JPH0637527B2 - Method for producing composite polymer particles - Google Patents
Method for producing composite polymer particlesInfo
- Publication number
- JPH0637527B2 JPH0637527B2 JP63183935A JP18393588A JPH0637527B2 JP H0637527 B2 JPH0637527 B2 JP H0637527B2 JP 63183935 A JP63183935 A JP 63183935A JP 18393588 A JP18393588 A JP 18393588A JP H0637527 B2 JPH0637527 B2 JP H0637527B2
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- monomer
- inorganic powder
- particles
- coupling agent
- added
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Description
【発明の詳細な説明】 （イ）産業上の利用分野 この発明は、複合体樹脂粒子の製造方法に関する。さら
に詳しくは、無機充填材を含有する複合重合体粒子の製
造方法に関する。TECHNICAL FIELD The present invention relates to a method for producing composite resin particles. More specifically, it relates to a method for producing composite polymer particles containing an inorganic filler.
（ロ）従来の技術および課題 近年、樹脂の用途の拡大を目的として、樹脂に顔料特性
や耐衝撃性、導電性等の機能を付与する試みがなされて
いる。樹脂に顔料特性や導電性等の機能を付与する方法
としては、例えば樹脂と顔料微粒子、導電性微粒子等の
無機物微粒子粉末とを単に混合するか、もしくは混練、
混合した後に粉砕する方法および重合性モノマの懸濁重
合反応に際して、無機物微粒子を存在させる方法等が知
られている。(B) Conventional Technology and Problems In recent years, attempts have been made to impart functions such as pigment characteristics, impact resistance, and conductivity to resins for the purpose of expanding the applications of the resins. As a method of imparting functions such as pigment characteristics and conductivity to the resin, for example, the resin and pigment fine particles, inorganic fine particle powder such as conductive fine particles are simply mixed or kneaded,
Known methods include a method of pulverizing after mixing and a method of allowing inorganic fine particles to exist in a suspension polymerization reaction of a polymerizable monomer.
樹脂と無機物微粒子粉末を単に混合するか、または混
練、混合した後に粉砕する方法では、無機物微粒子粉末
の樹脂中への分散が困難であり、かつその分布も不均一
になりやすく、また得られた樹脂粒子は、不規則な形状
を呈するという欠点を有する。By the method of simply mixing the resin and the inorganic fine particle powder, or by kneading and mixing and then pulverizing, it is difficult to disperse the inorganic fine particle powder in the resin, and the distribution thereof is likely to be non-uniform Resin particles have the drawback of exhibiting an irregular shape.
一方、重合性モノマの懸濁重合反応については、モノマ
中に無機物微粒子粉末とともに、該単量体に可溶な重合
体を存在させることにより、粒子中に無機物微粒子粉末
を含有させる方法（特開昭55-106205号公報）が知られ
ているが、この方法でも、無機物微粒子粉末がモノマ中
に分散しにくく、また重合中、無機物微粒子粉末が一部
水中へ移るため、重合終了後、無機物微粒子粉末を酸な
どで分解するか、該粉末が酸などに対して安定な場合は
樹脂粒子と無機粉末とを分離する等煩雑な処理も必要と
なる。これらの点を改良するため、ステアリン酸、オレ
イン酸などの極性基を有する長鎖の炭化水素、あるいは
アクリル酸、メタクリル酸等の様な極性基を有するモノ
マ等の親油化剤を無機粉末と共にモノマ中に添加し、場
合によっては、モノマに可溶な重合体の共存下で、無機
粉末の表面を親油化したのち、懸濁重合の供する方法が
開示されている（特開昭52-92389号公報）。On the other hand, for the suspension polymerization reaction of the polymerizable monomer, a method in which the inorganic fine particle powder is contained in the monomer by allowing a polymer soluble in the monomer to be present in the monomer together with the inorganic fine particle powder (Japanese Patent Laid-Open No. 55-106205) is known, but even in this method, the inorganic fine particle powder is difficult to disperse in the monomer, and the inorganic fine particle powder partially moves into water during the polymerization. A complicated treatment such as decomposing the powder with an acid or separating the resin particles and the inorganic powder when the powder is stable to the acid is also required. In order to improve these points, a long-chain hydrocarbon having a polar group such as stearic acid and oleic acid, or a lipophilic agent such as a monomer having a polar group such as acrylic acid and methacrylic acid is used together with the inorganic powder. A method has been disclosed in which, when added to a monomer, and in some cases, in the presence of a polymer soluble in the monomer, the surface of the inorganic powder is made lipophilic, and then suspension polymerization is performed (JP-A-52- 92389 publication).
