JP2010235693A - Silica-containing organic composition and method for producing the same - Google Patents
Silica-containing organic composition and method for producing the same Download PDFInfo
- Publication number
- JP2010235693A JP2010235693A JP2009082984A JP2009082984A JP2010235693A JP 2010235693 A JP2010235693 A JP 2010235693A JP 2009082984 A JP2009082984 A JP 2009082984A JP 2009082984 A JP2009082984 A JP 2009082984A JP 2010235693 A JP2010235693 A JP 2010235693A
- Authority
- JP
- Japan
- Prior art keywords
- silica
- organic composition
- fine particles
- containing organic
- silicone
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 302
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 145
- 239000000203 mixture Substances 0.000 title claims abstract description 58
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 24
- 239000010419 fine particle Substances 0.000 claims abstract description 64
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 59
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 27
- 150000001875 compounds Chemical class 0.000 claims abstract description 20
- 238000007259 addition reaction Methods 0.000 claims abstract description 14
- 239000007809 chemical reaction catalyst Substances 0.000 claims abstract description 13
- 239000002245 particle Substances 0.000 claims description 13
- 230000003287 optical effect Effects 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 239000003566 sealing material Substances 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 4
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 abstract description 11
- 238000012360 testing method Methods 0.000 description 26
- 238000000034 method Methods 0.000 description 23
- 239000006185 dispersion Substances 0.000 description 16
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 15
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 14
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 239000000843 powder Substances 0.000 description 9
- 239000011863 silicon-based powder Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000000428 dust Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000012495 reaction gas Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004200 deflagration Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000000644 propagated effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 125000002568 propynyl group Chemical group [*]C#CC([H])([H])[H] 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Abstract
Description
本発明は、シリコーンにシリカを分散したシリカ含有有機組成物及びその製造方法に関する。 The present invention relates to a silica-containing organic composition in which silica is dispersed in silicone and a method for producing the same.
ＬＥＤなどの封止材料として透明樹脂の１つであるシリコーンを採用することがある。シリコーンは化学的にも物理的にも安定な樹脂である。 Silicone, which is one of transparent resins, may be employed as a sealing material for LEDs and the like. Silicone is a chemically and physically stable resin.
ところで、高い寸法安定性、熱安定性などの機械的特性を付与する目的で樹脂中にシリカを分散させた組成物が知られている。 By the way, a composition is known in which silica is dispersed in a resin for the purpose of imparting mechanical properties such as high dimensional stability and thermal stability.
近年、高機能化、高付加価値化が進み、物理的・化学的性能が高いシリコーンについても更なる物理的・化学的性能の向上が要求されるようになっている。そこで、本発明者らはシリコーン中にシリカ微粒子を含有させることで物理的・化学的性能を向上する試みを行った。 In recent years, high functionality and high added value have been advanced, and further improvement in physical and chemical performance is required for silicone having high physical and chemical performance. Accordingly, the present inventors have attempted to improve physical and chemical performance by incorporating silica fine particles into silicone.
すると、シリコーンは疎水性が高く、そのままでは親水性の高いシリカを均一に分散させることは困難であることが判明した。また、シリカ微粒子の表面に疎水基を導入し、シリコーンとの親和性向上を試みたが、更なる改良の余地が認められた。特にＬＥＤなどの封止材料として利用される透明性が高い樹脂組成物を得ることは困難であった。 As a result, it has been found that silicone is highly hydrophobic, and as it is, it is difficult to uniformly disperse highly hydrophilic silica. Further, a hydrophobic group was introduced on the surface of the silica fine particles to try to improve the affinity with silicone, but there was room for further improvement. In particular, it has been difficult to obtain a highly transparent resin composition used as a sealing material for LEDs and the like.
本発明は上記実情に鑑み、シリコーン中にシリカを分散させたシリカ含有有機組成物及びその製造方法を提供することを解決すべき課題とする。 In view of the above circumstances, an object of the present invention is to provide a silica-containing organic composition in which silica is dispersed in silicone and a method for producing the same.
上記課題を解決する請求項１に係るシリカ含有有機組成物の製造方法の特徴は、シリカ微粒子に複数のＳｉＨ基をもつ前処理用化合物の一部のＳｉＨ基を反応させて表面に残部のＳｉＨ基を導入してＳｉＨ基含有シリカ微粒子とする前処理工程と、
付加反応触媒の存在下、前記ＳｉＨ基含有シリカ微粒子にアルケニル基含有シリコーンを含むシリコーンを混合し、前記アルケニル基と反応させてシリカ微粒子分散シリコーンとする分散工程と、
を有することにある。
A feature of the method for producing a silica-containing organic composition according to claim 1 for solving the above-mentioned problem is that a part of SiH groups of a pretreatment compound having a plurality of SiH groups are reacted with silica fine particles to make the remaining SiH on the surface. A pretreatment step of introducing groups into SiH group-containing silica fine particles;
In the presence of an addition reaction catalyst, the SiH group-containing silica fine particles are mixed with a silicone containing an alkenyl group-containing silicone and reacted with the alkenyl group to form a silica fine particle-dispersed silicone;
It is in having.
上記課題を解決する請求項２に係るシリカ含有有機組成物の製造方法の特徴は、請求項１において、前記前処理用化合物は、一般式（１）：−（ＳｉＨＲ１−Ｏ）ｎ（ＳｉＲ２Ｒ３−Ｏ）ｍ−で表される化合物であることにある。 The feature of the method for producing a silica-containing organic composition according to claim 2 for solving the above-mentioned problem is that in claim 1, the pretreatment compound is represented by the general formula (1):-(SiHR 1 -O) n (SiR 2 R 3 —O) m —.
（式（１）中、Ｒ１〜Ｒ３はアルキル基からそれぞれ独立して選択可能である。ｎ，ｍはそれぞれ独立して選択可能な正の整数である。）
上記課題を解決する請求項３に係るシリカ含有有機組成物の製造方法の特徴は、請求項１又は２において、前記シリカ微粒子は粒径が５ｎｍ〜３０μｍであることにある。
(In formula (1), R 1 to R 3 can be independently selected from an alkyl group. N and m are each independently a positive integer that can be selected.)
