JP2008255195A - Composite granulated substance of inorganic material-macromolecular resin and method for producing the same - Google Patents
Composite granulated substance of inorganic material-macromolecular resin and method for producing the same Download PDFInfo
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本発明は、可撓性を有する無機材料−高分子樹脂複合造粒物とその製造方法、並びに無機材料と高分子樹脂からなる複合材料に関するものである。より詳しくは、無機材料と高分子樹脂を混合することにより得られる、可撓性を有し気孔がなく且つ高粉体含有量の無機材料−高分子樹脂複合造粒物とその製造方法、並びに無機材料と高分子樹脂からなる複合材料とその成形体に関するものである。 The present invention relates to a flexible inorganic material-polymer resin composite granulated product, a method for producing the same, and a composite material composed of an inorganic material and a polymer resin. More specifically, an inorganic material-polymer resin composite granule having flexibility and no pores and having a high powder content obtained by mixing an inorganic material and a polymer resin, and a production method thereof, and The present invention relates to a composite material composed of an inorganic material and a polymer resin and a molded body thereof.
最近では、急速に進展する情報・家電・自動車産業などの産業分野において、それらの製品の製造のために、高度な要求を満たした透明導電膜、半導体関連部材、光学材料などが必要とされている。これらの高機能材料では、高分子化合物、金属、セラミックスなどの個別の材料のみでは一般に達成が困難となる様々な相反する機能、例えば、絶縁性と熱伝導性、絶縁性と高屈折特性、加工性（易成形性）などのような様々な機能が必要とされ、このような材料特性を有する可撓性の無機材料−高分子樹脂ハイブリッド材料がその生産性と併せて求められている。 Recently, in the rapidly developing industrial fields such as information, home appliances, and automobile industries, transparent conductive films, semiconductor-related materials, optical materials, etc. that satisfy advanced requirements are required for the manufacture of those products. Yes. With these high-functional materials, various conflicting functions that are generally difficult to achieve with only individual materials such as polymer compounds, metals, and ceramics, such as insulation and thermal conductivity, insulation and high refractive properties, processing Various functions such as property (easy moldability) are required, and a flexible inorganic material-polymer resin hybrid material having such material characteristics is demanded together with its productivity.
このような優れた特性を有する材料を得るため、加工性の良い高分子樹脂に、高屈折率、高熱伝導性、高誘電率などの特性を有する無機粒子を混合した複合材料が種々提案されている。このような複合材料の製造に際しては、例えば、熱可塑性樹脂粉末またはペレットと無機粒子・粉体をそれぞれ単独で、もしくは両者をあらかじめ混合し、直接、成形機に供給することが一般的である（例えば、特許文献１、特許文献２参照）。しかしながら、このような方法では、ホッパー内で原料粉末が固まり、ブリッジ現象を生じるため、生産性の低下及び品質のばらつき等が起こる問題がある。 In order to obtain materials having such excellent characteristics, various composite materials in which inorganic particles having characteristics such as high refractive index, high thermal conductivity, and high dielectric constant are mixed with high-workability polymer resins have been proposed. Yes. In the production of such a composite material, for example, it is common to supply thermoplastic resin powder or pellets and inorganic particles / powder alone or both in advance and directly supply them to a molding machine ( For example, see Patent Document 1 and Patent Document 2). However, in such a method, since the raw material powders are solidified in the hopper and a bridge phenomenon occurs, there is a problem in that productivity decreases and quality variation occurs.
このような問題を解決するための一つの方法として、例えば、セラミックスなどの粉末粒子を扱う製造では、粉末粒子をそのまま扱うのではなく、あらかじめ粉末粒子を球状の顆粒形状に成形し、成型加工の工程でその顆粒を用いることにより、生産性を上げることが提案されている（例えば、特許文献３参照）。 As one method for solving such a problem, for example, in the production of powder particles such as ceramics, the powder particles are not treated as they are, but the powder particles are formed into a spherical granule shape in advance. It has been proposed to increase productivity by using the granules in the process (for example, see Patent Document 3).
一般的に顆粒の製造にはスプレードライヤーが用いられ、スラリーを噴霧し急速に加熱乾燥して製造される。このような方法で得られた顆粒は可撓性がなく、その顆粒の直径も２００μｍ以下程度のものとなる。また、乾燥の際に溶媒を蒸発させるため顆粒の内部が中空の球状体になり、このような顆粒を用いて得られた複合材料による成型体には気孔などの内部欠陥が生じるという問題があった（例えば、非特許文献１参照）。 In general, a granule is produced by using a spray dryer, which is produced by spraying a slurry and rapidly drying by heating. Granules obtained by such a method are not flexible, and the diameter of the granules is about 200 μm or less. Further, since the solvent evaporates during drying, the inside of the granule becomes a hollow sphere, and there is a problem that a molded body made of a composite material obtained using such a granule has internal defects such as pores. (For example, refer nonpatent literature 1).
更に、高分子樹脂にセラミックスなどの無機粒子や無機粉体を混入する場合、無機粉末の添加量が高くなると粉末粒子の凝集が起こり、混合物の流動性が著しく低下する。現状では高い粉体含有量の無機粒子や無機粉体を混合しながら、樹脂特性の一つである可撓性を発現させることは困難である。また、高い粉体含有量になると、粒子同士の凝集が起こっている状態で、それを熱間プレスなどで成型加工しても、成型体の構造中で高分子樹脂の偏析が生じ、品質ならびに特性のばらつきが生じるという問題もある。樹脂や無機粒子・粉体の種類によっては、受ける熱履歴によって変質を引き起こすという問題もある。 In addition, when inorganic particles such as ceramics or inorganic powder are mixed in the polymer resin, if the amount of inorganic powder added is high, the powder particles are aggregated, and the fluidity of the mixture is significantly reduced. At present, it is difficult to develop flexibility, which is one of the resin characteristics, while mixing inorganic particles or inorganic powders having a high powder content. Also, when the powder content is high, segregation of the polymer resin occurs in the structure of the molded body even if the particles are agglomerated and processed by hot pressing, etc. There is also a problem that variations in characteristics occur. Depending on the type of resin and inorganic particles / powder, there is also a problem of causing alteration due to the thermal history received.
