JPH0640084B2 - Method for manufacturing moisture sensitive element - Google Patents
Method for manufacturing moisture sensitive elementInfo
- Publication number
- JPH0640084B2 JPH0640084B2 JP63184746A JP18474688A JPH0640084B2 JP H0640084 B2 JPH0640084 B2 JP H0640084B2 JP 63184746 A JP63184746 A JP 63184746A JP 18474688 A JP18474688 A JP 18474688A JP H0640084 B2 JPH0640084 B2 JP H0640084B2
- Authority
- JP
- Japan
- Prior art keywords
- sensitive element
- moisture
- humidity
- monomer
- polymer electrolyte
- 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 - Lifetime
Links
- 238000000034 method Methods 0.000 title claims description 15
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 239000000178 monomer Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000005518 polymer electrolyte Substances 0.000 claims description 18
- 229920001577 copolymer Polymers 0.000 claims description 11
- 238000007334 copolymerization reaction Methods 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 4
- 229920000867 polyelectrolyte Polymers 0.000 claims description 4
- 239000010408 film Substances 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- 239000010409 thin film Substances 0.000 claims description 2
- 230000001678 irradiating effect Effects 0.000 claims 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 18
- 239000002904 solvent Substances 0.000 description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000005956 quaternization reaction Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000007654 immersion Methods 0.000 description 5
- 238000001226 reprecipitation Methods 0.000 description 5
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001350 alkyl halides Chemical class 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- CYNYIHKIEHGYOZ-UHFFFAOYSA-N 1-bromopropane Chemical compound CCCBr CYNYIHKIEHGYOZ-UHFFFAOYSA-N 0.000 description 2
- WWJCRUKUIQRCGP-UHFFFAOYSA-N 3-(dimethylamino)propyl 2-methylprop-2-enoate Chemical compound CN(C)CCCOC(=O)C(C)=C WWJCRUKUIQRCGP-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-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
- WPUJEWVVTKLMQI-UHFFFAOYSA-N benzene;ethoxyethane Chemical compound CCOCC.C1=CC=CC=C1 WPUJEWVVTKLMQI-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 description 1
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 1
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- QENRKQYUEGJNNZ-UHFFFAOYSA-N 2-methyl-1-(prop-2-enoylamino)propane-1-sulfonic acid Chemical compound CC(C)C(S(O)(=O)=O)NC(=O)C=C QENRKQYUEGJNNZ-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 description 1
- RUZXDTHZHJTTRO-UHFFFAOYSA-N 7-amino-4h-1,4-benzoxazin-3-one Chemical compound N1C(=O)COC2=CC(N)=CC=C21 RUZXDTHZHJTTRO-UHFFFAOYSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- -1 LiCl Chemical class 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- DIUWKIIUUNWJHU-UHFFFAOYSA-N [4-(3-oxo-3-phenylprop-1-enyl)phenyl] 2-methylprop-2-enoate Chemical compound C1=CC(OC(=O)C(=C)C)=CC=C1C=CC(=O)C1=CC=CC=C1 DIUWKIIUUNWJHU-UHFFFAOYSA-N 0.000 description 1
- XMEQKUYDQRWRMT-MDWZMJQESA-N [4-[(e)-3-phenylprop-2-enoyl]phenyl] 2-methylprop-2-enoate Chemical compound C1=CC(OC(=O)C(=C)C)=CC=C1C(=O)\C=C\C1=CC=CC=C1 XMEQKUYDQRWRMT-MDWZMJQESA-N 0.000 description 1
- 239000003708 ampul Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- GYDSPAVLTMAXHT-UHFFFAOYSA-N pentyl 2-methylprop-2-enoate Chemical compound CCCCCOC(=O)C(C)=C GYDSPAVLTMAXHT-UHFFFAOYSA-N 0.000 description 1
- ULSIYEODSMZIPX-UHFFFAOYSA-N phenylethanolamine Chemical compound NCC(O)C1=CC=CC=C1 ULSIYEODSMZIPX-UHFFFAOYSA-N 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Landscapes
- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
Description
【発明の詳細な説明】 ＜産業上の利用分野＞ 本発明は感湿素子の製造方法に関するものである。The present invention relates to a method for manufacturing a humidity sensitive element.
＜従来の技術＞ 従来の感湿素子に用いられる材料には、1)Fe2O3、SnO2
などの金属酸化物、2)LiClなどの金属塩、3)吸湿性樹脂
に炭素など導電性固体を分散させた複数材料、4)高分子
電解質などがある。<Prior Art> Materials used for conventional moisture sensitive elements include 1) Fe 2 O 3 and SnO 2
There are 2) metal salts such as LiCl, 3) multiple materials in which conductive solid such as carbon is dispersed in hygroscopic resin, 4) polymer electrolyte, etc.
金属酸化物を用いた感湿素子は、耐熱性に優れ、応答速
度が速いという特徴を有する反面、素子抵抗値の湿度依
存性が大きく、また金属酸化物からの水分の脱着が起こ
りにくいために、素子特性の経時変化が大きいなどの欠
点を有する。Moisture-sensitive elements using metal oxides have the characteristics of excellent heat resistance and fast response speed, but on the other hand, the humidity dependency of the element resistance value is large, and because desorption of water from the metal oxides does not occur easily. However, it has drawbacks such as a large change over time in device characteristics.
金属塩を用いた感湿素子は、検出できる湿度範囲が狭
く、特に高湿度域では金属塩の溶解、流失が起こるため
に長時間使用できないなどの欠点を有する。The humidity sensitive element using a metal salt has a drawback that the detectable humidity range is narrow, and particularly in a high humidity range, the metal salt is dissolved or washed out, so that it cannot be used for a long time.
吸湿性樹脂に導電性固体を分散させた複数材料を用いた
感湿素子は、高湿度域では急激な素子抵抗値の変化を生
じるが、低湿度域ではほとんど感度がなく広い湿度範囲
での測定に使用できない。A moisture-sensitive element that uses multiple materials in which conductive solids are dispersed in a hygroscopic resin causes a rapid change in element resistance value in high humidity regions, but it has little sensitivity in low humidity regions and can be measured in a wide humidity range. Cannot be used for.
高分子電解質を用いた感湿素子は、感湿範囲が広い、応
答速度が速い、高分子電解質を基板上に薄膜化すること
により容易に作製できる、などの特徴を有する反面、高
湿度で長時間置かれたり素子が水にぬれると、特性の劣
化を起こす欠点を有していた。A moisture-sensitive element using a polymer electrolyte has features such as a wide moisture-sensing range, fast response speed, and easy fabrication by thinning the polymer electrolyte on a substrate, but it has a long humidity It has a defect that its characteristics are deteriorated when it is left for a long time or the element gets wet with water.
橋かけを光橋かけモノマーをモノマーのまま配合し光重
合することによって、もしくはプレポリマーと光橋かけ
モノマーの加熱を必要とする反応によって、基板上に３
次元網状構造の高分子電解質膜を形成させた感湿素子
は、耐湿性を有し、感湿膜が高湿度雰囲気下で膨潤、溶
出するという欠点をもたないが、感湿膜中に光橋かけモ
ノマー等の未重合モノマーなど低分子の可溶性成分が残
るため、水にぬれた場合の特性劣化を避けることができ
なかった。The photocrosslinking monomer can be incorporated onto the substrate by photopolymerization by incorporating the photocrosslinking monomer as it is, or by a reaction requiring heating of the prepolymer and the photocrosslinking monomer.
A moisture-sensitive element with a polymer electrolyte membrane having a three-dimensional network structure has moisture resistance and does not have the drawback that the moisture-sensitive membrane swells and elutes in a high-humidity atmosphere. Since a low-molecular soluble component such as an unpolymerized monomer such as a crosslinking monomer remains, it is impossible to avoid deterioration of characteristics when wet with water.
＜本発明の目的＞ 本発明は、以上に述べたような従来の感湿素子がもって
いた欠点を解消するものであって、光橋かけモノマーを
あらかじめ共重合成分として含有させた高分子電解質を
合成し、該高分子電解質を精製した後、基板上に薄膜化
し、光橋かけすることにより、耐水性の優れた感湿素子
を得るための製造方法を提供することを目的とする。<Purpose of the present invention> The present invention is to eliminate the drawbacks of the conventional moisture-sensitive element as described above, and to provide a polymer electrolyte containing a photocrosslinking monomer as a copolymerization component in advance. An object of the present invention is to provide a manufacturing method for obtaining a moisture-sensitive element having excellent water resistance by synthesizing the polymer electrolyte, purifying the polymer electrolyte, forming a thin film on a substrate, and photocrosslinking.
＜問題点を解決するための手段＞ 橋かけを光橋かけモノマーをモノマーのまま配合し光重
合することによって、もしくはプレポリマーと光橋かけ
モノマーの加熱を必要とする反応によって、基板上に３
次元網状構造の高分子電解質膜を形成させた感湿素子
は、感湿膜中に残った未重合モノマーなど低分子の可溶
性成分が水にぬれたときに溶出し、特性劣化を起こす欠
点がある。<Means for Solving Problems> A photocrosslinking monomer is added as a monomer to the crosslinker and photopolymerized, or a reaction which requires heating of the prepolymer and the photocrosslinking monomer is used.
A moisture-sensitive element formed with a polymer electrolyte membrane having a three-dimensional network structure has the drawback that when a low-molecular soluble component such as an unpolymerized monomer remaining in the moisture-sensitive film is dissolved in water, it deteriorates its characteristics. .
これに対し、本発明では、橋かけ基を有する光橋かけモ
ノマーを共重合成分として含有する１次元線状高分子電
解質を合成し、十分精製して低分子の可溶性成分を除い
た後、製膜し橋かけするという方法により感湿素子を作
製することによって、水にぬれても特性の変化しない耐
水性の優れた感湿素子が得られる。On the other hand, in the present invention, a one-dimensional linear polyelectrolyte containing a photocrosslinking monomer having a crosslinking group as a copolymerization component is synthesized and sufficiently purified to remove low-molecular soluble components. By manufacturing a moisture-sensitive element by a method of film-forming and crosslinking, a moisture-sensitive element having excellent water resistance that does not change its characteristics even when wetted with water can be obtained.
また、この際に反応に加熱を要さず、解重合を起こす恐
れのない近紫外光による光橋かけを用いれば、橋かけに
よる素材の性質の変化を最小限に抑えることができる。Further, in this case, if the photocrosslinking by near-ultraviolet light, which does not require heating for the reaction and does not cause depolymerization, is used, the change in the properties of the material due to the crosslinking can be minimized.
そのため、適当な吸湿性及びイオン伝導性を有する高分
子電解質を調製することにより、目的とする特性を有す
る感湿素子を作製することができる。Therefore, by preparing a polymer electrolyte having appropriate hygroscopicity and ion conductivity, it is possible to manufacture a moisture-sensitive element having desired characteristics.
以下、本発明について詳しく述べる。Hereinafter, the present invention will be described in detail.
本発明は通常のラジカルあるいはイオン共重合法等によ
ることができる。The present invention can be carried out by an ordinary radical or ionic copolymerization method or the like.
本発明においては、光橋かけモノマーとして、４′−メ
タクリロイルオキシカルコン（4′MCと略す）、4-メタ
クリロイルオキシカルコン、シンナミルメタクリラート
などに、4-ビニルピリジン（4VPと略す）、2-ビニルピ
リジン、2-ジメチルアミノエチルメタクリラート（DMAE
Mと略す）、2-ジエチルアミノエチルメタクリラート、2
-ジメチルアミノプロピルメタクリラート、3-ジメチル
アミノプロピルメタクリラートなどの４級化できる窒素
原子を有するモノマー、またはスチレンスルホン酸ナト
リウム、アクリルアミド-2-メチルプロパンスルホン酸
などのイオン性モノマーを加え、共重合させることによ
ってコポリマーを得る。In the present invention, as photocrosslinking monomers, 4'-methacryloyloxychalcone (abbreviated as 4'MC), 4-methacryloyloxychalcone, cinnamylmethacrylate and the like, 4-vinylpyridine (abbreviated as 4VP), 2- Vinyl pyridine, 2-dimethylaminoethyl methacrylate (DMAE
Abbreviated as M), 2-diethylaminoethyl methacrylate, 2
-Copolymerization by adding a monomer having a nitrogen atom capable of quaternization such as dimethylaminopropyl methacrylate and 3-dimethylaminopropyl methacrylate, or an ionic monomer such as sodium styrenesulfonate and acrylamido-2-methylpropanesulfonic acid. To obtain a copolymer.
この時n-ブチルメタクリラート（BMAと略す）、メチル
メタクリラート、n-プロピルメタクリラート、n-ペンチ
ルメタクリラートなどの疎水性モノマーを加え３元共重
合体とすることができる。At this time, hydrophobic monomers such as n-butyl methacrylate (abbreviated as BMA), methyl methacrylate, n-propyl methacrylate, and n-pentyl methacrylate can be added to form a terpolymer.
上記において、４級化できる窒素原子を有するモノマー
を使用した時は、さらにこのコポリマーを1-ブロモプロ
パン、ブロモエタン、1-ブロモブタンなどのハロゲン化
アルキルにより４級化し、光橋かけ基を有する高分子電
解質を調製する。In the above, when a monomer having a nitrogen atom capable of quaternization is used, this copolymer is further quaternized with an alkyl halide such as 1-bromopropane, bromoethane or 1-bromobutane to give a polymer having a photocrosslinking group. Prepare the electrolyte.
これらの高分子電解質の吸湿性及びイオン伝導性は、共
重合させるモノマーの組成、４級化反応に用いるハロゲ
ン化アルキルの種類及びその反応率などにより調節する
ことができる。The hygroscopicity and ionic conductivity of these polymer electrolytes can be adjusted by the composition of the monomers to be copolymerized, the type of alkyl halide used in the quaternization reaction, the reaction rate thereof, and the like.
合成した高分子電解質は再沈殿などによって十分に精製
し、低分子の可溶性成分を除去しておくことが、この時
とりわけ重要である。At this time, it is particularly important that the synthesized polyelectrolyte is sufficiently purified by reprecipitation or the like to remove low-molecular soluble components.
精製法としては、粗製高分子電解質を溶剤に溶解し、再
沈殿を繰り返す方法による。The purification method is a method in which the crude polymer electrolyte is dissolved in a solvent and reprecipitation is repeated.
溶剤としては、ジメチルホルムアミド、ジメチルアセト
アミド、メタノール、エタノール、クロロホルム、アセ
トニトリル等が使用でき、沈殿剤としては、ベンゼン、
トルエン、エチルエーテル、アセトン等が使用できる。As the solvent, dimethylformamide, dimethylacetamide, methanol, ethanol, chloroform, acetonitrile and the like can be used, and as the precipitating agent, benzene,
Toluene, ethyl ether, acetone, etc. can be used.
上記の方法により得られた高分子電解質をN，N-ジメチ
ルホルムアミド（DMFと略す）、メタノール、エタノー
ル、クロロホルム、アセトニトリル、ジメチルアセトア
ミドなどの溶媒に溶かし、くし型金電極付アルミナ基板
上に塗布乾燥し、光照射、好ましくは近紫外光の照射を
行って感湿膜を形成する。Dissolve the polymer electrolyte obtained by the above method in a solvent such as N, N-dimethylformamide (abbreviated as DMF), methanol, ethanol, chloroform, acetonitrile, dimethylacetamide, and coat and dry it on an alumina substrate with a comb-shaped gold electrode. Then, light irradiation, preferably near-ultraviolet light irradiation is performed to form a moisture-sensitive film.
本発明で得られる感湿素子は、抵抗−相対湿度特性の直
線性がよく、ヒステリシスが小さく、応答速度が速い特
徴をもつ。The humidity-sensitive element obtained by the present invention is characterized by good resistance-relative humidity linearity, small hysteresis, and fast response speed.
さらに、この感湿素子は30分間純水に浸せきし、ついで
１晩空気中で乾燥するというサイクルを繰り返したと
き、その抵抗値はほとんど変化せず、優れた耐水性を示
す。Further, when the humidity-sensitive element was immersed in pure water for 30 minutes and then dried in the air overnight, the resistance value was hardly changed and excellent water resistance was exhibited.
［実施例１］ 共重合させるモノマーとして、4VP及び4′MCをそれぞれ
3.42mL及び0.93g用い、開始剤としてアゾビスイソブチ
ロニトリル（AIBNと略す）を0.0144g用い、溶媒としてD
MFを8.65mL用いる。[Example 1] 4VP and 4'MC were respectively used as monomers to be copolymerized.
Using 3.42 mL and 0.93 g, using 0.0144 g of azobisisobutyronitrile (abbreviated as AIBN) as an initiator and D as a solvent
Use 8.65 mL of MF.
以上の試薬または溶媒をアンプル中に入れ、脱気した後
に溶封し、時々振り混ぜながら1.5時間60℃で加熱す
る。Put the above reagents or solvent in an ampoule, degas, seal, and heat at 60 ° C for 1.5 hours with occasional shaking.
この重合物をエタノールに溶解し2%溶液とし、20倍量の
ベンゼン中に攪拌しながら注ぐことにより２回再沈殿し
て精製する。This polymer is dissolved in ethanol to give a 2% solution, and the mixture is poured into 20 volumes of benzene with stirring to reprecipitate twice for purification.
得られたコポリマーをDMFに溶解し10%溶液とし、この溶
液に同体積の1-ブロモプロパンを加え、攪拌しながら２
時間60℃で加熱し、４級化反応を行う。The obtained copolymer is dissolved in DMF to make a 10% solution, and the same volume of 1-bromopropane is added to this solution, and the mixture is stirred while stirring.
Heat at 60 ° C. for 4 hours to carry out the quaternization reaction.
４級化されたコポリマーをエタノールに溶解し2%溶液と
し、20倍量のベンゼン中に攪拌しながら注ぐことによ
り、２回再沈殿して精製する。The quaternized copolymer is dissolved in ethanol to make a 2% solution, which is then poured into 20 volumes of benzene with stirring to reprecipitate twice for purification.
上記の高分子電解質をDMFに溶解し約8%の溶液とし、く
し型金電極付アルミナ基板上に流廷し、60℃で１時間減
圧乾燥する。The above polymer electrolyte is dissolved in DMF to prepare a solution of about 8%, which is cast on an alumina substrate with a comb-shaped gold electrode and dried under reduced pressure at 60 ° C. for 1 hour.
次に、250w超高圧水銀灯でパイレックスガラスフィルタ
ーを通して基板を10分間照射し、感湿素子を得た。Next, the substrate was irradiated with a 250w ultra-high pressure mercury lamp through a Pyrex glass filter for 10 minutes to obtain a humidity sensitive element.
この感湿素子の抵抗−相対湿度特性を第１図に示す。The resistance-relative humidity characteristics of this humidity sensitive element are shown in FIG.
また、純水への浸せき回数と素子抵抗値の関係を第２図
に示す。The relationship between the number of immersions in pure water and the element resistance value is shown in FIG.
１回目の浸せきにより生じるごくわずかの変化を除き、
ほとんど抵抗値の変化を示さず、優れた耐水性を示す。Except for the very slight changes caused by the first dip,
It shows almost no change in resistance and shows excellent water resistance.
［実施例２］ 実施例１と同様の方法によって、4VP、4′MC、及びBMA
をそれぞれ1.08mL、0.584g、及び1.59mL用い、AIBNを0.
009g用い、DMFを5mL用い共重合を行い、得られたコポリ
マーをさらに４級化した。Example 2 In the same manner as in Example 1, 4VP, 4′MC, and BMA
1.08 mL, 0.584 g, and 1.59 mL, respectively, with AIBN of 0.
Copolymerization was performed using 009 g and 5 mL of DMF, and the obtained copolymer was further quaternized.
この際、重合時間は2.3時間とし、コポリマーの再沈殿
に用いる良溶媒と貧溶媒の組合せはベンゼン−エチルエ
ーテルとし、その他の手法及び条件は実施例１と同じに
した。At this time, the polymerization time was 2.3 hours, the combination of the good solvent and the poor solvent used for the reprecipitation of the copolymer was benzene-ethyl ether, and the other methods and conditions were the same as in Example 1.
この高分子電解質から作製した感湿素子は、相対湿度52
%において830kΩ、91%において24kΩの抵抗値を示し、
また純水への浸せきによって素子抵抗値はほとんど変化
しなかった。A humidity sensitive element made from this polymer electrolyte has a relative humidity of 52%.
Shows a resistance value of 830 kΩ at%, 24 kΩ at 91%,
Further, the element resistance value hardly changed due to the immersion in pure water.
［実施例３］ 実施例１と同様の方法によって、DMAEM及び4′MCをそれ
ぞれ17.7mL及び3.3g用い、AIBNを0.102g用い、DMFを20m
L用い共重合を行い、得られたコポリマーをさらに４級
化した。[Example 3] By the same method as in Example 1, 17.7 mL and 3.3 g of DMAEM and 4'MC, respectively, 0.102 g of AIBN and 20 m of DMF were used.
Copolymerization was performed using L, and the obtained copolymer was further quaternized.
この際、重合時間は８時間とし、コポリマーの再沈殿に
用いる良溶媒と貧溶媒の組合せはベンゼン−エチルエー
テルとし、その他の手法及び条件は実施例１と同じにし
た。At this time, the polymerization time was 8 hours, the combination of the good solvent and the poor solvent used for the reprecipitation of the copolymer was benzene-ethyl ether, and the other methods and conditions were the same as in Example 1.
この高分子電解質から作製した感質素子の抵抗−相対湿
度特性を第１図に、純水への浸せき回数と素子抵抗値の
関係を第２図に示す。純水への浸せきを繰り返しても抵
抗値の変化はほとんどなく、優れた耐水性を示す。The resistance-relative humidity characteristics of the sensitive element produced from this polymer electrolyte are shown in FIG. 1, and the relationship between the number of immersions in pure water and the element resistance value is shown in FIG. It shows excellent water resistance with almost no change in resistance value even after repeated immersion in pure water.
［実施例４］ 実施例１と同様の方法によって、DMEAM、4′MC、及びBM
Aをそれぞれ2.86mL、0.99g、及び2.70mL用い、AIBNを0.
0153g用い、DMFを8.5mL用い共重合を行い、得られたコ
ポリマーをさらに４級化した。[Example 4] By the same method as in Example 1, DMEAM, 4'MC, and BM
2.86 mL, 0.99 g, and 2.70 mL of A, respectively, and AIBN of 0.
Copolymerization was carried out using 8.53 mL of DMF using 8.53 g, and the obtained copolymer was further quaternized.
この際、重合時間は７時間とし、４級化反応時間は５時
間とし、コポリマーの再沈殿に用いる良溶媒と貧溶媒の
組合せはベンゼン−メタノールとし、その他の手法及び
条件は実施例１と同じにした。At this time, the polymerization time was 7 hours, the quaternization reaction time was 5 hours, the combination of the good solvent and the poor solvent used for reprecipitation of the copolymer was benzene-methanol, and the other methods and conditions were the same as in Example 1. I chose
この高分子電解質から作製した感湿素子は、相対湿度52
%において480kΩ、91%において7.0kΩの抵抗値を示し、
また純水への浸せきによって素子抵抗値はほとんど変化
しなかった。A humidity sensitive element made from this polymer electrolyte has a relative humidity of 52%.
% Shows a resistance value of 480 kΩ, 91% shows a resistance value of 7.0 kΩ,
Further, the element resistance value hardly changed due to the immersion in pure water.
＜本発明の効果＞ 本発明により共重合させるモノマーの組成、４級化反応
に用いるハロゲン化アルキルの種類及びその反応率など
を変え、適当な吸湿性及びイオン伝導性を有する高分子
電解質を用意することにより、目的とする特性を有する
感湿素子を再現性よく作製することができる。<Effects of the Present Invention> A polymer electrolyte having appropriate hygroscopicity and ion conductivity is prepared by changing the composition of the monomer to be copolymerized according to the present invention, the type of alkyl halide used in the quaternization reaction and the reaction rate thereof By doing so, it is possible to manufacture a moisture-sensitive element having desired characteristics with good reproducibility.
また本発明によって得た感湿素子は、抵抗−相対湿度特
性の直線性がよく、ヒステリシスが小さく、応答速度が
速い特徴をもち、また水ぬれによって特性の変化しない
優れた耐水性を有する。Further, the humidity-sensitive element obtained by the present invention has characteristics of good linearity of resistance-relative humidity characteristics, small hysteresis and fast response speed, and has excellent water resistance in which characteristics do not change due to water wetting.
そのため、これまで困難であった水滴の付きやすい環境
での湿度計測が可能となり、感湿素子の新しい用途を開
拓することができる。Therefore, it becomes possible to measure humidity in an environment where it is difficult to get water droplets, which has been difficult until now, and it is possible to develop a new application of the humidity sensitive element.
第１図は本発明の製造方法の実施例で作製した感湿素子
の抵抗を、25℃、信号レベル1V、及び周波数1KHzの条件
で測定することによって得られた感湿特性を示す図であ
る。 第２図は上記と同じ感湿素子を純水に浸せきした回数
と、同じ条件で測定した相対湿度66.4%におけるその抵
抗値の変化の関係を示す説明図である。FIG. 1 is a diagram showing the humidity-sensitive characteristics obtained by measuring the resistance of the humidity-sensitive element manufactured in the example of the manufacturing method of the present invention under the conditions of 25 ° C., signal level 1 V, and frequency 1 KHz. . FIG. 2 is an explanatory diagram showing the relationship between the number of times the same moisture-sensitive element was immersed in pure water and the change in its resistance value at a relative humidity of 66.4% measured under the same conditions.
フロントページの続き 審査官 能美 知康 (56)参考文献 特開 昭55−10502（ＪＰ，Ａ) 特開 昭61−56952（ＪＰ，Ａ) 特開 昭62−83642（ＪＰ，Ａ) 特開 昭62−52446（ＪＰ，Ａ)Continuation of front page Examiner Tomoyasu Nomi (56) Reference JP-A-55-10502 (JP, A) JP-A-61-56952 (JP, A) JP-A-62-83642 (JP, A) JP-A 62-52446 (JP, A)
Claims (2)
する高分子電解質を合成し、該高分子電解質を精製した
後、基板上に薄膜化し光照射することにより感湿膜を形
成することを特徴とする、耐水性を有する感湿素子の製
造方法。1. A method of synthesizing a polyelectrolyte containing a photocrosslinking monomer as a copolymerization component, purifying the polyelectrolyte, forming a thin film on a substrate and irradiating with light to form a moisture-sensitive film. A method for manufacturing a moisture-sensitive element having water resistance, which is characterized.
を有するモノマーを共重合成分として含有するコポリマ
ーを合成し、該４級化できる窒素原子を４級化すること
により高分子電解質を合成することを特徴とする特許請
求の範囲第１項記載の感湿素子の製造方法。2. A polymer electrolyte is synthesized by synthesizing a copolymer containing a photocrosslinking monomer and a monomer having a quaternizable nitrogen atom as a copolymerization component and quaternizing the quaternizable nitrogen atom. The method for manufacturing a moisture-sensitive element according to claim 1, wherein
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63184746A JPH0640084B2 (en) | 1988-07-26 | 1988-07-26 | Method for manufacturing moisture sensitive element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63184746A JPH0640084B2 (en) | 1988-07-26 | 1988-07-26 | Method for manufacturing moisture sensitive element |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0236343A JPH0236343A (en) | 1990-02-06 |
| JPH0640084B2 true JPH0640084B2 (en) | 1994-05-25 |
Family
ID=16158619
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63184746A Expired - Lifetime JPH0640084B2 (en) | 1988-07-26 | 1988-07-26 | Method for manufacturing moisture sensitive element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0640084B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6814409B2 (en) * | 2001-04-12 | 2004-11-09 | A-Dec, Inc. | Hydraulic drive system |
-
1988
- 1988-07-26 JP JP63184746A patent/JPH0640084B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0236343A (en) | 1990-02-06 |
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