JPS6235058B2 - - Google Patents
Info
- Publication number
- JPS6235058B2 JPS6235058B2 JP53091758A JP9175878A JPS6235058B2 JP S6235058 B2 JPS6235058 B2 JP S6235058B2 JP 53091758 A JP53091758 A JP 53091758A JP 9175878 A JP9175878 A JP 9175878A JP S6235058 B2 JPS6235058 B2 JP S6235058B2
- Authority
- JP
- Japan
- Prior art keywords
- moisture
- dew condensation
- condensation sensor
- resistance
- powders
- 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
- 238000009833 condensation Methods 0.000 claims description 21
- 230000005494 condensation Effects 0.000 claims description 21
- 239000000843 powder Substances 0.000 claims description 20
- 239000004065 semiconductor Substances 0.000 claims description 14
- 239000000758 substrate Substances 0.000 claims description 13
- 239000012212 insulator Substances 0.000 claims description 9
- 229920000620 organic polymer Polymers 0.000 claims description 8
- 239000012528 membrane Substances 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 239000010408 film Substances 0.000 description 13
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 239000001856 Ethyl cellulose Substances 0.000 description 4
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 229920001249 ethyl cellulose Polymers 0.000 description 4
- 235000019325 ethyl cellulose Nutrition 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910002113 barium titanate Inorganic materials 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229920001477 hydrophilic polymer Polymers 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011521 glass Substances 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
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Description
この発明は水分などの付着により生じた結露状
態を抵抗値の変化として検知することができる結
露センサーに関するものである。
従来より、水分の検出を行う結露センサーとし
て、親水性高分子−塩化リチウム、塩化亜鉛など
の塩化物からなるダンモア型のものが使用されて
いる。この結露センサーは親水性高分子が吸湿し
た際に、塩化リチウム、塩化亜鉛などの電解質が
電離することにより、インピーダンスが変化する
ように構成されている。しかし高湿度の結露状態
になると感湿膜が耐水性に乏しく、安定性に欠け
るという欠点があつた。
またこのほかに、絶縁基板上にくし歯状電極を
形成し、この電極間に水分が付着したとき電極間
抵抗を検出するようにしたものや、上記したくし
歯状電極を被覆するように絶縁基板上に金属酸化
物からなる感湿膜を形成し、水分が付着したとき
膜自体の抵抗変化を検出するようにしたものがあ
る。しかし、いずれのものも長時間使用すると抵
抗値が上昇し、このため特性の比較改善を行なわ
なければならず、実用には不向であつた。
この発明は上記した問題を解消せんとしてなさ
れたもので、その要旨とするところは、絶縁基板
上に対向電極が形成され、少なくともこの対向電
極間の絶縁基板表面に感湿膜が形成されている結
露センサーにおいて、前記感湿膜は、温度抵抗変
化率の小さい有機高分子と、半導体粉末または絶
縁体粉末の１種または２種との混合物からなり、
半導体粉末または絶縁体粉末の１種または２種の
量が有機高分子の量にくらべて多く、かつ感湿膜
自体が微小な空孔を有する多孔質状態であること
を特徴とするものである。
感湿膜を構成するもののうち有機高分子として
は、水溶性高分子、エポキシ樹脂、エチルセルロ
ース、ポリビニルアルコール、シリコン樹脂、フ
ツ素樹脂などほとんどのものが使用できる。また
半導体粉末としては、CrO2、NiO、Fe3O4、
ZnO、SnO2、MnO2、TiO2-x、チタン酸バリウム
系半導体、チタン酸ストロンチウム系半導体など
の半導体チタン酸塩などがあり、さらに絶縁体粉
末にはTiO2、ZrO2、SiO2、Al2O3などがある。
有機高分子、半導体粉末、絶縁体粉末の種類、
混合比率の選択は所望の初期抵抗（相対湿度０％
における抵抗）、変化率の値に応じて任意に混合
すればよい。
この発明にかかる結露センサーは、ガラス、セ
ラミツクなどの絶縁基板上に形成された対向電極
を感湿膜が覆うように形成されるのが通常であ
る。
第１図はこの発明にかかる結露センサーの一例
を示したものである。
図において、１は絶縁基板、２，３はくし歯を
互いに交叉させた対向電極、４は感湿膜で、対向
電極２，３を覆つている。５，６はリード端子
で、対向電極２，３にそれぞれ電気接続されてい
る。
この発明により得られる結露センサーは、感湿
膜が非常に微小な空孔を有する多孔質であり、吸
水時には空孔より水分が吸着されるため、確実に
結露状態を検知することができる。また、通電状
態で水の分解が生じたとしても、感湿膜が多孔質
なため発生ガスを容易に逃がせることができる。
以下、この発明を実施例に従つて説明する。
実施例 １
酸無水物タイプのエポキシ樹脂、二酸化マンガ
ン、二酸化チタンを第１表の比率にて混合した。
混合物にエチルアルコールを加えてペースト状と
し、対向電極を形成しているアルミナ基板に塗布
した。アルミナ基板上の対向電極の形状は、細片
状の金よりなる導体２本を対向させたもので、電
極間隔は0.5mm、対向長は30.0mmである。次に、
150℃、20分間の条件で熱処理して焼付けし結露
センサーを作成した。
この結露センサーについて、相対湿度と抵抗値
の変化を測定し、その結果を第２図に示した。
図中の番号は試料番号と一致する。
The present invention relates to a dew condensation sensor that can detect dew condensation caused by adhesion of moisture or the like as a change in resistance value. Conventionally, as a dew condensation sensor for detecting moisture, a Dunmore type sensor made of a hydrophilic polymer and a chloride such as lithium chloride or zinc chloride has been used. This dew condensation sensor is configured so that when a hydrophilic polymer absorbs moisture, an electrolyte such as lithium chloride or zinc chloride is ionized, resulting in a change in impedance. However, the moisture-sensitive film has poor water resistance and lacks stability when exposed to high humidity and dew condensation. In addition to this, there are also devices in which comb-shaped electrodes are formed on an insulated substrate and the resistance between the electrodes is detected when moisture adheres between the electrodes, and an insulated one that covers the comb-shaped electrodes described above. There is a method in which a moisture-sensitive film made of metal oxide is formed on a substrate, and a change in resistance of the film itself is detected when moisture is attached. However, when used for a long period of time, the resistance value of any of them increases, and therefore the characteristics must be comparatively improved, making them unsuitable for practical use. This invention was made to solve the above-mentioned problems, and its gist is that a counter electrode is formed on an insulating substrate, and a moisture-sensitive film is formed at least on the surface of the insulating substrate between the counter electrodes. In the dew condensation sensor, the moisture sensitive film is made of a mixture of an organic polymer with a small rate of change in temperature resistance and one or two of semiconductor powder or insulator powder,
The amount of one or both of the semiconductor powder or the insulating powder is larger than the amount of the organic polymer, and the moisture sensitive film itself is porous with minute pores. . Among the organic polymers constituting the moisture-sensitive membrane, most can be used, such as water-soluble polymers, epoxy resins, ethyl cellulose, polyvinyl alcohol, silicone resins, and fluorine resins. In addition, semiconductor powders include CrO 2 , NiO, Fe 3 O 4 ,
There are semiconductor titanates such as ZnO, SnO 2 , MnO 2 , TiO 2-x , barium titanate semiconductors, and strontium titanate semiconductors, and insulator powders include TiO 2 , ZrO 2 , SiO 2 , Al 2 O 3 etc. Types of organic polymers, semiconductor powders, insulator powders,
The selection of the mixing ratio is based on the desired initial resistance (relative humidity 0%).
(resistance in ) and may be mixed arbitrarily depending on the value of the rate of change. The dew condensation sensor according to the present invention is usually formed such that a moisture sensitive film covers a counter electrode formed on an insulating substrate such as glass or ceramic. FIG. 1 shows an example of a dew condensation sensor according to the present invention. In the figure, 1 is an insulating substrate, 2 and 3 are counter electrodes having intersecting comb teeth, and 4 is a moisture sensitive film that covers the counter electrodes 2 and 3. Lead terminals 5 and 6 are electrically connected to the opposing electrodes 2 and 3, respectively. In the dew condensation sensor obtained according to the present invention, the moisture sensitive membrane is porous with very small pores, and when water is absorbed, water is adsorbed from the pores, so that the dew condensation state can be reliably detected. Further, even if water decomposes when electricity is applied, the generated gas can easily escape because the moisture-sensitive membrane is porous. Hereinafter, this invention will be explained according to examples. Example 1 An acid anhydride type epoxy resin, manganese dioxide, and titanium dioxide were mixed in the ratios shown in Table 1.
Ethyl alcohol was added to the mixture to form a paste, which was applied to an alumina substrate forming a counter electrode. The shape of the counter electrode on the alumina substrate is two conductors made of gold strips facing each other, the electrode spacing is 0.5 mm, and the opposing length is 30.0 mm. next,
A dew condensation sensor was created by heat-treating and baking at 150℃ for 20 minutes. Regarding this dew condensation sensor, changes in relative humidity and resistance were measured, and the results are shown in FIG. The numbers in the figure match the sample numbers.
【表】
実施例 ２
エチルセルロースをブチルセロソルブに溶解し
て20％エチルセルロース溶液を作成した。
次に20％エチルセルロース溶液、ブチルセロソ
ルブ、二酸化マンガン、二酸化チタンを第２表に
示す比率にて混合し、ペースト状とした。このペ
ーストを実施例１と同様にアルミナ基板の上に
170℃、20分間の熱処理条件で焼付けし、結露セ
ンサーを作成した。
この結露センサーについて相対湿度と抵抗値の
変化を測定し、その結果を第３図に示した。図中
の番号は試料番号と一致する。[Table] Example 2 A 20% ethyl cellulose solution was prepared by dissolving ethyl cellulose in butyl cellosolve. Next, 20% ethyl cellulose solution, butyl cellosolve, manganese dioxide, and titanium dioxide were mixed in the ratios shown in Table 2 to form a paste. Apply this paste on the alumina substrate as in Example 1.
A dew condensation sensor was created by baking at 170℃ for 20 minutes. Changes in relative humidity and resistance were measured for this dew condensation sensor, and the results are shown in FIG. The numbers in the figure match the sample numbers.
【表】
実施例 ３
10％ポリビニルアルコール水溶液、二酸化マン
ガン、酸化チタンを第３表に示す比率で混合し、
さらに純水を加えてペースト状とし、このペース
トを実施例１と同様にアルミナ基板の上120℃、
20分間の熱処理条件で焼付けし、結露センサーを
作成した。
この結露センサーについて相対湿度と抵抗値の
変化を測定し、その結果を第４図に示した。図中
の番号は試料番号と一致する。[Table] Example 3 10% polyvinyl alcohol aqueous solution, manganese dioxide, and titanium oxide were mixed in the ratio shown in Table 3,
Further, pure water was added to make a paste, and this paste was placed on an alumina substrate at 120°C in the same manner as in Example 1.
A dew condensation sensor was created by baking under heat treatment conditions for 20 minutes. Changes in relative humidity and resistance were measured for this dew condensation sensor, and the results are shown in FIG. The numbers in the figure match the sample numbers.
【表】
実施例 ４
10％ポリビニルアルコール水溶液と二酸化マン
ガンを第４表に示すように比率を変えて混合し、
実施例３と同様にして結露センサーを作成した。
第４表から有機高分子量と半導体粉末の量を変
化させることにより初期抵抗値を調節できること
がわかる。なお、この実施例では半導体粉末につ
いて説明したが、絶縁体粉末についても同様の効
果が得られることについて確認できた。[Table] Example 4 10% polyvinyl alcohol aqueous solution and manganese dioxide were mixed at different ratios as shown in Table 4,
A dew condensation sensor was created in the same manner as in Example 3. Table 4 shows that the initial resistance value can be adjusted by changing the organic polymer weight and the amount of semiconductor powder. Although this example describes semiconductor powder, it has been confirmed that similar effects can be obtained with insulator powder.
【表】
実施例 ５
感湿膜の抵抗値は有機高分子量と、半導体粉末
量または絶縁体粉末量によつて調節できることは
実施例４で示したが、抵抗の温度特性は使用する
半導体粉末や絶縁体粉末の特性によつて決定され
る。したがつて抵抗温度特性の良好なものや、そ
の変化率が負または正のものを適宜組み合わせる
ことにより任意の特性を有する結露センサーが得
られる。
この実施例は第５表に示した混合比率のポリビ
ニルアルコール−二酸化マンガン、エチルセルロ
ース−チタン酸バリウム系半導体よりなる各感湿
膜をそれぞれ実施例３、２と同様の処理にて作成
し、25℃、85℃における抵抗値を測定した。な
お、測定時における相対湿度は52％であつた。[Table] Example 5 It was shown in Example 4 that the resistance value of the moisture sensitive film can be adjusted by the organic polymer weight and the amount of semiconductor powder or insulator powder, but the temperature characteristics of the resistance depend on the semiconductor powder used and the amount of insulator powder. Determined by the properties of the insulator powder. Therefore, a dew condensation sensor having arbitrary characteristics can be obtained by appropriately combining those with good resistance-temperature characteristics and those with a negative or positive rate of change. In this example, moisture-sensitive films made of polyvinyl alcohol-manganese dioxide and ethyl cellulose-barium titanate semiconductors having the mixing ratios shown in Table 5 were prepared in the same manner as in Examples 3 and 2. , the resistance value at 85°C was measured. Note that the relative humidity at the time of measurement was 52%.
【表】【table】
【表】
以上各実施例から明らかなようにこの発明によ
れば、水分の付着で初めて抵抗変化を示し、結露
センサーとして確実に動作する。また、構成材料
の混合比を変えることにより抵抗値の調節、なら
びに抵抗温度特性の調節が行える。また、感湿膜
は熱処理により形成されており、耐水性、耐久性
にすぐれたもので、長時間使用しても特性の劣化
が生じないという特徴を有している。さらに金属
酸化物の蒸着やスパツタリングにより形成された
薄膜タイプのものにくらべ、印刷、塗布などの手
段で膜厚を制御でき、任意の特性を有するものが
安価に得られるという効果を有している。[Table] As is clear from the above embodiments, according to the present invention, a resistance change occurs only when moisture is attached, and the sensor operates reliably as a dew condensation sensor. Furthermore, by changing the mixing ratio of the constituent materials, the resistance value and resistance temperature characteristics can be adjusted. Furthermore, the moisture-sensitive film is formed by heat treatment, and has excellent water resistance and durability, and has the characteristic that its properties do not deteriorate even after long-term use. Furthermore, compared to thin film types formed by vapor deposition or sputtering of metal oxides, the film thickness can be controlled by means such as printing or coating, and it has the advantage that films with arbitrary properties can be obtained at low cost. .
第１図は感湿素子の一例を示す平面図、第２図
〜第４図は各相対湿度と抵抗値の関係を示す図で
ある。
１……絶縁基板、２，３……対向電極、４……
感湿膜。
FIG. 1 is a plan view showing an example of a humidity sensing element, and FIGS. 2 to 4 are diagrams showing the relationship between each relative humidity and resistance value. 1... Insulating substrate, 2, 3... Counter electrode, 4...
Moisture sensitive membrane.
Claims (1)
もこの対向電極間の絶縁基板表面に感湿膜が形成
されている結露センサーにおいて、 前記感湿膜は、温度抵抗変化率の小さい有機高
分子と、半導体粉末または絶縁体粉末の１種また
は２種との混合物からなり、半導体粉末または絶
縁体粉末の１種または２種の量が有機高分子の量
にくらべて多く、かつ該感湿膜自体が微小な空孔
を有する多孔質状態であることを特徴とする結露
センサー。[Scope of Claims] 1. A dew condensation sensor in which a counter electrode is formed on an insulating substrate, and a moisture-sensitive film is formed on the surface of the insulating substrate at least between the counter electrodes, wherein the moisture-sensitive film has a temperature resistance change rate. consisting of a mixture of a small organic polymer and one or two semiconductor powders or insulator powders, the amount of the one or two semiconductor powders or insulator powders being greater than the amount of the organic polymer, and A dew condensation sensor characterized in that the moisture sensitive membrane itself is porous with minute pores.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9175878A JPS5518947A (en) | 1978-07-26 | 1978-07-26 | Dew formation sensor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9175878A JPS5518947A (en) | 1978-07-26 | 1978-07-26 | Dew formation sensor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5518947A JPS5518947A (en) | 1980-02-09 |
| JPS6235058B2 true JPS6235058B2 (en) | 1987-07-30 |
Family
ID=14035434
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9175878A Granted JPS5518947A (en) | 1978-07-26 | 1978-07-26 | Dew formation sensor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5518947A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6221052A (en) * | 1985-07-19 | 1987-01-29 | Tokyo Kosumosu Denki Kk | Dew formation sensor |
-
1978
- 1978-07-26 JP JP9175878A patent/JPS5518947A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5518947A (en) | 1980-02-09 |
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