JPWO2016068129A1 - 吸湿材およびこれを用いた除湿機 - Google Patents
吸湿材およびこれを用いた除湿機 Download PDFInfo
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- JPWO2016068129A1 JPWO2016068129A1 JP2016556580A JP2016556580A JPWO2016068129A1 JP WO2016068129 A1 JPWO2016068129 A1 JP WO2016068129A1 JP 2016556580 A JP2016556580 A JP 2016556580A JP 2016556580 A JP2016556580 A JP 2016556580A JP WO2016068129 A1 JPWO2016068129 A1 JP WO2016068129A1
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Abstract
Description
本発明者らは、上記課題に鑑み鋭意検討した結果、刺激応答性高分子と親水性高分子とが、相互浸入高分子網目構造またはセミ相互浸入高分子網目構造を形成している高分子ゲルの乾燥体を吸湿材として用いることにより、従来の吸湿材とは全く異なる機構により、過冷却や大きな熱量を用いずに効率よく除湿することができることを見出し、本発明を完成させるに至った。
本発明において高分子ゲルとは、高分子が架橋されて形成された3次元の網目構造が、水、有機溶媒等の溶媒を吸収して膨潤したものをいう。
刺激応答性高分子とは、外部刺激に応答して、その性質を可逆的に変化させる高分子をいう。本発明においては、外部刺激に応答して水との親和性が可逆的に変化する刺激応答性高分子を用いる。
本発明に係る吸湿材に用いられる親水性高分子は、当該親水性高分子とともに、相互浸入高分子網目構造またはセミ相互浸入高分子網目構造を形成している刺激応答性高分子以外の親水性の高分子であれば特に限定されるものではない。
従来溶媒中で外部刺激に応答して膨潤と収縮を繰り返す刺激応答性ゲルは知られているが、その乾燥体を吸湿材として用いても、空気中の水分を吸収する能力は十分ではない。高い吸湿性を持つ材料としては、水酸化ナトリウム等の塩、吸水性高分子等が知られているが、水酸化ナトリウム等の塩は吸湿とともにゾル化してしまうため、形のくずれない吸湿材が求められる。また、吸水性高分子を用いる場合、吸湿材からの水分の脱離のためには、水分を気化する必要がある。
本発明に係る吸湿材の製造方法は、前記刺激応答性高分子と前記親水性高分子とを含む高分子ゲルであって、前記刺激応答性高分子と前記親水性高分子とが、相互浸入高分子網目構造またはセミ相互浸入高分子網目構造を形成している高分子ゲルを製造する高分子ゲル製造工程と、前記高分子ゲル製造工程で得られた高分子ゲルを乾燥する乾燥工程とを少なくとも含んでいればよい。本発明に係る吸湿材の製造方法は、さらに、前記乾燥工程により得られた高分子乾燥体を粉砕する粉砕工程を含んでいてもよい。
高分子ゲル製造工程は、前記高分子ゲルを製造することができる工程であれば特に限定されるものではないが、前記高分子ゲルは、例えば、以下の方法により製造することができる。
〔1〕前記刺激応答性高分子を構成するモノマーを重合および架橋することにより、前記刺激応答性高分子の架橋体の架橋網目(a)を形成する工程(i)と、
架橋網目(a)の存在下で、前記親水性高分子を構成するモノマーを重合および架橋することにより、架橋網目(a)と、前記親水性高分子の架橋体の架橋網目(b)とからなる相互浸入高分子網目構造を形成する工程(ii)とを含む方法。
〔2〕前記刺激応答性高分子を構成するモノマーを重合および架橋することにより、前記刺激応答性高分子の架橋体の架橋網目(a)を形成する工程(i)と、
架橋網目(a)の存在下で、前記親水性高分子を構成するモノマーを重合することにより、架橋網目(a)と、直鎖状の前記親水性高分子とからなるセミ相互浸入高分子網目構造を形成する工程(ii)とを含む方法。
〔3〕前記刺激応答性高分子を構成するモノマーを重合することにより、直鎖状の前記刺激応答性高分子を製造する工程(i)と、
直鎖状の前記刺激応答性高分子の存在下で、前記親水性高分子を構成するモノマーを重合および架橋することにより、直鎖状の前記刺激応答性高分子と、前記親水性高分子の架橋体の架橋網目(b)とからなるセミ相互浸入高分子網目構造を形成する工程(ii)とを含む方法。
乾燥工程では、前記高分子ゲル製造工程で得られた高分子ゲルを乾燥して、高分子ゲルの乾燥体を得る。
乾燥工程によって得られた、前記高分子ゲルの乾燥体は、必要に応じて、粉砕工程において、粉砕する。
