JP2520238B2 - Method for producing inclusion body - Google Patents
Method for producing inclusion bodyInfo
- Publication number
- JP2520238B2 JP2520238B2 JP61229840A JP22984086A JP2520238B2 JP 2520238 B2 JP2520238 B2 JP 2520238B2 JP 61229840 A JP61229840 A JP 61229840A JP 22984086 A JP22984086 A JP 22984086A JP 2520238 B2 JP2520238 B2 JP 2520238B2
- Authority
- JP
- Japan
- Prior art keywords
- film
- inclusion
- mica
- organic
- clay mineral
- 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.)
- Expired - Lifetime
Links
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- Silicates, Zeolites, And Molecular Sieves (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Medicinal Preparation (AREA)
Description
【発明の詳細な説明】 「産業上の利用分野」 本発明は、主として光学用、生体用、遅効性医薬、農
薬等の用途に好適な包摂体の製造方法に関するものであ
る。TECHNICAL FIELD The present invention relates to a method for producing an inclusion body, which is suitable mainly for applications such as optics, living bodies, slow-acting pharmaceuticals, and agricultural chemicals.
「従来の技術」 粘土鉱物若しくは雲母鉱物からなる包摂体の製造方法
としては、成形用原料の製造方法（特公昭53−22947
号）、反応性無機、有機複合体の製造方法（特公昭53−
42480号）、バーミキュライトからの成形物品の製法
（特開昭53−39318号）、無機ゲル及びその製造方法
（特開昭55−142539号）等が知られている。"Prior Art" As a method for producing an inclusion body made of clay mineral or mica mineral, a method for producing a forming raw material (Japanese Patent Publication No. 53-22947).
No.), a method for producing a reactive inorganic / organic composite (Japanese Patent Publication No. 53-
42480), a method for producing a molded article from vermiculite (JP-A-53-39318), an inorganic gel and a method for producing the same (JP-A-55-142539), and the like.
これらは粘土鉱物若しくは雲母鉱物の懸濁体を形成
し、他のカチオンにより包摂凝集させ、ついで脱水洗浄
した後再分散させ、遠心若しくは流延乾燥してフイルム
化するか、或いは粘土鉱物若しくは雲母鉱物の懸濁体を
形成し、これを遠心若しくは流延乾燥した後、他のカチ
オンにより包摂させ、これを洗浄乾燥して包摂体とする
ものである。しかして、前者のフイルムは、凝集した後
成形するため、フイルムの強度が低く、透明性が悪く、
耐水性に劣る欠点があり、また後者のフイルムは、カチ
オン特に長鎖有機カチオンがイオン交換しにくいため、
フイルムの強度が低く、耐水性に劣る欠点があった。ま
た、包摂体は一般に懸濁体に包摂されるべきカチオンを
加えることにより得られるが、上記従来の方法によった
のでは、カチオンの種類が限定される問題があった。These form suspensions of clay minerals or mica minerals, are encapsulated and aggregated with other cations, then dehydrated and washed, redispersed, centrifuged or cast and dried to form a film, or clay minerals or mica minerals. After forming a suspension of the above, centrifuging or casting and drying the suspension, it is included by other cations, washed and dried to obtain an inclusion body. Since the former film is formed after agglomeration, the film has low strength and poor transparency.
It has a drawback of poor water resistance, and the latter film is difficult to ion-exchange cations, especially long-chain organic cations.
The strength of the film was low and the water resistance was poor. Further, the inclusion body is generally obtained by adding a cation to be included in the suspension, but the conventional method described above has a problem that the kind of the cation is limited.
本発明は、上記問題点を改善し、粘土鉱物若しくは雲
母鉱物と包摂物質（但し、無機ピラー及び有機ピラーを
除く）とからなる耐水性、透明性、機械的強度に優れた
包摂体の製造法を提供することを目的としている。The present invention solves the above problems, and is a method for producing an inclusion body which is excellent in water resistance, transparency and mechanical strength, which is made of a clay mineral or a mica mineral and an inclusion substance (excluding inorganic pillars and organic pillars). Is intended to provide.
「問題点を解決するための手段」 本発明者等は、上記目的を達成するため鋭意研究の結
果、層状構造を有する粘土鉱物若しくは雲母鉱物を単に
加熱して包摂処理したのでは、満足な結果は得られなか
ったが、密閉容器内で加熱して包摂処理することによ
り、透明性、耐熱性、耐水性に優れた従来の製法では得
ることのできない包摂体が得られるという驚くべき事実
を見出しなされたものである。“Means for Solving Problems” The inventors of the present invention have conducted intensive studies to achieve the above-mentioned object, and as a result of inclusive treatment by simply heating a clay mineral or mica mineral having a layered structure, satisfactory results are obtained. However, the surprising fact that by heating in a closed container for inclusion treatment, an inclusion body excellent in transparency, heat resistance, and water resistance, which cannot be obtained by the conventional manufacturing method, is obtained. It was made.
即ち本発明は、層状構造を有する粘土鉱物若しくは雲
母を、密閉容器内の溶媒中で、包摂物質（但し、無機ピ
ラー及び有機ピラーを除く）と加熱して包摂処理するこ
とを特徴とする。That is, the present invention is characterized in that a clay mineral or mica having a layered structure is heated with an inclusion substance (excluding inorganic pillars and organic pillars) in a solvent in a closed container to perform an inclusion treatment.
本発明に用いられる粘土鉱物若しくは雲母とは、SiO4
四面体のSi対Ｏの比が、2:5のフィロケイ酸塩であり、
好ましくは天然のモンモリロナイト及びバーミキュライ
ト、合成物である合成マイカ等が挙げられるが、合成マ
イカが特に好ましい。The clay mineral or mica used in the present invention means SiO 4
A tetrahedral Si to O ratio of 2: 5 phyllosilicate,
Preferable examples include natural montmorillonite and vermiculite, synthetic synthetic mica, and the like, and synthetic mica is particularly preferable.
上記合成マイカとは、フッ素雲母の一種であるテトラ
シリシックマイカ及びテニオライト等であるが、ナトリ
ウムテニオライトが特に好ましい。The synthetic mica is, for example, tetrasilicic mica, which is a type of fluoromica, and teniolite, and sodium teniolite is particularly preferable.
本発明の方法に使用する粘土鉱物若しくは雲母は、例
えばフイルム、紙、ボード、繊維等として使用される。The clay mineral or mica used in the method of the present invention is used, for example, as a film, paper, board, fiber or the like.
粘土鉱物若しくは雲母に包摂させる物質としては、有
機系色素例えばクマリン誘導体、キサンチン色素、オキ
サジン色素及びシアニン色素等の塩基性を示すものが使
用される。具体例としては、ローダミン590,640、クマ
リン460、オキサジン725,750が挙げられる。アミラーゼ
等の酵素を使用することもできる。また上記有機物に限
らずKCl、AlCl3、Pb(NO3)2等の無機物を使用することも
できる。As the substance to be included in the clay mineral or mica, organic dyes such as coumarin derivatives, xanthine dyes, oxazine dyes and cyanine dyes, which have basicity, are used. Specific examples include Rhodamine 590,640, Coumarin 460 and Oxazine 725,750. Enzymes such as amylase can also be used. Further, not only the above organic substances, but also inorganic substances such as KCl, AlCl 3 , Pb (NO 3 ) 2 and the like can be used.
使用する粘土鉱物等と包摂物質との割合は、粘土鉱物
一式量に対して、包摂物質１〜10当量好ましくは２〜５
当量使用される。The ratio of the clay mineral to be used and the inclusion substance is 1 to 10 equivalents of the inclusion substance, preferably 2 to 5 relative to the set amount of the clay mineral.
Used in equivalent amounts.
反応pHは、有機物カチオンを包摂させる場合はpH2〜1
2、好ましくは３〜６特に好ましくは３〜４とするのが
よい。pHが低すぎても高すぎてもフイルムが弱くなる。
包摂物質としては、カチオン化すれば包摂し易くなる。The reaction pH is pH 2-1 when including organic cations.
2, preferably 3 to 6, particularly preferably 3 to 4. If the pH is too low or too high, the film will weaken.
As an inclusion substance, if it is cationized, it can be easily included.
有機系色素を粘土鉱物若しくは雲母に包摂させるに
は、例えば粘土鉱物等と上記色素とを、密閉容器内で、
水若しくは有機溶媒中加熱すればよい。この場合、粘土
鉱物等の層間に存在する交換性陽イオンを、Ca若しくは
Naの単独イオン種に交換した後、上記色素と交換させる
と高い包摂率が得られる。こうした操作によって、各種
有機系色素は粘土鉱物等の層格子構造を損なうことな
く、層間距離のみを変化させて層空間に着床する。有機
系色素分子或いはイオンの最大包摂量は、粘土鉱物等の
層面の電荷密度、有機色素分子若しくはイオンの大きさ
及び立体配置等に影響されるが、反応温度、pH、反応時
間を制御すれば、特定の包摂量とすることも可能で、所
要の機能を有する包摂体を設計・合成することができ
る。In order to make an organic pigment included in a clay mineral or mica, for example, a clay mineral and the above pigment are placed in a closed container,
It may be heated in water or an organic solvent. In this case, the exchangeable cations existing between the layers of clay minerals, Ca or
After exchanging with a single ion species of Na and then exchanging with the above dye, a high inclusion rate can be obtained. By such an operation, various organic dyes are implanted in the layer space by changing only the interlayer distance without impairing the layer lattice structure of clay mineral or the like. The maximum encapsulation of organic dye molecules or ions is affected by the charge density of the layer surface of clay minerals, the size and configuration of the organic dye molecules or ions, etc., but if the reaction temperature, pH, and reaction time are controlled It is also possible to set a specific inclusion, and an inclusion body having a required function can be designed and synthesized.
密閉容器内で加熱するには、モーレー型耐圧容器（商
品名：ユニシール）等の耐圧容器中に、粘土鉱物等の懸
濁体、フイルム、紙、ボード等を溶媒と共にいれて、密
閉後加熱すればよい。To heat in a closed container, put a suspension of clay minerals, film, paper, board, etc. in a pressure resistant container such as a Moray type pressure resistant container (trade name: Uniseal) together with a solvent, and heat after sealing. Good.
溶媒としては、水、アルコール、アセトン等あらゆる
溶媒を使用することができ、包摂物質の溶解度に応じて
適宜選択すればよい。As the solvent, any solvent such as water, alcohol, and acetone can be used, and may be appropriately selected depending on the solubility of the inclusion substance.
反応温度は、50〜500℃、好ましくは80〜300℃、特に
好ましくは100〜200℃である。The reaction temperature is 50 to 500 ° C, preferably 80 to 300 ° C, particularly preferably 100 to 200 ° C.
本発明の出発物質の粘土鉱物等をフイルム化するに
は、粘土鉱物等のゾルを形成してフイルム化する公知の
方法で行えばよい。粘土鉱物等の中で自由膨潤型のもの
は、これに水を加えれば、容易にゾルが形成される。The clay mineral or the like as the starting material of the present invention may be formed into a film by a known method of forming a sol of the clay mineral or the like to form a film. Among the clay minerals, free swelling type ones can easily form a sol by adding water thereto.
ゾルの形成方法の詳細は、例えば特開昭61−63521号
（特願昭59−184692号明細書）に記載されている。Details of the method for forming a sol are described in, for example, JP-A-61-63521 (Japanese Patent Application No. 59-184692).
「実施例」 次に実施例を挙げ本発明を更に詳しく説明するが、本
発明はこれら実施例に限定されるものではない。"Examples" Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.
実施例１ モンモリロナイトの２％懸濁液を調整し、これをガラ
ス板上に流延し、室温で乾燥した後ガラス板から剥離し
てフイルムを得た。このフイルムを100ml密閉耐圧容器
（ユニシール）中で、100℃、48時間包摂処理した後、
取り出して水洗し、透明性、耐水性、耐熱性、層間距離
を測定した。結果を後記表に示す。尚、使用した包摂液
は、染料ローダミン6GCP1gを90mlの水に溶解させたpH3.
0の水溶液である。Example 1 A 2% suspension of montmorillonite was prepared, cast on a glass plate, dried at room temperature, and then peeled from the glass plate to obtain a film. This film was treated in a 100 ml closed pressure-resistant container (Uniseal) at 100 ° C for 48 hours, and then,
It was taken out and washed with water, and the transparency, water resistance, heat resistance, and interlayer distance were measured. The results are shown in the table below. The inclusion liquid used was pH 3.3 in which 1 g of the dye rhodamine 6GCP was dissolved in 90 ml of water.
It is an aqueous solution of 0.
実施例２ 合成雲母のナトリウムテニオライト（NaMg2LiSi4O10F
2）を、塩化リチウム液に懸濁して調整した２％懸濁液
を使用する以外は実施例１と同様に行ない、後記表に示
す結果を得た。Example 2 Sodium teniolite of synthetic mica (NaMg 2 LiSi 4 O 10 F)
2 ) was carried out in the same manner as in Example 1 except that a 2% suspension prepared by suspending it in a lithium chloride solution was used, and the results shown in the table below were obtained.
実施例３ 包摂液として、染料ローダミンB1gを90mlの水に溶解
させたpH3.0の水溶液を使用する以外は、実施例２と同
様に実施し、後記表に示す結果を得た。Example 3 The same procedure as in Example 2 was carried out except that an aqueous solution having a pH of 3.0 in which 1 g of the dye rhodamine B was dissolved in 90 ml of water was used as the inclusion liquid, and the results shown in the table below were obtained.
実施例４ 包摂液として、ポリオキシエチレンラウリルアミン1g
を90mlの水に溶解させたpH3.0の水溶液を使用する以外
は、実施例２と同様に実施し、後記表に示す結果を得
た。Example 4 As an infusion liquid, 1 g of polyoxyethylene lauryl amine
Was carried out in the same manner as in Example 2 except that an aqueous solution of pH 3.0 dissolved in 90 ml of water was used, and the results shown in the table below were obtained.
実施例５ 包摂液として、無機イオンのKCl0.5gを90mlの水に溶
解させたpH5.0の水溶液を使用する以外は、実施例２と
同様に実施し、後記表に示す結果を得た。Example 5 The same procedure as in Example 2 was carried out except that an aqueous solution of pH 5.0 in which 0.5 g of inorganic ion KCl was dissolved in 90 ml of water was used as the inclusion liquid, and the results shown in the table below were obtained.
比較例１ 実施例１と同じフイルムを、100mlビーカー中常温で
包摂させる以外は、実施例１と同様に実施し、後記表に
示す結果を得た。Comparative Example 1 Example 1 was repeated except that the same film as in Example 1 was included in a 100 ml beaker at room temperature, and the results shown in the table below were obtained.
比較例２ 実施例３と同じフイルムを、100ml密閉容器中加熱し
て包摂させる以外は、実施例３と同様に実施し、後記表
に示す結果を得た。Comparative Example 2 The same film as in Example 3 was heated in a 100 ml closed container to be included in the same manner as in Example 3, and the results shown in the table below were obtained.
比較例３ 実施例４と同じフイルムを、100mlビーカー中常温で
包摂させる以外は、実施例４と同様に実施し、後記表に
示す結果を得た。Comparative Example 3 Example 4 was repeated except that the same film as Example 4 was included in a 100 ml beaker at room temperature, and the results shown in the table below were obtained.
表中透明性の○は、フイルムに曇りがあることを表わ
し、◎は、フイルムに曇りが全くないことを表わす。 In the table, the transparency ◯ means that the film has fog, and the open mark means that the film has no fog.
耐水性は、フイルムを水に１時間浸漬させ、フイルム
が完全に溶けた場合を×、ややもろくなった場合を△、
全く影響がない場合を◎で表わした。The water resistance is evaluated by immersing the film in water for 1 hour, and when the film is completely melted, it is x, when it is slightly fragile, it is Δ,
The case where there is no effect is indicated by ⊚.
耐熱性は、示差熱分析における熱減量温度で表わし
た。The heat resistance was represented by the thermal loss temperature in the differential thermal analysis.
「発明の効果」 以上述べたように、本発明の製法は、密閉容器中で加
熱するため、通常の方法では包摂し得ないような長大有
機分子も包摂が可能となり、また従来包摂できないか或
いは包摂しにくい包摂物質についても包摂が可能となる
ほか、フイルム状に成形した包摂体は、透明性、耐熱
性、耐水性に優れ、しかも光学、絶縁、導電、半導電、
触媒、ガス透過等の種々の機能を持ったフイルムとする
ことができる等多くの利点を併有する。"Effects of the Invention" As described above, in the production method of the present invention, since heating is carried out in a closed container, it is possible to include long organic molecules that cannot be included by a normal method, and it is impossible to include conventional organic molecules. In addition to inclusion substances that are difficult to include, inclusions formed into a film shape have excellent transparency, heat resistance, and water resistance, and also include optical, insulating, conductive, semiconductive,
It has many advantages such as a film having various functions such as catalyst and gas permeation.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 小杉 哲史 豊橋市明海町１番地 トピー工業株式会 社内 (72)発明者 安藤 彰嗣 豊橋市明海町１番地 トピー工業株式会 社内 (56)参考文献 特開 昭62−278174（ＪＰ，Ａ) ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Satoshi Kosugi 1 Meikai-cho, Toyohashi City Topy Kogyo Co., Ltd. (72) Inventor Akitsu Ando 1 Meikai-cho, Toyohashi City Topy Kogyo Co., Ltd. (56) References Sho 62-278174 (JP, A)
Claims (1)
を、密閉容器内の溶媒中で、包摂物質（但し、無機ピラ
ー及び有機ピラーを除く）と加熱して包摂処理すること
を特徴とする包摂体の製造方法。1. An inclusion body characterized in that a clay mineral or mica having a layered structure is heated with an inclusion substance (excluding inorganic pillars and organic pillars) in a solvent in a closed container for inclusion treatment. Manufacturing method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61229840A JP2520238B2 (en) | 1986-09-30 | 1986-09-30 | Method for producing inclusion body |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61229840A JP2520238B2 (en) | 1986-09-30 | 1986-09-30 | Method for producing inclusion body |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6389415A JPS6389415A (en) | 1988-04-20 |
| JP2520238B2 true JP2520238B2 (en) | 1996-07-31 |
Family
ID=16898504
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61229840A Expired - Lifetime JP2520238B2 (en) | 1986-09-30 | 1986-09-30 | Method for producing inclusion body |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2520238B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5137050B2 (en) * | 2003-12-17 | 2013-02-06 | 独立行政法人産業技術総合研究所 | Nylon composite clay membrane and method for producing the same |
| JP4997493B2 (en) * | 2004-08-10 | 2012-08-08 | 独立行政法人産業技術総合研究所 | Clay film manufacturing method |
| JP4784914B2 (en) * | 2005-03-31 | 2011-10-05 | 独立行政法人産業技術総合研究所 | Capsule membrane |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62278174A (en) * | 1986-05-26 | 1987-12-03 | 松下電工株式会社 | Manufacture of inorganic layer porous body |
-
1986
- 1986-09-30 JP JP61229840A patent/JP2520238B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6389415A (en) | 1988-04-20 |
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| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |