが可能である。 Furthermore, as a method not using a hydrosilylation reaction,

(In the formula, R ³ , R ⁴ , R ⁵ and R ⁶ are the same groups as described above. N and a are the same numbers as described above.)
A silicon atom-bonded hydroxyl group-containing organopolysiloxane represented by:
R _b SiX _(4-b)
(In the formula, R is a monovalent hydrocarbon group having 10 or more carbon atoms containing a functional group having a plurality of aromatic rings, and X is hydrolyzable such as a halogen atom, an alkoxy group, and an acyloxy group. And b is an integer of 1 to 4)
It can obtain by carrying out a substitution reaction with the organosilicon compound represented by these.

  The functional group having a plurality of aromatic rings, which is a feature of the present invention, is included in the raw material (a-1) or the raw material (b-2).

  Examples of the silicon atom-bonded hydrogen atom-containing organopolysiloxane (a-1) containing functional groups having a plurality of aromatic rings include the following compounds.

  Examples of (b-1) hydrocarbon compounds or organosilicon compounds having one or more aliphatic double bonds in one molecule and not having a plurality of aromatic functional groups include ethylene, acetylene, 1-propene, 1 -Butene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1,3-butadiene, 1,5-hexadiene, 1,7-octadiene, 1 , 9-decadiene, vinyltrimethylsilane, vinyltriethylsilane, vinylethyldimethylsilane, vinylpropyldimethylsilane, vinyldiethylmethylsilane, vinyl (t-butyl) dimethylsilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyldimethylmethoxy Silane, vinyltriethoxysilane, vinyl methyl Diethoxysilane, vinyldimethylethoxysilane, vinyltriisopropoxysilane, vinyltriacetoxysilane, vinylmethyldiacetoxysilane, vinyltris (methylethylketoiminoxy) silane, vinyltriisopropenoxysilane, vinylpentamethyldisiloxane, trivinyltris (Trimethyl) silane, vinyltris (trimethoxysiloxy) silane, vinylmethylbis (trimethylsiloxy) silane, vinylheptamethyltrisiloxane, allyltrimethylsilane, allyltrimethoxysilane, allyltriethoxysilane, allyltris (trimethylsiloxy) silane, 5 -Hexenyltrimethoxysilane, 5-hexenylmethyldimethoxysilane, 5-hexenyldimethylmethoxysilane, 5-hexenyltri Toxisilane, 5-hexenylmethyldiethoxysilane, 5-hexenyldimethylethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyldimethylmethoxysilane, 3-methacryloxypropyltri And ethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-acryloxypropylmethyldimethoxysilane.

が挙げられる。 Examples of silicon atom-bonded hydrogen atom-containing organopolysiloxane (a-2) not containing a functional group having a plurality of aromatic rings include pentamethyldisiloxane, ethyltetramethyldisiloxane, n-propyltetramethyldisiloxane, iso- Propyltetramethyldisiloxane, n-butyltetramethyldisiloxane, iso-butyltetramethyldisiloxane, n-hexyltetramethyldisiloxane, n-octyltetramethyldisiloxane, n-decyltetramethyldisiloxane, n-dodecyltetra Methyldisiloxane, n-tetradecyltetramethyldisiloxane, n-hexadecyltetramethyldisiloxane, n-octadecyltetramethyldisiloxane,

Is mentioned.

  (B-2) Examples of raw materials containing a functional group having a plurality of aromatic rings in a hydrocarbon compound or organosilicon compound having one or more aliphatic double bonds in one molecule include vinyl naphthalenes, vinyl Anthracene, vinyl phenanthrene, vinyl pyrene, vinyl biphenyl, vinyl terphenyl, vinyl phenyl naphthalene, vinyl phenyl anthracene, vinyl phenyl phenanthrene, vinyl phenyl pyrene, vinyl phenyl terphenyl, phenoxy styrene, phenyl Carbonylstyrenes, phenylcarboxystyrenes, phenoxycarbonylstyrenes, allylnaphthalenes, allylanthracenes, allylphenanthrenes, allylpyrenes, allylbiphenyls, allylterphenyls, allylphenylna Talenes, allylphenylanthracenes, allylphenylphenanthrenes, allylphenylpyrenes, allylphenylterphenyls, allylphenoxybenzenes, allyl (phenylcarbonyl) benzenes, allyl (phenylcarboxy) benzenes and allyl (phenoxycarbonyl) Examples include benzenes.

  More specifically, 1-vinylnaphthalene, 2-vinylnaphthalene, 1-vinylanthracene, 2-vinylanthracene, 9-vinylanthracene, 1-vinylphenanthrene, 2-vinylphenanthrene, 3-vinylphenanthrene, 4-vinylphenanthrene. 9-vinylphenanthrene, 1,2-vinylphenylbenzene, 1,3-vinylphenylbenzene, 1,4-vinylphenylbenzene, 1,2-vinyl (1-naphthyl) benzene, 1,2-vinyl (2- Naphthyl) benzene, 1,3-vinyl (1-naphthyl) benzene, 1,3-vinyl (2-naphthyl) benzene, 1,4-vinyl (1-naphthyl) benzene, 1,4-vinyl (2-naphthyl) Benzene, 1-naphthyl-4-vinylnaphthalene, 4-vinyl-1,1 ′-(4′-fu Nyl) biphenylene, 1-allylnaphthalene, 2-allylnaphthalene, 1-allylanthracene, 2-allylanthracene, 9-allylanthracene, 1-allylphenanthrene, 2-allylphenanthrene, 3-allylphenanthrene, 4-allylphenanthrene, 9 -Allylphenanthrene, 1,2-allylphenylbenzene, 1,3-allylphenylbenzene, 1,4-allylphenylbenzene, 1,2-allyl (1-naphthyl) benzene, 1,2-allyl (2-naphthyl) Benzene, 1,3-allyl (1-naphthyl) benzene, 1,3-allyl (2-naphthyl) benzene, 1,4-allyl (1-naphthyl) benzene, 1,4-allyl (2-naphthyl) benzene, 1-allyl-4-naphthylnaphthalene, 4-vinyl-1,1 ′-(4 -Phenyl) biphenylene, 1-vinyl-4- (phenyloxy) benzene, 1-vinyl-3- (phenyloxy) benzene, 1-vinyl-2- (phenyloxy) benzene, 1-vinyl-4- (phenylcarbonyl) ) Benzene, 1-vinyl-3- (phenylcarboxy) benzene, 1-vinyl-2- (phenoxycarbonyl) benzene, 1-allyl-4- (phenyloxy) benzene, 1-allyl-3- (phenyloxy) benzene 1-allyl-2- (phenyloxy) benzene, 1-allyl-4- (phenylcarbonyl) benzene, 1-allyl-3- (phenylcarboxy) benzene, 1-allyl-2- (phenoxycarbonyl) benzene, and the like. Illustrated.

  The hydrosilylation reaction is usually performed using a metal complex catalyst, but is not particularly limited in the production method of the present invention. In the catalyst used in the production method of the present invention, the silicon atom-bonded hydrogen atom in the raw material (a-1) or (a-2) is an aliphatic double bond in the component (b-1) or (b-2). A catalyst that promotes the reaction to be added to the catalyst, for example, a Group VIII transition metal catalyst of the long periodic table, preferably a platinum-based catalyst, specifically, chloroplatinic acid, platinum chloride Examples include acid alcohol solutions, platinum olefin complexes, platinum alkenylsiloxane complexes, and platinum carbonyl complexes.

  In the production method of the present invention, the molar ratio of the component (a-1) and the component (b-1) or the component (a-2) and the component (b-2) is not particularly limited, but the component (a-1) or (A-2) The component (b-1) or the component (b-2) is preferably reacted in an amount of 0.5 to 1.5 mol per mol of the component (a-2). It is particularly preferable to react in an amount of 1 mol.

  Moreover, it is arbitrary to use an organic solvent in the production method of the present invention. Examples of the 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; acetone and methyl ethyl ketone Ketones; and esters such as ethyl acetate and butyl acetate.

  Moreover, in the manufacturing method of this invention, reaction temperature is not specifically limited, It can carry out under room temperature or a heating. When the reaction is performed under heating, the reaction temperature is preferably 50 to 200 ° C. In addition, the progress of the reaction is performed by analyzing the reaction solution by a method such as gas chromatography analysis, infrared spectroscopic analysis or nuclear magnetic resonance analysis, and the residual ratio of raw materials in the reaction system, silicon-bonded hydrogen atoms or aliphatic unsaturation, respectively. This can be followed by determining the group content. After completion of the reaction, the desired organopolysiloxane can be obtained by removing unreacted components and organic solvent.

  In addition, as one of the methods for producing the organopolysiloxane of the present invention, a siloxane (c) having a hydroxyl group at one end, a substituent having a plurality of aromatic functional groups, and an organic silicon having one hydrolyzable group A method of reacting the compound (d) is also mentioned.

が例示され、これらの片方の末端に水酸基を有するポリシロキサンは、既知の製造方法（特開平８−１１３６４９号公報及び特許２８２６９３９号公報）に従って得ることができる。 As the siloxane (c) having a hydroxyl group at one terminal, the following compounds:

These polysiloxanes having a hydroxyl group at one end can be obtained according to known production methods (Japanese Patent Laid-Open Nos. 8-113649 and 28826939).

  Moreover, as the organosilicon compound (d) having a substituent having a plurality of aromatic functional groups and one hydrolyzable group, 1-naphthylchlorodimethylsilane, 1-naphthyldimethylmethoxysilane, 1-naphthyldimethylethoxysilane, 2-naphthylchlorodimethylsilane, 1-anthracenylchlorodimethylsilane, 1-anthracenyldimethylmethoxysilane, 2-anthracenylchlorodimethylsilane, 9-anthracenyldimethylmethoxysilane, 1-phenanthrenyldimethyl Methoxysilane, 2-phenanthrenyldimethylmethoxysilane, 1,4-phenyl (dimethylmethoxysilyl) benzene, 1,4-phenyl (dimethylmethoxysilyl) benzene, 1,4- (1′-naphthyl) (chlorodimethyl) Silyl) benzene, 4,4'-di Tylmethoxysilyl (phenyl) -1,1′-biphenylene, 1,4-chlorodimethylsilyl (phenyloxy) benzene, 1,2-dimethylmethoxysilyl (phenyloxy) benzene, 1,3-dimethylmethoxysilyl (phenyloxy) ) Benzene, 1,4-dimethylmethoxysilyl (phenylcarbonyl) benzene, 1,3-dimethylmethoxysilyl (phenylcarboxy) benzene, 1,2-dimethylmethoxysilyl (phenoxycarbonyl) benzene, and the like.

  These organosilicon compounds can be synthesized in accordance with the method described in, for example, Journal of Organometallic Chemistry (1998), 550 (1-2), 283-300.

  When 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, it can be used only as a surface treatment agent. And can also be used as all or part of the main component of various functional resin compositions. For example, as the curable silicone resin composition, the organopolysiloxane having one or more condensation-reactive functional groups or hydrosilylation-reactive functional groups in the molecule, reactive silicone as a crosslinking agent, and various functions described later After adding a functional filler and a curing reaction catalyst and treating the surface of the functional filler in situ (integral blend method), the entire composition can be cured. In particular, since the organopolysiloxane of the present invention is excellent in blending stability with respect to a silicone resin composition (hereinafter, sometimes simply referred to as “silicone composition”), the functional filler in the cured product is obtained by the above curing reaction. Even if these functional fillers are blended in a large amount with excellent dispersibility and thermal stability, a cured product or a non-curable composition that is uniform throughout and excellent in desired functions can be obtained. There are advantages.

  The organopolysiloxane of the present invention has improved thermal stability and is provided with the surface hydrophobicity, fine dispersibility, and dispersion stability of a fine member having a fine particle shape or a highly refined structure. In particular, when used for the surface treatment of various functional fillers, even when these fillers are highly filled in the resin composition, the handling workability such as rapid thickening can be improved. By using the organopolysiloxane of the present invention as a surface treatment agent because there is no reduction, the resin composition can be highly filled with various functional fillers that could not be highly filled or stably dispersed by the conventionally known surface treatment. There is an advantage that a resin composition having high performance and excellent handling workability can be obtained. Hereinafter, the use of the surface treatment agent of the organopolysiloxane of the present invention will be described.

  The surface treatment agent of the present invention contains the above organopolysiloxane, and particularly preferably contains 50% by mass or more of the above organopolysiloxane as a main component. On the other hand, the surface treatment agent of the present invention may be used after diluting in a conventionally known solvent and the like, as long as it does not contradict the purpose of the present invention, antioxidant, anti-aging agent, pigment, dye, other organic Other additives such as silanol condensation catalysts such as silicon compounds such as silane coupling agents and silylating agents, organic titanate compounds, organic aluminate compounds, organotin compounds, waxes, fatty acids, fatty acid esters, fatty acid salts, organotin compounds May be added. Other surface treatment compounds included in the surface treatment agent of the present invention include, for example, methyl (trimethoxy) silane, ethyl (trimethoxy) silane, hexyl (trimethoxy) silane, decyl (trimethoxy) silane, vinyl (trimethoxy) silane, 2 -[(3,4) -epoxycyclohexyl] ethyl (trimethoxy) silane, 3-glycididoxypropyl (trimethoxy) silane, 3-methacryloxypropyl (trimethoxy) silane, 3-methacryloxypropyl (trimethoxy) silane, 3- Examples thereof include silane compounds such as acryloxypropyl (trimethoxy) silane and 1- (trimethoxy) 3,3,3-trimethylsiloxane. Moreover, you may contain another reactive silicone compound in the range which does not impair the effect of this invention.

  The surface treating agent of the present invention is useful for treating various substrate surfaces, and the substrate to be treated is not particularly limited. Examples of substrates that can be surface treated other than the various functional fillers described below include, for example, soda glass, heat ray reflective glass, vehicle glass, marine glass, aircraft glass, building glass, glass containers, and glass appliances. Glass; Metal plates such as copper, iron, stainless steel, aluminum, and zinc; Paper such as fine paper and straw half paper; Synthetic resin films such as polyester resin, polycarbonate resin, polystyrene resin, and acrylic resin; Natural fiber, synthetic fiber, etc. Fibers or fabrics; plastic substrates made of the above-mentioned synthetic resins; and various materials such as ceramics and ceramics.

  Furthermore, the surface treatment agent of the present invention is useful as a surface treatment agent for various functional fillers, and the surface properties of various functional fillers, such as hydrophobicity, cohesiveness, fluidity, polymers, particularly in curable resins. The dispersibility and compounding property can be improved. These functional fillers are not particularly limited, but the surface treatment agent of the present invention is a heat conductive filler, a fluorescent filler, a conductive filler, a dielectric filler, an insulating filler. , A light diffusing filler, a translucent filler, a coloring filler and a reinforcing filler can be used particularly suitably for the surface treatment of one or more fillers selected from these fillers. Even when the resin composition is highly filled in the resin composition, there is an advantage that a desired function can be improved without accompanying a decrease in handling workability such as a rapid thickening. At this time, the shape of the functional filler (spherical, rod-like, needle-like, plate-like, indefinite shape, spindle-like, bowl-like, etc.), particle diameter (smoke-like, fine particles, pigment grade, etc.), and particle structure (crystal , Porous, non-porous, etc.) is not limited at all, but the average primary particle diameter is preferably in the range of 1 nm to 100 μm. The shape and average primary particle size of the functional filler can be appropriately selected according to the intended use and function, and have a plurality of average primary particle sizes and the like in order to improve the filling rate. The use of a filler is included in the preferred form of the invention.

  As a method for treating the surface of such a functional filler, for example, while stirring the functional filler with a stirrer, the surface treatment agent or a solution thereof (including a dispersion in an organic solvent or the like is included at room temperature to 200 ° C. ) After spraying; the functional filler and the surface treatment agent or a solution thereof are mixed in a stirrer (including a pulverizer such as a ball mill and a jet mill, and an ultrasonic disperser) and then dried. And a treatment method in which a treatment agent is blended in a solvent, a functional filler is dispersed and adsorbed on the surface, and then dried and sintered. Furthermore, a method (integral blend method) in which a functional filler and a surface treatment agent are added to a resin to be blended with the functional filler and treated in-situ is exemplified. When the surface of the functional filler is treated, the amount of the surface treatment agent added is preferably 0.1 to 50 parts by mass with respect to 100 parts by mass of the functional filler, and particularly 0.1 to 25 parts. It is preferable that it is a mass part.

  In particular, the filler suitably treated with the surface treatment agent of the present invention is an inorganic filler, an organic filler, a nanocrystal structure, a quantum dot, and a filling in which a part or all of these surfaces are covered with a silica layer. One type or two or more types of fillers selected from the materials. These are particularly known as raw materials for heat conductive materials, conductive materials, semiconductor sealing materials, optical materials, functional paints, cosmetics, etc., and the surface treatment agent of the present invention is the surface of these fillers. Suitable for treatment, particularly when used as a surface treatment agent for metal oxide fine particles having a particle diameter of 1 to 500 nm or a part or all of these surfaces coated with a silica layer, a hydrophobic curable resin, In particular, there is an advantage that the fine dispersibility and dispersion stability in the silicone resin can be remarkably improved, and the function of the resulting curable resin can be improved.

  The filler suitably treated with the surface treating agent of the present invention is an inorganic filler, and particularly preferably a heat conductive filler described later, but is not limited thereto.

The fluorescent filler is an inorganic fine particle, nanocrystal structure, quantum dot or the like that emits fluorescence having a wavelength longer than the wavelength of the excitation light when ultraviolet or visible excitation light is incident, and is particularly excited at a wavelength of 300 to 500 nm. One having a band and having an emission peak at a wavelength of 380 to 780 nm, particularly emitting blue (wavelength 440 to 480 nm), green (wavelength 500 to 540 nm), yellow (wavelength 540 to 595 nm), or red (wavelength 600 to 700 nm) It is preferable to use phosphor fine particles. As phosphor fine particles generally available on the market, garnets such as YAG and other oxides, nitrides, oxynitrides, sulfides, oxysulfides, rare earth sulfides, Y ₃ Al ₅ O ₁₂ : Ce, ( Y, Gd) ₃ Al ₅ O ₁₂ : Ce, Y ₃ (Al, Ga) ₅ O ₁₂ : Rare earth aluminate chlorides and halophosphoric acid mainly activated by lanthanoid elements such as Ce represented by Ce The thing which consists of chlorides etc. is mentioned. Specific examples of these phosphor fine particles include inorganic phosphor fine particles disclosed in JP2012-052018A.

  The phosphor fine particles to be treated using the surface treating agent of the present invention generally have an average particle size in the range of 0.1 to 300 μm, and are treated in a mixture with glass powder such as glass beads. May be. Furthermore, it may be used for processing a mixture of a plurality of phosphor fine particles in accordance with the wavelength range of excitation light or light emission. For example, when white light is obtained by irradiating ultraviolet excitation light, it is desirable to surface-treat a mixture of phosphor fine particles that emit blue, green, yellow, and red fluorescence.

  Nanocrystal structures, especially semiconductor nanocrystal structures, can control the emission wavelength according to the size of nanocrystals and particle diameters due to the quantum confinement effect. In particular, semiconductor nanocrystals called quantum dots It is useful as an optical material such as a light-emitting semiconductor such as an LED, particularly a light-emitting material, a radiator instead of a phosphor, or a wavelength conversion material in that it can control the wavelength of luminescent light emission by controlling the nanocrystal particle diameter. These nanocrystal structures consist of Si-based nanocrystals, II-VI group compound semiconductor nanocrystals, III-V group compound semiconductor nanocrystals, IV-VI group compound semiconductor nanocrystals, and mixtures thereof. In particular, II-VI group semiconductor nanocrystals represented by CdSe semiconductors, III-V group compound semiconductor nanocrystals represented by GaN semiconductors, and IV-VI group compound semiconductor nanocrystals represented by SbTe semiconductors are used. It has been. These semiconductor nanocrystals may be obtained by vapor phase growth at a high temperature, or may be colloidal semiconductor nanocrystals synthesized by an organic chemical method (including a liquid phase method). Further, it may have a core-shell structure.

  Nanocrystal structures used for light-emitting semiconductors and the like, in particular, the average particle diameter of quantum dots is in the range of about 0.1 nm to several tens of nm, and is selected according to the emission wavelength. By subjecting such nanocrystals to the surface treatment agent of the present invention, it is possible to orient or bond organopolysiloxane to the nanocrystal surface, prevent aggregation thereof, improve fine dispersion and dispersion stability, and cure. There is a possibility that the light emission characteristics and the light extraction efficiency in the conductive resin can be further improved.

  The conductive filler is a component used to impart conductivity to the composition, and various carbon blacks; metal powders such as silver, copper, iron, and aluminum; metal oxides such as zinc oxide and tin oxide; In addition, conductive coating fillers in which a core material such as barium sulfate or titanium oxide is coated are exemplified. In addition, various surfactants can be blended as conductivity-imparting assistants, and these may be used in combination. Some of these are components that also function as a thermally conductive filler.

  The dielectric filler is a ferroelectric filler, a paraelectric filler, or a combination of the two, which can impart a relatively high dielectric constant so that the composition can store a charge. . These dielectric fillers are: lead zirconate titanate, barium titanate, calcium metaniobate, bismuth metaniobate, iron metaniobate, lanthanum metaniobate, strontium metaniobate, lead metaniobate, lead metatantalate, barium strontium titanate Examples thereof include sodium barium niobate, potassium barium niobate, rubidium barium niobate, titanium oxide, tantalum oxide, hafnium oxide, niobium oxide, aluminum oxide and steatite. In particular, from the viewpoint of improving the dielectric constant, the treatment of barium titanate and titanium oxide is suitable, but is not limited thereto.

  The insulating filler imparts electrical insulation to the composition, and fumed silica, precipitated silica, fused silica, or the like can be used in addition to the thermally conductive filler described later. Some or all of these are components that also function as reinforcing fillers.

  The light diffusing filler is for imparting light diffusibility to the composition. In addition to calcium carbonate and barium sulfate, the crosslinked polymethyl methacrylate resin particles, silicone resin particles, polyorganosilsesquioxane particles, silica particles Examples thereof include quartz particles, silica fibers, quartz fibers, and glass fibers. These light diffusing fillers are used in the liquid crystal display field such as light diffusing plates, optical elements such as optical lenses and light guide plates, street light covers, vehicles and glass substitute applications such as laminated glass for building materials, Spherical silicone particles for the purpose of wrinkle concealment (soft focus) in cosmetics can also be suitably used.

  The light-transmitting filler is a fine particle having a high refractive index and a light scattering that can be ignored, and can impart a high refractive index and high transparency to the composition. The surface treating agent of the present invention can be suitably used for the surface treatment of metal oxide fine particles used for optical materials. The average particle diameter of the metal oxide fine particles used as the translucent filler is in the range of 1 to 500 nm, particularly preferably 1 to 100 nm. From the viewpoint of the transparency of the optical material containing the particles, 1 to 20 nm is preferable. More preferred. Furthermore, these metal oxide fine particles may be nanocrystalline particles having a crystallite diameter of 10 to 100 nm and are preferable for the purpose of improving optical, electromagnetic and mechanical properties of the optical material. Further, the translucent filler treated with the surface treating agent of the present invention has an advantage that it is excellent in heat resistance and hardly causes yellowing or discoloration when used in an optical semiconductor element or the like.

  Metal oxide fine particles are barium titanate, zirconium oxide, aluminum oxide (alumina), silicon oxide (silica), titanium oxide, strontium titanate, barium zirconate titanate, cerium oxide, cobalt oxide, indium tin oxide, hafnium oxide Yttrium oxide, tin oxide, niobium oxide, and iron oxide. In particular, a metal oxide containing at least one metal element selected from titanium, zirconium, and barium is preferable in terms of optical properties and electrical properties. Some of these are components that also function as a thermally conductive filler, a dielectric filler, or a reinforcing filler.

  In particular, zirconium oxide has a relatively high refractive index (refractive index 2.2), and thus is useful for optical material applications that require high refractive index and high transparency. Similarly, barium titanate has a high dielectric constant and refractive index, and is useful for imparting performance to organic materials both optically and electromagnetically. The surface treatment agent of the present invention enables fine and stable dispersion of the metal oxide fine particles in the hydrophobic curable resin by the surface treatment of the metal oxide fine particles such as barium titanate. Enables stable mass blending compared to products. As a result, there is an advantage that the optical properties (particularly, high refractive index) and electromagnetic properties of the resulting resin composition can be remarkably improved.

The reinforcing filler is a component for imparting high mechanical strength required depending on the use of the composition. Examples of such reinforcing fillers include fumed silica, precipitated silica, fused silica, and fumed titanium oxide. These reinforcing fillers may have a surface hydrophobized with polyorganosiloxanes other than the organopolysiloxane of the present invention, or hexamethyldisilazane. In particular, from the viewpoint of improving the mechanical strength, it is preferable to use a reinforcing filler having a specific surface area of 130 cm ² / g or more by the BET method.

  In addition, the surface treating agent of the present invention is a conventionally known reinforcing filler, and can be used for the treatment of a substrate used in a functional resin composition. Examples thereof include talc, clay, mica powder, glass powder (glass beads), glass frit, glass cloth, glass tape, glass mat and the like, or a part or all of these surfaces coated with a silica layer.

  The surface treatment agent of the present invention is used for the surface treatment of a swellable layered clay material, particularly a nanoclay material, which is formulated for the purpose of improving the mechanical properties, gas permeability or water vapor permeability of the functional resin composition. Thus, there is an advantage that the mechanical strength and gas permeability or water vapor permeability of the resin composition can be improved without impairing the blending amount and dispersion stability of other functional fillers. Here, “nanoclay” means a natural or synthetic, modified or unmodified ionic phyllosilicate having a predominantly layered structure, and smectite clay minerals such as montmorillonite, in particular sodium montmorillonite; bentonite; hectorite Saponite; stevensite; smectite and hectorite clay including phyllosilicates such as beidelite. Since the layered structure of nanoclay has a spread only in the one-dimensional direction in the nanometer range, delamination or swelling occurs easily, and can be separated from each other when incorporated into the resin composition. A thickness of less than 25 mm (about 2.5 nm), more preferably less than 10 mm (about 1 nm), most preferably 5-8 mm (about 0.5-0.8 nm), and an aspect ratio (length) greater than 10: 1 / Thickness) is preferable.

  The surface treating agent of the present invention can be further used in a synthesis process or a post-treatment process of the functional filler or a part or all of these surfaces coated with a silica layer. The method of use in the synthesis process or the post-treatment process is not particularly limited, but in the solid phase method, the functional filler before being refined or a part or all of these surfaces are covered with a silica layer. Examples of the method include treating the surface of the material with the surface treatment agent according to the present invention by the above method and then dispersing or finely pulverizing the material using mechanical force or ultrasonic waves. As an apparatus used for dispersion or pulverization, known means can be used without any particular limitation.

  The functional filler can be coated with the silica layer by a conventionally known method. For example, after dispersing these fine members in an appropriate solvent, an aqueous sodium silicate solution is added under acidic conditions. A method, a method of adding a silicic acid solution, or a method of hydrolyzing hydrolyzable tetrafunctional silanes in the presence of an acidic or basic catalyst can be used.

  On the other hand, the surface treating agent of the present invention can also be used for the synthesis of a functional filler by a liquid phase method. When the surface treatment agent of the present invention is used in the liquid phase synthesis method, the particle surface of the functional filler obtained is partially or entirely coated with the organopolysiloxane according to the present invention in the particle formation process. In addition to the advantage that fine and uniform dispersion can be performed in the redispersion step, the surface characteristics of the obtained fine member can be selected by selecting the refractive index of the organosilicon compound or the type of reactive functional group. There is an advantage that it can be designed as desired. Furthermore, by performing liquid phase synthesis in the state where the surface treatment agent of the present invention coexists, the surface-treated metal nanoparticles, semiconductor nanoparticles, core-shell nanoparticles, doped nanoparticles, nanorods, nano There is an advantage that fine members of various shapes such as plates can be synthesized by an integrated process.

  When the organopolysiloxane of the present invention and the filler whose surface is treated with the above organopolysiloxane are blended in various resin compositions, the handling workability and dispersion stability of various functional fillers are impaired. In addition, a large amount of various functional fillers can be blended in the resin composition, and there is an advantage that a resin composition in which these functional fillers are stably and highly filled can be obtained. Hereinafter, these resin compositions will be described.

  The resin portion constituting the resin composition is not particularly limited as long as the organopolysiloxane of the present invention can be mixed without impairing its practicality and the above-mentioned various functional fillers can be supported or dispersed. In particular, it is preferably thickened, curable or phase changeable.

  Here, the thickening means that the initial viscosity does not change greatly, but by heating or using a thickener under the desired use conditions, the overall viscosity is increased, resulting in a gel-like or viscous It exhibits a liquid or paste form, and examples thereof include a grease composition.

  Curability is cured by heating or the like, and in addition to a hard coat resin composition, a semiconductor sealing resin composition, etc., a resin composition that can be molded into a sheet form, a resin composition that is cured into a flexible gel form And a semi-curable resin composition forming a soft rubber having plasticity.

  Phase change is exemplified by a so-called phase change material in which a functional filler is filled in a heat softening resin having a softening point, such as wax, and the phase changes according to the operating temperature of an exothermic electronic component, etc. it can.

  Such a resin component is not particularly limited. For example, hydrocarbon resins such as polyethylene, polypropylene, polymethylpentene, polybutene, crystalline polyptadiene, polystyrene, and styrene-butadiene resin; polyvinyl chloride, and polyvinyl acetate Acrylic resins such as polymethyl methacrylate; polyvinylidene chloride; polytetrafluoroethylene; ethylene-polytetrafluoroethylene resin; ethylene-vinyl acetate resin; acrylonitrile-styrene (AS) resin; acrylonitrile-butadiene-styrene (ABS) resin; acrylonitrile-acrylate-styrene (AAS) resin; acrylonitrile-chlorinated polyethylene-styrene (ACS) resin; ionomer, linear structural yarn (Engineering Plus) Polyacetal of tic); Polyamide (nylon); Polycarbonate; Polyphenylene oxide; Polyethylene terephthalate; Polybutylene terephthalate; Polyarylate; Polysulfone; Polyethersulfone; Polyimide; Polyamideimide; Polyetheretherketone; Polyphenylene sulfide; Unsaturated polyester; Epoxy resin; modified melamine resin; fluororesin; silicone resin; cellulosic resin such as celluloid, cellophane, cellulose acetate and cellulose acetate butyrate; resin derived from natural rubber such as ebonite; and resin derived from protein such as gelatin; Can be mentioned.

  Preferably, the resin used in the present invention is a heat softening resin such as wax, epoxy resin, phenol resin, silicone resin, melamine resin, urea resin, unsaturated polyester resin, diallyl terephthalate resin, polyphenylene oxide resin, polyimide resin. At least selected from the group consisting of polyamide resin, (meth) acrylic ester resin, benzocyclobutene resin, fluorine resin, polyurethane resin, polycarbonate resin, norbornene resin, polyolefin resin and polystyrene resin A resin composition containing one kind of resin. In particular, the resin composition of the present invention is preferably a silicone composition.

  These resin compositions may be curable resin compositions, thermoplastic resin compositions, or non-curable or thickening resin compositions. Further, when the resin is a thermosoftening resin, it may be a phase change material. The resin composition of the present invention can be used in various applications depending on the type of functional filler and resin, and in particular, a heat conductive material, a conductive material, a semiconductor encapsulating material, an optical material, a functional property. It can be used for applications selected from paints and cosmetics.

  In particular, the organosilicon compound of the present invention and the filler whose surface is treated with the organosilicon compound are preferably blended into the silicone composition, and particularly used for the surface treatment of the thermally conductive filler. In order to achieve high thermal conductivity, even when the composition is highly filled with a thermally conductive filler, the viscosity of the composition does not increase and handling operability is good, and in the case of a curable composition, it is uniform. The characteristic is that a cured product can be obtained. Hereinafter, the surface treatment of the thermally conductive filler and the thermally conductive silicone composition, which are the most suitable uses of the organosilicon compound of the present invention, will be described.

  The thermally conductive silicone composition of the present invention comprises (A) the above organosilicon compound and (B) a thermally conductive filler, and (A) the organosilicon compound of the thermally conductive filler. The surface treatment used is as described in the surface treatment of the functional filler.

  Component (B) is a thermally conductive filler for imparting thermal conductivity to the composition of the present invention. Pure metal, alloy, metal oxide, metal hydroxide, metal nitride, metal carbide, metal silica Preferably, at least one powder and / or fiber selected from the group consisting of chemical compounds, carbon, soft magnetic alloys and ferrite. It is particularly preferable that the surface contains a heat conductive material that does not contain a hydroxyl group and that is expected to interact with an aromatic group or has a flat appearance. As these powders and / or fibers, those treated with various surface treating agents known as coupling agents may be used.

  Pure metals include bismuth, lead, tin, antimony, indium, cadmium, zinc, silver, copper, nickel, aluminum, iron and metallic silicon. Examples of the alloy include alloys made of two or more metals selected from the group consisting of bismuth, lead, tin, antimony, indium, cadmium, zinc, silver, aluminum, iron, and metallic silicon. Examples of the metal oxide include alumina, zinc oxide, silicon oxide, magnesium oxide, beryllium oxide, chromium oxide, and titanium oxide. Examples of the metal hydroxide include magnesium hydroxide, aluminum hydroxide, barium hydroxide, and calcium hydroxide. Examples of the metal nitride include boron nitride, aluminum nitride, and silicon nitride. Examples of the metal carbide 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. Examples of carbon include diamond, graphite, fullerene, carbon nanotube, graphene, activated carbon, and amorphous carbon black. Examples of soft magnetic alloys include Fe-Si alloys, Fe-Al alloys, Fe-Si-Al alloys, Fe-Si-Cr alloys, Fe-Ni alloys, Fe-Ni-Co alloys, Fe-Ni-Mo alloys, Fe -Co alloy, Fe-Si-Al-Cr alloy, Fe-Si-B alloy and Fe-Si-Co-B alloy. Examples of the ferrite include Mn—Zn ferrite, Mn—Mg—Zn ferrite, Mg—Cu—Zn ferrite, Ni—Zn ferrite, Ni—Cu—Zn ferrite and Cu—Zn ferrite. Preferably, the component (B) is at least one powder and / or fiber selected from these.

  (B) The thermally conductive filler is (B1) plate-like boron nitride powder having an average particle diameter of 0.1 to 30 μm, and (B2) granular boron nitride having an average particle diameter of 0.1 to 50 μm. Powder, (B3) spherical and / or crushed aluminum oxide powder having an average particle diameter of 0.01 to 50 μm, or (B4) spherical and / or crushed graphite having an average particle diameter of 0.01 to 50 μm, Or it is especially preferable that it is a mixture of two or more of these.

  Examples of the shape of the component (B) include a spherical shape, a needle shape, a disc shape, a rod shape, a flat shape, an indefinite shape, and a fiber shape.

  Examples of the surface treatment agent for treating the powder and / or fiber of the component (B) include surfactants, silane coupling agents, aluminum coupling agents, and silicone surface treatment agents.

  In the present composition, the content of the component (B) is not particularly limited, but in order to form a silicone composition having good thermal conductivity, it is preferably 30% by volume or more in the present composition, It is more preferably in the range of 30 to 90% by volume, still more preferably in the range of 60 to 90% by volume, and particularly preferably in the range of 80 to 90% by volume. Similarly, in order to form a silicone composition having good thermal conductivity, the content of the component (B) is preferably 50% by mass or more in the present composition, and is 70 to 98% by mass. More preferably, it is in the range, and particularly preferably in the range of 90 to 97% by mass.

  Specifically, the content of the component (B) is preferably in the range of 100 to 3,500 parts by mass with respect to a total of 100 parts by mass of the component (A) and the component (C). , 500 parts by mass, and more preferably within a range of 100 to 2,500 parts by mass. This is because if the content of the component (B) is less than the lower limit of the range, the resulting silicone composition tends to be insufficient in thermal conductivity, whereas if the content exceeds the upper limit of the range. This is because the viscosity of the obtained silicone composition becomes too high, and the component (B) cannot be uniformly dispersed in the obtained silicone composition, or its handling workability tends to be remarkably lowered.

  The organopolysiloxane of component (C) is not particularly limited, but a hydrolyzable functional group bonded to a silicon atom in the molecule, for example, an alkoxy group, an alkoxyalkoxy group, an alkenoxy group, an acyloxy group, or a trialkoxysilylalkyl group. It is possible to use an organopolysiloxane having the same.

  The organopolysiloxane of component (C) is an organopolysiloxane having a monovalent hydrocarbon group having an aliphatic unsaturated bond bonded to a silicon atom in the molecule, and a hydrogen bonded to a silicon atom in the molecule. An organopolysiloxane having an atom, and an organopolysiloxane having a hydrolyzable group bonded to a silicon atom in the molecule may be used.

  In the organopolysiloxane having at least one monovalent hydrocarbon group having an aliphatic unsaturated bond bonded to a silicon atom in one molecule, the monovalent hydrocarbon group having an aliphatic unsaturated bond is preferably a straight chain. A chain alkenyl group, particularly preferably a vinyl group, an allyl group or a hexenyl group. Examples of the group bonded to the silicon atom bond other than the monovalent hydrocarbon group having an aliphatic unsaturated bond include a monovalent hydrocarbon group having no aliphatic unsaturated bond, preferably an alkyl group. A group or an aryl group, more preferably an alkyl group having 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 in the range of 20 to 100,000 mPa · s, more preferably in the range of 50 to 100,000 mPa · s, and 50 to More preferably, it is in the range of 50,000 mPa · s, and particularly preferably in the range of 100 to 50,000 mPa · s. The molecular structure of the organopolysiloxane is not particularly limited, and examples thereof include linear, branched, partially branched linear, cyclic, and dendritic (dendrimer). Examples of the organopolysiloxane include a single polymer having these molecular structures, a copolymer having these molecular structures, or a mixture thereof.

