JP5099867B2 - Organic-inorganic composite hydrogel and method for producing the dried product - Google Patents
Organic-inorganic composite hydrogel and method for producing the dried product Download PDFInfo
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本発明は、アクリルアミド、メタクリルアミドまたはそれらの誘導体などの重合体と粘土鉱物からなる有機無機複合ヒドロゲルの製造方法に関する。 The present invention relates to a method for producing an organic-inorganic composite hydrogel comprising a polymer such as acrylamide, methacrylamide or a derivative thereof and a clay mineral.
ポリアミド、ポリスチレン、ポリプロピレン、ポリイミド、ポリウレタンなどの有機高分子を粘土と複合させることによりナノコンポジットと呼ばれる高分子複合体が調製されている。得られた高分子複合体はアスペクト比の大きい粘土層を微細に分散させていることから、弾性率、熱変形温度、ガス透過性、および燃焼速度などが効果的に改良されることが報告されている（例えば非特許文献１参照）。 Polymer composites called nanocomposites have been prepared by combining organic polymers such as polyamide, polystyrene, polypropylene, polyimide, and polyurethane with clay. Since the resulting polymer composite has finely dispersed clay layers with a large aspect ratio, it has been reported that the elastic modulus, heat distortion temperature, gas permeability, and burning rate are effectively improved. (For example, refer nonpatent literature 1).
高分子複合体中に含まれる粘土鉱物量としては、性能強化の観点からは高い粘土鉱物含有量が望まれるが、より低い粘土鉱物量で効果的な性能強化が達成されることも重要である。これまでの研究では通常０．２〜５質量％が用いられ、０．１質量％以下の低無機含有高分子複合体や１０質量％を超える高無機含有高分子複合体は用いられていない。これは無機含有率が低くなると性能向上の効果が無視されるほど小さくなり、一方、無機含有率が高くなると製造時の粘度増加が大きく、得られる複合体中での、粘土鉱物のナノスケールでの微細且つ均一な分散が達成できなかったり、或いは複合体が脆くなり力学物性（強度や伸び）が大きく低下したりするためである。 As the amount of clay mineral contained in the polymer composite, a high clay mineral content is desired from the viewpoint of performance enhancement, but it is also important to achieve effective performance enhancement with a lower amount of clay mineral. . In the studies so far, 0.2 to 5% by mass is usually used, and a low inorganic content polymer complex of 0.1% by mass or less and a high inorganic content polymer complex exceeding 10% by mass are not used. This is so small that the performance improvement effect is ignored when the inorganic content is low, while the increase in viscosity at the time of production is large when the inorganic content is high, at the nanoscale of the clay mineral in the resulting composite. This is because fine and uniform dispersion cannot be achieved, or the composite becomes brittle and mechanical properties (strength and elongation) are greatly reduced.
このような問題に対し、優れた力学物性を示すナノコンポジット材料として、広い範囲の粘土鉱物含有率において粘土鉱物が有機高分子中に均一に分散した有機無機複合ヒドロゲルが開示されており、該有機無機複合ヒドロゲルは水媒体中で水膨潤性粘土鉱物と重合開始剤の存在下にアクリルアミドやメタクリルアミドの誘導体、(メタ)アクリル酸エステルなどを重合させることにより、力学物性の良い高分子複合体を製造できることが開示されている（例えば特許文献１、特許文献２参照）。 To solve such problems, an organic-inorganic composite hydrogel in which clay mineral is uniformly dispersed in an organic polymer in a wide range of clay mineral content is disclosed as a nanocomposite material exhibiting excellent mechanical properties. Inorganic composite hydrogels form polymer composites with good mechanical properties by polymerizing acrylamide, methacrylamide derivatives, (meth) acrylates, etc. in the presence of water-swellable clay minerals and polymerization initiators in aqueous media. It is disclosed that it can be manufactured (for example, refer to Patent Document 1 and Patent Document 2).
しかし、この製造方法は、水溶性の過酸化物を用いるものであり、重合溶液中の酸素を取り除いた状態で、一定温度、例えば室温では数十分〜十数時間静置させて、高分子複合体を重合させる方法であったため、工程の更なる単純化や製造時間の短縮が求められていた。 However, this production method uses a water-soluble peroxide, and after leaving oxygen in the polymerization solution, the polymer is allowed to stand at a certain temperature, for example, room temperature, for several tens of minutes to several tens of hours. Since it was a method of polymerizing a composite, further simplification of the process and reduction of manufacturing time were demanded.
