JP3221153B2 - Method for supporting fine particles - Google Patents
Method for supporting fine particlesInfo
- Publication number
- JP3221153B2 JP3221153B2 JP13569193A JP13569193A JP3221153B2 JP 3221153 B2 JP3221153 B2 JP 3221153B2 JP 13569193 A JP13569193 A JP 13569193A JP 13569193 A JP13569193 A JP 13569193A JP 3221153 B2 JP3221153 B2 JP 3221153B2
- Authority
- JP
- Japan
- Prior art keywords
- fine particles
- dispersion
- stirring
- zirconia
- aqueous
- 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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Description
【０００１】[0001]
【産業上の利用分野】本発明は無機カルコゲナイド物の
微粒子を種々の担体に担持させる方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for supporting fine particles of an inorganic chalcogenide on various carriers.
【０００２】[0002]
【従来の技術】従来の酸化物、カルコゲナイド物微粒子
の吸着方法としては、界面活性剤を使用して吸着担持す
る方法（特開平２−４１３７０号公報）、表面に水分子
を吸着させた担体と金属アルコキシドを有機溶媒中に分
散させて加水分解を行ない化学吸着により担持させる方
法（特開平２−２５３８３７号公報）、樹脂粉体に微粒
子を混合摩砕等により静電吸着する方法（特開昭６３−
１８８０８１号公報）、酸化性ガス中で生成した酸化物
微粒子を高速気体に同伴させて基体表面に吹き付けた後
めっき処理する複合めっき法（特開平１−１８８６９７
号公報）等が挙げられる。2. Description of the Related Art Conventional methods for adsorbing oxide and chalcogenide fine particles include a method of adsorbing and supporting the particles by using a surfactant (Japanese Patent Application Laid-Open No. 2-41370) and a method of adsorbing water molecules on the surface. A method of dispersing a metal alkoxide in an organic solvent, carrying out hydrolysis and supporting the dispersion by chemical adsorption (JP-A-2-253837), and a method of electrostatically adsorbing fine particles to a resin powder by mixing and grinding (Japanese Patent Application Laid-Open No. 63-
No. 188081), a composite plating method in which fine particles of oxide generated in an oxidizing gas are sprayed on the surface of a substrate while being accompanied by a high-speed gas, followed by plating (see JP-A-1-18897).
Publication).
【０００３】[0003]
【発明が解決しようとする課題】しかし上記の方法では
次のような問題が挙げられる。まず界面活性剤等を使用
する場合には界面活性剤等に起因する不純物の混入の恐
れがある。あるいは各種微粒子が表面を界面活性剤等に
より被覆されることによりその活性が低下するのを免れ
ない。静電吸着方法の場合、担体は静電気を帯びるもの
あるいは混合摩砕操作で変質しないものに限定される。
また複合めっき法に於ては特別な、もしくは高価な装置
を必要とし、複雑な形状の基体に均一に吸着させること
が困難である。更に溶媒中で微粒子の形成を行なう場合
には粒径制御が困難で微粒子の粒度分布はかなりの幅を
もっており微粒子担持体比表面積等の担持挙動に再現性
を期待できない等の問題点がある。However, the above method has the following problems. First, when a surfactant or the like is used, there is a possibility that impurities due to the surfactant or the like may be mixed. Alternatively, it is inevitable that the activity is reduced by coating the surface of various fine particles with a surfactant or the like. In the case of the electrostatic adsorption method, the carrier is limited to a carrier that is charged with static electricity or a carrier that is not deteriorated by the mixing and grinding operation.
In addition, the composite plating method requires a special or expensive device, and it is difficult to uniformly adsorb the substrate on a substrate having a complicated shape. Further, in the case of forming fine particles in a solvent, there is a problem that it is difficult to control the particle size, and the particle size distribution of the fine particles has a considerable width, and reproducibility cannot be expected in the carrying behavior such as the specific surface area of the fine particle carrier.
【０００４】[0004]
【課題を解決するための手段】本発明は以上の問題点を
解決するためのものであって、すなわち水と相溶しない
非水溶媒中に無機カルコゲナイト物の微粒子を分散させ
た分散液を担体と接触させて上記微粒子を吸着せしめる
ことを特徴とする微粒子の担持方法である。DISCLOSURE OF THE INVENTION The present invention has been made to solve the above-mentioned problems, that is, the present invention relates to a method for dispersing fine particles of an inorganic chalcogenite in a non-aqueous solvent insoluble in water. A method for supporting fine particles, wherein the fine particles are adsorbed by contacting the fine particles.
【０００５】本発明に使用される無機カルコゲナイト物
の微粒子としては、以下に示す酸化物、硫化物、セレン
化物及びテルル化物が挙げられる。例えば長周期型周期
律表においてラジウムを除く第２A亜族、第３A亜族、第
４A亜族、第５A亜族、第６A亜族、第７A亜族、第８族、
第１B亜族、第２B亜族、ホウ素を除く第３B亜族、炭素
を除く第４B亜族、窒素を除く第５B亜族、及びテルルを
含む元素のうち、少なくとも１種類以上の成分を含む酸
化物、硫化物、セレン化物及びテルル化物等の微粒子が
挙げられる。好ましい例としてはマグネシア、シリカ、
アルミナ、ジルコニア、チタニア、酸化鉄、酸化コバル
ト、酸化亜鉛、酸化インジウム、酸化錫、硫化ニッケル
及び硫化銅等の微粒子が挙げられる。The fine particles of the inorganic chalcogenite used in the present invention include the following oxides, sulfides, selenides and tellurides. For example, in the long period type periodic table, except for radium, 2A subgroup, 3A subgroup, 4A subgroup, 5A subgroup, 6A subgroup, 7A subgroup, 8th group,
Sub-group 1B, sub-group 2B, sub-group 3B excluding boron, sub-group 4B excluding carbon, sub-group 5B excluding nitrogen, and at least one or more of the elements containing tellurium Fine particles such as oxides, sulfides, selenides and tellurides. Preferred examples are magnesia, silica,
Fine particles such as alumina, zirconia, titania, iron oxide, cobalt oxide, zinc oxide, indium oxide, tin oxide, nickel sulfide, and copper sulfide are exemplified.
【０００６】本発明における分散液としての非水溶媒
は、特に限定されないが、例えば芳香族溶媒としてキシ
レン、トルエン、ベンゼン等、塩素系溶媒として四塩化
炭素、クロロホルム、また炭化水素系溶媒としてシクロ
ヘキサン、ノルマルヘキサン等の各種非水溶媒が挙げら
れる。The non-aqueous solvent used as the dispersion in the present invention is not particularly limited. For example, xylene, toluene, benzene or the like as an aromatic solvent, carbon tetrachloride or chloroform as a chlorine-based solvent, cyclohexane as a hydrocarbon-based solvent, or the like. Various non-aqueous solvents such as normal hexane are exemplified.
【０００７】本発明に使用される水と相分離する非水液
体に分散した無機カルコゲナイト物の微粒子を製造する
には種々の方法が採用される。例えば、真空中において
ガス状態の金属あるいは金属化合物を酸素等と反応させ
（気相反応法）、得られた微粒子を非水溶媒に分散させ
る方法、また金属アルコキシドを非水液体に溶解させ、
これに水を添加して加水分解させる方法等が実施可能で
ある。Various methods are employed for producing the fine particles of the inorganic chalcogenite dispersed in the non-aqueous liquid which is phase-separated from water used in the present invention. For example, a metal or metal compound in a gaseous state is reacted with oxygen or the like in a vacuum (gas phase reaction method), and the obtained fine particles are dispersed in a non-aqueous solvent. Alternatively, a metal alkoxide is dissolved in a non-aqueous liquid,
A method in which water is added to the mixture and the mixture is hydrolyzed can be used.
【０００８】特に好ましい方法として本発明者の中の１
人の発明にかかわる次の方法が挙げられる（特願平３ー
３５８５４８号）。すなわち金属微粒子及び／又は金属
化合物微粒子の水分散液を界面活性剤の存在下、水と相
分離する非水液体を接触させ、その接触前及び／又は接
触後に、水溶性無機酸塩及び／又は水溶性有機酸塩を添
加し、微粒子を水分散液より非水液体中に移動させ、こ
の二相混合物より非水分散液を単離することができる。
本法によれば簡便な操作で特殊な装置を必要とせず、大
量又は高濃度の酸化物、硫化物、セレン化物及びテルル
化物微粒子の非水分散液を容易に調製することができ
る。[0008] As a particularly preferred method, one of the present inventors
The following method relating to human invention is disclosed (Japanese Patent Application No. 3-358548). That is, in the presence of a surfactant, an aqueous dispersion of metal fine particles and / or metal compound fine particles is brought into contact with a non-aqueous liquid that separates from water, and before and / or after the contact, a water-soluble inorganic acid salt and / or A water-soluble organic acid salt is added to move the fine particles from the aqueous dispersion into the non-aqueous liquid, and the non-aqueous dispersion can be isolated from the two-phase mixture.
According to this method, a large amount or high concentration of non-aqueous dispersion of oxide, sulfide, selenide, and telluride fine particles can be easily prepared by a simple operation without requiring a special apparatus.
【０００９】このようにして得られた非水分散液に分散
する微粒子の粒径は用いる水分散液中の粒径と実質的に
同様であり、１ｎｍ〜１μｍの範囲である。そして均一
に分散される微粒子濃度は約０.０５〜５００ｍｍｏｌ
／ｌである。The particle size of the fine particles dispersed in the non-aqueous dispersion thus obtained is substantially the same as the particle size in the aqueous dispersion used, and is in the range of 1 nm to 1 μm. The concentration of fine particles dispersed uniformly is about 0.05 to 500 mmol.
/ L.
【００１０】本発明に使用される担体としては、特に限
定されないが、溶媒との接触により変質あるいは溶媒に
溶解しないものが好ましく、例えば炭素、金属、合金類
等、無機化合物としてはアルミナ、シリカ、チタニア、
ジルコニア、粘土鉱物のような複合酸化物、ゼオライ
ト、ガラス等、また有機化合物としてセルロース、でん
ぷん、繊維等の天然高分子物質、ポリスチレン、ナイロ
ン、ポリアセタール等の合成高分子物質が挙げられる。
非水溶媒を用いるので水溶性物質、例えば溶性でんぷ
ん、ヒドロキシプロピルセルロース等を担体として使用
することもできる。坦体の形状としては膜状、ゲル状、
粉体状、ウィスカー状、ファイバー状、ハニカム状等が
挙げられ、多孔体あるいは非多孔体のいずれであっても
よい。これらの1種あるいは2種以上の混合物、複合物及
び成型体を坦体とすることができる。[0010] The carrier used in the present invention is not particularly limited, but those which are altered or do not dissolve in the solvent upon contact with a solvent are preferable. Examples of inorganic compounds such as carbon, metals and alloys include alumina, silica and the like. Titania,
Examples thereof include complex oxides such as zirconia and clay minerals, zeolites, glass, and the like, and natural polymers such as cellulose, starch, and fiber, and synthetic polymer such as polystyrene, nylon, and polyacetal as organic compounds.
Since a non-aqueous solvent is used, a water-soluble substance such as soluble starch and hydroxypropylcellulose can also be used as a carrier. The shape of the carrier is film-like, gel-like,
Examples thereof include powder, whisker, fiber, and honeycomb, and may be either porous or non-porous. One or a mixture of two or more of these, a composite, and a molded article can be used as a carrier.
【００１１】本発明における無機カルコゲナイド物の微
粒子非水分散液と上記坦体との接触手段は、特に限定は
されないが、撹拌子、撹拌羽根を用いた機械的撹拌操作
以外にも超音波を利用する方法、市販のホモジナイザー
を用いる方法又は担体の充填層に微粒子非水溶液を接
触、循環させる方式等種々の手段を適用しうる。また吸
着速度が速いため、吸着装置は回分式、連続式のいずれ
も適用可能である。The means for contacting the fine particle non-aqueous dispersion of the inorganic chalcogenide with the carrier in the present invention is not particularly limited, but ultrasonic waves may be used in addition to mechanical stirring using a stirrer or a stirring blade. , A method using a commercially available homogenizer, or a method in which a non-aqueous solution of fine particles is brought into contact with and circulated in a packed bed of a carrier. In addition, since the adsorption speed is high, any of a batch type and a continuous type can be applied to the adsorption device.