A feature of the method for producing a silica-containing organic composition according to claim 3 for solving the above-mentioned problem is that, in claim 1 or 2, the silica fine particles have a particle diameter of 5 nm to 30 μm.
上記課題を解決する請求項４に係るシリカ含有有機組成物の特徴は、請求項１〜３の何れか１項に記載に記載のシリカ含有有機組成物の製造方法にて製造しうることにある。 The characteristic of the silica containing organic composition which concerns on Claim 4 which solves the said subject exists in being able to manufacture with the manufacturing method of the silica containing organic composition of any one of Claims 1-3. .
上記課題を解決する請求項５に係るシリカ含有有機組成物の特徴は、シリカ微粒子と、
前記シリカ微粒子の表面に−（ＳｉＯ）ｎ−（：ｎは１以上）と炭素−炭素結合を介して結合され、前記シリカ微粒子を分散するシリコーンと、
を有することにある。
The characteristics of the silica-containing organic composition according to claim 5 for solving the above-mentioned problems are silica fine particles,
-(SiO) n- (where n is 1 or more) and a silicone that disperses the silica particles, and bonded to the surface of the silica particles through a carbon-carbon bond;
It is in having.
上記課題を解決する請求項６に係るシリカ含有有機組成物の特徴は、請求項４又は５において、電子基板用プリプレグ、絶縁フィルム、電子部品用封止材、及び光学材料のうちのいずれかに用いることにある。 The feature of the silica-containing organic composition according to claim 6 for solving the above-mentioned problem is that in claim 4 or 5, the electronic substrate prepreg, the insulating film, the electronic component sealing material, and the optical material There is to use.
請求項１に係るシリカ含有有機組成物の製造方法は、シリカ微粒子の表面にＳｉＨ基を導入し、アルケニル基を持つシリコーンに反応させることで、シリカ微粒子をシリコーン中に高度に分散させることに成功した。特に請求項２に係るシリカ含有有機組成物の製造方法のように、シリカ微粒子に反応させる化合物としてシリコーンに親和性が高いＳｉＯ結合を分子構造中に備える式（１）の化合物を採用することにより、より高度な分散が実現できる。また、請求項３に係る発明のように、分散させるシリカ微粒子の粒径を制御することにより、目的の波長をもつ光線に対する透明性を確保することが可能になった。 The method for producing a silica-containing organic composition according to claim 1 succeeds in highly dispersing silica fine particles in silicone by introducing SiH groups on the surface of silica fine particles and reacting with silicone having alkenyl groups. did. In particular, by adopting a compound of formula (1) having a SiO bond having a high affinity for silicone in the molecular structure as a compound to be reacted with silica fine particles, as in the method for producing a silica-containing organic composition according to claim 2 More advanced dispersion can be realized. Further, as in the invention according to claim 3, by controlling the particle size of the silica fine particles to be dispersed, it becomes possible to ensure transparency to light having a target wavelength.
請求項４に係るシリカ含有有機組成物は、請求項１〜３のような製造方法により実現されたシリカ含有有機組成物であるため、高い分散性を示すものである。また、請求項５に係るシリカ含有有機組成物についてもシリカ微粒子とシリコーンとを適正な化学結合により結合したため、高い分散性が実現できた。このようなシリカ含有有機組成物は請求項６のような用途で高い性能を実現できる。 Since the silica-containing organic composition according to claim 4 is a silica-containing organic composition realized by the production method as in claims 1 to 3, the silica-containing organic composition exhibits high dispersibility. In addition, since the silica-containing organic composition according to the fifth aspect is obtained by bonding silica fine particles and silicone by an appropriate chemical bond, high dispersibility can be realized. Such a silica-containing organic composition can realize high performance in the application as claimed in claim 6.
本発明のシリカ含有有機組成物及びその製造方法について以下実施形態に基づいて詳細に説明を行う。本実施形態のシリカ含有有機組成物、シリカ含有有機組成物の製造方法にて製造されたシリカ含有有機組成物の用途は特に限定しないが、電子基板用プリプレグ、絶縁フィルム、電子部品用封止材、ディスプレーの前面部の基材又は表面コート材料、半導体を接着する接着剤、フィルムの材料、異方導電フィルムの材料、ハードコート、及び光学材料などに用いることができる。 The silica-containing organic composition and the production method thereof of the present invention will be described in detail based on the following embodiments. The use of the silica-containing organic composition and the silica-containing organic composition produced by the method for producing a silica-containing organic composition of the present embodiment is not particularly limited, but a prepreg for an electronic substrate, an insulating film, and an electronic component sealing material It can be used as a substrate or surface coating material for the front part of a display, an adhesive for adhering a semiconductor, a film material, an anisotropic conductive film material, a hard coat, an optical material, and the like.
（シリカ含有有機組成物の製造方法）
本実施形態のシリカ含有有機組成物の製造方法は前処理工程と分散工程とを有する。
・前処理工程
前処理工程はシリカ微粒子に前処理用化合物を反応させることによりその表面にＳＩＨ基を導入してＳｉＨ基含有シリカ微粒子にする工程である。シリカ微粒子は特に限定しないが真球度が高いことが望ましい。例えば真球度が０．９以上であることが望ましい。シリカ微粒子の粒径は必要に応じて適正に設定することができ、例えば５ｎｍ〜３０μｍであることが好ましい。シリカ微粒子は粒径、真球度に応じて適正な方法にて製造できる。例えば、金属ケイ素を酸素雰囲気中で燃焼させる方法（ＶＭＳ法）、シリカを破砕する方法、破砕したシリカなどのシリカ微粒子を更に溶融して真球度を向上する方法（火炎熔融法）、乾式法としてのＰＶＳ（Physical Vapor Synthesisi）法などによりシリカ微粒子を得ることができる。また、ゾルゲル法などの常法により合成されるコロイダルシリカを採用することができる。
(Method for producing silica-containing organic composition)
The manufacturing method of the silica containing organic composition of this embodiment has a pre-processing process and a dispersion | distribution process.