しかしながら、この方法で用いられる親油化剤の様に、
単に粒子に吸着される極性基を有し、モノマと親和性の
高い、炭化水素を有する物質を使用した場合、それの極
性基と親油化されるべき無機粉末との結合作用が吸着作
用によるものであるため、水性懸濁重合に際して、水相
とモノマ相との界面あるいはその近傍では、水分の影響
をうけ、該親油化剤と無機粉末との結合が阻害され、無
機粉末が水相に移行し易い傾向がみられる。一方、シリ
カ又はアルミナの微細粒子を均一かつ高い分散性で含有
する樹脂組成物を製造するために、粒径１〜1000ミリミ
クロンのシリカ又はアルミナからなる水性または水と極
性溶媒との混合溶剤を媒体とする膠質ゾル中にシリカ系
結合剤を添加し、これに重合性ビニル化合物を加えて懸
濁または乳化重合する方法が開示されている（特公昭49
-30702号公報）が、この方法によれば、無機粉末の粒径
が大きくなればなる程、無機粉末とモノマとの比重差に
より、モノマ相中で無機粉末の偏在が起こりやすくなる
ため、均質な複合重合体粒子は得られにくい。However, like the lipophilic agent used in this method,
When a substance having a hydrocarbon that has a polar group that is simply adsorbed on the particles and has a high affinity for a monomer is used, the binding action between the polar group and the inorganic powder to be lipophilic is due to the adsorption action. Therefore, in the aqueous suspension polymerization, at the interface between the water phase and the monomer phase or in the vicinity thereof, the effect of water is exerted, the binding between the lipophilic agent and the inorganic powder is inhibited, and the inorganic powder becomes an aqueous phase. There is a tendency to easily shift to. On the other hand, in order to produce a resin composition containing fine particles of silica or alumina uniformly and with high dispersibility, a mixed solvent of an aqueous or water and polar solvent consisting of silica or alumina having a particle size of 1 to 1000 mm is used. A method has been disclosed in which a silica-based binder is added to a colloidal sol as a medium, and a polymerizable vinyl compound is added thereto to carry out suspension or emulsion polymerization (Japanese Patent Publication No. Sho 49).
However, according to this method, the larger the particle size of the inorganic powder, the more likely it is that the inorganic powder is unevenly distributed in the monomer phase due to the difference in specific gravity between the inorganic powder and the monomer. It is difficult to obtain such complex polymer particles.
この発明者は、重合性モノマ中に、ビニル基を有するシ
ランカップリング剤および無機粉末を加え、無機粉末の
表面を処理すると共に、該モノマに可溶な重合体を溶解
させて、上記モノマの粘度を上昇させることにより、該
無機粉末が上記モノマ中で偏在せず均質に分散し、か
つ、無機粉末の上記モノマ中から水系への離脱が高度に
抑制され、その結果、無機粉末の実質的全量を樹脂中に
含有させ、さらにその無機粉末が樹脂中に均質に分散さ
れることを見いだし、この発明を完成させるに至った。This inventor adds a silane coupling agent having a vinyl group and an inorganic powder to a polymerizable monomer to treat the surface of the inorganic powder, and at the same time dissolve a polymer soluble in the monomer, By increasing the viscosity, the inorganic powder is uniformly distributed without uneven distribution in the monomer, and the separation of the inorganic powder from the monomer into the water system is highly suppressed, and as a result, the inorganic powder is substantially dispersed. The whole amount was contained in the resin, and it was further found that the inorganic powder was uniformly dispersed in the resin, and the present invention was completed.
（ハ）課題を解決するための手段 かくしてこの発明によれば、重合性ビニル系モノマと、
ビニル基を有するシラン系カップリング剤で表面処理さ
れた無機粉末と、上記モノマに可溶な重合体とから成る
モノマ組成物を水系に分散し、該モノマを重合させるこ
とにより、無機粉末が分散された樹脂粒子を得ることを
特徴とする複合重合体粒子の製造方法が提供される。(C) Means for Solving the Problems Thus, according to the present invention, a polymerizable vinyl-based monomer,
Inorganic powder surface-treated with a silane-based coupling agent having a vinyl group, and a monomer composition comprising a polymer soluble in the monomer is dispersed in an aqueous system, and the monomer is polymerized to disperse the inorganic powder. There is provided a method for producing composite polymer particles, characterized in that the obtained resin particles are obtained.
この発明は、モノマ組成物中に用いる無機粉末の実質的
全量が、最終生成物である樹脂粒子中に分散して含有さ
れ、かつ、得られる個々の樹脂粒子中において上記無機
粉末が均一に分散された複合重合体粒子を製造しうる方
法であることを特徴とする。In the present invention, substantially the entire amount of the inorganic powder used in the monomer composition is contained in the final product resin particles in a dispersed state, and the inorganic powder is uniformly dispersed in the individual resin particles obtained. It is a method capable of producing the thus-obtained composite polymer particles.
この発明の複合重合体粒子の製造に用いる上記重合性ビ
ニル系モノマとしては、ラジカル重合が可能であれば特
に制約はないが、アクリロニトリル、メタクリロニトリ
ル等のニトリル系モノマ、スチレン、α−メチルスチレ
ン、クロロスチレン等のスチレン系モノマ、アクリル酸
メチル、アクリル酸エチル等のアクリル酸アルキルエス
テル系モノマ、メタクリル酸メチル、メタクリル酸エチ
ル等のメタクリル酸アルキルエステル系モノマ、アクリ
ル酸、メタクリル酸等の不飽和カルボン酸等が代表的で
ある。ビニル系モノマは単独又は２種以上のモノマ混合
物として使用する。また、前記重合開始剤としては、使
用するモノマに可溶なものであればよく、例えば、通常
使用される過酸化ベンゾイル、過酸化ラウロイル、過酸
化ジアセチル等の過酸化物およびアゾビスイソブチロニ
トリル、アゾビスメチルバレロニトリル等のアゾ化合物
等を挙げることができる。The polymerizable vinyl-based monomer used for producing the composite polymer particles of the present invention is not particularly limited as long as radical polymerization is possible, but acrylonitrile, nitrile monomers such as methacrylonitrile, styrene, and α-methylstyrene. , Styrene monomers such as chlorostyrene, alkyl acrylate monomers such as methyl acrylate and ethyl acrylate, methacrylic acid alkyl ester monomers such as methyl methacrylate and ethyl methacrylate, unsaturated acrylic acid and methacrylic acid A carboxylic acid and the like are typical. The vinyl monomers are used alone or as a mixture of two or more kinds. The polymerization initiator may be any one that is soluble in the monomer used, and examples thereof include benzoyl peroxide, lauroyl peroxide, diacetyl peroxide, and other commonly used peroxides and azobisisobutyro. Examples thereof include azo compounds such as nitrile and azobismethylvaleronitrile.
この発明に用いる前記シラン系カップリング剤として
は、前記モノマ組成物を後述する水系中に分散状態で行
う重合条件下において、該カップリング剤の効果が十分
発揮できる様、モノマと共重合しうるビニル基を有する
ものが選択される。該カップリング剤としては、例えば
ビニルトリクロルシラン、ビニルトリメトキシシラン、
ビニルトリエトキシシラン、ビニルトリス（2-メトキシ
エトキシ）シラン、ビニルトリアセトキシシラン、γ−
メタクリルオキシプロピルトリメトキシシラン等が好適
に用いられる。この発明に用いる前記無機粉末は、水に
不溶性又は難溶性のもので、かつ、上記シラン系カップ
リング剤の効果が認められるものであれば、公知のもの
をそのまま制限なく用いることができる。該無機粉末と
しては、例えばシリカ、アルミナ、ガラス、石英粉末
や、タルク、クレイ、鉄粉、酸化チタン、酸化亜鉛、酸
化ジルコニウム、酸化鉄等が挙げられ、これらのいずれ
のものでも十分に効果は認められるが、特にシリカ、ガ
ラスなど無機粉末表面にシラノール基をもつものの効果
が顕著である。The silane coupling agent used in the present invention may be copolymerized with a monomer so that the effect of the coupling agent can be sufficiently exerted under the polymerization conditions in which the monomer composition is dispersed in an aqueous system described below. Those having a vinyl group are selected. Examples of the coupling agent include vinyltrichlorosilane, vinyltrimethoxysilane,
Vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, vinyltriacetoxysilane, γ-
Methacryloxypropyltrimethoxysilane and the like are preferably used. As the above-mentioned inorganic powder used in the present invention, any known inorganic powder can be used without any limitation as long as it is insoluble or sparingly soluble in water and the effect of the silane coupling agent is recognized. Examples of the inorganic powder include silica, alumina, glass, quartz powder, talc, clay, iron powder, titanium oxide, zinc oxide, zirconium oxide, iron oxide, and the like, and any one of them is sufficiently effective. Although it is recognized, the effect of silanol groups such as silica and glass having a silanol group on the surface thereof is remarkable.