Examples of such an organopolysiloxane include dimethylpolysiloxane blocked with dimethylvinylsiloxy group at both ends of the molecular chain, dimethylpolysiloxane blocked with methylphenylvinylsiloxy group at both ends of the molecular chain, dimethylsiloxane / methylphenyl blocked with dimethylvinylsiloxy group blocked at both ends of the molecular chain. Siloxane copolymer, dimethylvinylsiloxy group-capped dimethylsiloxane / methylvinylsiloxane copolymer with both ends of molecular chain, trimethylsiloxy group-capped dimethylsiloxane / methylvinylsiloxane copolymer with both ends of molecular chain, dimethylvinylsiloxy group-capped methyl (3,3) , 3-trifluoropropyl) polysiloxane, molecular chain both ends silanol-blocked dimethylsiloxane / methylvinylsiloxane copolymer, molecular chain both ends silanol-blocked di Chill-methylvinyl siloxane-methylphenylsiloxane copolymer, the _{formula: (CH 3)} 3 siloxane units of the formula represented by _{SiO 1/2:} represented by _{(CH 3) 2 (CH 2} = CH) SiO 1/2 An organosiloxane copolymer comprising a siloxane unit and a siloxane unit represented by the formula: CH ₃ SiO _3/2 and a siloxane unit represented by the formula: (CH ₃ ) ₂ SiO _2/2; Polysiloxane, molecular chain both ends silanol-blocked dimethylsiloxane / methylphenylsiloxane copolymer, molecular chain both ends trimethoxysiloxy-blocked dimethylpolysiloxane, molecular chain both ends trimethoxysilyl-blocked dimethylsiloxane / methylphenylsiloxane copolymer, molecular chain Both end methyl dimeth Examples include xysiloxy group-capped dimethylpolysiloxane, molecular chain both ends triethoxysiloxy group-capped dimethylpolysiloxane, molecular chain both ends trimethoxysilylethyl group-capped dimethylpolysiloxane, and mixtures of two or more thereof.

  In the organopolysiloxane having at least one hydrogen atom bonded to a silicon atom, a group bonded to a silicon atom bond other than a hydrogen atom is a monovalent group having no aliphatic unsaturated bond. A hydrocarbon group is illustrated, Preferably it is an alkyl group or an aryl group, More preferably, it is a C1-C4 alkyl group, Most preferably, it is a methyl group or an ethyl group. The viscosity of the organopolysiloxane at 25 ° C. is not particularly limited, but is preferably in the range of 1 to 100,000 mPa · s, and particularly preferably in the range of 1 to 5,000 mPa · s. The molecular structure of the organopolysiloxane is not particularly limited, and examples thereof include linear, branched, partially branched linear, cyclic, and dendritic (dendrimer). Examples of the organopolysiloxane include single polymers having these molecular structures, copolymers having these molecular structures, and mixtures thereof.

  In the organopolysiloxane having a hydrolyzable group bonded to a silicon atom in the molecule, the hydrolyzable group is preferably an alkoxy group, an alkoxyalkoxy group, an alkenoxy group, an acyloxy group, a silanol group or a trialkoxysilylalkyl group.

  Such organopolysiloxanes include molecular chain fragment terminal trimethoxysiloxy group (trimethylsiloxy group) blocked dimethylpolysiloxane, molecular chain fragment end trimethoxysiloxy group (dimethylvinylsiloxy group) blocked dimethylpolysiloxane, molecular chain fragment end Trimethoxysiloxy group (dimethylvinylsiloxy group) capped dimethylsiloxane / methylphenylsiloxane copolymer, molecular chain terminal trimethoxysiloxy group (dimethylvinylsiloxy group) capped dimethylpolysiloxane, molecular chain both ends trimethoxysiloxy group capped dimethylpolysiloxane , A trimethylsiloxy group-capped dimethylsiloxane / methylmethoxysiloxane copolymer at both ends of a molecular chain, a trimethylsiloxy group-capped dimethylsiloxane / methylethoxysiloxane copolymer at both ends of a molecular chain Limer, molecular chain both ends trimethoxysiloxy group-blocked methyl (3-trimethoxysilylpropyl) dimethylsiloxane copolymer, molecular chain both ends dimethyl (5-trimethoxysilylhexyl) group-blocked dimethylpolysiloxane, molecular chain both ends silanol Blocked dimethylpolysiloxane, Silanol group-blocked dimethylsiloxane / methylphenylsiloxane copolymer, Molecular chain both ends methyldimethoxysiloxy group-blocked dimethylpolysiloxane, Molecular chain both ends triethoxysiloxy group-blocked dimethylpolysiloxane, Both molecular chains Examples thereof include terminal trimethoxysilylethyl group-capped dimethylpolysiloxane and a mixture of two or more thereof.

  The method for preparing this composition is not particularly limited. For example, [1] a method in which component (A) is mixed with component (B), and component (C) is gradually added thereto and mixed; [2 The component (A) and the component (C) can be mixed in advance, and the component (B) can be gradually added and prepared. The method [1] is particularly preferable. Various devices can be used as the mixing device, and in particular, a rotating / revolving mixing device (commercially available products such as Shinky Awatori Nerita series, UNIX UM-118, EME UFO series, and Housechild) The speed mixer is preferable from the viewpoint of mixing efficiency.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to an Example. The physical properties in the examples are values at 25 ° C. The degree of polymerization in the formula is an average degree of polymerization.

[Example 1]
Synthesis of 1-{(2-naphthyl) ethyl} -3- (n-octyl) -1 ′, 1 ″, 3 ′, 3 ″ -tetramethyldisiloxane Stirrer, thermometer, condenser, and dropping funnel Under a nitrogen atmosphere, 103 g of ion-exchanged water and 48 g of concentrated hydrochloric acid were added, stirred and cooled to 10 ° C. or lower. 30.4 g (0.222 mol) of 1,1,3,3-tetramethyldisiloxane was added. Subsequently, 82.0 g (0.387 mol) of n-octyldimethylchlorosilane was added dropwise while cooling with water or air so that the temperature of the reaction solution did not exceed 10 ° C. After completion of dropping, the mixture was stirred at 10 ° C. or lower for 2 hours. As a result of analyzing the reaction mixture by gas chromatography (hereinafter referred to as GLC), the peak of n-octyldimethylchlorosilane disappeared, and thus the reaction was terminated. The reaction mixture was allowed to stand, and the upper layer was mixed and washed three times with 100 ml of ion-exchanged water, twice with 100 ml of a saturated aqueous sodium hydrogen carbonate solution and three times with 100 ml of a saturated aqueous sodium chloride solution. Dehydration was performed with anhydrous sodium sulfide, and 62 g (yield: 65%) of a 61-65 ° C./1 hPa fraction was obtained by distillation under reduced pressure. When this fraction was analyzed by nuclear magnetic resonance analysis (hereinafter referred to as NMR) and infrared spectroscopic analysis (hereinafter referred to as IR), this fraction was determined to be 3- (n-octyl) -1 ′, 1 ″, 3 ′. It was found to be a silicon atom-bonded hydrogen atom-containing organopolysiloxane represented by 3,3 ″ -tetramethyldisiloxane. The purity of this siloxane by GLC was 99.5%.

  Furthermore, in a 200 ml four-necked flask equipped with a stirrer, a thermometer, a condenser, and a dropping funnel, 23.4 g of 2-vinylnaphthalene (purity 93.9%, 0.142 mol), toluene under a nitrogen atmosphere 22 g and a complex of platinum and 1,3-divinyltetramethyldisiloxane were added and mixed so that the amount of platinum metal was 5 ppm with respect to the total mass of the reaction mixture, and heated to 40 ° C. 35.3 g (0.143 mol) of 3- (n-octyl) -1 ′, 1 ″, 3 ′, 3 ″ -tetramethyldisiloxane was added so that the temperature of the reaction solution did not exceed 50 ° C. The solution was added dropwise while cooling with water or air. After completion of dropping, the mixture was stirred at 60 ° C. for 2 hours, and the reaction mixture was analyzed by IR. As a result, 3- (n-octyl) -1 ′, 1 ″, 3 ′, 3 ″ -tetramethyldisiloxane vinyltrimethoxy was obtained. Since the SiH peak due to silane had disappeared, the reaction was terminated. The reaction mixture was heated to 90 ° C./1 hPa under reduced pressure to remove the solvent, low-boiling unreacted substances and the like, and 55.0 g (yield 94%) of the reaction product was obtained. This fraction was analyzed by NMR and IR and found to be 1-{(2-naphthyl) ethyl} -3- (n-octyl) -1 ′, 1 ″, 3 ′, 3 ″ -tetramethyldisiloxane. It was found to be the organopolysiloxane represented.

[Example 2]
Synthesis of 1-{(2-naphthyl) ethyl} -3 ′, 3 ″, 5 ′, 5 ″ -tetramethyl-3,5-disila-10-undecene In the same manner as in Example 1, n-octyldimethyl The title compound was synthesized by replacing chlorosilane with (2-naphthyl) ethyldimethylchlorosilane and 2-vinylnaphthalene with 1,5-hexadiene to obtain 40.3 g (yield 69%). This fraction was analyzed by NMR and IR and found to be 1-{(2-naphthyl) ethyl} -3 ′, 3 ″, 5 ′, 5 ″ -tetramethyl-3,5-disila-10-undecene. It was confirmed that the organopolysiloxane was represented.

[Example 3]
Synthesis of α, ω-trimethylsilyl {(2-naphthyl) ethyl} -polydimethylsiloxane (degree of polymerization: 25) In a 100 ml four-necked flask equipped with a stirrer, thermometer, condenser, and dropping funnel, a nitrogen atmosphere Below, 2.41 g of 2-vinylnaphthalene (purity 93.9%, 0.142 mol), 10 g of toluene, and a complex of platinum and 1,3-divinyltetramethyldisiloxane, the amount of platinum metal in the reaction mixture The mixture was added and mixed to 5 ppm with respect to the total weight, and heated to 40 ° C. 27.5 g of α, ω-trimethylsilyl hydrogen-polydimethylsiloxane (degree of polymerization: 25, SiH = 0.55%) was added dropwise while cooling with water or air so that the temperature of the reaction solution did not exceed 50 ° C. After completion of the dropwise addition, the mixture was stirred at 60 ° C. for 2 hours, and the reaction mixture was analyzed by IR. As a result, the SiH peak attributed to α, ω-trimethylsilylhydrogen-polydimethylsiloxane had disappeared. The reaction mixture was heated to 90 ° C./1 hPa under reduced pressure to remove the solvent, low boiling point unreacted substances, etc., and 28.9 g (yield 96%) of the reaction product was obtained. When this fraction was analyzed by NMR and IR, it was found to be α, ω-trimethylsilyl {(2-naphthyl) ethyl} -polydimethylsiloxane (degree of polymerization: 25).

[Example 4]
Synthesis of α, ω-trimethylsilyl (1-naphthyl) -polydimethylsiloxane (degree of polymerization: 50) To a 100 ml four-necked flask equipped with a stirrer, thermometer, condenser, and dropping funnel under a nitrogen atmosphere , Ω-trimethylsilylhydroxyl-polydimethylsiloxane (degree of polymerization: 50, SiOH = 0.45%), 50 g of toluene, and 1.7 g (0.023 mol) of diethylamine are added and mixed to give 1-naphthyldimethylchlorosilane. 2.91 g (0.013 mol) was added dropwise at room temperature. After the addition was complete, the system was heated at 60 ° C. for 8 hours. Then, after cooling to room temperature and filtering off the formed salt, the filtrate was heated to 90 ° C./1 hPa under reduced pressure to remove the solvent, low boiling unreacted substances, etc., and 51.0 g of reaction product (97% yield) ) When this fraction was analyzed by NMR and IR, it was found to be α, ω-trimethylsilyl {(1-naphthyl)}-polydimethylsiloxane (degree of polymerization: 50).

  The thermally conductive silicone composition of the present invention will be described in more detail below. Moreover, the viscosity and thermal conductivity of the heat conductive silicone composition were measured as follows.

[Viscosity of thermally conductive silicone composition]
The viscosity at 25 ° C. of the heat conductive silicone composition was measured using a rheometer (AR550) manufactured by TA Instruments. A parallel plate having a diameter of 20 mm was used as the geometry, and measurement was performed under the conditions of a gap of 200 μm and a shear rate of 10.0 (1 / s). A low viscosity value means that the thermally conductive silicone composition has a low viscosity and is excellent in handleability.

[Thermal conductivity]
The thermal resistance value at 25 ° C. of a thermally conductive silicone grease composition having an area of 1 cm × 1 cm, a thickness of 200 μm and a thickness of 500 μm was measured by a thermal conductivity measuring device C-ThermTCi manufactured by C-Therm Co. The conductivity was determined.

[Example 5]
The vessel 100 ml of the _{formula: (n-C 8 H 17} ) with _{(CH 3) 2 SiOSi (CH} 3) 2 C 2 H 4 Np Example 1 (Np is 2-naphthyl represents a group) represented by 10.3 parts by mass of the obtained organopolysiloxane, 79.6 parts by mass of spherical alumina powder having an average particle size of 12 μm, 4.4 parts by mass of boron nitride having an average particle size of 20 μm, and an average particle size of 0.1 μm. 8.8 parts by mass of boron nitride having a thickness of 8 μm was added to prepare a thermally conductive silicone grease having a filler content of 70% by volume. The mixture was mixed for 30 seconds using a rotating / revolving mixer AR-100 manufactured by Sinky, and after mixing by scraping, the mixture was mixed again for 30 seconds. The viscosity (share rate: 10.0 (1 / s)) of this thermally conductive silicone grease was 100 Pa · s, and the thermal conductivity was 4.5 W / m · K.

[Examples 6 to 11]
Example except that organopolysiloxane (1) and / or organopolysiloxane (2) shown in Table 1 was used instead of the one obtained in Example 1 as the organopolysiloxane, and the composition was changed to the composition shown in Table 1. In the same manner as in No. 5, a thermally conductive silicone composition was prepared. Table 1 shows the viscosity (share rate: 10.0 (1 / s)) and thermal conductivity of these thermally conductive silicone compositions. By using the organopolysiloxane according to the present invention for a part or all of the treating agent, it was possible to obtain a paste having a practical viscosity and excellent uniformity and showing high thermal conductivity. .

[Comparative Example 1 and Comparative Example 2]
A thermally conductive silicone composition was prepared in the same manner as in Example 5 except that the organopolysiloxane shown in Table 2 was used instead of the one obtained in Example 1 as the organopolysiloxane and the composition shown in Table 2 was used. Was prepared. Table 2 shows the viscosity (share rate: 10.0 (1 / s)) and thermal conductivity of this thermally conductive silicone composition. When the organopolysiloxane according to these comparative examples was used, the resulting composition did not form a uniform paste, and its thermal conductivity could not be measured.

Organopolysiloxane in Table (* 1) (CH ₂ = CHC ₄ H ₈ ) (CH ₃ ) ₂ SiOSi (CH ₃ ) ₂ C ₂ H ₄ Np (Np represents a 2-naphthyl group)
(* 2) (CH ₃ ) ₃ SiO [(CH ₃ ) ₂ SiO] _n Si (OCH ₃ ) ₃ (n (average) = 20)
(* 3) (CH ₃ ) ₃ SiO [(CH ₃ ) ₂ SiO] _n Si (CH ₃ ) ₂ C ₂ H ₄ Np (n (average) = 25)
(* 4) (CH ₃ ) ₃ SiO [(CH ₃ ) ₂ SiO] _n Si (CH ₃ ) ₂ C ₂ H ₄ Np (n (average) = 50)
(* 5) (CH ₃ ) ₃ SiO [(CH ₃ ) ₂ SiO] _n Si (CH ₃ ) ₂ Np (n (average) = 25)
(* 6) (MeO) ₃ SiC ₃ H ₆ (CH ₃ ) ₂ SiOSi (CH ₃ ) ₂ C ₂ H ₄ Np (Np represents a 2-naphthyl group, Me represents a methyl group)
(* 7) C ₈ H ₁₇ (CH ₃ ) ₂ SiOSi (CH ₃ ) ₂ (C ₈ H ₁₇ )
(* 8) (CH ₃ ) ₃ SiO [(CH ₃ ) ₂ SiO] _n Si (CH ₃ ) ₃ (n (average) = 45)
_{(* 9) NpC 2 H 4} (CH 3) 2 SiOSi (CH 3) 2 C 2 H 4 Np ( the Np indicates a 2-naphthyl group)

Filler in table (* a) Spherical alumina powder having an average particle size of 12 μm (* b) Granular boron nitride having an average particle size of 20 μm (* c) Plate-shaped boron nitride having an average particle size of 0.8 μm (* d) Graphite with an average particle size of 20 μm

[Example 12]
Organopolysiloxane represented by the formula: (CH ₂ = CHC ₄ H ₈ ) (CH ₃ ) ₂ SiOSi (CH ₃ ) ₂ C ₂ H ₄ Np (Np represents a 2-naphthyl group) in a 100 ml container 6.0 parts by mass, organo represented by the formula: CH ₂ ═CH (CH ₃ ) ₂ SiO [(CH ₃ ) ₂ SiO] _n Si (CH ₃ ) ₂ CH ₂ ═CH (n (average) = 300) 8.1 parts by weight of polysiloxane, formula: (CH ₃ ) ₃ SiO [(CH ₃ ) HSiO] _n [(CH ₃ ) ₂ SiO] _m Si (CH ₃ ) ₃ (n (average) = 30, m (average) ) = 30) 2.1 parts by mass of the organopolysiloxane, 25.6 parts by mass of boron nitride having an average particle size of 20 μm, 0.09 parts by mass of tetravinyltetramethylcyclotetrasiloxane, and a platinum content of 0.9 mass part of 1,3-divinyltetramethyldisiloxane complex of platinum, which is 0.5 mass%, is added for 30 seconds using a rotating revolution mixer AR-100 manufactured by Sinky Co., and scraped and mixed again. Mix for 30 seconds. This composition was subjected to a hydrosilylation reaction by heating at 150 ° C. for 15 minutes to prepare thermally conductive silicone cured products (thicknesses 1 mm and 2 mm). The thermal conductivity of this thermally conductive silicone cured product was 5.5 W / m · K.

[Comparative Example 3]
Instead of (CH ₂ ═CHC ₄ H ₈ ) (CH ₃ ) ₂ SiOSi (CH ₃ ) ₂ C ₂ H ₄ Np (Np represents a 2-naphthyl group) as the organopolysiloxane, (C ₈ H ₁₇ ) ( A thermally conductive silicone cured product was prepared in the same manner as in Example 12 except that CH ₃ ) ₂ SiOSi (CH ₃ ) ₂ (C ₈ H ₁₇ ) was used. The viscosity (share rate: 10.0 (1 / s)) before curing of this composition was 350, and the viscosity was too high to obtain a uniform cured product.

Claims (17)

The following formula (1):

(Where
R ¹ is a monovalent hydrocarbon group having 10 or more carbon atoms having a plurality of aromatic rings,
R ² is a divalent hydrocarbon group that may contain a hetero atom or a direct bond to a silicon (Si) atom;
R ³ and R ⁴ are each independently 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 an alkyl group, an alkenyl group, an aryl group and an alkoxy group;
n is an integer from 0 to 200;
a is an integer of 1 to 3. )
An organopolysiloxane represented by   A surface treatment agent comprising the organopolysiloxane of claim 1.   Selected from heat conductive filler, fluorescent filler, conductive filler, dielectric filler, insulating filler, light diffusing filler, translucent filler, coloring filler and reinforcing filler The surface treating agent according to claim 2 for use in surface treatment of one type or two or more types of fillers.   Used for surface treatment of one or more fillers selected from inorganic fillers, organic fillers, nanocrystal structures, quantum dots, and fillers in which part or all of these surfaces are coated with a silica layer The surface treating agent according to claim 2 for.   A resin composition comprising the organopolysiloxane of claim 1 and a filler whose surface is treated with the organopolysiloxane of claim 1.   The resin composition according to claim 5, for use in a use selected from a heat conductive material, a conductive material, a semiconductor sealing material, an optical material, a functional paint, and a cosmetic.   The resin composition according to claim 5 or 6, which is thickened, curable, or phase changeable.   (A) The heat conductive silicone composition containing the organopolysiloxane of said Formula (1), and (B) heat conductive filler.   (C) The silicone composition according to claim 8, further comprising at least one organopolysiloxane other than the organopolysiloxane of the formula (1).   The (B) thermally conductive filler is selected from the group consisting of pure metal, alloy, metal oxide, metal hydroxide, metal nitride, metal carbide, metal silicide, carbon, soft magnetic alloy and ferrite. The silicone composition according to claim 8 or 9, which is at least one powder and / or fiber. The pure metal is bismuth, lead, tin, antimony, indium, cadmium, zinc, silver, copper, nickel, aluminum, iron or metallic silicon, or
The alloy is an alloy made of two or more metals selected from the group consisting of bismuth, lead, tin, antimony, indium, cadmium, zinc, silver, copper, nickel, aluminum, iron and 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 nanotube, graphene, activated carbon or amorphous carbon black, or
The soft magnetic alloy is Fe-Si alloy, Fe-Al alloy, Fe-Si-Al alloy, Fe-Si-Cr alloy, Fe-Ni alloy, Fe-Ni-Co alloy, Fe-Ni-Mo alloy, Fe -Co alloy, Fe-Si-Al-Cr alloy, Fe-Si-B alloy or Fe-Si-Co-B alloy, or
The silicone composition according to claim 10, wherein the ferrite is Mn—Zn ferrite, Mn—Mg—Zn ferrite, Mg—Cu—Zn ferrite, Ni—Zn ferrite, Ni—Cu—Zn ferrite, or Cu—Zn ferrite. object.   (B) Thermally conductive filler is (B1) plate-like boron nitride powder having an average particle size of 0.1 to 30 μm, (B2) granular nitriding having an average particle size of 0.1 to 50 μm Boron powder, (B3) spherical and / or crushed aluminum oxide powder having an average particle size of 0.01 to 50 μm, or (B4) graphite having an average particle size of 0.01 to 50 μm, or these two types The silicone composition according to any one of claims 8 to 11, which is a mixture of the above.   The content of the component (B) is 100 to 3,500 parts by mass with respect to a total of 100 parts by mass of the component (A) and the component (C). The silicone composition described.   The silicone composition according to any one of claims 9 to 13, wherein the organopolysiloxane of the component (C) 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 bonded to a silicon atom in the molecule, and an organopolysiloxane having a hydrogen atom bonded to a silicon atom in the molecule. The silicone composition according to any one of claims 9 to 14, which is a siloxane and further contains a catalyst for thickening or curing these organopolysiloxanes by a hydrosilylation reaction.   An organopolysiloxane in which the component (C) has a monovalent hydrocarbon group having a hydrolyzable functional group bonded to a silicon atom in the molecule and an aliphatic unsaturated bond bonded to a silicon atom; And an organopolysiloxane having a hydrogen atom bonded to a silicon atom in the molecule, and further containing a catalyst for thickening or curing the organopolysiloxane by a hydrosilylation reaction. The silicone composition according to item.   A gel or cured product obtained by thickening or curing the silicone composition according to claim 15 or 16.