JPS6133129B2 - - Google Patents
Info
- Publication number
- JPS6133129B2 JPS6133129B2 JP53077012A JP7701278A JPS6133129B2 JP S6133129 B2 JPS6133129 B2 JP S6133129B2 JP 53077012 A JP53077012 A JP 53077012A JP 7701278 A JP7701278 A JP 7701278A JP S6133129 B2 JPS6133129 B2 JP S6133129B2
- Authority
- JP
- Japan
- Prior art keywords
- fluorine
- humidity
- electrodes
- moisture
- containing polymer
- 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
- 229920000642 polymer Polymers 0.000 claims description 25
- 229910052731 fluorine Inorganic materials 0.000 claims description 20
- 239000011737 fluorine Substances 0.000 claims description 20
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 19
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000000524 functional group Chemical group 0.000 claims description 4
- 239000001257 hydrogen Chemical group 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 3
- 239000000460 chlorine Chemical group 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical group [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 125000001153 fluoro group Chemical group F* 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 239000000758 substrate Substances 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 8
- 239000010408 film Substances 0.000 description 8
- 239000011521 glass Substances 0.000 description 7
- 239000000178 monomer Substances 0.000 description 6
- 230000035945 sensitivity Effects 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 159000000002 lithium salts Chemical class 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Landscapes
- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Non-Adjustable Resistors (AREA)
Description
本発明は湿度を電気的に検出するための感湿素
子に関するものである。
電気抵抗式の感湿素子としては、適宜の電解質
を利用するもの、水に難溶性の塩の吸着水を利用
するもの、膨潤性物質に電導性物質を埋め込んだ
もの、半導体薄膜を利用するもの等種々知られて
いるが、いずれの場合も、化学的、熱的安定性に
欠け、また汚染されるために感度の低下が起り、
耐久性の点で不十分であるばかりでなく、更に、
感度特性についても必ずしも満足できるものでは
なかつた。特に腐食性で且つ高温のガス中の水分
測定などの工業的に使用される感湿素子として有
効なものは従来は見られない。
本発明は上記したような欠点を有さない、耐久
性の点でも感度特性でも優れた感湿素子を提供す
ることを目的とする。
即ち、本発明では一般式−COOM（Ｍは、水
素，アルカリ金属又はアルカリ土類金属を表わ
す）のカルボン酸型基を有し、しかもその当量が
400〜2000である含フツ素重合体を感湿素子とし
て使用した場合には、化学的にも熱的にも安定で
あり、また使用中も汚染もされにくく、従つて、
長期にわたつて使用しても感度低下を起すことな
く、更に重要なことには、低電気抵抗であり、且
つ湿度に対する抵抗値変化が直線的に変化すると
いう優れた動作特性を示すことが見い出された。
以下に、本発明を更に詳細な説明すると、本発
明で感湿素子として使用される含フツ素重合体
は、上記のように一般式−COOM（Ｍは上記と
同じ）のカルボキシル基を有さなければならな
い。Ｍの種類によつて特性が異なるが、Ｍは、好
ましくは、リチウム、ナトリウム、カリウムが、
低電気抵抗などの理由からして適切である。含フ
ツ素重合体中におけるカルボキシル基の当量（カ
ルボキシル基１当量を含む重合体のグラム数）
も、感湿素子の特性と関係するので重要であり、
好ましくは、400〜2000特には500〜1000が好まし
い。カルボキシル基の当量が余りに大きいと感湿
素子の強度低下が起こるので好ましくなく、一方
小さ過ぎると電気抵抗が高くなるので好ましくな
い。
含フツ素重合体の分子量は、重合体の機械的強
度と関係するので重要であるが、該分子量をこれ
と密接な関係を有するＴQ値で表わした場合、ＴQ
値が好ましくは、130〜380℃、特には160〜300℃
である場合が好ましい。ここでＴQ値は、30Kg／
cm2の加圧下、径１mm、長さ２mmのオリフイスを、
メチルエステル型の含フツ素重合体が、100mm
３／秒の容量流速で通過する温度である。
上記含フツ素重合体としては好ましくはそれぞ
れ以下の(イ)，(ロ)の重合単位を有する含フツ素共重
合体、特にはパーフルオロカーボン重合体の使用
が好ましい。
(イ) −（CF2−CXX′）−，(ロ)
The present invention relates to a humidity sensing element for electrically detecting humidity. Electrical resistance type moisture sensing elements include those that use an appropriate electrolyte, those that use adsorbed water of poorly soluble salts, those that have a conductive substance embedded in a swellable substance, and those that use a semiconductor thin film. Various methods are known, but in all cases, sensitivity decreases due to lack of chemical and thermal stability and contamination.
Not only is it insufficient in terms of durability, but also
The sensitivity characteristics were also not necessarily satisfactory. In particular, no moisture sensing element has been found to be effective as an industrially used moisture sensing element for measuring moisture in corrosive and high temperature gases. An object of the present invention is to provide a moisture-sensitive element that does not have the above-mentioned drawbacks and has excellent durability and sensitivity characteristics. That is, the present invention has a carboxylic acid type group of the general formula -COOM (M represents hydrogen, an alkali metal or an alkaline earth metal), and the equivalent thereof is
When a fluorine-containing polymer having a molecular weight of 400 to 2000 is used as a moisture-sensitive element, it is chemically and thermally stable, and is less susceptible to contamination during use.
It was discovered that there is no decrease in sensitivity even after long-term use, and more importantly, it exhibits excellent operating characteristics such as low electrical resistance and a linear change in resistance value with respect to humidity. It was. To explain the present invention in more detail below, the fluorine-containing polymer used as the moisture-sensitive element in the present invention has a carboxyl group of the general formula -COOM (M is the same as above) as described above. There must be. The properties vary depending on the type of M, but M is preferably lithium, sodium, or potassium.
This is suitable for reasons such as low electrical resistance. Equivalent weight of carboxyl group in fluorine-containing polymer (number of grams of polymer containing 1 equivalent of carboxyl group)
is also important as it is related to the characteristics of the moisture sensitive element.
Preferably, 400 to 2000, particularly 500 to 1000. If the equivalent weight of the carboxyl group is too large, the strength of the moisture-sensitive element will decrease, which is undesirable, while if it is too small, the electrical resistance will become high, which is not preferable. The molecular weight of a fluorine-containing polymer is important because it is related to the mechanical strength of the polymer, but when the molecular weight is expressed by the T Q value, which is closely related to this, T Q
The value is preferably 130-380℃, especially 160-300℃
It is preferable that Here, the T Q value is 30Kg/
Under a pressure of cm 2 , an orifice with a diameter of 1 mm and a length of 2 mm,
100mm of methyl ester type fluorine-containing polymer
The temperature is passed at a volumetric flow rate of 3 /sec. As the above-mentioned fluorine-containing polymer, it is preferable to use a fluorine-containing copolymer having the following polymerized units (a) and (b), respectively, and particularly a perfluorocarbon polymer. (a) −(CF 2 −CXX′) −, (b)
【式】
こゝで、Ｘは、水素，塩素好ましくはフツ素又
は−CF3であり、X′はＸ又はCF3（CF2）−nであ
り、ｍは１〜５であり、Ｙは、次のものから選ば
れる。
−（CF2）−x，−Ｏ−（CF2）−x，
[Formula] Here, X is hydrogen, chlorine, preferably fluorine or -CF3 , X' is X or CF3 ( CF2 ) -n , m is 1 to 5, and Y is , selected from the following: -( CF2 ) -x , -O-( CF2 ) -x ,
ｘ，ｙ，ｚは、ともに１〜10であり、Ｚ，Ｒf
は、−Ｆ又は炭素数１〜10のパーフルオロアルキ
ル基から選ばれた基であり、Ａは、−COOM又
は、−CN，−COF，−COOR等の−COOMに転換
しうる官能基を示し、こゝでＲは、炭素数１〜10
のアルキル基を示す。
上記(イ)，(ロ)の重合単位からなる共重合体の場
合、含フツ素重合体が上記のカルボン酸型基当量
を達成するために好ましくは、共重合体中の(ロ)の
重合単位が５〜40モル％であることが好ましい。
また、かゝる含フツ素共重合体の製造に当つて
は、上記の各単量体の一種以上を使用し、更には
第三の単量体をも共重合することにより、得られ
る膜を改質することができる。かくして、例えば
CF2＝CFORf（Ｒfは炭素数１〜10のパーフルオ
ロアルキル基）を併用することにより、得られる
膜に可撓性を付与したり、或いはCF2＝CF−CF
＝CF2、CF2＝CFO（CF2）1〜4OCF＝CF2等のジ
ビニルモノマーを少量併用することにより、得ら
れる共重合体を上記容量流速を与える範囲内で一
部架橋せしめ、膜に機械的強度を付与することが
できる。
弗素化オレフイン単量体と、カルボン酸基若し
くは該基に転換しうる官能基を有する重合能ある
単量体、更には第三の単量体との共重合は、溶液
重合、乳化重合、懸濁重合などの既知の任意の系
で、例えば、必要に応じてハロゲン化炭化水素な
どの溶媒を使用し、触媒重合、熱重合、放射線重
合などにより重合できる。
かくして製造される含フツ素重合体は、所望に
よりその物理的強度を改善するために、例えば四
フツ化エチレン重合体、エチレン−四フツ化エチ
レン共重合体の布、ネツトなどの織物、不織布又
はフイブリル（小繊維）により補強することもで
きる。
また、含フツ素重合体が、上記の−CN，−
COF，−COOR等の官能基を有する場合は、感湿
素子として使用する前に加水分解その他の処理に
より、−COOMに転換する必要がある。
本発明の含フツ素重合体からなる感湿素子を使
用するにあたつては既知の種々の方式が使用可能
であるが、好ましくは陰，陽の両電極を有する絶
縁基板上に、感湿素子たる含フツ素重合体を被膜
として配置する方式が採用される。かかる絶縁基
板としては、ガラス、プラスチツクス、セラミツ
クス、絶縁被覆した金属等からなる各種絶縁基板
が用いられる。
又、本発明における湿度センサーの電極は、該
電極間に形成された被膜上に付着した水分により
電気抵抗値の変化を電気的に検出する端子となる
ものであり、例えば、絶縁基板上に対向して一本
ないし複数本の櫛状の電極を配し、該電極間に水
分が付着した時、電極間の抵抗変化を検出する様
にしたタイプである。この電極はAl，Ag，Pt，
Au，Pdなどの金属の粉末あるいは酸化ルテニウ
ム等の金属酸化物の粉末をガラスフリツトとビヒ
クルとを混合したペースト状導電性組成物を絶縁
基板上に焼付けて形成されるか、あるいは蒸着法
によりIn2O3，SnO2等の電導性金属酸化物を被着
して形成される。
電極のパターンは第１図に示した如く、絶縁基
板１の表面に0.5mm〜２mmの巾を持つ電極線条
２，３を0.5mm〜５mm程度の間隔をもつて対向し
て、あるいは櫛状に対向して形成されたものが使
用できる。又上記電極の線条はいくつかの分岐に
わかれたパターンとしても使用できる。
感湿素子となる本発明の含フツ素重合体は、上
記電極間に被膜として形成される含フツ素重合体
の被膜は、液状重合体のものはそのまゝで、また
固体重合体の場合には、メタノール，エタノー
ル，エチレングリコール，プロピレングリコール
などの適宜の有機溶媒の溶液とし、この溶液を対
向した電極間の絶縁基板上にスプレー塗布、浸漬
塗布又はハケ塗りその他の方法により塗布し、塗
布後所定時間加熱又は乾燥して溶媒を揮散させて
被膜を形成する。形成された被膜は、必要により
更に加熱するなどの養生が施こされる。
含フツ素重合体の被膜は厚みが大きくなるほど
抵抗値が下がり好ましいが、あまり厚くなると被
膜が剥離しやすくなり、従つて膜厚は１μ〜30μ
の範囲が好ましい。
本発明の湿度検出の抵抗値を所望に応じて調節
する場合には、膜厚、液組成、電極パターンを変
えることによつて行なうことができる。
かくして使用される本発明の感湿素子は、以下
に示す実施例からも明らかなように、湿度に対す
る感湿素子の電気抵抗の変化がほぼ直線的に変化
するので、広い湿度の範囲にわたつて感度が１定
であるとともに、その電気抵抗値も低いという特
性を有する。しかも、本発明の感湿素子は、含フ
ツ素重合体から形成されるので、耐熱性も高く、
また化学薬品に対する性蝕性も高く、且つ耐汚染
性も高い。従つて、例えば、腐食性の大きい塩素
等のハロゲンガス中の水分測定等の素子は、長期
にわたつて使用しても、その感度特性はほとんど
低下することがない。
以下に、本発明の実施例を記載する。
実施例 １
ガラス基板上に第１図に示す様な電極線条巾
0.6mm、電極間隔0.4mm、電極長さ50mmの櫛状電極
パターンにIn2O3を蒸着し対向した電極を形成し
た。この電極間のガラス基板面上及び電極上を覆
つて次の様に調製された溶液を塗布した。この溶
液は四フツ化エチレンとCF2＝CFO
（CF2）3COOCH3の共重合体からなり、当量が700
でＴQが230℃であるポリマーをリチウ塩としてメ
タノールに溶かした。塗布後室温で風乾した後湿
度93％の雰囲気中で24時間養生し、安定化させ
た。
この様にして形成された湿度センサーについて
湿度と電気抵抗値との関係を試験した結果を第２
図の曲線Ａに示した。
実施例 ２
実施例１と同様に電極の形成されたガラス基板
上の電極間及び電極上を覆つて次の様に調製され
た溶液を塗布した。
この溶液は、四フツ化エチレンとCF2＝
CFOCF2CF（CF3）Ｏ（CF2）3COOCH3の共重
合体からなり、当量が600でＴQが200℃であるポ
リマーをリチウム塩としてメタノールに溶解し
た。塗布後室温で風乾した後、湿度93％の雰囲気
中で１日養生し安定化させた。
この様にして形成された湿度センサーについ
て、湿度と電気抵抗値との関係を試験した結果を
第２図曲線Ｂに示した。
実施例 ３
実施例１と同様に電極の形成されたガラス基板
上の電極間及び電極上を覆つて次の様に調製され
た溶液を塗布した。
この溶液は、四フツ化エチレンとCF2＝CFO
（CF2）3COOCH3の共重合体からなり、当量が500
でＴQが160℃であるポリマーをナトリウム塩とし
て、メタノールに溶解した。塗布後室温で風乾し
た後、湿度93％の雰囲気中で１日養生し安定化さ
せた。
この様にして形成された湿度センサーについ
て、湿度と電気抵抗値との関係を試験した結果を
第２図曲線Ｃに示した。
実施例 ４
実施例１と同様に電極の形成された３枚のガラ
ス基板上の電極間及び電極上を覆つて次の様に調
製された溶液を塗布した。
この溶液は、実施例３と同様のポリマーを用
い、リチウム塩としてメタノールに溶解した。塗
布後室温で風乾した後、湿度93％の雰囲気中で１
日養生し安定化させた。
このようにして形成された湿度センサーについ
て、湿度と電気抵抗値との関係を試験した結果を
第２図曲線Ｄに示した。 x, y, z are all 1 to 10, and Z, R f
is a group selected from -F or a perfluoroalkyl group having 1 to 10 carbon atoms, and A represents -COOM or a functional group convertible to -COOM such as -CN, -COF, -COOR, etc. , where R is a carbon number of 1 to 10
represents an alkyl group. In the case of a copolymer consisting of the polymerized units of (a) and (b) above, in order for the fluorine-containing polymer to achieve the above carboxylic acid type group equivalent, it is preferable that the polymerization unit of (b) in the copolymer is It is preferable that the unit is 5 to 40 mol%. In addition, in producing such a fluorine-containing copolymer, one or more of the above-mentioned monomers may be used, and a third monomer may also be copolymerized to produce a film. can be modified. Thus, for example
By using CF 2 = CFOR f (R f is a perfluoroalkyl group having 1 to 10 carbon atoms), flexibility can be imparted to the obtained film, or CF 2 = CF-CF
= CF 2 , CF 2 = CFO (CF 2 ) 1 to 4 OCF = By using a small amount of a divinyl monomer such as CF 2 , the resulting copolymer is partially crosslinked within the range that gives the above volumetric flow rate, and the membrane is formed. can be given mechanical strength. Copolymerization of a fluorinated olefin monomer with a polymerizable monomer having a carboxylic acid group or a functional group convertible to the carboxylic acid group, or a third monomer can be carried out by solution polymerization, emulsion polymerization, suspension polymerization, etc. Polymerization can be carried out in any known system such as turbidity polymerization, for example, by catalytic polymerization, thermal polymerization, radiation polymerization, etc., using a solvent such as a halogenated hydrocarbon as necessary. The fluorine-containing polymer produced in this way may be coated with a woven fabric such as a tetrafluoroethylene polymer, an ethylene-tetrafluoroethylene copolymer cloth, a nonwoven fabric, or a net, to improve its physical strength, if desired. It can also be reinforced with fibrils. Further, the fluorine-containing polymer may be the above-mentioned -CN,-
If it has a functional group such as COF or -COOR, it is necessary to convert it to -COOM by hydrolysis or other treatment before using it as a humidity sensing element. Various known methods can be used to use the humidity-sensitive element made of the fluorine-containing polymer of the present invention, but it is preferable to use a humidity-sensitive element on an insulating substrate having both negative and positive electrodes. A method is adopted in which the fluorine-containing polymer serving as the element is arranged as a coating. As such an insulating substrate, various insulating substrates made of glass, plastics, ceramics, metal coated with insulation, etc. are used. Further, the electrodes of the humidity sensor in the present invention serve as terminals for electrically detecting changes in electrical resistance due to moisture adhering to the film formed between the electrodes. This is a type in which one or more comb-shaped electrodes are arranged, and when moisture adheres between the electrodes, a change in resistance between the electrodes is detected. This electrode is made of Al, Ag, Pt,
It is formed by baking a paste-like conductive composition made by mixing powder of metals such as Au and Pd or powders of metal oxides such as ruthenium oxide with glass frit and a vehicle on an insulating substrate, or by vapor deposition . It is formed by depositing a conductive metal oxide such as O 3 or SnO 2 . As shown in Fig. 1, the electrode pattern is such that electrode strips 2 and 3 with a width of 0.5 mm to 2 mm are arranged on the surface of an insulating substrate 1, facing each other with an interval of about 0.5 mm to 5 mm, or in a comb shape. Those formed facing the can be used. Moreover, the above-mentioned electrode stripes can also be used as a pattern divided into several branches. In the fluorine-containing polymer of the present invention, which is a moisture-sensitive element, the fluorine-containing polymer coating formed as a coating between the electrodes is as it is when it is a liquid polymer, and when it is a solid polymer. To do this, make a solution of an appropriate organic solvent such as methanol, ethanol, ethylene glycol, propylene glycol, etc., and apply this solution onto the insulating substrate between the opposing electrodes by spraying, dipping, brushing, or other methods. After that, it is heated or dried for a predetermined period of time to volatilize the solvent and form a film. The formed film is further cured by heating, if necessary. The greater the thickness of the fluorine-containing polymer film, the lower the resistance value, which is preferable, but if it becomes too thick, the film will easily peel off, so the film thickness should be 1μ to 30μ.
A range of is preferred. The resistance value for humidity detection of the present invention can be adjusted as desired by changing the film thickness, liquid composition, and electrode pattern. As is clear from the examples shown below, the humidity sensing element of the present invention used in this way changes almost linearly in the electrical resistance of the humidity sensing element with respect to humidity, so it can be used over a wide humidity range. It has the characteristics of constant sensitivity and low electrical resistance. Moreover, since the moisture-sensitive element of the present invention is formed from a fluorine-containing polymer, it has high heat resistance.
It also has high corrosion resistance against chemicals and high stain resistance. Therefore, even if an element for measuring moisture in a highly corrosive halogen gas such as chlorine is used for a long period of time, its sensitivity characteristics hardly deteriorate. Examples of the present invention are described below. Example 1 Electrode wire width as shown in Figure 1 was placed on a glass substrate.
In 2 O 3 was evaporated onto a comb-shaped electrode pattern of 0.6 mm, electrode spacing 0.4 mm, and electrode length 50 mm to form opposing electrodes. A solution prepared as follows was applied to cover the glass substrate surface between the electrodes and the electrodes. This solution consists of tetrafluoroethylene and CF 2 = CFO
(CF 2 ) 3 COOCH 3 copolymer with an equivalent weight of 700
A polymer having a T Q of 230°C was dissolved in methanol as a lithium salt. After coating, it was air-dried at room temperature and then cured for 24 hours in an atmosphere with a humidity of 93% to stabilize it. The results of testing the relationship between humidity and electrical resistance for the humidity sensor formed in this way are shown in the second section.
It is shown in curve A in the figure. Example 2 In the same manner as in Example 1, a solution prepared as follows was applied between and over the electrodes on a glass substrate on which electrodes were formed. This solution consists of tetrafluoroethylene and CF 2 =
A polymer consisting of a copolymer of CFOCF 2 CF (CF 3 ) O (CF 2 ) 3 COOCH 3 , having an equivalent weight of 600 and a T Q of 200° C. was dissolved in methanol as a lithium salt. After coating, it was air-dried at room temperature and then cured for one day in an atmosphere with a humidity of 93% to stabilize it. Curve B in FIG. 2 shows the results of testing the relationship between humidity and electrical resistance of the humidity sensor thus formed. Example 3 In the same manner as in Example 1, a solution prepared as follows was applied on a glass substrate on which electrodes were formed, between the electrodes and covering the electrodes. This solution consists of tetrafluoroethylene and CF 2 =CFO
(CF 2 ) 3 COOCH 3 copolymer with an equivalent weight of 500
A polymer having a TQ of 160°C was dissolved in methanol as a sodium salt. After coating, it was air-dried at room temperature and then cured for one day in an atmosphere with a humidity of 93% to stabilize it. Curve C in FIG. 2 shows the results of testing the relationship between humidity and electrical resistance of the humidity sensor thus formed. Example 4 As in Example 1, a solution prepared as follows was applied between and over the electrodes on three glass substrates on which electrodes were formed. This solution used the same polymer as in Example 3 and was dissolved in methanol as a lithium salt. After coating, air dry at room temperature, then apply 1 coat in an atmosphere with a humidity of 93%.
It was stabilized by curing for a day. Curve D in FIG. 2 shows the results of testing the relationship between humidity and electrical resistance of the humidity sensor thus formed.
第１図は本発明における湿度センサーの具体例
を示したものであり、第２図は本発明の湿度セン
サーの試験結果を示す図面である。
１……絶縁基板、２，３……電極、４……湿度
検出被膜。
FIG. 1 shows a specific example of the humidity sensor of the present invention, and FIG. 2 is a diagram showing test results of the humidity sensor of the present invention. 1... Insulating substrate, 2, 3... Electrode, 4... Humidity detection coating.
Claims (1)
ン酸基の当量が400〜２，000である含フツ素重合
体からなる感湿素子 (イ) −（CF2−CXX′）−，(ロ)【式】 ここで、Ｘは、フツ素，塩素，水素又は−CF3
であり、X′は、Ｘ又はCF3（CF2）n−であり、ｍ
は１〜５であり、Ｙは次のものから選ばれる。 −（CF2）−x，−Ｏ−（CF2）−x，−（Ｏ−CF2−CF
−）
ｙ， ｘ，ｙ，ｚは、ともに１〜10であり、Ｚ，Rf
は、−Ｆ又は炭素数１〜10のパーフルオロアルキ
ル基から選ばれた基であり、Ａは−COOM（Ｍ
は、水素，アルカリ金属又はアルカリ土類金属を
表す）、又は、−CN，−COF，−COOR1等の加水分
解により−COOMに転換しうる官能基を示し、
R1は炭素数１〜10のアルキル基を示す。[Scope of Claims] 1. A moisture-sensitive element (a) comprising a fluorine-containing polymer having the following polymerized units (a) and (b) and having an equivalent weight of carboxylic acid groups of 400 to 2,000. -(CF 2 -CXX')-, (b) [Formula] Here, X is fluorine, chlorine, hydrogen or -CF 3
, X′ is X or CF 3 (CF 2 ) n −, and m
is from 1 to 5, and Y is selected from the following: −(CF 2 )− x , −O−(CF 2 )− x , −(O−CF 2 −CF
−)
y , x, y, z are all 1 to 10, and Z, Rf
is a group selected from -F or a perfluoroalkyl group having 1 to 10 carbon atoms, and A is -COOM (M
represents hydrogen, alkali metal or alkaline earth metal), or a functional group that can be converted to -COOM by hydrolysis, such as -CN, -COF, -COOR 1 , etc.
R 1 represents an alkyl group having 1 to 10 carbon atoms.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7701278A JPS554531A (en) | 1978-06-27 | 1978-06-27 | Humidity sensitive element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7701278A JPS554531A (en) | 1978-06-27 | 1978-06-27 | Humidity sensitive element |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS554531A JPS554531A (en) | 1980-01-14 |
| JPS6133129B2 true JPS6133129B2 (en) | 1986-07-31 |
Family
ID=13621835
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7701278A Granted JPS554531A (en) | 1978-06-27 | 1978-06-27 | Humidity sensitive element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS554531A (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58147712U (en) * | 1982-03-30 | 1983-10-04 | 日本コンクリ−ト工業株式会社 | Tightening and loosening device for concrete column forming formwork tightening bolts |
| JPS58206389A (en) * | 1982-05-28 | 1983-12-01 | 日産自動車株式会社 | Controller for robot |
| JPS597532A (en) * | 1982-07-02 | 1984-01-14 | Mitsubishi Motors Corp | Nut tightener |
| JPS597533A (en) * | 1982-07-02 | 1984-01-14 | Mitsubishi Motors Corp | Nut tightening method and its device |
| JPS59156738U (en) * | 1983-04-01 | 1984-10-20 | アサノ精機株式会社 | Formwork bolt automatic fastening device |
| JPS6124124U (en) * | 1984-07-16 | 1986-02-13 | 株式会社明電舎 | Self-propelled bolt tightening machine |
| JPS6191553A (en) * | 1984-10-11 | 1986-05-09 | Japan Storage Battery Co Ltd | Manufacture of humidity sensor |
| JPS6191554A (en) * | 1984-10-11 | 1986-05-09 | Japan Storage Battery Co Ltd | Manufacture of humidity sensor |
| JPS61241036A (en) * | 1985-04-16 | 1986-10-27 | Araya Kogyo Kk | Tightening method of tack stopping screw |
| JPS62181843A (en) * | 1986-02-01 | 1987-08-10 | Araya Kogyo Kk | Tool positioning device |
| JPH0429948Y2 (en) * | 1986-01-21 | 1992-07-20 | ||
| US8564310B2 (en) | 2009-08-18 | 2013-10-22 | 3M Innovative Properties Company | Capacitive oil quality monitoring sensor with fluorinated barrier coating |
-
1978
- 1978-06-27 JP JP7701278A patent/JPS554531A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS554531A (en) | 1980-01-14 |
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