JP2001342010A - Inorganic hollow particle and its manufacturing method - Google Patents
Inorganic hollow particle and its manufacturing methodInfo
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- JP2001342010A JP2001342010A JP2000160748A JP2000160748A JP2001342010A JP 2001342010 A JP2001342010 A JP 2001342010A JP 2000160748 A JP2000160748 A JP 2000160748A JP 2000160748 A JP2000160748 A JP 2000160748A JP 2001342010 A JP2001342010 A JP 2001342010A
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- Prior art keywords
- inorganic
- powder
- inorganic compound
- hollow powder
- hollow
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、無機質中空粉体お
よびその製造法に関するものである。TECHNICAL FIELD The present invention relates to an inorganic hollow powder and a method for producing the same.
【０００２】[0002]
【従来技術】従来、無機質中空体は、軽量材、塗料の充
填材、補強用充填材、低誘電率化のための特性改善材、
爆薬の増感剤などの様々な用途に用いるために種々の開
発が行なわれている。2. Description of the Related Art Conventionally, inorganic hollow bodies are made of lightweight materials, fillers for paints, fillers for reinforcement, materials for improving properties for lowering the dielectric constant,
Various developments have been made for use in various applications such as sensitizers for explosives.
【０００３】このような中空粉体として、例えば、ガラ
ス質の中空粉体やアルミナ、ジルコニアなどの中空粉体
が知られている。これらの中空粉体は、ガラスなどを高
温に加熱溶融して発泡剤によって発泡させながら、粒子
状に吹き飛ばして形成される（特公平２−２７２９５
号）。また、シラスなどの火山ガラス質堆積物を原料と
して、中空ガラス球状体を作製すること（特開昭６１−
２２２９６９号）等が報告されている。As such a hollow powder, for example, a glassy hollow powder and a hollow powder such as alumina and zirconia are known. These hollow powders are formed by heating and melting glass or the like at a high temperature and blowing it into particles while foaming with a foaming agent (Japanese Patent Publication No. 2-27295).
issue). Further, a hollow glass spherical body is produced from a volcanic glassy deposit such as shirasu as a raw material (Japanese Patent Application Laid-Open No. 61-1986)
No. 222969) has been reported.
【０００４】また、金属炭化物やその前駆体を含む溶液
または分散液を微小液滴化し、これを高温雰囲気に微小
液滴を噴霧することによって、炭化物からなる微小中空
体を形成することが提案されている（特開平６−３２１
５２０号）。[0004] It has also been proposed to form a fine hollow body made of carbide by forming a microdroplet from a solution or dispersion containing a metal carbide or its precursor and spraying the microdroplet in a high-temperature atmosphere. (Japanese Patent Laid-Open No. 6-321)
520).
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、これら
の手法による無機中空体によれば、ガラス質材料を原料
とする方法では、ガラス質中に低融点化するために少な
からずアルカリ元素を含有しており、また、これらの無
機中空粉体の平均粒径は、そのほとんどが３０μｍより
も大きいものであった。そのために、アルカリ元素が水
や酸に対して容易に溶出し、耐候性に劣るという欠点が
あった。しかも、電子部品材料、例えば絶縁基板材料の
１成分として混合、複合化することも行なわれている
が、このような場合にも、絶縁信頼性が劣化するなどの
問題があった。However, according to the inorganic hollow bodies obtained by these methods, in the method using a vitreous material as a raw material, not a small amount of an alkali element is contained in the vitreous material in order to lower the melting point. Most of the inorganic hollow powders had an average particle size of more than 30 μm. For this reason, there is a disadvantage that the alkali element is easily eluted with water or acid, and the weather resistance is poor. Moreover, mixing and compounding as one component of an electronic component material, for example, an insulating substrate material, are also performed. However, in such a case, there is a problem that insulation reliability is deteriorated.
【０００６】また、粒子径が３０μｍ以上と大きいと、
これを他の材料と複合化することによって軽量化を図る
場合、大きな無機中空体が破壊源となるために高強度が
要求される構造部材には適用できないものであった。When the particle diameter is as large as 30 μm or more,
When this is combined with another material to reduce the weight, it cannot be applied to a structural member requiring high strength because a large inorganic hollow body becomes a destruction source.
