JPH0618879B2 - Polyorganosilsesquioxane fine particles - Google Patents

Polyorganosilsesquioxane fine particles

Info

Publication number
JPH0618879B2
JPH0618879B2 JP63042303A JP4230388A JPH0618879B2 JP H0618879 B2 JPH0618879 B2 JP H0618879B2 JP 63042303 A JP63042303 A JP 63042303A JP 4230388 A JP4230388 A JP 4230388A JP H0618879 B2 JPH0618879 B2 JP H0618879B2
Authority
JP
Japan
Prior art keywords
group
fine particles
polyorganosilsesquioxane
reaction
solution
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.)
Expired - Lifetime
Application number
JP63042303A
Other languages
Japanese (ja)
Other versions
JPH01217039A (en
Inventor
博 木村
健司 齋藤
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Momentive Performance Materials Japan LLC
Original Assignee
Toshiba Silicone Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Toshiba Silicone Co Ltd filed Critical Toshiba Silicone Co Ltd
Priority to JP63042303A priority Critical patent/JPH0618879B2/en
Priority to GB8904201A priority patent/GB2216535B/en
Priority to DE3905785A priority patent/DE3905785C2/en
Priority to IT8947687A priority patent/IT1230485B/en
Priority to FR8902442A priority patent/FR2627773B1/en
Priority to KR1019890002525A priority patent/KR930006260B1/en
Publication of JPH01217039A publication Critical patent/JPH01217039A/en
Publication of JPH0618879B2 publication Critical patent/JPH0618879B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/06—Preparatory processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2383/04—Polysiloxanes

Description

【発明の詳細な説明】 ［発明の技術分野］ 本発明はポリオルガノシルセスキオキサン微粒子に関
し、さらに詳しくは、ケイ素原子に結合可能な有機基の
範囲が広く、粒子径が非常に小さく、かつ粒子の形状が
球状で、その粒子径がよく揃ったポリオルガノシルセス
キオキサン微粒子に関する。TECHNICAL FIELD OF THE INVENTION The present invention relates to polyorganosilsesquioxane fine particles, and more specifically, it has a wide range of organic groups that can be bonded to silicon atoms, has a very small particle size, and The present invention relates to polyorganosilsesquioxane fine particles having a spherical shape and a uniform particle diameter.

［発明の技術的背景とその問題点］ 従来、ポリオルガノシルセスキオキサン粉末を得る方法
として、オルガノトリクロロシラン、オルガノトリアル
コキシシランのような３官能性シランをアルカリの水溶
液中で反応させる方法が知られている。例えば、ベルギ
ー国特許第５７２，４１２号公報には、メチルトリクロ
ロシランを噴霧水中で加水分解させるか、または多量の
水中に撹拌しながら滴下して加水分解させ、固体状のポ
リメチルシルセスキオキサンを得る方法が開示されてい
る。[Technical background of the invention and its problems] Conventionally, as a method of obtaining a polyorganosilsesquioxane powder, a method of reacting a trifunctional silane such as organotrichlorosilane and organotrialkoxysilane in an alkaline aqueous solution has been proposed. Are known. For example, in Belgian Patent No. 572,412, methyltrichlorosilane is hydrolyzed in spray water or is added dropwise to a large amount of water while stirring to hydrolyze the solid polymethylsilsesquioxane. Is disclosed.

しかしこの方法では、加水分解反応時の発熱量が大き
く、多量の塩化水素が副成するので装置が腐食されると
いう問題のほか、生成したポリメチルシルセスキオキサ
ン粉末とともに副成した塩化水素と未加水分解のメチル
トリクロロシランが残ることから、比較的多量の塩素原
子が残存するという問題点がある。However, in this method, the amount of heat generated during the hydrolysis reaction is large and a large amount of hydrogen chloride is by-produced, so the equipment is corroded, and in addition to the hydrogen chloride by-produced with the polymethylsilsesquioxane powder produced. Since unhydrolyzed methyltrichlorosilane remains, there is a problem that a relatively large amount of chlorine atoms remain.

上記の問題点を解決する方法として、特開昭５４−７２
３００号公報には、塩素量が０．１〜５．０重量％であ
るメチルトリアルコキシシランおよび／またはその部分
加水分解物を、アルカリ土類金属水酸化物またはアルカ
リ金属炭酸塩を含む水溶液中で、加水分解・縮合させる
方法が開示されている。As a method for solving the above-mentioned problems, JP-A-54-72
No. 300 publication discloses that methyltrialkoxysilane and / or its partial hydrolyzate having a chlorine content of 0.1 to 5.0% by weight in an aqueous solution containing an alkaline earth metal hydroxide or an alkali metal carbonate. Discloses a method of hydrolysis / condensation.

しかし、この方法では生成するポリメチルシルセスキオ
キサン粉末とともにアルカリ土類金属やアルカリ金属が
比較的多量に残存するので各種合成樹脂用充填剤などと
して利用する場合、吸湿しやすいという問題点がある。
またこの方法では、原料のメチルトリアルコキシシラン
および／またはその部分加水分解物の塩素量を予め０．
１〜０．５重量％に調整しなければならないという問題
点もある。However, in this method, since a relatively large amount of alkaline earth metal and alkali metal remain together with the polymethylsilsesquioxane powder produced, when used as a filler for various synthetic resins, there is a problem that it tends to absorb moisture. .
Further, in this method, the chlorine amount of the raw material methyltrialkoxysilane and / or its partial hydrolyzate is adjusted to 0.
There is also a problem in that it must be adjusted to 1 to 0.5% by weight.

本発明者の一人は、先にメチルトリアルコキシシランお
よび／またはその部分加水分解縮合物を該シランおよび
／またはその部分加水分解縮合物中に存在する塩素原子
を中和するのに十分な量に触媒としての量を加えた量の
アンモニアまたはアミンの水溶液中で加水分解・縮合さ
せることによって、上記の問題点を解決し、自由流動性
に優れたポリメチルシルセスキオキサン粉末を得る技術
を提案している（特開昭６０−１３８１３号公報参
照）。One of the inventors of the present invention has previously prepared methyltrialkoxysilane and / or its partial hydrolysis-condensation product in an amount sufficient to neutralize chlorine atoms present in the silane and / or its partial hydrolysis-condensation product. Proposed a technology to solve the above problems and obtain polymethylsilsesquioxane powder with excellent free-flowing property by hydrolyzing and condensing in an aqueous solution of ammonia or amine with an amount added as a catalyst. (See JP-A-60-13813).