本発明が解決しようとする課題は、広い範囲の粘土鉱物含有率において、粘土鉱物が有機高分子中に均一に分散し、優れた力学物性を示す有機無機複合ヒドロゲル、およびその乾燥物を簡便に短時間で製造できる製造方法を提供することにある。 The problem to be solved by the present invention is to easily prepare an organic-inorganic composite hydrogel having excellent mechanical properties in which clay minerals are uniformly dispersed in an organic polymer in a wide range of clay mineral content, and a dried product thereof. The object is to provide a production method capable of producing in a short time.
本発明らは、上記課題を解決すべく鋭意研究した結果、非水溶性の重合開始剤（ｄ）を水媒体（ｃ）中に分散させた反応溶液中で、水膨潤性粘土鉱物（ｂ）の共存下において、水溶性のアクリル系モノマー（ａ）をエネルギー線の照射により反応させることにより、酸素の影響を受けにくく、反応がほぼ瞬時に完了し、力学物性の優れた有機無機複合ヒドロゲルを製造できる方法を見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a water-swellable clay mineral (b) in a reaction solution in which a water-insoluble polymerization initiator (d) is dispersed in an aqueous medium (c). In the coexistence of water, an organic-inorganic composite hydrogel having excellent mechanical properties is obtained by reacting the water-soluble acrylic monomer (a) by irradiation with energy rays, which is hardly affected by oxygen and the reaction is completed almost instantaneously. A method that can be manufactured has been found and the present invention has been completed.
本発明の製造方法によれば、有機無機複合ヒドロゲルを重合する際に酸素の影響を受けにくいため、酸素を除去するための設備や工程が不要であることから簡便に有機無機複合ヒドロゲルを製造できる。さらに、エネルギー線による照射により重合することにより極短時間で製造できる。 According to the production method of the present invention, an organic-inorganic composite hydrogel can be easily produced because it is not easily affected by oxygen when polymerizing the organic-inorganic composite hydrogel, and equipment and processes for removing oxygen are unnecessary. . Furthermore, it can manufacture in a very short time by superposing | polymerizing by irradiation with an energy ray.
また、本発明により得られた有機無機複合ヒドロゲル（及びその乾燥物）は、広い範囲の粘土鉱物含有率において、粘土鉱物が有機高分子中に均一に分散し、優れた力学物性や柔軟性などを示すと同時に、重合に対する酸素の影響を受けにくく、重合も極短時間で完了できる特徴を持っており、医療や介護用具、各種工業用材料として用いられる。 In addition, the organic-inorganic composite hydrogel (and its dried product) obtained by the present invention has a wide range of clay mineral content, the clay mineral is uniformly dispersed in the organic polymer, and has excellent mechanical properties and flexibility. At the same time, it is less susceptible to the influence of oxygen on the polymerization, and has characteristics that the polymerization can be completed in a very short time, and is used as a medical or nursing tool or various industrial materials.
本発明で用いる水溶性のアクリル系モノマー（ａ）は、その重合体が粘土鉱物と相互作用し、エネルギー線による重合により有機無機複合ヒドロゲルを形成できるものであれば、好適に使用できるが、中でも、アクリルアミド、メタクリルアミド、および／またはこれらの誘導体（Ｎ−またはＮ，Ｎ置換（メタ）アクリルアミド）やアクリル酸エステルが好ましく用いられ、特に好ましくはアクリルアミド、メタクリルアミド、および／またはこれらの誘導体（Ｎ−またはＮ，Ｎ置換（メタ）アクリルアミド）が用いられる。 The water-soluble acrylic monomer (a) used in the present invention can be suitably used as long as the polymer interacts with the clay mineral and can form an organic-inorganic composite hydrogel by polymerization with energy rays. , Acrylamide, methacrylamide, and / or derivatives thereof (N- or N, N-substituted (meth) acrylamide) and acrylic esters are preferably used, and acrylamide, methacrylamide, and / or derivatives thereof (N -Or N, N-substituted (meth) acrylamide) is used.
更に好ましくは下記式（１）〜（６）のアクリル系モノマーが用いられる。 More preferably, acrylic monomers of the following formulas (1) to (6) are used.
これらのアクリル系モノマーの使用により、非水溶性の開始剤がより微細且つ均一に分散でき、エネルギー線による重合時酸素の影響が受けにくく、より物性の優れる有機無機複合ヒドロゲルが得られる。 By using these acrylic monomers, a water-insoluble initiator can be dispersed more finely and uniformly, and an organic-inorganic composite hydrogel having excellent physical properties can be obtained because it is less susceptible to oxygen during polymerization by energy rays.
上記のアクリル系モノマーは、要求される力学物性や化学物性などにより、一種以上を混合して使用してもよい The above acrylic monomers may be used in combination of one or more depending on the required mechanical properties and chemical properties.
