JP5003310B2 - Surface hydrophobized metal oxide powder and method for producing the same - Google Patents
Surface hydrophobized metal oxide powder and method for producing the same Download PDFInfo
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Description
本発明は、表面疎水化金属酸化物粉末およびその製造方法に関する。 The present invention relates to a surface-hydrophobized metal oxide powder and a method for producing the same.
金属酸化物粉末は、機械的強度の向上などの目的でポリマーに充填される充填剤として広く用いられており、その表面に表面疎水化処理剤を吸着させた表面疎水化処理金属酸化物粉末も広く用いられている。 Metal oxide powders are widely used as fillers filled in polymers for the purpose of improving mechanical strength, and surface hydrophobized metal oxide powders having a surface hydrophobizing agent adsorbed on the surface thereof are also used. Widely used.
かかる表面疎水化金属酸化物粉末の製造方法としては、金属酸化物粉末を表面疎水化処理剤と乾式混合する方法が一般的であり、表面疎水化処理剤は、比較的緩やかで脱離し易い物理吸着したものよりも、比較的強固で脱離し難い化学吸着したものが多いほど、機械的強度が向上するものと考えられていた。 As a method for producing such a surface hydrophobized metal oxide powder, a method of dry mixing the metal oxide powder with a surface hydrophobizing agent is generally used. It was considered that the mechanical strength improved as the amount of chemically adsorbed that was relatively strong and difficult to desorb than the adsorbed one.
化学吸着したものがより多い表面疎水化金属酸化物粉末を製造しうる方法としては、例えば特許文献１〔特開昭５９−８１３６２号公報の実施例の欄〕に開示されるように、振動強度６Ｇの条件下に２０分以上、乾式混合する方法が挙げられる。同文献には、攪拌時の温度に関する記載はないが、かかる振動強度および攪拌時間で金属酸化物粉末および表面疎水化処理剤を攪拌すると、攪拌開始から短時間で５０℃を超える温度に上昇する。 As a method for producing a surface-hydrophobized metal oxide powder with a larger amount of chemically adsorbed powder, as disclosed in, for example, Patent Document 1 (Example column of JP-A-59-81362), vibration strength The method of dry-mixing for 20 minutes or more on 6G conditions is mentioned. Although there is no description regarding the temperature at the time of stirring in this document, when the metal oxide powder and the surface hydrophobizing agent are stirred with such vibration strength and stirring time, the temperature rises to over 50 ° C. in a short time from the start of stirring. .
しかし、表面疎水化金属酸化物粉末としては、ポリマーの機械的強度を、より向上させうるものが求められている。 However, the surface hydrophobized metal oxide powder is required to further improve the mechanical strength of the polymer.
そこで本発明者は、ポリマーに充填することにより、その機械的強度を、より向上させうる表面疎水化金属酸化物粉末を提供するべく鋭意検討した結果、振動強度１Ｇ以上の条件下に、５０℃以下を維持しながら攪拌することにより、化学吸着率０．５〜０．９の表面疎水化金属酸化物粉末が得られ、これをポリマーに充填した組成物は、より高い機械的強度を示すことを見出し、本発明に至った。 Therefore, the present inventor has eagerly studied to provide a surface hydrophobized metal oxide powder capable of further improving the mechanical strength by filling the polymer, and as a result, under the condition that the vibration strength is 1 G or more, 50 ° C. By stirring while maintaining the following, a surface hydrophobized metal oxide powder having a chemical adsorption rate of 0.5 to 0.9 is obtained, and the composition filled with the polymer exhibits higher mechanical strength. And found the present invention.
すなわち本発明は、金属酸化物粉末の表面に表面疎水化処理剤が吸着されてなり、該表面疎水化処理剤の全吸着量(Ａ)に対する化学吸着量(Ａｃ)の比(Ａｃ／Ａ)で示される化学吸着率が０．５〜０．９であることを特徴とする表面疎水化金属酸化物粉末を提供するものである。 That is, in the present invention, the surface hydrophobizing agent is adsorbed on the surface of the metal oxide powder, and the ratio (Ac / A) of the chemical adsorption amount (Ac) to the total adsorption amount (A) of the surface hydrophobizing agent. The surface hydrophobized metal oxide powder is characterized by having a chemical adsorption rate of 0.5 to 0.9.
