JPS6319020B2 - - Google Patents
Info
- Publication number
- JPS6319020B2 JPS6319020B2 JP57201587A JP20158782A JPS6319020B2 JP S6319020 B2 JPS6319020 B2 JP S6319020B2 JP 57201587 A JP57201587 A JP 57201587A JP 20158782 A JP20158782 A JP 20158782A JP S6319020 B2 JPS6319020 B2 JP S6319020B2
- Authority
- JP
- Japan
- Prior art keywords
- humidity
- present
- moisture
- electrical resistance
- resistance value
- 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
Links
- 239000000758 substrate Substances 0.000 claims description 11
- RAHZWNYVWXNFOC-UHFFFAOYSA-N sulfur dioxide Inorganic materials O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 5
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims 1
- 229920000642 polymer Polymers 0.000 description 9
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000004044 response Effects 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 229920001477 hydrophilic polymer Polymers 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical group 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- 150000003863 ammonium salts Chemical group 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229920006317 cationic polymer Polymers 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
- G01N27/121—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid for determining moisture content, e.g. humidity, of the fluid
Description
【発明の詳細な説明】
本発明は雰囲気中の湿度に依存して電気抵抗値
の変化することを利用する感湿素子に関するもの
である。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a moisture sensing element that utilizes changes in electrical resistance depending on the humidity in the atmosphere.
感湿素子は、雰囲気中の湿度に依存して電気抵
抗値の変化する性質を利用して湿度を測定する場
合に用いられるものであるが、このような感湿素
子としては、
１ 電気抵抗値が低く、かつ湿度変化に対する電
気抵抗値の変化が大きいこと、
２ いわゆる履歴現象（ヒステリシス）がないこ
と、すなわち高湿度から低湿度に変化させた場
合と、低湿度から高湿度に変化させた場合に電
気抵抗値がほぼ同一値を与えること、
３ 広い湿度範囲を計測できること
４ 電気抵抗値が湿度にのみ依存し、温度等他の
要素の変化に対する応答性が少ないこと、及び
５ 長時間の使用にたえること、すなわち長時間
使用しても素子の劣化がなく、また電気的特性
にも変化が生じないこと
等の性質を備えていることが要求されている。 Moisture sensing elements are used to measure humidity by utilizing the property that the electrical resistance value changes depending on the humidity in the atmosphere. 2. There is no so-called hysteresis, that is, when changing from high humidity to low humidity and when changing from low humidity to high humidity. 3. It is possible to measure a wide humidity range. 4. The electrical resistance value depends only on humidity and has little responsiveness to changes in other factors such as temperature, and 5. It can be used for a long time. In other words, the device is required to have properties such that the device does not deteriorate even after long-term use, and the electrical characteristics do not change.
このような雰囲気中の湿度に依存して電気抵抗
値が変化することを利用する感湿素子としては、
従来、塩化リチウムのような低分子電解質、樹脂
に導電性粉末を混合したもの、金属表面を酸化し
たもの、親水性高分子を用いたもの、親水性高分
子を半導体基板に接して設けたものが用いられて
いた。しかしながらこれ等は、いずれも前記１）
〜５）の要求特性のいずれか或は二以上を充足せ
ず、新しい感湿素材の開発が望まれていた。 Moisture sensing elements that utilize this change in electrical resistance depending on the humidity in the atmosphere include:
Conventional methods include low-molecular electrolytes such as lithium chloride, resins mixed with conductive powder, metal surfaces oxidized, hydrophilic polymers, and hydrophilic polymers placed in contact with semiconductor substrates. was used. However, these are all 1) above.
It has been desired to develop a new moisture-sensitive material that does not satisfy any one or more of the required characteristics of 5) to 5).
一方このような欠点を解消することを目的とし
て、特開昭55―10502号公報に記載のように、ア
ルミナ基板上に、一対の櫛状の電極を対向接着し
て該電極間にギヤツプを形成し、該基体上に少く
とも該ギヤツプを覆うようにカチオン性モノマー
を重合させた高分子を被覆してなる感湿素子が提
案されている。 On the other hand, in order to eliminate such drawbacks, as described in Japanese Patent Application Laid-Open No. 10502/1983, a pair of comb-shaped electrodes are bonded facing each other on an alumina substrate to form a gap between the electrodes. However, a moisture-sensitive element has been proposed in which the substrate is coated with a polymer made by polymerizing a cationic monomer so as to cover at least the gap.
しかしながら通常のカチオン性ポリマーでは、
それが第１級、第２級あるいは第３級アミンより
成る場合には電気抵抗が大きすぎて感度が悪くな
り、また第４級アンモニウム塩型ポリマーの場合
には電気抵抗は低いが、あまりに親水的であるた
め高湿度になると吸湿して表面がべたつき形態的
変化を生じ、ひいては電気的特性に変化を生ぜし
める等の欠点があつた。 However, with ordinary cationic polymers,
If it consists of a primary, secondary or tertiary amine, the electrical resistance will be too high and the sensitivity will deteriorate; if it is a quaternary ammonium salt type polymer, the electrical resistance will be low but it will be too hydrophilic. Because of its high humidity, it absorbs moisture, causing the surface to become sticky and change in shape, which in turn causes changes in electrical characteristics.
本発明者は、かかる欠点を解消するために鋭意
研究を進めた結果、次式：
（式中、ｎは10ないし1000を表わす。）
で表わされるように、第３級アミンのアンモニウ
ム塩型窒素と第４級アンモニウム塩型窒素とを含
み、且つ対イオンが過塩素酸イオンである場合に
は、前記のような欠点がなく、感湿素子としての
前記１）〜５）の要求特性のすべてを実質的に満
し得ることを見出し、本発明を完成した。 As a result of intensive research to eliminate such drawbacks, the present inventor found the following formula: (In the formula, n represents 10 to 1000.) As shown, it contains nitrogen in the ammonium salt form of a tertiary amine and nitrogen in the quaternary ammonium salt form, and the counter ion is a perchlorate ion. The present invention has been completed based on the discovery that, in some cases, the above-mentioned drawbacks do not exist and substantially all of the required characteristics 1) to 5) above as a moisture-sensitive element can be satisfied.
即ち本発明は、絶縁基板上に設けた一対の電極
間に前記式で表わされる重合体を設けてなる感湿
素子に関するものである。 That is, the present invention relates to a moisture-sensitive element in which a polymer represented by the above formula is provided between a pair of electrodes provided on an insulating substrate.
本発明の前記式で表わされる重合体は、例えば
ジアリルアミノプロピルジメチルアリルアンモニ
ウムクロライドの塩酸塩と二酸化イオウとを共重
合してなる重合体に、過塩素酸水溶液を加えるこ
とによつて製造される。 The polymer represented by the above formula of the present invention is produced, for example, by adding a perchloric acid aqueous solution to a polymer obtained by copolymerizing diallylaminopropyldimethylallylammonium chloride hydrochloride and sulfur dioxide. .
このようにして得た重合体は、少なくとも電極
間を覆うように設ければよく、電極間を越えて基
板を覆うように設けてもよい。 The polymer thus obtained may be provided so as to cover at least the space between the electrodes, or may be provided so as to cover the substrate beyond the space between the electrodes.
本発明で使用する電極及び絶縁基板は、この種
目的に使用されるものはいずれも使用することが
でき、特に限定されない。 The electrodes and insulating substrates used in the present invention are not particularly limited, and any electrodes and insulating substrates used for this type of purpose can be used.
次に実施例を挙げて、本発明を更に説明する。
ジアリルアミノプロピルジメチルアリルアンモニ
ウムクロライドの塩酸塩と二酸化イオウとを共重
合してなるポリマーを水に溶解させ、これを10％
過塩素酸水溶液に撹拌しながら加える。生成した
沈澱を取し、水で洗浄して過剰の過塩素酸を除
き、過、乾燥して白色粉末を得る。このものは
水には溶けないが、ジメチルスルホオキサイド等
の有機溶媒には溶解し、これらは全て良好な皮膜
形成態を有する。 Next, the present invention will be further explained with reference to Examples.
A polymer formed by copolymerizing diallylaminopropyldimethylallylammonium chloride hydrochloride and sulfur dioxide is dissolved in water, and 10% of this is dissolved in water.
Add to perchloric acid aqueous solution while stirring. The formed precipitate is collected, washed with water to remove excess perchloric acid, filtered and dried to obtain a white powder. This material is insoluble in water, but soluble in organic solvents such as dimethyl sulfoxide, all of which have good film-forming properties.
一方アルミナ等のような絶縁基板上に一対の電
極を接着し、各電極にはリード線を接続させる。
この基板上に前記重合体の溶液を塗布し、加熱乾
燥して溶媒を除去し、基板上に高分子被膜を形成
させて感湿素子を完成させる。このようにして得
た本発明の高分子被膜は強じんであり、かつ水不
溶性であるので高湿度においても膨潤したり、溶
解したりすることがなく耐久性に優れていた。 On the other hand, a pair of electrodes is bonded onto an insulating substrate such as alumina, and a lead wire is connected to each electrode.
A solution of the polymer is applied onto this substrate, and the solvent is removed by heating and drying to form a polymer film on the substrate, thereby completing the moisture-sensitive element. The polymer film of the present invention thus obtained was strong and water-insoluble, so it did not swell or dissolve even under high humidity and had excellent durability.
次にこのようにして得た感湿素子の電気的特性
を測定した試験例を示す。 Next, a test example will be shown in which the electrical characteristics of the moisture-sensitive element thus obtained were measured.
本発明の感湿素子を使用して、測定すべき雰囲
気の相対湿度と電気抵抗値との関係を測定した。
結果を第１図に示す。図中、Ａは、湿度を下げて
いつた場合の抵抗値を示し、Ｂは湿度を上げてい
つた場合の抵抗値を示す。 Using the humidity sensing element of the present invention, the relationship between the relative humidity of the atmosphere to be measured and the electrical resistance value was measured.
The results are shown in Figure 1. In the figure, A indicates the resistance value when the humidity is lowered, and B indicates the resistance value when the humidity is increased.
図より明らかな如く、本発明の感湿素子は湿度
30〜85％の広い範囲にわたつて、電気抵抗値は
107Ω以下であり、かつ湿度の変化による抵抗値
の変化率が大きい。 As is clear from the figure, the humidity sensing element of the present invention
Over a wide range of 30 to 85%, the electrical resistance value is
10 7 Ω or less, and the rate of change in resistance value due to changes in humidity is large.
また湿度を上げていつた場合と下げていつた場
合とでほぼ同一の抵抗値を示すが、このことから
本発明の感湿素子ではヒステリシス現象がないこ
とを理解することができる。 Further, the resistance value is almost the same when the humidity is increased and when the humidity is decreased, and from this fact it can be understood that there is no hysteresis phenomenon in the humidity sensing element of the present invention.
次に、本発明の感湿素子の応答特性を確認する
ため、初め相対湿度33.6％にあつた素子を相対湿
度86％へ上げた場合、逆に86％から33.6％へ下げ
た場合の電気抵抗値の変化を経時的に測定した。
結果を第２図に示す。図中Ｃは、相対湿度33.6％
から86％へ上げた場合の結果を示し、Ｄは86％か
ら33.6％へ下げた場合の結果を示す。 Next, in order to confirm the response characteristics of the humidity sensing element of the present invention, we investigated the electrical resistance of an element initially at 33.6% relative humidity when raised to 86% relative humidity, and conversely when lowered from 86% to 33.6%. Changes in values were measured over time.
The results are shown in Figure 2. C in the diagram is relative humidity 33.6%
D shows the results when increasing from 86% to 86%, and D shows the results when decreasing from 86% to 33.6%.
図より、本発明の感湿素子の応答特性は極めて
優れており、感度がよいことがわかる。 From the figure, it can be seen that the response characteristics of the moisture-sensitive element of the present invention are extremely excellent, and the sensitivity is good.
次に湿度を50％とし、温度を10℃、20℃、30
℃、40℃とした場合の抵抗値を測定した。結果
は、それぞれ温度10℃で8.9×105Ω、温度20℃で
5.6×105Ω、温度30℃で1.3×105Ω、温度40℃で
6.8×104Ωであつた。これより、本発明の感湿素
子の電気抵抗値は、温度依存性があるが、従来の
高分子センサーに比較してその依存性は小さいこ
とがわかる。 Next, the humidity is set to 50%, and the temperature is set to 10℃, 20℃, and 30℃.
The resistance value was measured at 40°C and 40°C. The results are 8.9×10 5 Ω at a temperature of 10°C and 20°C, respectively.
5.6×10 5 Ω at 30°C temperature 1.3×10 5 Ω at 40°C temperature
It was 6.8×10 4 Ω. This shows that although the electrical resistance value of the humidity sensing element of the present invention is temperature dependent, the dependence is smaller than that of conventional polymer sensors.
更に本発明の感湿素子について、湿度50％から
90％までの間の湿度リサイクルテストを行つた。
結果は、800時間経過後に於いても、本発明の感
湿素子は製造直後の電気的特性をそのまま保持し
ていた。 Furthermore, regarding the humidity sensing element of the present invention, humidity from 50%
Humidity recycling tests up to 90% were conducted.
The results showed that even after 800 hours had passed, the moisture-sensitive element of the present invention retained its electrical characteristics immediately after manufacture.
以上述べたように、本発明の感湿素子は、感湿
素子として要求される性能をすべての面に於いて
実質的に満足させるものであり、従来の感湿素子
に比して著しい利点を有する。 As described above, the humidity sensing element of the present invention substantially satisfies the performance required for a humidity sensing element in all aspects, and has significant advantages over conventional moisture sensing elements. have
第１図は、本発明の感湿素子を使用して、相対
湿度と電気抵抗値との関係を測定したグラフ、第
２図は、本発明の感湿素子の応答特性を示すため
のグラフである。
Figure 1 is a graph showing the relationship between relative humidity and electrical resistance using the humidity sensing element of the invention, and Figure 2 is a graph showing the response characteristics of the humidity sensing element of the invention. be.
Claims (1)
ンモニウムクロライド塩酸塩・二酸化イオウ共重
合体を設けてなる感湿素子。[Claims] 1 Between a pair of electrodes provided on an insulating substrate, the following formula: (In the formula, n represents 10 to 1000.) A moisture-sensitive element comprising a diaminopropyldimethylallylammonium chloride hydrochloride/sulfur dioxide copolymer represented by the formula:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57201587A JPS5991351A (en) | 1982-11-17 | 1982-11-17 | Humidity sensor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57201587A JPS5991351A (en) | 1982-11-17 | 1982-11-17 | Humidity sensor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5991351A JPS5991351A (en) | 1984-05-26 |
| JPS6319020B2 true JPS6319020B2 (en) | 1988-04-21 |
Family
ID=16443523
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57201587A Granted JPS5991351A (en) | 1982-11-17 | 1982-11-17 | Humidity sensor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5991351A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60113140A (en) * | 1983-11-25 | 1985-06-19 | Hokuriku Denki Kogyo Kk | Production of moisture sensor element using ionene polymer |
| JPS61237044A (en) * | 1985-04-12 | 1986-10-22 | Hamamatsu Photonics Kk | Moisture detection element and manufacture thereof |
| JPH0653702U (en) * | 1991-03-29 | 1994-07-22 | 茂 千代 | Fixed valve and rocker arm |
| KR100550805B1 (en) * | 2001-08-30 | 2006-02-10 | 공명선 | Humidity sensor comprising polymeric membrane |
-
1982
- 1982-11-17 JP JP57201587A patent/JPS5991351A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5991351A (en) | 1984-05-26 |
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