-Pretreatment process A pretreatment process is a process which introduce | transduces SIH group into the surface by making the compound for pretreatment react with a silica particle, and makes it a SiH group containing silica particle. The silica fine particles are not particularly limited, but desirably have a high sphericity. For example, it is desirable that the sphericity is 0.9 or more. The particle size of the silica fine particles can be appropriately set as necessary, and is preferably 5 nm to 30 μm, for example. Silica fine particles can be produced by an appropriate method according to the particle diameter and sphericity. For example, a method of burning metallic silicon in an oxygen atmosphere (VMS method), a method of crushing silica, a method of further melting silica fine particles such as crushed silica and improving the sphericity (flame melting method), a dry method Silica fine particles can be obtained by the PVS (Physical Vapor Synthesisi) method. Also, colloidal silica synthesized by a conventional method such as a sol-gel method can be employed.
ＶＭＳ法は、酸素を含む雰囲気中でバーナーにより化学炎を形成し、この化学炎中に金属ケイ素粉末を粉塵雲が形成される程度の量投入し、爆燃を起こさせてシリカ粒子を得る方法である。 The VMS method is a method in which a chemical flame is formed by a burner in an atmosphere containing oxygen, and metal silicon powder is introduced into the chemical flame in such an amount that a dust cloud is formed, and deflagration is caused to obtain silica particles. is there.
ＶＭＳ法の作用について説明すれば以下のようになる。まず、容器中に反応ガスである酸素を含有するガスを充満させ、この反応ガス中で化学炎を形成する。次いで、この化学炎に金属ケイ素粉末を投入し高濃度（５００ｇ／ｍ３以上）の粉塵雲を形成する。すると、化学炎により金属ケイ素粉末表面に熱エネルギが与えられ、金属ケイ素粉末の表面温度が上昇し、金属ケイ素粉末表面から金属ケイ素の蒸気が周囲に広がる。この金属ケイ素蒸気が酸素ガスと反応して発火し火炎を生じる。この火炎により生じた熱は、さらに金属ケイ素粉末の気化を促進し、生じた金属ケイ素蒸気と反応ガスが混合され、連鎖的に発火伝播する。このとき金属ケイ素粉末自体も破壊して飛散し、火炎伝播を促す。燃焼後に生成ガスが自然冷却されることにより、シリカ微粒子（球状シリカ）の雲ができる。得られた球状シリカは、バグフィルターや電気集塵器等により捕集される。 The operation of the VMS method will be described as follows. First, the container is filled with a gas containing oxygen as a reaction gas, and a chemical flame is formed in the reaction gas. Next, metal silicon powder is charged into the chemical flame to form a dust cloud having a high concentration (500 g / m 3 or more). Then, thermal energy is given to the surface of the metal silicon powder by the chemical flame, the surface temperature of the metal silicon powder rises, and the vapor of the metal silicon spreads from the surface of the metal silicon powder to the surroundings. The metal silicon vapor reacts with oxygen gas to ignite and produce a flame. The heat generated by the flame further promotes the vaporization of the metal silicon powder, and the generated metal silicon vapor and the reaction gas are mixed and propagated in a chain. At this time, the metal silicon powder itself is destroyed and scattered, which promotes flame propagation. When the product gas is naturally cooled after combustion, a cloud of silica fine particles (spherical silica) is formed. The obtained spherical silica is collected by a bag filter, an electric dust collector or the like.
ＶＭＳ法は粉塵爆発の原理を利用するものである。ＶＭＳ法によれば、瞬時に大量の球状シリカが得られる。得られる球状シリカは、略真球状の形状をなす。投入する金属ケイ素粉末の粒子径、投入量、火炎温度等を調整することにより、得られる球状シリカの粒子径分布を調整することが可能である。また、原料物質としては金属ケイ素粉末に加えて、シリカ粉末も添加することができる。シリカ粉末は本方法により得られる球状シリカ粉末を採用することで得られる球状シリカ粉末の純度を保つことができる。 The VMS method uses the principle of dust explosion. According to the VMS method, a large amount of spherical silica can be obtained instantaneously. The obtained spherical silica has a substantially spherical shape. It is possible to adjust the particle size distribution of the resulting spherical silica by adjusting the particle size, amount of input, flame temperature, etc. of the metal silicon powder to be added. In addition to the metal silicon powder, silica powder can be added as a raw material. The silica powder can maintain the purity of the spherical silica powder obtained by adopting the spherical silica powder obtained by this method.
火炎溶融法はシリカ粉末を火炎中に噴霧して高温に曝すことにより熔融させて球状化する方法である。シリカ粉末の融点以上の温度にすること以外は、火炎の種類としては特に限定されず、プロパンガスや天然ガスなどを燃料に採用した火炎を挙げることができる。火炎は耐火煉瓦などにて区画した炉内に形成し、その中にシリカ粉末を噴霧することができる。 The flame melting method is a method in which silica powder is sprayed into a flame and melted by exposure to a high temperature to be spheroidized. There are no particular limitations on the type of flame except that the temperature is equal to or higher than the melting point of the silica powder, and examples thereof include a flame that uses propane gas, natural gas, or the like as the fuel. A flame can be formed in a furnace partitioned with refractory bricks, and silica powder can be sprayed into the furnace.
シリカ粉末の噴霧は何らかのキャリヤガスにガラス粉末を混合して行うことができる。キャリヤガスとしては特に限定しないが、空気、前述の火炎に用いられる燃料、それらの混合物が例示できる。 The spraying of the silica powder can be performed by mixing the glass powder with some carrier gas. Although it does not specifically limit as carrier gas, Air, the fuel used for the above-mentioned flame, and those mixtures can be illustrated.
破砕シリカは原料シリカを粉砕して得られる微粒子である。原料シリカとしては特に限定しない。例えば、天然ケイ石やその熔融物、合成シリカなどが挙げられる。粉砕方法としては特に限定しない。例えば、ハンマーミル、ボールミル、振動ミル、ジェットミルなどを単独乃至組み合わせることで必要な粒径分布を実現する。必要に応じて分級操作を組み合わせても良い。 Crushed silica is fine particles obtained by grinding raw material silica. The raw material silica is not particularly limited. For example, natural silica, its melt, and synthetic silica can be used. There is no particular limitation on the grinding method. For example, a necessary particle size distribution is realized by combining a hammer mill, a ball mill, a vibration mill, a jet mill, or the like. You may combine classification operation as needed.
