JPS61241643A - Moisture responsive element - Google Patents
Moisture responsive elementInfo
- Publication number
- JPS61241643A JPS61241643A JP8350885A JP8350885A JPS61241643A JP S61241643 A JPS61241643 A JP S61241643A JP 8350885 A JP8350885 A JP 8350885A JP 8350885 A JP8350885 A JP 8350885A JP S61241643 A JPS61241643 A JP S61241643A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- moisture
- copolymer
- humidity
- average degree
- 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
Landscapes
- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
Abstract
Description
【発明の詳細な説明】
(イ)産業上の利用分野
この発明は感湿素子に関する。さらに詳しくは種々の雰
囲気中の湿度を検出する感湿素子に関する。DETAILED DESCRIPTION OF THE INVENTION (a) Field of Industrial Application This invention relates to a moisture sensitive element. More specifically, the present invention relates to a humidity sensing element that detects humidity in various atmospheres.
(ロ)従来の技術
湿度を検出する感湿素子として実用化されているものと
して金属酸化物(Si 02 、AI 20s等)及び
有機高分子(高分子電解質)を使用したものが挙げられ
る。これらはいずれも雰囲気中の水分の吸収や吸着によ
る物理的変化(抵抗、電気容量等)を検知して湿度を測
定する方式のものであり、ことに有機高分子を感湿剤と
して、絶縁基板上の一対の電極間に被覆した感湿素子が
汎用されている。この場合、有機高分子の雰囲気湿度を
検出する原理は、これが雰囲気中の水分を吸収すること
で電離を起こし、表面抵抗値が減少することを利用した
ものである。種々の有機高分子の相対湿度と表面抵抗値
の関係はすでに公知である(Chem 、 Techn
ol、、1971.5月号304〜309による)。(B) Conventional Technology Moisture-sensitive elements that have been put into practical use to detect humidity include those using metal oxides (Si 02 , AI 20s, etc.) and organic polymers (polymer electrolytes). All of these methods measure humidity by detecting physical changes (resistance, capacitance, etc.) due to the absorption or adsorption of moisture in the atmosphere. A moisture-sensitive element coated between the upper pair of electrodes is widely used. In this case, the principle of detecting the atmospheric humidity of the organic polymer is based on the fact that the organic polymer absorbs moisture in the atmosphere, causes ionization, and decreases the surface resistance value. The relationship between relative humidity and surface resistance of various organic polymers is already known (Chem, Techn.
ol, May 1971. No. 304-309).
(ハ)発明が解決しようとする問題点
量産性を考慮した場合、有機高分子を使用したものの方
が金属酸化物に比べて有利である反面、耐熱性に乏しい
という問題がある。従って、架橋反応等の耐熱性を向上
させるための特別の処理を行なわない限り、使用範囲は
限られてくる。そのため、有機高分子感湿剤を用いた感
湿素子の耐熱性を向上させることが望まれているが、耐
熱性以外に、かかる感湿素子に一般的に要求される特性
は極めて厳しいものがある。すなわち要求される特性と
しては、
(1) 相対湿度を変化させたとき、抵抗値が、対数
直線的に変化し、通常の室内雰囲気中に放置させても再
現性を有すること。(c) Problems to be Solved by the Invention When considering mass productivity, organic polymers are more advantageous than metal oxides, but they have a problem of poor heat resistance. Therefore, unless special treatment such as crosslinking reaction is carried out to improve heat resistance, the range of use is limited. Therefore, it is desired to improve the heat resistance of moisture-sensitive elements using organic polymer moisture-sensing agents, but in addition to heat resistance, the characteristics generally required for such moisture-sensitive elements are extremely strict. be. In other words, the required characteristics are: (1) When the relative humidity is changed, the resistance value changes logarithmically and linearly, and it has reproducibility even when left in a normal indoor atmosphere.
(H) 高湿度雰囲気から低湿度雰囲気に変化させた
際、(1)の直線に対して誤差が少なく戻ること(即ち
ヒステリシスが小さい)。(H) When changing from a high-humidity atmosphere to a low-humidity atmosphere, there should be little error in returning to the straight line in (1) (that is, small hysteresis).
(至) 一般に有機高分子感湿剤は水溶性(吸水性)部
分を含むため、高湿度雰囲気に放置したとき、感湿剤の
溶解脱着を起こし抵抗特性が上昇してしまう場合が多い
が、かような高湿度下においても充分な耐久性を有する
こと。(To) Generally, organic polymer moisture-sensing agents contain water-soluble (water-absorbing) parts, so when left in a high-humidity atmosphere, the moisture-sensing agent often dissolves and desorbs, resulting in an increase in resistance properties. It must have sufficient durability even under such high humidity.
等があげられる。etc. can be mentioned.
本発明は有機高分子を使用した感湿素子の耐熱性を向上
させるためになされたものであり、ことに架橋反応等の
特別な処理無しに耐熱温度を飛躍的に向上させかつ上記
諸条件(1)〜(至)を満足する感湿素子を提供するこ
とを目的とする。The present invention was made in order to improve the heat resistance of a moisture-sensitive element using an organic polymer, and in particular, to dramatically improve the heat resistance temperature without special treatment such as a crosslinking reaction, and under the above conditions ( It is an object of the present invention to provide a moisture-sensitive element that satisfies 1) to (to).
(ニ)問題点を解決するための手段
かくして本発明によれば、絶縁基板上の一対の電極間に
、感湿剤として2−アクリルアミド−2メチルプロパン
スルホン酸塩と特定のメタクリル義金フッ素アルキルエ
ステルとの共重合体を用いてなる感湿素子が提供される
。上記2−アクリルアミド−2−メチルプロパンスルホ
ン酸塩としては下式(工);
H3
II )−1
0’(I)
(式中、Xはリチウム、ナトリウム、又はカリウム原子
を示す)で表わされる化合物が適している。(d) Means for Solving the Problems Thus, according to the present invention, 2-acrylamide-2methylpropanesulfonate and a specific methacrylic metal fluorine alkyl are used as a moisture sensitive agent between a pair of electrodes on an insulating substrate. A moisture-sensitive element using a copolymer with an ester is provided. The above-mentioned 2-acrylamido-2-methylpropanesulfonate is a compound represented by the following formula (E); is suitable.
かような化合物自体は従来繊維等の帯電防止剤として知
られており、例えばTBAS (日東化学工業の商標名
)の名称で入手可能である。また一方のメタクリル酸含
フツ素アルキルエステルは下式(■):
Hs
82C=C
(式中、Yはトリフルオロメチル基、ジフルオロメチル
基又+2モノフルオロメチル基を示す)で表わされる化
合物が適している。かような化合物は通常、メタクリル
酸誘導体と、対応するフルオロアルキルアルコール誘導
体より合成可能なものであるがこれもまた、ごスコート
#3FM(大阪有機化字間の商品名)の名称で入手可能
である。Such a compound itself is conventionally known as an antistatic agent for fibers, etc., and is available, for example, under the name TBAS (trade name of Nitto Chemical Industry Co., Ltd.). As one of the fluorine-containing alkyl esters of methacrylic acid, a compound represented by the following formula (■): Hs 82C=C (in the formula, Y represents a trifluoromethyl group, a difluoromethyl group, or a +2 monofluoromethyl group) is suitable. ing. Such compounds can usually be synthesized from methacrylic acid derivatives and corresponding fluoroalkyl alcohol derivatives, which are also available under the name Goskort #3FM (trade name of Osaka Organic Chemical). be.
本発明に用いる重合体は、式(I)及び式(Ill)で
示される単位を主構成成分とする共重合体であり、それ
らの平均重合度は通常的100〜8,000に調整する
のが好ましい。また、共重合体の他の単量体成分として
共重合可能なビニル系単量体(例えば、スチレン、メタ
クリル酸メチル、アクリル酸メチル等)を含んでもよい
。ただし、上記平均重合度範囲外でも感湿性を発揮する
範囲であれば適用できる。尚、Xとしてはナトリウムが
好ましく、Yにはトリフルオロメチル基が好ましい。か
ような共重合体は通常ラジカル発生剤を用いるラジカル
重合等の公知の重合方法により合成できる。The polymer used in the present invention is a copolymer mainly composed of units represented by formula (I) and formula (Ill), and the average degree of polymerization thereof is usually adjusted to 100 to 8,000. is preferred. The copolymer may also contain copolymerizable vinyl monomers (eg, styrene, methyl methacrylate, methyl acrylate, etc.) as other monomer components. However, it can be applied even outside the above-mentioned average degree of polymerization as long as it exhibits moisture sensitivity. Note that X is preferably sodium, and Y is preferably a trifluoromethyl group. Such a copolymer can be synthesized by a known polymerization method such as radical polymerization using a radical generator.