また本発明は、かかる表面疎水化金属酸化物粉末の製造方法として、金属酸化物粉末および表面疎水化処理剤を振動強度１Ｇ以上の条件下に５０℃以下の温度を維持しながら乾式混合する方法を提供するものである。 Further, the present invention provides a method for producing such a surface hydrophobized metal oxide powder by dry mixing the metal oxide powder and the surface hydrophobizing agent while maintaining a temperature of 50 ° C. or less under a vibration strength of 1 G or more. Is to provide.
本発明の表面疎水化金属酸化物粉末は充填剤として有用であり、これをポリマーに充填した組成物は、従来の表面疎水化金属酸化物粉末を充填したものと比べて機械的強度に優れている。また、本発明の製造方法によれば、本発明の表面疎水化金属酸化物粉末を容易に製造することができる。 The surface hydrophobized metal oxide powder of the present invention is useful as a filler, and the composition filled with the polymer is superior in mechanical strength compared with the conventional surface hydrophobized metal oxide powder filled. Yes. Moreover, according to the manufacturing method of this invention, the surface hydrophobization metal oxide powder of this invention can be manufactured easily.
本発明の表面疎水化金属酸化物粉末を構成する金属酸化物粉末としては、例えばアルミニ
ウム酸化物、チタン酸化物、ケイ素酸化物などの粉末が挙げられる。
Examples of the metal oxide powder constituting the surface hydrophobized metal oxide powder of the present invention include powders such as aluminum oxide, titanium oxide, and silicon oxide.
アルミニウム酸化物の結晶型は特に限定されるものではなく、例えばα型、γ型、θ型などが挙げられ、２以上の結晶型を含んでいてもよい。 The crystal type of the aluminum oxide is not particularly limited, and examples thereof include an α type, a γ type, and a θ type, and may include two or more crystal types.
金属酸化物粉末の平均粒子径は、通常０．１μｍ〜１０μｍであり、ＢＥＴ比表面積は通常１ｍ2／ｇ〜２０ｍ2／ｇである。 The average particle diameter of the metal oxide powder is generally 0.1 m to 10 m, BET specific surface area is usually 1m 2 / g~20m 2 / g.
表面疎水化処理剤としては、例えばシランカップリング剤、チタンカップリング剤などが挙げられ、好ましくはシランカップリング剤である。 Examples of the surface hydrophobizing agent include a silane coupling agent and a titanium coupling agent, and a silane coupling agent is preferable.
シランカップリング剤としては、例えばオクチルトリエトキシシラン、ヘキシルトリエト
キシシラン、エチルトリメトキシシラン、グリシドキシプロピルトリメトキシシラン、メ
ルカプトプロピルトリメトキシシラン、アミノプロピルトリメトキシシラン、メタアクリ
ロキシプロピルメトキシシランなどが挙げられる。
Examples of silane coupling agents include octyltriethoxysilane, hexyltriethoxysilane, ethyltrimethoxysilane, glycidoxypropyltrimethoxysilane, mercaptopropyltrimethoxysilane, aminopropyltrimethoxysilane, and methacryloxypropylmethoxysilane. Is mentioned.
本発明の表面疎水化金属酸化物粉末は、金属酸化物粉末の表面に表面疎水化処理剤が吸着
されてなるものであり、表面疎水化処理剤の全吸着量(Ａ)は、金属酸化物粉末１００質量
部あたり０．０５質量部〜５質量部、好ましくは０．１質量部〜３質量部である。
The surface hydrophobized metal oxide powder of the present invention is obtained by adsorbing a surface hydrophobizing agent on the surface of the metal oxide powder, and the total adsorption amount (A) of the surface hydrophobizing agent is metal oxide. It is 0.05 mass part-5 mass parts per 100 mass parts of powder, Preferably it is 0.1 mass part-3 mass parts.
本発明の表面疎水化金属酸化物粉末は、化学吸着率が０．５〜０．９、好ましくは０．６〜０．８である。化学吸着率が０．５未満であったり、０．９を超えると、ポリマー中に均一に分散させることが困難となる。 The surface hydrophobized metal oxide powder of the present invention has a chemical adsorption rate of 0.5 to 0.9, preferably 0.6 to 0.8. When the chemical adsorption rate is less than 0.5 or exceeds 0.9, it is difficult to uniformly disperse in the polymer.