前処理用化合物はその分子構造中に複数のＳｉＨ基をもつ化合物である。複数のＳｉＨ基のうちの一部がシリカ微粒子表面に存するＯＨ残基と反応し、残部のＳｉＨ基が結合された状態で残ることになる。前処理用化合物としては複数のＳｉＨ基をもつこと以外は特に限定しない。例えば、主鎖としてシロキサン結合の繰り返し単位をもつ重合体の側鎖の一部を水素とした化合物が挙げられる。水素が結合している以外のケイ素原子にはアルキル基が結合するものが例示できる。具体的には上述した一般式（１）の化合物が挙げられる。ここで、Ｒ１〜Ｒ３は全てメチル基であることが望ましい。一般式（１）の化合物を反応させると、シリカ微粒子の表面にはＳｉＨ基が導入されると共に、ＳｉＯ構造も導入されて疎水性が向上するものと考えられる。 The pretreatment compound is a compound having a plurality of SiH groups in its molecular structure. A part of the plurality of SiH groups reacts with the OH residue existing on the surface of the silica fine particles, and the remaining SiH groups remain in a bonded state. The pretreatment compound is not particularly limited except that it has a plurality of SiH groups. For example, a compound in which a part of a side chain of a polymer having a repeating unit of a siloxane bond as a main chain is hydrogen can be mentioned. An example in which an alkyl group is bonded to a silicon atom other than hydrogen is exemplified. Specifically, the compound of General formula (1) mentioned above is mentioned. Here, it is preferable all R 1 to R 3 is a methyl group. When the compound of the general formula (1) is reacted, it is considered that SiH groups are introduced on the surface of the silica fine particles and an SiO structure is also introduced to improve the hydrophobicity.
シリカ微粒子と前処理用化合物とはそれぞれを単純に混合させたり、前処理用化合物に対して不活性な溶媒にて希釈してシリカ微粒子に混合したりできる。混合後はそのまま放置したり、加熱したりすることができる。 The silica fine particles and the pretreatment compound can be simply mixed, or diluted with a solvent inert to the pretreatment compound and mixed with the silica fine particles. After mixing, it can be left as it is or heated.
前処理用化合物を反応させる量としては、ＳｉＨ基のうちの一部のみがシリカ微粒子の表面と反応し、残部がＳｉＨ基として残るような量とする。例えば、シリカ微粒子の表面積１ｍ２あたり、ＳｉＨ基が１×１０−４ｍｏｌ〜５×１０−２ｍｏｌ程度になるように前処理用化合物を反応させることが望ましく、１×１０−２ｍｏｌ〜３×１０−２ｍｏｌ程度になるように前処理用化合物を反応させることが更に望ましい。
・分散工程
分散工程はアルケニル基をもつシリコーン（アルケニル基含有シリコーン）中にＳｉＨ基含有シリカ微粒子を分散させて、アルケニル基とＳｉＨ基とを反応・結合させて、シリコーン中にシリカ微粒子を高度に分散させる工程である。
The amount of the pretreatment compound to be reacted is such that only a part of the SiH groups reacts with the surface of the silica fine particles, and the remainder remains as SiH groups. For example, surface area 1 m 2 per silica fine particles, SiH groups desirably reacting pretreatment compound to be about 1 × 10 -4 mol~5 × 10 -2 mol, 1 × 10 -2 mol~3 It is further desirable to react the pretreatment compound so as to be about × 10 −2 mol.
・ Dispersing step In the dispersing step, SiH group-containing silica fine particles are dispersed in an alkenyl group-containing silicone (alkenyl group-containing silicone), and the alkenyl group and SiH group are reacted and bonded to each other. This is a step of dispersing.
シリコーンはシロキサン結合からなる繰り返し単位をもつ重合体でケイ素にはアルキル基が結合している。アルキル基としてはメチル基が望ましい。アルケニル基はシリコーンのどの部位に結合していても良いが、いずれかのアルキル基の代わりに導入することができる。アルケニル基を導入する数は特に限定しない。アルケニル基としてはビニル基、プロピニル基が望ましい。アルケニル基含有シリコーンはアルケニル基を過剰に有するようにしたり、その他の反応基を有するようにしたりすることで、製造したシリカ含有有機組成物を適正に硬化させることができる。 Silicone is a polymer having a repeating unit composed of a siloxane bond, and an alkyl group is bonded to silicon. A methyl group is desirable as the alkyl group. The alkenyl group may be bonded to any part of the silicone, but can be introduced in place of any alkyl group. The number of alkenyl groups introduced is not particularly limited. As the alkenyl group, a vinyl group and a propynyl group are desirable. By making the alkenyl group-containing silicone excessively contain alkenyl groups or other reactive groups, the produced silica-containing organic composition can be properly cured.
アルケニル基含有シリコーンのアルケニル基とＳｉＨ基含有シリカ微粒子のＳｉＨ基とは付加反応触媒の存在下混合することにより反応する。付加反応触媒としては特に限定しないが、白金系触媒が例示できる。白金系触媒としては、白金黒、塩化白金酸、塩化白金酸−一価アルコール、塩化白金酸−オレフィン化合物、白金−ビニルシロキサン錯体が例示できる。付加反応触媒の添加量はいわゆる触媒量として添加すれば充分である。 The alkenyl group of the alkenyl group-containing silicone reacts with the SiH group of the SiH group-containing silica fine particles by mixing in the presence of an addition reaction catalyst. Although it does not specifically limit as an addition reaction catalyst, A platinum-type catalyst can be illustrated. Examples of the platinum-based catalyst include platinum black, chloroplatinic acid, chloroplatinic acid-monohydric alcohol, chloroplatinic acid-olefin compound, and platinum-vinylsiloxane complex. It is sufficient to add the addition reaction catalyst as a so-called catalyst amount.
アルケニル基含有シリコーンとＳｉＨ基含有シリカ微粒子と付加反応触媒とを混合後、必要に応じて加熱することにより反応させる。この混合状態に応じて最終生成物中におけるシリカ微粒子の分散状態が変化するため、できるだけ均一になるまで混合・分散を行う。 The alkenyl group-containing silicone, SiH group-containing silica fine particles and the addition reaction catalyst are mixed, and then reacted by heating as necessary. Since the dispersion state of the silica fine particles in the final product changes in accordance with the mixing state, mixing and dispersion are performed until it is as uniform as possible.
ＳｉＨ基含有シリカ微粒子とアルケニル基含有シリコーンとの混合比は特に限定しないが、全体の質量を基準としてＳｉＨ基含有シリカ微粒子の質量が１％〜７０％とすることが望ましく、１０％〜６０％とすることが更に望ましい。 The mixing ratio of the SiH group-containing silica fine particles and the alkenyl group-containing silicone is not particularly limited, but the mass of the SiH group-containing silica fine particles is preferably 1% to 70% based on the total mass, and is preferably 10% to 60%. Is more desirable.
（シリカ含有有機組成物：その１）
本実施形態のシリカ含有有機組成物は上述した製造方法にて製造され得る形態をもつ。つまり、シリカ微粒子の表面にＳＩＨ基由来のＳｉＯ結合を介して結合したＳＩＨ基に対して、アルケニル基が付加反応することによりシリコーンが結合された分子構造をもつものである。シリカ微粒子とシリコーンとの混合比は上述した製造方法と同様の混合比を採用できる。
(Silica-containing organic composition: 1)
The silica-containing organic composition of the present embodiment has a form that can be produced by the production method described above. That is, it has a molecular structure in which silicone is bonded to an SIH group bonded to the surface of a silica fine particle via an SIH group-derived SiO bond by an addition reaction of an alkenyl group. As the mixing ratio of the silica fine particles and the silicone, the same mixing ratio as that in the manufacturing method described above can be adopted.
（シリカ含有有機組成物：その２）
本実施形態のシリカ含有有機組成物はシリカ微粒子とそのシリカ微粒子の表面に−（ＳｉＯ）ｎ−（：ｎは１以上）と炭素−炭素結合を介して結合され、そのシリカ微粒子を分散するシリコーンとを有する。シリカ微粒子とシリコーンとの混合比は上述した製造方法と同様の混合比を採用できる。
(Silica-containing organic composition: 2)
The silica-containing organic composition of the present embodiment is a silicone in which silica particles are bonded to the surface of the silica particles through — (SiO) n — (where n is 1 or more) and a carbon-carbon bond, and the silica particles are dispersed. And have. As the mixing ratio of the silica fine particles and the silicone, the same mixing ratio as that in the manufacturing method described above can be adopted.
・試験例１
１００質量部のシリカ微粒子（体積平均粒径０．５μｍ：ＳＯ−２５Ｒ：アドマテックス製）と、１質量部のジメチルシリコーン誘導体（ＫＦ−９９０１：信越化学工業製：メチル基の一部が水素に置換されている）とを混合した。ジメチルシリコーン誘導体のＳＩＨ基がシリカ微粒子の表面に反応してＳｉＨ基含有シリカ微粒子Ａを得た。
Test example 1
100 parts by mass of silica fine particles (volume average particle size 0.5 μm: SO-25R: manufactured by Admatechs) and 1 part by mass of dimethyl silicone derivative (KF-9901: manufactured by Shin-Etsu Chemical Co., Ltd .: part of the methyl group is converted to hydrogen. Substituted). The SIH group of the dimethyl silicone derivative reacted with the surface of the silica fine particles to obtain SiH group-containing silica fine particles A.
ＳｉＨ基含有シリカ微粒子Ａを６０質量部、末端にビニル基をもつシリコーン（アルケニル基含有シリコーン：ＫＥ−１０５１Ｊ：信越化学工業製）を４０質量部、付加反応触媒としての塩化白金酸を２質量％含む２−エチルヘキサノール溶液を０．００１質量部とをプラネタリーミキサー、更には３本ロールで混合した。その後、１２０℃で１時間加熱して本試験例のシリカ含有有機組成物とした。 60 parts by mass of silica fine particles A containing SiH groups, 40 parts by mass of silicone having a vinyl group at the terminal (alkenyl group-containing silicone: KE-1051J: manufactured by Shin-Etsu Chemical Co., Ltd.), and 2% by mass of chloroplatinic acid as an addition reaction catalyst The 2-ethylhexanol solution containing 0.001 part by mass was mixed with a planetary mixer and further with three rolls. Then, it heated at 120 degreeC for 1 hour, and was set as the silica containing organic composition of this test example.
本試験例のシリカ含有有機組成物を２枚のスライドガラスの間に挟持して光学顕微鏡にて分散状態を観察したところ、凝集体はなく均一に分散されていた。
・試験例２
１００質量部のシリカ微粒子（体積平均粒径３０μｍ：ＦＥＥ００Ｂ：アドマテックス製）と、１質量部のジメチルシリコーン誘導体（ＫＦ−９９０１：信越化学工業製：メチル基の一部が水素に置換されている）とを混合した。ジメチルシリコーン誘導体のＳＩＨ基がシリカ微粒子の表面に反応してＳｉＨ基含有シリカ微粒子Ｂを得た。
The silica-containing organic composition of this test example was sandwiched between two glass slides and the dispersion state was observed with an optical microscope. As a result, there was no aggregate and it was uniformly dispersed.
Test example 2
100 parts by mass of silica fine particles (volume average particle size 30 μm: FEE00B: manufactured by Admatechs) and 1 part by mass of dimethyl silicone derivative (KF-9901: manufactured by Shin-Etsu Chemical Co., Ltd.): Part of the methyl group is replaced with hydrogen. ). The SIH group of the dimethyl silicone derivative reacted with the surface of the silica fine particles to obtain SiH group-containing silica fine particles B.