本発明は、以上のような無機材料−高分子複合体の種々の問題点を解決することのできる、無機材料−高分子複合材料やその成型体の製造に使用することのできる、無機材料を高い含有量で含み、かつ可撓性を有する、取扱性や作業性に優れた球状造粒物とその製造法を提供することをその目的とするものである。 The present invention provides an inorganic material that can solve the various problems of the inorganic material-polymer composite as described above, and can be used for the production of an inorganic material-polymer composite material or a molded body thereof. It is an object of the present invention to provide a spherical granulated product which has a high content and is flexible and which is excellent in handleability and workability and a method for producing the same.
本発明者らは、上記のような課題を解決すべく鋭意研究を重ねた結果、無機材料を高分子樹脂に配合するに際して公転又は自転公転を有する攪拌方式を採用することによってこれらの課題を解決したものが得られることを見出し、本発明を完成した。 As a result of intensive studies to solve the above problems, the present inventors have solved these problems by adopting a stirring method having revolution or rotation revolution when blending an inorganic material into a polymer resin. As a result, the present invention was completed.
即ち、本発明は、以下の内容をその要旨とするものである。
（１）無機粒子又は無機粉体及び液状の有機高分子樹脂を、公転又は自転公転を有する攪拌造粒装置によって混合し、造粒して得られる、平均粒子径が０．１〜５ｍｍの無機材料−高分子樹脂複合造粒物。
（２）前記造粒物中の無機粒子又は無機粉体の含有量が、４０〜８０ｖｏｌ％の範囲である、前記（１）に記載の無機材料−高分子樹脂複合造粒物。
（３）前記無機粒子又は無機粉体の一次粒子径が、１０〜３０００ｎｍの範囲である、前記（１）又は（２）に記載の無機材料−高分子樹脂複合造粒物。
（４）前記無機粒子又は無機粉体が、アルミナ、ジルコニア、窒化アルミニウム、窒化ホウ素、窒化珪素、炭化珪素、チタン酸バリウム、シリカ、および二酸化チタンからなる群より選ばれる１種又は２種以上の粉末無機材料である、前記（１）ないし（３）のいずれかに記載の無機材料−高分子樹脂複合造粒物。
（５）前記有機高分子樹脂が、エポキシ樹脂、アクリル樹脂、ポリイミド樹脂、ポリスチレン樹脂、ポリビニルアルコール樹脂、およびポリビニルブチル樹脂からなる群より選ばれる１種又は２種以上の高分子材料である、前記（１）ないし（４）のいずれかに記載の無機材料−高分子樹脂複合造粒物。
（６）無機粒子又は無機粉体及び液状の有機高分子樹脂を、公転又は自転公転を有する攪拌造粒装置によって混合し、造粒する、無機材料−高分子樹脂複合造粒物の製造方法。
（７）攪拌造粒装置の収納容器の公転数が毎分５００〜５０００回転である、前記（６）に記載の無機材料−高分子樹脂複合造粒物の製造方法。
（８）攪拌造粒装置が、その収納容器が公転すると同時に自転する自転公転方式である、前記（６）又は（７）に記載の無機材料−高分子樹脂複合造粒物の製造方法。
（９）攪拌造粒装置の収納容器の公転数が毎分５００〜５０００回転、自転数が毎分０〜２０００回転である、前記（８）に記載の無機材料−高分子樹脂複合造粒物の製造方法。
（１０）無機粒子又は無機粉体の含有量が、４０〜８０ｖｏｌ％の範囲である、前記（６）ないし（９）のいずれかに記載の無機材料−高分子樹脂複合造粒物の製造方法。
（１１）液状の有機高分子樹脂が、造粒温度で液状である、又は高分子樹脂を溶媒に溶解した樹脂溶液である、前記（６）ないし（１０）のいずれかに記載の無機材料−高分子樹脂複合造粒物の製造方法。
（１２）前記（１）ないし（５）のいずれかに記載の無機材料−高分子樹脂複合造粒物を圧縮成型して得られる無機材料−高分子樹脂複合材料。
（１３）前記（１）ないし（５）のいずれかに記載の無機材料−高分子樹脂複合造粒物を圧縮成型して得られる無機材料−高分子樹脂複合材料成型体。
That is, the gist of the present invention is as follows.
(1) An inorganic particle having an average particle diameter of 0.1 to 5 mm obtained by mixing and granulating inorganic particles or inorganic powder and a liquid organic polymer resin with a stirring granulator having revolution or rotation revolution. Material-polymer resin composite granulated product.
(2) The inorganic material-polymer resin composite granulated product according to (1), wherein the content of inorganic particles or inorganic powder in the granulated product is in the range of 40 to 80 vol%.
(3) The inorganic material-polymer resin composite granulated product according to (1) or (2), wherein a primary particle diameter of the inorganic particles or the inorganic powder is in a range of 10 to 3000 nm.
(4) The inorganic particles or the inorganic powder is one or more selected from the group consisting of alumina, zirconia, aluminum nitride, boron nitride, silicon nitride, silicon carbide, barium titanate, silica, and titanium dioxide. The inorganic material-polymer resin composite granulated product according to any one of (1) to (3), which is a powdered inorganic material.