さらに本発明者の一人は、メチルトリアルコキシシラン
および／またはその部分加水分解縮合物またはメチルト
リアルコキシシランおよび／またはその部分加水分解縮
合物と有機溶剤との混合液を上層にし、アンモニアおよ
び／またはアミンと有機溶剤との混合液を下層にして、
これらの界面でメチルトリアルコキシシランおよび／ま
たはその部分加水分解縮合物を加水分解・縮合させて、
粒子の形状が各々独立した真球状であり、粒度分布が平
均粒子径の±３０％の範囲であるポリメチルシルセスキ
オキサン粉末を製造し得ることを見出した（特開昭６３
−７７９４０号公報参照）。Further, one of the inventors of the present invention is to provide an upper layer of methyltrialkoxysilane and / or a partial hydrolysis-condensation product thereof or a mixture of methyltrialkoxysilane and / or a partial hydrolysis-condensation product thereof and an organic solvent, and to add ammonia and / or A mixture of amine and organic solvent is the lower layer,
By hydrolyzing and condensing methyltrialkoxysilane and / or its partial hydrolysis-condensation product at these interfaces,
It has been found that a polymethylsilsesquioxane powder in which the shape of each particle is an independent spherical shape and the particle size distribution is within a range of ± 30% of the average particle diameter can be produced (JP-A-63).
-77940).

さらに本発明者らは、上記の反応において、メチルトリ
アルコキシシランおよび／またはその部分加水分解物の
使用量を水の重量の1/10以下とすること、とくにアンモ
ニアおよび／またはアミンの濃度を０．０１〜５重量％
とすることにより、平均粒子径が０．０５〜０．８μｍ
の球状ポリメチルシルセスキオキサン粉末が得られるこ
とを見出した（特開昭６３−２９５６３７号公報参
照）。Furthermore, the inventors of the present invention set the amount of methyltrialkoxysilane and / or its partial hydrolyzate to be 1/10 or less of the weight of water in the above reaction, and particularly, the concentration of ammonia and / or amine should be 0. 0.01 to 5% by weight
The average particle size is 0.05 to 0.8 μm
It was found that the spherical polymethylsilsesquioxane powder of No. 6 was obtained (see JP-A-63-295637).

このような方法で得られたポリメチルシルセスキオキサ
ン粉末は、粒子の形状が球状で、粒子径が小さく、疎水
性が高く、凝集性が小さく、比重が小さいという特徴を
もつうえに、粒子径の揃ったものが得られるという利点
がある。それゆえ、塗料、プラスチック、ゴム、化粧
品、紙などの改質用添加剤としても用いられている。The polymethylsilsesquioxane powder obtained by such a method is characterized in that the particle shape is spherical, the particle size is small, the hydrophobicity is high, the cohesiveness is small, and the specific gravity is small. There is an advantage that products with a uniform diameter can be obtained. Therefore, it is also used as an additive for modifying paints, plastics, rubbers, cosmetics, paper and the like.

しかし、このような製造方法において、ケイ素原子に結
合した有機基はメチル基に限定され、メチル基以外の有
機基をもつオルガノトリアルコキシシランから直接ポリ
オルガノシルセスキオキサン粉末を得ようとしても、粒
子径の揃った微粒子を収率よく得ることはできない。そ
のため、屈折率の高い透明プラスチックに添加しても透
明性を保つような、任意の高い屈折率を有するポリオル
ガノシルセスキオキサン粉末を得ようとする場合、また
はフィルムに添加した場合にフィルム面が擦れあっても
傷つかないように硬さを調整したポリオルガノシルセス
キオキサン粉末を得ようとする場合など、分子中のケイ
素原子に結合した有機基の一部または全部としてメチル
基以外の基を導入しようとする試みは成功していなかっ
た。However, in such a production method, the organic group bonded to the silicon atom is limited to a methyl group, even if it is attempted to directly obtain a polyorganosilsesquioxane powder from an organotrialkoxysilane having an organic group other than a methyl group, Fine particles having a uniform particle size cannot be obtained in good yield. Therefore, when trying to obtain a polyorganosilsesquioxane powder having an arbitrary high refractive index such that the transparency is maintained even when it is added to a transparent plastic having a high refractive index, or when it is added to a film, the film surface When it is desired to obtain a polyorganosilsesquioxane powder whose hardness is adjusted so that it will not be damaged even if it is rubbed, a group other than a methyl group as a part or all of the organic groups bonded to the silicon atom in the molecule, etc. Attempts to introduce the were unsuccessful.

また、ポリメチルシルセスキオキサン微粒子であって
も、その平均粒子径が０．０５μｍ未満の小さなものは
未だ得られていない。Further, even polymethylsilsesquioxane fine particles having a small average particle diameter of less than 0.05 μm have not yet been obtained.

［発明の目的］ 本発明は、ケイ素原子に広範囲の有機基が結合した、球
状で粒子径が揃っており、かつその粒子径がきわめて小
さいものであるポリオルガノシルセスキオキサン微粒子
およびその製造方法を提供することを目的とする。[Object of the Invention] The present invention is a polyorganosilsesquioxane fine particle in which a wide range of organic groups are bonded to silicon atoms, which are spherical and have a uniform particle diameter and whose particle diameter is extremely small, and a method for producing the same. The purpose is to provide.

［発明の構成］ 本発明は、平均粒子径が０．０１〜１μｍのポリオルガ
ノシルセスキオキサン（ただし、ケイ素原子に結合する
炭化水素基は炭素数２〜６のアルキル基、シクロアルキ
ル基、アラルキル基、アリール基、アルケニル基および
置換アルキル基から選ばれた基、または上記の基とメチ
ル基との組合せである）微粒子に関する。[Constitution of the Invention] The present invention relates to a polyorganosilsesquioxane having an average particle diameter of 0.01 to 1 μm (however, the hydrocarbon group bonded to a silicon atom is an alkyl group having 2 to 6 carbon atoms, a cycloalkyl group, A group selected from an aralkyl group, an aryl group, an alkenyl group and a substituted alkyl group, or a combination of the above group and a methyl group).

