JPH06142491A - Composite particle, hollow particle and their production - Google Patents
Composite particle, hollow particle and their productionInfo
- Publication number
- JPH06142491A JPH06142491A JP30259292A JP30259292A JPH06142491A JP H06142491 A JPH06142491 A JP H06142491A JP 30259292 A JP30259292 A JP 30259292A JP 30259292 A JP30259292 A JP 30259292A JP H06142491 A JPH06142491 A JP H06142491A
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- JP
- Japan
- Prior art keywords
- particles
- polymer
- core
- particle
- spherical polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、複合粒子、中空粒子と
それらの製造方法に関し、さらに詳しくは高強度、かつ
高耐熱性であり、高機能を発現することができ、化粧
品、電子材料、半導体材料、研磨剤、コーティング剤、
塗料、スペーサー、光学材料、触媒、充填剤、医薬、診
断薬、トナー、樹脂改質剤、インク、吸着剤、耐紫外線
材料等に好適に使用される複合粒子とその製造方法、並
びに隠蔽率、吸着率、比表面積等が大きく、光学材料、
マイクロカプセル材料、隠蔽材料、カラム充填剤、触
媒、化粧品、耐紫外線材料等に好適に使用される中空粒
子とその製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to composite particles, hollow particles and a method for producing them, and more specifically, it has high strength and high heat resistance and is capable of exhibiting high functions. Semiconductor materials, polishing agents, coating agents,
Paint particles, spacers, optical materials, catalysts, fillers, medicines, diagnostic agents, toners, resin modifiers, inks, adsorbents, composite particles preferably used for UV resistant materials and the like, and a method for producing the same, and a hiding rate, Large adsorption rate, specific surface area, etc.
The present invention relates to hollow particles suitably used for microcapsule materials, concealing materials, column fillers, catalysts, cosmetics, UV-resistant materials and the like, and a method for producing the same.
【０００２】[0002]
【従来の技術】標準粒子、診断薬用担体粒子、滑剤等に
は、粒子径分布の狭い重合体粒子等が用いられている。
しかし、該重合体粒子は、強度が劣るため、例えば標準
粒子および滑剤に用いる場合、シェアのかかる、あるい
は高温となる条件では、しばしば粒子が変形若しくは崩
壊してしまう。その結果、重合体粒子の本来有する特性
が生かされず、その使用範囲は非常に限られたものとな
っている。これらの欠点を改善するために、重合体粒
子、例えば架橋性単量体等を共重合させて高架橋体にす
る等の方法が提案されているが、当該方法により得られ
る重合体粒子も未だ満足すべき性能を発揮するまでに至
ってはいない。Polymer particles having a narrow particle size distribution are used as standard particles, carrier particles for diagnostic agents, lubricants and the like.
However, since the polymer particles are poor in strength, when used as standard particles and lubricants, for example, the particles are often deformed or disintegrated under the condition of high shear or high temperature. As a result, the inherent properties of the polymer particles are not utilized and the range of use thereof is extremely limited. In order to improve these drawbacks, a method of polymer particles, for example, a method of copolymerizing a crosslinkable monomer or the like into a highly crosslinked product has been proposed, but the polymer particles obtained by the method are still satisfactory. It has not yet reached the desired performance.
【０００３】また、上記重合体粒子は、診断薬用、医薬
用等にも応用されているが、抗原や抗体との親和性、生
体適合性等に限界があるため、その応用範囲が限られて
いる。Further, the polymer particles have been applied to diagnostic agents, pharmaceutical agents, etc., but their application range is limited due to their limited affinity with antigens and antibodies, biocompatibility, etc. There is.
【０００４】一方、電子材料、磁性材料、光学材料、耐
熱性材料等のセラミック用途には、数多くの種類の金属
化合物粒子が使用されており、また、用途の多様化、性
能の多様化に応ずるため、種々の複合粒子が提案されて
いる。例えば酸化鉄粒子にケイ素化合物を被覆した複合
粒子を熱処理して針状の磁性体を製造する際の形崩れや
磁性体間の焼結を防止させようとするもの、鉄粉に銅を
被覆した複合粒子を用いて粉末冶金材料としての強度を
上げようとするもの、あるいは酸化鉄粒子にアンチモン
およびアルミニウム酸化物を被覆した複合粒子を用いて
耐熱性を上げようとするもの等が報告されている。しか
し、これらのほとんどが金属化合物同士の複合粒子であ
ることから用途の多様化に充分対応できないため、さら
に種々の機能を発現させ得る複合粒子の開発が特に電子
材料、光学材料等の分野で要求されている。On the other hand, many kinds of metal compound particles are used for ceramics such as electronic materials, magnetic materials, optical materials, heat resistant materials, etc., and in response to diversification of applications and diversification of performance. Therefore, various composite particles have been proposed. For example, iron oxide particles coated with a silicon compound are subjected to heat treatment to prevent the shape of the needle-shaped magnetic material from being deformed or sintering between magnetic materials, and iron powder coated with copper. It has been reported that the composite particles are used to increase the strength as a powder metallurgy material, or the composite particles in which iron oxide particles are coated with antimony and aluminum oxide are used to increase the heat resistance. . However, since most of these are composite particles of metal compounds, it is not possible to sufficiently cope with the diversification of applications. Therefore, the development of composite particles capable of expressing various functions is required especially in the fields of electronic materials, optical materials, etc. Has been done.
【０００５】また、近年、セラミック系粒子のなかでも
特に中空金属化合物粒子が有用なものとして注目されて
おり、その製法としては、例えばエアロゾル法により基
本粒子を製造し加熱、乾燥する方法、金属化合物水性ゾ
ルを噴霧、乾燥し焼成する方法、ｗ／ｏ型またはｏ／ｗ
／ｏ型エマルジョンを調製し加熱して水および油を除去
する方法等が提案されている。しかし、これらの製法に
より得られた中空粒子はいずれも、強度が著しく劣り、
また、その粒子径分布が広がる傾向にある。In recent years, among the ceramic particles, hollow metal compound particles have attracted attention as being particularly useful. As a method for producing the same, for example, a method of producing basic particles by an aerosol method, heating and drying, a metal compound is used. Method of spraying, drying and firing an aqueous sol, w / o type or o / w
A method of preparing an / o type emulsion and heating it to remove water and oil has been proposed. However, the hollow particles obtained by these production methods are all significantly inferior in strength,
Also, the particle size distribution tends to widen.
【０００６】[0006]
【発明が解決しようとする課題】前述のとおり、粒子径
分布の狭い重合体粒子は、標準粒子、医薬、診断薬等の
高付加価値分野に使用されて優れた性能を示すにもかか
わらず、高分子であるがゆえに、耐熱性、強靱性、耐光
性、耐摩耗性等において劣り、また生体適合性、粒子表
面の抗原、抗体に対する親和性にも限界がある。従っ
て、これらの欠点を是正する、例えば当該粒子表面を金
属化合物で被覆した複合粒子の開発が望まれている。ま
た、その他の重合体粒子の用途、例えば隠蔽材料、滑
剤、カラム充填剤等の分野においても、従来の重合体粒
子とは異なる性能を有する金属化合物粒子の開発が望ま
れている。As described above, the polymer particles having a narrow particle size distribution have excellent performance when used in high value-added fields such as standard particles, pharmaceuticals and diagnostic agents. Since it is a polymer, it is inferior in heat resistance, toughness, light resistance, abrasion resistance, and the like, and also has biocompatibility and affinity for particle surface antigens and antibodies. Therefore, there is a demand for the development of composite particles in which these defects are corrected, for example, the surface of the particles is coated with a metal compound. Further, also in applications of other polymer particles, for example, in the fields of hiding materials, lubricants, column fillers, etc., development of metal compound particles having performance different from that of conventional polymer particles is desired.
【０００７】一方、光学材料、電子材料等多くの分野に
応用可能なセラミックについて、紫外線遮蔽性、吸着
性、増粘性等を有する組成とそれらの性質を有しない組
成とからなる複合粒子の開発が望まれていた。また、近
年、触媒、マイクロカプセル、化粧品等の分野で使用さ
れてきている中空金属化合物粒子に紫外線遮蔽性、吸着
性等を付与することも望まれている。On the other hand, for ceramics applicable to many fields such as optical materials and electronic materials, the development of composite particles composed of a composition having an ultraviolet shielding property, an adsorptive property, a thickening property and the like, and a composition not having these properties has been developed. Was wanted. Further, it has been desired to impart ultraviolet ray shielding property, adsorptivity, etc. to the hollow metal compound particles which have been used in the fields of catalysts, microcapsules, cosmetics, etc. in recent years.
【０００８】[0008]
【課題を解決するための手段】本発明は、第一に、
（ａ）コアが重合体、（ｂ）シェルがチタニウム化合物
および／またはシリコン化合物からなることを特徴とす
る球状重合体−金属化合物複合粒子を提供するものであ
る。The present invention is, first of all, to
The present invention provides a spherical polymer-metal compound composite particle, wherein (a) the core is a polymer and (b) the shell is a titanium compound and / or a silicon compound.
【０００９】本発明は、第二に、チタニウムアルコキシ
ドおよび／またはシリコンアルコキシドのアルコール溶
液中またはアルコール／水混合溶液中に球状重合体粒子
を均一に分散せしめ、加水分解反応により該球状重合体
粒子の表面に均一なチタニウム化合物および／またはシ
リコン化合物被覆層を設け、さらに必要に応じ、加熱処
理することにより球状重合体−金属化合物複合粒子を得
ることを特徴とする上記複合粒子の製造方法を提供する
ものである。Secondly, according to the present invention, spherical polymer particles are uniformly dispersed in an alcohol solution of titanium alkoxide and / or a silicon alkoxide or an alcohol / water mixed solution, and the spherical polymer particles are hydrolyzed to give a solution. A spherical polymer-metal compound composite particle is obtained by providing a uniform titanium compound and / or silicon compound coating layer on the surface and further heat-treating, if necessary, to provide a method for producing the composite particle. It is a thing.
【００１０】本発明は、第三に、チタニウム化合物およ
び／またはシリコン化合物からなり、内部に空孔を有す
ることを特徴とする球状中空粒子を提供するものであ
る。Thirdly, the present invention provides a spherical hollow particle comprising a titanium compound and / or a silicon compound and having pores inside.
【００１１】本発明は、第四に、上記複合粒子を加熱す
ることによりコアの重合体を分解し、粒子内部に空孔を
持たせ、さらに必要に応じ還元処理することを特徴とす
る上記中空粒子の製造方法を提供するものである。Fourthly, the present invention is characterized in that the polymer of the core is decomposed by heating the above-mentioned composite particles, pores are provided inside the particles, and further reduction treatment is carried out if necessary. A method for producing particles is provided.
【００１２】〔球状重合体−金属化合物複合粒子〕以下
に球状重合体−金属化合物複合粒子について説明する。[Spherical Polymer-Metal Compound Composite Particles] The spherical polymer-metal compound composite particles will be described below.
【００１３】該複合粒子のコアとなる球状重合体粒子と
しては、耐熱性に特に優れたものにする場合、コアの球
状重合体粒子の重合時に、必要に応じて、架橋性単量体
を使用し、架橋させることが好ましい。該球状重合体粒
子を形成する重合体の具体例としては、スチレン、α−
メチルスチレン、ハロゲン化スチレン、ジビニルベンゼ
ン等の不飽和芳香族類；酢酸ビニル、プロピオン酸ビニ
ル等の不飽和エステル類；アクリロニトリル等の不飽和
ニトリル類；メチルアクリレート、エチルアクリレー
ト、エチルメタクリレート、ブチルアクリレート、２−
エチルヘキシルアクリレート、２−エチルヘキシルメタ
クリレート、ラウリルアクリレート、ラウリルメタクリ
レート、エチレングリコールジアクリレート、エチレン
グリコールジメタクリレート等の不飽和カルボン酸アル
キルエステル；その他に、ブタジエン、イソプレン、ア
クリル酸、メタクリル酸、アクリルアミド、メタクリル
アミド、グリシジルアクリレート、グリシジルメタクリ
レート、Ｎ−メチロールアクリルアミド、Ｎ−メチロー
ルメタクリルアミド、２−ヒドロキシエチルアクリレー
ト、アクリルアクリレート、アリルメタクリレート等が
挙げられる。これらは、単独で、または二種以上を混合
して使用してもよい。As the spherical polymer particles serving as the core of the composite particles, in order to have particularly excellent heat resistance, a crosslinkable monomer is used, if necessary, during the polymerization of the spherical polymer particles of the core. However, it is preferable to crosslink. Specific examples of the polymer forming the spherical polymer particles include styrene and α-
Unsaturated aromatics such as methylstyrene, halogenated styrene and divinylbenzene; unsaturated esters such as vinyl acetate and vinyl propionate; unsaturated nitriles such as acrylonitrile; methyl acrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, 2-
Unsaturated carboxylic acid alkyl esters such as ethylhexyl acrylate, 2-ethylhexyl methacrylate, lauryl acrylate, lauryl methacrylate, ethylene glycol diacrylate, and ethylene glycol dimethacrylate; other than these, butadiene, isoprene, acrylic acid, methacrylic acid, acrylamide, methacrylamide, Examples thereof include glycidyl acrylate, glycidyl methacrylate, N-methylol acrylamide, N-methylol methacrylamide, 2-hydroxyethyl acrylate, acrylic acrylate, and allyl methacrylate. You may use these individually or in mixture of 2 or more types.
【００１４】球状重合体粒子の製造は、例えば上記単量
体の乳化重合、懸濁重合、分散重合等により得ることが
できる。また、予め形成した重合体バルクを粉砕するこ
とによっても得ることができる。以上により得られる球
状重合体粒子の粒子径は、通常、０．０５〜５０μｍ、
好ましくは０．０５〜２０μｍ、さらに好ましくは０．
１〜１０μｍである。The spherical polymer particles can be produced by, for example, emulsion polymerization, suspension polymerization, dispersion polymerization or the like of the above monomers. It can also be obtained by crushing a preformed polymer bulk. The particle size of the spherical polymer particles obtained as described above is usually 0.05 to 50 μm,
It is preferably 0.05 to 20 μm, more preferably 0.
It is 1 to 10 μm.
【００１５】一方、上記複合粒子のシェルを形成するの
は、チタニウム化合物および／またはシリコン化合物で
ある。チタニウム化合物は、とくに紫外線遮蔽性に優れ
たものにする場合、ＴｉＯ、ＴｉＯ2等の酸化物が好ま
しい。シリコン化合物は、とくに吸着性、増粘性等に優
れたものにする場合、ＳｉＯ2 が好ましい。On the other hand, it is the titanium compound and / or the silicon compound that form the shell of the composite particles. The titanium compound is preferably an oxide such as TiO or TiO 2 when it is desired to have an excellent ultraviolet shielding property. As the silicon compound, SiO 2 is preferable in order to make the compound particularly excellent in adsorptivity and thickening property.
【００１６】〔球状重合体−金属化合物複合粒子の製造
方法〕以下に、本発明の重合体−金属化合物複合粒子の
製造方法について説明する。上記複合粒子の製造は、ア
ルコール溶液中またはアルコール／水混合溶液中で、チ
タニウムアルコキシドおよび／またはシリコンアルコキ
シドから選ばれる金属アルコキシドを加水分解すること
により得られる金属化合物をコアとなる球状重合体粒子
の表面に均一に被覆せしめ、必要に応じ加熱処理を施こ
すことによりなされる。[Method for Producing Spherical Polymer-Metal Compound Composite Particles] The method for producing the polymer-metal compound composite particles of the present invention will be described below. The production of the composite particles is carried out in a alcohol solution or an alcohol / water mixed solution by hydrolyzing a metal alkoxide selected from titanium alkoxide and / or silicon alkoxide to obtain a spherical polymer particle having a core of a metal compound. The surface is uniformly coated and, if necessary, subjected to heat treatment.
【００１７】上記金属アルコキシドとしては、例えばＴ
ｉ（ＯＣＨ3）4、Ｔｉ（ＯＣ2Ｈ5） 4、Ｔｉ（ｉｓｏ−
ＯＣ3Ｈ7）4、Ｔｉ（ＯＣ4Ｈ9）4等のチタニウムアルコ
キシド、Ｓｉ（ＯＣＨ3）4、Ｓｉ（ＯＣ2Ｈ5）、Ｓｉ
（ｉｓｏ−ＯＣ3Ｈ7）4、Ｓｉ（ｔ−ＯＣ4Ｈ9）4等のシ
リコンアルコキシドが挙げられる。これらの金属アルコ
キシドは単独で、または二種以上を混合して使用するこ
とができる。Examples of the metal alkoxide include T
i (OCH3)Four, Ti (OC2HFive) Four, Ti (iso-
OC3H7)Four, Ti (OCFourH9)FourTitanium Arco etc.
Xide, Si (OCH3)Four, Si (OC2HFive), Si
(Iso-OC3H7)Four, Si (t-OCFourH9)FourEtc.
Examples include recon alkoxide. These metal arco
The oxidants may be used alone or in combination of two or more.
You can
【００１８】上記金属アルコキシドの使用量は０．０１
ミリモル／反応混合液１ｌ以上、さらに好ましくは０．
１ミリモル／反応混合液１ｌ以上、とくに好ましくは１
ミリモル／反応混合液１ｌ以上であり、上限は一般に
１，０００ミリモル／反応混合液１ｌ以下である。な
お、上記反応混合液とは、金属アルコキシドとアルコー
ル溶液またはアルコール／水混合溶液との混合液のこと
をいう。The amount of the above metal alkoxide used is 0.01.
Mmol / reaction mixture 1 liter or more, more preferably 0.1.
1 mmol / l or more of reaction mixture, particularly preferably 1
Mmol / reaction mixture 1 liter or more, and the upper limit is generally 1,000 mmol / reaction mixture 1 liter or less. The reaction mixture means a mixture of a metal alkoxide and an alcohol solution or an alcohol / water mixed solution.
【００１９】金属アルコキシドは、室温でまたは加熱に
より容易に加水分解して、例えばＴｉ（ＯＨ）4、Ｔｉ
Ｏ2、Ｓｉ（ＯＨ）4、ＳｉＯ2のような水酸化物または
酸化物となり、これらがコアとなる球状重合体粒子の表
面に均一に被覆される。Metal alkoxides are easily hydrolyzed at room temperature or by heating, for example Ti (OH) 4 , Ti.
A hydroxide or oxide such as O 2 , Si (OH) 4 and SiO 2 is formed, and these are uniformly coated on the surface of the spherical polymer particle serving as the core.
【００２０】上記複合粒子の製造において溶媒として使
用されるアルコールとしては、例えばメタノール、エタ
ノール、１−プロパノール、２−プロパノール、１−ブ
タノール、２−ブタノール、ｔ−ブタノール等の飽和ア
ルコールが挙げられる。これらのアルコールは単独で、
または二種以上混合しても使用できる。また、アルコー
ルと水との使用割合については、アルコール１ｌ当り水
が１ｌ以下であることが好ましい。Examples of the alcohol used as a solvent in the production of the above composite particles include saturated alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol and t-butanol. These alcohols alone
Alternatively, two or more kinds can be mixed and used. Regarding the usage ratio of alcohol and water, it is preferable that the amount of water is 1 liter or less per liter of alcohol.
【００２１】球状重合体粒子の使用量は、０．００１ｇ
／反応混合液１ｌ以上、さらに好ましくは０．０１ｇ／
反応混合液１ｌ以上、とくに好ましくは０．０５ｇ／反
応混合液１ｌ以上であり、上限は一般に１０００ｇ／反
応混合液１ｌ以下である。The amount of spherical polymer particles used is 0.001 g.
/ Reaction mixture 1 l or more, more preferably 0.01 g /
The reaction mixture is 1 liter or more, particularly preferably 0.05 g / reaction mixture 1 liter or more, and the upper limit is generally 1000 g / reaction mixture 1 liter or less.
【００２２】上記複合粒子の製造方法において重要なの
はアルコール溶液中に、コアとなる球状重合体粒子を均
一に分散させることである。例えば分散状態が悪く、コ
ア粒子となる球状重合体粒子が凝集し、数個〜数百個の
かたまりとなっていれば、その上から金属化合物が被覆
されてしまい、均一な複合粒子が生成されない。また、
生成される複合粒子同士が溶液中で会合、凝集してしま
い、再分散できない場合もある。What is important in the method for producing the composite particles is to uniformly disperse the spherical polymer particles as the core in the alcohol solution. For example, if the dispersion state is poor and the spherical polymer particles that become the core particles aggregate and form a few to several hundreds of agglomerates, the metal compound will be coated from above and uniform composite particles will not be generated. . Also,
In some cases, the produced composite particles are associated with each other and aggregated in the solution, and cannot be redispersed.
【００２３】これらの欠点を改良する為に、アルコール
溶液中にアルコール可溶性高分子および／または界面活
性剤を分散性改良剤として添加することが好ましい。こ
れらの分散性改良剤の使用量は、コアとなる球状重合体
粒子１００重量部に対し、好ましくは１重量部以上、さ
らに好ましくは３〜３００重量部、特に好ましくは５〜
２５０重量部である。In order to improve these drawbacks, it is preferable to add an alcohol-soluble polymer and / or a surfactant as a dispersibility improving agent to the alcohol solution. The amount of these dispersibility improvers used is preferably 1 part by weight or more, more preferably 3 to 300 parts by weight, and particularly preferably 5 to 100 parts by weight of the spherical polymer particles to be the core.
It is 250 parts by weight.
【００２４】アルコール可溶性高分子または界面活性剤
として好ましいものは、ポリビニルピロリドン、ポリビ
ニルアルコール、ポリカルボン酸ソーダ、ヘキサメタリ
ン酸ソーダ、ナフタレンスルホン酸ソーダ、ドデシルベ
ンゼンスルホン酸ソーダ、ドデシル硫酸ソーダ等であ
る。さらに好ましくは、ポリビニルピロリドン、ドデシ
ル硫酸ソーダ等である。これらは単独で、または二種以
上を混合して使用してもよい。Preferred as the alcohol-soluble polymer or surfactant are polyvinylpyrrolidone, polyvinyl alcohol, sodium polycarboxylate, sodium hexametaphosphate, sodium naphthalenesulfonate, sodium dodecylbenzenesulfonate, sodium dodecylsulfate and the like. More preferred are polyvinylpyrrolidone and sodium dodecyl sulfate. You may use these individually or in mixture of 2 or more types.
【００２５】球状重合体−金属化合物複合粒子の生成の
メカニズムは、原則として二種類ある。一つは加水分解
された金属イオンまたは加水分解により生成した錯体が
コアの球状重合体粒子の表面に吸着し、被覆層を形成し
ていくというメカニズムである。もう一つは、非常に小
さな金属化合物微粒子が初期に形成され、ヘテロ凝集に
よって、該金属化合物微粒子がコアである球状重合体粒
子の表面に吸着し、その粒子表面で金属化合物層が成長
していくというメカニズムである。この後者のメカニズ
ムでは、コアである球状重合体粒子の表面に吸着する金
属化合物微粒子の数と粒径により被覆層の厚みをコント
ロールできる。In principle, there are two types of mechanisms for forming spherical polymer-metal compound composite particles. One is a mechanism in which a hydrolyzed metal ion or a complex formed by hydrolysis is adsorbed on the surface of the core spherical polymer particles to form a coating layer. The other is that very small metal compound fine particles are initially formed, and by heteroaggregation, the metal compound fine particles are adsorbed on the surface of the spherical polymer particle as the core, and the metal compound layer grows on the particle surface. It is a mechanism to go. With this latter mechanism, the thickness of the coating layer can be controlled by the number and particle size of the metal compound fine particles adsorbed on the surface of the spherical polymer particles as the core.
【００２６】上記ヘテロ凝集を起こさせるには、コアで
ある球状重合体粒子に電荷を持たせる必要は必ずしもな
いが、プラスまたはマイナスの電荷を持たせることが好
ましい。In order to cause the above-mentioned heteroaggregation, it is not always necessary to give the spherical polymer particles as the core a charge, but it is preferable to give a positive or negative charge.
【００２７】例えば、金属塩の加水分解反応が金属化合
物微粒子の等電点以上のpHで起こる場合、コアとして正
電荷を有する球状重合体粒子を使用すれば効率よく吸着
させることができる。また、金属塩の加水分解反応が金
属化合物微粒子の等電点以下のpHで起こる場合、コアと
して負電荷を有する球状重合体粒子を使用すれば効率よ
く吸着させることができる。For example, when the hydrolysis reaction of the metal salt occurs at a pH higher than the isoelectric point of the metal compound fine particles, spherical polymer particles having a positive charge can be used as the core for efficient adsorption. Further, when the hydrolysis reaction of the metal salt occurs at a pH lower than the isoelectric point of the metal compound fine particles, the spherical polymer particles having a negative charge can be used for the efficient adsorption.
【００２８】シェル組成がチタニウムおよび／またはシ
リコンの水酸化物である場合、加熱処理することによ
り、酸化物に変換できる。例えばシェルがＴｉ（ＯＨ）
4および／またはＳｉ（ＯＨ）4の場合には、不活性ガス
雰囲気下もしくは酵素存在下に、好ましくは５０℃以
上、さらに好ましくは１００℃以上、コアの重合体粒子
の分解温度以下に加熱することにより、ＴｉＯ2および
／またはＳｉＯ2に変換できる。When the shell composition is a hydroxide of titanium and / or silicon, it can be converted into an oxide by heat treatment. For example, the shell is Ti (OH)
In the case of 4 and / or Si (OH) 4 , heating is performed in an inert gas atmosphere or in the presence of an enzyme, preferably at 50 ° C. or higher, more preferably at 100 ° C. or higher, and below the decomposition temperature of the core polymer particles. By doing so, it can be converted into TiO 2 and / or SiO 2 .
【００２９】さらに、上記ＴｉＯ2および／またはＳｉ
Ｏ2の場合は水素ガス雰囲気下に好ましくは１００℃以
上、さらに好ましくは２００℃以上、コアの重合体粒子
の分解温度以下で部分還元することにより、ＴｉＯおよ
び／またはＳｉＯに変換することができる。Further, the above TiO 2 and / or Si
In the case of O 2 , it can be converted to TiO and / or SiO by partial reduction in a hydrogen gas atmosphere, preferably at 100 ° C. or higher, more preferably at 200 ° C. or higher, and below the decomposition temperature of the core polymer particles. .
【００３０】以上により得られる球状重合体−金属化合
物複合粒子の粒子径は０．０７〜５０μｍ、さらに好ま
しくは０．１〜５０μｍ、特に好ましくは０．１〜１０
μｍであり、該複合粒子の粒子径に対するコアとなる球
状重合体粒子の粒径の比は好ましくは０．４〜０．９
９、さらに好ましくは０．５〜０．９９、特に好ましく
は０．６〜０．９９である。The spherical polymer-metal compound composite particles obtained as described above have a particle diameter of 0.07 to 50 μm, more preferably 0.1 to 50 μm, and particularly preferably 0.1 to 10.
μm, and the ratio of the particle size of the core spherical polymer particles to the particle size of the composite particles is preferably 0.4 to 0.9.
9, more preferably 0.5 to 0.99, and particularly preferably 0.6 to 0.99.
【００３１】〔中空粒子の製造方法〕以下にチタニウム
化合物および／またはシリコン化合物からなり、内部に
空孔を有する球状中空粒子の製造方法について述べる。
中空粒子の製造は、前記で得られる球状重合体−金属化
合物複合粒子を、空気または酸素の存在下、コアの重合
体の種類により異なるが好ましくは１００℃以上、さら
に好ましくは４５０℃以上に加熱して、コアの重合体を
分解しガス化させて粒子内部から飛散させ粒子内部に空
孔を形成することによりなされる。さらに、必要に応じ
還元処理して種々の組成の中空粒子を得ることもでき
る。[Method for Producing Hollow Particles] A method for producing spherical hollow particles made of a titanium compound and / or a silicon compound and having pores inside will be described below.
In the production of hollow particles, the spherical polymer-metal compound composite particles obtained above are heated to 100 ° C or higher, more preferably 450 ° C or higher, depending on the type of the core polymer in the presence of air or oxygen. Then, the polymer of the core is decomposed and gasified to be scattered from the inside of the particles to form pores inside the particles. Further, if necessary, reduction treatment can be performed to obtain hollow particles having various compositions.
【００３２】すなわち、球状中空粒子のシェル組成がＴ
ｉＯ2、ＳｉＯ2等である場合、例えば上記中空粒子を水
素ガス雰囲気下に好ましくは１００℃以上、さらに好ま
しくは２００℃以上で部分還元することにより、Ｔｉ
Ｏ、ＳｉＯ等に変換することができる。That is, the shell composition of the spherical hollow particles is T
In the case of iO 2 , SiO 2 or the like, for example, the hollow particles are partially reduced in a hydrogen gas atmosphere at preferably 100 ° C. or higher, more preferably 200 ° C. or higher to obtain Ti.
It can be converted to O, SiO, or the like.
【００３３】上記中空粒子の製造方法において、コアの
球状重合体粒子には特に制約はないが、完全に分解し、
ガス化させやすくするためには、架橋していないことが
好ましい。これにより、低温で短時間に空孔を形成させ
ることができる。例えばコアの球状重合体粒子が架橋さ
れている場合、８００℃以上、さらに好ましくは１１０
０℃以上で加熱する必要がある。従って、コアの重合体
の単量体成分としては、加熱により分解する点で、スチ
レン、アクリロニトリル、酢酸ビニル等の単量体を主成
分とし、架橋されていないものが好ましい。In the above method for producing hollow particles, the spherical polymer particles of the core are not particularly limited, but they are completely decomposed,
In order to facilitate gasification, it is preferably not crosslinked. As a result, it is possible to form pores at a low temperature in a short time. For example, when the spherical polymer particles of the core are crosslinked, the temperature is 800 ° C or higher, more preferably 110 ° C or higher.
It is necessary to heat above 0 ° C. Therefore, as the monomer component of the polymer of the core, it is preferable to use a monomer such as styrene, acrylonitrile or vinyl acetate as a main component and not be crosslinked, from the viewpoint of being decomposed by heating.
【００３４】なお、加熱温度が１２００℃以上の場合
は、中空粒子の表面にクラックが入りやすくなり、ま
た、昇温率および冷却率が急激である場合、シェルが崩
壊しやすくなる。このため、昇温率としては３０℃／分
以下、冷却率としては２０℃／分以下が好ましい。When the heating temperature is 1200 ° C. or higher, cracks are easily formed on the surface of the hollow particles, and when the heating rate and the cooling rate are rapid, the shell tends to collapse. Therefore, the rate of temperature rise is preferably 30 ° C./min or less, and the rate of cooling is preferably 20 ° C./min or less.
【００３５】上記製造方法により、単分散で均一なシェ
ル層を有する中空粒子を得ることができ、しかも粒子
径、空孔径を自由にコントロールすることができる。By the above production method, hollow particles having a monodisperse and uniform shell layer can be obtained, and the particle diameter and the pore diameter can be freely controlled.
【００３６】以上により得られる中空粒子の粒子径は通
常、０．０４〜５０μｍ、好ましくは０．０４〜４０μ
ｍ、さらに好ましくは０．１〜１０μｍ、特に好ましく
は０．２〜１μｍである。また、粒子外径に対する内径
の比は、通常、０．３〜０．９９、好ましくは０．５〜
０．９９、特に好ましくは０．６〜０．９９である。The particle size of the hollow particles obtained as described above is usually 0.04 to 50 μm, preferably 0.04 to 40 μm.
m, more preferably 0.1 to 10 μm, and particularly preferably 0.2 to 1 μm. The ratio of the inner diameter to the outer diameter of the particles is usually 0.3 to 0.99, and preferably 0.5 to 0.99.
0.99, particularly preferably 0.6 to 0.99.
【００３７】[0037]
【実施例】以下に実施例により本発明を詳細に説明する
が、本発明はこれらにより限定されるものではない。The present invention is described in detail below with reference to examples, but the present invention is not limited to these.
【００３８】 合成例（コアとなる球状重合体粒子の製造） 例−１ １ｌ重合用４つ口フラスコに蒸留水５７４ｇ、過硫酸カ
リウム１．０ｇおよびドデシル硫酸ナトリウム０．３０
ｇを入れ、１０分間攪拌し、それらを完全溶解させた。
次いで、スチレンを１００ｇ添加し、Ｎ2ガスをパージ
しながら５分間攪拌した。その後フラスコをウォーター
バスに入れ８０℃で４時間反応させ、次いで室温まで冷
却した。冷却後、濾紙を使用し、凝集物を除去した。得
られたスチレン重合体からなる球状重合体粒子分散液の
全固形分は１４．７重量％であった。この球状重合体粒
子の平均粒子径は、０．４２μｍであった。この球状重
合体粒子分散液の濃度を５ｇ／ｌとなるように蒸留水を
加え調製した。Synthesis Example (Production of Spherical Polymer Particles Used as Core) Example-1 574 g of distilled water, 1.0 g of potassium persulfate and 0.30 sodium dodecyl sulfate were placed in a 4-neck flask for 1 l polymerization.
g was added and stirred for 10 minutes to completely dissolve them.
Next, 100 g of styrene was added, and the mixture was stirred for 5 minutes while purging with N 2 gas. After that, the flask was put in a water bath and reacted at 80 ° C. for 4 hours, and then cooled to room temperature. After cooling, filter paper was used to remove agglomerates. The total solid content of the obtained spherical polymer particle dispersion liquid comprising the styrene polymer was 14.7% by weight. The average particle size of the spherical polymer particles was 0.42 μm. Distilled water was added so that the concentration of the spherical polymer particle dispersion liquid would be 5 g / l.
【００３９】例−２ １ｌ重合用４つ口フラスコに蒸留水５７６ｇ、Ｔｒｉｔ
ｏｎ Ｘ−１００（ロームアンドハース社製、非イオン
性界面活性剤）０．５ｇおよび２，２′−アゾビス（２
−メチルプロピオニトリル）（ＡＩＢＮ．アルドリッチ
社製）１．０ｇを入れ１０分間攪拌し、完全にＴｒｉｔ
ｏｎ Ｘ−１００、ＡＩＢＮを溶解させた。次いで、ス
チレン１００ｇを添加し、Ｎ2ガスをパージしながら５
分間攪拌した。その後、このフラスコをウォーターバス
に入れ７０℃で１２時間反応させ、次いで室温まで冷却
した。冷却後、濾紙を使用し、凝集物を除去した。得ら
れたスチレン重合体粒子からなる球状重合体粒子分散液
の全固形分は１４．２重量％であった。この球状重合体
粒子の平均粒子径は、０．１７μｍであった。この球状
重合体粒子分散液の濃度を５ｇ／ｌとなるように蒸留水
を加え調製した。Example-2 576 g of distilled water and Trit in a four-necked flask for 1 l polymerization.
on X-100 (Rohm and Haas Company, nonionic surfactant) 0.5 g and 2,2'-azobis (2
-Methylpropionitrile) (AIBN. Aldrich) 1.0 g was added and stirred for 10 minutes to completely complete Trit.
on X-100, AIBN was dissolved. Next, 100 g of styrene was added, and while purging with N 2 gas, 5
Stir for minutes. Then, this flask was put in a water bath and reacted at 70 ° C. for 12 hours, and then cooled to room temperature. After cooling, filter paper was used to remove agglomerates. The total solid content of the obtained spherical polymer particle dispersion liquid comprising styrene polymer particles was 14.2% by weight. The average particle size of the spherical polymer particles was 0.17 μm. Distilled water was added so that the concentration of the spherical polymer particle dispersion liquid would be 5 g / l.
【００４０】例−３ １ｌ重合用４つ口フラスコに例−２で得られた球状重合
体粒子分散液７０ｇ、蒸留水９２９ｇおよび過硫酸ナト
リウム１．０ｇを入れ１０分間攪拌し、過硫酸ナトリウ
ムを溶解させた。次いでスチレン９０ｇおよびジビニル
ベンゼン１０ｇを添加し、Ｎ2ガスをパージしながら５
分間攪拌した。その後フラスコをウォーターバスに入れ
７０℃で１２時間反応させ、次いで室温まで冷却した。
冷却後、濾紙を使用し、凝集物を除去した。得られたス
チレン／ジビニルベンゼン共重合体からなる球状重合体
粒子分散液の全固形分は９．６重量％、この球状重合体
粒子の平均粒子径は、０．３５μｍであった。この球状
重合体粒子分散液の濃度を５ｇ／ｌとなるように蒸留水
を加え調製した。Example-3 70 g of the spherical polymer particle dispersion obtained in Example-2, 929 g of distilled water and 1.0 g of sodium persulfate were placed in a 1-liter four-necked flask for polymerization and stirred for 10 minutes to remove sodium persulfate. Dissolved. Next, 90 g of styrene and 10 g of divinylbenzene were added, and while purging with N 2 gas, 5
Stir for minutes. After that, the flask was put in a water bath and reacted at 70 ° C. for 12 hours, and then cooled to room temperature.
After cooling, filter paper was used to remove agglomerates. The total solid content of the obtained spherical polymer particle dispersion liquid comprising the styrene / divinylbenzene copolymer was 9.6% by weight, and the average particle diameter of the spherical polymer particles was 0.35 μm. Distilled water was added so that the concentration of the spherical polymer particle dispersion liquid would be 5 g / l.
【００４１】例−４ 日本合成ゴム（株）社製、ＳＴＡＤＥＸ ＳＣ−３１０
−Ｓ（球状スチレン重合体粒子）を使用した。平均粒子
径は３．１μｍであった。この球状重合体粒子分散液の
濃度を５ｇ／ｌとなるように蒸留水を加えて調製した。Example-4 STADEX SC-310 manufactured by Nippon Synthetic Rubber Co., Ltd.
-S (spherical styrene polymer particles) was used. The average particle size was 3.1 μm. It was prepared by adding distilled water so that the concentration of the spherical polymer particle dispersion was 5 g / l.
【００４２】例−５ ジビニルベンゼン、アゾ系重合開始剤［Ｖ−５９、和光
純薬（株）製］、ｔ−ブチルハイドロキノン、ラウリル
硫酸ナトリウムおよび水を重量比で１００：１０：０．
５：０．５：２の割合で混合・攪拌して乳化し、粒径が
０．３〜２０μｍである重合性単量体の水分散液を得
た。平均粒径３μｍのポリスチレン単分散液（固形分１
８．１重量％）１４．３部を水１１３．３部に添加し分
散させ、さらにこのシード粒子の水分散体にポリビニル
アルコールの５重量％水溶液６０部を加えて、８３℃に
昇温した。このシード粒子の水分散体に上記重合性単量
体の水分散液およびポリビニルアルコールの１重量％水
溶液を６時間かけて滴下し平均粒径２０μｍの単分散重
合体粒子を得た。この球状重合体粒子分散液の濃度を５
ｇ／ｌとなるように蒸留水を加えて調製した。Example 5 Divinylbenzene, an azo polymerization initiator [V-59, manufactured by Wako Pure Chemical Industries, Ltd.], t-butylhydroquinone, sodium lauryl sulfate and water in a weight ratio of 100: 10: 0.
The mixture was mixed and stirred at a ratio of 5: 0.5: 2 to emulsify to obtain an aqueous dispersion of a polymerizable monomer having a particle size of 0.3 to 20 μm. Polystyrene monodisperse liquid with an average particle size of 3 μm (solid content 1
8.1% by weight) was added to 113.3 parts of water to disperse the mixture, and 60 parts of a 5% by weight aqueous solution of polyvinyl alcohol was added to the aqueous dispersion of the seed particles, and the temperature was raised to 83 ° C. . An aqueous dispersion of the polymerizable monomer and a 1% by weight aqueous solution of polyvinyl alcohol were added dropwise to the aqueous dispersion of the seed particles over 6 hours to obtain monodisperse polymer particles having an average particle diameter of 20 μm. The concentration of this spherical polymer particle dispersion is 5
It was prepared by adding distilled water so as to be g / l.
【００４３】実施例１ 例−１で得られた球状重合体粒子分散液（濃度５ｇ／
ｌ）６０ml、ポリビニルピロリドン（Ｍｗ、３６万）
０．６ｇ、チタン酸テトラ−ｎ−ブチル（モノマー）１
０ｇおよび水／エタノール２ｌをセパラブルフラスコに
入れた。この反応混合液を、ホモジナイザーでよく攪拌
した後、８０℃で４時間加熱し加水分解させた。その
後、室温まで冷却し、遠心分離により複合粒子を沈降さ
せ、上澄溶液を分離後、蒸留水を加え、ホモジナイザー
で完全に粒子を分散させた後、複合粒子を分離するとい
う洗浄工程を５回繰り返した。その後、得られた複合粒
子を常温で乾燥した。得られた複合粒子を電子顕微鏡に
て観察したところ、平均粒子径は０．４６μｍ、粒子径
に対するコアの粒径の比が０．９１の完全に粒子表面が
均一な層で被覆された球状の複合粒子であった。この複
合粒子を赤外吸収スペクトル、Ｘ線回折、熱重量分析、
元素分析、電気泳動装置等にて分析したところ、コアが
ポリスチレン重合体、シェルがＴｉＯ2からなる複合粒
子であることが確認された。この複合粒子の電子顕微鏡
写真を図１に示す。Example 1 Spherical polymer particle dispersion liquid obtained in Example 1 (concentration 5 g /
l) 60 ml, polyvinylpyrrolidone (Mw, 360,000)
0.6 g, tetra-n-butyl titanate (monomer) 1
0 g and 2 l of water / ethanol were placed in a separable flask. The reaction mixture was stirred well with a homogenizer and then heated at 80 ° C. for 4 hours for hydrolysis. Then, the mixture is cooled to room temperature, the composite particles are settled by centrifugation, the supernatant solution is separated, distilled water is added, the particles are completely dispersed by a homogenizer, and then the washing step of separating the composite particles is performed five times. I repeated. Then, the obtained composite particles were dried at room temperature. When the obtained composite particles were observed with an electron microscope, the average particle size was 0.46 μm, and the particle size ratio of the core to the particle size was 0.91. It was a composite particle. Infrared absorption spectrum, X-ray diffraction, thermogravimetric analysis,
When analyzed by elemental analysis and an electrophoresis apparatus, it was confirmed that the core was a polystyrene polymer and the shell was a composite particle composed of TiO 2 . An electron micrograph of this composite particle is shown in FIG.
【００４４】なお、実施例１の反応系は以下の成分割合
となる。 例−１のスチレン重合体 １．５ｇ／反応混合液１ｌ、 チタン酸テトラ−ｎ−ブチル（モノマー） ５ｇ／反応混合液１ｌ、 ポリビニルピロリドン（Ｍｗ、３６万） ０．３ｇ／反応混合液１ｌ、 水／エタノール ３（体積％）。The reaction system of Example 1 has the following component ratios. Styrene polymer of Example-1 1.5 g / reaction mixture 1 l, tetra-n-butyl titanate (monomer) 5 g / reaction mixture 1 l, polyvinylpyrrolidone (Mw, 360,000) 0.3 g / reaction mixture 1 l, Water / ethanol 3 (% by volume).
【００４５】実施例２〜１５ 基本的には実施例１と同様の方法であるが、加水分解さ
せる時に使用する成分および製造条件を表１〜３に示す
ように変えたものを実施例２〜１５とした。結果として
得られた複合粒子の形状、組成等について実施例１と併
せて表１〜３に示す。Examples 2 to 15 Basically the same method as in Example 1, except that the components used during hydrolysis and the production conditions were changed as shown in Tables 1 to 3. It was set to 15. The shapes and compositions of the resulting composite particles are shown in Tables 1 to 3 together with Example 1.
【００４６】[0046]
【表１】 [Table 1]
【００４７】[0047]
【表２】 [Table 2]
【００４８】[0048]
【表３】 [Table 3]
【００４９】実施例１６ 実施例４で得られたコアがスチレン／ジビニルベンゼン
共重合体、シェルがＴｉＯの複合粒子５ｇを水素ガス雰
囲気下で室温から３００℃まで１０℃／分の条件で昇温
し、３００℃で３時間ホールドした。その後１０℃／分
の割合で室温まで冷却した。得られた複合粒子の平均粒
子径は０．４２μｍ、粒子外径に対するコア粒子径の比
が０．８６であった。この複合粒子を実施例１と同様に
して分析したところ、コアがスチレン／ジビニルベンゼ
ン共重合体であり、シェルがＴｉＯであった。Example 16 5 g of composite particles having a core of styrene / divinylbenzene copolymer and a shell of TiO 2 obtained in Example 4 were heated from room temperature to 300 ° C. under the condition of 10 ° C./min in a hydrogen gas atmosphere. Then, it was held at 300 ° C. for 3 hours. Then, it was cooled to room temperature at a rate of 10 ° C./min. The average particle size of the obtained composite particles was 0.42 μm, and the ratio of the core particle size to the particle outer diameter was 0.86. When the composite particles were analyzed in the same manner as in Example 1, the core was a styrene / divinylbenzene copolymer and the shell was TiO 2.
【００５０】実施例１７〜２１ 基本的には実施例１６と同様の方法であるが、使用する
複合粒子および焼成条件を表４に示すように変えたもの
を実施例１７〜２１とした。結果として得られた複合粒
子の形状、組成等について、実施例１６と併せて表４に
示した。Examples 17 to 21 Basically the same method as in Example 16, except that the composite particles used and the firing conditions were changed as shown in Table 4 were Examples 17 to 21. The shape, composition, etc. of the resulting composite particles are shown in Table 4 together with Example 16.
【００５１】[0051]
【表４】 [Table 4]
【００５２】実施例２２ 実施例１で得られたコアがスチレン重合体、シェルがＴ
ｉＯ2の複合粒子５ｇを空気雰囲気下で室温から６００
℃まで１０℃／分の条件で昇温し、６００℃で３時間ホ
ールドした。その後１０℃／分の割合で室温まで冷却し
た。得られた中空粒子を電子顕微鏡にて観察したとこ
ろ、平均粒子径は０．４２μｍ、粒子外径に対する内部
空孔径の比は０．８６であった。この中空粒子を赤外吸
収スペクトル、Ｘ線回折、元素分析、電気泳動装置等に
て分析したところ、コアが空孔、シェルがＴｉＯ2から
なる中空粒子であることが確認された。この複合粒子の
電子顕微鏡写真を図２に示す。Example 22 The core obtained in Example 1 was a styrene polymer, and the shell was T.
5 g of composite particles of iO 2 was heated from room temperature to 600 in an air atmosphere.
The temperature was raised to 10 ° C./min and held at 600 ° C. for 3 hours. Then, it was cooled to room temperature at a rate of 10 ° C./min. When the obtained hollow particles were observed with an electron microscope, the average particle diameter was 0.42 μm, and the ratio of the inner pore diameter to the particle outer diameter was 0.86. When the hollow particles were analyzed by infrared absorption spectrum, X-ray diffraction, elemental analysis, electrophoresis, etc., it was confirmed that the hollow particles were hollow particles having a core of TiO 2 and a shell of TiO 2 . An electron micrograph of this composite particle is shown in FIG.
【００５３】実施例２３〜３１ 基本的には実施例２２と同様の方法であるが、使用する
複合粒子および製造条件を表５および表６に示すように
変えたものを実施例２３〜３１とした。結果として得ら
れた中空粒子の形状、組成等について、実施例２２と併
せて表５および表６に示す。Examples 23 to 31 Basically, the same method as in Example 22 was used, except that the composite particles used and the production conditions were changed as shown in Tables 5 and 6 to obtain Examples 23 to 31. did. The shape, composition, etc. of the resulting hollow particles are shown in Tables 5 and 6 together with Example 22.
【００５４】[0054]
【表５】 [Table 5]
【００５５】[0055]
【表６】 [Table 6]
【００５６】実施例３２ 実施例２２で得られたＴｉＯ2粒子２ｇを水素ガス雰囲
気下で室温から３００℃まで１０℃／分の条件で昇温
し、３００℃で１時間ホールドした。その後１０℃／分
の割合で室温まで冷却した。得られた中空粒子の平均粒
子径は０．４０μｍ、粒子径に対する内部空孔径の比が
０．８８であった。この中空粒子を赤外吸収スペクト
ル、Ｘ線回折、元素分析等にて分析したところ、コアが
空孔、シェルがＴｉＯであった。Example 32 2 g of the TiO 2 particles obtained in Example 22 was heated from room temperature to 300 ° C. under the conditions of 10 ° C./min in a hydrogen gas atmosphere and held at 300 ° C. for 1 hour. Then, it was cooled to room temperature at a rate of 10 ° C./min. The obtained hollow particles had an average particle size of 0.40 μm and a ratio of internal pore size to particle size of 0.88. When the hollow particles were analyzed by infrared absorption spectrum, X-ray diffraction, elemental analysis and the like, the core was void and the shell was TiO 2.
【００５７】実施例３３〜３５ 基本的には実施例３２と同様の方法であるが、使用する
中空粒子および製造条件を表７に示すように変えたもの
を実施例３３〜３５とした。結果として得られた中空粒
子の形状、組成等について、実施例３２と併せて表７に
示す。Examples 33 to 35 Basically, the same method as in Example 32 was used, except that the hollow particles used and the production conditions were changed as shown in Table 7 to obtain Examples 33 to 35. The shape, composition, etc. of the resulting hollow particles are shown in Table 7 together with that of Example 32.
【００５８】[0058]
【表７】 [Table 7]
【００５９】[0059]
【発明の効果】本発明は、各用途で広く使用されている
複合粒子、中空粒子とそれらの製造方法に関し、高強
度、高耐熱性であり、高機能を発現することができ、化
粧品、電子材料、半導体材料、塗料、研磨剤、スペーサ
ー、コーティング剤、光学材料、触媒、充填剤、医薬、
診断薬、トナー、樹脂改質剤、インク、吸着剤、耐紫外
線材料等に好適に使用される複合粒子とその製造方法、
並びに隠蔽率、吸着率、比表面積等が大きく、光学材
料、マイクロカプセル材料、隠蔽材料、化粧品、カラム
充填剤、触媒等に好適に使用される中空粒子とその製造
方法に関する。INDUSTRIAL APPLICABILITY The present invention relates to composite particles and hollow particles which are widely used in various applications, and a method for producing them, which has high strength, high heat resistance, can exhibit high functions, and can be used in cosmetics and electronic products. Materials, semiconductor materials, paints, abrasives, spacers, coating agents, optical materials, catalysts, fillers, pharmaceuticals,
Composite particles suitably used for diagnostic agents, toners, resin modifiers, inks, adsorbents, UV resistant materials, etc., and a method for producing the same,
The present invention also relates to hollow particles having a large hiding rate, adsorption rate, specific surface area and the like, which are suitably used for optical materials, microcapsule materials, hiding materials, cosmetics, column fillers, catalysts and the like, and a method for producing the same.
【図１】実施例１で得られた球状スチレン重合体（コ
ア）／ＴｉＯ2複合粒子構造を示す電子顕微鏡写真であ
る。図中の目盛りは０．５μｍを示す。FIG. 1 is an electron micrograph showing the structure of a spherical styrene polymer (core) / TiO 2 composite particle obtained in Example 1. The scale in the figure indicates 0.5 μm.
【図２】実施例２２で得られた中空ＴｉＯ2粒子構造を
示す電子顕微鏡写真である。図中の目盛りは０．５μｍ
を示す。2 is an electron micrograph showing the structure of hollow TiO 2 particles obtained in Example 22. FIG. The scale in the figure is 0.5 μm
Indicates.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０４Ｂ 38/06 Ｊ ─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 5 Identification code Office reference number FI technical display location C04B 38/06 J
Claims (4)
タニウム化合物および／またはシリコン化合物からなる
ことを特徴とする球状重合体−金属化合物複合粒子。1. Spherical polymer-metal compound composite particles, wherein (a) the core is a polymer and (b) the shell is a titanium compound and / or a silicon compound.
シリコンアルコキシドのアルコール溶液中またはアルコ
ール／水混合溶液中に球状重合体粒子を均一に分散せし
め、加水分解反応により該球状重合体粒子の表面に均一
なチタニウム化合物またはシリコン化合物被覆層を設
け、さらに必要に応じ、加熱処理することを特徴とする
請求項１記載の複合粒子の製造方法。2. Spherical polymer particles are uniformly dispersed in an alcohol solution of a titanium alkoxide and / or a silicon alkoxide or in an alcohol / water mixed solution, and a titanium compound is uniformly formed on the surface of the spherical polymer particles by a hydrolysis reaction. Alternatively, the method for producing composite particles according to claim 1, wherein a silicon compound coating layer is provided, and if necessary, heat treatment is performed.
ン化合物からなり、内部に空孔を有することを特徴とす
る球状中空粒子。3. A spherical hollow particle comprising a titanium compound and / or a silicon compound and having pores inside.
によりコアの重合体を分解し、粒子内部に空孔を持た
せ、さらに必要に応じ、還元処理することを特徴とする
請求項３記載の中空粒子の製造方法。4. The polymer of the core is decomposed by heating the composite particle according to claim 1, to give pores inside the particle, and further, if necessary, reduction treatment is performed. A method for producing the hollow particles described above.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30259292A JP3265653B2 (en) | 1992-11-12 | 1992-11-12 | Composite particles, hollow particles and their production method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30259292A JP3265653B2 (en) | 1992-11-12 | 1992-11-12 | Composite particles, hollow particles and their production method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06142491A true JPH06142491A (en) | 1994-05-24 |
| JP3265653B2 JP3265653B2 (en) | 2002-03-11 |
Family
ID=17910835
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30259292A Expired - Lifetime JP3265653B2 (en) | 1992-11-12 | 1992-11-12 | Composite particles, hollow particles and their production method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3265653B2 (en) |
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