JP3321601B2 - Clay / organic composite humidity sensor - Google Patents
Clay / organic composite humidity sensorInfo
- Publication number
- JP3321601B2 JP3321601B2 JP35244099A JP35244099A JP3321601B2 JP 3321601 B2 JP3321601 B2 JP 3321601B2 JP 35244099 A JP35244099 A JP 35244099A JP 35244099 A JP35244099 A JP 35244099A JP 3321601 B2 JP3321601 B2 JP 3321601B2
- Authority
- JP
- Japan
- Prior art keywords
- clay
- humidity sensor
- organic
- organic composite
- organic substance
- 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
Landscapes
- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、湿度の制御をする
ための湿度センサーに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a humidity sensor for controlling humidity.
【０００２】[0002]
【従来の技術】湿度センサーは、通常毛髪や高分子など
が用いられている。これらのセンサーは、水分子の吸着
により材料が伸縮することで湿度を感知している。無機
物を用いた湿度センサーは、ＮｉＦｅ2 Ｏ4 系やＭｇＣ
ｒ2 Ｏ4 系湿度センサーがある。前者は、水分子が吸着
した際に表面のエネルギー準位の変化による内部抵抗の
変化を利用している。後者は、水分子の吸着によりＣｒ
イオンが水分子を水酸基にしてプロトンを放出する現象
を利用している。2. Description of the Related Art For a humidity sensor, hair, a polymer or the like is usually used. These sensors sense humidity by the expansion and contraction of the material due to the adsorption of water molecules. Humidity sensors using inorganic materials include NiFe 2 O 4 and MgC
There is an r 2 O 4 based humidity sensor. The former utilizes a change in internal resistance due to a change in surface energy level when water molecules are adsorbed. In the latter case, the adsorption of water molecules
It utilizes the phenomenon that ions release protons from water molecules as hydroxyl groups.
【０００３】[0003]
【発明が解決しようとする課題】湿度制御を必要とする
環境下で、毛髪や高分子を用いた湿度センサーは、経年
変化があるので適宜交換する必要がある。また、無機物
センサーは、経年変化は起きにくいが、湿度センサーの
感度と装置の応答に差が生じる場合がある。そこで、本
発明は、経年変化が起きにくく、湿度に対して適度に鈍
感な湿度センサーを作成することにより、湿度を制御す
る装置との組み合わせを良くすることを目的とするもの
である。In an environment where humidity control is required, a humidity sensor using hair or a polymer needs to be appropriately replaced because it changes over time. In addition, although the inorganic sensor is unlikely to change over time, there may be a difference between the sensitivity of the humidity sensor and the response of the device. Accordingly, an object of the present invention is to improve the combination with a device that controls humidity by creating a humidity sensor that is less likely to change over time and is moderately insensitive to humidity.
【０００４】[0004]
【課題を解決するための手段】層状珪酸塩粘土鉱物は、
古くから水分子を包接し、親水的な鉱物として知られて
いるが、相対湿度の変化に対して層間距離が直線的に変
化しない。したがって、層状珪酸塩粘土鉱物の単独では
湿度センサーとして利用できないが、本発明者は、層状
珪酸塩粘土鉱物に双極イオン性有機物を包接させること
により作成された粘土／有機複合体は、層状珪酸塩粘土
鉱物の親水的性質と有機物の水を吸着する性質とを有
し、経年変化しにくく、湿度制御装置に似合った湿度セ
ンサーを作ることが可能であることを見出した。The layered silicate clay mineral is
It has long been known as a hydrophilic mineral that includes water molecules, but its interlayer distance does not change linearly with changes in relative humidity. Therefore, although the layered silicate clay mineral alone cannot be used as a humidity sensor, the present inventor has determined that a clay / organic composite made by including a zwitterionic organic substance in the layered silicate clay mineral is a layered silicate clay. It has been found that it has a hydrophilic property of salt clay mineral and a property of adsorbing organic water, is hard to change over time, and can make a humidity sensor suitable for a humidity control device.
【０００５】すなわち、本発明は、層状粘土鉱物に双極
イオン性を有する低分子有機物または高分子有機物を包
接する粘土／有機複合体からなることを特徴とする粘土
／有機複合体湿度センサーである。That is, the present invention is a clay / organic composite humidity sensor comprising a clay / organic composite in which a low molecular weight organic substance or a high molecular weight organic substance having zwitterionicity is included in a layered clay mineral.
【０００６】また、本発明は、双極イオン性を有する低
分子有機物、または高分子有機物がアミノ基とカルボキ
シル基を有する有機物であることを特徴とする上記の粘
土／有機複合体湿度センサーである。Further, the present invention is the above clay / organic composite humidity sensor, wherein the low molecular weight organic substance having a zwitterionic property or the high molecular weight organic substance is an organic substance having an amino group and a carboxyl group.
【０００７】層状粘土鉱物は、水分子や親水性有機物を
容易に包接するという性質がある。また、親水性有機物
は、水分子が容易に吸着する性質を持つ。これらの性質
を利用することにより、相対湿度の変化に対して層間距
離が線形的に変化する粘土／有機複合体の作製が可能と
なる。[0007] Layered clay minerals have the property of easily including water molecules and hydrophilic organic substances. Further, the hydrophilic organic substance has a property that water molecules are easily adsorbed. By utilizing these properties, it is possible to produce a clay / organic composite in which the interlayer distance changes linearly with changes in relative humidity.
【０００８】双極イオン性、例えばアミノ基とカルボキ
シル基を有する有機物を用いて作製された粘土／有機複
合体は、プラス電荷を示す官能基が層状粘土鉱物のある
層と水素結合し、マイナス電荷を示す官能基は粘土鉱物
の層と結合できないため、マイナス電荷の官能基に水分
子が容易に吸着できる。水分子がマイナス電荷の官能基
に吸着することにより、粘土／有機複合体の層間距離が
広がる。In a clay / organic composite prepared using an organic substance having a dipolar ionic property, for example, having an amino group and a carboxyl group, a functional group having a positive charge is hydrogen-bonded to a layer of a layered clay mineral, and a negative charge is formed. Since the functional groups shown cannot bind to the clay mineral layer, water molecules can be easily adsorbed on the negatively charged functional groups. Adsorption of water molecules to the negatively charged functional groups increases the interlayer distance of the clay / organic composite.
【０００９】有機物を層状粘土鉱物に包接する時のｐＨ
条件を調節することにより、水分子が複合体に包接する
割合が相対湿度の変化に対して直線的に変化する粘土／
有機複合体の作成を行うことができ、この特徴を用いる
ことにより、粘土／有機複合体湿度センサーとして利用
できる。PH at the time of inclusion of organic matter in layered clay mineral
By adjusting the conditions, the rate of inclusion of water molecules in the complex changes linearly with changes in relative humidity.
An organic composite can be produced, and by using this feature, it can be used as a clay / organic composite humidity sensor.
【００１０】有機物の中には、双極イオン性の有機物、
例えばアミノ基やカルボキシル基を有する有機物、例え
ばアミノ酸などがある。このような有機物が層状粘土鉱
物に包接し、粘土／有機複合体が作製された時、相対湿
度に対する変化はアミノ酸自身の解離や側鎖に影響され
ると考えられる。例として、リシンやアルギニン、ヒス
チジンは、側鎖にアミノ基を持ち、アスパラギン酸やグ
ルタミン酸は側鎖にカルボキシル基を持つ。リシンの解
離定数ｐＫ1 （−ＣＯＯＨ）、ｐＫ2 （一ＮＨ 3 + ）、
ｐＫR （側鎖）は、それぞれ２．１６、９．１８、１
０．７９である。ｐＨが９．１８までは２つのアミノ基
がプラス電荷を持つ。層状粘土鉱物に包接した場合、リ
シンの上下層を強く結合させるため、粘土／有機複合体
への水分子の包接はほとんど起こらないが、ｐＨ９．１
８から１０．７９までは、プラス電荷のアミノ基が１つ
になり、またカルボキシル基がマイナス電荷を示す。そ
めためリシンの層状粘土鉱物への包接は可能であるが、
リシン分子は上下層を強く結合することができない。ま
た、カルボキシル基は親水的なために水分子を容易に吸
着できる性質がある。そのため、相対湿度の増加で層間
に水分子を包接し易くなる。[0010] Among the organic substances, there are zwitterionic organic substances,
For example, an organic substance having an amino group or a carboxyl group, for example,
There are amino acids. Such organic matter is a layered clay ore
When the clay / organic composite is made to be included
Changes in degree are affected by the dissociation of amino acids themselves and side chains
It is thought that. For example, lysine, arginine, hiss
Thidine has an amino group in the side chain, and aspartic acid and
Rutamic acid has a carboxyl group in the side chain. Ricin's solution
Separation constant pK1(-COOH), pKTwo(One NH Three +),
pKR(Side chains) are 2.16, 9.18, 1
0.79. Two amino groups up to pH 9.18
Has a positive charge. When included in layered clay minerals,
Clay / organic composite for strong bonding between upper and lower layers of thin
Inclusion of water molecules in water hardly occurs, but pH 9.1
8 to 10.79, one positively charged amino group
And the carboxyl group shows a negative charge. So
Therefore, inclusion of lysine in layered clay minerals is possible,
The lysine molecule cannot bind the upper and lower layers strongly. Ma
In addition, carboxyl groups are hydrophilic and easily absorb water molecules.
There is a property that can be worn. Therefore, the increase in relative humidity
Water molecules easily.
【００１１】他の例として、アスパラギン酸の解離定数
ｐＫ1 （−ＣＯＯＨ）、ｐＫ2 （−ＮＨ3 + ）、ｐＫR
（側鎖）は、それぞれ１．９９、９．９０、３．９０で
ある。ｐＨ１．９９以下ではカルボキシル基は電荷を持
たないが、それ以外ではカルボキシル基はマイナス電荷
を持つ。このため、層状粘土鉱物に包接しにくくはなる
が、アミノ基がプラス電荷を持つ条件（ｐＨ９．９０以
下）では、包接は可能である。この場合も、リシンと同
様に層状粘土鉱物の層間にある親水的なカルボキシル基
に水分子が吸着することにより、水分子が粘土／有機複
合体層間に包接され、複合体層間に広がると考えられ
る。As another example, the dissociation constants of aspartic acid pK 1 (—COOH), pK 2 (—NH 3 + ), pK R
(Side chains) are 1.99, 9.90, and 3.90, respectively. At pH 1.99 or lower, the carboxyl group has no charge, but otherwise the carboxyl group has a negative charge. For this reason, it becomes difficult to include in the layered clay mineral, but inclusion is possible under the condition that the amino group has a positive charge (pH of 9.90 or less). Also in this case, it is considered that water molecules are adsorbed on hydrophilic carboxyl groups between layers of the layered clay mineral similarly to lysine, whereby the water molecules are included between the clay / organic composite layers and spread between the composite layer layers. Can be
【００１２】このような考察から、層状粘土鉱物に双極
イオン性を有する低分子有機物や高分子有機物、例え
ば、アミノ基やカルボキシル基を有する有機物を包接す
る粘土／有機複合体による湿度センサーを作製すること
が可能である。Based on the above considerations, a humidity sensor using a clay / organic composite in which a low molecular weight organic substance or a high molecular weight organic substance having a zwitterionic property, for example, an organic substance having an amino group or a carboxyl group is included in a layered clay mineral is prepared. It is possible.
【００１３】[0013]
【作用】双極イオン性有機物を包接することにより有機
物のプラスイオン的な部分が粘土鉱物に吸着し、マイナ
スイオン的な部分が粘土鉱物の各層間の結合を弱くする
ことにより、水分子が粘土の層間に包接しやすくなる。
また、マイナスイオン的部分に湿度に対して適度に水分
子を吸着するため、相対湿度に対して、粘土／有機複合
体の層間が直線的広がる作用がある。[Function] Inclusion of zwitterionic organic matter causes the positive ionic part of the organic matter to be adsorbed on the clay mineral, and the negative ionic part weakens the bond between the layers of the clay mineral. It becomes easy to include between layers.
In addition, since the water molecules are appropriately adsorbed to the negative ion portion with respect to the humidity, there is an effect that the layers of the clay / organic composite spread linearly with respect to the relative humidity.
【００１４】[0014]
【実施例】出発物質は天然のモンモリロナイトとＤＬ−
グルタミン酸一水和物である。２００ｍｇのモンモリロ
ナイトにｐＨ４のグルタミン酸の２０ｍＭ溶液１５ｍｌ
を加え、１昼夜撹拌した。その後遠心分離で固液分離を
し、上澄み液を除去した後、再びグルタミン酸溶液を１
５ｍ１加え１昼夜撹拌した。この操作を６回繰り返し
た。作製された複合体は脱イオン水で３回洗浄した。複
合体は温湿度制御Ｘ線装置により、１０％から９０％ま
で１０％毎に３０分間湿度を保持した後測定した。複合
体の層間距離を測定すると、図１のように相対湿度の変
化に対して直線的に層間距離が変化した。また、湿度を
９０％から１０％まで下降した場合も同様に直線的に層
間距離が変化した。５分間保持においても層間距離はほ
ぼ同じであった。EXAMPLES Starting materials were natural montmorillonite and DL-
Glutamic acid monohydrate. 15 ml of a 20 mM solution of glutamic acid at pH 4 in 200 mg of montmorillonite
And stirred for one day. Thereafter, solid-liquid separation was performed by centrifugation, and the supernatant was removed.
5 ml was added and the mixture was stirred for one day. This operation was repeated six times. The prepared complex was washed three times with deionized water. The composite was measured with a temperature-humidity control X-ray apparatus after keeping the humidity from 10% to 90% every 10% for 30 minutes. When the interlayer distance of the composite was measured, the interlayer distance changed linearly with the change in relative humidity as shown in FIG. Similarly, when the humidity was reduced from 90% to 10%, the interlayer distance also changed linearly. The interlayer distance was almost the same even after 5 minutes.
【００１５】[0015]
【発明の効果】本発明の粘土／有機複合体センサーは、
用いる粘土鉱物は天然物で充分対応ができ、作成は安価
であり、さらに容易に作れる。さらに天然素材の有機物
を複合体に用いれば、自然環境にも影響が全くない。The clay / organic composite sensor of the present invention is
The clay mineral to be used can be sufficiently made of natural products, is inexpensive to make, and can be made more easily. Furthermore, if an organic substance of a natural material is used for the composite, there is no effect on the natural environment.
【図１】相対湿度に対する粘土／有機複合体の層間距離
の関係を示すグラフである。FIG. 1 is a graph showing the relationship between the relative humidity and the interlayer distance of a clay / organic composite.
Claims (2)
分子有機物または高分子有機物を包接する粘土／有機複
合体からなることを特徴とする粘土／有機複合体湿度セ
ンサー。1. A clay / organic composite humidity sensor comprising a clay / organic composite in which a low molecular weight organic substance or a high molecular weight organic substance having zwitterionicity is included in a layered clay mineral.
たは高分子有機物がアミノ基とカルボキシル基を有する
有機物であることを特徴とする請求項１記載の粘土／有
機複合体湿度センサー。2. The clay / organic composite humidity sensor according to claim 1, wherein the low molecular weight organic substance having a zwitterionic property or the high molecular weight organic substance is an organic substance having an amino group and a carboxyl group.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35244099A JP3321601B2 (en) | 1999-12-10 | 1999-12-10 | Clay / organic composite humidity sensor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35244099A JP3321601B2 (en) | 1999-12-10 | 1999-12-10 | Clay / organic composite humidity sensor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2001165849A JP2001165849A (en) | 2001-06-22 |
| JP3321601B2 true JP3321601B2 (en) | 2002-09-03 |
Family
ID=18424099
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP35244099A Expired - Lifetime JP3321601B2 (en) | 1999-12-10 | 1999-12-10 | Clay / organic composite humidity sensor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3321601B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107209138A (en) * | 2014-12-23 | 2017-09-26 | 马克思-普朗克科学促进协会 | Gas and vapor sensing device based on 2D nanometer sheet materials |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007150264A (en) * | 2005-10-27 | 2007-06-14 | Hitachi Chem Co Ltd | Organic insulating material, polishing material for copper film compound material, and polishing method |
| JP5288560B2 (en) * | 2009-10-29 | 2013-09-11 | 国立大学法人広島大学 | Moisture detection method |
-
1999
- 1999-12-10 JP JP35244099A patent/JP3321601B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107209138A (en) * | 2014-12-23 | 2017-09-26 | 马克思-普朗克科学促进协会 | Gas and vapor sensing device based on 2D nanometer sheet materials |
| US10488335B2 (en) | 2014-12-23 | 2019-11-26 | MAX-PLANCK-Gesellschaft zur Förderung der Wissenschaften e.V. | Gas and vapor sensing devices based on 2D nanosheet material |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2001165849A (en) | 2001-06-22 |
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