【００１２】本発明によれば常温、常圧において撹拌等
の簡易な手段で広範囲の無機カルコゲナイド物微粒子が
担体に担持可能であることが判明した。また微粒子非水
分散液と比較して微粒子水分散液を用いた場合は殆んど
微粒子を吸着しないか吸着速度がかなり遅いことが明ら
かとなった。また、２種類以上の微粒子を同時あるいは
逐次に担体に担持することにより異種微粒子の積層、複
合担持が可能であることも明らかになった。According to the present invention, it has been found that a wide range of inorganic chalcogenide fine particles can be supported on a carrier by simple means such as stirring at normal temperature and normal pressure. In addition, it was found that when the aqueous dispersion of fine particles was used as compared with the non-aqueous dispersion of fine particles, almost no fine particles were adsorbed or the adsorption speed was considerably slow. It has also been clarified that by simultaneously or sequentially loading two or more types of fine particles on a carrier, it is possible to laminate and compositely support different types of fine particles.
【００１３】[0013]
【実施例】次に実施例、比較例により本発明を具体的に
説明するが、本発明はこれらに限定されるものではな
い。なお金属化合物微粒子分散液の調製方法は前記の特
願平３−３５８５４８号に基づいて行なった。その具体
的な態様は次のとおりである。Next, the present invention will be described specifically with reference to examples and comparative examples, but the present invention is not limited to these examples. The method for preparing the dispersion of metal compound fine particles was carried out based on Japanese Patent Application No. 3-358548. The specific mode is as follows.
【００１４】以下の各実施例に示す無機カルコゲナイド
物の微粒子水分散液の所定量を採取し、これに界面活性
剤を水分散液の水の量に対し、０.０１〜５重量％、好
ましくは０.０５〜０.５重量％になるように添加する。
これに水分散液の容量の０.０１〜５０倍、好ましくは
０.０５〜１０倍の非水液体を加えて１５分〜８時間、
好ましくは２〜６時間、混合撹拌し非水液体を水分散液
中に（又は逆でもよい）分散し乳化させる。この場合、
温度は０〜９０℃、好ましくは２０〜６０℃の範囲で一
定に保つことが望ましい。その後、水溶性無機酸塩及び
／又は実質的に界面活性作用を有さない水溶性有機酸塩
を水分散液の水の量に対し、０.００５〜３０重量％、
好ましくは０.０１〜１５重量％になるように添加し、
３０秒〜３０分間、好ましくは１〜２分間撹拌を加え
る。これにより実質的に全部の金属微粒子が水相より非
水液体相へ移動する。その後、２時間〜２日間静置する
と微粒子の分散していない水相と微粒子の分散した非水
液体相とが上下二相に分離するので分液ロートを用いる
か、あるいは非水液体相の吸い出しにより、微粒子の分
散した非水液体を容易に得ることができる。A predetermined amount of the aqueous dispersion of inorganic chalcogenide fine particles shown in each of the following examples was sampled, and a surfactant was added thereto in an amount of 0.01 to 5% by weight, preferably 0.01 to 5% by weight, based on the amount of water in the aqueous dispersion. Is added so as to be 0.05 to 0.5% by weight.
To this, 0.01 to 50 times, preferably 0.05 to 10 times the volume of the aqueous dispersion is added, and 15 minutes to 8 hours,
The non-aqueous liquid is dispersed and emulsified in an aqueous dispersion (or vice versa) by mixing and stirring preferably for 2 to 6 hours. in this case,
It is desirable to keep the temperature constant in the range of 0 to 90 ° C, preferably 20 to 60 ° C. Thereafter, the water-soluble inorganic acid salt and / or the water-soluble organic acid salt having substantially no surface activity are added to the aqueous dispersion in an amount of 0.005 to 30% by weight,
Preferably added so as to be 0.01 to 15% by weight,
Stirring is applied for 30 seconds to 30 minutes, preferably 1-2 minutes. Thereby, substantially all of the metal fine particles move from the aqueous phase to the non-aqueous liquid phase. After that, if left for 2 hours to 2 days, an aqueous phase in which fine particles are not dispersed and a non-aqueous liquid phase in which fine particles are dispersed are separated into upper and lower two phases, so that a separating funnel is used or a non-aqueous liquid phase is sucked out. Thereby, a non-aqueous liquid in which fine particles are dispersed can be easily obtained.
【００１５】この方法において用いられる水溶性無機酸
塩及び／又は水溶性有機酸塩の例としては、水溶性のア
ンモニウム、リチウム、ナトリウム、カリウム、マグネ
シウム、カルシウム、ストロンチウム、バリウム、アル
ミニウム、ランタン等の硫酸塩、ハロゲン化物、酢酸
塩、硝酸塩、炭酸塩、クエン酸塩及び酒石酸塩等が挙げ
られる。Examples of the water-soluble inorganic acid salt and / or water-soluble organic acid salt used in this method include water-soluble ammonium, lithium, sodium, potassium, magnesium, calcium, strontium, barium, aluminum, lanthanum and the like. Sulfate, halide, acetate, nitrate, carbonate, citrate, tartrate and the like.
【００１６】微粒子の水分散液の調製方法は公知の方
法、例えば、日本化学会編、新実験化学講座１８巻、界
面とコロイド、３１９〜３４０頁、丸善、１９７７ の
記載を応用して行なうことができる。また、界面活性剤
を加えることにより分散状態を安定化した金属微粒子の
水分散液の調製は公知の方法、例えば、Y. Nakao and
K.Kaeriyama, Journal of Colloid and Interface Scie
nce １１０巻、No.1、８２〜８７頁、March １９８６に
記載の方法を応用して行なうことができる。微粒子の水
分散液中における濃度は０.００５〜１００ｍｍｏｌ／
ｌであり、通常０.０２〜７０ｍｍｏｌ／ｌであるが濃
度の高い方が好ましい。The aqueous dispersion of fine particles is prepared by applying a well-known method, for example, the method described in The Chemical Society of Japan, New Experimental Chemistry, Vol. 18, Interfaces and Colloids, pp. 319-340, Maruzen, 1977. Can be. The preparation of an aqueous dispersion of fine metal particles in which the dispersion state is stabilized by adding a surfactant is a known method, for example, Y. Nakao and
K. Kaeriyama, Journal of Colloid and Interface Scie
nce, Vol. 110, No. 1, pp. 82-87, March 1986. The concentration of the fine particles in the aqueous dispersion is 0.005 to 100 mmol /
and usually from 0.02 to 70 mmol / l, but a higher concentration is preferred.