また、有機無機複合ヒドロゲルの物性に影響を及ぼさない程度に、その他の共重合モノマーとして、例えば、スルホン基やカルボキシル基のようなアニオン基を有するアクリル系モノマー、４級アンモニウム基のようなカチオン基を有するアクリル系モノマー、４級アンモニウム基と燐酸基とを持つ両性イオン基を有するアクリル系モノマー、カルボキシル基とアミノ基とをもつアミノ酸残基を有するアクリル系モノマー、糖残基を有するアクリル系モノマー、また、水酸基を有するアクリル系モノマー、ポリエチレングリコール、ポリプロピレングリコール鎖を有するアクリル系モノマー、更にポリエチレングリコールのような親水性鎖とノニルフェニル基のような疎水基を合わせ持つ両親媒性アクリル系モノマー、ポリエチレングリコールジアクリレート、Ｎ，Ｎ’−メチレンビスアクリルアミドなどを併用することができる。 In addition, as other copolymerization monomers, for example, acrylic monomers having an anion group such as a sulfone group or a carboxyl group, cationic groups such as a quaternary ammonium group, to the extent that the physical properties of the organic-inorganic composite hydrogel are not affected. Acrylic monomer having quaternary ammonium group and phosphoric acid group, acrylic monomer having zwitterion group, acrylic monomer having amino acid residue having carboxyl group and amino group, acrylic monomer having sugar residue In addition, an acrylic monomer having a hydroxyl group, polyethylene glycol, an acrylic monomer having a polypropylene glycol chain, an amphiphilic acrylic monomer having a hydrophilic chain such as polyethylene glycol and a hydrophobic group such as a nonylphenyl group, Polyethylene glycol Diacrylate, N, may be used in combination such as N'- methylenebisacrylamide.
アクリル系モノマーの重合体と粘土鉱物との相互作用には、静電相互作用、疎水性部分の相互作用、水素結合、配位結合による相互作用、またはこれらの相互作用の組み合わせがある。これらの相互作用により、本発明の有機無機複合ヒドロゲルの力学物性が非常に優れていると推測される。 The interaction between the polymer of the acrylic monomer and the clay mineral includes electrostatic interaction, interaction of the hydrophobic portion, hydrogen bond, interaction by coordination bond, or a combination of these interactions. Due to these interactions, it is presumed that the mechanical properties of the organic-inorganic composite hydrogel of the present invention are very excellent.
本発明に用いる水膨潤性粘土鉱物（ｂ）としては、層状に剥離可能な膨潤性粘土鉱物が挙げられ、好ましくは水または水と有機溶剤との混合溶液中で膨潤し均一に分散可能な粘土鉱物、特に好ましくは水中で分子状（単一層）またはそれに近いレベルで均一分散可能な無機粘土鉱物が用いられる。具体的にはナトリウムを層間イオンとして含む水膨潤性ヘクトライト、水膨潤性モンモリライト、水膨潤性サポナイト、水膨潤性合成雲母等が挙げられる。これらの粘土鉱物を混合して用いても良い。 Examples of the water-swellable clay mineral (b) used in the present invention include swellable clay minerals that can be peeled in layers, preferably clay that can swell and uniformly disperse in water or a mixed solution of water and an organic solvent. Minerals are used, particularly preferably inorganic clay minerals that can be uniformly dispersed in water at molecular (single layer) or close to that level. Specific examples include water-swellable hectorite containing sodium as an interlayer ion, water-swellable montmorlite, water-swellable saponite, and water-swellable synthetic mica. You may mix and use these clay minerals.
本発明の有機無機複合ヒドロゲルを製造する際、水膨潤性粘土鉱物（ｂ）と水溶性のアクリルモノマー（ａ）との重量比（ｂ）／（ａ）が、０．０１〜１０であることが好ましく、０．０３〜５がより好ましく、０．０５〜３が特に好ましい。重量比（ｂ）／（ａ）が０．０１未満では、得られる有機無機複合ヒドロゲルの力学物性が不十分になりやすく、また１０を超えると粘土鉱物の分散が困難になってくる。 When producing the organic-inorganic composite hydrogel of the present invention, the weight ratio (b) / (a) of the water-swellable clay mineral (b) to the water-soluble acrylic monomer (a) is 0.01-10. Is preferable, 0.03 to 5 is more preferable, and 0.05 to 3 is particularly preferable. If the weight ratio (b) / (a) is less than 0.01, the mechanical properties of the resulting organic-inorganic composite hydrogel tend to be insufficient, and if it exceeds 10, the dispersion of the clay mineral becomes difficult.