また本発明のポリオルガノシルセスキオキサン微粒子
は、一般式： Ｒ１Ｓｉ（ＯＲ２）３ （Ｉ） （式中、Ｒ１は炭素数２〜６のアルキル基、シクロアル
キル基、アラルキル基、アリール基、アルケニル基およ
び置換アルキル基から選ばれた基、または上記の基とメ
チル基との組合せであり、Ｒ２は置換または非置換のア
ルキル基を表す）で示されるオルガノトリアルコキシシ
ランを有機酸の存在下に加水分解して、一般式： Ｒ１Ｓｉ（ＯＨ）３ （II） （式中のＲ１の意味は上記のとおりである） で示されるオルガノシラントリオールまたはその部分縮
合物を得る工程、 ついで、該オルガノシラントリオールまたはその部分縮
合物をアルカリの水溶液または該水溶液と有機溶媒との
混合液中で重縮合反応させる工程、を具備する方法によ
って製造される。The polyorganosilsesquioxane fine particles of the present invention have the general formula: R 1 Si (OR 2 ) 3 (I) (wherein R 1 is an alkyl group having 2 to 6 carbon atoms, a cycloalkyl group, an aralkyl group, An organotrialkoxysilane represented by a group selected from an aryl group, an alkenyl group and a substituted alkyl group, or a combination of the above group and a methyl group, and R 2 represents a substituted or unsubstituted alkyl group). An organosilanetriol represented by the general formula: R 1 Si (OH) 3 (II) (wherein R 1 is as defined above) or a partial condensate thereof is hydrolyzed in the presence of an acid. A step of obtaining, and then a step of subjecting the organosilanetriol or a partial condensate thereof to a polycondensation reaction in an aqueous solution of an alkali or a mixed solution of the aqueous solution and an organic solvent. It is produced by.

本発明のポリオルガノシルセスキオキサン微粒子は、平
均粒子径が０．０１〜１μｍである。このポリオルガノ
シルセスキオキサン微粒子は、ケイ素原子に結合する炭
化水素基がメチル基以外のもの、またはメチル基以外の
炭化水素基とメチル基であるものであり、ケイ素原子に
結合する炭化水素基がメチル基のみのものは含まない。The polyorganosilsesquioxane fine particles of the present invention have an average particle diameter of 0.01 to 1 μm. The polyorganosilsesquioxane fine particles have a hydrocarbon group bonded to a silicon atom other than a methyl group, or a hydrocarbon group other than a methyl group and a methyl group, and a hydrocarbon group bonded to a silicon atom. Does not include methyl groups alone.

本発明のポリオルガノシルセスキオキサン微粒子におい
てケイ素原子に結合する炭化水素基としては、例えば置
換または非置換の１価の炭化水素基を例示することがで
きる。具体的には、メチル基、エチル基、プロピル基、
ブチル基、ヘキシル基のようなアルキル基；シクロヘキ
シル基のようなシクロアルキル基；２−フェニルプロピ
ル基のようなアラルキル基；フェニル基、トリル基のよ
うなアリール基；ビニル基、アリル基のようなアルケニ
ル基；およびクロロメチル基、γ−クロロプロピル基、
γ−メタクリロキシプロピル基、γ−グリシドキシプロ
ピル基、３，４−エポキシシクロヘキシルエチル基、γ
−メルカプトプロピル基、３，３，３−トリフルオロプ
ロピル基のような置換炭化水素基を例示することができ
る。Examples of the hydrocarbon group bonded to a silicon atom in the polyorganosilsesquioxane fine particles of the present invention include a substituted or unsubstituted monovalent hydrocarbon group. Specifically, a methyl group, an ethyl group, a propyl group,
Alkyl group such as butyl group and hexyl group; cycloalkyl group such as cyclohexyl group; aralkyl group such as 2-phenylpropyl group; aryl group such as phenyl group and tolyl group; vinyl group, allyl group An alkenyl group; and a chloromethyl group, a γ-chloropropyl group,
γ-methacryloxypropyl group, γ-glycidoxypropyl group, 3,4-epoxycyclohexylethyl group, γ
Examples thereof include substituted hydrocarbon groups such as a mercaptopropyl group and a 3,3,3-trifluoropropyl group.

以下において、ポリオルガノシルセスキオキサン微粒子
という場合は、特に断わらない限り、ケイ素原子に結合
する炭化水素基がメチル基以外のもの、メチル基以外の
ものとメチル基であるもの、およびメチル基のみのもの
を言うものとする。In the following, when referring to polyorganosilsesquioxane fine particles, unless otherwise specified, a hydrocarbon group bonded to a silicon atom is other than a methyl group, a group other than a methyl group and a methyl group, and only a methyl group Shall be said.

本発明の製造方法は、２つの工程から構成される。The manufacturing method of the present invention comprises two steps.

本発明の製造方法の第１工程は、前記一般式（Ｉ）で示
されるオルガノトリアルコキシシランを有機酸の存在下
で加水分解して前記一般式（II）で示されるオルガノシ
ラントリオールまたはその部分縮合物を得る工程であ
る。The first step of the production method of the present invention is to hydrolyze the organotrialkoxysilane represented by the general formula (I) in the presence of an organic acid to produce the organosilanetriol represented by the general formula (II) or a portion thereof. This is a step of obtaining a condensate.

前記一般式（Ｉ）中のＲ１の置換または非置換の１価の
炭化水素基としては、上記したようにポリオルガノシル
セスキオキサン微粒子のケイ素原子に結合するものと同
一の１価の炭化水素基を例示することができる。The substituted or unsubstituted monovalent hydrocarbon group represented by R 1 in the above general formula (I) is the same monovalent hydrocarbon group bonded to the silicon atom of the polyorganosilsesquioxane fine particles as described above. A hydrogen group can be exemplified.

これらの基のうちでも、平均粒子径が非常に小さく、か
つ粒子径の揃った球状のポリオルガノシルセスキオキサ
ン微粒子を得ることができるということからは、メチル
基、エチル基、プロピル基、ブチル基、ペンチル基、ヘ
キシル基、ビニル基またはフェニル基が好ましい。ま
た、化学的に安定で、かつ炭素官能性基により極性など
の特異な性質を生成物に与え、さらに粒子径が小さく、
かつ揃っている球状のポリオルガノシルセスキオキサン
微粒子を得ることができるということからは、γ−クロ
ロプロピル基、γ−メタクリロキシプロピル基、γ−グ
リシドキシプロピル基のような置換プロピル基；および
3,4-エポキシシクロヘキシルエチル基が好ましい。これ
らの基のうち、γ−グリシドキシプロピル基、3,4-エポ
キシシクロヘキシルエチル基のようなエポキシ環含有基
の場合は、加水分解反応の触媒である有機酸や重縮合反
応の触媒であるアルカリにより、一部のエポキシ環が開
環し、とくに後者の触媒としてアンモニアを用いるとき
は、開環反応により窒素含有基が生成するが、それは本
発明の目的を何ら損なうものではない。Among these groups, the average particle size is very small, and from the fact that it is possible to obtain spherical polyorganosilsesquioxane fine particles having a uniform particle size, methyl group, ethyl group, propyl group, butyl A group, pentyl group, hexyl group, vinyl group or phenyl group is preferred. Further, it is chemically stable, and the carbon functional group imparts unique properties such as polarity to the product, and further, the particle size is small,
From the fact that it is possible to obtain spherical polyorganosilsesquioxane fine particles that are uniform, a substituted propyl group such as γ-chloropropyl group, γ-methacryloxypropyl group, γ-glycidoxypropyl group; and
The 3,4-epoxycyclohexylethyl group is preferred. Among these groups, in the case of an epoxy ring-containing group such as γ-glycidoxypropyl group and 3,4-epoxycyclohexylethyl group, it is an organic acid which is a catalyst for hydrolysis reaction or a catalyst for polycondensation reaction. Alkali opens some epoxy rings, especially when ammonia is used as the catalyst of the latter, the nitrogen-containing group is formed by the ring-opening reaction, but this does not impair the object of the present invention.

前記一般式（Ｉ）中のＲ２の置換または非置換のアルキ
ル基としては、メチル基、エチル基、プロピル基、ブチ
ル基などのアルキル基；およびメトキシエチル基、エト
キシエチル基、ブトキシエチル基などの置換アルキル基
を例示することがでる。これらの中でも、反応速度の点
からメチル基、エチル基が好ましく、とくにメチル基が
好ましい。Examples of the substituted or unsubstituted alkyl group represented by R 2 in the general formula (I) include an alkyl group such as a methyl group, an ethyl group, a propyl group and a butyl group; and a methoxyethyl group, an ethoxyethyl group, a butoxyethyl group and the like. The substituted alkyl group can be exemplified. Among these, a methyl group and an ethyl group are preferable from the viewpoint of reaction rate, and a methyl group is particularly preferable.

かかる前記一般式（Ｉ）で示されるオルガノトリアルコ
キシシランとしては、メチルトリメトキシシラン、メチ
ルトリエトキシシラン、メチルトリイソプロポキシシラ
ン、メチルトリス（メトキシエトキシ）シラン、エチル
トリメトキシシラン、ビニルトリメトキシシラン、ビニ
ルトリス（メトキシエトキシ）シラン、フェニルトリメ
トキシシラン、γ−クロロプロピルトリメトキシシラ
ン、γ−メタクリロキシプロピルトリメトキシシラン、
γ−グリシドキシプロピルトリメトキシシラン、3,4-エ
ポキシシクロヘキシルエチルトリメトキシシラン、γ−
メルカプトプロピルトリメトキシシランなどを例示する
ことができ、これらは１種類を用いても２種類以上を併
用しても差し支えない。Examples of the organotrialkoxysilane represented by the general formula (I) include methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltris (methoxyethoxy) silane, ethyltrimethoxysilane, vinyltrimethoxysilane, Vinyltris (methoxyethoxy) silane, phenyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane,
γ-glycidoxypropyltrimethoxysilane, 3,4-epoxycyclohexylethyltrimethoxysilane, γ-
Examples thereof include mercaptopropyltrimethoxysilane, and these may be used alone or in combination of two or more.

第１工程の加水分解反応は、過剰の水に触媒となる有機
酸を溶解させた水溶液中において、オルガノトリアルコ
キシシランと有機酸とを、撹拌、混合等の方法で接触さ
せることにより行なう。The hydrolysis reaction in the first step is carried out by bringing the organotrialkoxysilane and the organic acid into contact with each other by a method such as stirring and mixing in an aqueous solution in which an organic acid serving as a catalyst is dissolved in excess water.

このように触媒として有機酸を用いることは反応速度が
速いことと、最終的に得られるポリオルガノシルセスキ
オキサン微粒子の用途を制限するようなイオン性物質な
どの不純物を残さないか、もしくは残しても少量である
点から優れているものである。かかる有機酸としては、
ギ酸、酢酸、プロピオン酸、モノクロロ酢酸、シュウ
酸、クエン酸などを例示することができるが、少量で加
水分解の反応速度を上げ、かつ生成したポリオルガノシ
ラントリオールの部分縮合反応を抑制することからギ酸
および酢酸が好ましい。Thus, using an organic acid as a catalyst has a high reaction rate, and leaves or does not leave impurities such as ionic substances that limit the use of the finally obtained polyorganosilsesquioxane fine particles. However, it is excellent because it is a small amount. As such an organic acid,
Formic acid, acetic acid, propionic acid, monochloroacetic acid, oxalic acid, citric acid and the like can be exemplified, but they increase the reaction rate of hydrolysis with a small amount and suppress the partial condensation reaction of the produced polyorganosilanetriol. Formic acid and acetic acid are preferred.

有機酸の使用量は、シランおよび有機酸の種類によって
も異なるが、オルガノトリアルコキシシランを加水分解
する場合に用いる水の量１００重量部に対して１×１０
−３〜１重量部が好ましく、５×１０−３〜０．１重量
部がさらに好ましい。１×１０−３重量部未満の場合に
は反応が十分に進行せず、１重量部を超える場合には不
純物中の酸基として系中に残存する濃度が高くなるばか
りでなく、生成したオルガノシラントリオールが縮合し
やすくなる。The amount of the organic acid used varies depending on the types of the silane and the organic acid, but it is 1 × 10 5 relative to 100 parts by weight of water used for hydrolyzing the organotrialkoxysilane.
-3 to 1 part by weight is preferable, and 5 x 10 -3 to 0.1 part by weight is more preferable. When it is less than 1 × 10 −3 parts by weight, the reaction does not proceed sufficiently, and when it exceeds 1 part by weight, not only the concentration of acid groups in the impurities remaining in the system becomes high, but also the formed organo Silanetriol easily condenses.

加水分解反応に用いる水の量は、オルガノトリアルコキ
シシラン１モルに対して２〜１０モルが好ましい。水の
量が２モル未満の場合には加水分解反応が十分に進行せ
ず、１０モルを超える場合にはオルガノシラントリオー
ルの部分縮合物が析出してしまう。The amount of water used for the hydrolysis reaction is preferably 2 to 10 mol per 1 mol of organotrialkoxysilane. When the amount of water is less than 2 mol, the hydrolysis reaction does not proceed sufficiently, and when it exceeds 10 mol, a partial condensate of organosilanetriol is precipitated.

加水分解時の温度はとくに制限されず、常温または加熱
状態で行なってもよいが、オルガノシラントリオールを
収率よく得るためには５〜６０℃に保持した状態で反応
を行なわせることが好ましい。The temperature at the time of hydrolysis is not particularly limited, and it may be carried out at room temperature or in a heated state, but in order to obtain the organosilanetriol in good yield, it is preferable to carry out the reaction in a state of being kept at 5 to 60 ° C.

本発明の製造方法の第２工程は、第１工程で得られたオ
ルガノシラントリオールまたはその部分縮合物から重縮
合反応によりポリオルガノシルセスキオキサン微粒子を
得る工程である。この第２工程の反応は、アルカリの水
溶液または該アルカリの水溶液と有機溶媒との混合液中
で行なう。The second step of the production method of the present invention is a step of obtaining polyorganosilsesquioxane fine particles from the organosilanetriol obtained in the first step or a partial condensate thereof by a polycondensation reaction. The reaction of the second step is carried out in an aqueous solution of alkali or a mixed solution of the aqueous solution of alkali and an organic solvent.

アルカリは、その水溶液が塩基性を示すものであり、第
１工程で用いられた有機酸の中和剤として、また第２工
程の重縮合反応の触媒として作用するものである。かか
るアルカリとしては、水酸化リチウム、水酸化ナトリウ
ム、水酸化カリウムのようなアルカリ金属水酸化物；ア
ンモニア；およびモノメチルアミン、ジメチルアミンの
ような有機アミン類を例示することができる。これらの
なかでも、ポリオルガノシルセスキオキサン微粒子の用
途を制限するような微量の不純物を残さないことからア
ンモニアおよび有機アミン類が好ましく、さらには毒性
が低く、除去が容易なことからアンモニアがとくに好ま
しい。The alkali is one whose aqueous solution exhibits basicity, and acts as a neutralizing agent for the organic acid used in the first step and as a catalyst for the polycondensation reaction in the second step. Examples of the alkali include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide; ammonia; and organic amines such as monomethylamine and dimethylamine. Among these, ammonia and organic amines are preferable because they do not leave a trace amount of impurities that limit the use of polyorganosilsesquioxane fine particles, and ammonia is particularly preferable because it has low toxicity and is easy to remove. preferable.

アルカリは、取り扱いや反応の制御が容易なことから水
溶液として用いる。Alkali is used as an aqueous solution because it is easy to handle and control the reaction.

アルカリの使用量は、有機酸を中和し、重縮合反応の触
媒として有効に作用する量であり、例えばアルカリとし
てアンモニアを用いた場合には水または水と有機溶媒と
の混合物１００重量部に対して０．０５重量部以上を用
いる。The amount of the alkali used is such an amount that neutralizes the organic acid and effectively acts as a catalyst for the polycondensation reaction. For example, when ammonia is used as the alkali, 100 parts by weight of water or a mixture of water and an organic solvent is added. On the other hand, 0.05 part by weight or more is used.

第２工程においてはアルカリの水溶液とともに有機溶媒
を併用することが、微粒子を得るためには好ましい。In the second step, it is preferable to use an organic solvent together with an aqueous alkali solution in order to obtain fine particles.

かかる有機溶媒は水可溶性のものが好ましく、メタノー
ル、エタノール、ｎ−プロパノール、イソプロパノー
ル、ｎ−ブタノール、イソブタノール、エチレングリコ
ール、プロピレングリコール、エチレングリコールモノ
エチルエーテル、アセトン、ジエチルエーテル、テトラ
ヒドロフラン、ジアセトンアルコールなどを例示するこ
とができる。Such an organic solvent is preferably water-soluble, and methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, ethylene glycol, propylene glycol, ethylene glycol monoethyl ether, acetone, diethyl ether, tetrahydrofuran, diacetone alcohol. And the like.

第２工程の重縮合反応は、アルカリの水溶液またはこれ
と有機溶媒との混合液（以下、「アルカリ溶液」とい
う）を反応容器に仕込んだのち、この反応容器内に第１
工程で得られたオルガノシラントリオールまたはその部
分縮合物（以下、「シラノール化合物」という）の水溶
液もしくはこのシラノール化合物の水溶液をさらに水ま
たは上記の有機溶媒で希釈した溶液（以下、「シラノー
ル溶液」という）を添加して前記アルカリ溶液と接触さ
せることにより行なう。In the polycondensation reaction of the second step, an aqueous alkali solution or a mixed solution of the same and an organic solvent (hereinafter referred to as “alkaline solution”) is charged into a reaction vessel, and then the first reaction vessel is placed in the reaction vessel.
An aqueous solution of the organosilanetriol or its partial condensate obtained in the step (hereinafter referred to as "silanol compound") or a solution obtained by further diluting the aqueous solution of this silanol compound with water or the above organic solvent (hereinafter referred to as "silanol solution"). ) Is added and brought into contact with the alkaline solution.

シラノール溶液の添加方法は特に制限されない。シラノ
ール溶液の添加速度もとくに制限されず、例えば最適の
添加速度はシラノール化合物の種類と、アルカリ溶液中
の有機溶媒の有無、その種類により決定される。例え
ば、シラノール溶液をアルカリの水溶液に添加する場合
には５分以上かけることが好ましく、１０〜２４０分か
けることがさらに好ましい。また、シラノール溶液を有
機溶媒を含むアルカリ溶液中に添加する場合には５分以
内で行なうことが好ましい。The addition method of the silanol solution is not particularly limited. The addition rate of the silanol solution is not particularly limited, and the optimum addition rate is determined by the type of silanol compound, the presence or absence of an organic solvent in the alkaline solution, and the type thereof. For example, when the silanol solution is added to the alkaline aqueous solution, it is preferable to spend 5 minutes or more, and more preferably 10 to 240 minutes. Further, when the silanol solution is added to the alkaline solution containing the organic solvent, it is preferable that the addition is performed within 5 minutes.

このようにして重縮合反応を行なうことによりポリオル
ガノシルセスキオキサン微粒子を、水または水／有機溶
媒の混合液中にディスパージョンまたはゾルとして得る
ことができる。本発明のポリオルガノシルセスキオキサ
ン微粒子はこのようなディスパージョンまたはゾルの形
で用いることができるが、必要に応じてさらに乾燥、解
砕などの適当な処理を施して微粉体としたものを用いる
こともできる。By carrying out the polycondensation reaction in this manner, the polyorganosilsesquioxane fine particles can be obtained as a dispersion or sol in water or a mixed liquid of water / organic solvent. The polyorganosilsesquioxane fine particles of the present invention can be used in the form of such a dispersion or sol, but if necessary, further subjected to appropriate treatment such as drying and crushing to obtain a fine powder. It can also be used.

また、このようにして得られる本発明のポリオルガノシ
ルセスキオキサン微粒子は、その比表面積（ＢＥＴ法に
より測定）が１００〜１，０００m2／ｇ程度のものであ
る。Further, the polyorganosilsesquioxane fine particles of the present invention thus obtained have a specific surface area (measured by the BET method) of about 100 to 1,000 m 2 / g.

［発明の効果］ 本発明の製造方法によれば、従来方法では製造が困難で
あったポリオルガノシルセスキオキサン微粒子（ケイ素
原子に結合する炭化水素基がメチル基のみのものを除
く）を原料組成比どおりの組成で、収率および装置効率
よく得ることができる。[Effects of the Invention] According to the production method of the present invention, polyorganosilsesquioxane fine particles (excluding those having only a methyl group as a hydrocarbon group bonded to a silicon atom), which has been difficult to produce by a conventional method, are used as raw materials. With the composition according to the composition ratio, the yield and the device efficiency can be obtained efficiently.

本発明のポリオルガノシルセスキオキサン微粒子は、塗
料、プラスチック、ゴム、紙などの充填剤や添加剤とし
て有用である。とくにプラスチックフィルムの滑り性向
上剤、透明プラスチック用充填剤および補強剤として好
適である。The polyorganosilsesquioxane fine particles of the present invention are useful as fillers and additives for paints, plastics, rubbers, papers and the like. In particular, it is suitable as a slipperiness improving agent for plastic films, a filler for transparent plastics, and a reinforcing agent.

また、本発明によりケイ素原子に各種の炭素官能性有機
基が結合したポリオルガノシルセスキオキサン微粒子の
提供が可能になったが、これらはその炭素官能性を生か
して、プラスチック成形品の表面改質処理などに用いる
ことができる。Further, according to the present invention, it becomes possible to provide polyorganosilsesquioxane fine particles in which various carbon-functional organic groups are bonded to silicon atoms, but these carbon functionalities are utilized to improve the surface modification of plastic molded articles. It can be used for quality treatment.

［実施例］ 以下、本発明を実施例および比較例により、さらに詳し
く説明する。これらの例において部は重量部を表す。[Examples] Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. In these examples, parts represent parts by weight.

参考例１ 第１工程 温度計、還流器および撹拌機を備えた反応容器に水１，
０８０部を仕込み、酢酸０．２部を添加して均一な溶液
とした。これを３０℃で撹拌しつつ、メチルトリメトキ
シシラン１，３６０部を添加したところ、加水分解反応
が進行し、１０分間で温度は６０℃に上昇し、透明な反
応液が得られた。ついで、撹拌を４時間継続したのち濾
過を行なってシラノール溶液を得た。Reference Example 1 First Step Water 1 in a reaction vessel equipped with a thermometer, a reflux condenser and a stirrer
080 parts were charged, and 0.2 part of acetic acid was added to obtain a uniform solution. When this was stirred at 30 ° C. and 1,360 parts of methyltrimethoxysilane was added, the hydrolysis reaction proceeded, the temperature rose to 60 ° C. in 10 minutes, and a transparent reaction liquid was obtained. Then, stirring was continued for 4 hours and then filtration was performed to obtain a silanol solution.

第２工程 温度計、還流器および撹拌機を備えた反応容器に水２，
０００部と２８％アンモニア水溶液５０部をとり、温度
を２５℃に設定した。これを撹拌しながら第１工程で得
られたシラノール溶液４８８部を約１０分間かけて滴下
した。滴下終了後、１６時間撹拌を続けた。撹拌中にポ
リメチルシルセスキオキサン微粒子が析出して、反応液
は乳白色のディスパージョンに変わった。これを遠心分
離機にかけて微粒子を沈降させたのち取出し、２００℃
の乾燥機で２４時間乾燥させたところ、１３１部の白色
微粒子が得られた。これはメチルトリメトキシシランを
基準にした理論収量の９８％に相当する。Second step Water 2 in a reaction vessel equipped with a thermometer, a reflux condenser and a stirrer.
000 parts and 50 parts of 28% aqueous ammonia solution were taken, and the temperature was set to 25 ° C. While stirring this, 488 parts of the silanol solution obtained in the first step was added dropwise over about 10 minutes. After completion of dropping, stirring was continued for 16 hours. During the stirring, polymethylsilsesquioxane fine particles were deposited, and the reaction liquid changed to a milky white dispersion. This is put into a centrifuge to settle the fine particles and then taken out, and the temperature is 200 ° C.
When dried for 24 hours with a dryer of No. 1, 131 parts of white fine particles were obtained. This corresponds to a theoretical yield of 98% based on methyltrimethoxysilane.

この微粒子を電子顕微鏡で観察したところ、ほとんどの
粒子は球状を呈しており、粒子径は最大値が０．３μ
ｍ、最小値は０．０５μｍであり、平均粒子径は０．１
μｍであった。When these fine particles were observed with an electron microscope, most of the particles were spherical, and the maximum particle size was 0.3 μm.
m, the minimum value is 0.05 μm, and the average particle size is 0.1
was μm.

この微粒子を磁性ルツボに入れ空気中で９００℃に加熱
して熱分解させたところ、残量は８９．０％であった。
これはポリメチルシルセスキオキサンが酸化熱分解して
二酸化ケイ素になる理論量８９．６％に近い値である。
また、この熱分解物をＸ線分析した結果、非晶質シリカ
であることが確認された。このことから得られた白色微
粒子がポリメチルシルセスキオキサンであることが確認
された。When the fine particles were placed in a magnetic crucible and heated in air to 900 ° C. for thermal decomposition, the remaining amount was 89.0%.
This is a value close to the theoretical amount of 89.6% when polymethylsilsesquioxane is oxidized and thermally decomposed into silicon dioxide.
As a result of X-ray analysis of this thermal decomposition product, it was confirmed to be amorphous silica. From this, it was confirmed that the white fine particles obtained were polymethylsilsesquioxane.

実施例１〜４ 第１表に示す各種のオルガノトリアルコキシシラン、酢
酸および水を用いて、反応温度を３０〜４０℃に制御
し、反応時間を２４時間にしたほかは参考例１と同様の
方法で第１工程を行ないシラノール溶液を得た。このシ
ラノール溶液を第１表に示す量用い、アンモニア水溶液
および水の量と滴下時間を第１表に示すようにしたほか
は参考例１と同様にして、ケイ素原子にメチル基と他の
炭化水素基とが結合したポリオルガノシルセスキオキサ
ン微粒子を得た。得られた微粒子の収率、形状、粒子
径、加熱残分は第１表のとおりである。Examples 1 to 4 Similar to Reference Example 1 except that the reaction temperature was controlled to 30 to 40 ° C. and the reaction time was set to 24 hours by using various organotrialkoxysilanes, acetic acid and water shown in Table 1. The first step was carried out by the method to obtain a silanol solution. This silanol solution was used in the amounts shown in Table 1, and the amounts of the aqueous ammonia solution and water and the dropping time were changed to those shown in Table 1 in the same manner as in Reference Example 1 except that methyl groups and other hydrocarbons were added to the silicon atom. Polyorganosilsesquioxane fine particles having a group bonded thereto were obtained. The yield, shape, particle size, and heating residue of the obtained fine particles are shown in Table 1.

実施例２で得られた微粒子の赤外分光分析をＫＢｒ錠剤
法によって行った。第１図はそのスペクトルである。
１，０００〜１，１６０cm-1のＳｉ−Ｏ−Ｓｉ結合の吸
収、２，９６０cm-1のＣ−Ｈ結合の吸収、１，２６５cm
-1および７７５cm-1のメチル基の吸収のほか、３０５５
cm-1、１６００cm-1、１４２９cm-1および７００cm-1に
フェニル基に帰属する吸収が見られる。Infrared spectroscopic analysis of the fine particles obtained in Example 2 was performed by the KBr tablet method. FIG. 1 shows the spectrum.
The bond of Si-O-Si absorption of 1,000~1,160cm -1, absorption of C-H bonds of 2,960cm -1, 1,265cm
-1 and 775 cm -1 absorption of methyl group, 3055
Absorptions attributable to the phenyl group are observed at cm -1 , 1600 cm -1 , 1429 cm -1 and 700 cm -1 .

実施例５〜８ 参考例１と同様にして、第２表に示すような条件でケイ
素原子にメチル基と炭素官能性基が結合したポリオルガ
ノシルセスキオキサン微粒子を得た。各測定結果を第２
表に示す。 Examples 5 to 8 In the same manner as in Reference Example 1, polyorganosilsesquioxane fine particles in which a methyl group and a carbon functional group were bonded to a silicon atom were obtained under the conditions shown in Table 2. Second each measurement result
Shown in the table.

実施例９ 温度計、還流器、滴下装置および撹拌機を備えた反応容
器にエタノール９００部、水１８０部および２８％アン
モニア水溶液９部をとり、温度を２５℃に設定した。つ
いで、撹拌しながら参考例１の第１工程で得られたシラ
ノール溶液５４０部を約１０秒間で添加し、系が均一に
なるようにさらに３０秒間撹拌を続行した。その後、撹
拌を止め、静置状態で２４時間放置したところ、系は半
透明なゲル状を呈していた。このゲル状物を取出し乾燥
して、ポリメチルシルセスキオキサン微粒子を得た。 Example 9 900 parts of ethanol, 180 parts of water and 9 parts of 28% aqueous ammonia solution were placed in a reaction vessel equipped with a thermometer, a reflux device, a dropping device and a stirrer, and the temperature was set to 25 ° C. Then, 540 parts of the silanol solution obtained in the first step of Reference Example 1 was added with stirring for about 10 seconds, and stirring was continued for another 30 seconds so that the system became uniform. Then, when the stirring was stopped and the system was left standing for 24 hours, the system exhibited a semitransparent gel state. The gel-like substance was taken out and dried to obtain polymethylsilsesquioxane fine particles.

得られた微粒子の粒子径を透過型電子顕微鏡により測定
したところ、最大値は０．０４μｍであり、最小値は
０．０１μｍであった。When the particle size of the obtained fine particles was measured by a transmission electron microscope, the maximum value was 0.04 μm and the minimum value was 0.01 μm.

実施例９で得られた微粒子の赤外分光分析をＫＢｒ錠剤
法によって行った。第２図はそのスペクトルである。
１，０００〜１，１６０cm-1のＳｉ−Ｏ−Ｓｉ結合の吸
収、２，９６０cm-1のＣ−Ｈ結合の吸収、１，２６５cm
-1および７７５cm-1のメチル基の吸収が見られる。Infrared spectroscopic analysis of the fine particles obtained in Example 9 was performed by the KBr tablet method. FIG. 2 shows the spectrum.
The bond of Si-O-Si absorption of 1,000~1,160cm -1, absorption of C-H bonds of 2,960cm -1, 1,265cm
Absorption of methyl groups at -1 and 775 cm -1 is seen.

また実施例９で得られた微粒子を透過型電子顕微鏡によ
って撮影した像を第３図に示す。An image of the fine particles obtained in Example 9 taken by a transmission electron microscope is shown in FIG.

実施例１０〜１３ 参考例１並びに実施例２および６のそれぞれ第１工程で
得られたシラノール溶液を用い、第３表に示す配合量に
よったほかは実施例９と同様にして有機溶媒を併用する
方法でポリオルガノシルセスキオキサン微粒子を得た。
得られた微粒子の粒子径は第３表に示すとおりであっ
た。Examples 10 to 13 An organic solvent was prepared in the same manner as in Example 9 except that the silanol solutions obtained in the first step of Reference Example 1 and Examples 2 and 6 were used, and the blending amounts shown in Table 3 were used. Polyorganosilsesquioxane fine particles were obtained by the combined use method.
The particle size of the obtained fine particles was as shown in Table 3.

実施例１４〜１７ 第１工程において酢酸の代わりに第４表に示す有機酸を
用い（実施例１４〜１６）、またはメチルトリメトキシ
シランの代わりにメチルトリス（メトキシエトキシ）シ
ランを用いた（実施例１７）ほかは参考例１と同様にし
てポリメチルシルセスキオキサン微粒子を得た。得られ
た微粒子の収率および形状、粒子径、加熱残分は第４表
のとおりであった。 Examples 14 to 17 Organic acids shown in Table 4 were used in place of acetic acid in the first step (Examples 14 to 16), or methyltris (methoxyethoxy) silane was used in place of methyltrimethoxysilane (Examples). 17) Polymethylsilsesquioxane fine particles were obtained in the same manner as in Reference Example 1 except for the above. The yield and shape of the obtained fine particles, the particle size, and the heating residue are shown in Table 4.

比較例１ シラノール溶液を調製することなく、その代わりにメチ
ルトリメトキシシラン６８部とフェニルトリメトキシシ
ラン９９部の混合物を滴下したほかは実施例１の第２工
程と同様にしてポリオルガノシルセスキオキサン微粒子
の製造を行なった。この場合にアルコキシシラン混合物
を滴下したのち撹拌を続けると、約１０分後に系は乳白
色を呈し、粒子が形成されていることが観察されたが、
一方、反応容器の底部に油状物が沈降した。この油状物
を分液して分析を行なったところ、ほとんどが未反応の
フェニルトリメトキシシランであることが確認された。
生成した白色の粒子は赤外分光分析の結果、ケイ素原子
に結合したフェニル基が僅かに存在するポリメチルフェ
ニルシルセスキオキサンであった。また、沈降したフェ
ニルトリメトキシシランはその後の加水分解反応と縮合
反応の進行によりゲル状の塊を形成した。 Comparative Example 1 Polyorganosilsesquioxy was prepared in the same manner as in the second step of Example 1 except that a silanol solution was not prepared and a mixture of 68 parts of methyltrimethoxysilane and 99 parts of phenyltrimethoxysilane was added dropwise instead. Sun fine particles were manufactured. In this case, when the alkoxysilane mixture was added dropwise and stirring was continued, it was observed that the system became milky white after about 10 minutes and particles were formed.
On the other hand, an oily substance settled at the bottom of the reaction vessel. When this oily substance was separated and analyzed, it was confirmed that most of it was unreacted phenyltrimethoxysilane.
As a result of infrared spectroscopic analysis, the produced white particles were polymethylphenylsilsesquioxane in which phenyl groups bonded to silicon atoms were slightly present. Further, the precipitated phenyltrimethoxysilane formed a gel-like mass due to the progress of the subsequent hydrolysis reaction and condensation reaction.

比較例２ 実施例４の第１工程で得られたシラノール溶液の代わり
に、メチルトリメトキシシラン３０３部、ヘキシルトリ
メトキシシラン２０．５部およびフェニルトリメトキシ
シラン４０部の混合物を用いたほかは実施例４の第２工
程と同様にして重縮合反応を行った。この場合にアルコ
キシシラン混合物の全量を速やかに添加して、上層にア
ルコキシシラン層、下層にアンモニア水溶液層の２層状
態を保持するようにゆっくりと撹拌した。添加後、約１
０分余りで反応容器の底部にフェニルトリメトキシシラ
ンが沈降し、さらに反応容器の壁面に油状物が確認され
た。この油状物を取出して分析したところ、ヘキシルト
リメトキシシランとその部分加水分解物であることが確
認された。沈降したフェニルトリメトキシシランは時間
の経過とともに加水分解反応および縮合反応の進行によ
りゲル状の塊となり、反応容器の壁面の油状物は弾性の
あるゲル状物に変わった。Comparative Example 2 Example 2 was repeated except that a mixture of 303 parts of methyltrimethoxysilane, 20.5 parts of hexyltrimethoxysilane and 40 parts of phenyltrimethoxysilane was used in place of the silanol solution obtained in the first step of Example 4. A polycondensation reaction was carried out in the same manner as in the second step of Example 4. In this case, the entire amount of the alkoxysilane mixture was rapidly added, and the mixture was slowly stirred so as to maintain the two-layer state of the upper layer of the alkoxysilane layer and the lower layer of the aqueous ammonia solution layer. About 1 after addition
Phenyltrimethoxysilane was precipitated at the bottom of the reaction vessel in about 0 minutes, and an oily substance was confirmed on the wall surface of the reaction vessel. When this oily substance was taken out and analyzed, it was confirmed to be hexyltrimethoxysilane and its partial hydrolyzate. The precipitated phenyltrimethoxysilane became a gel-like mass due to the progress of the hydrolysis reaction and the condensation reaction over time, and the oily substance on the wall surface of the reaction vessel changed to an elastic gel-like substance.

【図面の簡単な説明】[Brief description of drawings]

第１図は、実施例２のポリオルガノシルセスキオキサン
微粒子のＩＲスペクトルであり、第２図は実施例９のポ
リオルガノシルセスキオキサン微粒子のＩＲスペクトル
である。第３図は、実施例９のポリオルガノシルセスキ
オキサン微粒子の粒子構造を示す写真である。1 is an IR spectrum of the polyorganosilsesquioxane fine particles of Example 2, and FIG. 2 is an IR spectrum of the polyorganosilsesquioxane fine particles of Example 9. FIG. 3 is a photograph showing the particle structure of the polyorganosilsesquioxane fine particles of Example 9.

Claims (2)

【特許請求の範囲】[Claims] 【請求項１】平均粒子径が０．０１〜１μｍであるポリ
オルガノシルセスキオキサン（ただし、ケイ素原子に結
合する炭化水素基は、炭素数２〜６のアルキル基、シク
ロアルキル基、アラルキル基、アリール基、アルケニル
基および置換アルキル基から選ばれた基、または上記の
基とメチル基との組合せである）微粒子。1. A polyorganosilsesquioxane having an average particle diameter of 0.01 to 1 μm (where the hydrocarbon group bonded to a silicon atom is an alkyl group having 2 to 6 carbon atoms, a cycloalkyl group or an aralkyl group). , A group selected from an aryl group, an alkenyl group and a substituted alkyl group, or a combination of the above group and a methyl group). 【請求項２】ケイ素原子に結合する炭化水素基が炭素数
６以下のアルキル基、ビニル基、フェニル基、置換プロ
ピル基または置換シクロヘキシルエチル基である請求項
１記載のポリオルガノシルセスキオキサン微粒子。2. The polyorganosilsesquioxane fine particles according to claim 1, wherein the hydrocarbon group bonded to the silicon atom is an alkyl group having 6 or less carbon atoms, a vinyl group, a phenyl group, a substituted propyl group or a substituted cyclohexylethyl group. .
JP63042303A 1988-02-26 1988-02-26 Polyorganosilsesquioxane fine particles Expired - Lifetime JPH0618879B2 (en)

Priority Applications (6)

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JP63042303A JPH0618879B2 (en) 1988-02-26 1988-02-26 Polyorganosilsesquioxane fine particles
GB8904201A GB2216535B (en) 1988-02-26 1989-02-23 "process for producing polyorganosilsesquioxane spherical particles"
DE3905785A DE3905785C2 (en) 1988-02-26 1989-02-24 Process for the production of fine polyorganosilsesquioxane particles
IT8947687A IT1230485B (en) 1988-02-26 1989-02-24 FINE PARTS OF POLYORGANOSILSESQUIOSSANO AND PROCEDURE TO PRODUCE THE SAME
FR8902442A FR2627773B1 (en) 1988-02-26 1989-02-24 FINE POLYORGANOSILSESQUIOXANE PARTICLES AND PROCESS FOR PRODUCING THE SAME
KR1019890002525A KR930006260B1 (en) 1988-02-26 1989-02-27 Polyorganosilsesquioxane fines particles and process for producing them

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JP63042303A JPH0618879B2 (en) 1988-02-26 1988-02-26 Polyorganosilsesquioxane fine particles

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Publications (2)

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JPH01217039A JPH01217039A (en) 1989-08-30
JPH0618879B2 true JPH0618879B2 (en) 1994-03-16

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ID=12632257

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KR (1) KR930006260B1 (en)
DE (1) DE3905785C2 (en)
FR (1) FR2627773B1 (en)
GB (1) GB2216535B (en)
IT (1) IT1230485B (en)

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GB2216535A (en) 1989-10-11
GB2216535B (en) 1992-08-05
IT1230485B (en) 1991-10-24
FR2627773A1 (en) 1989-09-01
FR2627773B1 (en) 1994-02-25
JPH01217039A (en) 1989-08-30
GB8904201D0 (en) 1989-04-05
IT8947687A0 (en) 1989-02-24
DE3905785C2 (en) 1994-06-09
KR930006260B1 (en) 1993-07-09
KR890013091A (en) 1989-09-21
DE3905785A1 (en) 1989-08-31

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