本発明に係る吸湿材は上述した構成を備えていることにより、該吸湿材を用いた除湿機によれば、過冷却や大きな熱量を用いずに効率よく除湿を行うことができる。それゆえ、本発明の吸湿材を利用した除湿機も本発明に含まれる。以下、本発明に係る除湿機の実施の形態を、図面を参照して詳細に説明する。
図10は本発明の実施の形態1に係る除湿機101の縦断面図を示し、図11は除湿機101の横断面図を示す。図10に示すように、除湿機101は、吸気口9と、排気口10とを有する除湿機本体8を備え、除湿機本体8の内部には、本発明の吸湿材を担持した複数の吸湿ユニット1と、吸湿ユニット1が空気中の水分を吸収する領域である吸湿エリア16と、空気中の水分を吸収した吸湿ユニット1が吸収した水分を水として放出する領域である脱水エリア17と、放出された水を貯水する排水タンク14と、除湿される空気を吸気口9から取り込み、除湿された空気を排気口10から排出するための送風ファン11とが備えられている。なお、本実施の形態では、吸湿材としては、前記刺激応答性高分子として温度応答性高分子を含む吸湿材を用いている。
図15は本発明の実施の形態2に係る除湿機102の縦断面図を示し、図16は除湿機102の横断面図を示す。また、除湿機102の吸湿ユニット1の構造を、図12〜図14に示す。
本発明の態様1に係る吸湿材は、外部刺激に応答して水との親和性が可逆的に変化する刺激応答性高分子と、親水性高分子とを含む高分子ゲルの乾燥体を含有する吸湿材であって、前記刺激応答性高分子と、前記親水性高分子とが、相互浸入高分子網目構造またはセミ相互浸入高分子網目構造を形成している構成を備えている。
実施の形態3として、以下、本発明を実施例により具体的に説明するが、本発明は実施例によって限定されるものではない。
<アルギン酸とポリN−イソプロピルアクリルアミドとが相互浸入高分子網目構造を形成する高分子ゲルの合成>
N−イソプロピルアクリルアミド(NIPAMと略称することがある。)700mg、アルギン酸ナトリウム(Algと略称することがある。)700mg、およびメチレンビスアクリルアミド(MBAAと略称することがある。)58mgを純水23mLに溶解した。得られた溶液に、0.8mol/LのN,N,N´,N´−テトラメチルエチレンジアミン(TEMEDと略称することがある。)および0.1mol/Lの過硫酸アンモニウム(APSと略称することがある。)をそれぞれ1mLずつ加え、氷浴下で6時間反応させることにより、ポリN−イソプロピルアクリルアミドがMBAAで架橋されたヒドロゲルを製造した。その後、得られたヒドロゲルを、0.25mol/Lの塩化カルシウム水溶液100mLに浸漬し、2日間静置することにより、カルシウムイオンでAlgを架橋させた。このようにして、ポリN−イソプロピルアクリルアミドとアルギン酸とが相互浸入高分子網目構造を形成する高分子ゲル(Alg/PNIPAM IPNゲルと略称することがある。)を合成した。合成したAlg/PNIPAM IPNゲルおよびその製造方法を図1に示す。
得られたAlg/PNIPAM IPNゲルを純水に浸漬し、一定の温度下で24時間静置した後、ゲルの重量を測定した。その後、ゲルを加熱乾燥させて乾燥重量を測定した。24時間静置後のゲルの重量および乾燥重量から、下記式により含水率を算出した。
含水率=(24時間静置後のゲルの重量−乾燥重量)/乾燥重量
ゲルを15℃、25℃、30℃、35℃、40℃、および50℃の一定温度下でそれぞれ24時間静置したときの含水率を算出し、温度変化に伴うAlg/PNIPAM IPNゲルの相転移挙動について検討した。
得られたAlg/PNIPAM IPNゲルを−20℃で凍結し、20Paの減圧条件下で24時間乾燥させた。このようにして得られたAlg/PNIPAM IPNゲルの乾燥体を、温度20℃、湿度80%RHの恒温恒湿条件下で静置し、重量変化を経時的に測定することにより、Alg/PNIPAM IPNゲルの乾燥体の吸湿挙動について検討した。
Alg/PNIPAM IPNゲルの乾燥体を、温度25.5℃、約80%RHの恒温恒湿条件下で80時間静置して十分に吸湿させた。このようにして吸湿させたAlg/PNIPAM IPNゲルの乾燥体を、ヒーターを用いて60℃で加熱し、ゲル表面の様子を動画撮影して脱水挙動について検討した。
<N−イソプロピルアクリルアミドとアクリル酸ナトリウムとの共重合ゲルの合成>
N−イソプロピルアクリルアミド(NIPAM)538.6mg、アクリル酸ナトリウム(AAcNa)191.8mg、メチレンビスアクリルアミド(MBAA)77.8mgを純水3.4mLに溶解した。得られた溶液に、0.8mol/LのN,N,N´,N´−テトラメチルエチレンジアミン(TEMED)および0.4mol/Lの過硫酸アンモニウム(APS)をそれぞれ1mLずつ加え、氷浴下で6時間反応させることにより、AAcNaの含有量(AAc contentと略称する。)が30mol%のN−イソプロピルアクリルアミドとアクリル酸ナトリウムとのランダム共重合体からなるヒドロゲル(以下、PNIPAM/PAAcNa共重合ゲルと略称する。)を合成した。合成した共重合ゲルおよびその製造方法を図17に示す。
測定温度を、20℃、25℃、30℃、35℃、40℃、50℃および60℃とした以外は、実施例1と同様にして、得られたPNIPAM/PAAcNa共重合ゲルを純水に浸漬し、一定温度下でそれぞれ24時間静置したときの含水率を算出し、温度変化に伴うPNIPAM/PAAcNa共重合ゲルの相転移挙動について検討した。
<アルギン酸とヒドロキシプロピルセルロース(以下、HPCと略称することがある。)とがセミ相互浸入高分子網目構造を形成する高分子ゲルの合成>
ヒドロキシプロピルセルロース(和光純薬工業株式会社、ヒドロキシプロピルセルロース150〜400cP)700mg、およびアルギン酸ナトリウム700mgを純水25mLに溶解した。得られた溶液に、0.5mol/Lの塩化カルシウム水溶液100mLを流し込み、2日間静置することにより、ヒドロキシプロピルセルロースとアルギン酸とがセミ相互浸入高分子網目構造を形成する高分子ゲル(HPC/Alg セミIPNゲルと略称することがある。)を調製した。
得られたHPC/Alg セミIPNゲルを−30℃で凍結し、20Paの減圧条件下で24時間乾燥させた。このようにして得られたHPC/Alg セミIPNゲルの乾燥体を、温度25℃、湿度80%RHの恒温恒湿条件下で静置し、重量変化を経時的に測定することにより、HPC/Alg セミIPNゲルの乾燥体の吸湿挙動について検討した。
<HPC/Alg セミIPNゲルの乾燥体の脱水挙動>
HPC/Alg セミIPNゲルの乾燥体を、温度25℃、約80%RHの恒温恒湿条件下で24時間静置して十分に吸湿させた。このようにして吸湿させたHPC/Alg セミIPNゲルの乾燥体を、ヒーター温度60℃で加熱し、ゲル表面の様子を動画撮影して脱水挙動について検討した。
HPCとして、ヒドロキシプロピルセルロース6.0〜10.0(和光純薬工業株式会社)を用いた以外は実施例2と同様にして、アルギン酸とHPCとがセミ相互浸入高分子網目構造を形成する高分子ゲルの製造及び評価を行った。その乾燥体が、高い吸湿・脱水能力を有することが確認された。
HPCとして、ヒドロキシプロピルセルロース1000〜5000cP(和光純薬工業株式会社)を用いた以外は実施例2と同様にして、アルギン酸とHPCとがセミ相互浸入高分子網目構造を形成する高分子ゲルの製造及び評価を行った。その乾燥体が、高い吸湿・脱水能力を有することが確認された。
2 基材(水集積部)
3 吸水溝
4 滴下口
5 加熱ヒーター(刺激付与部)
6 ヒーター電極
7 吸湿材
8 除湿機本体
9 吸気口
10排気口
11 送風ファン
12 ユニット回転用モーター
13 ユニット回転軸
14 排水タンク
15 ヒーター用固定電極
16 吸湿エリア
17 脱水エリア
18 吸気(湿り空気)
19 排気(乾燥空気)
Claims (7)
- 外部刺激に応答して水との親和性が可逆的に変化する刺激応答性高分子と、親水性高分子とを含む高分子ゲルの乾燥体を含有する吸湿材であって、
前記刺激応答性高分子と、前記親水性高分子とが、相互浸入高分子網目構造またはセミ相互浸入高分子網目構造を形成していることを特徴とする吸湿材。 - 前記外部刺激は熱、光、電場、またはpHであることを特徴とする請求項1に記載の吸湿材。
- 前記刺激応答性高分子は、ポリ(N−アルキル(メタ)アクリルアミド)、ポリ(N−ビニルアルキルアミド)、ポリ(N−ビニルピロリドン)、ポリ(2−アルキル−2−オキサゾリン)、ポリビニルアルキルエーテル、ポリエチレンオキサイドとポリプロピレンオキサイドの共重合体、ポリ(オキシエチレンビニルエーテル)、セルロース誘導体、およびこれらの共重合体からなる群より選択される少なくとも1種類の高分子またはその架橋体であることを特徴とする請求項1または2に記載の吸湿材。
- 前記親水性高分子は、アルギン酸、ヒアルロン酸、キトサン、セルロース誘導体、ポリ(メタ)アクリル酸、ポリエチレングリコール、およびこれらの共重合体からなる群より選択される少なくとも1種類の高分子またはその架橋体であることを特徴とする請求項1〜3のいずれか1項に記載の吸湿材。
- 請求項1〜4のいずれか1項に記載の吸湿材と、
前記吸湿材に外部刺激を付与するための刺激付与部と、
を備えていることを特徴とする除湿機。 - さらに、前記吸湿材に接して配置され、刺激の付与により前記吸湿材から滲出した水を集積する水集積部を備えていることを特徴とする請求項5に記載の除湿機。
- 前記水集積部は、前記吸湿材に接する面に吸水溝を有することを特徴とする請求項6に記載の除湿機。
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