(5) The organic polymer resin is one or more polymer materials selected from the group consisting of epoxy resin, acrylic resin, polyimide resin, polystyrene resin, polyvinyl alcohol resin, and polyvinyl butyl resin, (1) The inorganic material-polymer resin composite granulated product according to any one of (1) to (4).
(6) A method for producing an inorganic material-polymer resin composite granulated product, in which inorganic particles or inorganic powder and a liquid organic polymer resin are mixed and granulated by a stirring granulator having revolution or rotation revolution.
(7) The method for producing an inorganic material-polymer resin composite granulated product according to (6), wherein the revolution number of the storage container of the stirring granulator is 500 to 5000 revolutions per minute.
(8) The method for producing an inorganic material-polymer resin composite granulated product according to the above (6) or (7), wherein the stirring granulator is a rotational revolution method in which the storage container revolves simultaneously with the revolution of the storage container.
(9) The inorganic material-polymer resin composite granulated product according to (8), wherein the revolution number of the storage container of the stirring granulator is 500 to 5000 revolutions per minute and the rotation number is 0 to 2,000 revolutions per minute. Manufacturing method.
(10) The method for producing an inorganic material-polymer resin composite granule according to any one of (6) to (9), wherein the content of inorganic particles or inorganic powder is in the range of 40 to 80 vol%. .
(11) The inorganic material according to any one of (6) to (10), wherein the liquid organic polymer resin is a liquid at a granulation temperature or is a resin solution obtained by dissolving a polymer resin in a solvent. A method for producing a polymer resin composite granulated product.
(12) An inorganic material-polymer resin composite material obtained by compression molding the inorganic material-polymer resin composite granule according to any one of (1) to (5).
(13) An inorganic material-polymer resin composite material molded body obtained by compression molding the inorganic material-polymer resin composite granule according to any one of (1) to (5).
本発明の無機材料−高分子樹脂複合造粒物は、造粒物中に４０〜８０ｖｏｌ％という非常に高い含有量で無機粒子又は無機粉体を含んでおり、しかも可撓性を有している。更に、無機粉体と高分子樹脂が緊密かつ均一に混じりあっていて造粒物の内部に空隙や気孔などが存在しない。従って、本発明の造粒物を用いて、これを圧縮成型することによって、任意の形状に、容易に、かつ空隙や中空部などの欠陥のない高品質の成型体に加工することができる。しかも、４０〜８０ｖｏｌ％という非常に高い含有量で無機粒子又は無機粉体を含んだ成型体を得ることができ、導電性、絶縁性、高屈折性、耐摩耗性など様々な特性を有する複合材料を容易に製造することができる。 The inorganic material-polymer resin composite granulated product of the present invention contains inorganic particles or inorganic powder in a very high content of 40 to 80 vol% in the granulated product, and has flexibility. Yes. Furthermore, the inorganic powder and the polymer resin are intimately and uniformly mixed, and there are no voids or pores inside the granulated product. Therefore, by compressing and molding the granulated product of the present invention, it can be processed into an arbitrary shape and easily into a high-quality molded product free from defects such as voids and hollow portions. Moreover, it is possible to obtain a molded body containing inorganic particles or inorganic powder with a very high content of 40 to 80 vol%, and a composite having various properties such as conductivity, insulation, high refraction, and wear resistance. The material can be manufactured easily.
以下に本発明についてさらに詳しく説明する。
本発明の無機材料−高分子樹脂複合造粒物は、従来の無機材料複合体のように樹脂粉末と無機材料を単純に混合して複合化したものではなく、液状の高分子樹脂中に無機粒子や無機粉体などの無機材料を混合し、これを公転又は自転公転を有する攪拌・造粒装置で造粒して得られた造粒物であり、その造粒物の粒径が０．１ｍｍから５ｍｍであり、さらにその造粒物が可撓性を有することを特徴とする造粒物である。
The present invention will be described in more detail below.
The inorganic material-polymer resin composite granulated product of the present invention is not a composite obtained by simply mixing a resin powder and an inorganic material as in the case of a conventional inorganic material composite, but it is inorganic in a liquid polymer resin. It is a granulated product obtained by mixing inorganic materials such as particles and inorganic powder, and granulating it with a stirring / granulating apparatus having revolution or rotation revolution, and the granulated product has a particle size of 0.00. The granulated product is 1 mm to 5 mm, and the granulated product is flexible.
無機粒子や無機粉体を液状高分子樹脂とともに攪拌・造粒装置の容器の中に加え、この容器を公転又は自転公転処理することにより高粉体含有量で且つ可撓性を持つ本発明の球状造粒物を製造することができる。この造粒物を成型用の型に入れ圧縮することにより、造粒物から液状高分子樹脂が滲み出し、さらにはその可撓性により造粒物が変形し、高粉体含有量の無機材料−有機高分子複合材料あるいはその成型体を得ることができる。 By adding inorganic particles and inorganic powder together with a liquid polymer resin to the container of the agitation / granulating device, the container is subjected to revolution or rotation / revolution treatment, thereby having a high powder content and flexibility. Spherical granules can be produced. When this granulated product is put into a mold for compression and compressed, the liquid polymer resin oozes out of the granulated product, and further, the granulated product is deformed by its flexibility, and an inorganic material having a high powder content. -An organic polymer composite material or a molded body thereof can be obtained.
使用する無機粒子又は無機粉体としては、金属粉末、金属間化合物粉末、酸化物、炭化物、窒化物などのアルミナ、ジルコニア、窒化アルミニウム、窒化ホウ素、窒化珪素、炭化珪素、チタン酸バリウム、シリカ、二酸化チタンなどのセラミックス粉末あるいはこれらの混合粉末であればよく、無機物の種類に制限はない。 As inorganic particles or inorganic powders to be used, metal powders, intermetallic compound powders, oxides, carbides, nitrides such as alumina, zirconia, aluminum nitride, boron nitride, silicon nitride, silicon carbide, barium titanate, silica, Any ceramic powder such as titanium dioxide or a mixed powder thereof may be used, and the kind of the inorganic substance is not limited.