また式(I)の単位と式(II)の単位との比率は特に
限定されるものではないが通常式(I)二式(IF)の
モル比率として1:0,5〜1:3とするのが感湿効果
及び湿度安定性の点から好ましい。Further, the ratio of the units of formula (I) and the units of formula (II) is not particularly limited, but is usually 1:0.5 to 1:3 as a molar ratio of formula (I) and formula (IF). It is preferable to do so from the viewpoint of humidity sensitivity effect and humidity stability.
かようにして得た共重合体をメタノール、エタノール、
アセトン等の有機溶媒に溶解したのち、感湿素子の基板
、ことに電極間に塗布し乾燥して感湿膜を形成させるこ
とにより本発明の感湿膜が得られる。The thus obtained copolymer was mixed with methanol, ethanol,
The moisture-sensitive film of the present invention can be obtained by dissolving it in an organic solvent such as acetone, applying it to a substrate of a humidity-sensitive element, especially between electrodes, and drying it to form a moisture-sensitive film.
このようにして得られた本発明の感湿膜は、耐熱性に優
れ、かつ上記(1)〜(至)の諸条件を満足するもので
ある。ことに、耐熱湿度が高いことは特筆される。した
がって、湿度測定を必要とする種々の分野に有用である
。とりわけ、空調機器等の感湿素子として好適である。The moisture-sensitive film of the present invention thus obtained has excellent heat resistance and satisfies the conditions (1) to (2) above. Particularly notable is its high heat and humidity resistance. Therefore, it is useful in various fields requiring humidity measurement. In particular, it is suitable as a humidity sensing element for air conditioners and the like.
(ホ)実施例
以下、本発明を実施例及び図面により詳説するが、これ
により本発明は限定されるものではない。(E) Examples Hereinafter, the present invention will be explained in detail with reference to Examples and drawings, but the present invention is not limited thereby.
1111匹1え
実施例 1
無水メタノール251!中で炭酸ソーダ2,250に2
−アクリルアミド−2−メチルプロパンスルホン酸モノ
マ−8,30を加え、ナトリウム塩を作る、。1111 animals 1 Example 1 Anhydrous methanol 251! Inside, carbonated soda 2,250 to 2
- Add acrylamide-2-methylpropanesulfonic acid monomer 8,30 to form the sodium salt.
得られた溶液を250 xlの乾燥アセトンにそそぎ、
沈澱物を乾燥して粉末試料を得る。Pour the resulting solution into 250 xl of dry acetone,
Dry the precipitate to obtain a powder sample.
上記2−アクリルアミド−2−メチルプロパンスルホン
酸ナトリウム塩10gと2.2.2−トリフルオロエチ
ルメタクリレート16.80と重合開始剤としてアゾビ
スイソブチロニトリル150mgを5011のDMFで
溶解した。10 g of the above 2-acrylamido-2-methylpropanesulfonic acid sodium salt, 16.8 g of 2.2.2-trifluoroethyl methacrylate, and 150 mg of azobisisobutyronitrile as a polymerization initiator were dissolved in 5011 DMF.
これをガラス製容器に入れ、凍結脱気して封管とした。This was placed in a glass container and frozen and degassed to form a sealed tube.
この封管を50〜80℃の温水溶中に静置して約65時
間重合反応を行う。反応物を水等の溶媒に滴下させて共
重合物の白色沈澱物を得た。This sealed tube is left standing in a hot water solution at 50 to 80°C to carry out a polymerization reaction for about 65 hours. The reaction product was added dropwise to a solvent such as water to obtain a white precipitate of a copolymer.
実施例 2
無水メタノール2511i中で炭酸リチウム3.0gに
2−アクリルアミド−2−メチルプロパンスルホン酸モ
ノマー8.3gを加え、リチウム塩モノマーを作る。得
られた溶液を250 yIの乾燥酢酸エチルにそそぎ、
沈澱物を乾燥して粉末試料を得た。上記2−アクリルア
ミドー2−メチルプロパンスルホン酸リチウム塩10(
]と]2.2.2−トリフルオロエチルメタクリレート
168gと重合開始剤としてアゾビスイソブチロニトリ
ル150すを用いて、実施例1と同様の操作で共重合物
の白色沈澱物を得た。Example 2 A lithium salt monomer is prepared by adding 8.3 g of 2-acrylamido-2-methylpropanesulfonic acid monomer to 3.0 g of lithium carbonate in anhydrous methanol 2511i. The resulting solution was poured into 250 yI dry ethyl acetate,
The precipitate was dried to obtain a powder sample. The above 2-acrylamido-2-methylpropanesulfonic acid lithium salt 10 (
] and] 2.2.2-Trifluoroethyl methacrylate (168 g) and azobisisobutyronitrile (150 g) as a polymerization initiator were used to obtain a white precipitate of a copolymer in the same manner as in Example 1.
上記の感湿剤(実施例1)をメタノールに溶かして約4
%の感湿剤溶液をつくる。この液中に第1図の如く一対
の櫛型の金電極fll (1)を設けたアルミナ製絶縁
基板(2)を浸漬したのち、焼成(乾燥)し、さらにこ
の上に気体透過性に優れるシリコーン皮膜を設けて感湿
素子(3)を完成させた。このようにして得た感湿素子
(3)を第2図の如くリード線[41[4)を接続して
、周波数120Hz、5■の交流電源(5)より 10
0にΩの抵抗(6)を介して加えることで、この抵抗(
6)にかかる両端電圧を測定することで各相対湿度に於
ける抵抗値を25℃下で測定した。次に感湿素子(3)
の耐久性試−として、過酷である高温高湿度(60℃、
95%RH)下で3日間放置後の感湿素子(3)を上記
方法と同様にして、相対湿度−抵抗特性図を測定した。Dissolve the above moisture sensitizer (Example 1) in methanol and
% moisture sensitizer solution. After immersing an alumina insulating substrate (2) with a pair of comb-shaped gold electrodes (1) in this liquid as shown in Figure 1, it is fired (dried), and then an insulating substrate (2) with excellent gas permeability is placed on top of this. A moisture sensitive element (3) was completed by providing a silicone film. The moisture sensing element (3) obtained in this way was connected to the lead wire [41 [4] as shown in Fig. 2, and connected to an AC power source (5) with a frequency of 120 Hz and 5 mm.
0 through a resistance (6) of Ω, this resistance (
6) By measuring the voltage across both ends, the resistance value at each relative humidity was measured at 25°C. Next, the moisture sensing element (3)
As a durability test of
The relative humidity-resistance characteristic diagram of the humidity-sensitive element (3) after being left for 3 days under (95% RH) was measured in the same manner as above.
この特性変化を初期特性と比較したものを第3図に示し
た。この図に示されるように、初期特性に比較して素子
の変化は少ない。FIG. 3 shows a comparison of this change in characteristics with the initial characteristics. As shown in this figure, there are few changes in the element compared to the initial characteristics.
また、次に感湿素子(3)を100℃、熱風乾燥炉内に
放置した後、上記方法と同様にして特性変化を調べた。Further, after the moisture sensitive element (3) was left in a hot air drying oven at 100° C., changes in characteristics were examined in the same manner as above.
フッ素を含まない従来の感湿素子は100℃で3日間放
置すると5%R)−1程度の熱劣化による誤差を生ずる
が本発明による感湿素子は際めで安定であり、第4図に
示される結果から分るように、生ずる誤差は1%RH以
下と非常に良好な耐熱性を有することが確認できた。合
成例2の感湿剤を使用した感湿素子についても、耐高温
高湿性及び耐高温性について同様な耐久性を有すること
が確認できた。Conventional moisture-sensing elements that do not contain fluorine produce errors due to thermal deterioration of about 5%R)-1 when left at 100°C for three days, but the moisture-sensing elements of the present invention are distinct and stable, as shown in Figure 4. As can be seen from the results, the resulting error was less than 1% RH, and it was confirmed that the film had very good heat resistance. It was confirmed that the moisture-sensitive element using the moisture-sensing agent of Synthesis Example 2 had similar durability in terms of high-temperature and high-humidity resistance and high-temperature resistance.
(へ)発明の効果
以上述べたように本発明の感湿素子用組成物を使用した
感湿素子は、過酷である高温高湿下で放置後も、また高
温乾燥下で放置後もいずれにおいても常に安定した特性
を示し、耐久性かつ耐熱性を兼ね備えた正確な湿度測定
が可能になる。従つって、その製造の容易さ、量産中に
富むなど正確で耐久性、耐熱性に富んだ感湿素子をより
安価に提供できることを含めて実用上多くの利点をもた
らすものである。(F) Effects of the Invention As described above, a humidity-sensitive device using the composition for a humidity-sensitive device of the present invention shows no damage after being left under harsh conditions of high temperature and high humidity, and even after being left under a high-temperature drying condition. It always shows stable characteristics, making it possible to accurately measure humidity with both durability and heat resistance. Therefore, it brings about many practical advantages, including ease of manufacture and the ability to provide accurate, durable, and heat-resistant moisture sensing elements at a lower cost, such as ease of manufacturing.
第1図は、本発明の感湿剤を適用する感湿素子の一例を
示す正面図であり、第2図は第1図の感湿素子を用いる
測定回路の一例を示す構成説明図であり、第3図は本発
明の初期のものと耐久性試験後との相対湿度−抵抗特性
図を比較した一例を示すグラフであり、第4図は本発明
の初期のものと耐熱性試験後との相対湿度−抵抗特性図
を比較した一例を示すグラフである。
(1)・・・・・・電極、 (21・・・・・・絶
縁基板、(3)・・・・・・感湿素子。
竿1図FIG. 1 is a front view showing an example of a humidity sensing element to which the moisture sensitive agent of the present invention is applied, and FIG. 2 is a configuration explanatory diagram showing an example of a measurement circuit using the humidity sensing element of FIG. 1. , FIG. 3 is a graph showing an example of a comparison of relative humidity-resistance characteristic diagrams between the initial model of the present invention and the one after the durability test, and FIG. It is a graph which shows an example which compared the relative humidity-resistance characteristic diagram of. (1)...Electrode, (21...Insulating substrate, (3)...Moisture sensing element. Rod 1 diagram
Claims (3)
I ); ▲数式、化学式、表等があります▼ (Xはリチウム、ナトリウム、又はカリウム原子を示す
)で表わされるメタクリルアミド誘導体と、下式(II)
; ▲数式、化学式、表等があります▼ (Yはトリフルオロメチル基、ジフルオロメチル基又は
モノフルオロメチル基を示す) で表わされるメタクリル酸含フツ素アルキルエステルと
を主構成単量体成分とする共重合体を用いてなる感湿素
子。1. The following formula (
I); ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Methacrylamide derivatives represented by (X represents lithium, sodium, or potassium atom) and the following formula (II)
; ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (Y represents a trifluoromethyl group, difluoromethyl group, or monofluoromethyl group) The main monomer component is methacrylic acid fluorine-containing alkyl ester A moisture-sensitive element using a copolymer.
1:3である特許請求の範囲第1項記載の組成物。2. The molar ratio of copolymerization of (I) and (II) is 1:0.5~
A composition according to claim 1, wherein the ratio is 1:3.
範囲第1項記載の組成物。3. The composition of claim 1 having an average degree of polymerization of about 100 to 8,000.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP8350885A JPS61241643A (en) | 1985-04-18 | 1985-04-18 | Moisture responsive element |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP8350885A JPS61241643A (en) | 1985-04-18 | 1985-04-18 | Moisture responsive element |
Publications (1)
Publication Number | Publication Date |
---|---|
JPS61241643A true JPS61241643A (en) | 1986-10-27 |
Family
ID=13804423
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP8350885A Pending JPS61241643A (en) | 1985-04-18 | 1985-04-18 | Moisture responsive element |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS61241643A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001281192A (en) * | 2000-03-31 | 2001-10-10 | Ngk Spark Plug Co Ltd | Gas sensor |
-
1985
- 1985-04-18 JP JP8350885A patent/JPS61241643A/en active Pending
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001281192A (en) * | 2000-03-31 | 2001-10-10 | Ngk Spark Plug Co Ltd | Gas sensor |
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