また、上記無機粉末の用いられる大きさは、上記モノマ
相中での沈降を防ぎ、最終的に得られる樹脂粒子中に均
質に分散させる点から、平均粒径が３μｍ以下であるこ
とが好ましく、１μｍ以下がさらに好ましい。The size of the inorganic powder used is preferably 3 μm or less in terms of average particle size in order to prevent sedimentation in the monomer phase and to uniformly disperse the resin particles in the finally obtained resin particles. It is more preferably 1 μm or less.
この発明に用いる上記モノマに可溶な重合体は、モノマ
組成物の粘度を調整して該組成物中での上記無機粉末の
偏在を防止する目的で用いられ、前記モノマに可溶で、
かつ、モノマ相の粘度上昇が可能なものであれば、その
種類および平均分子量を問わずいずれを使用することも
できる。該重合体としては、例えばアクリル酸エステル
重合体、スチレン重合体もしくはメタクリル酸エステル
重合体、およびこれらの重合体を主体とした共重合体等
が挙げられる。The monomer-soluble polymer used in the present invention is used for the purpose of adjusting the viscosity of the monomer composition to prevent uneven distribution of the inorganic powder in the composition, and is soluble in the monomer,
Further, as long as the viscosity of the monomer phase can be increased, any one can be used regardless of its type and average molecular weight. Examples of the polymer include acrylic acid ester polymers, styrene polymers or methacrylic acid ester polymers, and copolymers mainly containing these polymers.
この発明に用いるモノマ組成物は、上記重合性ビニル系
モノマと、上記特定のシラン系カップリング剤で表面処
理された無機粉末と、上記重合体とから調製されるが、
この場合予めシラン系カップリング剤で処理して得られ
た無機粉末を所定のモノマ中に導入し、さらに上記重合
体を加えて調製することもできるが、所定のモノマに上
記特定のシラン系カップリング剤を溶解しておき、ここ
に上記無機粉末を導入して撹拌下で処理し、この後所定
の重合体を添加して調製するものであってもよい。通
常、後者の方法がより好ましく用いられる。すなわち、
前記モノマの１種または２種以上のモノマの所定量から
なる単量体中に、前記所定量のシラン系カップリング剤
を加えて溶解し、ここに、未処理の所定量の無機粉末を
加えて上記モノマ相で無機粉末を分散して表面処理を行
った後、得られる無機粉末分散モノマ相に前記所定量の
ポリマーを溶解させて上記モノマ相の粘度を所定の値に
調節する。また、シラン系カップリング剤をモノマに添
加する際、予め該カップリング剤を酢酸水溶液等で加水
分解して添加することもできる。The monomer composition used in the present invention is prepared from the polymerizable vinyl-based monomer, the inorganic powder surface-treated with the specific silane-based coupling agent, and the polymer,
In this case, the inorganic powder obtained by previously treating with a silane coupling agent may be introduced into a predetermined monomer, and the above polymer may be added to prepare the monomer. It may be prepared by dissolving the ring agent, introducing the above-mentioned inorganic powder into the ring agent, treating the mixture under stirring, and then adding a predetermined polymer. Usually, the latter method is more preferably used. That is,
A predetermined amount of the silane coupling agent is added to and dissolved in a monomer composed of a predetermined amount of one or more monomers of the monomers, and an untreated predetermined amount of inorganic powder is added thereto. After the inorganic powder is dispersed in the monomer phase to perform surface treatment, the predetermined amount of the polymer is dissolved in the obtained inorganic powder-dispersed monomer phase to adjust the viscosity of the monomer phase to a predetermined value. In addition, when the silane coupling agent is added to the monomer, the coupling agent may be previously hydrolyzed with an acetic acid aqueous solution or the like and added.
上記無機粉末の分散および表面処理は、通常使用される
機械的方法等により常温で極めて容易に行うことができ
る。上記機械的方法として、例えばホモミキサー等で十
分であるが、高速回転ホモジナイザ、超音波等を用いる
場合にはより効果的に行うことができる。Dispersion and surface treatment of the above-mentioned inorganic powder can be carried out very easily at room temperature by a commonly used mechanical method or the like. As the mechanical method, for example, a homomixer or the like is sufficient, but when a high-speed rotating homogenizer, ultrasonic waves, or the like is used, it can be more effectively performed.
上記調製は、モノマ100重量部に対して無機粉末は１〜
９重量部が好ましく、前記重合開始剤は上記モノマの0.
1〜2.0重量％の範囲で用いられることが好ましい。In the above preparation, the inorganic powder is 1 to 100 parts by weight of the monomer.
9 parts by weight is preferable, and the polymerization initiator is 0.1
It is preferably used in the range of 1 to 2.0% by weight.
前記シラン系カップリング剤は、上記のごとく用いる無
機粉末の実質的全域を被覆するに足る量が通常用いら
れ、該無機粉末の表面積、使用量および使用するカップ
リング剤の１分子当りの処理可能面積によって決定され
るが、上記無機粉末に対して、0.1〜20重量部の割合で
用いられることが好ましい。前記重合体は、この重合体
を溶解した前記モノマの粘度が５〜5000センチポイズの
範囲となるように用いられることが適しており、上記モ
ノマ100重量部に対して、0.5〜40重量部が好ましく、さ
らに１〜30重量部の範囲で用いられることが好ましい。The silane coupling agent is usually used in an amount sufficient to cover substantially the entire area of the inorganic powder used as described above, and the surface area of the inorganic powder, the amount used, and the amount of the coupling agent used per molecule can be treated. Although it is determined by the area, it is preferably used in a proportion of 0.1 to 20 parts by weight with respect to the inorganic powder. The polymer is preferably used so that the viscosity of the monomer in which the polymer is dissolved is in the range of 5 to 5000 centipoise, and 0.5 to 40 parts by weight is preferable with respect to 100 parts by weight of the monomer. Further, it is preferably used in the range of 1 to 30 parts by weight.
この発明において、上記のごとく調製されたモノマ組成
物は、水系中に分散されかつ該モノマが重合条件に付さ
れることにより、用いた無機粉末の実質的全量が含有さ
れ、かつ、この無機粉末が最終的に得られる個々の樹脂
粒子中に均一に分散された複合重合体粒子を得ることが
できる。In the present invention, the monomer composition prepared as described above is dispersed in an aqueous system and the monomer is subjected to polymerization conditions to contain substantially all of the inorganic powder used, and the inorganic powder. It is possible to obtain composite polymer particles uniformly dispersed in individual resin particles finally obtained.
上記分散、重合によれば無機粉末が分散された粒子径１
μｍ〜３mmの複合重合体粒子が得られるが、この生成物
粒子の大きさは、使用目的に応じて適宜選択することが
できる。According to the above dispersion and polymerization, the particle size 1 in which the inorganic powder is dispersed
Although composite polymer particles having a size of μm to 3 mm can be obtained, the size of the product particles can be appropriately selected according to the purpose of use.
（ニ）作用 この発明において、水系中に分散されたモノマ組成物中
では、無機粉末は、シラン系カップリング剤による表面
処理の結果、モノマ組成物中に強力に保持され、該カッ
プリング剤が有するビニル基により、重合が進むにつれ
さらに強力に保持され、水系への離脱が抑えられかつ該
組成物中に共存する重合体により、その粘度が適度に上
昇されて無機粉末の偏在が緩和されるとともに、より一
層モノマ組成物中に無機粉末は保持されやすくなるた
め、無機粉末の実質的全量を含有し、かつ、個々には無
機粉末が均一に分散された複合重合体粒子が得られる。(D) Action In the present invention, in the monomer composition dispersed in the water system, the inorganic powder is strongly retained in the monomer composition as a result of the surface treatment with the silane coupling agent, and the coupling agent is The vinyl group has a stronger retention as the polymerization progresses, the separation into the water system is suppressed, and the polymer coexisting in the composition moderately increases the viscosity and alleviates uneven distribution of the inorganic powder. At the same time, since the inorganic powder is more easily retained in the monomer composition, composite polymer particles containing substantially the entire amount of the inorganic powder and individually dispersed with the inorganic powder are obtained.
以下実施例によりこの発明を詳細に説明するが、これに
よりこの発明は限定されるものではない。Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto.
（ホ）実施例 実施例１ ２のビーカに、メチルメタクリレート540ｇ、シラン
カップリング剤（γ−メタクリルオキシプロピルトリメ
トキシシラン、東レシリコーン（株）製SZ6030）8.0ｇ
を入れ、完全に溶解させた後、酸化亜鉛（粒径0.7μ
ｍ、正同化学（株）製、亜鉛華特号）400ｇを加えてホ
モミキサー（8,000rpm.）で20分間表面処理した。処理
後、過酸化ベンゾイル1.08ｇと、ポリメチルメタクリレ
ート（＝10万）60ｇを加えて溶解させた。このと
き、無機粉末を除くモノマ組成物の粘度は200cPであっ
た。(E) Example In the beaker of Example 12, 8.0 g of methyl methacrylate 540 g, silane coupling agent (γ-methacryloxypropyltrimethoxysilane, SZ6030 manufactured by Toray Silicone Co., Ltd.)
, And dissolve it completely, then add zinc oxide (particle size 0.7μ
m, manufactured by Shodo Kagaku Co., Ltd., Zinc Hua Special Number) (400 g) was added, and the surface was treated with a homomixer (8,000 rpm.) for 20 minutes. After the treatment, 1.08 g of benzoyl peroxide and 60 g of polymethylmethacrylate (= 100,000) were added and dissolved. At this time, the viscosity of the monomer composition excluding the inorganic powder was 200 cP.
５オートクレーブに、複分解ピロリン酸マグネシウム
26.0ｇとドデシルベンゼンスルホン酸ソーダ1.2ｇを含
む水3.0kgを入れ、ついで上記スラリーを加えて窒素置
換した後、撹拌速度を900rpm.に設定し、70℃で重合し
た。重合終了後100℃に昇温し、100℃に達してから１時
間後室温まで冷却し、分散剤を当量の塩酸と反応させ分
解した後、このスラリーを拡大投影機で100倍に拡大し
て観察したところ、中心粒径は約10μｍで粒子内部の酸
化亜鉛は均一に分散していた。また水相には酸化亜鉛は
全く移行していなかった。5 autoclave, metathesis magnesium pyrophosphate
Water (3.0 kg) containing 26.0 g and sodium dodecylbenzenesulfonate (1.2 g) was added, and then the above slurry was added to replace the atmosphere with nitrogen, and then the stirring speed was set to 900 rpm. After the polymerization was completed, the temperature was raised to 100 ° C, 1 hour after reaching 100 ° C, the temperature was cooled to room temperature, the dispersant was reacted with an equivalent amount of hydrochloric acid and decomposed, and this slurry was magnified 100 times with a magnifying projector. As a result of observation, the center particle size was about 10 μm, and zinc oxide inside the particles was uniformly dispersed. Moreover, zinc oxide did not migrate to the aqueous phase at all.
実施例２ ２のビーカーに、スチレン810ｇ、シランカップリン
グ剤（ビニルトリメトキシシラン、東レシリコーン
（株）製SZ6300）2.0ｇを入れ、完全に溶解させた後、
タルク（粒径1.8μｍ、松村産業（株）製、5,000PJ）10
0ｇを加えてホモミキサー（8,000rpm.）で20分間表面処
理した。処理後、過酸化ベンゾイル2.43ｇとポリスチレ
ン（＝15万）90ｇを加えて溶解させモノマ組成物を
得た。この時、無機粉末を除くモノマ組成物の粘度は30
0cPであった。Example 2 In a beaker of Example 2, 810 g of styrene and 2.0 g of a silane coupling agent (vinyltrimethoxysilane, SZ6300 manufactured by Toray Silicone Co., Ltd.) were placed and completely dissolved.
Talc (particle size 1.8 μm, Matsumura Sangyo Co., Ltd., 5,000 PJ) 10
0 g was added and the surface was treated with a homomixer (8,000 rpm.) For 20 minutes. After the treatment, 2.43 g of benzoyl peroxide and 90 g of polystyrene (= 150,000) were added and dissolved to obtain a monomer composition. At this time, the viscosity of the monomer composition excluding the inorganic powder is 30
It was 0 cP.
この後の操作は実施例１と同様にした。The subsequent operations were the same as in Example 1.
得られたスラリーを拡大投影機で観察すると、中心粒径
は約50μｍで粒子内部のタルクは均一に分散しており、
水相にはタルクは全く移行していなかった。When the obtained slurry is observed with a magnifying projector, the central particle size is about 50 μm and the talc inside the particles is uniformly dispersed.
No talc had migrated to the water phase.
実施例３ ２のビーカーにメチルメタクリレート855ｇ、シラン
カップリング剤（γ−メタクリルオキシプロピルトリメ
トキシシラン、東レシリコーン（株）製SZ6030）3.0ｇ
を入れ、完全に溶解させた後、酸化亜鉛（粒径0.2μ
ｍ、帝国化工（株）製、JR-600A）100ｇを加えてホモミ
キサー（8,000rpm.）で20分間表面処理した。処理後、
過酸化ベンゾイル1.62ｇとポリメチルメタクリレート
（＝10万）45ｇを加えて溶解させ、モノマ組成物を
得た。このとき、無機粉末を除くモノマ組成物の粘度は
100cPであった。この後の操作は実施例１と同様にし
た。In a beaker of Example 32, 855 g of methyl methacrylate, silane coupling agent (γ-methacryloxypropyltrimethoxysilane, SZ6030 manufactured by Toray Silicone Co., Ltd.) 3.0 g
And dissolve it completely, then add zinc oxide (particle size 0.2μ
m, Teikoku Kako Co., Ltd., JR-600A) 100 g was added, and the surface was treated with a homomixer (8,000 rpm.) for 20 minutes. After treatment,
1.62 g of benzoyl peroxide and 45 g of polymethylmethacrylate (= 100,000) were added and dissolved to obtain a monomer composition. At this time, the viscosity of the monomer composition excluding the inorganic powder is
It was 100 cP. The subsequent operations were the same as in Example 1.
得られたスラリーを拡大投影機で観察すると、中心粒径
は約10μｍで、粒子内部の酸化チタンは均一に分散して
おり水相には、酸化タルクは全く移行していなかった。When the obtained slurry was observed with a magnifying projector, the central particle size was about 10 μm, titanium oxide inside the particles was uniformly dispersed, and talc oxide did not migrate to the aqueous phase at all.
実施例４ ２のビーカーにメチルメタクリレート630ｇ、シラン
カップリング剤（γ−メタクリルオキシプロピルトリメ
トキシシラン、東レシリコーン（株）SZ6030）4.5ｇを
入れ、完全に溶解させた後、酸化鉄（Fe3O4、粒径0.1〜
0.8μｍ）300ｇを加えて、ホモミキサーで6,000rpm.で2
0分間表面処理した。処理後、過酸化ベンゾイル1.40ｇ
をポリメチルメタクリレート（＝10万）70ｇを加え
て溶解させた。この時の、無機粉末を除くモノマ組成物
の粘度は200cPであった。In a beaker of Example 4, 630 g of methyl methacrylate and 4.5 g of a silane coupling agent (γ-methacryloxypropyltrimethoxysilane, SZ6030 of Toray Silicone Co., Ltd.) were placed and completely dissolved, and then iron oxide (Fe 3 O 4 , particle size 0.1 ~
0.8μm) 300g and add 2 at 6,000rpm with homomixer.
The surface was treated for 0 minutes. After treatment, 1.40 g of benzoyl peroxide
70 g of polymethylmethacrylate (= 100,000) was added and dissolved. At this time, the viscosity of the monomer composition excluding the inorganic powder was 200 cP.
この後の操作は実施例１と同様にした。得られたスラリ
ーを拡大投影機で観察すると、中心粒径は約30μｍで粒
子内部の酸化チタンは均一に分散しており、水相には酸
化鉄は全く移行していなかった。The subsequent operations were the same as in Example 1. When the obtained slurry was observed with a magnifying projector, the central particle diameter was about 30 μm, titanium oxide inside the particles was uniformly dispersed, and iron oxide was not transferred to the aqueous phase at all.
比較例１ ２のビーカーにメチルメタクリレート855ｇ、ステア
リン酸３ｇを入れ、完全に溶解させた後、実施例３で使
用した酸化チタン100ｇを加えた。この後の操作は実施
例３と同様にした。855 g of methyl methacrylate and 3 g of stearic acid were placed in a beaker of Comparative Example 12 and completely dissolved, and then 100 g of titanium oxide used in Example 3 was added. The subsequent operation was the same as in Example 3.
得られたスラリーを拡大投影機で観察すると、粒子内部
の酸化チタンは均一に分散していたが、わずかに水相に
酸化チタンが移行していた。When the obtained slurry was observed with a magnifying projector, the titanium oxide inside the particles was uniformly dispersed, but the titanium oxide was slightly transferred to the aqueous phase.
比較例２ ２のビーカーにメチルメタクリレート900ｇ、シラン
カップリング剤（γ−メタクリルオキシプロピルトリメ
トキシシラン、東レシリコーン（株）製SZ6030）3.0ｇ
を入れ、完全に溶解させた後、実施例３で使用した酸化
チタン100ｇを加えて、ホモミキサー（8,000rpm.）で20
分間表面処理した。処理後、過酸化ベンゾイル1.80ｇを
加えて溶解させ、モノマ組成物を得た。この後の操作は
実施例１と同様にした。得られたスラリーを拡大投影機
で観察すると水相には、酸化チタンは移行していなかっ
たが、粒子内部の酸化チタンは均一に分散しておらず、
粒子内部あるいは粒子間で偏在していた。Comparative Example 2 900 g of methyl methacrylate, 3.0 g of silane coupling agent (γ-methacryloxypropyltrimethoxysilane, Toray Silicone SZ6030) in a beaker of Comparative Example 2
After completely dissolving the mixture, 100 g of titanium oxide used in Example 3 was added, and the mixture was mixed with a homomixer (8,000 rpm.) For 20 minutes.
Surface treated for minutes. After the treatment, 1.80 g of benzoyl peroxide was added and dissolved to obtain a monomer composition. The subsequent operations were the same as in Example 1. When the obtained slurry was observed with a magnifying projector, the titanium oxide was not transferred to the aqueous phase, but the titanium oxide inside the particles was not uniformly dispersed,
It was unevenly distributed within the particles or between the particles.
比較例３ ２のビーカーにメチルメタクリレート855ｇ、ビニル
基を持たないシランカップリング剤（メチルトリメトキ
シシラン、東レシリコーン（株）製SZ6070）3.0ｇを入
れ、完全に溶解させた後、実施例３で使用した酸化チタ
ン100ｇを加えた。この後の操作は実施例３と同様にし
た。Comparative Example 3 In a beaker of Example 2, 855 g of methyl methacrylate and 3.0 g of a silane coupling agent having no vinyl group (methyltrimethoxysilane, SZ6070 manufactured by Toray Silicone Co., Ltd.) were added and completely dissolved. 100 g of the titanium oxide used was added. The subsequent operation was the same as in Example 3.
得られたスラリーを拡大投影機で観察すると、粒子内部
の酸化チタンは均一に分散していたが、わずかに水相に
酸化チタンが移行していた。When the obtained slurry was observed with a magnifying projector, the titanium oxide inside the particles was uniformly dispersed, but the titanium oxide was slightly transferred to the aqueous phase.
（ヘ）発明の効果 この発明によれば、無機粉末が実質的に全量、生成され
る重合体粒子中に含有されており、かつ、重合体粒子中
の無機粉末が均一に分散している球状の無機粉末、樹脂
複合体粒子を得ることができる。(F) Effect of the Invention According to the present invention, substantially all of the inorganic powder is contained in the polymer particles to be produced, and the inorganic powder in the polymer particles is spherically dispersed uniformly. Inorganic powder and resin composite particles can be obtained.
Claims (1)
るシラン系カップリング剤で表面処理された無機粉末
と、上記モノマに可溶な重合体とからなるモノマ組成物
を水系に分散し、該モノマを重合させることにより、無
機粉末が分散された樹脂粒子を得ることを特徴とする複
合重合体粒子の製造方法。1. A monomer composition comprising a polymerizable vinyl-based monomer, an inorganic powder surface-treated with a silane-based coupling agent having a vinyl group, and a polymer soluble in the monomer is dispersed in an aqueous system, A method for producing composite polymer particles, characterized in that resin particles in which an inorganic powder is dispersed are obtained by polymerizing the monomer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63183935A JPH0637527B2 (en) | 1988-07-23 | 1988-07-23 | Method for producing composite polymer particles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63183935A JPH0637527B2 (en) | 1988-07-23 | 1988-07-23 | Method for producing composite polymer particles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0234602A JPH0234602A (en) | 1990-02-05 |
| JPH0637527B2 true JPH0637527B2 (en) | 1994-05-18 |
Family
ID=16144381
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63183935A Expired - Fee Related JPH0637527B2 (en) | 1988-07-23 | 1988-07-23 | Method for producing composite polymer particles |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0637527B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023145587A1 (en) | 2022-01-31 | 2023-08-03 | 株式会社不二宮製作所 | Coupling structure including plurality of coupling portions and shape varying member |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10260337A1 (en) * | 2002-12-20 | 2004-07-08 | Basf Ag | Use of aqueous dispersions of polymer and finely divided inorganic solid to prime mineral substrates |
| KR100717514B1 (en) * | 2005-12-30 | 2007-05-11 | 제일모직주식회사 | Organic/inorganic hybrid nanocomposites and thermoplastic nanocomposite resin compositions using the same |
| CN105482010A (en) * | 2015-12-10 | 2016-04-13 | 重庆三零三科技有限公司 | Preparation method of hydrophobic TiO2/PS core/shell material |
| CN106589269A (en) * | 2016-12-30 | 2017-04-26 | 华东理工大学 | Method of using styrene-acrylic ester to polymerize at surface of titanium dioxide |
| CN106749859A (en) * | 2016-12-30 | 2017-05-31 | 华东理工大学 | A kind of method that use acrylate is polymerized in titanium dioxide surface |
| CN114479536B (en) * | 2022-02-28 | 2022-11-18 | 南昌交通学院 | Diatomite hybrid supermolecule thermal insulation material and preparation method thereof |
-
1988
- 1988-07-23 JP JP63183935A patent/JPH0637527B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023145587A1 (en) | 2022-01-31 | 2023-08-03 | 株式会社不二宮製作所 | Coupling structure including plurality of coupling portions and shape varying member |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0234602A (en) | 1990-02-05 |
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