これらの無機粒子や無機粉体は、その一次粒子径が１０〜３０００ｎｍのものを使用することができ、１００〜２０００ｎｍのものがより好ましい。一次粒子径が１０ｎｍ未満のものでは十分な流動性が得られず、生産性が悪くなり、また３０００ｎｍを超えるものでは造粒物製造時の直径のばらつきが大きくなり、いずれも本発明の造粒物には好ましくない。 As these inorganic particles and inorganic powder, those having a primary particle diameter of 10 to 3000 nm can be used, and those having a primary particle diameter of 100 to 2000 nm are more preferable. When the primary particle size is less than 10 nm, sufficient fluidity cannot be obtained, resulting in poor productivity. When the primary particle size is more than 3000 nm, there is a large variation in diameter during the production of the granulated product. It is not preferable for the product.
また、使用する高分子樹脂としては、無機粒子又は無機粉体の分散媒として使用することのできる造粒加工時に液状である高分子樹脂であれば特に制限されない。このような高分子樹脂として、例えば、従来から使用されているエポキシ樹脂、アクリル樹脂、ポリイミド樹脂、ポリスチレン樹脂、ポリビニルアルコール樹脂、およびポリビニルブチル樹脂などを使用することができる。これらの高分子樹脂は、造粒加工時の温度で液状であるか、或いは溶媒に溶解した高分子樹脂の溶液であればよい。 The polymer resin to be used is not particularly limited as long as it is a polymer resin that is liquid during granulation and can be used as a dispersion medium for inorganic particles or inorganic powder. As such a polymer resin, for example, conventionally used epoxy resin, acrylic resin, polyimide resin, polystyrene resin, polyvinyl alcohol resin, and polyvinyl butyl resin can be used. These polymer resins may be liquid at the temperature at the time of granulation or a solution of polymer resin dissolved in a solvent.
また、本発明に使用する無機粒子や無機粉体ならびに高分子樹脂は、本発明の効果を損なわない限りにおいて、得られる無機材料−高分子樹脂複合造粒物ならびに無機材料―高分子樹脂複合材料の特性向上のために、複数種を用いて造粒物製造を行っても差し支えなく、本発明に包含されるものである。 In addition, the inorganic particles, the inorganic powder, and the polymer resin used in the present invention are obtained as long as the effects of the present invention are not impaired. The resulting inorganic material-polymer resin composite granulated product and inorganic material-polymer resin composite material In order to improve the characteristics, it is possible to produce a granulated product using a plurality of types, which are included in the present invention.
本発明にて提供される球状の無機材料−高分子樹脂複合造粒物は、公転又は自転公転を有する攪拌装置を用いて製造することができる。すなわち、無機粒子や無機粉体と液状高分子樹脂を攪拌造粒装置の容器の中で混合し、この容器を毎分５００から５０００回転、好適には１０００から２５００回転で公転させて、球状造粒物を形成させる。さらに好ましくは、公転と同時に、この容器を自転することによって扁平のない球状造粒物を形成させることができる。当然ながら、公転のみで球状造粒物を製造しても差し支えはないが、自転と公転を併せ持った攪拌による造粒物形成が、扁平のない球状形態を製造する上で好ましい。自転公転させる場合には、その容器の自転の回転数は毎分０〜２０００回転、好適には５００〜１０００回転である。 The spherical inorganic material-polymer resin composite granulated product provided in the present invention can be produced using a stirrer having revolution or rotation revolution. That is, inorganic particles or inorganic powder and liquid polymer resin are mixed in a container of an agitation granulator, and the container is revolved at 500 to 5000 revolutions per minute, preferably 1000 to 2500 revolutions, to form spherical particles. Granules are formed. More preferably, a spherical granulated product having no flatness can be formed by rotating the container simultaneously with the revolution. Of course, there is no problem in producing a spherical granulated product only by revolution, but formation of the granulated product by stirring having both rotation and revolution is preferable for producing a spherical form having no flatness. When rotating and revolving, the rotation speed of the container is 0 to 2000 rotations per minute, preferably 500 to 1000 rotations.
球状造粒物の形成において、自転時間と公転時間は特に制限されるものではなく、無機材料と高分子樹脂の種類とその量によって適宜選択すればよく、所望の特性並びに大きさと形状を有する造粒物が得られるまで行うことができる。 In the formation of the spherical granulated product, the rotation time and revolution time are not particularly limited, and may be appropriately selected depending on the kind and amount of the inorganic material and the polymer resin, and have a desired characteristic, size and shape. This can be done until granules are obtained.
無機粒子や無機粉体などの無機材料と液状高分子樹脂の混合割合は、得られる造粒物の中の無機材料の含有量が４０〜８０容積％とすることができ、非常に高い粉体含量の球状造粒物とすることができる。従って、このような球状造粒物を圧縮成型して得られる本発明の無機材料―高分子樹脂複合材料やその成型体も、無機材料の含有量が４０〜８０容積％という高い無機材料の含有量の複合体とすることができる。 The mixing ratio of the inorganic material such as inorganic particles and inorganic powder and the liquid polymer resin is such that the content of the inorganic material in the obtained granulated product can be 40 to 80% by volume, and the powder is very high. The content can be made into a spherical granulated product. Accordingly, the inorganic material-polymer resin composite material of the present invention obtained by compression molding such a spherical granulated product and its molded body also contain an inorganic material having a high inorganic material content of 40 to 80% by volume. Amount of complex.