【００１７】非水溶媒中におけるカルコゲナイド微粒子
濃度の測定は、該非水溶媒分散液を担体と分離した後
に、蒸発乾固させ、これをアルカリ及び又は酸水溶液処
理にてイオン化し、ＩＣＰ発光分析法により陽イオンの
定量分析を行ない、該微粒子濃度を求めた。The concentration of chalcogenide fine particles in the non-aqueous solvent is measured by separating the non-aqueous solvent dispersion from the carrier, evaporating it to dryness, ionizing it by treatment with an aqueous solution of an alkali and / or an acid, and performing ICP emission spectrometry. Quantitative analysis of cations was performed to determine the concentration of the fine particles.
【００１８】実施例１ ジルコニア濃度０.５重量％のジルコニア微粒子キシレ
ン分散液２０ｍｌをアルミナ粉末（和光純薬工業製(株)
製、試薬特級、平均粒度３００メッシュ）０.８ｇ と共
に５０ｍｌのフラスコに設置し、１０分間マグネチック
スターラーにより撹拌を行なった。乳白色透明であった
ジルコニア微粒子分散液は撹拌後無色透明となった。撹
拌後キシレンに残存するジルコニア微粒子濃度を定量分
析した結果、キシレン中に残存するジルコニア微粒子は
０％であり、すべてのジルコニア微粒子がアルミナ粉末
に吸着された。Example 1 20 ml of a zirconia fine particle xylene dispersion having a zirconia concentration of 0.5% by weight was mixed with alumina powder (manufactured by Wako Pure Chemical Industries, Ltd.).
(Special grade, special grade, average particle size: 300 mesh) in a 50 ml flask together with 0.8 g, and stirred with a magnetic stirrer for 10 minutes. The milky white transparent zirconia fine particle dispersion became colorless and transparent after stirring. As a result of quantitative analysis of the concentration of the zirconia fine particles remaining in the xylene after the stirring, the zirconia fine particles remaining in the xylene was 0%, and all the zirconia fine particles were adsorbed on the alumina powder.
【００１９】比較例１ ジルコニア濃度０.５重量％のジルコニア微粒子水分散
液２０ｍｌを実施例１と同様にアルミナ粉末０.８ｇ と
共に撹拌を行なった。乳白色を呈していたジルコニア微
粒子分散液は撹拌後も色変化がなかった。撹拌後水中に
残存するジルコニア微粒子濃度を定量分析した結果、水
中に残存するジルコニア微粒子は１００％であり、ジル
コニア微粒子がシリカゲルに吸着されなかった。Comparative Example 1 A 20 ml aqueous dispersion of zirconia fine particles having a zirconia concentration of 0.5% by weight was stirred together with 0.8 g of alumina powder in the same manner as in Example 1. The milky white zirconia fine particle dispersion did not change color even after stirring. As a result of quantitative analysis of the concentration of the zirconia fine particles remaining in the water after the stirring, 100% of the zirconia fine particles remained in the water, and the zirconia fine particles were not adsorbed on the silica gel.
【００２０】実施例２ ジルコニア濃度０.５重量％のジルコニア微粒子シクロ
ヘキサン分散液２０ｍｌをニッケル粉末（和光純薬工業
製(株)製、平均粒度１００メッシュ）０.８ｇ と共に５
０ｍｌのフラスコに設置し、１０分間マグネチックスタ
ーラーにより撹拌を行なった。乳白色透明であったジル
コニア微粒子分散液は撹拌後無色透明となった。撹拌後
シクロヘキサン中に残存するジルコニア微粒子濃度を定
量分析した結果、シクロヘキサン中に残存するジルコニ
ア微粒子は０％であり、すべてのジルコニア微粒子がニ
ッケル粉末に吸着された。Example 2 20 ml of a dispersion of zirconia microparticles in cyclohexane having a zirconia concentration of 0.5% by weight was mixed with 0.8 g of nickel powder (manufactured by Wako Pure Chemical Industries, Ltd., average particle size: 100 mesh) together with 0.8 g.
The flask was placed in a 0 ml flask and stirred with a magnetic stirrer for 10 minutes. The milky white transparent zirconia fine particle dispersion became colorless and transparent after stirring. As a result of quantitative analysis of the concentration of the zirconia fine particles remaining in the cyclohexane after the stirring, the zirconia fine particles remaining in the cyclohexane were 0%, and all the zirconia fine particles were adsorbed on the nickel powder.
【００２１】実施例３ ジルコニア濃度０.５重量％のジルコニア微粒子シクロ
ヘキサン分散液２０ｍｌを市販の６、６−ナイロン長繊
維（太さ15デニール）０.８ｇ と共に５０ｍｌのフラス
コに設置し、１０分間マグネチックスターラーにより撹
拌を行なった。乳白色透明であったジルコニア微粒子分
散液は撹拌後無色透明となった。撹拌後シクロヘキサン
中に残存するジルコニア微粒子濃度を定量分析した結
果、シクロヘキサン中に残存するジルコニア微粒子は０
％であり、すべてのジルコニア微粒子が６、６−ナイロ
ン長繊維に吸着された。Example 3 A 20 ml dispersion of zirconia microparticle cyclohexane having a zirconia concentration of 0.5% by weight was placed in a 50 ml flask together with 0.8 g of commercially available 6,6-nylon long fiber (thickness: 15 denier) for 10 minutes. Stirring was performed with a tick stirrer. The milky white transparent zirconia fine particle dispersion became colorless and transparent after stirring. As a result of quantitative analysis of the concentration of the zirconia fine particles remaining in the cyclohexane after stirring, the zirconia fine particles remaining in the cyclohexane were 0%.
%, And all the zirconia fine particles were adsorbed on the 6,6-nylon filaments.
【００２２】実施例４ ジルコニア濃度０.５重量％のジルコニア微粒子シクロ
ヘキサン分散液２０ｍｌをカーボン粉末（東海カーボン
(株)製、シーストS、平均粒径５８μｍ）１.２ｇと共に
５０ｍｌのフラスコに設置し、１０分間マグネチックス
ターラーにより撹拌を行なった。乳白色透明であったジ
ルコニア微粒子分散液は撹拌後無色透明となった。撹拌
後シクロヘキサン中に残存するジルコニア微粒子濃度を
定量分析した結果、シクロヘキサン中に残存するジルコ
ニア微粒子は０％であり、すべてのジルコニア微粒子が
カーボン粉末に吸着された。Example 4 20 ml of a zirconia fine particle cyclohexane dispersion having a zirconia concentration of 0.5% by weight was carbon powder (Tokai Carbon Co., Ltd.).
1.2 g of Seast S (manufactured by Co., Ltd., average particle size: 58 μm) was placed in a 50 ml flask, and stirred with a magnetic stirrer for 10 minutes. The milky white transparent zirconia fine particle dispersion became colorless and transparent after stirring. As a result of quantitative analysis of the concentration of the zirconia fine particles remaining in the cyclohexane after stirring, the zirconia fine particles remaining in the cyclohexane were 0%, and all the zirconia fine particles were adsorbed on the carbon powder.
【００２３】実施例５ ジルコニア濃度０.５重量％のジルコニア微粒子シクロ
ヘキサン分散液２０ｍｌをヒドロキシプロピルセルロー
ス粉末（和光純薬工業製、試薬１級）１.２ｇ と共に５
０ｍｌのフラスコに設置し、１０分間マグネチックスタ
ーラーにより撹拌を行なった。乳白色透明であったジル
コニア微粒子分散液は撹拌後無色透明となった。撹拌後
シクロヘキサン中に残存するジルコニア微粒子濃度を定
量分析した結果、シクロヘキサン中に残存するジルコニ
ア微粒子は０％であり、すべてのジルコニア微粒子がヒ
ドロキシプロピルセルロース粉末に吸着された。EXAMPLE 5 20 ml of a dispersion of zirconia microparticles in cyclohexane having a zirconia concentration of 0.5% by weight was mixed with 1.2 g of hydroxypropylcellulose powder (Wako Pure Chemical Industries, first grade reagent) for 5 minutes.
The flask was placed in a 0 ml flask and stirred with a magnetic stirrer for 10 minutes. The milky white transparent zirconia fine particle dispersion became colorless and transparent after stirring. As a result of quantitative analysis of the concentration of the zirconia fine particles remaining in the cyclohexane after stirring, 0% of the zirconia fine particles remained in the cyclohexane, and all the zirconia fine particles were adsorbed to the hydroxypropylcellulose powder.
【００２４】比較例２ ジルコニア濃度０.５重量％のジルコニア微粒子水分散
液２０ｍｌを実施例５と同様にヒドロキシプロピルセル
ロース粉末と共に撹拌を行なった。撹拌中にヒドロキシ
プロピルセルロース粉末は水に完全に溶解し、乳白色透
明であったジルコニア微粒子水分散液は撹拌後も色変化
がなく、ヒドロキシプロピルセルロース粉末への吸着は
認められなかった。Comparative Example 2 20 ml of an aqueous dispersion of zirconia fine particles having a zirconia concentration of 0.5% by weight was stirred with hydroxypropylcellulose powder in the same manner as in Example 5. During the stirring, the hydroxypropylcellulose powder was completely dissolved in water, and the milky white transparent aqueous dispersion of zirconia fine particles did not change color even after stirring, and no adsorption to the hydroxypropylcellulose powder was observed.
【００２５】実施例６ アルミナ濃度０.５重量％のアルミナ微粒子シクロヘキ
サン分散液２０ｍｌを市販の６、６−ナイロン長繊維
（太さ１５デニール）１.２ｇ と共に５０ｍｌのフラス
コに設置し、１０分間マグネチックスターラーにより撹
拌を行なった。乳白色透明であったアルミナ微粒子分散
液は撹拌後無色透明となった。撹拌後シクロヘキサン中
に残存するアルミナ微粒子濃度を定量分析した結果、シ
クロヘキサン中に残存するアルミナ微粒子は０％であ
り、すべてのアルミナ微粒子が６、６−ナイロン長繊維
に吸着された。Example 6 A dispersion of 20 ml of a cyclohexane dispersion of alumina fine particles having an alumina concentration of 0.5% by weight was placed in a 50 ml flask together with 1.2 g of a commercially available 6,6-nylon long fiber (thickness: 15 denier) for 10 minutes. Stirring was performed with a tick stirrer. The milky white transparent alumina fine particle dispersion became colorless and transparent after stirring. As a result of quantitative analysis of the concentration of alumina fine particles remaining in cyclohexane after stirring, 0% of the fine alumina particles remained in cyclohexane, and all the fine alumina particles were adsorbed to 6,6-nylon long fibers.
【００２６】実施例７ アルミナ濃度０.５重量％のアルミナ微粒子キシレン分
散液２０ｍｌをシリカゲル（ダイソー(株)製、平均粒径
５μｍ、細孔径１０ｎｍ、比表面積３００ｍ2／ｇ）
０．８ｇと共に５０ｍｌのフラスコに設置し、１０分間
マグネチックスターラーにより撹拌を行なった。乳白色
透明であったアルミナ微粒子分散液は撹拌後無色透明と
なった。撹拌後キシレン中に残存するアルミナ微粒子濃
度を定量分析した結果、キシレン中に残存するジルコニ
ア微粒子は０％であり、すべてのジルコニア微粒子がシ
リカゲルに吸着された。Example 7 20 ml of a xylene dispersion of fine alumina particles having an alumina concentration of 0.5% by weight was mixed with silica gel (manufactured by Daiso Co., Ltd., average particle diameter 5 μm, pore diameter 10 nm, specific surface area 300 m 2 / g).
The mixture was placed in a 50 ml flask together with 0.8 g, and stirred with a magnetic stirrer for 10 minutes. The milky white transparent alumina fine particle dispersion became colorless and transparent after stirring. As a result of quantitative analysis of the concentration of alumina fine particles remaining in xylene after stirring, the zirconia fine particles remaining in xylene was 0%, and all the zirconia fine particles were adsorbed on the silica gel.
【００２７】実施例８ アルミナ濃度０.５重量％のアルミナ微粒子シクロヘキ
サン分散液２０ｍｌを多孔質ガラス粉末（松浪硝子工業
(株)製、M-31、平均粒径１５０μｍ、細孔径４３ｎｍ、
比表面積８８ｍ2／ｇ）１.２ｇ と共に５０ｍｌのフラ
スコに設置し、１０分間マグネチックスターラーにより
撹拌を行なった。乳白色透明であったアルミナ微粒子分
散液は撹拌後無色透明となった。撹拌後シクロヘキサン
中に残存するアルミナ微粒子濃度を定量分析した結果、
シクロヘキサン中に残存するアルミナ微粒子は０％であ
り、すべてのアルミナ微粒子が多孔質ガラス粉末に吸着
された。Example 8 A porous glass powder (Matsunami Glass Industry Co., Ltd.) was used to prepare a dispersion of 20 ml of a cyclohexane dispersion of alumina fine particles having an alumina concentration of 0.5% by weight.
Co., Ltd., M-31, average particle size 150 μm, pore size 43 nm,
(Specific surface area: 88 m 2 / g) was placed in a 50 ml flask together with 1.2 g, and stirred by a magnetic stirrer for 10 minutes. The milky white transparent alumina fine particle dispersion became colorless and transparent after stirring. As a result of quantitative analysis of the concentration of alumina fine particles remaining in cyclohexane after stirring,
0% of the fine alumina particles remained in the cyclohexane, and all the fine alumina particles were adsorbed on the porous glass powder.
【００２８】比較例３ アルミナ濃度０.５重量％のアルミナ微粒子水分散液２
０ｍｌを実施例８と同様に多孔質ガラス粉末１.２ｇ と
共に撹拌を行なった。乳白色透明であったアルミナ微粒
子分散液は撹拌後も色変化がなかった。撹拌後水の透過
率を定量分析して残存するアルミナ微粒子濃度を定量分
析した結果、水中に残存するアルミナ微粒子は１００％
であり、アルミナ微粒子は多孔質ガラス粉末に吸着され
なかった。Comparative Example 3 Aqueous dispersion of fine alumina particles having an alumina concentration of 0.5% by weight 2
0 ml was stirred together with 1.2 g of the porous glass powder in the same manner as in Example 8. The dispersion of the milky white transparent alumina fine particles did not change color even after stirring. As a result of quantitative analysis of the transmittance of water after stirring and quantitative analysis of the concentration of the remaining alumina fine particles, 100% of the fine alumina particles remaining in the water were found.
The alumina fine particles were not adsorbed on the porous glass powder.
【００２９】実施例９ 硫化銅濃度０.０３重量％の硫化銅微粒子クロロホルム
分散液２０ｍｌを多孔質ガラス粉末（松浪硝子工業(株)
製、M−３１、平均粒径１５０μｍ、細孔径43 ｎｍ、比
表面積８８ｍ2／ｇ）１.２ｇ と共に５０ｍｌのフラス
コに設置し、１０分間マグネチックスターラーにより撹
拌を行なった。茶褐色であった硫化銅微粒子分散液は撹
拌後無色透明となった。撹拌後クロロホルム中に残存す
る硫化銅微粒子濃度を定量分析した結果、クロロホルム
中に残存する硫化銅微粒子は０％であり、すべての硫化
銅微粒子が多孔質ガラス粉末に吸着された。Example 9 20 ml of a dispersion liquid of copper sulfide fine particles having a copper sulfide concentration of 0.03% by weight was mixed with a porous glass powder (Matsunami Glass Industry Co., Ltd.).
(M-31, average particle size 150 μm, pore diameter 43 nm, specific surface area 88 m 2 / g) (1.2 g), and placed in a 50 ml flask, and stirred with a magnetic stirrer for 10 minutes. The brownish copper sulfide fine particle dispersion became colorless and transparent after stirring. As a result of quantitative analysis of the concentration of the copper sulfide fine particles remaining in chloroform after stirring, 0% of the copper sulfide fine particles remained in the chloroform, and all the copper sulfide fine particles were adsorbed on the porous glass powder.
【００３０】実施例１０ 硫化銅濃度０.０３重量％の硫化銅微粒子クロロホルム
分散液２０ｍｌを市販の６、６−ナイロン長繊維（太さ
１５デニール）１.２ｇ と共に５０ｍｌのフラスコに設
置し、１０分間マグネチックスターラーにより撹拌を行
なった。茶褐色であった硫化銅微粒子分散液は撹拌後無
色透明となった。撹拌後クロロホルム中に残存する硫化
銅微粒子濃度を定量分析した結果、クロロホルム中に残
存する硫化銅微粒子は０％であり、すべての硫化銅微粒
子が6、6-ナイロン長繊維に吸着された。Example 10 A dispersion of 20 ml of chloroform containing copper sulfide fine particles having a copper sulfide concentration of 0.03% by weight was placed in a 50 ml flask together with 1.2 g of commercially available 6,6-nylon long fiber (thickness: 15 denier). Stirring was performed with a magnetic stirrer for minutes. The brownish copper sulfide fine particle dispersion became colorless and transparent after stirring. As a result of quantitative analysis of the concentration of the copper sulfide fine particles remaining in the chloroform after stirring, 0% of the copper sulfide fine particles remained in the chloroform, and all the copper sulfide fine particles were adsorbed on the 6,6-nylon long fibers.
【００３１】実施例１１ 硫化銅濃度０.０３重量％の硫化銅微粒子クロロホルム
分散液２０ｍｌをヒドロキシプロピルセルロース粉末
（和光純薬工業製、試薬１級）１.２ｇ と共に５０ｍｌ
のフラスコに設置し、１０分間マグネチックスターラー
により撹拌を行なった。茶褐色であった硫化銅微粒子分
散液は撹拌後無色透明となった。撹拌後クロロホルム中
に残存する硫化銅微粒子濃度を定量分析した結果、クロ
ロホルム中に残存する硫化銅微粒子は０％であり、すべ
ての硫化銅微粒子がヒドロキシプロピルセルロース粉末
に吸着された。Example 11 50 ml of 20 ml of a dispersion liquid of copper sulfide fine particles having a copper sulfide concentration of 0.03% by weight together with 1.2 g of hydroxypropylcellulose powder (Wako Pure Chemical Industries, first grade reagent)
And stirred with a magnetic stirrer for 10 minutes. The brownish copper sulfide fine particle dispersion became colorless and transparent after stirring. As a result of quantitative analysis of the concentration of the copper sulfide fine particles remaining in the chloroform after stirring, 0% of the copper sulfide fine particles remained in the chloroform, and all the copper sulfide fine particles were adsorbed to the hydroxypropylcellulose powder.
【００３２】実施例１２ シリカ濃度０.５重量％のシリカ微粒子キシレン分散液
２０ｍｌをカーボン粉末（東海カーボン(株)製、シース
トS、平均粒径５８μｍ）１.２ｇ と共に５０ｍｌのフ
ラスコに設置し、１０分間マグネチックスターラーによ
り撹拌を行なった。乳白色透明であったシリカ微粒子分
散液は撹拌後無色透明となった。撹拌後キシレンに残存
するシリカ微粒子濃度を定量分析した結果、キシレン中
に残存するシリカ微粒子は０％であり、すべてのシリカ
微粒子がカーボン粉末に吸着された。Example 12 20 ml of a xylene dispersion of silica fine particles having a silica concentration of 0.5% by weight was placed in a 50 ml flask together with 1.2 g of carbon powder (SEAST S, manufactured by Tokai Carbon Co., Ltd., average particle size: 58 μm). Stirring was performed with a magnetic stirrer for 10 minutes. The milky white transparent silica fine particle dispersion became colorless and transparent after stirring. As a result of quantitative analysis of the concentration of the silica fine particles remaining in xylene after the stirring, 0% of the silica fine particles remained in the xylene, and all the silica fine particles were adsorbed on the carbon powder.
【００３３】比較例４ シリカ濃度０.５重量％のシリカコロイド水分散液２０
ｍｌをカーボン粉末（東海カーボン(株)製、シースト
S、平均粒径５８μｍ）１.２ｇ と共に５０ｍｌのフラ
スコに設置し、１０分間マグネチックスターラーにより
撹拌を行なった。乳白色透明であったシリカ微粒子分散
液は撹拌後無色透明となった。撹拌後水中に残存するシ
リカ微粒子濃度を定量分析した結果、水中に残存するシ
リカ微粒子は１００％であり、シリカ微粒子はカーボン
粉末に吸着されなかった。Comparative Example 4 Aqueous silica colloid dispersion 20 having a silica concentration of 0.5% by weight
ml of carbon powder (manufactured by Tokai Carbon Co., Ltd.
(S, average particle size 58 μm) was placed in a 50 ml flask together with 1.2 g, and stirred with a magnetic stirrer for 10 minutes. The milky white transparent silica fine particle dispersion became colorless and transparent after stirring. As a result of quantitative analysis of the concentration of the silica fine particles remaining in the water after stirring, 100% of the silica fine particles remained in the water, and the silica fine particles were not adsorbed on the carbon powder.
【００３４】実施例１３ シリカ濃度０.５重量％のシリカ微粒子シクロヘキサン
分散液２０ｍｌをヒドロキシプロピルセルロース粉末
（和光純薬工業製、試薬１級）１.２ｇ と共に５０ｍｌ
のフラスコに設置し、１０分間マグネチックスターラー
により撹拌を行なった。乳白色透明であったシリカ微粒
子分散液は撹拌後無色透明となった。撹拌後シクロヘキ
サンに残存するシリカ微粒子濃度を定量分析した結果、
シクロヘキサン中に残存するシリカ微粒子は０％であ
り、すべてのシリカ微粒子がヒドロキシプロピルセルロ
ース粉末に吸着された。Example 13 50 ml of 20 ml of a dispersion of cyclohexane having a silica concentration of 0.5% by weight was mixed with 1.2 g of hydroxypropylcellulose powder (Wako Pure Chemical Industries, first grade reagent).
And stirred with a magnetic stirrer for 10 minutes. The milky white transparent silica fine particle dispersion became colorless and transparent after stirring. As a result of quantitative analysis of the concentration of silica fine particles remaining in cyclohexane after stirring,
0% of the silica fine particles remained in the cyclohexane, and all the silica fine particles were adsorbed on the hydroxypropylcellulose powder.
【００３５】実施例１４ チタン酸バリウム濃度０.０１重量％のチタン酸バリウ
ム微粒子シクロヘキサン分散液２０ｍｌをアルミナ粉末
（和光純薬工業製(株)製、試薬特級、平均粒度３００メ
ッシュ）１.２ｇ と共に５０ｍｌのフラスコに設置し、
１０分間マグネチックスターラーにより撹拌を行なっ
た。白色透明であったチタン酸バリウム微粒子分散液は
撹拌後無色透明となった。撹拌後シクロヘキサンに残存
するチタン酸バリウム微粒子濃度を定量分析した結果、
シクロヘキサン中に残存するチタン酸バリウム微粒子は
０％であり、すべてのチタン酸バリウム微粒子がアルミ
ナ粉末に吸着された。Example 14 20 ml of barium titanate fine particle cyclohexane dispersion having a barium titanate concentration of 0.01% by weight was mixed with 1.2 g of alumina powder (special grade of reagent, average particle size 300 mesh, manufactured by Wako Pure Chemical Industries, Ltd.). Place in a 50 ml flask,
Stirring was performed with a magnetic stirrer for 10 minutes. The barium titanate fine particle dispersion which was white and transparent became colorless and transparent after stirring. As a result of quantitative analysis of the concentration of barium titanate fine particles remaining in cyclohexane after stirring,
The barium titanate fine particles remaining in the cyclohexane were 0%, and all the barium titanate fine particles were adsorbed on the alumina powder.
【００３６】実施例１５ チタン酸バリウム濃度０.０１重量％のチタン酸バリウ
ム微粒子クロロホルム分散液２０ｍｌを多孔質ガラス粉
末（松浪硝子工業(株)製、M−３１、平均粒径１５０μ
m、細孔径４３ｎｍ、比表面積８８ｍ2／ｇ）１.２ｇ と
共に５０ｍｌのフラスコに設置し、１０分間マグネチッ
クスターラーにより撹拌を行なった。白色透明であった
チタン酸バリウム微粒子分散液は撹拌後無色透明となっ
た。撹拌後クロロホルムに残存するチタン酸バリウム微
粒子濃度を定量分析した結果、クロロホルム中に残存す
るチタン酸バリウム微粒子は０％であり、すべてのチタ
ン酸バリウム微粒子が多孔質ガラス粉末に吸着された。Example 15 20 ml of a barium titanate fine particle chloroform dispersion having a barium titanate concentration of 0.01% by weight was mixed with a porous glass powder (M-31, manufactured by Matsunami Glass Industry Co., Ltd., average particle size 150 μm).
m, pore diameter 43 nm, specific surface area 88 m 2 / g) (1.2 g) were placed in a 50 ml flask, and stirred with a magnetic stirrer for 10 minutes. The barium titanate fine particle dispersion which was white and transparent became colorless and transparent after stirring. As a result of quantitative analysis of the concentration of barium titanate fine particles remaining in chloroform after stirring, the barium titanate fine particles remaining in chloroform were 0%, and all the barium titanate fine particles were adsorbed on the porous glass powder.
【００３７】実施例１６ ジルコニア、アルミナ各濃度０.２５重量％のジルコニ
アーアルミナ混合微粒子シクロヘキサン分散液２０ｍｌ
を多孔質ガラス粉末（松浪硝子工業(株)製、M−３１、
平均粒径１５０μｍ、細孔径４３ｎｍ、比表面積８８ｍ
2／ｇ）１.２ｇと共に５０ｍｌのフラスコに設置し、１
０分間マグネチックスターラーにより撹拌を行なった。
白色透明であったジルコニアーアルミナ混合微粒子シク
ロヘキサン分散液は撹拌後無色透明となった。撹拌後シ
クロヘキサンに残存するジルコニア、アルミナ微粒子濃
度を定量分析した結果、シクロヘキサン中に残存するジ
ルコニア、アルミナ微粒子は０％であり、すべてのジル
コニアーアルミナ混合微粒子が多孔質ガラス粉末に吸着
された。Example 16 Zirconia and Alumina Mixed 0.25% by weight of zirconia-alumina mixed fine particle cyclohexane dispersion 20 ml
Is a porous glass powder (M-31, manufactured by Matsunami Glass Industry Co., Ltd.)
Average particle size 150 μm, pore size 43 nm, specific surface area 88 m
2 / g) together with 1.2 g in a 50 ml flask,
Stirring was performed with a magnetic stirrer for 0 minutes.
The zirconia-alumina mixed fine particle cyclohexane dispersion which was white and transparent became colorless and transparent after stirring. As a result of quantitative analysis of the zirconia and alumina fine particles remaining in the cyclohexane after the stirring, the zirconia and alumina fine particles remaining in the cyclohexane were 0%, and all the zirconia-alumina mixed fine particles were adsorbed on the porous glass powder.
【００３８】[0038]
【発明の効果】本発明法により無機カルコゲナイド物微
粒子を担体に担持させる際の効果を列挙すると次の如く
である。 １）各種微粒子、各種担体に適用可能で応用範囲が広
い。 ２）常温、常圧で担持可能で操作が簡便であり、処理時
間も短くてよい（約１０分程度）。 ３）界面活性剤、保護コロイドの影響を最小限に抑制で
き、脱着し難く、また担持量の制御が容易である。 ４）混合微粒子の担持、異種微粒子の積層、複合担持が
可能である。 ５）小粒径の微粒子の担持が可能であり、また微粒子の
粒径制御が可能である。The effects of supporting inorganic chalcogenide microparticles on a carrier according to the method of the present invention are as follows. 1) It can be applied to various fine particles and various carriers, and has a wide application range. 2) It can be carried at normal temperature and normal pressure, the operation is simple, and the processing time may be short (about 10 minutes). 3) The influence of the surfactant and the protective colloid can be suppressed to a minimum, the desorption is difficult, and the control of the loading amount is easy. 4) Support of mixed fine particles, lamination of different types of fine particles, and composite support are possible. 5) Small particles having a small particle diameter can be supported, and the particle diameter of the fine particles can be controlled.
【００３９】本発明法による無機カルコゲナイド物微粒
子の担持体は導電体、触媒、センサー、クロマトグラフ
用充填剤、抗菌・消臭剤、顔料、光学材料、磁性材料、
超伝導材料、傾斜機能材料等の用途が期待される。The carrier of the inorganic chalcogenide fine particles according to the method of the present invention includes a conductor, a catalyst, a sensor, a filler for chromatography, an antibacterial / deodorant, a pigment, an optical material, a magnetic material,
Applications such as superconducting materials and functionally graded materials are expected.
フロントページの続き (58)調査した分野(Int.Cl.7，ＤＢ名) B01J 2/00 B01J 13/00 - 13/22 B01J 37/02 Continuation of the front page (58) Field surveyed (Int. Cl. 7 , DB name) B01J 2/00 B01J 13/00-13/22 B01J 37/02
Claims (4)
ゲナイド物の微粒子を分散させた分散液を、担体と接触
させて上記微粒子を吸着せしめることを特徴とする微粒
子の担持方法。1. A method for supporting fine particles, wherein a dispersion of fine particles of an inorganic chalcogenide in a non-aqueous solvent incompatible with water is brought into contact with a carrier to adsorb the fine particles.
化物、硫化物、セレン化物及びテルル化物の微粒子であ
る請求項１に記載の微粒子の担持方法。2. The method according to claim 1, wherein the inorganic chalcogenide fine particles are fine particles of inorganic oxide, sulfide, selenide and telluride.
合酸化物、ゼオライト、ガラス、天然高分子物質及び合
成高分子物質より選ばれる１種又は２種以上である請求
項１に記載の金属微粒子の担持方法。3. The carrier according to claim 1, wherein the carrier is at least one selected from carbon, metal, inorganic oxide, inorganic composite oxide, zeolite, glass, natural polymer, and synthetic polymer. A method for supporting metal fine particles.
を、界面活性剤の存在下、水と相分離する非水液体と接
触させ、その接触前及び／又は接触後に水溶性無機酸塩
及び／又は水溶性有機酸塩を添加し、上記微粒子を該水
分散液より該非水液体中に移動させ、このようにして水
性相と分離して得られた微粒子が分散した非水分散液相
を取り出して使用することを特徴とする請求項１に記載
の微粒子の担持方法。4. An aqueous dispersion of inorganic chalcogenide fine particles is brought into contact with a non-aqueous liquid which is phase-separated from water in the presence of a surfactant, and before and / or after the contact, a water-soluble inorganic acid salt and / or A water-soluble organic acid salt is added, the fine particles are transferred from the aqueous dispersion into the non-aqueous liquid, and the non-aqueous dispersion liquid phase in which the fine particles obtained by separating from the aqueous phase in this manner are dispersed is taken out. The method for supporting fine particles according to claim 1, wherein the method is used.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13569193A JP3221153B2 (en) | 1993-06-07 | 1993-06-07 | Method for supporting fine particles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13569193A JP3221153B2 (en) | 1993-06-07 | 1993-06-07 | Method for supporting fine particles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06343848A JPH06343848A (en) | 1994-12-20 |
| JP3221153B2 true JP3221153B2 (en) | 2001-10-22 |
Family
ID=15157663
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13569193A Expired - Fee Related JP3221153B2 (en) | 1993-06-07 | 1993-06-07 | Method for supporting fine particles |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3221153B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR200495715Y1 (en) | 2018-12-07 | 2022-08-02 | 제이. 와이. 몬티지 트레이드 인더스트리 컴퍼니 리미티드 | Stabilizing and combining structure in unfolding the folding tables |
-
1993
- 1993-06-07 JP JP13569193A patent/JP3221153B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR200495715Y1 (en) | 2018-12-07 | 2022-08-02 | 제이. 와이. 몬티지 트레이드 인더스트리 컴퍼니 리미티드 | Stabilizing and combining structure in unfolding the folding tables |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06343848A (en) | 1994-12-20 |
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