JP2002121230A - Temperature-sensitive polymer material having low viscosity at high temperature and high viscosity at low temperature - Google Patents
Temperature-sensitive polymer material having low viscosity at high temperature and high viscosity at low temperatureInfo
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- JP2002121230A JP2002121230A JP2000319119A JP2000319119A JP2002121230A JP 2002121230 A JP2002121230 A JP 2002121230A JP 2000319119 A JP2000319119 A JP 2000319119A JP 2000319119 A JP2000319119 A JP 2000319119A JP 2002121230 A JP2002121230 A JP 2002121230A
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- temperature
- viscosity
- low
- copolymer
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、転移温度以上の高
温においては、水とほとんど同じ程度の低い粘度を示す
が、転移温度よりも低い温度においては急激な粘度上昇
を示す、新規な感温性高分子材料に関するものである。BACKGROUND OF THE INVENTION The present invention relates to a novel thermosensitive material which exhibits a viscosity almost as low as that of water at a temperature higher than the transition temperature, but shows a sharp increase in viscosity at a temperature lower than the transition temperature. The present invention relates to a conductive polymer material.
【０００２】[0002]
【従来の技術】近年、温度によって水に対する挙動が可
逆的に変化する感温性高分子材料が開発され、その特異
的な性質を利用して、非イオン性界面活性剤の吸着剤、
遮光材、増粘剤、防染剤、海洋防汚材料、人工筋肉、ド
ラッグデリバリーシステム材料などへの応用研究が行わ
れている。2. Description of the Related Art In recent years, a thermosensitive polymer material whose behavior with respect to water changes reversibly with temperature has been developed, and by utilizing its specific properties, a nonionic surfactant adsorbent has been developed.
Research on application to light-shielding materials, thickeners, anti-staining agents, marine anti-fouling materials, artificial muscles, drug delivery system materials, and the like has been conducted.
【０００３】本発明者らも、Ｎ‐イソプロピルアクリル
アミド、Ｎ‐ｎ‐プロピルアクリルアミド、Ｎ‐シクロ
プロピルアクリルアミド、Ｎ，Ｎ‐ジエチルアクリルア
ミドの重合体又は共重合体からなる親水性−疎水性可逆
変化型感温性高分子材料を開発したが、これらはいずれ
も転移温度以下の低い温度においては、低粘度を示し、
転移温度よりも高い温度においては高粘度を示すという
性質を有するものであった。The present inventors have also proposed a hydrophilic-hydrophobic reversible type comprising a polymer or copolymer of N-isopropylacrylamide, Nn-propylacrylamide, N-cyclopropylacrylamide, N, N-diethylacrylamide. We have developed temperature-sensitive polymer materials, all of which show low viscosity at low temperatures below the transition temperature,
It had a property of exhibiting high viscosity at a temperature higher than the transition temperature.
【０００４】その後さらに研究を重ねた結果、上記のよ
うな単独で重合させたときに親水性−疎水性可逆型感温
性重合体を形成する単量体と反応性界面活性剤とを共重
合させることにより、感熱性ゲルマイクロビーズを製造
することに成功したが、このものも水に溶解したときに
は、転移温度以下では低粘度であり、転移温度を超える
と高粘度になるという性質のものであった。As a result of further studies, a monomer which forms a hydrophilic-hydrophobic reversible thermosensitive polymer when polymerized alone as described above is copolymerized with a reactive surfactant. By doing so, we succeeded in producing thermosensitive gel microbeads, but also when dissolved in water, they have a low viscosity below the transition temperature, and have a high viscosity above the transition temperature. there were.
【０００５】ところで、これらの感温性高分子材料にお
いて、従来のものとは逆に、高温下では低粘度である
が、低温下では高粘度になるものが得られたならば、こ
の種の感温性高分子材料の利用分野が拡大することは明
らかであるが、これまでこのような感温性高分子材料は
知られていない。[0005] By the way, if these temperature-sensitive polymer materials have a low viscosity at a high temperature but a high viscosity at a low temperature, contrary to the conventional materials, if this kind of material is obtained, Although it is clear that the field of application of the thermosensitive polymer material is expanding, such a thermosensitive polymer material has not been known so far.
【０００６】[0006]
【発明が解決しようとする課題】本発明は、温度変化に
対し、従来の親水性−疎水性可逆型感温性高分子材料と
は全く逆の挙動を示す新規な感温性高分子材料を提供す
ることを目的としてなされたものである。DISCLOSURE OF THE INVENTION The present invention provides a novel thermosensitive polymer material which exhibits a completely opposite behavior to temperature change from the conventional hydrophilic-hydrophobic reversible thermosensitive polymer material. It was made for the purpose of providing.
【０００７】[0007]
【課題を解決するための手段】本発明者は、単独で重合
させたときに親水性−疎水性可逆的変化を示す感温性重
合体を形成する単量体又はこの単量体と他の共重合可能
な単量体との混合物とある種の反応性界面活性剤とを共
重合させたときに、意外にも高温で低粘度を示し、低温
で高粘度を示す感温性高分子共重合体が得られることを
見出し、この知見に基づいて本発明をなすに至った。SUMMARY OF THE INVENTION The present inventors have developed a monomer which forms a thermosensitive polymer exhibiting a reversible change in hydrophilicity-hydrophobicity when polymerized alone, or a monomer having this monomer and another monomer. When a mixture of a copolymerizable monomer and a certain type of reactive surfactant is copolymerized, a temperature-sensitive polymer exhibiting a low viscosity at a high temperature and a high viscosity at a low temperature is unexpectedly obtained. The inventors have found that a polymer can be obtained, and have accomplished the present invention based on this finding.
【０００８】すなわち、本発明は、（Ａ）単独で重合さ
せたときに親水性−疎水性可逆的変化を示す感温性重合
体を与えるアクリル若しくはメタクリルアミド誘導体の
中から選ばれた少なくとも１種の単量体と、（Ｂ）一般
式That is, the present invention relates to (A) an acrylic or methacrylamide derivative selected from acrylic or methacrylamide derivatives which gives a thermosensitive polymer exhibiting a reversible change in hydrophilicity / hydrophobicity when polymerized alone. And a monomer of the formula (B)
【化３】 （式中のＲは炭素数１０〜２０の脂肪族飽和又は不飽和
長鎖状炭化水素基、Ｍはアルカリ金属原子又は第四級ア
ンモニウム残基である）で表わされる反応性界面活性剤
との共重合体を２〜３０質量％の濃度で含む水性溶液か
らなる高温低粘度低温高粘度型感温性高分子材料を提供
するものである。Embedded image (Wherein R is an aliphatic saturated or unsaturated long-chain hydrocarbon group having 10 to 20 carbon atoms, and M is an alkali metal atom or a quaternary ammonium residue). An object of the present invention is to provide a high-temperature, low-viscosity, low-viscosity, high-viscosity type thermosensitive polymer material comprising an aqueous solution containing a copolymer at a concentration of 2 to 30% by mass.
【０００９】[0009]
【発明の実施の形態】本発明の高温低粘度低温高粘度型
感温性高分子材料は、（Ａ）単独で重合させたときに親
水性−疎水性可逆的変化を示す感温性重合体を形成する
アクリル若しくはメタクリルアミド誘導体の中から選ば
れた少なくとも１種の単量体又はこの単量体とこのアク
リル若しくはメタクリルアミド誘導体と共重合可能なエ
チレン性不飽和化合物の中から選ばれた少なくとも１種
の共単量体との混合物と、（Ｂ）前記一般式（Ｉ）で表
わされる反応性界面活性剤との共重合体の水性溶液から
なっている。BEST MODE FOR CARRYING OUT THE INVENTION The high-temperature, low-viscosity, low-viscosity type thermosensitive polymer material of the present invention is a thermosensitive polymer exhibiting a reversible change in hydrophilicity / hydrophobicity when polymerized alone (A). At least one monomer selected from acrylic or methacrylamide derivatives forming at least one or at least one selected from ethylenically unsaturated compounds copolymerizable with this monomer and the acrylic or methacrylamide derivative. It comprises an aqueous solution of a mixture of a mixture with one kind of comonomer and (B) a reactive surfactant represented by the general formula (I).
【００１０】上記の共重合体を構成する（Ａ）成分を単
独で重合させたときに、親水性−疎水性可逆的変化を示
す感温性重合体を形成するアクリル若しくはメタクリル
アミド誘導体は公知であり、本発明においては、この公
知のアクリル又はメタクリルアミド誘導体の中から任意
に選んで用いることができる。Acrylic or methacrylamide derivatives which form a thermosensitive polymer exhibiting a reversible change in hydrophilicity / hydrophobicity when the component (A) constituting the copolymer is polymerized alone are known. In the present invention, any known acrylic or methacrylamide derivative can be arbitrarily selected and used.
【００１１】このようなアクリル若しくはメタクリルア
ミド誘導体としては、例えば、Ｎ‐ｎ‐プロピルアクリ
ルアミド、Ｎ‐イソプロピルアクリルアミド、Ｎ‐シク
ロプロピルアクリルアミド、Ｎ，Ｎ‐ジエチルアクリル
アミド、Ｎ‐メチル‐Ｎ‐エチルアクリルアミド、Ｎ‐
メチル‐Ｎ‐ｎ‐プロピルアクリルアミド、Ｎ‐メチル
‐Ｎ‐イソプロピルアクリルアミド、Ｎ‐アクリロイル
ピペリジン、Ｎ‐アクリロイルピロリジン、Ｎ‐アクリ
ロイルモルホリン、Ｎ‐メトキシプロピルアクリルアミ
ド、Ｎ‐エトキシプロピルアクリルアミド、Ｎ‐イソプ
ロポキシプロピルアクリルアミド、Ｎ‐エトキシエチル
アクリルアミド、Ｎ‐（２，２‐ジメトキシエチル）‐
Ｎ‐メチルアクリルアミド、Ｎ‐１‐メチル‐２‐メト
キシエチルアクリルアミド、Ｎ‐１‐メトキシメチルプ
ロピルアクリルアミド、Ｎ‐ジ（２‐メトキシエチル）
アクリルアミド、Ｎ‐２‐メトキシエチル‐Ｎ‐ｎ‐プ
ロピルアクリルアミド、Ｎ‐２‐メトキシエチル‐Ｎ‐
エチルアクリルアミド、Ｎ‐２‐メトキシエチル‐Ｎ‐
イソプロピルアクリルアミド、Ｎ‐メトキシエトキシプ
ロピルアクリルアミド、Ｎ‐テトラヒドロフルフリルア
クリルアミド、Ｎ‐（１，３‐ジオキソラン‐２‐イ
ル）メチルアクリルアミド、Ｎ‐メチル‐Ｎ‐（１，３
‐ジオキソラン‐２‐イル）メチルアクリルアミド、Ｎ
‐シクロプロピルアクリルアミド、Ｎ‐ピロリジノメチ
ルアクリルアミド、Ｎ‐ピペリジノメチルアクリルアミ
ド、Ｎ‐２‐モルホリノエチルアクリレート、Ｎ‐２‐
モルホリノエトキシエチルアクリレート及び対応するメ
タクリレートを挙げることができる。このほか、８‐ア
クリロイル‐１，４‐ジオキサ‐８‐アザスピロ［４，
５］デカンのようなスピロ型化合物も用いることができ
る。Examples of such acrylic or methacrylamide derivatives include Nn-propylacrylamide, N-isopropylacrylamide, N-cyclopropylacrylamide, N, N-diethylacrylamide, N-methyl-N-ethylacrylamide, N-
Methyl-Nn-propylacrylamide, N-methyl-N-isopropylacrylamide, N-acryloylpiperidine, N-acryloylpyrrolidine, N-acryloylmorpholine, N-methoxypropylacrylamide, N-ethoxypropylacrylamide, N-isopropoxypropyl Acrylamide, N-ethoxyethylacrylamide, N- (2,2-dimethoxyethyl)-
N-methylacrylamide, N-1-methyl-2-methoxyethylacrylamide, N-1-methoxymethylpropylacrylamide, N-di (2-methoxyethyl)
Acrylamide, N-2-methoxyethyl-Nn-propylacrylamide, N-2-methoxyethyl-N-
Ethyl acrylamide, N-2-methoxyethyl-N-
Isopropylacrylamide, N-methoxyethoxypropylacrylamide, N-tetrahydrofurfurylacrylamide, N- (1,3-dioxolan-2-yl) methylacrylamide, N-methyl-N- (1,3
-Dioxolan-2-yl) methylacrylamide, N
-Cyclopropylacrylamide, N-pyrrolidinomethylacrylamide, N-piperidinomethylacrylamide, N-2-morpholinoethyl acrylate, N-2-
Mention may be made of morpholinoethoxyethyl acrylate and the corresponding methacrylate. In addition, 8-acryloyl-1,4-dioxa-8-azaspiro [4,
5] Spiro compounds such as decane can also be used.
【００１２】これらのアクリル若しくはメタクリルアミ
ド誘導体の中で、入手が容易で、取り扱いやすい点で特
に好ましいのは、Ｎ‐ｎ‐プロピルアクリルアミド、Ｎ
‐イソプロピルアクリルアミド、Ｎ，Ｎ‐ジエチルアク
リルアミドである。これらのアクリル若しくはメタクリ
ルアミド誘導体は単独で用いてもよいし、また２種以上
組み合わせて用いてもよい。Among these acrylic or methacrylamide derivatives, particularly preferred in terms of easy availability and easy handling are Nn-propylacrylamide, N
-Isopropylacrylamide and N, N-diethylacrylamide. These acrylic or methacrylamide derivatives may be used alone or in combination of two or more.
【００１３】本発明における（Ａ）成分としては、前記
の単独で重合させたときに親水性−疎水性可逆的変化を
示す感温性重合体を形成するアクリル若しくはメタクリ
ルアミド誘導体に、それと共重合可能な他のエチレン性
不飽和化合物の中から選ばれた共重合体を組み合わせて
用いることができる。このようなエチレン性不飽和化合
物も既に知られており、本発明においては、この公知の
エチレン性不飽和化合物の中から任意に選んで用いるこ
とができる。As the component (A) in the present invention, an acrylic or methacrylamide derivative which forms a thermosensitive polymer which exhibits a reversible change in hydrophilicity / hydrophobicity when polymerized alone is copolymerized with the acrylic or methacrylamide derivative. Copolymers selected from other possible ethylenically unsaturated compounds can be used in combination. Such an ethylenically unsaturated compound is already known, and in the present invention, any known ethylenically unsaturated compound can be arbitrarily used.
【００１４】このようなエチレン性不飽和化合物の例と
しては、単独で重合させたときに親水性−疎水性可逆的
変化を示さない重合体を与えるアクリル若しくはメタク
リルアミド誘導体、例えばアクリルアミド、Ｎ‐エチル
アクリルアミド、Ｎ‐ｔｅｒｔ‐ブチルアクリルアミ
ド、Ｎ‐メチロールアクリルアミド、Ｎ‐ヒドロキシプ
ロピルアクリルアミド及び対応するメタクリルアミド
や、アクリル酸、メタクリル酸のような不飽和カルボン
酸や、メチルアクリレート、エチルアクリレート、ｎ‐
ブチルアクリレート、ｔｅｒｔ‐ブチルアクリレート、
２‐エチルヘキシルアクリレート、２‐アセトアセトキ
シエチルアクリレート、２‐アセトアセトキシプロピル
アクリレート、３‐アセトアセトキシプロピルアクリレ
ート、４‐シアノアセトアセトキシエチルアクリレー
ト、２‐ヒドロキシエチルアクリレート、３‐ヒドロキ
シプロピルアクリレートのようなアクリル酸エステル類
及び対応するメタクリル酸エステル類や、アクリルアミ
ド、Ｎ‐メチロールアクリルアミド、Ｎ‐ヒドロキシプ
ロピルアクリルアミドのようなアクリルアミド類及び対
応するメタクリルアミド類や、Ｎ‐アクリロイルベンズ
ヒドラジド類、Ｎ‐メタクリロイルベンズヒドラジドの
ような不飽和ヒドラジドや、アクリロニトリル、メタク
リロニトリルのような不飽和ニトリル類や、酢酸ビニ
ル、塩化ビニル、スチレン、α‐メチルスチレン、Ｎ‐
ビニルイミダゾール、ビニルメチルエーテル、ビニルエ
チルエーテルのようなビニル化合物類を挙げることがで
きる。これらの化合物はそれぞれ単独で用いてもよい
し、また２種以上を組み合わせて用いてもよい。Examples of such ethylenically unsaturated compounds include acrylic or methacrylamide derivatives which when polymerized alone do not exhibit a reversible change in hydrophilic-hydrophobic properties, such as acrylamide, N-ethyl Acrylamide, N-tert-butylacrylamide, N-methylolacrylamide, N-hydroxypropylacrylamide and the corresponding methacrylamide, unsaturated carboxylic acids such as acrylic acid and methacrylic acid, methyl acrylate, ethyl acrylate, n-
Butyl acrylate, tert-butyl acrylate,
Acrylic acid such as 2-ethylhexyl acrylate, 2-acetoacetoxyethyl acrylate, 2-acetoacetoxypropyl acrylate, 3-acetoacetoxypropyl acrylate, 4-cyanoacetoacetoxyethyl acrylate, 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate Esters and corresponding methacrylic esters, such as acrylamide, N-methylolacrylamide, acrylamides such as N-hydroxypropylacrylamide and corresponding methacrylamides, N-acryloylbenzhydrazides, N-methacryloylbenzhydrazides Unsaturated hydrazide, unsaturated nitriles such as acrylonitrile and methacrylonitrile, vinyl acetate, vinyl chloride, Emissions, alpha-methyl styrene, N-
Vinyl compounds such as vinyl imidazole, vinyl methyl ether and vinyl ethyl ether can be mentioned. These compounds may be used alone or in combination of two or more.
【００１５】本発明の感温性高分子材料においては、
（Ａ）成分中の共単量体として用いる上記のエチレン性
不飽和化合物の種類及び含有割合を選択することによっ
て、転移温度を０〜１００℃の範囲内で任意に調整する
ことができるが、親水性−疎水性変化を示す共重合体を
得るには、この共単量体の使用量を単独で重合させたと
きに親水性−疎水性可逆的変化を示す感温性重合体を与
えるアクリル若しくはメタクリルアミド誘導体１００質
量部当り、７０質量部を超えない範囲にすることが必要
である。In the thermosensitive polymer material of the present invention,
By selecting the type and content of the ethylenically unsaturated compound used as a comonomer in the component (A), the transition temperature can be arbitrarily adjusted within the range of 0 to 100 ° C. In order to obtain a copolymer exhibiting a hydrophilic-hydrophobic change, an acrylic which gives a thermosensitive polymer exhibiting a hydrophilic-hydrophobic reversible change when the amount of this comonomer is polymerized alone is used. Alternatively, it is necessary to keep the content within a range not exceeding 70 parts by mass per 100 parts by mass of the methacrylamide derivative.
【００１６】次に、本発明においては、（Ｂ）成分とし
て、前記一般式（Ｉ）で表わされる反応性界面活性剤、
すなわちアルキルスルホコハク酸アルケニルエーテル塩
型反応性界面活性剤を用いることが必要であり、これ以
外の反応性界面活性剤を用いた場合は、所望の高温低粘
度低温高粘度型感温性高分子材料を得ることができな
い。このアルキルコハク酸アルケニルエーテル塩型反応
性界面活性剤は市販されており、例えば「ラテムルＳ−
１２０」、「ラテムルＳ−１２０Ａ」、「ラテムルＳ−
１８０」、「ラテムルＳ−１８０Ａ」（以上花王株式会
社製）として入手することができる。これらの反応性界
面活性剤は単独で使用してもよいし、また２種以上組み
合わせて用いてもよい。Next, in the present invention, as the component (B), a reactive surfactant represented by the general formula (I),
That is, it is necessary to use an alkylsulfosuccinic acid alkenyl ether salt type reactive surfactant, and when other reactive surfactants are used, a desired high-temperature low-viscosity low-temperature high-viscosity type temperature-sensitive polymer material is used. Can not get. This alkyl succinic acid alkenyl ether salt type reactive surfactant is commercially available, for example, "Latemul S-
120 "," Latemur S-120A "," Latemul S-120A "
180 "and" Latemul S-180A "(all manufactured by Kao Corporation). These reactive surfactants may be used alone or in combination of two or more.
【００１７】本発明の高温低粘度低温高粘度型感温性高
分子材料の主成分を構成する共重合体は、（Ａ）成分か
ら誘導された単量体単位と（Ｂ）成分から誘導された単
量体単位とから構成されるが、（Ｂ）成分から誘導され
る単量体単位の割合は、全単量体単位に基づき０．００
１〜２０モル％、好ましくは０．０１〜１０モル％の範
囲内で選ばれる。これよりも（Ｂ）成分から誘導される
単量体単位が少ないと転移温度よりも高い温度において
は、水とほとんど同程度の粘度を示すが、転移温度以下
においては著しい高粘度を示すという特性をもつ感温性
高分子材料を得ることができないし、また、これよりも
（Ｂ）成分から誘導される単量体単位が多くなると、感
温特性が損われることになる。The copolymer constituting the main component of the high-temperature, low-viscosity, low-temperature, high-viscosity type thermosensitive polymer material of the present invention is a monomer unit derived from the component (A) and a copolymer derived from the component (B). Of the monomer unit derived from the component (B), and the proportion of the monomer unit is 0.00
It is selected in the range of 1 to 20 mol%, preferably 0.01 to 10 mol%. If the amount of the monomer unit derived from the component (B) is smaller than this, the viscosity is almost the same as that of water at a temperature higher than the transition temperature, but the viscosity is extremely high below the transition temperature. Cannot be obtained, and if the number of monomer units derived from the component (B) is larger than this, the temperature-sensitive characteristics will be impaired.
【００１８】上記の（Ａ）成分と（Ｂ）成分とを共重合
して得られる共重合体は、水性媒質中で転移温度よりも
高い温度においては、水とほとんど同様の低粘度である
が、転移温度以下においては著しく高粘度になるという
可逆的変化を示す。すなわち、転移温度よりも高い温度
においては、共重合体を構成している感温性高分子の疎
水性相互作用の強さよりも、反応性界面活性剤単位が水
中でミセル構造をよりとりやすく、共重合体は水中でミ
セル構造をとり、共重合体はサブミクロンサイズの粒子
として水系に分散しているために水とほとんど同様の低
粘度を示すが、転移温度以下においては共重合体は水溶
性になり、膨潤して共重合体分子間の絡み合いを起し、
著しく高い粘度を示す。The copolymer obtained by copolymerizing the above components (A) and (B) has a low viscosity almost equal to that of water at a temperature higher than the transition temperature in an aqueous medium. In addition, it shows a reversible change that the viscosity becomes extremely high below the transition temperature. That is, at a temperature higher than the transition temperature, the reactive surfactant unit more easily takes a micelle structure in water than the strength of the hydrophobic interaction of the temperature-sensitive polymer constituting the copolymer, The copolymer has a micellar structure in water, and the copolymer is dispersed as a submicron-sized particle in an aqueous system, and thus exhibits almost the same low viscosity as water, but below the transition temperature, the copolymer is water-soluble. Swelling, causing entanglement between copolymer molecules,
Shows a very high viscosity.
【００１９】本発明の高温低粘度低温高粘度型感温性高
分子材料は、（Ａ）成分と（Ｂ）成分の共重合体を水性
媒質に溶解した溶液であるが、この水性媒質としては、
水単独又は水と水溶性有機溶剤、例えばメチルアルコー
ル、エチルアルコールとの混合溶剤が用いられる。この
溶液中の共重合体濃度は２〜３０質量％、好ましくは３
〜２０質量％の範囲にする必要がある。この共重合体濃
度が２質量％よりも小さいと、転移温度以下に冷却して
も粘度の上昇は認められないし、また３０質量％よりも
大きくすると高温においてもすでに粘度がかなり大きく
なり、応答性が不良となる。The high-temperature low-viscosity low-temperature high-viscosity type thermosensitive polymer material of the present invention is a solution in which a copolymer of the component (A) and the component (B) is dissolved in an aqueous medium. ,
Water alone or a mixed solvent of water and a water-soluble organic solvent such as methyl alcohol and ethyl alcohol is used. The copolymer concentration in this solution is 2 to 30% by mass, preferably 3% by mass.
It needs to be in the range of 〜20% by mass. When the copolymer concentration is less than 2% by mass, no increase in viscosity is observed even when the copolymer is cooled below the transition temperature, and when it is greater than 30% by mass, the viscosity is already considerably increased even at a high temperature. Becomes defective.
【００２０】本発明の高温低粘度低温高粘度型感温性高
分子材料は、前記（Ａ）成分と前記（Ｂ）成分とを含む
水溶液を、常法に従ってラジカル重合させることによっ
て製造することができる。The high-temperature, low-viscosity, low-temperature, high-viscosity thermosensitive polymer material of the present invention can be produced by subjecting an aqueous solution containing the above-mentioned component (A) and the above-mentioned component (B) to radical polymerization according to a conventional method. it can.
【００２１】この場合の水溶液の濃度としては、通常、
単量体の合計量に基づき２〜１５質量％の範囲で選ばれ
るが、（Ｂ）成分の反応性界面活性剤の濃度としては、
ミセル内重合を行わせるために臨界ミセル濃度以上の濃
度を選ぶことが必要である。この濃度範囲は、普通単量
体合計量に対し、０．００１〜１０モル％、好ましくは
０．０１〜８モル％である。この反応性界面活性剤は、
所定の重合体又は共重合体を形成する重合反応において
乳化剤的役割を果たすものである。従来は、これに相当
するカチオン性界面活性剤又はアニオン性界面活性剤を
乳化剤として用いていたが、これらは重合終了後、反応
混合物中に残留し、生成した重合体又は共重合体中に混
入して汚染するおそれがあるため、特別に除去処理を行
う必要があった。これに対し、本発明においては、これ
が単量体単位の一部として分子中に取り込まれるため、
このような除去処理を行う必要はない。The concentration of the aqueous solution in this case is usually
It is selected in the range of 2 to 15% by mass based on the total amount of the monomers, and as the concentration of the reactive surfactant of the component (B),
It is necessary to select a concentration higher than the critical micelle concentration in order to carry out the intra-micellar polymerization. This concentration range is usually 0.001 to 10 mol%, preferably 0.01 to 8 mol%, based on the total amount of the monomers. This reactive surfactant is
It functions as an emulsifier in a polymerization reaction for forming a predetermined polymer or copolymer. Conventionally, the corresponding cationic surfactant or anionic surfactant was used as an emulsifier, but these remain in the reaction mixture after the completion of polymerization and are mixed into the produced polymer or copolymer. Therefore, it was necessary to perform a special removal treatment. In contrast, in the present invention, since this is incorporated into the molecule as a part of the monomer unit,
It is not necessary to perform such a removal process.
【００２２】重合を開始する手段としては、従釆公知の
手段、例えば放射線又は電子線を照射する方法、ラジカ
ル重合開始剤の存在下に加熱する方法、光増感剤の存在
下に光照射する方法などを用いることができるが、これ
らの方法の中でラジカル重合開始剤の存在下に加熱する
方法が好ましい。ラジカル重合開始剤としては、水溶性
のものであればよく、特に制限はない。例えば過硫酸ア
ンモニウム、過硫酸カリウム、過酸化水素、ｔｅｒｔ‐
ブチルヒドロパーオキシドなど、あるいは亜硫酸塩、亜
硫酸水素塩、硝酸第二セリウムアンモニウムなどのレド
ックス系開始剤さらには２，２′‐アゾビス‐２‐アミ
ジノプロパン塩酸塩、２，２′‐アゾビス‐２，４‐ジ
メチルバレロニトリル、４，４′‐アゾビス‐４‐シア
ノバレリン酸及びその塩などのアゾ化合物などを用いる
ことができる。これらのラジカル重合開始剤は単独で用
いてもよいし、２種以上を組み合わせて用いてもよい。
その使用量は、単量体の合計量に対して、通常０．０１
〜１００質量％、好ましくは０．０５〜８質量％の範囲
である。As means for initiating polymerization, conventionally known means, for example, a method of irradiating radiation or an electron beam, a method of heating in the presence of a radical polymerization initiator, and a method of irradiating light in the presence of a photosensitizer Although a method can be used, a method of heating in the presence of a radical polymerization initiator is preferred among these methods. The radical polymerization initiator is not particularly limited as long as it is a water-soluble one. For example, ammonium persulfate, potassium persulfate, hydrogen peroxide, tert-
Butyl hydroperoxide or a redox initiator such as sulfite, hydrogen sulfite, ceric ammonium nitrate and the like, furthermore 2,2'-azobis-2-amidinopropane hydrochloride, 2,2'-azobis-2 Azo compounds such as 4-dimethylvaleronitrile, 4,4'-azobis-4-cyanovaleric acid and salts thereof can be used. These radical polymerization initiators may be used alone or in combination of two or more.
The amount used is usually 0.01 to the total amount of the monomers.
To 100% by mass, preferably 0.05 to 8% by mass.
【００２３】また、反応温度は、使用する単量体及び開
始剤の種類により異なるが、通常０〜１００℃の範囲内
で選ばれる。この反応温度は、重合で生成する共重合体
水溶液の転移温度以上の温度であることが必要で、これ
よりも低い温度では、反応中に粘度が上昇し、重合が十
分に進行しない。The reaction temperature varies depending on the type of the monomer and the initiator used, but is usually selected from the range of 0 to 100 ° C. This reaction temperature must be higher than the transition temperature of the aqueous copolymer solution produced by the polymerization. At a lower temperature, the viscosity increases during the reaction, and the polymerization does not proceed sufficiently.
【００２４】このようにして反応させることにより、共
重合反応がミセル内で起こり、共重合体が効率よく得ら
れる。重合終了後、透析膜を用いて反応溶液を生成した
共重合体の転移温度で透析操作を行うことにより、未反
応単量体が完全に除去された共重合体を得ることができ
る。By reacting in this manner, a copolymerization reaction occurs in the micelle, and a copolymer can be obtained efficiently. After the completion of the polymerization, a dialysis operation is performed at the transition temperature of the copolymer that has produced the reaction solution using the dialysis membrane, whereby a copolymer from which unreacted monomers have been completely removed can be obtained.
【００２５】このようにして得られた共重合体が、その
分子鎖の構成単位として、反応性界面活性剤単位を含む
ことは、赤外線吸収スペクトルにおいてその特性ピーク
が認められること及び水による洗浄を繰り返しても共重
合体中の反応性界面活性剤含有量が低下しないことによ
って確認されている。The fact that the copolymer thus obtained contains a reactive surfactant unit as a constituent unit of its molecular chain means that its characteristic peak is recognized in an infrared absorption spectrum and that the copolymer is washed with water. It has been confirmed that the content of the reactive surfactant in the copolymer does not decrease even after repeating.
【００２６】本発明の感温性高分子化合物は、転移温度
以下では水溶性であり、転移温度よりも高い温度では疎
水化して、サブミクロンサイズの粒子として水系に分散
しているために水とほとんど同程度の低い粘度を示すと
いう特異的な性質を有している。The thermosensitive polymer compound of the present invention is water-soluble at a transition temperature or lower, becomes hydrophobic at a temperature higher than the transition temperature, and is dispersed as submicron-sized particles in an aqueous system. It has the unique property of exhibiting almost the same low viscosity.
【００２７】したがって、重合反応により得られる反応
溶液は、重合時の温度すなわち生成する共重合体の転移
温度以上に保持された状態では純水に近い特定の青味が
かった分散液となっているが、これを転移温度よりも低
い温度に冷却すると、ミセル構造が破壊され、水中に共
重合体分子が溶解あるいは膨潤し、透明な超高粘度の水
性液に変化する。この水性液は、再び加熱すると転移温
度に達するまでは温度上昇とともに粘度が低下するが、
転移温度を超えると、共重合体を構成している感温性高
分子の疎水性相互作用の強さよりも（Ｂ）成分の反応性
界面活性剤単位が水中でミセル構造をとろうとする作用
が勝ることになる。そして、共重合体は水中でミセル構
造をとり、共重合体はサブミクロンサイズの粒子として
水系に分散しているために水とほとんど同程度の低粘度
を示す。Therefore, the reaction solution obtained by the polymerization reaction is a specific bluish dispersion close to pure water when kept at a temperature higher than the polymerization temperature, that is, the transition temperature of the produced copolymer. However, when this is cooled to a temperature lower than the transition temperature, the micelle structure is destroyed, and the copolymer molecules dissolve or swell in water, and change to a transparent ultrahigh-viscosity aqueous liquid. When this aqueous liquid is heated again, the viscosity decreases with increasing temperature until the transition temperature is reached,
When the transition temperature is exceeded, the effect of the reactive surfactant unit of component (B) to take on a micellar structure in water is less than the strength of the hydrophobic interaction of the temperature-sensitive polymer constituting the copolymer. Will win. The copolymer has a micellar structure in water, and the copolymer is dispersed as a submicron-sized particle in an aqueous system, so that it exhibits almost the same low viscosity as water.
【００２８】したがって、本発明の感温性高分子化合物
は、各種の水性媒質に分散させた場合、広い温度範囲に
おいて低粘度から高粘度さらに流動性のない状態に至る
までの広範囲の粘度調節を可能にすることができる。そ
して、その転移温度は、単量体混合物中の各成分の種類
や含有割合を変えたり、あるいは媒質中に塩又はアルコ
ールを添加することにより調整することができる。Therefore, when the temperature-sensitive polymer compound of the present invention is dispersed in various aqueous media, the viscosity can be adjusted over a wide temperature range from a low viscosity to a high viscosity to a state without fluidity. Can be made possible. The transition temperature can be adjusted by changing the type and content of each component in the monomer mixture, or by adding a salt or alcohol to the medium.
【００２９】[0029]
【実施例】次に、実施例により本発明をさらに詳細に説
明する。Next, the present invention will be described in more detail with reference to examples.
【００３０】実施例１ キャピラリー栓と冷却管とを備えたＶ字管付き５００ｍ
ｌ体積の三角フラスコに、蒸留水２００ｇとＮ‐イソプ
ロピルアクリルアミド８．９４ｇとアルキルコハク酸ア
ルケニルエーテル型反応性界面活性剤（花王株式会社
製，商品名「ラテムルＳ−１８０Ａ」，有効成分含有量
５０質量％）１．４０ｇを入れ、窒素ガスを３０分間通
じたのち、過硫酸アンモニウム０．０５ｇを添加し、窒
素気流下にかきまぜながら、６０℃に加熱して重合を開
始させた。６０℃においてかきまぜながら３時間重合を
行ったのち、空気を吹き込んで重合を停止し、反応混合
物を室温まで放冷した。Example 1 500 m with a V-shaped pipe provided with a capillary plug and a cooling pipe
In a 1-volume Erlenmeyer flask, 200 g of distilled water, 8.94 g of N-isopropylacrylamide and an alkenyl succinate alkenyl ether-type reactive surfactant (trade name “Latemul S-180A” manufactured by Kao Corporation, active ingredient content: 50 (Mass%), and nitrogen gas was passed in for 30 minutes. Then, 0.05 g of ammonium persulfate was added, and the mixture was heated to 60 ° C. while stirring under a nitrogen stream to initiate polymerization. After polymerization at 60 ° C. for 3 hours with stirring, air was blown to stop the polymerization, and the reaction mixture was allowed to cool to room temperature.
【００３１】次に、得られた反応混合物を、透析膜を用
いて、生成した共重合体の転移温度（３４℃）で透析し
て不純分を除いたのち、凍結乾燥し、未反応単量体を完
全に除去した感温性共重合体を得た。次いで、この感温
性共重合体に、２０℃の蒸留水を所定量加えて、１質量
％、２質量％、３質量％及び５質量％の濃度の水性液を
調製した。これらの各水溶液についての昇温時及び降温
時における温度と粘度の関係を調べ、グラフとして図１
に示す。この図から分るように、濃度が２質量％以上の
水溶液は、転移温度（３４℃）以下において、粘度の急
激な上昇が認められるのに対し、２質量％未満の水溶液
は、粘度上昇がほとんど認められない。Next, the obtained reaction mixture is dialyzed using a dialysis membrane at the transition temperature of the formed copolymer (34 ° C.) to remove impurities, and then lyophilized to give unreacted monomer. A temperature-sensitive copolymer from which the body was completely removed was obtained. Next, a predetermined amount of distilled water at 20 ° C. was added to the temperature-sensitive copolymer to prepare aqueous liquids having a concentration of 1% by mass, 2% by mass, 3% by mass, and 5% by mass. The relationship between the temperature and the viscosity of each of these aqueous solutions at the time of raising and lowering the temperature was examined, and FIG.
Shown in As can be seen from this figure, an aqueous solution having a concentration of 2% by mass or more shows a sharp increase in viscosity below the transition temperature (34 ° C.), while an aqueous solution having a concentration of less than 2% by mass has an increase in viscosity. Almost no.
【００３２】実施例２ 実施例１におけるＮ‐イソプロピルアクリルアミドの代
りにＮ‐ｎ‐プロピルアクリルアミドを用い、実施例１
と同様にして感温性共重合体を製造した。次に、この感
温性共重合体に所定量の蒸留水を加え、１質量％、２質
量％、３質量％及び５質量％の濃度の水性液を調製し
た。これらの各水溶液についての昇温時及び降温時にお
ける温度と粘度の関係を調べ、グラフとして図２に示
す。この図から分るように、濃度が２質量％以上の水溶
液は、転移温度（２０℃）以下において、粘度の急激な
上昇が認められるのに対し、２質量％未満の水溶液は、
粘度上昇がほとんど認められない。Example 2 The procedure of Example 1 was repeated except that Nn-propylacrylamide was used in place of N-isopropylacrylamide.
A temperature-sensitive copolymer was produced in the same manner as described above. Next, a predetermined amount of distilled water was added to the temperature-sensitive copolymer to prepare aqueous liquids having concentrations of 1% by mass, 2% by mass, 3% by mass, and 5% by mass. The relationship between the temperature and the viscosity of each of these aqueous solutions at the time of raising and lowering the temperature was examined, and is shown as a graph in FIG. As can be seen from this figure, an aqueous solution having a concentration of 2% by mass or more shows a sharp increase in viscosity below the transition temperature (20 ° C.), whereas an aqueous solution having a concentration of less than 2% by mass
Almost no increase in viscosity is observed.
【００３３】実施例３ 実施例１におけるＮ‐イソプロピルアクリルアミド８．
９４ｇの代りにＮ，Ｎ‐ジエチルアクリルアミド２５．
４３ｇを用い、実施例１と同様にして感温性共重合体を
製造した。次に、この感温性共重合体に所定量の蒸留水
を加え、１質量％、２質量％、３質量％及び５質量％の
濃度の水性液を調製した。これらの各水溶液についての
昇温時及び降温時における温度と粘度の関係を調べ、グ
ラフとして図３に示す。この図から分るように、濃度が
２質量％以上の水溶液は、転移温度（２８℃）以下にお
いて、粘度の急激な上昇が認められるのに対し、２質量
％未満の水溶液は、粘度上昇がほとんど認められない。Example 3 N-isopropylacrylamide in Example 1
N, N-diethylacrylamide instead of 94 g.
Using 43 g, a temperature-sensitive copolymer was produced in the same manner as in Example 1. Next, a predetermined amount of distilled water was added to the temperature-sensitive copolymer to prepare aqueous liquids having concentrations of 1% by mass, 2% by mass, 3% by mass, and 5% by mass. The relationship between the temperature and the viscosity of each of these aqueous solutions at the time of raising and lowering the temperature was examined, and is shown in FIG. 3 as a graph. As can be seen from this figure, an aqueous solution having a concentration of 2% by mass or more shows a sharp increase in viscosity below the transition temperature (28 ° C.), whereas an aqueous solution having a concentration of less than 2% by mass has an increase in viscosity. Almost no.
【００３４】実施例４ キャピラリー栓と冷却管とを備えたＶ字管付き５００ｍ
ｌ体積の三角フラスコに、蒸留水２００ｇとＮ‐イソプ
ロピルアクリルアミド９．５３ｇとＮ‐ｔｅｒｔ‐ブチ
ルアクリルアミド１．２１ｇとアルキルコハク酸アルケ
ニルエーテル型反応性界面活性剤（花王株式会社製，商
品名「ラテムルＳ−１８０Ａ」，有効成分含有量５０
％）１．４０ｇを入れ、窒素ガスを３０分間通じたの
ち、過硫酸アンモニウム０．０５ｇを添加し、窒素気流
下にかきまぜながら、６０℃に加熱して重合を開始させ
た。６０℃においてかきまぜながら２時間重合を行った
のち、空気を吹き込んで重合を停止し、反応混合物を室
温まで放冷した。Example 4 500 m with a V-shaped pipe equipped with a capillary plug and a cooling pipe
In a 1-liter Erlenmeyer flask, 200 g of distilled water, 9.53 g of N-isopropylacrylamide, 1.21 g of N-tert-butylacrylamide, and an alkenyl succinate alkenyl ether-type reactive surfactant (trade name “Latemul” manufactured by Kao Corporation) S-180A ", active ingredient content 50
%), Nitrogen gas was passed through for 30 minutes, then 0.05 g of ammonium persulfate was added, and the mixture was heated to 60 ° C. while stirring under a nitrogen stream to initiate polymerization. After polymerization at 60 ° C. for 2 hours with stirring, air was blown to stop the polymerization, and the reaction mixture was allowed to cool to room temperature.
【００３５】次に、得られた反応混合物を、透析膜を用
いて、生成した共重合体の転移温度（２７℃）で透析し
て、不純分を除いたのち、凍結乾燥し、未反応単量体を
完全に除去した感温性共重合体を得た。次いで、この感
温性共重合体を２０℃の蒸留水に溶解し、濃度５．５質
量％の水性液を調製し、その温度による粘度変化を調
べ、グラフとして図４に示す。この図から分るように、
この水溶液は、転移温度（２７℃）以下において、急激
な粘度上昇を示す。Next, the obtained reaction mixture is dialyzed using a dialysis membrane at a transition temperature of the formed copolymer (27 ° C.) to remove impurities, freeze-dried, and unreacted A temperature-sensitive copolymer from which the monomer was completely removed was obtained. Next, this temperature-sensitive copolymer was dissolved in distilled water at 20 ° C. to prepare an aqueous liquid having a concentration of 5.5% by mass, and the change in viscosity with temperature was examined. The graph is shown in FIG. 4 as a graph. As you can see from this figure,
This aqueous solution shows a sharp increase in viscosity below the transition temperature (27 ° C.).
【００３６】実施例５ 実施例４におけるＮ‐イソプロピルアクリルアミド９．
５３ｇとＮ‐ｔｅｒｔ‐ブチルアクリルアミド１．２１
ｇの代りに、Ｎ‐イソプロピルアクリルアミド９．８２
ｇとジメチルアクリルアミド１．５４ｇを用い、実施例
４と同様にして感温性共重合体を製造した。次いで、こ
の感温性共重合体を２０℃の蒸留水に溶解し、濃度６質
量％の水性液を調製し、その温度による粘度変化を調
べ、グラフとして図５に示す。この図から分るように、
この水溶液は、転移温度（３７℃）以下において急激な
粘度上昇を示す。Example 5 N-isopropylacrylamide in Example 4
53 g and N-tert-butylacrylamide 1.21
g instead of N-isopropylacrylamide 9.82
g and 1.54 g of dimethylacrylamide, and a temperature-sensitive copolymer was produced in the same manner as in Example 4. Next, this temperature-sensitive copolymer was dissolved in distilled water at 20 ° C. to prepare an aqueous liquid having a concentration of 6% by mass, and the change in viscosity with temperature was examined. The graph is shown in FIG. As you can see from this figure,
This aqueous solution shows a sharp increase in viscosity below the transition temperature (37 ° C.).
【００３７】比較例１ キャピラリー栓と冷却管とを備えたＶ字管付き５００ｍ
ｌ体積の三角フラスコに、蒸留水２００ｇとＮ‐イソプ
ロピルアクリルアミド９．００ｇと式Comparative Example 1 500 m with a V-shaped pipe provided with a capillary plug and a cooling pipe
In a 1 volume Erlenmeyer flask, 200 g of distilled water and 9.00 g of N-isopropylacrylamide
【化４】 で表わされる反応性界面活性剤（第一工業製薬株式会社
製，商品名「アクアロンＨＳ−１０」）０．７０ｇを入
れ、窒素ガスを３０分間通じたのち、過硫酸アンモニウ
ム０．０５ｇを添加し、窒素気流下にかきまぜながら、
６０℃に加熱して重合を開始させた。６０℃においてか
きまぜながら４時間重合を行ったのち、空気を吹き込ん
で重合を停止し、反応混合物を室温まで放冷した。Embedded image 0.70 g of a reactive surfactant (available from Dai-ichi Kogyo Seiyaku Co., Ltd., trade name “AQUALON HS-10”) was added, nitrogen gas was passed through for 30 minutes, and 0.05 g of ammonium persulfate was added. While stirring under a nitrogen stream,
The polymerization was started by heating to 60 ° C. After the polymerization was carried out at 60 ° C. for 4 hours while stirring, the polymerization was stopped by blowing air, and the reaction mixture was allowed to cool to room temperature.
【００３８】次に、得られた反応混合物を、透析膜を用
いて、生成した共重合体の転移温度（３４℃）で透析し
て、不純分を除いたのち、凍結乾燥し、未反応単量体を
完全に除去した感温性共重合体を得た。次いで、この感
温性共重合体に、２０℃の蒸留水を所定量加えて、１質
量％、２質量％、３質量％及び５質量％の濃度の水性液
を調製した。これらの昇温時及び降温時における温度と
粘度の関係を調べ、グラフとして図６に示す。この図か
ら分るように、この例で得られた感温性共重合体は、転
移温度（３４℃）以下に降温しても急激な粘度上昇を示
さないし、また降温時及び昇温時での可逆的な挙動も認
められない。Next, the obtained reaction mixture is dialyzed using a dialysis membrane at a transition temperature of the formed copolymer (34 ° C.) to remove impurities, and then lyophilized to give unreacted monohydrate. A temperature-sensitive copolymer from which the monomer was completely removed was obtained. Next, a predetermined amount of distilled water at 20 ° C. was added to the temperature-sensitive copolymer to prepare aqueous liquids having a concentration of 1% by mass, 2% by mass, 3% by mass, and 5% by mass. The relationship between the temperature and the viscosity at the time of temperature rise and temperature fall was examined, and is shown as a graph in FIG. As can be seen from the figure, the temperature-sensitive copolymer obtained in this example does not show a sharp increase in viscosity even when the temperature is lowered below the transition temperature (34 ° C.). Is not observed.
【００３９】比較例２ キャピラリー栓と冷却管とを備えたＶ字管付き５００ｍ
ｌ体積の三角フラスコに、蒸留水２００ｇとＮ‐イソプ
ロピルアクリルアミド４０ｇと一般式Comparative Example 2 500 m with a V-shaped pipe provided with a capillary plug and a cooling pipe
In a 1 volume Erlenmeyer flask, 200 g of distilled water, 40 g of N-isopropylacrylamide and the general formula
【化５】 （式中のＲは炭素数１２〜１３の飽和炭化水素基であ
る）で表わされる反応性界面活性剤（三洋化成工業株式
会社製，商品名「エレミノールＪＳ−２」，有効成分３
８質量％）２．６ｇを入れ、窒素ガスを３０分間通じた
のち、過硫酸アンモニウム０．０５ｇを添加し、６０℃
において窒素気流中でかきまぜながら、２時間重合を行
わせた。この反応混合物を室温まで放冷したのち、透析
処理して精製し、凍結乾燥して感温性共重合体を得た。
このようにして得た感温性共重合体を所定量の蒸留水に
溶解して、１質量％、２質量％及び３質量％の濃度の水
性液を調製した。これらの水溶液についての温度と粘度
の関係を調べ、その結果をグラフとして図７に示す。こ
の図から分るように、この例で得られた感温性共重合体
の水溶液は、転移温度（３０℃）以下において急激な粘
度上昇を示さない。Embedded image (R in the formula is a saturated hydrocarbon group having 12 to 13 carbon atoms) (manufactured by Sanyo Chemical Industry Co., Ltd., trade name “Eleminol JS-2”, active ingredient 3)
2.6 g), nitrogen gas was passed through for 30 minutes, and 0.05 g of ammonium persulfate was added.
Was stirred in a nitrogen stream for 2 hours to carry out polymerization. The reaction mixture was allowed to cool to room temperature, purified by dialysis, and freeze-dried to obtain a temperature-sensitive copolymer.
The temperature-sensitive copolymer thus obtained was dissolved in a predetermined amount of distilled water to prepare aqueous liquids having concentrations of 1% by mass, 2% by mass and 3% by mass. The relationship between temperature and viscosity for these aqueous solutions was examined, and the results are shown in FIG. 7 as a graph. As can be seen from this figure, the aqueous solution of the temperature-sensitive copolymer obtained in this example does not show a sharp increase in viscosity below the transition temperature (30 ° C.).
【００４０】比較例３ キャピラリー栓と冷却管とを備えたＶ字管付き５００ｍ
ｌ体積の三角フラスコに、蒸留水１９５ｇとＮ‐イソプ
ロピルアクリルアミド２６．５ｇと式Comparative Example 3 500 m with a V-shaped pipe provided with a capillary plug and a cooling pipe
In a 1 volume Erlenmeyer flask, 195 g of distilled water and 26.5 g of N-isopropylacrylamide
【化６】 で表わされる反応性界面活性剤（三洋化成工業株式会社
製，商品名「エレミノールＲＳ−３０」，有効成分５０
質量％）１．４ｇを入れ、窒素ガスを３０分間通じたの
ち、過硫酸アンモニウム０．０５ｇを添加し、６０℃に
おいて窒素気流中でかきまぜながら、１．５時間重合を
行わせた。この反応混合物を室温まで放冷したのち、透
析処理して精製し、凍結乾燥して感温性共重合体を得
た。このようにして得た感温性共重合体を所定量の蒸留
水に溶解して、１質量％、２質量％３質量％及び５質量
％の濃度の水性液を調製した。これらの水溶液について
の温度と粘度の関係を調べ、その結果をグラフとして図
８に示す。なお、ｓｐ１８はブルックフィールド粘度計
におけるスピンドル１８を、またｓｐ３４はスピンドル
３４を用いて測定したものである。この図から分るよう
に、この例で得られた感温性共重合体の水溶液は、その
転移温度（３４℃）以下において急激な粘度上昇を示さ
ない。Embedded image Reactive surfactant represented by the formula (manufactured by Sanyo Chemical Industry Co., Ltd., trade name "Eleminol RS-30", active ingredient 50)
(Mass%), nitrogen gas was passed through for 30 minutes, then 0.05 g of ammonium persulfate was added, and polymerization was carried out for 1.5 hours while stirring at 60 ° C. in a nitrogen stream. The reaction mixture was allowed to cool to room temperature, purified by dialysis, and freeze-dried to obtain a temperature-sensitive copolymer. The temperature-sensitive copolymer thus obtained was dissolved in a predetermined amount of distilled water to prepare aqueous liquids having concentrations of 1% by mass, 2% by mass, 3% by mass and 5% by mass. The relationship between the temperature and the viscosity for these aqueous solutions was examined, and the results are shown in FIG. 8 as a graph. Note that sp18 was measured using the spindle 18 in the Brookfield viscometer, and sp34 was measured using the spindle 34. As can be seen from this figure, the aqueous solution of the temperature-sensitive copolymer obtained in this example does not show a sharp increase in viscosity below its transition temperature (34 ° C.).
【００４１】以上の各比較例から明らかなように、
（Ｂ）成分として前記一般式（Ｉ）で示される反応性界
面活性剤以外の反応性界面活性剤を用いた場合には、高
温低粘度低温高粘度型感温性高分子材料は得られない。As is clear from the above comparative examples,
When a reactive surfactant other than the reactive surfactant represented by the general formula (I) is used as the component (B), a high-temperature, low-viscosity, low-viscosity, high-viscosity type thermosensitive polymer material cannot be obtained. .
【００４２】[0042]
【発明の効果】本発明によると、従来全く知られていな
かった特異的な性質を示す、新規な感温性高分子材料が
得られる。この感温性高分子材料は、塗工紙用塗料の増
粘剤として好適である。According to the present invention, there can be obtained a novel thermosensitive polymer material having specific properties which have never been known before. This temperature-sensitive polymer material is suitable as a thickener for a coating material for coated paper.
【図１】 実施例１で得た共重合体水溶液の温度と粘度
との関係を示すグラフ。FIG. 1 is a graph showing the relationship between the temperature and the viscosity of the aqueous copolymer solution obtained in Example 1.
【図２】 実施例２で得た共重合体水溶液の温度と粘度
との関係を示すグラフ。FIG. 2 is a graph showing the relationship between the temperature and the viscosity of the aqueous copolymer solution obtained in Example 2.
【図３】 実施例３で得た共重合体水溶液の温度と粘度
との関係を示すグラフ。FIG. 3 is a graph showing the relationship between the temperature and the viscosity of the aqueous copolymer solution obtained in Example 3.
【図４】 実施例４で得た共重合体水溶液の温度と粘度
との関係を示すグラフ。FIG. 4 is a graph showing the relationship between the temperature and the viscosity of the aqueous copolymer solution obtained in Example 4.
【図５】 実施例５で得た共重合体水溶液の温度と粘度
との関係を示すグラフ。FIG. 5 is a graph showing the relationship between the temperature and the viscosity of the aqueous copolymer solution obtained in Example 5.
【図６】 比較例１で得た共重合体水溶液の温度と粘度
との関係を示すグラフ。FIG. 6 is a graph showing the relationship between the temperature and the viscosity of the aqueous copolymer solution obtained in Comparative Example 1.
【図７】 比較例２で得た共重合体水溶液の温度と粘度
との関係を示すグラフ。FIG. 7 is a graph showing the relationship between the temperature and the viscosity of the aqueous copolymer solution obtained in Comparative Example 2.
【図８】 比較例３で得た共重合体水溶液の温度と粘度
との関係を示すグラフ。FIG. 8 is a graph showing the relationship between the temperature and the viscosity of the aqueous copolymer solution obtained in Comparative Example 3.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ０８Ｆ 216:14） Ｃ０８Ｆ 216:14） (72)発明者 伊藤 昭二 茨城県つくば市東１丁目１番 工業技術院 物質工学工業技術研究所内 (72)発明者 阿形 明 東京都中央区日本橋二丁目10番５号 第２ ＳＫビル９階 特許キャピタル株式会社内 (72)発明者 二宮 扶実 東京都中央区日本橋二丁目10番５号 第２ ＳＫビル９階 特許キャピタル株式会社内 Ｆターム(参考） 4J100 AB02R AB03R AC03R AE03R AE18Q AG04R AJ02R AL03R AL04R AL08P AL08R AL09R AM02R AM15R AM17P AM17R AM19P AM21P AM21R AQ06R BA02P BA03Q BA03R BA05P BA06P BA14R BA15Q BA20Q BA40R BA56Q BC03P BC53P BC58P BC65P BC79P CA04 CA05 JA15 JA24 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification FI FI Theme Court ゛ (Reference) C08F 216: 14) C08F 216: 14) (72) Inventor Shoji Ito 1-1-1, Higashi, Tsukuba City, Ibaraki Prefecture Industrial Technology (72) Inventor Akira Agata 2nd-5-10 Nihonbashi, Chuo-ku, Tokyo 2nd SK Building 9th floor Inside Patent Capital Corporation (72) Inventor Yumi Ninomiya 2-chome Nihonbashi, Chuo-ku, Tokyo No. 10-5 2nd SK Building 9F 9th term Patent Capital Co., Ltd. F-term (reference) 4J100 AB02R AB03R AC03R AE03R AE18Q AG04R AJ02R AL03R AL04R AL08P AL08R AL09R AM02R AM15R AM17P AM17R AM19P AM21P AM21R AQ06R BA03P BA03P BA03P BA56Q BC03P BC53P BC58P BC65P BC79P CA04 CA05 JA15 JA24
Claims (5)
疎水性可逆的変化を示す感温性重合体を与えるアクリル
若しくはメタクリルアミド誘導体の中から選ばれた少な
くとも１種の単量体と、（Ｂ）一般式 【化１】 （式中のＲは炭素数１０〜２０の脂肪族飽和又は不飽和
長鎖状炭化水素基、Ｍはアルカリ金属原子又は第四級ア
ンモニウム残基である）で表わされる反応性界面活性剤
との共重合体を２〜３０質量％の濃度で含む水性溶液か
らなる高温低粘度低温高粘度型感温性高分子材料。(1) When the polymer (A) is polymerized alone, it is hydrophilic.
At least one monomer selected from acrylic or methacrylamide derivatives giving a thermosensitive polymer exhibiting a hydrophobic reversible change, and (B) a compound represented by the general formula: (Wherein R is an aliphatic saturated or unsaturated long-chain hydrocarbon group having 10 to 20 carbon atoms, and M is an alkali metal atom or a quaternary ammonium residue). A high-temperature, low-viscosity, low-viscosity, high-viscosity type thermosensitive polymer material comprising an aqueous solution containing a copolymer at a concentration of 2 to 30% by mass.
疎水性可逆的変化を示す感温性重合体を与えるアクリル
若しくはメタクリルアミド誘導体の中から選ばれた少な
くとも１種の単量体及びこれと共重合可能な他のエチレ
ン性不飽和化合物の中から選ばれた少なくとも１種の共
単量体との混合物と、（Ｂ）一般式 【化２】 （式中のＲは炭素数１０〜２０の脂肪族飽和又は不飽和
長鎖状炭化水素基、Ｍはアルカリ金属原子又は第四級ア
ンモニウム残基である）で表わされる反応性界面活性剤
との共重合体を２〜３０質量％の濃度で含む水性溶液か
らなる高温低粘度低温高粘度型感温性高分子材料。2. A polymer having a hydrophilic property when polymerized alone.
At least one monomer selected from acrylic or methacrylamide derivatives that provide a thermosensitive polymer exhibiting a reversible change in hydrophobicity, and at least one other ethylenically unsaturated compound copolymerizable therewith. A mixture of at least one comonomer and (B) a compound represented by the general formula: (Wherein R is an aliphatic saturated or unsaturated long-chain hydrocarbon group having 10 to 20 carbon atoms, and M is an alkali metal atom or a quaternary ammonium residue). A high-temperature, low-viscosity, low-viscosity, high-viscosity type thermosensitive polymer material comprising an aqueous solution containing a copolymer at a concentration of 2 to 30% by mass.
性剤の含有量が全単量体の０．００１〜２０モル％であ
る請求項１又は２記載の高温低粘度低温高粘度型感温性
高分子材料。3. The high-temperature, low-viscosity, low-temperature, high-temperature, low-temperature, high-temperature copolymer according to claim 1, wherein the content of the reactive surfactant of the component (B) in the copolymer is from 0.001 to 20 mol% of all monomers. Viscosity type thermosensitive polymer material.
水性−疎水性可逆的変化を示す感温性重合体を与えるア
クリル若しくはメタクリルアミド誘導体に対する、それ
と共重合可能な共単量体の含有割合が、前者１００質量
部当り、後者７０質量部以下である請求項２又は３記載
の高温低粘度低温高粘度型感温性高分子材料。4. An acrylic or methacrylamide derivative which gives a thermosensitive polymer exhibiting a hydrophilic-hydrophobic reversible change when polymerized alone in a copolymer, and a copolymerizable monomer with the acrylic or methacrylamide derivative. 4. The high-temperature, low-viscosity, low-viscosity, high-viscosity type thermosensitive polymer material according to claim 2 or 3, wherein the content is 70 parts by mass or less per 100 parts by mass of the former.
可逆的変化を示す感温性重合体を与えるアクリル若しく
はメタクリルアミド誘導体が、Ｎ‐ｎ‐プロピルアクリ
ルアミド、Ｎ‐イソプロピルアクリルアミド、Ｎ‐シク
ロプロピルアクリルアミド、Ｎ，Ｎ‐ジエチルアクリル
アミド又は対応するメタクリルアミドである請求項１な
いし４のいずれかに記載の高温低粘度低温高粘度型感温
性高分子材料。5. An acrylic or methacrylamide derivative which gives a thermosensitive polymer exhibiting a reversible hydrophilic-hydrophobic change when polymerized alone is Nn-propylacrylamide, N-isopropylacrylamide, N-isopropylacrylamide, The high-temperature, low-viscosity, low-viscosity, high-viscosity type thermosensitive polymer material according to any one of claims 1 to 4, which is cyclopropylacrylamide, N, N-diethylacrylamide or a corresponding methacrylamide.
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