また、造粒物の直径は液状高分子樹脂の粘度、混合する無機粉体の量によって制御可能である。 The diameter of the granulated product can be controlled by the viscosity of the liquid polymer resin and the amount of inorganic powder to be mixed.
混合する高分子樹脂は液状のものであればよいが、その粘度が高い場合は造粒物の直径は大きく、粘度が低い場合は造粒物の直径が小さくなる。高分子樹脂の粘度は必要に応じ溶媒を加え調整し使用することが可能であるが、その溶媒の種類は、高分子樹脂が溶ける溶媒であれば限定されるものではなく、好ましくは比較的低沸点のものを用いることで乾燥コストを削減できる。また、造粒物の粒径が０．１ｍｍに満たないものは十分な流動性が得られず生産性が悪く、５ｍｍを超えるものは造粒物製造時の直径のばらつきが大きいため、造粒物の粒径が０．１から５ｍｍの範囲で製造するのが好ましい。 The polymer resin to be mixed may be in a liquid form, but if the viscosity is high, the diameter of the granulated product is large, and if the viscosity is low, the diameter of the granulated product is small. The viscosity of the polymer resin can be adjusted and used if necessary, but the type of the solvent is not limited as long as the polymer resin is soluble and is preferably relatively low. Drying costs can be reduced by using the boiling point. In addition, when the granulated product has a particle size of less than 0.1 mm, sufficient fluidity cannot be obtained and the productivity is poor. It is preferable to produce the product with a particle size of 0.1 to 5 mm.
また、混合する粉体量が減少すると、造粒物形成のための核となった粒子表面に樹脂が充分に吸着し、新たな粉体が付着しやすくなり、造粒物粒径は大きくなる。その混合粉体量は必要に応じて決定するもので限定されるものではないが、混合する粉体の好ましい含有量は４０〜８０容積％の範囲である。４０容積％未満では、液状高分子樹脂が多すぎて造粒物を形成しない。また、８０容積％を超える場合には、粒子表面への樹脂の吸着量が足りず良好な造粒物を形成しないため、どちらも好ましくない。好適には、無機粒子の一次粒子径が１０ｎｍ〜３０００ｎｍの範囲では５０から７０容積％を用いる。 In addition, when the amount of powder to be mixed is reduced, the resin is sufficiently adsorbed on the surface of the particles that have become the core for the formation of the granulated material, so that new powder is likely to adhere and the granulated particle size increases. . The amount of the mixed powder is determined as needed and is not limited, but the preferable content of the powder to be mixed is in the range of 40 to 80% by volume. If it is less than 40% by volume, the liquid polymer resin is too much to form a granulated product. Moreover, when it exceeds 80 volume%, since the adsorption amount of resin to the particle | grain surface is insufficient and favorable granulated material is not formed, neither is preferable. Preferably, 50 to 70% by volume is used when the primary particle diameter of the inorganic particles is in the range of 10 nm to 3000 nm.
以上のような本発明の無機材料−高分子樹脂複合造粒物は、次のような特徴を有する。即ち、第１に無機材料と高分子材料を混練、造粒することによって得られた造粒物であって、その造粒物の粒径が０．１〜５ｍｍであり、第２にこの造粒物中の粉体含有量が、４０〜８０容積％の範囲である高粉体含有量の球状造粒物である。第３に造粒物を構成する無機粒子や無機粉体が、少なくとも１種類の粉末無機材料を含有する造粒物であり、第４に造粒物を構成する無機材料の一次粒子径が１０〜３０００ｎｍの範囲である。また、第５として造粒物を構成する高分子樹脂材料が、少なくとも１種類、または複数種類の液状高分子樹脂を含有している。第６として形成される複合体造粒物には中空気孔がなく、第７として無機材料と高分子材料の配合比を調整し、あるいは造粒の条件を変えることにより造粒物の粒子径を０．１ｍｍから５ｍｍの範囲で制御可能である。さらに、第８に形成された球状造粒物に可撓性があることを特徴とする易成形性の造粒物であり、第９としてそのため加熱をせずとも圧縮成形して簡単に無機材料−有機高分子複合材料あるいはその成型体を得ることが可能である。第１０にその圧縮成形して得られた無機材料―有機高分子複合材料やその成型体の粉体含有量が、４０から８０容積％という高い粉体含有量の複合体である特徴を有する。さらに第１１として、無機材料と高分子樹脂材料を配合並びに混合し自転公転もしくは公転を有する攪拌造粒装置により造粒物を製造するという特徴がある。 The inorganic material-polymer resin composite granulated product of the present invention as described above has the following characteristics. That is, first, a granulated product obtained by kneading and granulating an inorganic material and a polymer material, and the granulated product has a particle size of 0.1 to 5 mm, and secondly, this granulated product. It is a spherical granulated product with a high powder content in which the powder content in the granule is in the range of 40 to 80% by volume. Third, the inorganic particles and inorganic powder constituting the granulated product are granulated products containing at least one kind of powdered inorganic material, and fourth, the primary particle diameter of the inorganic material constituting the granulated product is 10 It is in the range of ˜3000 nm. Further, fifthly, the polymer resin material constituting the granulated material contains at least one kind or plural kinds of liquid polymer resins. The composite granulated product formed as the sixth has no medium air holes, and as the seventh, the particle size of the granulated product is adjusted by adjusting the blending ratio of the inorganic material and the polymer material or by changing the granulating conditions. Can be controlled within a range of 0.1 mm to 5 mm. Furthermore, it is an easily moldable granulated product characterized in that the spherical granulated product formed in the eighth is flexible, and ninthly, it can be easily formed by compression molding without heating. -It is possible to obtain an organic polymer composite material or a molded body thereof. Tenth, the inorganic material-organic polymer composite material obtained by the compression molding or the molded product has a feature that the powder content is a composite having a high powder content of 40 to 80% by volume. Further, as an eleventh aspect, there is a feature that a granulated product is manufactured by a stirring granulator having a rotation and revolution by mixing and mixing an inorganic material and a polymer resin material.
