JPH04183727A - Production of fine spherical silicone resin particle - Google Patents
Production of fine spherical silicone resin particleInfo
- Publication number
- JPH04183727A JPH04183727A JP2312854A JP31285490A JPH04183727A JP H04183727 A JPH04183727 A JP H04183727A JP 2312854 A JP2312854 A JP 2312854A JP 31285490 A JP31285490 A JP 31285490A JP H04183727 A JPH04183727 A JP H04183727A
- Authority
- JP
- Japan
- Prior art keywords
- silicone resin
- silicone composition
- surfactant
- fine particles
- curable 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.)
- Pending
Links
- 239000002245 particle Substances 0.000 title claims abstract description 18
- 229920002050 silicone resin Polymers 0.000 title claims description 15
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 239000000203 mixture Substances 0.000 claims abstract description 34
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 26
- 239000004094 surface-active agent Substances 0.000 claims abstract description 12
- 239000002612 dispersion medium Substances 0.000 claims abstract description 10
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000001804 emulsifying effect Effects 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 22
- 239000002253 acid Substances 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000010419 fine particle Substances 0.000 abstract description 19
- 239000000839 emulsion Substances 0.000 abstract description 15
- 239000003945 anionic surfactant Substances 0.000 abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 10
- 239000000945 filler Substances 0.000 abstract description 4
- 239000012776 electronic material Substances 0.000 abstract description 3
- -1 polysiloxane Polymers 0.000 description 13
- 238000001723 curing Methods 0.000 description 10
- 230000010355 oscillation Effects 0.000 description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- 239000007809 chemical reaction catalyst Substances 0.000 description 6
- 238000006482 condensation reaction Methods 0.000 description 6
- 238000004945 emulsification Methods 0.000 description 6
- 239000002736 nonionic surfactant Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 239000011882 ultra-fine particle Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000007259 addition reaction Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- 238000002525 ultrasonication Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 239000004944 Liquid Silicone Rubber Substances 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229920002379 silicone rubber Polymers 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 229920001214 Polysorbate 60 Polymers 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical class [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- LWZFANDGMFTDAV-BURFUSLBSA-N [(2r)-2-[(2r,3r,4s)-3,4-dihydroxyoxolan-2-yl]-2-hydroxyethyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O LWZFANDGMFTDAV-BURFUSLBSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 1
- 125000005594 diketone group Chemical group 0.000 description 1
- 229920005645 diorganopolysiloxane polymer Polymers 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008393 encapsulating agent Substances 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229940070765 laurate Drugs 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229950006451 sorbitan laurate Drugs 0.000 description 1
- 235000011067 sorbitan monolaureate Nutrition 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、球状シリコーン樹脂微粒子の製造方法に関し
、さらに詳しくは、各種電子材料の充填物として有用な
、極微細な球状シリコーン樹脂微粒子の製造方法に関す
る。Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a method for producing fine spherical silicone resin particles, and more specifically, to a method for producing ultrafine spherical silicone resin particles useful as fillers for various electronic materials. Regarding the method.
（従来の技術および発明が解決しようとする課題）シリ
コーン樹脂微粒子は、弾性、滑り性、耐熱性、椀水性、
耐薬品性、電気特性および球状単分散による粉体特性等
の性質に優れているため、各種合成樹脂フィルムおよび
成形品、インキ、トナー、機能性塗料、化粧品、半導体
封止剤等の充填物に利用される。(Prior art and problems to be solved by the invention) Silicone resin fine particles have elasticity, slipperiness, heat resistance, water resistance,
Due to its excellent properties such as chemical resistance, electrical properties, and powder properties due to monodispersion of spherical particles, it can be used as fillers for various synthetic resin films and molded products, inks, toners, functional paints, cosmetics, semiconductor encapsulants, etc. used.
シリコーン樹脂微粒子は一般的に、原料となる硬化性シ
リコーン組成物を分散媒中でエマルション化して製造さ
れる。その際、界面活性剤を使用することが知られてい
る。また一般にノニオン系界面活性剤が好ましいとされ
ている。例えば特開昭６２−２４３６２１号公報には、
液状シリコーンゴム組成物を、トリメチルノナールのエ
チレンオキシド付加物のようなノニオン系界面活性剤を
用いて水性エマルション化し、この水性エマルションを
加温水中に分散させて硬化する方法が開示されている。Silicone resin fine particles are generally produced by emulsifying a curable silicone composition as a raw material in a dispersion medium. In this case, it is known to use a surfactant. Additionally, nonionic surfactants are generally preferred. For example, in Japanese Patent Application Laid-Open No. 62-243621,
A method is disclosed in which a liquid silicone rubber composition is made into an aqueous emulsion using a nonionic surfactant such as an ethylene oxide adduct of trimethylnonal, and the aqueous emulsion is dispersed in heated water and cured.