本発明の表面疎水化金属酸化物粉末における化学吸着率は、表面疎水化処理剤の全吸着量(Ａ)に対する化学吸着量(Ａｃ)の比(Ａｃ／Ａ)で示される。本発明の表面疎水化金属酸化物粉末の表面に吸着した表面疎水化処理剤には、化学吸着したものと、物理吸着したものとがあるが、全吸着量(Ａ)とは、これら化学吸着した表面疎水化処理剤と物理吸着した表面疎水化処理剤との合計である。全吸着量(Ａ)は、例えば表面疎水化金属酸化物粉末を構成する元素のうち、表面疎水化処理剤を構成し、金属酸化物粉末を構成しない元素の含有量を発光分光法により求め、得られた含有量から算出することができる。 The chemical adsorption rate in the surface hydrophobized metal oxide powder of the present invention is represented by the ratio (Ac / A) of the chemical adsorption amount (Ac) to the total adsorption amount (A) of the surface hydrophobizing agent. The surface hydrophobizing treatment agent adsorbed on the surface of the surface hydrophobized metal oxide powder of the present invention includes those that are chemically adsorbed and those that are physically adsorbed. The total adsorption amount (A) is the chemical adsorption. It is the sum of the surface hydrophobizing agent and the surface-hydrophobizing agent physically adsorbed. The total adsorption amount (A) is, for example, the surface hydrophobizing agent among the elements constituting the surface hydrophobized metal oxide powder, and the content of the element not constituting the metal oxide powder is determined by emission spectroscopy. It can be calculated from the obtained content.
化学吸着量(Ａｃ)は、金属酸化物粉末の表面に化学吸着した表面疎水化処理剤の量であり、例えば表面疎水化金属酸化物粉末を溶媒で洗浄することにより、物理吸着した表面疎水化処理剤を除去したのちの、表面疎水化金属酸化物粉末に含まれる表面疎水化処理剤の含有量として求めることができる。洗浄に用いる溶媒としては、表面疎水化処理剤を溶解し得、金属酸化物粉末は溶解しないものが用いられ、通常はメタノール、エタノールなどのアルコール類が用いられる。表面疎水化処理剤の含有量は、上記と同様に発光分光法により求めることができる。 The amount of chemical adsorption (Ac) is the amount of the surface hydrophobizing agent chemically adsorbed on the surface of the metal oxide powder. For example, the surface hydrophobized by physical adsorption by washing the surface hydrophobized metal oxide powder with a solvent. The content of the surface hydrophobizing agent contained in the surface hydrophobized metal oxide powder after removing the treating agent can be obtained. As the solvent used for washing, those capable of dissolving the surface hydrophobizing agent and not dissolving the metal oxide powder are used, and alcohols such as methanol and ethanol are usually used. The content of the surface hydrophobizing agent can be determined by emission spectroscopy as described above.
かかる本発明の表面疎水化金属酸化物粉末は、金属酸化物粉末および表面疎水化処理剤を振動強度１Ｇ以上の条件下に、５０℃以下の温度を維持しながら乾式混合する方法により製造することができる。 Such a surface-hydrophobized metal oxide powder of the present invention is produced by a method in which the metal oxide powder and the surface-hydrophobizing agent are dry-mixed while maintaining a temperature of 50 ° C. or less under a vibration strength of 1 G or more. Can do.
振動強度１Ｇ以上で乾式混合するには、例えば振動ミルなどを用いればよく、具体的には、例えば金属酸化物粉末および表面疎水化処理剤を、ボール状の媒体と共に容器に入れた状態で、この容器を振動させればよい。媒体としては、例えばアルミニウム酸化物、チタン酸化物、ケイ素酸化物などのセラミックスからなり直径１ｍｍ〜３０ｍｍ程度のセラミックスボールが使用される。容器を振動させることにより、容器の内部では媒体同士が衝突したり、媒体と容器とが衝突するが、その衝突の衝撃により、金属酸化物粉末および表面疎水化処理剤が攪拌される。 In order to dry-mix at a vibration intensity of 1 G or more, for example, a vibration mill or the like may be used. Specifically, for example, in a state where a metal oxide powder and a surface hydrophobizing agent are placed in a container together with a ball-shaped medium, What is necessary is just to vibrate this container. As the medium, for example, ceramic balls made of ceramics such as aluminum oxide, titanium oxide, and silicon oxide and having a diameter of about 1 mm to 30 mm are used. By vibrating the container, the medium collides inside the container or the medium and the container collide. The metal oxide powder and the surface hydrophobizing agent are agitated by the impact of the collision.
振動強度（Ｋ）は、容器を振動させる際の振幅（α）および振動角速度（ω）から式（１
）
Ｋ ＝ α・ω2／ｇ（Ｇ）・・・（１）
〔式中、ｇは重力加速度（９．８ｍ／秒2）を示す。〕
により、重力加速度に対する倍率で算出され〔非特許文献１：「粉砕・分級と表面改質」
第１版（有限会社エヌジーティー、２００１年４月２０日発行）第１０５頁〕、振動強度
を大きくするには、例えば容器を短い周期で振動させたり、大きな振幅で振動させればよ
い。
The vibration intensity (K) is calculated from the amplitude (α) and the vibration angular velocity (ω) when the container is vibrated using the equation (1).
)
K = α · ω 2 / g (G) (1)
[Wherein g represents the acceleration of gravity (9.8 m / sec 2 ). ]
[Non-patent document 1: “Crushing / classification and surface modification”
First edition (limited company NG, issued on April 20, 2001, page 105)] In order to increase the vibration intensity, for example, the container may be vibrated with a short period or with a large amplitude.
振動強度が１Ｇ未満であると、表面疎水化処理剤の化学吸着率が低くなり、好ましくは５
Ｇ以上である。振動強度は通常１０Ｇ以下である。
When the vibration strength is less than 1 G, the chemical adsorption rate of the surface hydrophobizing agent is lowered, preferably 5
G or more. The vibration intensity is usually 10G or less.
温度を５０℃以下に維持するには、例えば容器を外部から水冷する方法が挙げられる。温
度が５０℃を超えると、化学吸着率(Ａｃ)が高くなって化学吸着率(Ａｃ／Ａ)が０．９を超え易くなり、好ましくは４５℃以下、通常は２０℃以上である。
In order to maintain the temperature at 50 ° C. or lower, for example, a method of water-cooling the container from the outside can be mentioned. When the temperature exceeds 50 ° C., the chemical adsorption rate (Ac) increases and the chemical adsorption rate (Ac / A) tends to exceed 0.9, preferably 45 ° C. or lower, and usually 20 ° C. or higher.
攪拌時間は通常２０分〜２時間である。２０分未満では化学吸着率が低くなり、２時間を超えると、媒体、容器などに起因する異物が混入し易くなるほか、生産性の点で不利である。 The stirring time is usually 20 minutes to 2 hours. If it is less than 20 minutes, the chemical adsorption rate is low, and if it exceeds 2 hours, foreign substances originating from the medium, containers, etc. are likely to be mixed, and this is disadvantageous in terms of productivity.
混合は、大気中で行われてもよいが、用いる表面疎水化処理剤の種類によっては、窒素ガ
ス、アルゴンガス、ヘリウムガス、二酸化炭素ガスなどの不活性ガス中で乾式で混合して
もよい。
Mixing may be performed in the atmosphere, but depending on the type of surface hydrophobizing agent used, it may be mixed dry in an inert gas such as nitrogen gas, argon gas, helium gas, carbon dioxide gas. .
本発明の表面疎水化金属酸化物粉末は、ポリマーに充填される充填剤として有用である。
樹脂としては、例えばスチレン−ブタジエン共重合体ゴムなどの熱可塑性ポリマー、シリ
コーン樹脂、エポキシ樹脂、フェノール樹脂などの熱硬化性ポリマーなどが挙げられる。
本発明の表面疎水化金属酸化物粉末の充填量は、例えばポリマー１００質量部あたり４０
質量部〜１００質量部である。
The surface hydrophobized metal oxide powder of the present invention is useful as a filler filled in a polymer.
Examples of the resin include thermoplastic polymers such as styrene-butadiene copolymer rubber, and thermosetting polymers such as silicone resin, epoxy resin, and phenol resin.
The filling amount of the surface hydrophobized metal oxide powder of the present invention is, for example, 40 per 100 parts by mass of the polymer.
Parts by mass to 100 parts by mass.
ポリマーに、本発明の表面疎水化金属酸化物粉末を充填するには、例えばポリマーとして
熱可塑性ポリマーを用いる場合には、加熱溶融状態の熱可塑性ポリマーに本発明の表面疎
水化金属酸化物粉末を加え、溶融混練すればよい。またポリマーが加熱により硬化する熱
硬化性ポリマーである場合には、熱硬化する前の前駆体に、本発明の表面疎水化金属酸化
物粉末を加え、混合したのち加熱すればよい。
In order to fill the polymer with the surface hydrophobized metal oxide powder of the present invention, for example, when a thermoplastic polymer is used as the polymer, the surface hydrophobized metal oxide powder of the present invention is added to the heat-melted thermoplastic polymer. In addition, melt kneading may be performed. Further, when the polymer is a thermosetting polymer that is cured by heating, the surface hydrophobized metal oxide powder of the present invention is added to the precursor before thermosetting, mixed, and then heated.
かくして本発明の表面疎水化金属酸化物粉末をポリマーに充填することにより、ポリマー
中に本発明の表面疎水化金属酸化物粉末が分散されてなるポリマー組成物を得ることがで
きる。この組成物は、その製造時に加熱溶融状態の熱可塑性ポリマーと激しく溶融混練し
たり、熱硬化性ポリマーの前駆体と激しく攪拌しても、機械的強度などに優れている。
Thus, a polymer composition in which the surface hydrophobized metal oxide powder of the present invention is dispersed in the polymer can be obtained by filling the polymer with the surface hydrophobized metal oxide powder of the present invention. This composition is excellent in mechanical strength and the like even when it is vigorously melt-kneaded with a thermoplastic polymer in a heated and molten state at the time of production, or vigorously stirred with a precursor of a thermosetting polymer.
以下、実施例によって本発明をより詳細に説明するが、本発明は、かかる実施例によって
限定されるものではない。
EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by this Example.
なお、実施例における評価方法は以下のとおりである。
（１）平均粒子径
粒度分布測定装置〔日機装社製「マイクロトラック」〕を用いてレーザー回折法により、
質量基準で累積百分率５０％相当粒子径を平均粒子径として測定した。
（２）ＢＥＴ比表面積
ＢＥＴ比表面積測定装置〔島津製作所社製「２３００−ＰＣ−１Ａ」〕を用いて窒素吸着
法により測定した。
（３）化学吸着率
実施例および比較例で得た表面疎水化金属酸化物粉末に含まれる表面疎水化処理剤の含有量を求め、これを全吸着量(Ａ)とした。また、表面疎水化金属酸化物粉末をメタノールで洗浄したのち、洗浄後の表面疎水化金属酸化物粉末に含まれる表面疎水化処理剤の含有量を求め、これを化学吸着量(Ａｃ)とした。得られた表面疎水化金属酸化物粉末および洗浄後の表面疎水化金属酸化物粉末に含まれる表面疎水化処理剤の含有量は、それぞれ発光分光法により求めた。上記で求めた全吸着量(Ａ)と化学吸着量(Ａｃ)とから、化学吸着率(Ａｃ／Ａ)を算出した。
（４）デュロ強度
ＪＩＳ Ｋ−７２１５「プラスチックのデュロメーター硬さ」に従って測定した。
In addition, the evaluation method in an Example is as follows.
(1) Laser diffraction using an average particle size particle size distribution measuring device ["MICROTRACK" manufactured by Nikkiso Co., Ltd.]
The particle size corresponding to a cumulative percentage of 50% on a mass basis was measured as the average particle size.
(2) BET specific surface area The BET specific surface area was measured by a nitrogen adsorption method using a BET specific surface area measuring device [“2300-PC-1A” manufactured by Shimadzu Corporation].
(3) Chemical adsorption rate The content of the surface hydrophobizing agent contained in the surface hydrophobized metal oxide powders obtained in Examples and Comparative Examples was determined, and this was defined as the total adsorption amount (A). Further, after washing the surface hydrophobized metal oxide powder with methanol, the content of the surface hydrophobizing agent contained in the surface hydrophobized metal oxide powder after washing was determined, and this was defined as the amount of chemical adsorption (Ac). . The contents of the surface hydrophobizing agent contained in the obtained surface hydrophobized metal oxide powder and the surface hydrophobized metal oxide powder after washing were each determined by emission spectroscopy. The chemical adsorption rate (Ac / A) was calculated from the total adsorption amount (A) and chemical adsorption amount (Ac) determined above.
(4) Durometer Strength Measured according to JIS K-7215 “Plastic Durometer Hardness”.
実施例１
〔表面疎水化アルミニウム酸化物粉末の製造〕
容器を備えた振動ミル〔中央加工機社製「ＭＢ」〕の該容器に、アルミニウム酸化物粉末
〔住友化学社製「ＡＫＰ３０」、純度９９．９９質量％以上のα型アルミニウム酸化物、
平均粒子径０．３μｍ、ＢＥＴ比表面積７ｍ2／ｇ〕１００質量部およびシランカップリング剤〔ＧＥ東芝シリコーン社製「Ａ−１３７」、オクチルトリエトキシシラン〕２．４
質量部を入れ、６０分間振動させて混合し、表面疎水化アルミニウム酸化物粉末を得た。
振動強度は、８．１６Ｇであった。なお、用いた振動ミルは、容器の内容積が、アルミニ
ウム酸化物粉末の見掛け容積に対して２．０倍であった。また、媒体としては直径１６ｍ
ｍアルミナボール〔αアルミナ製〕を用いた。混合中、容器は水冷により外部から冷却し
、その内温を２８℃〜３９℃に保った。
Example 1
[Production of surface hydrophobized aluminum oxide powder]
In the container of the vibration mill equipped with the container [“MB” manufactured by Chuo Kabuki Co., Ltd.], aluminum oxide powder [“AKP30” manufactured by Sumitomo Chemical Co., Ltd., α-type aluminum oxide having a purity of 99.99% by mass or more,
Average particle size 0.3 μm, BET specific surface area 7 m 2 / g] 100 parts by mass and silane coupling agent [“A-137” manufactured by GE Toshiba Silicone, Octyltriethoxysilane] 2.4
A mass part was put and mixed by shaking for 60 minutes to obtain a surface-hydrophobized aluminum oxide powder.
The vibration intensity was 8.16G. In the vibration mill used, the inner volume of the container was 2.0 times the apparent volume of the aluminum oxide powder. The medium is 16m in diameter.
m alumina balls (manufactured by α alumina) were used. During mixing, the container was cooled from the outside by water cooling, and the internal temperature was kept at 28 ° C to 39 ° C.
得られた表面疎水化アルミニウム酸化物粉末のケイ素含有量を発光分光法により求め、シ
ランカップリング剤の全吸着量(Ａ)を算出したところ、アルミニウム酸化物粉末１００質
量部あたり０．２１質量部であった。また、この表面疎水化アルミニウム酸化物粉末をメ
タノールで洗浄し、その後、発光分光法によりケイ素含有量を求めて、シランカップリング剤の化学吸着量(Ａｃ)を求めたところ、アルミニウム酸化物粉末１００質量部あたり０．１３質量部であった。化学吸着率(Ａｃ／Ａ)は０．６２である。
The silicon content of the obtained surface-hydrophobized aluminum oxide powder was determined by emission spectroscopy, and the total amount of adsorption (A) of the silane coupling agent was calculated to be 0.21 parts by mass per 100 parts by mass of the aluminum oxide powder. Met. Further, this surface hydrophobized aluminum oxide powder was washed with methanol, and then the silicon content was determined by emission spectroscopy, and the chemical adsorption amount (Ac) of the silane coupling agent was determined. It was 0.13 mass part per mass part. The chemical adsorption rate (Ac / A) is 0.62.
〔ゴム組成物の製造〕
スチレン−ブタジエン共重合体ゴムに上記で得た表面疎水化アルミニウム酸化物粉末を加え、溶融混練して得られるゴム組成物のデュロ強度は、ＨＤＡ３２であった。
[Production of rubber composition]
The duro strength of the rubber composition obtained by adding the surface-hydrophobized aluminum oxide powder obtained above to styrene-butadiene copolymer rubber and melt-kneading was HDA32.
比較例１
混合中、容器を外部から冷却することなく、そのままアルミニウム酸化物粉末〔ＡＫＰ３０〕およびシランカップリング剤〔Ａ−１３７〕を混合する以外は実施例１と同様に操作すると、混合中の容器の内温は５０℃を超え、得られる表面疎水化アルミニウム酸化物粉末の化学吸着率(Ａｃ／Ａ)は０．９を超える。
また、実施例１で得た表面疎水化アルミニウム酸化物粉末に代えて上記で得た表面疎水化アルミニウム酸化物粉末を用いる以外は実施例１と同様にして得られるゴム組成物は、実施例１で得たゴム組成物と比較して低いデュロ強度を示す。
Comparative Example 1
During mixing, the same procedure as in Example 1 was performed except that the aluminum oxide powder [AKP30] and the silane coupling agent [A-137] were mixed without cooling the container from the outside. The temperature exceeds 50 ° C., and the chemical adsorption rate (Ac / A) of the resulting surface hydrophobized aluminum oxide powder exceeds 0.9.
The rubber composition obtained in the same manner as in Example 1 except that the surface-hydrophobized aluminum oxide powder obtained above was used in place of the surface-hydrophobized aluminum oxide powder obtained in Example 1, Compared with the rubber composition obtained in (1), it shows a low duro strength.
比較例２
実施例１で得た表面疎水化アルミニウム酸化物粉末を６０℃を越える温度に保持することにより、化学吸着率(Ａｃ／Ａ)が０．９を超える表面疎水化アルミニウム酸化物粉末が得られる。実施例１で得た表面疎水化アルミニウム酸化物粉末に代えて、上記で得た表面疎水化アルミニウム酸化物粉末を用いる以外は実施例１と同様に操作して得られるゴム組成物のデュロ強度は、実施例１で得たゴム組成物と比較して低いデュロ強度を示す。
Comparative Example 2
By maintaining the surface hydrophobized aluminum oxide powder obtained in Example 1 at a temperature exceeding 60 ° C., a surface hydrophobized aluminum oxide powder having a chemical adsorption rate (Ac / A) exceeding 0.9 is obtained. In place of the surface-hydrophobized aluminum oxide powder obtained in Example 1, the duro strength of the rubber composition obtained by operating in the same manner as in Example 1 except that the surface-hydrophobized aluminum oxide powder obtained above is used is Compared with the rubber composition obtained in Example 1, the duro strength is low.
Claims (4)
金属酸化物粉末および表面疎水化処理剤を、振動強度１Ｇ以上の条件下に５０℃以下の温度を維持しながら乾式混合することを特徴とする表面疎水化金属酸化物粉末の製造方法。 A chemical adsorption represented by the ratio (Ac / A) of the amount of chemical adsorption (Ac) to the total amount of adsorption (A) of the surface hydrophobization treatment agent, wherein the surface hydrophobic treatment agent is adsorbed on the surface of the metal oxide powder. A method for producing a surface-hydrophobized metal oxide powder having a rate of 0.5 to 0.9 ,
A method for producing a surface-hydrophobized metal oxide powder, wherein the metal-oxide powder and the surface hydrophobizing agent are dry-mixed while maintaining a temperature of 50 ° C. or less under a vibration strength of 1 G or more .
求項１に記載の表面疎水化金属酸化物粉末の製造方法。 The method for producing a surface-hydrophobized metal oxide powder according to claim 1, wherein the metal oxide powder is a powder of aluminum oxide, titanium oxide or silicon oxide.
または請求項２に記載の表面疎水化金属酸化物粉末の製造方法。 The surface hydrophobizing agent is a silane coupling agent or a titanium coupling agent.
Or the manufacturing method of the surface hydrophobization metal oxide powder of Claim 2.
質量部である請求項１〜請求項３のいずれかに記載の表面疎水化金属酸化物粉末の製造方法。 The total amount of adsorption of the surface hydrophobizing agent is 0.05 to 5 parts by mass per 100 parts by mass of the metal oxide powder.
It is a mass part, The manufacturing method of the surface hydrophobization metal oxide powder in any one of Claims 1-3 .
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