次に、本発明で提供される可撓性の無機材料−高分子樹脂複合造粒物を用いた無機材料−高分子樹脂複合材料とその成型体の特徴について説明する。 Next, the characteristics of the inorganic material-polymer resin composite material using the flexible inorganic material-polymer resin composite granulated product provided in the present invention and the molded product thereof will be described.
本発明で提供される球状造粒物である無機材料−高分子樹脂複合造粒物は、液状の高分子樹脂を２０から６０ｖｏｌ％含んでいる。そのため、乾式プレス機、熱間プレス機、ロール機など圧力を用いた圧縮成型すなわち公知の圧縮成型工法を用いて成型加工することによって、造粒物から液状高分子樹脂が染み出し、造粒物の間をつなぐ作用をもたらす。その際、造粒物が可撓性であるために破壊されることなく変形する。その結果、このような圧縮成型加工法によって易成形性の高い粉体含有量を有する無機材料-高分子樹脂複合材料およびその成型体が得られる。 The inorganic material-polymer resin composite granulated product, which is a spherical granulated product provided by the present invention, contains 20 to 60 vol% of a liquid polymer resin. Therefore, the liquid polymer resin oozes out from the granulated product by molding using a compression molding method using pressure, that is, a known compression molding method, such as a dry press machine, a hot press machine, a roll machine, etc. It brings about the action which connects between. At that time, the granulated material is deformed without being broken because it is flexible. As a result, an inorganic material-polymer resin composite material having a powder content with high moldability and a molded body thereof can be obtained by such a compression molding method.
図１はこのような可撓性の本発明の無機材料−高分子樹脂複合造粒物を圧縮成型加工する際の様子を模式的に示した説明図である。まず、図１の（Ａ）に示すように、圧縮成型の金型内に、無機粒子１と液状高分子樹脂２からなる無機材料−高分子樹脂複合造粒物３が敷き詰められる。この造粒物３は液状高分子樹脂２を２０〜６０ｖｏｌ％含んでいる。この造粒物３が圧縮されると、図１の（Ｂ）に示すように、粒子が破壊されることなく変形して、圧縮に伴って造粒物３から液状高分子樹脂２が染み出る。変形が進む過程で、造粒物３の間に染み出した液状高分子樹脂２が隣接した造粒物３をつなぐ。更に圧縮が進み、圧縮加工が完了すると、図１の（Ｃ）に示すように、造粒物３中の無機粒子１も変形して造粒物３の粒子全体が変形し、液状高分子樹脂２とともに隣接する造粒物３同士が互いに一体化して成型体が得られる。 FIG. 1 is an explanatory view schematically showing a state in which such a flexible inorganic material-polymer resin composite granule of the present invention is compression molded. First, as shown in FIG. 1A, an inorganic material-polymer resin composite granulated product 3 composed of inorganic particles 1 and liquid polymer resin 2 is spread in a compression mold. This granulated product 3 contains 20-60 vol% of liquid polymer resin 2. When the granulated product 3 is compressed, as shown in FIG. 1B, the particles are deformed without being broken, and the liquid polymer resin 2 oozes out of the granulated product 3 along with the compression. . In the process of progress of deformation, the liquid polymer resin 2 oozed out between the granulated products 3 connects the adjacent granulated products 3. When the compression further proceeds and the compression process is completed, as shown in FIG. 1C, the inorganic particles 1 in the granulated product 3 are also deformed and the entire particles of the granulated product 3 are deformed. 2 and adjacent granulated products 3 are integrated with each other to obtain a molded body.
この圧縮成型加工に使用する造粒物は単一の直径のものでも良いし、粒子径の異なる造粒物を配合しても差し支えない。加圧する圧力を印加した際に造粒物から液状高分子樹脂が染み出れば、造粒物の間をつなぎ互いに接着するため、成型体が大型小型であるを問わず、また成型体の厚さを問わず成型加工が可能である。 The granulated product used for the compression molding process may have a single diameter, or granulated products having different particle diameters may be blended. If the liquid polymer resin oozes out from the granulated product when pressure is applied, the granulated product is connected and bonded to each other, so the molded product can be large or small, and the thickness of the molded product It can be processed regardless of the shape.
以上述べたように、本発明では、液状高分子樹脂を含んだ高粉体含有量を有した可撓性の球状造粒物が得られるので、これを用いて容易に無機材料−高分子樹脂複合材料とその成型体を製造することができ、樹脂複合体やその成型体の生産性と加工性が向上する。従って、金属、金属間化合物、セラミックスなどの無機材料と高分子樹脂とを複合化した複合材料・部材や成型加工した製品の高性能化を期待することができる。このように、本発明は、無機材料−高分子樹脂複合材料や部材の産業だけでなく、それを利用して製品を製造する諸産業において与える影響は大きい。 As described above, in the present invention, a flexible spherical granulated product having a high powder content containing a liquid polymer resin can be obtained. A composite material and its molded body can be manufactured, and the productivity and workability of the resin composite and its molded body are improved. Therefore, it is possible to expect higher performance of composite materials / members obtained by compounding inorganic materials such as metals, intermetallic compounds, and ceramics with polymer resins, and molded products. As described above, the present invention has a great influence not only in the inorganic material-polymer resin composite material and member industries but also in various industries for producing products using the inorganic material-polymer resin composite material and members.
次に、本発明を実施例によって具体的に説明するが、本発明はこれらの実施例によって何ら限定されるものではない。 EXAMPLES Next, although an Example demonstrates this invention concretely, this invention is not limited at all by these Examples.
（実施例１）
原料無機粉末として酸化アルミニウム粉末（アルミナ粉末：平均一次粒子径約５００ｎｍ）を、液状高分子樹脂としてエポキシ樹脂及びキシレンを体積比１：１として粘度調整した混合溶液を用いた。このエポキシ樹脂とキシレンの混合溶液に、アルミナ粉末をその粉体含有量が５７．３ｖｏｌ％となるように加え、室温で攪拌造粒機により試料容器の公転回転数２０００ｒｐｍで、かつ自転回転数８００ｒｐｍの条件で、合計１１分間の攪拌造粒処理を行った。その結果、平均粒子径が１．４６ｍｍの球状造粒物を得た。この造粒物の断面の電子顕微鏡写真（倍率：６５倍）を図２に示す。この電子顕微鏡写真では、粒子の断面に中空気孔は見られなかった。乾燥によって混入したキシレンが揮発するため、乾燥後の造粒物の粉体含有量は７７．３ｖｏｌ％となった。
Example 1
An aluminum oxide powder (alumina powder: average primary particle diameter of about 500 nm) was used as the raw material inorganic powder, and a mixed solution in which the viscosity was adjusted with a volume ratio of 1: 1 epoxy resin and xylene as the liquid polymer resin was used. Alumina powder is added to the mixed solution of epoxy resin and xylene so that the powder content is 57.3 vol%, and the revolution speed of the sample container is 2000 rpm and the rotation speed is 800 rpm by a stirring granulator at room temperature. Under the above conditions, the stirring granulation treatment was performed for a total of 11 minutes. As a result, a spherical granulated product having an average particle size of 1.46 mm was obtained. The electron micrograph (magnification: 65 times) of the cross section of this granulated material is shown in FIG. In this electron micrograph, no medium air holes were observed in the cross section of the particles. Since xylene mixed by drying volatilizes, the powder content of the granulated product after drying was 77.3 vol%.
（実施例２）
原料無機粉末として実施例１と同じアルミナ粉末を、液状高分子樹脂としてエポキシ樹脂を用いた。エポキシ樹脂に、アルミナ粉末をその濃度が６６．７ｖｏｌ％となるように加え、実施例１と同じ攪拌造粒機により、試料容器の公転回転数２０００ｒｐｍで、かつ自転回転数８００ｒｐｍで合計６分間の攪拌造粒処理を行った。次に、この造粒物にアルミナ粉末の粉体含有量が全量に対し５０ｖｏｌ％となるようにキシレンを加え、公転回転数２０００ｒｐｍで、かつ自転回転数８００ｒｐｍの条件で５分間攪拌造粒処理を行った。その結果、平均粒子径が２．７４ｍｍの球状造粒物を得た。得られた造粒物の断面を観察するとその断面に中空気孔は見られなかった。
(Example 2)
The same alumina powder as in Example 1 was used as the raw inorganic powder, and an epoxy resin was used as the liquid polymer resin. Alumina powder is added to the epoxy resin so that its concentration becomes 66.7 vol%, and the same stirring granulator as in Example 1 is used for a total of 6 minutes at the revolution speed of 2000 rpm of the sample container and at the rotation speed of 800 rpm. Agitation granulation was performed. Next, xylene is added to the granulated product so that the powder content of the alumina powder is 50 vol% with respect to the total amount, and agitation granulation treatment is performed for 5 minutes under the conditions of a revolution speed of 2000 rpm and a rotation speed of 800 rpm. went. As a result, a spherical granulated product having an average particle size of 2.74 mm was obtained. When the cross section of the obtained granulated material was observed, no medium air holes were found in the cross section.
（実施例３）
実施例１と同じアルミナ粉末およびエポキシ樹脂とキシレンの混合溶液を準備した。まず、最初にアルミナ粉末の粉体含有量が６６．７ｖｏｌ％となるように混合溶液を加え、攪拌造粒機により公転回転数２０００ｒｐｍで、かつ自転回転数８００ｒｐｍの条件で、合計６分間の攪拌造粒処理を行った。その後、この造粒物にさらに混合溶液を加えてアルミナ粉末の粉体含有量が全量に対し５７．３ｖｏｌ％となるように調整し、公転回転数２０００ｒｐｍで、かつ自転回転数８００ｒｐｍの条件で５分間の攪拌造粒処理を行った。その結果、平均粒子径が０．６２ｍｍの球状造粒物を得た。ここでは実施例１で得られた造粒物よりも小さな粒子径の造粒物が得られた。得られた造粒物の断面を観察するとその断面に中空気孔は見られなかった。
(Example 3)
The same alumina powder as in Example 1 and a mixed solution of epoxy resin and xylene were prepared. First, a mixed solution is added so that the powder content of the alumina powder is 66.7 vol%, and stirring is performed for a total of 6 minutes using a stirring granulator at a revolution speed of 2000 rpm and a rotation speed of 800 rpm. A granulation process was performed. Thereafter, a mixed solution is further added to the granulated product to adjust the powder content of the alumina powder to 57.3 vol% with respect to the total amount, and the condition is 5 under the conditions of a revolution speed of 2000 rpm and a rotation speed of 800 rpm. A minute stirring granulation process was performed. As a result, a spherical granulated product having an average particle diameter of 0.62 mm was obtained. Here, a granulated product having a particle diameter smaller than that of the granulated product obtained in Example 1 was obtained. When the cross section of the obtained granulated material was observed, no medium air holes were found in the cross section.
（実施例４）
原料無機粉末として酸化アルミニウム粉末（アルミナ粉末：平均一次粒子径約５００ｎｍ）及び窒化アルミニウム粉末（窒化アルミ粉末：平均一次粒子径約１０００ｎｍ）を体積比１：１で混合した粉末を、液状高分子樹脂としてエポキシ樹脂及びキシレンを体積比１：１として作製した混合溶液を用いた。酸化アルミニウムと窒化アルミニウムの混合粉末の粉体含有量が５０から６０ｖｏｌ％となるようにエポキシ樹脂とキシレンの混合溶液を加え、攪拌造粒機により、自転回転数８００ｒｐｍで、かつ公転回転数２０００ｒｐｍの条件で５分間の攪拌造粒処理を行った。
Example 4
Liquid polymer resin obtained by mixing aluminum oxide powder (alumina powder: average primary particle diameter of about 500 nm) and aluminum nitride powder (aluminum nitride powder: average primary particle diameter of about 1000 nm) as a raw material inorganic powder at a volume ratio of 1: 1 A mixed solution prepared by using an epoxy resin and xylene at a volume ratio of 1: 1 was used. Add a mixed solution of epoxy resin and xylene so that the powder content of the mixed powder of aluminum oxide and aluminum nitride is 50 to 60 vol%, and with a stirring granulator, the rotational speed is 800 rpm and the revolution speed is 2000 rpm. The stirring granulation treatment was performed for 5 minutes under the conditions.
その結果、平均粒子径が２．３９ｍｍの球状造粒物を得た。この造粒物の断面の電子顕微鏡写真（倍率：３５倍）を図３に示す。この電子顕微鏡写真では、粒子の断面に中空気孔は見られず、アルミナ粉末と窒化アルミニウム粉末がエポキシ樹脂と一体化した造粒物が形成されていることが認められた。 As a result, a spherical granulated product having an average particle size of 2.39 mm was obtained. An electron micrograph (magnification: 35 times) of the cross section of this granulated product is shown in FIG. In this electron micrograph, no medium air holes were observed in the cross section of the particles, and it was confirmed that a granulated product in which the alumina powder and the aluminum nitride powder were integrated with the epoxy resin was formed.
（実施例５）
実施例１で得た球状造粒物０．４２ｇを、直径１１．５ｍｍの金型の中に敷き詰め、３００ＭＰａの圧力でプレスした。造粒物同士が圧縮変形することで、厚さ１ｍｍの成型体が得られた。プレス加工後の成型体の断面の実体顕微鏡写真（倍率：１０倍）を図４に示す。
(Example 5)
0.42 g of the spherical granulated product obtained in Example 1 was spread in a mold having a diameter of 11.5 mm and pressed at a pressure of 300 MPa. A granulated product was compressed and deformed to obtain a molded body having a thickness of 1 mm. A stereomicrograph (magnification: 10 times) of a cross section of the molded body after press working is shown in FIG.
この電子顕微鏡写真によれば、プレス加工の際に球状造粒物は破壊せず、扁平率約６２％で変形し、可撓性を示した。さらに、図４からわかるように、この成型体では球状造粒物からエポキシ樹脂が染み出し、扁平になった造粒物の間の空隙を埋めている様子が観察された。この無機材料-高分子樹脂複合材料は、粉体含有量が６８．５％であった。この様に本発明の造粒物は高い粉体含有量の無機材料-高分子樹脂複合材料とその成型体を容易に成形加工で製造することができる。 According to this electron micrograph, the spherical granulated material was not broken during the press working, and deformed at a flatness ratio of about 62%, indicating flexibility. Furthermore, as can be seen from FIG. 4, it was observed that in this molded body, the epoxy resin oozes out from the spherical granulated material and fills the gaps between the flattened granulated materials. This inorganic material-polymer resin composite material had a powder content of 68.5%. As described above, the granulated product of the present invention can easily produce an inorganic material-polymer resin composite material having a high powder content and a molded product thereof by molding.
以上詳述したように、本発明は、圧縮成型に適合した可撓性を有する無機材料−高分子樹脂複合造粒物、その製造方法、この造粒物を使用して作製した高い粉体含有量の成型体に係るものであり、公転又は自転公転を有する攪拌造粒装置により製造された可撓性を有する造粒物である。さらに、この造粒物を圧縮成型加工することにより容易に粉体含有率を４０−８０％の無機材料−高分子樹脂複合材料とその成型体を提供することができる。従って、各種の金属やアルミナ、ジルコニア、窒化珪素、炭化珪素、シリカなどの無機材料を高い含有量で含む複合体とするこができ、これらの無機材料の特性を生かした絶縁性、熱伝導性、導電性、高屈折特性、耐摩耗性などのさまざまな特性を有する高分子樹脂複合体とすることができ、情報・家電・自動車産業などのさまざまな産業分野の機能性部材として有用である。 As described above in detail, the present invention includes a flexible inorganic material-polymer resin composite granulated product suitable for compression molding, a production method thereof, and a high powder content produced using the granulated product. It is a granulated product having flexibility, manufactured by an agitation granulator having revolution or autorotation. Furthermore, an inorganic material-polymer resin composite material having a powder content of 40 to 80% and a molded body thereof can be easily provided by compression molding the granulated product. Therefore, it can be a composite containing various metals and inorganic materials such as alumina, zirconia, silicon nitride, silicon carbide, silica, etc. with a high content, and insulation and thermal conductivity utilizing the characteristics of these inorganic materials It can be made into a polymer resin composite having various properties such as conductivity, high refractive properties, and abrasion resistance, and is useful as a functional member in various industrial fields such as information, home appliances, and automobile industries.
１：無機粒子、２：液状高分子樹脂、３：無機材料−高分子樹脂複合造粒物。 1: inorganic particles, 2: liquid polymer resin, 3: inorganic material-polymer resin composite granulated product.
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