ＳｉＨ基含有シリカ微粒子Ｂを４０質量部、末端にビニル基をもつシリコーン（アルケニル基含有シリコーン：ＫＥ−１０５１Ｊ：信越化学工業製）を６０質量部、付加反応触媒としての塩化白金酸を２質量％含む２−エチルヘキサノール溶液を０．００１質量部とをプラネタリーミキサー、更には３本ロールで混合した。その後、１２０℃で１時間加熱して本試験例のシリカ含有有機組成物とした。 40 parts by mass of silica fine particles B containing SiH groups, 60 parts by mass of silicone having a vinyl group at the terminal (alkenyl group-containing silicone: KE-1051J: manufactured by Shin-Etsu Chemical Co., Ltd.), and 2% by mass of chloroplatinic acid as an addition reaction catalyst The 2-ethylhexanol solution containing 0.001 part by mass was mixed with a planetary mixer and further with three rolls. Then, it heated at 120 degreeC for 1 hour, and was set as the silica containing organic composition of this test example.
本試験例のシリカ含有有機組成物を２枚のスライドガラスの間に挟持して光学顕微鏡にて分散状態を観察したところ、凝集体はなく均一に分散されていた。
・試験例３
１００質量部のシリカ微粒子（体積平均粒径５０ｎｍ：ＰＶＳ法にて製造：株式会社シーアイ化成製）と、１質量部のジメチルシリコーン誘導体（ＫＦ−９９０１：信越化学工業製：メチル基の一部が水素に置換されている）とを混合した。ジメチルシリコーン誘導体のＳＩＨ基がシリカ微粒子の表面に反応してＳｉＨ基含有シリカ微粒子Ｃを得た。
The silica-containing organic composition of this test example was sandwiched between two glass slides and the dispersion state was observed with an optical microscope. As a result, there was no aggregate and it was uniformly dispersed.
Test example 3
100 parts by mass of silica fine particles (volume average particle size 50 nm: manufactured by PVS method: manufactured by C-I Kasei Co., Ltd.) and 1 part by mass of dimethyl silicone derivative (KF-9901: manufactured by Shin-Etsu Chemical Co., Ltd.): Mixed with hydrogen). The SIH group of the dimethyl silicone derivative reacted with the surface of the silica fine particles to obtain SiH group-containing silica fine particles C.
ＳｉＨ基含有シリカ微粒子Ｃを４０質量部、末端にビニル基をもつシリコーン（アルケニル基含有シリコーン：ＫＥ−１０５１Ｊ：信越化学工業製）を６０質量部、付加反応触媒としての塩化白金酸を２質量％含む２−エチルヘキサノール溶液を０．００１質量部とをプラネタリーミキサー、更には３本ロールで混合した。その後、１２０℃で１時間加熱して本試験例のシリカ含有有機組成物とした。 40 parts by mass of SiH group-containing silica fine particles C, 60 parts by mass of silicone having a vinyl group at the end (alkenyl group-containing silicone: KE-1051J: manufactured by Shin-Etsu Chemical Co., Ltd.), and 2% by mass of chloroplatinic acid as an addition reaction catalyst The 2-ethylhexanol solution containing 0.001 part by mass was mixed with a planetary mixer and further with three rolls. Then, it heated at 120 degreeC for 1 hour, and was set as the silica containing organic composition of this test example.
本試験例のシリカ含有有機組成物を２枚のスライドガラスの間に挟持して光学顕微鏡にて分散状態を観察したところ、凝集体はなく均一に分散されていた。
・試験例４
６０質量部のシリカ微粒子（ＳＯ−２５Ｒ：アドマテックス製）と、末端にビニル基をもつシリコーン（アルケニル基含有シリコーン：ＫＥ−１０５１Ｊ：信越化学工業製）を４０質量部、付加反応触媒としての塩化白金酸を２質量％含む２−エチルヘキサノール溶液を０．００１質量部とをプラネタリーミキサー、更には３本ロールで混合した。その後、１２０℃で１時間加熱して本試験例のシリカ含有有機組成物とした。
The silica-containing organic composition of this test example was sandwiched between two glass slides and the dispersion state was observed with an optical microscope. As a result, there was no aggregate and it was uniformly dispersed.
Test example 4
60 parts by mass of silica fine particles (SO-25R: manufactured by Admatex) and 40 parts by mass of silicone having a vinyl group at the terminal (alkenyl group-containing silicone: KE-1051J: manufactured by Shin-Etsu Chemical Co., Ltd.) 0.001 part by mass of a 2-ethylhexanol solution containing 2% by mass of platinic acid was mixed with a planetary mixer and further three rolls. Then, it heated at 120 degreeC for 1 hour, and was set as the silica containing organic composition of this test example.
本試験例のシリカ含有有機組成物を２枚のスライドガラスの間に挟持して光学顕微鏡にて分散状態を観察したところ、凝集体が認められて充分な分散は実現されていなかった。
・試験例５
６０質量部のシリカ微粒子（ＦＥＥ００Ｂ：アドマテックス製）と、末端にビニル基をもつシリコーン（アルケニル基含有シリコーン：ＫＥ−１０５１Ｊ：信越化学工業製）を４０質量部、付加反応触媒としての塩化白金酸を２質量％含む２−エチルヘキサノール溶液を０．００１質量部とをプラネタリーミキサー、更には３本ロールで混合した。その後、１２０℃で１時間加熱して本試験例のシリカ含有有機組成物とした。
When the silica-containing organic composition of this test example was sandwiched between two glass slides and the dispersion state was observed with an optical microscope, aggregates were observed and sufficient dispersion was not realized.
Test example 5
60 parts by mass of silica fine particles (FEE00B: manufactured by Admatex) and 40 parts by mass of silicone having a vinyl group at the terminal (alkenyl group-containing silicone: KE-1051J: manufactured by Shin-Etsu Chemical Co., Ltd.), chloroplatinic acid as an addition reaction catalyst 0.002 part by mass of 2-ethylhexanol solution containing 2% by mass of the mixture was mixed with a planetary mixer and further with three rolls. Then, it heated at 120 degreeC for 1 hour, and was set as the silica containing organic composition of this test example.