【０００７】また、無機質の炭化物を溶媒とともに高温
雰囲気中に噴霧する方法は、装置が大がかりになるとと
もに、溶媒の揮発とともに球状および中空化するため
に、中空であっても多孔質化しやすく、閉気孔が形成さ
れにくいという問題があった。Further, the method of spraying an inorganic carbide together with a solvent in a high-temperature atmosphere requires a large-scale apparatus, and because the solvent is volatilized and becomes spherical and hollow, it is easy to make it porous even if it is hollow. There is a problem that pores are not easily formed.
【０００８】また、従来の方法では、中空粉体を形成す
る無機材料が限定されており、あらゆる無機材料の中空
粉体を形成することが難しいものであった。Further, in the conventional method, the inorganic material forming the hollow powder is limited, and it is difficult to form the hollow powder of any inorganic material.
【０００９】従って、本発明は、無機中空粉体における
上記問題点を解決し、微小粉体からなるとともに内部に
閉気孔を具備する無機質中空粉体と、それを簡単な方法
で作製することのできる製造方法を提供することを目的
とするものである。Accordingly, the present invention solves the above-mentioned problems of the inorganic hollow powder, and provides an inorganic hollow powder comprising fine powder and having closed pores therein, and a method for producing the same by a simple method. It is an object of the present invention to provide a manufacturing method which can be performed.
【００１０】[0010]
【課題を解決するための手段】本発明者は、上記課題に
対して検討を重ねた結果、所定の大きさの有機樹脂球を
用いて、球表面に無機化合物、あるいはその前駆体を形
成してなる複合体を形成し、この複合体を加熱処理して
有機樹脂球を分解除去して無機化合物からなる皮膜を作
製した後、さらに所定温度に加熱して前記無機化合物か
らなる皮膜を緻密化することによって、無機化合物粉体
内に閉気孔を具備する中空粉体が得られることを見いだ
し、本発明に至った。Means for Solving the Problems As a result of repeated studies on the above problems, the present inventor has formed an inorganic resin or a precursor thereof on the surface of a sphere by using an organic resin sphere of a predetermined size. After forming a composite made of, and heat-treating the composite to decompose and remove the organic resin spheres to produce a coating made of an inorganic compound, the coating is further heated to a predetermined temperature to densify the coating made of the inorganic compound. By doing so, it was found that a hollow powder having closed pores in the inorganic compound powder was obtained, and the present invention was achieved.
【００１１】即ち、本発明の無機質中空粉体は、平均粒
径２０μｍ以下、粉体内部の平均気孔径が０．１〜１５
μｍ、閉気孔率が３０％以上、ＢＥＴ比表面積が３０ｍ
2／ｇ以下であることを特徴とするものであって、この
中空粉体を形成する無機質材料は、実質的に単一金属酸
化物からなっても、実質的に２種以上の金属酸化物の混
合物あるいは化合物からなってもよい。また、アルカリ
元素の含有率が酸化物換算で５００ｐｐｍ以下であるこ
とも大きな特徴である。That is, the inorganic hollow powder of the present invention has an average particle diameter of 20 μm or less and an average pore diameter inside the powder of 0.1 to 15 μm.
μm, closed porosity is 30% or more, BET specific surface area is 30m
2 / g or less, wherein the inorganic material forming the hollow powder is substantially composed of a single metal oxide or substantially two or more metal oxides. Or a mixture of the above. Another significant feature is that the alkali element content is 500 ppm or less in terms of oxide.
【００１２】また、かかる無機質中空粉体を製造する方
法としては、平均粒径が０．１〜１５μｍの有機樹脂球
の表面に無機化合物、あるいはその前駆体を形成した複
合体を形成した後、この複合体を加熱処理して、前記有
機樹脂球を分解除去して無機化合物からなる皮膜を作製
した後、さらに所定温度に加熱して前記無機化合物から
なる皮膜を緻密化して、無機化合物粉体内に閉気孔を具
備する中空粉体を形成することを特徴とするものであ
る。As a method for producing such an inorganic hollow powder, a composite in which an inorganic compound or a precursor thereof is formed on the surface of an organic resin sphere having an average particle diameter of 0.1 to 15 μm is formed. After heating the composite to decompose and remove the organic resin spheres to produce a film made of an inorganic compound, the film is further heated to a predetermined temperature to densify the film made of the inorganic compound, and the inorganic compound powder In which a hollow powder having closed pores is formed.
【００１３】前記無機化合物が、実質的に単一金属酸化
物からなっても、実質的に２種以上の金属酸化物の混合
物または複合化合物からなってもよい。The inorganic compound may consist essentially of a single metal oxide, or may consist essentially of a mixture or composite compound of two or more metal oxides.
【００１４】[0014]
【発明の実施の形態】以下に本発明の無機中空粉体の製
造方法について説明する。本発明によれば、まず、有機
樹脂球を準備する。この有機樹脂球は最終的に得られる
中空粉体における独立平均気孔径を決定する要素である
ことから、有機樹脂球の大きさとしては、平均粒径が
０．１〜１５μｍ、特に２〜５μｍであることが必要で
ある。つまり、０．１μｍよりも小さいと、中空粉体中
の閉気孔が小さく、所定の空隙率を達成することが難し
く、１５μｍよりも大きいと、微小な中空粉体を形成す
ることが困難となるためである。BEST MODE FOR CARRYING OUT THE INVENTION The method for producing an inorganic hollow powder of the present invention will be described below. According to the present invention, first, an organic resin ball is prepared. Since this organic resin sphere is an element that determines the independent average pore diameter in the finally obtained hollow powder, the size of the organic resin sphere is 0.1 to 15 μm, particularly 2 to 5 μm. It is necessary to be. That is, if it is smaller than 0.1 μm, the closed pores in the hollow powder are small, and it is difficult to achieve a predetermined porosity. If it is larger than 15 μm, it is difficult to form a fine hollow powder. That's why.
【００１５】次に、この有機樹脂球の表面に無機化合物
あるいはその前駆体を被覆する。被覆方法としては、所
定の無機化合物のアルコキシド法や沈殿法等の液相を利
用して有機樹脂球の表面に無機化合物あるいはその前駆
体を析出形成させる手法や、有機樹脂球の表面に、サブ
ミクロンの無機化合物粉末を付着させる手法が挙げられ
るが、有機樹脂球表面に無機化合物を均一に形成する上
で、前者の方が好適である。Next, the surface of the organic resin sphere is coated with an inorganic compound or its precursor. As a coating method, a method of depositing and forming an inorganic compound or its precursor on the surface of an organic resin sphere by using a liquid phase such as an alkoxide method or a precipitation method of a predetermined inorganic compound, A method of adhering a micron inorganic compound powder may be mentioned, but the former is more suitable for uniformly forming the inorganic compound on the surface of the organic resin sphere.
【００１６】その後、得られた複合体を有機樹脂球が分
解消失しうる温度、雰囲気下で１次熱処理して、有機樹
脂を分解除去することによって、無機化合物のみからな
る皮膜内部に空洞を有する見かけ上、中空粉体が形成さ
れる。ところが、この段階では、無機化合物からなる皮
膜は緻密化されておらず、多孔質からなるために、粉体
中の空洞は、閉気孔とはなっておらず、比表面積も大き
い状態である。Thereafter, the obtained composite is subjected to a first heat treatment in an atmosphere at a temperature at which the organic resin spheres can be decomposed and disappeared to decompose and remove the organic resin, thereby forming a cavity inside the coating made of only the inorganic compound. Apparently, a hollow powder is formed. However, at this stage, since the film made of the inorganic compound is not densified and made of a porous material, the cavities in the powder are not closed pores and have a large specific surface area.
【００１７】そこで、本発明によれば、さらに昇温にて
２次熱処理を施し、上記処理後の粉体の無機化合物から
なる皮膜を緻密化する。この場合の２次熱処理の温度
は、無機化合物の組成等に応じて緻密化が進行し得る温
度に加熱される。この２次熱処理によって、一次処理後
の一次粉体における皮膜の緻密化の進行とともに、粉体
の比表面積も次第には小さくなり、緻密な無機化合物か
らなる皮膜内に閉気孔を有する中空粉体を作製すること
ができる。Therefore, according to the present invention, a secondary heat treatment is further performed at an elevated temperature to densify the coating of the powdered inorganic compound after the above treatment. The temperature of the secondary heat treatment in this case is heated to a temperature at which densification can proceed according to the composition of the inorganic compound and the like. Due to this secondary heat treatment, the specific surface area of the powder gradually decreases with the progress of densification of the film in the primary powder after the primary treatment, and the hollow powder having closed pores in the film made of the dense inorganic compound is formed. Can be made.
【００１８】なお、本発明の上記の製造方法によれば、
有機樹脂球の大きさによって、中空粉体の大きさを任意
に定めることができ、有機樹脂球の大きさを平均で０．
１〜１５μｍとすることによって、内部の平均気孔径が
０．１〜１５μｍであり、平均粒径が２０μｍ以下の微
細な中空粉体を作製することができる。また、かかる中
空粉体は、閉気孔率が３０％以上、特に４０％以上であ
ることも大きな特徴であって、この閉気孔率が３０％よ
りも低いと、軽量化等を目的とした部材等に適用した場
合に、充分な効果が得られないという問題がある。ま
た、本発明の中空粉体は、無機化合物からなる皮膜が緻
密質からなるために、ＢＥＴ比表面積が３０ｍ2／ｇ以
下、特に１５ｍ2／ｇ以下であることも大きな特徴であ
る。According to the above-mentioned manufacturing method of the present invention,
The size of the hollow powder can be arbitrarily determined according to the size of the organic resin sphere, and the average size of the organic resin sphere is 0.1 mm.
By setting the average pore diameter to 1 to 15 μm, a fine hollow powder having an average internal pore diameter of 0.1 to 15 μm and an average particle diameter of 20 μm or less can be produced. Further, such a hollow powder is characterized by having a closed porosity of 30% or more, particularly 40% or more. If the closed porosity is lower than 30%, a member intended for weight reduction or the like is used. However, there is a problem that a sufficient effect cannot be obtained when the method is applied to, for example, the present invention. In addition, the hollow powder of the present invention is also characterized by having a BET specific surface area of 30 m 2 / g or less, particularly 15 m 2 / g or less, because the film made of the inorganic compound is dense.
【００１９】しかも、本発明の上記の製造方法において
は、有機樹脂球の表面に形成する無機化合物の種類は何
ら問うものではなく、有機樹脂球の表面に被覆可能なも
のであれば、あらゆる無機化合物によって、中空粉体を
形成することができることも大きな特徴である。Further, in the above-mentioned production method of the present invention, the type of the inorganic compound formed on the surface of the organic resin sphere does not matter at all, as long as it can cover the surface of the organic resin sphere. It is also a great feature that a compound can form a hollow powder.
【００２０】従って、従来のようなガラスのみならず、
あらゆる無機化合物、例えば、ＳｉＯ2、Ａｌ2Ｏ3、Ｚ
ｒＯ2、ＺｎＯ、ＢａＯ、ＣａＯ、ＭｇＯ、ＳｒＯの群
から選ばれる１種による単一金属化合物、特に酸化物か
らなる中空粉体を形成することができる。Therefore, not only conventional glass but also
Any inorganic compounds, such as SiO 2 , Al 2 O 3 , Z
It is possible to form a hollow powder made of a single metal compound, particularly an oxide, of one kind selected from the group consisting of rO 2 , ZnO, BaO, CaO, MgO, and SrO.
【００２１】また、２種以上の金属化合物との混合物あ
るいは化合物によって中空粉体を形成することもでき、
２種以上の混合系では、上記の有機樹脂球を除去した後
の熱処理による緻密化処理を低温で行なうことができ
る。Further, a hollow powder can be formed by a mixture or compound with two or more metal compounds,
In a mixed system of two or more types, the densification treatment by heat treatment after removing the organic resin spheres can be performed at a low temperature.
【００２２】しかも、本発明の製造方法によれば、ガラ
スなどの発泡によって形成する場合、必然的にアルカリ
金属が含有されるが、本発明によれば、上記のように、
あらゆる任意の無機化合物によって中空粉体を形成でき
るために、アルカリ金属量が５００ｐｐｍ以下、特に３
００ｐｐｍ以下とすることができる。Further, according to the production method of the present invention, when the glass is formed by foaming, an alkali metal is inevitably contained, but according to the present invention, as described above,
Since the hollow powder can be formed by any arbitrary inorganic compound, the content of the alkali metal is 500 ppm or less, particularly 3 ppm.
It can be set to 00 ppm or less.
【００２３】[0023]
【実施例】実施例１ テトラメトキシシラン：１０００ｇに対し、平均粒径が
０．１５μｍ、２．０μｍ、５．０μｍ、１０．０μ
ｍ、１５．０μｍの単分散アクリル樹脂球をそれぞれ１
５０ｇ添加し撹拌しながらさらに水５００ｇを添加して
加水分解反応を開始させた。Example 1 Tetramethoxysilane: 1000 g, average particle size 0.15 μm, 2.0 μm, 5.0 μm, 10.0 μm
m and 15.0 μm monodispersed acrylic resin
While adding 50 g and stirring, 500 g of water was further added to start a hydrolysis reaction.
【００２４】ゲル化したものを＃１００のナイロンメッ
シュを用いて粉砕し、２００℃で真空乾燥を行い、さら
に振動ミルを用いて粉砕した。この状態の粉体のＢＥＴ
比表面積はいずれもほぼ３００ｍ2／ｇであった。作製
した粉体を電子顕微鏡にて観察した結果、アクリル樹脂
球の表面にシリカゲルが被覆されたものが凝集した状態
であった。The gelled product was pulverized using a # 100 nylon mesh, vacuum-dried at 200 ° C., and further pulverized using a vibration mill. BET of powder in this state
The specific surface areas were all about 300 m 2 / g. As a result of observing the produced powder with an electron microscope, it was found that the surface of the acrylic resin sphere was coated with silica gel and was in an agglomerated state.
【００２５】得られたこの粉末をアルミナ製るつぼに入
れ大気中４５０℃、５時間の条件で保持し、有機樹脂分
を完全に分解消失させた。その後、さらに温度を上げ、
１０００℃〜１６００℃の温度で１０時間保持して粉体
を作製した。The obtained powder was placed in an alumina crucible and kept at 450 ° C. for 5 hours in the atmosphere to completely decompose and eliminate the organic resin component. After that, raise the temperature further,
The powder was held at a temperature of 1000 ° C. to 1600 ° C. for 10 hours to produce a powder.
【００２６】作製した粉体のＢＥＴ比表面積を測定し、
また、ピクノメーターによって粉体密度を測定し理論密
度で割ることで閉気孔率を計算した。The BET specific surface area of the produced powder was measured,
The closed porosity was calculated by measuring the powder density with a pycnometer and dividing by the theoretical density.
【００２７】また、粉体の断面の走査電子顕微鏡写真を
観察して、任意に抽出した１０個の粉体中の空隙のうち
最大のものを気孔径の平均値とみなした。評価結果を表
１に示す。Further, by observing a scanning electron micrograph of the cross section of the powder, the largest one of the 10 voids in the arbitrarily extracted powder was regarded as the average value of the pore diameter. Table 1 shows the evaluation results.
【００２８】[0028]
【表１】 [Table 1]
【００２９】この実施例によれば、熱処理温度が１４０
０℃よりも低い場合、粉体は多孔質のままで、閉気孔率
は０であり、中空粉体にはならなかった。さらに熱処理
温度を１４００℃以上に高めた場合、ＢＥＴ比表面積は
３０ｍ2／ｇ以下に減少し、同時に閉気孔率が３０体積
％以上の中空粉体を作製することができた。According to this embodiment, the heat treatment temperature is 140
When the temperature was lower than 0 ° C., the powder remained porous, had a closed porosity of 0, and did not become a hollow powder. Further, when the heat treatment temperature was increased to 1400 ° C. or higher, the BET specific surface area was reduced to 30 m 2 / g or less, and at the same time, a hollow powder having a closed porosity of 30% by volume or more could be produced.
【００３０】なお、作製した中空粉体について、Ｘ線回
折測定を行なって結果、いずれもＳｉＯ2（クオーツ）
またはクリストバライトからなる結晶相からなることが
わかった。また、ＩＣＰ発光分光分析の結果、この粉体
中におけるアルカリ金属の総量は酸化物換算で４０ｐｐ
ｍ以下と非常に少ないものであった。An X-ray diffraction measurement was performed on the produced hollow powder, and as a result, all of the powders were SiO 2 (quartz).
Alternatively, it was found that the crystal phase was composed of cristobalite. As a result of ICP emission spectroscopy, the total amount of alkali metals in the powder was 40 pp in terms of oxide.
m or less.
【００３１】実施例２ 食塩水溶液と、珪酸アルカリ水溶液と、平均粒径５、１
０μｍのアクリル樹脂球の混合液にさらに塩酸を加え、
ｐＨ６、８０℃に維持し、熟成を行い、アクリル樹脂球
の表面にシリカゲルの皮膜を析出させた平均粒径が６μ
ｍおよび１１μｍの複合体を得た。Example 2 A saline solution, an alkali silicate aqueous solution and an average particle size of 5, 1
Hydrochloric acid was further added to a mixture of 0 μm acrylic resin balls,
The pH was maintained at 80 ° C., aging was performed, and an average particle diameter of 6 μm was obtained by depositing a silica gel film on the surface of the acrylic resin sphere.
m and 11 μm complexes were obtained.
【００３２】得られた複合体をアルカリ成分が５００ｐ
ｐｍ以下となるまで酸洗浄した。そして、洗浄後の複合
体を、さらにＢ2Ｏ3、ＺｎＯ、ＢａＯ、ＣａＯ、ＺｒＯ
2のうちの少なくと１種を含む水溶液に浸漬した後、こ
れを乾燥して有機樹脂球の表面に、シリカゲルと上記金
属化合物を被覆した複合体を作製した。The obtained composite was prepared by adding 500 p
pm or less. Then, the complex after washing is further subjected to B 2 O 3 , ZnO, BaO, CaO, ZrO.
After immersion in an aqueous solution containing at least one of the two , it was dried to produce a composite in which silica gel and the above-mentioned metal compound were coated on the surface of an organic resin sphere.
【００３３】この粉末を大気中、４５０℃で５時間熱処
理して有機樹脂分を完全に分解消失させた。そして、８
００℃〜１５００℃の温度範囲で熱処理し、実施例１の
場合と同様の評価を行った。評価結果を表２、表３に示
す。This powder was heat-treated at 450 ° C. for 5 hours in the air to completely decompose and eliminate the organic resin component. And 8
Heat treatment was performed in the temperature range of 00 ° C to 1500 ° C, and the same evaluation as in Example 1 was performed. The evaluation results are shown in Tables 2 and 3.
【００３４】[0034]
【表２】 [Table 2]
【００３５】[0035]
【表３】 [Table 3]
【００３６】熱処理を全く行なわなかった場合（試料Ｎ
ｏ．３１、３７、４３、４９、５５）粉体は多孔質のま
まであり閉気孔率は０％のままで中空粉体は形成されな
かった。また、複合化した酸化物の種類によって中空粉
体が形成されるための熱処理温度は様々変化し、ＺｎＯ
の場合、８００℃以上、ＢａＯ、ＣａＯ，ＺｒＯ2の場
合、１５００℃以上、Ｂ2Ｏ3では８５０℃以上での熱処
理によって、中空粉体が形成され比表面積３０ｍ2／ｇ
以下となり同時に２０体積％以上の閉気孔が形成された
が、Ｂ2Ｏ3の場合、１０００℃よりも温度が高いと、粉
体が凝集して閉気孔が形成されなかった。When no heat treatment was performed (sample N
o. 31, 37, 43, 49, 55) The powder remained porous, the closed porosity remained 0%, and no hollow powder was formed. Further, the heat treatment temperature for forming the hollow powder varies depending on the type of the composite oxide, and ZnO
In the case of the above, hollow powder is formed by heat treatment at 800 ° C. or more, at 1500 ° C. or more for BaO, CaO, and ZrO 2 and at 850 ° C. or more for B 2 O 3 , and the specific surface area is 30 m 2 / g.
At the same time, 20% by volume or more of closed pores were formed. However, in the case of B 2 O 3 , if the temperature was higher than 1000 ° C., the powder aggregated and no closed pores were formed.
【００３７】また、作製した各中空粉体について、Ｘ線
回折測定を行なって主結晶相を同定した結果、試料Ｎ
ｏ．３２〜３６、６２〜６６では、クオーツ、試料Ｎ
ｏ．４２、４８、５４、７２、７８、８４ではアモルフ
ァス、試料Ｎｏ．５７〜６０、８７〜９０ではクリスト
バライトの結晶相からなることがわかった。また、ＩＣ
Ｐ発光分光分析の結果、この粉体中におけるアルカリ金
属の総量は酸化物換算でいずれも３００ｐｐｍ以下と非
常に少ないものであった。The main crystal phase was identified by performing X-ray diffraction measurement on each of the produced hollow powders.
o. For 32-36 and 62-66, quartz, sample N
o. Samples No. 42, 48, 54, 72, 78 and 84 were amorphous. 57 to 60 and 87 to 90, it was found that they consisted of a crystal phase of cristobalite. Also, IC
As a result of P emission spectroscopy, the total amount of alkali metals in this powder was very small at 300 ppm or less in terms of oxide.
【００３８】実施例３ 平均粒径：０．４μｍのＡｌ2Ｏ3と平均粒径：０．４μ
ｍのＺｎＯと、Ａｌ2Ｏ3とＺｎＯの比率が重量比で１０
０：０、７５：２５、５０：５０、２５：７５、０：１
００の５種の比率混合した。そして、この無機化合物と
平均粒径が２μｍの有機アクリル樹脂球を無機成分：有
機成分＝２：５の体積比率になるように計量し、奈良機
械製ハイブリダイザーを用いて混合処理した。処理後の
粉末について電子顕微鏡写真で観察した結果、有機樹脂
球の表面にＡｌ2Ｏ3とＺｎＯの混合粉末が付着した状態
であることがわかった。Example 3 Al 2 O 3 having an average particle size of 0.4 μm and an average particle size of 0.4 μm
m of ZnO and Al 2 O 3: ZnO in a weight ratio of 10
0: 0, 75:25, 50:50, 25:75, 0: 1
00 were mixed in five ratios. Then, this inorganic compound and an organic acrylic resin sphere having an average particle diameter of 2 μm were weighed so as to have a volume ratio of inorganic component: organic component = 2: 5, and mixed using a hybridizer manufactured by Nara Machinery. As a result of observing the powder after the treatment with an electron micrograph, it was found that a mixed powder of Al 2 O 3 and ZnO was attached to the surface of the organic resin sphere.
【００３９】この粉末を大気中、４５０℃で５時間熱処
理して有機樹脂分を完全に分解消失させた。そして、こ
の複合体を９００℃〜１６００℃の温度範囲で熱処理
し、実施例１，２と同様に評価した。評価結果を表４に
示す。This powder was heat-treated at 450 ° C. for 5 hours in the air to completely decompose and eliminate the organic resin component. Then, this composite was heat-treated in a temperature range of 900 ° C. to 1600 ° C. and evaluated in the same manner as in Examples 1 and 2. Table 4 shows the evaluation results.
【００４０】[0040]
【表４】 [Table 4]
【００４１】Ａｌ2Ｏ3：ＺｎＯの比率によって、中空粉
体が形成される温度が変化しており、Ａｌ2Ｏ3１００％
では１６００℃で、中空粉体が形成された。Ａｌ2Ｏ3：
ＺｎＯ＝７５：２５では、１１００℃以上、Ａｌ2Ｏ3：
ＺｎＯ＝５０：５０では、１０００℃以上、Ａｌ2Ｏ3：
ＺｎＯ＝２５：７５では、１０００℃以上、ＺｎＯ１０
０％では、１６００℃の加熱温度で、閉気孔率が２０％
以上の中空粉体を作製することができた。[0041] Al 2 O 3: by the ratio of ZnO, the temperature of the hollow powder is formed are changed, Al 2 O 3 100%
At 1600 ° C., a hollow powder was formed. Al 2 O 3 :
When ZnO = 75: 25, the temperature is 1100 ° C. or higher, and Al 2 O 3 :
When ZnO = 50: 50, the temperature is 1000 ° C. or higher, and Al 2 O 3 :
In the case of ZnO = 25: 75, 1000 ° C. or more, ZnO10
At 0%, the closed porosity is 20% at a heating temperature of 1600 ° C.
The above hollow powder could be produced.
【００４２】また、作製した各中空粉体について、Ｘ線
回折測定によって主結晶相の同定を行なった結果、試料
Ｎｏ．９５では、Ａｌ2Ｏ3、試料Ｎｏ．９９、１００、
１０３〜１０５、１０８〜１１０では、ＺｎＯ・Ａｌ2
Ｏ3、試料Ｎｏ．１１５ではＺｎＯが観察された。ま
た、ＩＣＰ発光分光分析の結果、この粉体中におけるア
ルカリ金属の総量は酸化物換算でいずれも７０ｐｐｍ以
下と非常に少ないものであった。The main crystal phase of each of the produced hollow powders was identified by X-ray diffraction measurement. 95, Al 2 O 3 , sample no. 99, 100,
In 103 to 105 and 108 to 110, ZnO.Al 2
O 3 , sample no. In No. 115, ZnO was observed. As a result of ICP emission spectroscopy, the total amount of alkali metals in this powder was as very small as 70 ppm or less in terms of oxide.
【００４３】[0043]
【発明の効果】以上詳述したように、本発明によれば有
機樹脂球の表面に無機成分を析出あるいは付着させ、加
熱によって有機樹脂球を分解除去した後、さらに加熱す
ることで種々の組成の閉気孔を有する無機質中空粉体を
容易に作製することが可能となる。また、アルカリ元素
を実質的に含まないため様々な用途への適応が可能とな
る。しかも、空孔径および隔壁の厚さについても自由に
設計することが可能であるために構造材料への適用にお
いても強度劣化などの問題発生を防ぐことができる。As described above in detail, according to the present invention, various components can be obtained by precipitating or adhering an inorganic component to the surface of the organic resin sphere, decomposing and removing the organic resin sphere by heating, and further heating. It is possible to easily produce an inorganic hollow powder having closed pores. Further, since it does not substantially contain an alkali element, it can be applied to various uses. In addition, since it is possible to freely design the hole diameter and the thickness of the partition walls, it is possible to prevent the occurrence of problems such as deterioration in strength when applied to a structural material.
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Claims (7)
気孔径が０．１〜１５μｍ、閉気孔率が３０体積％以
上、ＢＥＴ比表面積が３０ｍ2／ｇ以下であることを特
徴とする無機質中空粉体。(1) an average particle diameter of 20 μm or less, an average pore diameter of internal pores of 0.1 to 15 μm, a closed porosity of 30% by volume or more, and a BET specific surface area of 30 m 2 / g or less. Inorganic hollow powder.
徴とする請求項１記載の無機質中空粉体。2. The inorganic hollow powder according to claim 1, which is substantially composed of a single metal oxide.
たは化合物からなることを特徴とする請求項１記載の無
機質中空粉体。3. The inorganic hollow powder according to claim 1, wherein the powder is substantially composed of a mixture or compound of two or more metal oxides.
０ｐｐｍ以下であることを特徴とする請求項１記載の無
機質中空粉体。4. An alkali element content of 50 in terms of oxide.
The inorganic hollow powder according to claim 1, wherein the content is 0 ppm or less.
の表面に無機化合物、あるいはその前駆体を被覆した複
合体を形成した後、この複合体を加熱処理して、前記有
機樹脂球を分解除去して無機化合物からなる皮膜を作製
した後、さらに所定温度に加熱して前記無機化合物から
なる皮膜を緻密化して、無機化合物粉体内に閉気孔を具
備する中空粉体を形成することを特徴とする無機質中空
粉体の製造方法。5. An organic resin sphere having an average particle diameter of 0.1 to 15 μm is coated with an inorganic compound or a precursor thereof to form a composite on the surface thereof. After the spheres are decomposed and removed to form a coating made of an inorganic compound, the coating is further heated to a predetermined temperature to densify the coating made of the inorganic compound to form a hollow powder having closed pores in the inorganic compound powder. A method for producing an inorganic hollow powder.
物からなる請求項５記載の無機質中空粉体の製造方法。6. The method for producing an inorganic hollow powder according to claim 5, wherein said inorganic compound substantially comprises a single metal oxide.
属酸化物の混合物または複合化合物からなる請求項５記
載の無機質中空粉体の製造方法。7. The method for producing an inorganic hollow powder according to claim 5, wherein said inorganic compound substantially comprises a mixture or a composite compound of two or more metal oxides.
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