また、特開昭６３−２０２６５８号公報には、液状シリ
コーンゴム組成物を、トリメチルノナールのエチレンオ
キシド付加物等の界面活性剤の共存下で、市販のホモミ
キサー、ホモジナイザー、コロイドミル等の乳化機を通
過させてエマルション化し、加温水中に投入するか、熱
気流中に噴霧させて硬化させる方法が開示されている。Furthermore, JP-A No. 63-202658 discloses that a liquid silicone rubber composition is mixed in a commercially available emulsifier such as a homomixer, homogenizer, or colloid mill in the presence of a surfactant such as an ethylene oxide adduct of trimethylnonal. A method is disclosed in which the emulsion is made into an emulsion by passing through the emulsion, and the emulsion is poured into heated water or sprayed into a hot air stream to harden the emulsion.
ところがこれらの方法でシリコーン樹脂微粒子を製造し
ようとすると、通常は、シリコーン樹脂微粒子の平均粒
径は１μｍ以下にならない。However, when silicone resin fine particles are produced by these methods, the average particle size of the silicone resin fine particles is usually not less than 1 μm.
そこで、特開平１−３０６４７１号公報のように、マイ
クロフルイダイゼーションのような特殊な方法でエマル
ション化を行った場合には、ノニオン系界面活性剤との
組合せで、かなり（平均粒径約０．８μｍ）の微粒化が
可能である。しかしながら、その程度の粒径を得るため
には、多量のノニオン系界面活性剤を添加する必要があ
り、コスト高となって、工業的な製造方法には適しない
。Therefore, when emulsification is carried out using a special method such as microfluidization, as in JP-A-1-306471, in combination with a nonionic surfactant, it is possible to significantly increase the .8 μm) is possible. However, in order to obtain such a particle size, it is necessary to add a large amount of nonionic surfactant, which results in high cost and is not suitable for industrial production methods.
また、界面活性剤としてアニオン系界面活性剤を使用し
て上記したような硬化性シリコーン組成物のエマルショ
化を実際に行った例は見当たらない。しかも、時開＠６
３−３０９５６５号公報には、アニオン系界面活性剤を
使用してエマルション化を行うと、縮合反応型のシリコ
ーン樹脂微粒子を製造する際にはオルガノハイドロジエ
ンポリシロキサンの安定性を損なうので好ましくない旨
の記載もある。Further, there has been no example of actually emulsifying the above-mentioned curable silicone composition using an anionic surfactant as a surfactant. Moreover, time opening @6
Publication No. 3-309565 states that emulsification using an anionic surfactant is not preferable when producing condensation reaction type silicone resin particles because it impairs the stability of organohydrodiene polysiloxane. There is also a description of
そこで本発明は、アニオン系界面活性剤を使用して、平
均粒径が０．２μｍ以下の極微細な球状シリコーン樹脂
微粒子を効率的に製造方法を提供することを目的とする
。Therefore, an object of the present invention is to provide a method for efficiently producing ultrafine spherical silicone resin particles having an average particle size of 0.2 μm or less using an anionic surfactant.
（課題を解決するための手段）
本発明は、硬化性シリコーン組成物を、分散媒中で界面
活性剤の存在下にエマルション化し、次いで硬化させて
シリコーン樹脂微粒子を製造する方法において、
（ａ）界面活性剤がジアルキルスルホコハク酸塩であり
、かつ
（ｂ）硬化を１０〜３５℃で行う
ことを特徴とする。ここで上記の（ａ）および（ｂ）の
２つを満たすことが必要であり、これによって本発明で
は、上記した特開昭６３−３０９５８５号公報における
、アニオン系界面活性剤を使用した場合の不都合を解消
した。すなわち、アニオン系界面活性剤であるジアルキ
ルスルホコハク酸塩を使用しても、後の硬化を室温（１
０〜３５℃）で行うことにより、効率よ＜０．２μｍ以
下の極微粒子を製造することに成功した。(Means for Solving the Problems) The present invention provides a method for producing silicone resin fine particles by emulsifying a curable silicone composition in a dispersion medium in the presence of a surfactant and then curing the composition, comprising: (a) It is characterized in that the surfactant is a dialkyl sulfosuccinate, and (b) curing is carried out at 10 to 35°C. Here, it is necessary to satisfy the above two conditions (a) and (b), and thereby, in the present invention, in the case of using an anionic surfactant in the above-mentioned Japanese Patent Application Laid-Open No. 63-309585, Solved the inconvenience. That is, even if dialkyl sulfosuccinates, which are anionic surfactants, are used, the subsequent curing is delayed to room temperature (1
By carrying out the process at a temperature of 0 to 35°C, we succeeded in efficiently producing ultrafine particles of <0.2 μm or less.
本発明で使用する硬化性シリコーン組成物とは、目的と
するシリコーン樹脂の微粒子を製造するための原料とな
るポリシロキサン類の混合物をいい、任意的にポリシロ
キサン類を溶解する有機溶媒を含むことも可能である。The curable silicone composition used in the present invention refers to a mixture of polysiloxanes that is a raw material for producing the target silicone resin fine particles, and may optionally contain an organic solvent that dissolves the polysiloxanes. is also possible.
付加反応硬化型、縮合反応硬化型等によって、使用する
ポリシロキサン類を適宜選択する。例えば付加反応硬化
型のシリコーン樹脂の微粒子を製造する場合には、１分
子中に少なくとも２個のアルケニル基を有するオルガノ
ポリシロキサン（例えば分子鎖両末端がトリメチルシロ
キシ基で封鎖されたポリビニルシロキサン）、および１
分子中に少なくとも２個のケイ素原子結合水素原子を有
するオルガノハイドロジエンポリシロキサンを含む。こ
のとき付加反応触媒として白金系硬化触媒をさらに含む
ことができる。使用する白金系触媒としては、例えば塩
化白金酸もしくはこれをアルコール、ケトンなどの溶媒
に溶解させた塩化白金酸溶液またはこの溶液を熟成させ
たもの、または塩化白金酸とアルデヒド、オレフィン、
アルケニルシロキサン、ジケトンなどとの錯体、白金黒
、白金を担体に担持させたものなどが挙げられる。これ
らの付加反応触媒は、硬化性シリコーン組成物１００万
重量部に対して白金系金属として０．１〜１０００重量
部使用され、好ましくは１０〜２００重量部が使用され
る。The polysiloxane to be used is appropriately selected depending on whether it is an addition reaction curing type, a condensation reaction curing type, or the like. For example, when manufacturing fine particles of addition reaction-curable silicone resin, organopolysiloxane having at least two alkenyl groups in one molecule (for example, polyvinylsiloxane in which both ends of the molecular chain are capped with trimethylsiloxy groups), and 1
Contains organohydrodiene polysiloxanes having at least two silicon-bonded hydrogen atoms in the molecule. At this time, a platinum-based curing catalyst may be further included as an addition reaction catalyst. Examples of the platinum-based catalyst used include chloroplatinic acid, a chloroplatinic acid solution prepared by dissolving this in a solvent such as an alcohol or a ketone, or an aged solution of chloroplatinic acid, or chloroplatinic acid and an aldehyde, an olefin,
Examples include complexes with alkenylsiloxanes and diketones, platinum black, and platinum supported on carriers. These addition reaction catalysts are used in an amount of 0.1 to 1000 parts by weight, preferably 10 to 200 parts by weight, as platinum metal based on 1 million parts by weight of the curable silicone composition.
また、縮合反応型のシリコーン樹脂の微粒子を製造する
場合には、１分子中に少なくとも２個の水酸基を有する
ジオルガノポリシロキサン、および１分子中に少なくと
も２個のケイ素原子結合水素原子を有するオルガノハイ
ドロジエンポリシロキサンを含む。このとき、さらに縮
合反応触媒を含むことができる。そのような縮合反応触
媒としては、有機酸金属塩、例えばジブチル チン ジ
オクテート、ラウリン酸鉛、チタン酸エステル等が挙げ
られる。これらの縮合反応触媒は、硬化性シリコーン組
成物１００重量部に対して、有機酸金属塩として０．０
１〜２０重量部、好ましくは０．１〜１０重量部が使用
される。In addition, when producing fine particles of condensation reaction type silicone resin, diorganopolysiloxane having at least two hydroxyl groups in one molecule and organopolysiloxane having at least two silicon-bonded hydrogen atoms in one molecule are used. Contains hydrogen polysiloxane. At this time, a condensation reaction catalyst may be further included. Examples of such condensation reaction catalysts include organic acid metal salts, such as dibutyl tin dioctate, lead laurate, and titanate esters. These condensation reaction catalysts are used in an amount of 0.0 as an organic acid metal salt per 100 parts by weight of the curable silicone composition.
1 to 20 parts by weight are used, preferably 0.1 to 10 parts by weight.
本発明においては、上記した硬化性シリコーン組成物を
、分散媒中で特定のアニオン系界面活性剤の存在下にエ
マルション化する。使用する分散媒としては、水が主と
して使用されるが、水とアルコールなどの有機溶媒（た
だし、シリコーンを溶解しない）との混合物またはこの
ような有機溶媒を用いることもできる。分散媒は、硬化
性シリコーン組成物１重量部に対して１０〜１重量部の
量で使用するのが好ましい。In the present invention, the above-described curable silicone composition is emulsified in a dispersion medium in the presence of a specific anionic surfactant. Water is mainly used as the dispersion medium, but a mixture of water and an organic solvent such as alcohol (which does not dissolve silicone) or such an organic solvent can also be used. The dispersion medium is preferably used in an amount of 10 to 1 part by weight per 1 part by weight of the curable silicone composition.
本発明で使用する界面活性剤は、ジアルキルスルホコハ
ク酸塩であり、ナトリウム塩、カリウム塩、アンモニウ
ム塩等が使用できる。ジアルキルエステル部分は、同じ
でも異なっていても良く、２−エチルヘキシル、オクチ
ル、ヘプチル、ヘキシル、イソブチル、ブチル、プロピ
ル、エチル等であることができる。このような界面活性
剤は、上記の硬化性シリコーン組成物１００重量部に対
して０．０１〜３０重量部、好ましくは０．１〜２０重
量部使用する。The surfactant used in the present invention is a dialkyl sulfosuccinate, and sodium salt, potassium salt, ammonium salt, etc. can be used. The dialkyl ester moieties may be the same or different and can be 2-ethylhexyl, octyl, heptyl, hexyl, isobutyl, butyl, propyl, ethyl, and the like. Such a surfactant is used in an amount of 0.01 to 30 parts by weight, preferably 0.1 to 20 parts by weight, per 100 parts by weight of the above-mentioned curable silicone composition.
さらに、上記の硬化性シリコーン組成物、分散媒および
界面活性剤からなる混合物に、必要に応じて、エマルシ
ョンの硬化を抑制するため、硬化抑制剤として、アセチ
レン系化合物、ヒドラジン類、トリアゾール類、ホスフ
ィン類、メルカプタン等を加えても良い。また耐熱剤、
難燃剤、可塑剤等を添加することもできる。Furthermore, in order to suppress the hardening of the emulsion, an acetylene compound, hydrazine, triazole, or phosphine may be added to the mixture consisting of the above-mentioned curable silicone composition, dispersion medium, and surfactant as a hardening inhibitor, if necessary. mercaptan, etc. may be added. Also heat resistant agent,
Flame retardants, plasticizers, etc. can also be added.
エマルション化は、慣用の乳化機、例えばホモミキサー
、ホモジナイザー、コロイドミル等、また、超音波装置
、マイクロフルイダイゼーション等の公知の方法が使用
できる。好ましいエマルジョン化の方法は、超音波処理
工程およびマイクロフルイダイゼーション工程を組合せ
た方法である。この方法を用いると、狭い粒径分布を有
する微粒子が得られる。また、この超音波処理工程およ
びマイクロフルイダイゼーション工程を行う前に、任意
的に、ホモミキサー等の公知の乳化機を使用してプレエ
マルション化すると、より微細な粒子が得られるので特
に好ましい。For emulsification, a conventional emulsifying machine such as a homomixer, a homogenizer, a colloid mill, etc., or a known method such as an ultrasonic device, microfluidization, etc. can be used. A preferred emulsification method is a method that combines an ultrasonication step and a microfluidization step. Using this method, fine particles with a narrow particle size distribution are obtained. Furthermore, before performing the ultrasonication step and the microfluidization step, it is particularly preferable to optionally perform pre-emulsion using a known emulsifier such as a homomixer, since finer particles can be obtained.
超音波処理には、好ましくは出力５０〜１２００Ｗ、発
振周波数２８〜１５ＫＨｚおよび発振振幅１０〜８０μ
ｍ、さらに好ましくは出力３００〜１２００Ｗ、発振周
波数２０〜１５Ｋ Ｈｚ 、発振振幅２０〜５０μｍの
高出力超音波発振性能を有する装置を使用する。超音波
処理方法は特に限定されないが、円柱形発振チップの先
端から超音波が発生するものを使用するのが好ましい。For ultrasonic treatment, preferably a power of 50 to 1200 W, an oscillation frequency of 28 to 15 KHz, and an oscillation amplitude of 10 to 80 μ
m, more preferably an apparatus having high-output ultrasonic oscillation performance with an output of 300 to 1200 W, an oscillation frequency of 20 to 15 KHz, and an oscillation amplitude of 20 to 50 μm. Although the ultrasonic treatment method is not particularly limited, it is preferable to use a method in which ultrasonic waves are generated from the tip of a cylindrical oscillation tip.
例えば、超音波を効果的に照射するために、音響的に鋼
壁体になるように肉厚の構造で、発振チップを包囲する
照射壁を有するホルダーを使用して、シリコーン組成物
を供給する方法が好ましく挙げられる。その際、供給平
均速度は２０〜１０００ ｍｌ ７分であり、好ましく
は４０〜８ｏｏ ｍｌ／分である。１０００ ｍｌ ７
分を超えるとエマルション化が効率よく進まず、２０
ｍｌ ７分より低いと発熱が激しくなるので、微粒化の
前に硬化してしまう。簡易的には、慣用のビーカーに界
面活性剤を含む分散媒を入れ、そこに上記した円柱形発
振チップを入れて、超音波を照射しながら硬化性シリコ
ーン組成物を投入する方法も使用できる。For example, for effective ultrasonic irradiation, a silicone composition is supplied using a holder with an irradiation wall that surrounds the oscillation chip, with a thick-walled structure that is acoustically steel-walled. Methods are preferred. In this case, the average feed rate is 20-1000 ml 7 minutes, preferably 40-8oo ml/min. 1000ml 7
If the time exceeds 20 minutes, emulsion will not proceed efficiently.
If the time is lower than 7 minutes, heat generation will become intense and the mixture will harden before being atomized. A simple method can also be used in which a dispersion medium containing a surfactant is placed in a conventional beaker, the above-described cylindrical oscillation chip is placed therein, and the curable silicone composition is added while irradiating with ultrasonic waves.
超音波処理工程は、単独の装置での処理でも良く、また
２つ以上の装置を組合せた多連式の処理でもよい。多連
式にすることにより、処理量を増大させることができる
。The ultrasonic treatment step may be performed using a single device, or may be a multi-stage process using a combination of two or more devices. By using a multiple system, the throughput can be increased.
次にマイクロフルイダイゼーション工程について説明す
る。マイクロフルイダイゼーションとは、複数の高圧流
体を衝突区域で衝突させて液／′液分散する方法を意味
する。そのような方法を実施するには、例えば高圧ホモ
ジナイザーといわれる公知の装置が使用でき、具体的に
は、マイクロフルイデイクスコーポレーション社製のマ
イクロフルイダイザー（商標）が挙げられる。供給速度
は、２０〜１０００ ｍｌ ７分であり、好ましくは４
０〜８００ｍ１／分である。マイクロフルイダイゼーシ
ョン工程もまた、２回以上組合せることが可能である。Next, the microfluidization process will be explained. Microfluidization refers to a method of liquid/liquid dispersion by colliding multiple high-pressure fluids in a collision zone. To carry out such a method, a known device called a high-pressure homogenizer can be used, and a specific example is Microfluidizer (trademark) manufactured by Microfluidics Corporation. The feed rate is 20-1000 ml 7 minutes, preferably 4
0 to 800 m1/min. Microfluidization steps can also be combined two or more times.
上記した超音波処理工程およびマイクロフルイダイゼー
ション工程は、その順序を逆にすることも可能である。The order of the above-described ultrasonication step and microfluidization step can also be reversed.
上記のエマルション化の際の液温は通常−１０°Ｃ〜９
０℃、好ましくは０〜４０℃である。−１０℃未満では
、混合物の粘度が高くなり過ぎる傾向があり、一方、９
０℃より高いとエマルション化の際に硬化反応が進行し
て、微小なシリコーン樹脂を得ることが困難となる傾向
がある。The liquid temperature during the above emulsion is usually -10°C to 9°C.
0°C, preferably 0 to 40°C. Below -10°C, the viscosity of the mixture tends to become too high;
If the temperature is higher than 0°C, the curing reaction tends to proceed during emulsification, making it difficult to obtain fine silicone resin.
先に述べた硬化性シリコーン組成物に反応触媒を含まな
かった場合には、ここで得られたエマルションに触媒を
添加した後、次の硬化の工程を行う。If the curable silicone composition described above does not contain a reaction catalyst, the catalyst is added to the emulsion obtained here, and then the next curing step is carried out.
本発明においては、得られた微粒子を加熱せずに、室温
、すなわち１０〜３５℃、好ましくは２０〜３０℃で硬
化することが必要である。硬化時間は５〜４８時間、好
ましくは１０〜３０時間である。In the present invention, it is necessary to cure the obtained fine particles at room temperature, that is, 10 to 35°C, preferably 20 to 30°C, without heating. Curing time is 5 to 48 hours, preferably 10 to 30 hours.
また回収は、懸濁液をスプレードライヤーを用いて水分
蒸発させる、懸濁液を濾過する等の公知の手段を使用で
きる。For recovery, known means such as evaporating water from the suspension using a spray dryer or filtering the suspension can be used.
本発明の方法では、アニオン系界面活性剤であるジアル
キルスルホコハク酸塩を用いてエマルション化を行なっ
ているので、超微粒子（０，１μｍ以下）に近い極微細
な微粒子が得られ、また、その後の硬化を室温で行うこ
とにより、得られた極微粒子を安定に回収できる。した
がって、特に微細であることが要求される各種電子材料
用の充填物のような用途に特に適している。In the method of the present invention, emulsification is carried out using dialkyl sulfosuccinate, which is an anionic surfactant, so ultrafine particles close to ultrafine particles (0.1 μm or less) are obtained, and By performing curing at room temperature, the obtained ultrafine particles can be stably recovered. Therefore, it is particularly suitable for applications such as fillers for various electronic materials that are required to be particularly fine.
（実施例） 以下、実施例により、本発明をさらに詳しく説明する。(Example) EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples.
実施ヨ
平均組成が、次式：
（ｍ ＋ ｎ ＝ ３６、ビニル基含有量７．２重量％
）で表されるポリビニルシロキサン１００ ｇに、白金
−ビニルシロキサン錯体のベンゼン溶液２・２ｇ（白金
含有量４．３ ｘｌＯ−５モル／ｇ）を添加し、混合し
たくこれを混合物Ａとする）。The average composition in practice was as follows: (m + n = 36, vinyl group content 7.2% by weight
2.2 g of a benzene solution of platinum-vinylsiloxane complex (platinum content: 4.3 x lO-5 mol/g) is added to 100 g of polyvinylsiloxane represented by ), and the mixture is referred to as mixture A). .
次に、上記と同じポリビニルシロキサン５０ｇおよび、
平均組成が次式；
％式％
（ケイ素原子結合水素原子含有量１．５重量％）で表さ
れるポリハイドロジエンシロキサン５０ｇを混合したく
これを混合物Ｂとする）。Next, 50 g of the same polyvinylsiloxane as above and
50 g of polyhydrodiene siloxane having an average composition expressed by the following formula: % (Silicon-bonded hydrogen atom content: 1.5% by weight) was mixed and this was designated as mixture B).