本試験例のシリカ含有有機組成物を２枚のスライドガラスの間に挟持して光学顕微鏡にて分散状態を観察したところ、凝集体が認められて充分な分散は実現されていなかった。
・試験例６
６０質量部のシリカ微粒子（株式会社シーアイ化成製）と、末端にビニル基をもつシリコーン（アルケニル基含有シリコーン：ＫＥ−１０５１Ｊ：信越化学工業製）を４０質量部、付加反応触媒としての塩化白金酸を２質量％含む２−エチルヘキサノール溶液を０．００１質量部とをプラネタリーミキサー、更には３本ロールで混合した。その後、１２０℃で１時間加熱して本試験例のシリカ含有有機組成物とした。
When the silica-containing organic composition of this test example was sandwiched between two glass slides and the dispersion state was observed with an optical microscope, aggregates were observed and sufficient dispersion was not realized.
Test example 6
60 parts by mass of silica fine particles (manufactured by Cii Kasei Co., Ltd.) and 40 parts by mass of silicone having a vinyl group at the terminal (alkenyl group-containing silicone: KE-1051J: manufactured by Shin-Etsu Chemical Co., Ltd.), chloroplatinic acid as an addition reaction catalyst 0.002 part by mass of 2-ethylhexanol solution containing 2% by mass of the mixture was mixed with a planetary mixer and further with three rolls. Then, it heated at 120 degreeC for 1 hour, and was set as the silica containing organic composition of this test example.
本試験例のシリカ含有有機組成物を２枚のスライドガラスの間に挟持して光学顕微鏡にて分散状態を観察したところ、凝集体が認められて充分な分散は実現されていなかった。
・試験例７
１００質量部のシリカ微粒子（ＳＯ−２５Ｒ）と、１質量部のジメチルシリコーン誘導体（ＫＦ−９９０１：信越化学工業製：メチル基の一部が水素に置換されている）とを混合した。ジメチルシリコーン誘導体のＳＩＨ基がシリカ微粒子の表面に反応してＳｉＨ基含有シリカ微粒子Ａを得た。
When the silica-containing organic composition of this test example was sandwiched between two glass slides and the dispersion state was observed with an optical microscope, aggregates were observed and sufficient dispersion was not realized.
Test example 7
100 parts by mass of silica fine particles (SO-25R) and 1 part by mass of a dimethyl silicone derivative (KF-9901: manufactured by Shin-Etsu Chemical Co., Ltd .: a part of the methyl group was substituted with hydrogen) were mixed. The SIH group of the dimethyl silicone derivative reacted with the surface of the silica fine particles to obtain SiH group-containing silica fine particles A.
ＳｉＨ基含有シリカ微粒子Ａを６０質量部、アルケニル基をもたないシリコーンを４０質量部、付加反応触媒としての塩化白金酸を２質量％含む２−エチルヘキサノール溶液を０．００１質量部とをプラネタリーミキサー、更には３本ロールで混合した。その後、１２０℃で１時間加熱して本試験例のシリカ含有有機組成物とした。 A planetar containing 60 parts by mass of SiH group-containing silica fine particles A, 40 parts by mass of silicone having no alkenyl group, and 0.001 part by mass of a 2-ethylhexanol solution containing 2% by mass of chloroplatinic acid as an addition reaction catalyst. The mixture was mixed with a Lee mixer and three rolls. Then, it heated at 120 degreeC for 1 hour, and was set as the silica containing organic composition of this test example.
本試験例のシリカ含有有機組成物を２枚のスライドガラスの間に挟持して光学顕微鏡にて分散状態を観察したところ、凝集体が認められて充分な分散は実現されていなかった。
・その他評価
試験例１〜３、７におけるＳｉＨ基含有シリカ微粒子についてＩＲ測定を行った結果、２１１〜２２００ｃｍ−１程度にＳｉＨ基の吸収が認められた。
・結論
試験例１〜３にて得られたシリカ含有有機組成物はシリカ微粒子が高度に分散されており、非常に安定性が高いものであり、光学的にも高い均一性が認められた。それに対して試験例４〜７にて得られたシリカ含有有機組成物は分散直後においても凝集体を形成しており、充分な透明性も示さなかった。試験例４〜６においては親水性が高いシリカ微粒子が疎水性が高いシリコーンと分離したために分散性が充分でないものと考えられる。試験例７においては表面をある程度疎水化したとしてもシリカ微粒子は疎水性が高いシリコーン中ではそのまま安定して分散できず、分散性が充分でないものと考えられる。
When the silica-containing organic composition of this test example was sandwiched between two glass slides and the dispersion state was observed with an optical microscope, aggregates were observed and sufficient dispersion was not realized.
-Other evaluation As a result of performing IR measurement about the SiH group containing silica fine particle in Test Examples 1-3, the absorption of SiH group was recognized by about 211-2200 cm < -1 >.
Conclusion The silica-containing organic compositions obtained in Test Examples 1 to 3 have highly dispersed silica fine particles, are very stable, and have high optical uniformity. In contrast, the silica-containing organic compositions obtained in Test Examples 4 to 7 formed aggregates even immediately after dispersion, and did not show sufficient transparency. In Test Examples 4 to 6, it is considered that dispersibility is not sufficient because silica particles having high hydrophilicity are separated from silicone having high hydrophobicity. In Test Example 7, even if the surface is hydrophobized to some extent, the silica fine particles cannot be stably dispersed as they are in the highly hydrophobic silicone, and it is considered that the dispersibility is not sufficient.
Claims (6)
付加反応触媒の存在下、前記ＳｉＨ基含有シリカ微粒子にアルケニル基含有シリコーンを含むシリコーンを混合し、前記アルケニル基と反応させてシリカ微粒子分散シリコーンとする分散工程と、
を有することを特徴とするシリカ含有有機組成物の製造方法。 A pretreatment step of reacting a part of the SiH groups of the pretreatment compound having a plurality of SiH groups with the silica particles to introduce the remaining SiH groups on the surface to form SiH group-containing silica particles;
In the presence of an addition reaction catalyst, the SiH group-containing silica fine particles are mixed with a silicone containing an alkenyl group-containing silicone and reacted with the alkenyl group to form a silica fine particle-dispersed silicone;
A method for producing a silica-containing organic composition, comprising:
（式（１）中、Ｒ１〜Ｒ３はアルキル基からそれぞれ独立して選択可能である。ｎ，ｍはそれぞれ独立して選択可能な正の整数である。） The pretreatment compound of the general formula (1) :-( SiHR 1 -O) n (SiR 2 R 3 -O) m - in the silica-containing organic composition according to claim 1 which is a compound represented Production method.
(In formula (1), R 1 to R 3 can be independently selected from an alkyl group. N and m are each independently a positive integer that can be selected.)
前記シリカ微粒子の表面に−（ＳｉＯ）ｎ−（：ｎは１以上）と炭素−炭素結合を介して結合され、前記シリカ微粒子を分散するシリコーンと、
を有することを特徴とするシリカ含有有機組成物。 Silica fine particles,
-(SiO) n- (where n is 1 or more) and a silicone that disperses the silica particles, and bonded to the surface of the silica particles through a carbon-carbon bond;
A silica-containing organic composition characterized by comprising:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009082984A JP5265434B2 (en) | 2009-03-30 | 2009-03-30 | Silica-containing organic composition and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009082984A JP5265434B2 (en) | 2009-03-30 | 2009-03-30 | Silica-containing organic composition and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2010235693A true JP2010235693A (en) | 2010-10-21 |
| JP5265434B2 JP5265434B2 (en) | 2013-08-14 |
Family
ID=43090333
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2009082984A Active JP5265434B2 (en) | 2009-03-30 | 2009-03-30 | Silica-containing organic composition and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5265434B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011202115A (en) * | 2010-03-26 | 2011-10-13 | Admatechs Co Ltd | Silicone resin composition and method for producing the same |
| EP3640210A4 (en) * | 2017-10-04 | 2020-06-03 | Admatechs Co., Ltd. | Silicone-coated filler, method of producing same, and resin composition |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09241129A (en) * | 1996-03-07 | 1997-09-16 | Shiseido Co Ltd | Composite powder material and its production |
| JPH09255793A (en) * | 1996-03-22 | 1997-09-30 | Toray Dow Corning Silicone Co Ltd | Silicone rubber powder and production thereof |
| JPH10120905A (en) * | 1996-08-29 | 1998-05-12 | Shin Etsu Chem Co Ltd | Production of silicone rubber |
| JP2002179920A (en) * | 2000-12-18 | 2002-06-26 | Shin Etsu Chem Co Ltd | Liquid type addition curable silicone rubber composition and preparation method therefor |
-
2009
- 2009-03-30 JP JP2009082984A patent/JP5265434B2/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09241129A (en) * | 1996-03-07 | 1997-09-16 | Shiseido Co Ltd | Composite powder material and its production |
| JPH09255793A (en) * | 1996-03-22 | 1997-09-30 | Toray Dow Corning Silicone Co Ltd | Silicone rubber powder and production thereof |
| JPH10120905A (en) * | 1996-08-29 | 1998-05-12 | Shin Etsu Chem Co Ltd | Production of silicone rubber |
| JP2002179920A (en) * | 2000-12-18 | 2002-06-26 | Shin Etsu Chem Co Ltd | Liquid type addition curable silicone rubber composition and preparation method therefor |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011202115A (en) * | 2010-03-26 | 2011-10-13 | Admatechs Co Ltd | Silicone resin composition and method for producing the same |
| EP3640210A4 (en) * | 2017-10-04 | 2020-06-03 | Admatechs Co., Ltd. | Silicone-coated filler, method of producing same, and resin composition |
| US11021590B2 (en) | 2017-10-04 | 2021-06-01 | Admatechs Co., Ltd. | Silicone-coated filler and production process for the same as well as resinous composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5265434B2 (en) | 2013-08-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5079450B2 (en) | Dispersible silica nano hollow particles and method for producing dispersion of silica nano hollow particles | |
| CN101296874B (en) | Process for producing spherical inorganic particle | |
| JP4460968B2 (en) | Method for producing resin composition | |
| Zhou et al. | Preparation and characterization of film-forming raspberry-like polymer/silica nanocomposites via soap-free emulsion polymerization and the sol–gel process | |
| JP5112157B2 (en) | Silica fine particles and silica fine particle-containing resin composition | |
| Hu et al. | Novel multifunctional microspheres of polysiloxane@ CeO2-PMMA: optical properties and their application in optical diffusers | |
| JP2006290724A (en) | Spherical silica particle, its production method, and resin composition | |
| JP5042529B2 (en) | Fine particle-containing composition and method for producing the same | |
| JP7194167B2 (en) | Powders and mixed powders | |
| JP2019524919A (en) | Composite particles having a coated aggregate having a low-structure carbon black core, coating and ink having high resistivity and optical density, apparatus made using these, and method for making the same | |
| JP4927363B2 (en) | Composition containing fine particles | |
| JP5265434B2 (en) | Silica-containing organic composition and method for producing the same | |
| JP5426869B2 (en) | Method for producing mesoporous silica fine particles, mesoporous silica fine particle-containing composition, and mesoporous silica fine particle-containing molded product | |
| JPWO2006104290A1 (en) | Water-based paint composition and heat shielding paint | |
| JP6618144B2 (en) | Spherical calcium fluoride | |
| WO2007020855A1 (en) | Process for producing spherical inorganic particle | |
| KR19990069189A (en) | Process for preparing organic-inorganic composite | |
| JP4559212B2 (en) | Organic-inorganic hybrid material, hybrid film formed thereby, and manufacturing method thereof | |
| YUAN et al. | Synthesis and characterization of polystyrene/nanosilica organic-inorganic hybrid | |
| JP5637691B2 (en) | polymer | |
| Li et al. | Design of different structure colloidal particles with unusual high content of methyltrimethoxysilane and their films properties | |
| JP7082257B1 (en) | Fillers for semiconductor mounting materials, their manufacturing methods, and semiconductor mounting materials | |
| TW202231581A (en) | Filler for semiconductor mounting materials, method for producing same and semiconductor mounting material | |
| JP2012087027A (en) | Metal oxide ultrafine powder, manufacturing method of the same, and use of the same | |
| JP2020007223A (en) | Spherical calcium fluoride |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20120113 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20130130 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20130205 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20130408 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20130423 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20130501 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 Ref document number: 5265434 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |