JPS62245149A - Humidity-sensitive element - Google Patents
Humidity-sensitive elementInfo
- Publication number
- JPS62245149A JPS62245149A JP61089392A JP8939286A JPS62245149A JP S62245149 A JPS62245149 A JP S62245149A JP 61089392 A JP61089392 A JP 61089392A JP 8939286 A JP8939286 A JP 8939286A JP S62245149 A JPS62245149 A JP S62245149A
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- humidity
- moisture
- pyridyl group
- electrodes
- 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.)
- Pending
Links
- 229920000642 polymer Polymers 0.000 claims abstract description 18
- 125000004076 pyridyl group Chemical group 0.000 claims abstract description 10
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 5
- 239000000758 substrate Substances 0.000 claims abstract description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 9
- BXXWFOGWXLJPPA-UHFFFAOYSA-N 2,3-dibromobutane Chemical compound CC(Br)C(C)Br BXXWFOGWXLJPPA-UHFFFAOYSA-N 0.000 abstract description 5
- 238000010438 heat treatment Methods 0.000 abstract description 4
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 4
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 2
- ULTHEAFYOOPTTB-UHFFFAOYSA-N 1,4-dibromobutane Chemical compound BrCCCCBr ULTHEAFYOOPTTB-UHFFFAOYSA-N 0.000 abstract 1
- 229920006037 cross link polymer Polymers 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920002717 polyvinylpyridine Polymers 0.000 description 2
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical group CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000005956 quaternization reaction Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は、各種機器において湿度センサーとして使用さ
れる感湿素子に関する。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a humidity sensing element used as a humidity sensor in various devices.
〈従来技術〉
従来広く使用されている感湿素子は、電極間に親木性ポ
リマーを主体とする感湿膜を形成したものが多く使用さ
れている。<Prior Art> Many moisture-sensitive elements that have been widely used in the past have a moisture-sensitive film mainly made of a wood-philic polymer formed between electrodes.
〈発明が解決しようとする問題点〉
しかし、上記従来の感湿素子は、高湿度雰囲気中におい
て結露したりするような場合にはポリマーの感湿膜は、
吸湿して変形したり、或は湿気を多量に吸収してポリマ
ー自体が部分的に溶解したりして再使用できないことが
あり、又、ある程度は能が残っていても再現性が低下し
たり、或は復帰時間が長くなったりして８！能低下が著
しくなり、使用不能の場合が多く発生していた。<Problems to be Solved by the Invention> However, in the above-mentioned conventional moisture-sensitive element, in cases where dew condensation occurs in a high-humidity atmosphere, the polymer moisture-sensitive film is
The polymer may become deformed due to moisture absorption, or the polymer itself may partially dissolve due to absorption of a large amount of moisture, making it impossible to reuse, or even if some performance remains, reproducibility may deteriorate. , or the return time becomes longer and 8! The performance of the equipment had deteriorated significantly, and there were many cases where it became unusable.
そこで、本発明においては、上記従来の感湿素子の欠点
に対処し、高温度の雰囲気中で反復使用しても機能低下
を来さない高品質の素子を提供することを目的とするも
のである。Therefore, the present invention aims to address the above-mentioned drawbacks of the conventional moisture-sensitive elements and provide a high-quality element that does not deteriorate in functionality even when used repeatedly in a high-temperature atmosphere. be.
く問題点を解決する為の手段〉
ピリジル基を有するポリマーと、ジハロゲン化炭化水素
との加熱反応によって得た架橋形分子構造をもった感湿
膜からなる感湿素子。Means for Solving the Problems> A moisture-sensitive element comprising a moisture-sensitive membrane having a crosslinked molecular structure obtained by a heating reaction between a polymer having a pyridyl group and a dihalogenated hydrocarbon.
〈作用〉
各ポリマーに結合したピリジニウム基が他のポリマー上
のピリジニウム基と炭化水素で架橋されている為に湿気
に対して不溶性となり分子構造が安定化する。<Function> Since the pyridinium groups bonded to each polymer are cross-linked with the pyridinium groups on other polymers with hydrocarbons, they become insoluble in moisture and the molecular structure is stabilized.
〈実施例〉
以下、本発明について、実施例を挙げて詳細に説明する
と、ポリ−４−ビニルピリノンへと、１−４ジブロモブ
タンＢとを式■のように混入する。<Example> Hereinafter, the present invention will be described in detail with reference to Examples. 1-4 dibromobutane B is mixed into poly-4-vinylpyrinone as shown in formula (2).
そして、メタノール溶媒に溶解して溶液を形成し、この
溶液を予めアルミナ基盤上に焼付は形成した金対向電極
上において両電極間に跨がって塗布後、これを一定時間
（５時間以上）６０℃の温度で加熱することにより、各
ポリマー鎖体Ａ上に結合したピリジル基Ｃと、１−４ジ
ブロモブタンＢとは熱化学反応を起こして、ピリジル基
Ｃに１−４ジブロモブタンＢのハロゲンが結合し、式■
のようにｖＡａ反応を生じる。Then, dissolve it in a methanol solvent to form a solution, apply this solution across the gap between both electrodes on a gold counter electrode that has been baked on an alumina substrate, and then apply this solution for a certain period of time (5 hours or more). By heating at a temperature of 60°C, the pyridyl group C bonded to each polymer chain A and 1-4 dibromobutane B undergo a thermochemical reaction, and the pyridyl group C is converted into 1-4 dibromobutane B. Halogen is combined with the formula■
A vAa reaction occurs as in
（ＣＨ２）ｎ （ＣＨ２）ｎ −■ピリジ
ル基Ｃはピリジニウム基りに変化する。(CH2)n (CH2)n -■Pyridyl group C changes to a pyridinium group.
そして、その反応は各ポリ−４−ビニルピリジンについ
ても同様に反応が起こり、四級化して親水性を生じるよ
うになる。The same reaction occurs for each poly-4-vinylpyridine, resulting in quaternization and hydrophilicity.
こうした反応の後、前記アルミナ基盤上における未反応
のポリ−４−ビニルピリジン及び１−４ジブロモブタン
をメタノールで洗浄することにより化学的に安定したし
かも湿気に対しても安定した構造をもった感湿膜を有す
る感湿素子が形成される。After this reaction, the unreacted poly-4-vinylpyridine and 1-4 dibromobutane on the alumina substrate are washed with methanol, thereby creating a structure that is chemically stable and stable against moisture. A moisture sensitive element having a wet film is formed.
次に、上記によって反応時間を変えて製作した感湿素子
のインピーダンスと温度の特性について調べると第１図
のように温度６０℃で一定に保ち反応時間をｉ、ｓ、ｔ
ｏ待時間変えた場合、反応時間が１ｖｆＩｉ］と５時間
以上の場合を比較すると、反応時間が短いものでは僅か
にヒステリシス現象を示すが、充分時間をかけて反応さ
せたものでは殆どヒステリシス現象が見られない。Next, we investigated the impedance and temperature characteristics of the moisture-sensitive element fabricated by changing the reaction time as shown in Figure 1.The temperature was kept constant at 60°C and the reaction time was i, s, t.
oWhen the waiting time is changed, comparing the reaction time of 1vfIi] and the case of 5 hours or more, the short reaction time shows a slight hysteresis phenomenon, but the reaction time of enough time shows almost no hysteresis phenomenon. can not see.
又、第２図に示すものは、本発明の感湿素子を水中に異
なる時間浸漬した後、これを夫々異なる湿度の雰囲気中
においてインピーダンスを測定した耐水試験の結果を示
し、素子を１０分間水中に浸した後各湿度におけるイン
ピーダンスを測定し、更に３０分間と６０分間浸したも
のについても同様に夫々各湿度におけるインピーダンス
を測定したが、グラフから明らかなように殆ど湿度の影
響を受けることなく不変であることが判明する。Moreover, what is shown in FIG. 2 shows the results of a water resistance test in which the impedance was measured in atmospheres with different humidity after the moisture sensing element of the present invention was immersed in water for different times. The impedance was measured at each humidity after being immersed in water, and the impedance was similarly measured at each humidity for those soaked for 30 minutes and 60 minutes, but as is clear from the graph, the impedance remained unchanged with almost no influence of humidity. It turns out that.
このことは本発明素子が湿度即ち水分によって感湿膜が
変化せず安定した感湿特性を有することを示すものであ
り、念の為に点線で示すよう１こ架橋されてないポリビ
ニルピリジンをブチルプロミドで四級化した感湿膜から
なる素子を上記同様条件下で試験すると者しく変化し、
これからも明らかなように単に四級化しただけのポリビ
ニルピリジンには耐水性が失われることが云える。This shows that the device of the present invention has stable moisture-sensitive characteristics without changing the moisture-sensitive film due to humidity, that is, moisture.For convenience, as shown by the dotted line, one layer of uncrosslinked polyvinylpyridine was replaced with butyl bromide. When an element consisting of a quaternized moisture-sensitive film is tested under the same conditions as above, it changes significantly,
As is clear from this, polyvinylpyridine that has simply been quaternized loses its water resistance.
このようにして本発明の感湿素子は多くのピリジル基を
有するポリマーと１−４ノプロモブタンとを加熱反応さ
せることにより、ビリノル基を四級化させて親水性を高
めると共に各ポリマー鎖体同士が架橋して水に対し不溶
性となり、大気中の水分を吸収しても劣化することなく
、且つ湿気に対し敏感で、しかも可逆的に湿気を吸脱す
る安定した感湿膜を得ることができる。In this way, the moisture-sensitive element of the present invention is made by subjecting a polymer having many pyridyl groups to a thermal reaction with 1-4-nopromobutane to quaternize the bilinol groups to increase hydrophilicity and to bond each polymer chain with each other. It is possible to obtain a stable moisture-sensitive film that is crosslinked and becomes insoluble in water, does not deteriorate even if it absorbs moisture in the atmosphere, is sensitive to moisture, and reversibly absorbs and desorbs moisture.
〈発明の効果〉
本発明は、上述のように生成された分子構造の感湿膜を
、基盤上の電極間に塗布して得たものであるから、高湿
度雰囲気中や、結露を生じるような悪条件下であっても
感湿膜の分子構造を損ねたりしない極めて耐水性の高い
、しかも高湿度のみでなく低＠度領域においても性能低
下を伴うことなく、広範囲の湿度領域での使用が可能で
あると共に、ヒステリシス現象が極度に少なく再現性の
良い、その上応答速度ら速く、長期間安定した感湿特性
を保つなど多くの優れた効果を有する理想的な発明であ
る。<Effects of the Invention> Since the present invention is obtained by applying the moisture-sensitive film having the molecular structure produced as described above between the electrodes on a substrate, it cannot be used in a high humidity atmosphere or in a place where dew condensation may occur. It has extremely high water resistance that does not damage the molecular structure of the moisture-sensitive film even under adverse conditions, and can be used in a wide range of humidity without deteriorating its performance not only in high humidity but also in low temperature range. It is an ideal invention that has many excellent effects such as extremely low hysteresis phenomenon, good reproducibility, fast response speed, and maintaining stable moisture sensitivity characteristics for a long period of time.
第１図は、本発明感湿素子の相対湿度対インピーグンス
特性図、
第２図は、浸漬時間対インビーグンス特性図である。FIG. 1 is a relative humidity versus impedance characteristic diagram of the humidity sensitive element of the present invention, and FIG. 2 is a immersion time versus impedance characteristic diagram.
Claims (1)
リジル基を有するポリマーを少なくとも２個所以上をハ
ロゲンで置換した炭化水素で四級化すると同時に架橋し
た分子構造のものであることを特徴とする感湿素子。1. The moisture-sensitive membrane covering the electrodes placed oppositely on the alumina substrate has a molecular structure in which a polymer having pyridyl groups is quaternized with a hydrocarbon substituted with at least two halogens and at the same time cross-linked. Features a moisture-sensitive element.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61089392A JPS62245149A (en) | 1986-04-17 | 1986-04-17 | Humidity-sensitive element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61089392A JPS62245149A (en) | 1986-04-17 | 1986-04-17 | Humidity-sensitive element |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62245149A true JPS62245149A (en) | 1987-10-26 |
Family
ID=13969382
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61089392A Pending JPS62245149A (en) | 1986-04-17 | 1986-04-17 | Humidity-sensitive element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62245149A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5473933A (en) * | 1992-04-24 | 1995-12-12 | Matsushita Electric Industrial Co., Ltd. | Humidity sensor |
| WO2005014700A1 (en) * | 2003-08-12 | 2005-02-17 | Haeun Chemtec Co., Ltd. | The polyelectrolyte composition for humidity senser, polyelectrolyte ink and preparation method of polyelectrolyte membrane for sensor by inkjet printing |
-
1986
- 1986-04-17 JP JP61089392A patent/JPS62245149A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5473933A (en) * | 1992-04-24 | 1995-12-12 | Matsushita Electric Industrial Co., Ltd. | Humidity sensor |
| WO2005014700A1 (en) * | 2003-08-12 | 2005-02-17 | Haeun Chemtec Co., Ltd. | The polyelectrolyte composition for humidity senser, polyelectrolyte ink and preparation method of polyelectrolyte membrane for sensor by inkjet printing |
| US7771620B2 (en) | 2003-08-12 | 2010-08-10 | Haeun Chemtec Co., Ltd | Polyelectrolyte composition for humidity senser, polyelectrolyte ink and preparation method of poly electrolyte membrane for sensor by inkjet printing |
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