この混合物ＡおよびＢを、水冷下に均一に混合した。次
いでこの混合物２００ ｇを、アニオン系界面活性剤ネ
オコール側（商標、第−工業製薬味製、ジアルキルスル
ホコハク酸ナトリウム）２ｇとイオン交換水２０００ｇ
との混合物に添加し、ホモジナイザーで１分間混合した
。These mixtures A and B were uniformly mixed under water cooling. Next, 200 g of this mixture was mixed with 2 g of anionic surfactant Neocol (trademark, Dai-Kogyo Yakuhin Aji Co., Ltd., sodium dialkyl sulfosuccinate) and 2000 g of ion-exchanged water.
and mixed with a homogenizer for 1 minute.
次にこれを、循環式超音波ホモジナイザー（日本精機製
作所■製、ＲＵＳ−６００ＴＨＶ型、出力６００Ｗ、発
振周波数２０Ｋ Ｈｚ 、発振振幅４０μｍ）を用いて
、室温にて供給速度１００ ｍ１７分で超音波照射をし
、続いてマイクロフルイダイザー（商標、マイクロフル
イデイクスコーポレーション製、Ｍ−１１０８型）を用
いて、１００ ｍ１７分の供給速度で室温にて撹拌する
ことにより、エマルション化を行った。次いでこのエマ
ルションを、２５°Ｃで２４時間静置することにより硬
化させた。Next, this was subjected to ultrasonic irradiation at room temperature using a circulating ultrasonic homogenizer (manufactured by Nippon Seiki Seisakusho, model RUS-600THV, output 600 W, oscillation frequency 20 KHz, oscillation amplitude 40 μm) at a supply rate of 100 m for 17 minutes. The mixture was then emulsified by stirring at room temperature using a microfluidizer (trademark, manufactured by Microfluidics Corporation, model M-1108) at a feed rate of 100 ml/17 min. This emulsion was then allowed to stand at 25°C for 24 hours to harden.
得られた微粒子の懸濁液をスプレードライヤー（ヤマト
科学■製、ミニスプレィ ＧＡ−３１型）を用いて、液
送大速度２０ｇ／′分、熱風流量０．５ ｍ３／分（入
口温度１５０℃、出口温度８０°Ｃ）で水分を蒸発除去
した。The resulting suspension of fine particles was dried using a spray dryer (Mini Spray GA-31, manufactured by Yamato Kagaku ■) at a high liquid feeding speed of 20 g/min and a hot air flow rate of 0.5 m3/min (inlet temperature 150°C, Water was removed by evaporation at an outlet temperature of 80°C.
得られた微粒子は顆粒状であったが、小さな剪断力を加
えることにより容易に分散することができた。この微粒
子を走査型電子顕微鏡（ＳＥＭ）で観察したところ、は
とんどの粒子は球状であり、平均粒径は０．１９μｍで
あった。Although the obtained fine particles were granular, they could be easily dispersed by applying a small shearing force. When the fine particles were observed using a scanning electron microscope (SEM), most of the particles were spherical, and the average particle size was 0.19 μm.
ル較孤ユ
界面活性剤を、アニオン系界面活性剤ネオコールＳ−の
代わりに、ノニオン系界面活性剤レオドールＴＷ−１１
２０（商標、花王■製、ポリオキシエチレンソルビタン
ラウリン酸エステル、ＨＬＢ ＝ １６．９＞を用いた
以外は実施例と同様にして微粒子を製造した。得られた
微粒子をＳＥＭで観察したところ、平均粒径は０．５μ
ｍであった。The nonionic surfactant Rheodol TW-11 was used instead of the anionic surfactant Neocol S-.
Fine particles were produced in the same manner as in the example except that 20 (trademark, manufactured by Kao ■, polyoxyethylene sorbitan laurate, HLB = 16.9) was used. When the obtained fine particles were observed with SEM, it was found that the average Particle size is 0.5μ
It was m.
Ｌ較信ユ
硬化を２５℃で２４時間静置する代わりに、エマルショ
ン化直後に９０℃で２時間加熱硬化を行った以外は実施
例と同様にして微粒子を製造した。得られた微粒子をＳ
ＥＭで観察しなところ、平均粒径は約０．２μｍであっ
たが、一部に粒子同志が融着した部分が認められた。Fine particles were produced in the same manner as in the example except that instead of leaving the L-containing resin to cure at 25° C. for 24 hours, heat curing was performed at 90° C. for 2 hours immediately after emulsion formation. The obtained fine particles were
When observed by EM, the average particle size was approximately 0.2 μm, but some portions were observed where the particles were fused together.
（発明の効果）
本発明により、平均粒径０，２μｍ以下の極微細な粒子
を得ることができる。(Effects of the Invention) According to the present invention, extremely fine particles having an average particle diameter of 0.2 μm or less can be obtained.
し−一一一一shi-1111
Claims (1)
在下にエマルション化し、次いで硬化させて球状シリコ
ーン樹脂微粒子を製造する方法において、 （ａ）界面活性剤がジアルキルスルホコハク酸塩であり
、かつ （ｂ）硬化を１０〜３５℃で行う ことを特徴とする方法。[Scope of Claims] A method for producing spherical silicone resin particles by emulsifying a curable silicone composition in a dispersion medium in the presence of a surfactant and then curing the composition, comprising: (a) the surfactant is a dialkyl sulfosuccinate; A method characterized in that it is an acid salt, and (b) curing is carried out at 10 to 35°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2312854A JPH04183727A (en) | 1990-11-20 | 1990-11-20 | Production of fine spherical silicone resin particle |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2312854A JPH04183727A (en) | 1990-11-20 | 1990-11-20 | Production of fine spherical silicone resin particle |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04183727A true JPH04183727A (en) | 1992-06-30 |
Family
ID=18034235
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2312854A Pending JPH04183727A (en) | 1990-11-20 | 1990-11-20 | Production of fine spherical silicone resin particle |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04183727A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000017174A (en) * | 1998-03-03 | 2000-01-18 | General Electric Co <Ge> | Emulsion of silicone and non-aqueous hydroxyl solvent |
| JP2001040214A (en) * | 1999-08-03 | 2001-02-13 | Dow Corning Toray Silicone Co Ltd | Organic cross-linked particle, its suspension and their production |
| JP2001139819A (en) * | 1999-11-16 | 2001-05-22 | Dow Corning Toray Silicone Co Ltd | Emulsion, its production method, and method of producing oil composition |
| JP2009062553A (en) * | 1998-06-10 | 2009-03-26 | Dow Corning Toray Co Ltd | Emulsion and process for its production |
| JP2013522028A (en) * | 2010-03-22 | 2013-06-13 | エムジェイアール ファームジェット ゲーエムベーハー | Method and apparatus for generating microparticles or nanoparticles |
| WO2014185500A1 (en) * | 2013-05-16 | 2014-11-20 | 旭硝子株式会社 | Method for producing porous organic/inorganic hybrid particles and emulsification device |
-
1990
- 1990-11-20 JP JP2312854A patent/JPH04183727A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000017174A (en) * | 1998-03-03 | 2000-01-18 | General Electric Co <Ge> | Emulsion of silicone and non-aqueous hydroxyl solvent |
| JP2010235954A (en) * | 1998-03-03 | 2010-10-21 | Momentive Performance Materials Inc | Emulsion of silicone with non-aqueous hydroxylic solvent |
| JP2012031433A (en) * | 1998-03-03 | 2012-02-16 | Momentive Performance Materials Inc | Emulsion of silicone with non-aqueous hydroxylic solvent |
| JP2012229441A (en) * | 1998-03-03 | 2012-11-22 | Momentive Performance Materials Inc | Emulsion of silicone with non-aqueous hydroxylic solvent |
| JP2009062553A (en) * | 1998-06-10 | 2009-03-26 | Dow Corning Toray Co Ltd | Emulsion and process for its production |
| JP2001040214A (en) * | 1999-08-03 | 2001-02-13 | Dow Corning Toray Silicone Co Ltd | Organic cross-linked particle, its suspension and their production |
| JP2001139819A (en) * | 1999-11-16 | 2001-05-22 | Dow Corning Toray Silicone Co Ltd | Emulsion, its production method, and method of producing oil composition |
| JP2013522028A (en) * | 2010-03-22 | 2013-06-13 | エムジェイアール ファームジェット ゲーエムベーハー | Method and apparatus for generating microparticles or nanoparticles |
| WO2014185500A1 (en) * | 2013-05-16 | 2014-11-20 | 旭硝子株式会社 | Method for producing porous organic/inorganic hybrid particles and emulsification device |
| JPWO2014185500A1 (en) * | 2013-05-16 | 2017-02-23 | 旭硝子株式会社 | Method for producing porous organic-inorganic hybrid particles and emulsifying device |
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