本発明に用いる水媒体（ｃ）は、水溶性のアクリルモノマー（ａ）や水膨潤性粘土鉱物などを含むことができ、エネルギー線による重合によって、力学物性のよい有機無機複合ヒドロゲルが得られれば良く、特に限定されない。例えば水、または水と混和性を有する溶剤及び／またはその他の化合物を含む水溶液であってよく、その中には更に、防腐剤や抗菌剤、着色剤、香料、酵素、たんぱく質、糖類、アミノ酸類、細胞、ＤＮＡ類、塩類、水溶性有機溶剤類、界面活性剤、レベリング剤などを含むことができる。 The aqueous medium (c) used in the present invention can contain a water-soluble acrylic monomer (a), a water-swellable clay mineral, and the like, and an organic-inorganic composite hydrogel having good mechanical properties can be obtained by polymerization using energy rays. Good, not particularly limited. For example, it may be water or an aqueous solution containing a solvent miscible with water and / or other compounds, and further includes antiseptics, antibacterial agents, coloring agents, fragrances, enzymes, proteins, saccharides, amino acids. , Cells, DNAs, salts, water-soluble organic solvents, surfactants, leveling agents and the like.
本発明に用いられる非水溶性の重合開始剤（ｄ）としては、ｐ−ｔｅｒｔ−ブチルトリクロロアセトフェノンなどのアセトフェノン類、４，４’−ビスジメチルアミノベンゾフェノンなどのベンゾフェノン類、２−メチルチオキサントンなどのケトン類、ベンゾインメチルエーテルなどのベンゾインエーテル類、ヒドロキシシクロヘキシルフェニルケトンなどのα−ヒドロキシケトン類、メチルベンゾイルホルメートなどのフェニルグリオキシレート類、メタロセン類などが挙げられる。 Examples of the water-insoluble polymerization initiator (d) used in the present invention include acetophenones such as p-tert-butyltrichloroacetophenone, benzophenones such as 4,4′-bisdimethylaminobenzophenone, and 2-methylthioxanthone. Examples include ketones, benzoin ethers such as benzoin methyl ether, α-hydroxy ketones such as hydroxycyclohexyl phenyl ketone, phenylglyoxylates such as methylbenzoyl formate, and metallocenes.
ここで言う非水溶性とは、重合開始剤の水に対する溶解量が０．５重量％以下であることを意味する。水に対する溶解性が高いと、得られる有機無機複合ヒドロゲルの力学物性が不十分になりやすく、好ましくない。 The term “water-insoluble” as used herein means that the amount of polymerization initiator dissolved in water is 0.5% by weight or less. If the solubility in water is high, the mechanical properties of the resulting organic-inorganic composite hydrogel tend to be insufficient, which is not preferable.
本発明の最も重要なところは、上記非水溶性の重合開始剤（ｄ）を前記水媒体（ｃ）に分散させ、この状態でエネルギー線を照射し重合させることである。この際、重合開始剤（ｄ）を水媒体（ｃ）中に分散させるには、（ｄ）を溶媒（ｅ）に溶解させた状態で分散させることが好ましい。この方法によって力学物性のよい有機無機複合ヒドロゲルがエネルギー線照射により得られる。逆に水溶性の重合開始剤を用いた場合は、得られる有機無機複合ヒドロゲルの力学物性の低下や、リニアポリマーの溶出を生じる場合がある。 The most important point of the present invention is to disperse the water-insoluble polymerization initiator (d) in the aqueous medium (c), and in this state, irradiate it with energy rays to polymerize it. At this time, in order to disperse the polymerization initiator (d) in the aqueous medium (c), it is preferable that (d) be dispersed in the solvent (e). By this method, an organic-inorganic composite hydrogel with good mechanical properties can be obtained by energy beam irradiation. On the other hand, when a water-soluble polymerization initiator is used, the mechanical properties of the resulting organic-inorganic composite hydrogel may be deteriorated or the linear polymer may be eluted.
本発明の溶媒（ｅ）としては、非水溶性重合開始剤（ｄ）を溶解できる水溶性の溶剤、または非水溶性重合開始剤（ｄ）を溶解し且つＨＬＢ（親水疎水バランス）値が８以上のアクリル系モノマー（以下、該アクリル系モノマーをアクリル系モノマー（ａ’）と略記する。）を用いることができる。ここのＨＬＢ値はデービス式（「界面活性剤−物性・応用・化学生態学」、北原文雄ら編、講談社、１９７９、ｐ２４−２７）に従って求められた値である。例えば、トリプロピレングリコールジアクリレートのようなポリプロピレングリコールジアクリレート類、ポリエチレングリコールジアクリレート類、ペンタプロピレングリコールアクリレートのようなポリプロピレングリコールアクリレート類、ポリエチレングリコールアクリレート類、メトキシエチルアクリレート、メトキシトリエチレングリコールアクリレートのようなメキシポリエチレングリコールアクリレート類、ノニルフェノキシポリエチレングリコ−ルアクリレート類、ジメチルアクリルアミドのようなＮ置換アクリルアミド類、ヒドロキシエチルアクリレート、ヒドロキシプロピルアクリレート、などが挙げられる。溶媒（ｅ）としてのアクリル系モノマーのＨＬＢ値が８以上であると、水媒体（ｃ）への溶解生または分散性に優れるため好ましい。これらのアクリル系モノマーは、一種以上を混合して用いることができる。 As the solvent (e) of the present invention, a water-soluble solvent capable of dissolving the water-insoluble polymerization initiator (d), or a water-insoluble polymerization initiator (d) is dissolved and the HLB (hydrophobic balance) value is 8. The above acrylic monomers (hereinafter, the acrylic monomers are abbreviated as acrylic monomers (a ′)) can be used. The HLB value here is a value determined according to the Davis formula (“surfactant—physical properties / application / chemical ecology”, edited by Fumio Kitahara, Kodansha, 1979, p. 24-27). For example, polypropylene glycol diacrylates such as tripropylene glycol diacrylate, polyethylene glycol diacrylates, polypropylene glycol acrylates such as pentapropylene glycol acrylate, polyethylene glycol acrylates, methoxyethyl acrylate, methoxytriethylene glycol acrylate Examples thereof include non-methyl polyethylene glycol acrylates, nonyl phenoxy polyethylene glycol acrylates, N-substituted acrylamides such as dimethyl acrylamide, hydroxyethyl acrylate, hydroxypropyl acrylate, and the like. It is preferable that the acrylic monomer as the solvent (e) has an HLB value of 8 or more because it is excellent in solubility or dispersibility in the aqueous medium (c). These acrylic monomers can be used by mixing one or more.
また、本発明の溶媒（ｅ）としては、非水溶性重合開始剤（ｄ）を溶解でき、且つ一定以上の水溶性を有する溶剤を用いることができる。ここで言う水溶性を有する溶剤とは、水１００ｇに対し５０ｇ以上溶解できる溶剤であることが好ましい。水への溶解性が５０ｇ未満であると、非水溶性の重合開始剤（ｄ）の水媒体（ｃ）への分散性が低下し、得られる有機無機複合ヒドロゲルの力学物性が低い場合がある。 In addition, as the solvent (e) of the present invention, a solvent that can dissolve the water-insoluble polymerization initiator (d) and has a certain level of water solubility can be used. The water-soluble solvent mentioned here is preferably a solvent that can dissolve 50 g or more with respect to 100 g of water. If the solubility in water is less than 50 g, the dispersibility of the water-insoluble polymerization initiator (d) in the aqueous medium (c) may be reduced, and the mechanical properties of the resulting organic-inorganic composite hydrogel may be low. .
例えば、水溶性溶剤としては、ジメチルアセトアミド、ジメチルホルムアミドなどのアミド類、ジメチルスルホキシド、メタノール、エタノールなどのアルコール類、テトラヒドロフラン、などが挙げられる。これらの溶剤を混合して用いても良い。 For example, examples of the water-soluble solvent include amides such as dimethylacetamide and dimethylformamide, alcohols such as dimethyl sulfoxide, methanol and ethanol, and tetrahydrofuran. You may mix and use these solvents.
非水溶性重合開始剤（ｄ）を溶媒（ｅ）に溶解させた溶液中における重合開始剤（ｄ）と溶媒（ｅ）の重量比（ｄ）／（ｅ）は、０．００１〜０．１であることが好ましく、０．０１〜０．０５が更に好ましい。０．００１以上であると、エネルギー線の照射によるラジカルの発生量が十分に得られるため好適に重合反応を進行させることができ、０．１以下であれば、開始剤による発色や、臭気を実質的に生じることがなく、またコストの低減が可能である。 The weight ratio (d) / (e) of the polymerization initiator (d) to the solvent (e) in a solution in which the water-insoluble polymerization initiator (d) is dissolved in the solvent (e) is 0.001 to 0.00. 1 is preferable, and 0.01 to 0.05 is more preferable. When the amount is 0.001 or more, a sufficient amount of radicals are generated by irradiation with energy rays, so that the polymerization reaction can be suitably performed. When the amount is 0.1 or less, coloring by an initiator and odor are caused. It does not occur substantially and the cost can be reduced.
以上のアクリル系モノマー（ａ’）および水溶性を有する溶剤のいずれの場合においても、重合開始剤（ｄ）を溶媒（ｅ）に溶解させた溶液の分散量が、水溶性のアクリル系モノマー（ａ）、水膨潤性粘土鉱物（ｂ）、水系溶媒（ｃ）、重合開始剤（ｄ）及び溶媒（ｅ）の総重量に対し、０．１重量％〜５重量%であることが好ましく、０．２重量％〜２重量％であることが更に好ましい。該分散量が０．１重量％以上であると、重合が十分に開始され、５重量％未満であると、有機無機複合ヒドロゲルに関与しないリニアポリマーの生成やゲル中の重合開始剤の増加による臭気の発生、更には一旦分散された重合開始剤または重合開始剤と溶媒（ｅ）との溶液が再び凝集する等の問題を低減でき、均一な有機無機複合ヒドロゲルを得ることができるため好ましい。 In any case of the acrylic monomer (a ′) and the water-soluble solvent, the amount of dispersion of the solution obtained by dissolving the polymerization initiator (d) in the solvent (e) is such that the water-soluble acrylic monomer ( a), the water-swellable clay mineral (b), the aqueous solvent (c), the polymerization initiator (d) and the solvent (e) are preferably 0.1% by weight to 5% by weight, More preferably, it is 0.2 to 2% by weight. When the dispersion amount is 0.1% by weight or more, the polymerization is sufficiently started, and when it is less than 5% by weight, it is caused by generation of a linear polymer not involved in the organic-inorganic composite hydrogel or an increase in the polymerization initiator in the gel. Odor generation and further problems such as aggregation of the polymerization initiator once dispersed or the solution of the polymerization initiator and the solvent (e) can be reduced, and a uniform organic-inorganic composite hydrogel can be obtained.
本発明で力学物性のよい有機無機複合ヒドロゲルを得るためには、重合開始剤（ｄ）を溶媒（ｅ）に溶解させた溶液を水媒体（ｃ）に、１μｍ以下に分散させることが好ましく、０．１μｍ以下が特に好ましく、０．０１μｍ以下が最も好ましい。１μｍ以下であると、反応溶液が均一になりやすく、有機無機複合ヒドロゲルの均一性や透明性を向上させることができるため好ましい。 In order to obtain an organic-inorganic composite hydrogel having good mechanical properties in the present invention, it is preferable to disperse a solution prepared by dissolving the polymerization initiator (d) in the solvent (e) in an aqueous medium (c) to 1 μm or less, 0.1 μm or less is particularly preferable, and 0.01 μm or less is most preferable. When the thickness is 1 μm or less, the reaction solution is likely to be uniform, and the uniformity and transparency of the organic-inorganic composite hydrogel can be improved.
本発明に用いられるエネルギー線としては、電子線、γ線、Ｘ線、紫外線、可視光などを用いることができる。中でも装置や取り扱いの簡便さから紫外線を用いることが好ましい。照射する紫外線の強度は１０〜５００ｍＷ／ｃｍ２が好ましく、照射時間は一般に０．１秒〜２００秒程度である。通常の加熱によるラジカル重合においては、酸素が重合の阻害因子として働くが、本発明では、必ずしも酸素を遮断した雰囲気で溶液の調製およびエネルギー線照射による重合を行う必要がなく、空気雰囲気でこれらを行うことが可能である。但し、紫外線照射を不活性ガス雰囲気下で行うことによって、更に重合速度を速めることが可能で、望ましい場合がある。 As the energy rays used in the present invention, electron beams, γ rays, X rays, ultraviolet rays, visible light, and the like can be used. Among these, it is preferable to use ultraviolet rays because of the simplicity of the apparatus and handling. The intensity of the irradiated ultraviolet light is preferably 10 to 500 mW / cm 2 and the irradiation time is generally about 0.1 to 200 seconds. In radical polymerization by normal heating, oxygen acts as an inhibitor of polymerization, but in the present invention, it is not always necessary to prepare a solution and perform polymerization by irradiation with energy rays in an atmosphere in which oxygen is cut off. Is possible. However, it may be desirable that the polymerization rate can be further increased by performing ultraviolet irradiation in an inert gas atmosphere.
本発明における有機無機複合ヒドロゲルの製造方法は、水溶性のアクリル系モノマー（ａ）、水膨潤性粘土鉱物（ｂ）、水媒体（ｃ）、重合開始剤（ｄ）及び溶媒（ｅ）を含む反応溶液を、任意の形（例えば板状、シート状、薄膜上、棒状、球状、糸状、中空糸状など）に賦形し、エネルギー線を照射し、水溶性のアクリル系モノマー（ａ）を重合させることにより有機無機複合ヒドロゲルを製造する方法である。また、ベルト状の支持体を用いることにより、枚葉式または連続してシート状の有機無機複合ヒドロゲルを製造することもできる。 The method for producing an organic-inorganic composite hydrogel in the present invention includes a water-soluble acrylic monomer (a), a water-swellable clay mineral (b), an aqueous medium (c), a polymerization initiator (d), and a solvent (e). The reaction solution is shaped into any shape (for example, plate, sheet, thin film, rod, sphere, thread, hollow fiber, etc.) and irradiated with energy rays to polymerize the water-soluble acrylic monomer (a). To produce an organic-inorganic composite hydrogel. Further, by using a belt-like support, a sheet-like or continuous sheet-like organic-inorganic composite hydrogel can also be produced.
支持体としては、金属、セラミックス、ガラス、プラスチック、布、不織布、紙、木材などを用いることができる。シート状のゲルは最終的に支持体から剥離してもよいし、支持体と一体化されたまま使用しても良い。 As the support, metal, ceramics, glass, plastic, cloth, nonwoven fabric, paper, wood and the like can be used. The sheet-like gel may be finally peeled off from the support, or may be used while being integrated with the support.
更に、上記の反応液を支持体に塗布し、マスクを介してエネルギー線を照射すれば、任意のパターンを持つ有機無機複合ヒドロゲルを作ることもできる。パターンの大きさはマイクロメーターレベルまたはそれ以下の微細なものが可能である。 Furthermore, an organic-inorganic composite hydrogel having an arbitrary pattern can be produced by applying the reaction solution to a support and irradiating it with energy rays through a mask. The pattern size can be as fine as a micrometer level or less.
以上の支持体（基材）の上に有機無機複合ヒドロゲルを形成した後、必要に応じて洗浄を行った後、支持体（基材）に貼り付いた状態で乾燥させることにより、有機無機複合ヒドロゲル乾燥物を製造することができる。また、支持体（基材）の上に形成された有機無機複合ヒドロゲルを支持体（基材）から剥がし、必要に応じて洗浄し、乾燥させることにより、有機無機複合ヒドロゲル単独の乾燥物も製造することができる。 After forming the organic-inorganic composite hydrogel on the above support (base material), after washing as necessary, the organic-inorganic composite composite is dried by sticking to the support (base material). A dried hydrogel can be produced. In addition, the organic-inorganic composite hydrogel formed on the support (base material) is peeled off from the support (base material), washed as necessary, and dried to produce a dried product of the organic-inorganic composite hydrogel alone. can do.
以下、実施例により本発明を具体的に説明するが、本発明の範囲がこれらの実施例にのみ限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, the scope of the present invention is not limited only to these Examples.
（実施例１）
［水溶性のアクリル系モノマー（ａ）、水膨潤性粘土鉱物（ｂ）、水媒体（ｃ）を含む反応溶液の調製］
水溶性のアクリル系モノマー（ａ）としてＮ，Ｎージメチルアクリルアミド（株式会社興人製）２ｇ、粘土鉱物（ｂ）としてLaponite XLG（Rockwood Additives Ltd.社製）０．８ｇ、水媒体（ｃ）として水２０ｇ、を均一に混合して反応溶液（１）を調製した。
Example 1
[Preparation of reaction solution containing water-soluble acrylic monomer (a), water-swellable clay mineral (b), aqueous medium (c)]
2 g of N, N-dimethylacrylamide (manufactured by Kojin Co., Ltd.) as the water-soluble acrylic monomer (a), 0.8 g of Laponite XLG (manufactured by Rockwood Additives Ltd.) as the clay mineral (b), aqueous medium (c) As a result, 20 g of water was uniformly mixed to prepare a reaction solution (1).
［重合開始剤（ｄ）を溶媒（ｅ）に溶解させた溶液の調整］
溶媒（ｅ）として、ポリオキシプロピレン モノアクリレート「ブレンマーＡＰ−４００」（日本油脂株式会社製）９８ｇ、重合開始剤（ｄ）として１−ヒドロキシシクロヘキシルフェニルケトン「イルガキュアー１８４」（チバガイギー社製）２ｇを、均一に混合して溶液（１）を調製した。
[Preparation of a solution in which the polymerization initiator (d) is dissolved in the solvent (e)]
As a solvent (e), 98 g of polyoxypropylene monoacrylate “Blenmer AP-400” (manufactured by NOF Corporation), 2 g of 1-hydroxycyclohexyl phenyl ketone “Irgacure 184” (manufactured by Ciba Geigy) as a polymerization initiator (d) Were mixed uniformly to prepare a solution (1).
［有機無機複合ヒドロゲルの作製］
上記反応溶液（１）全量に、溶液（１）を５０μｌ入れ、超音波分散機で、均一に分散させた後、内径５．５ｍｍのガラス管に封入し、３６５ｎｍにおける紫外線強度が４０ｍＷ／ｃｍ２の紫外線を１２０秒照射しＮ，Ｎージメチルアクリルアミドを重合させて、棒状の有機無機複合ヒドロゲル（Ｄ−ＮＣ５−Ｍ１）を作製した。
[Preparation of organic-inorganic composite hydrogel]
50 μl of the solution (1) is placed in the total amount of the reaction solution (1), and is uniformly dispersed by an ultrasonic disperser, and then enclosed in a glass tube having an inner diameter of 5.5 mm, and the ultraviolet intensity at 365 nm is 40 mW / cm 2. Was irradiated for 120 seconds to polymerize N, N-dimethylacrylamide to produce a rod-like organic-inorganic composite hydrogel (D-NC5-M1).
［ゲルの物性］
上記作製したゲルを、引っ張り試験機（ＡＧＳ−Ｈ型、島津製作所製）を用いて、測定したところ、破断点応力は６０ＫＰａで、破断点歪みは１９５０％であった。該ゲルは、目視で無色透明であった。
[Physical properties of gel]
When the gel prepared above was measured using a tensile tester (AGS-H type, manufactured by Shimadzu Corporation), the stress at break was 60 KPa and the strain at break was 1950%. The gel was colorless and transparent visually.
（実施例２）
［水溶性のアクリル系モノマー（ａ）、水膨潤性粘土鉱物（ｂ）、水媒体（ｃ）を含む反応溶液の調製］
水溶性のアクリル系モノマー（ａ）としてＮーイソプロピルアクリルアミド（株式会社興人製）２．３ｇ、粘土鉱物（ｃ）としてLaponite XLG（Rockwood Additives Ltd.社製）０．８ｇ、水媒体（ｃ）として水２０ｇ、を均一に混合して反応溶液（２）を調製した。
(Example 2)
[Preparation of reaction solution containing water-soluble acrylic monomer (a), water-swellable clay mineral (b), aqueous medium (c)]
2.3 g of N-isopropylacrylamide (manufactured by Kojin Co., Ltd.) as the water-soluble acrylic monomer (a), 0.8 g of Laponite XLG (manufactured by Rockwood Additives Ltd.) as the clay mineral (c), aqueous medium (c) As a result, 20 g of water was uniformly mixed to prepare a reaction solution (2).
［重合開始剤（ｄ）を溶媒（ｅ）に溶解させた溶液］
溶媒（ｅ）として、アクリル酸２−ヒドロキシエチル（和光純薬工業株式会社製）９５ｇ、重合開始剤（ｄ）として１−ヒドロキシシクロヘキシルフェニルケトン「イルガキュアー１８４」（チバガイギー社製）５ｇを、均一に混合して溶液（２）を調製した。
[Solution of polymerization initiator (d) in solvent (e)]
As a solvent (e), 95 g of 2-hydroxyethyl acrylate (manufactured by Wako Pure Chemical Industries, Ltd.) and 5 g of 1-hydroxycyclohexyl phenyl ketone “Irgacure 184” (manufactured by Ciba Geigy) as a polymerization initiator (d) To prepare a solution (2).
［有機無機複合ヒドロゲルの作製］
上記反応溶液（２）全量に、溶液（２）を１００μｌ入れ、超音波分散機で、均一に分散させた後、内径５．５ｍｍのガラス管に封入し、３６５ｎｍにおける紫外線強度が４０ｍＷ／ｃｍ２の紫外線を１２０秒照射しＮーイソプロピルアクリルアミドを重合させて、棒状の有機無機複合ヒドロゲル（N−ＮＣ５−Ｍ１）を作製した。
[Preparation of organic-inorganic composite hydrogel]
100 μl of the solution (2) is added to the total amount of the reaction solution (2), dispersed uniformly with an ultrasonic disperser, and then sealed in a glass tube having an inner diameter of 5.5 mm. The ultraviolet intensity at 365 nm is 40 mW / cm 2. Was irradiated for 120 seconds to polymerize N-isopropylacrylamide to produce a rod-like organic-inorganic composite hydrogel (N-NC5-M1).
［ゲルの物性］
上記作製したゲルを、引っ張り試験機（ＡＧＳ−Ｈ型、島津製作所製）を用いて、測定したところ、破断点応力は１２５ＫＰａで、破断点歪みは１２００％であった。該ゲルは、目視で無色透明であった。
[Physical properties of gel]
When the gel prepared above was measured using a tensile tester (AGS-H type, manufactured by Shimadzu Corporation), the stress at break was 125 KPa and the strain at break was 1200%. The gel was colorless and transparent visually.
このゲルを２０℃の水中に１６５時間浸漬したところ、ゲルが膨潤し重量が初期の約４００％になった。また、この膨潤したゲルを５０℃の水に２４時間浸漬したところ、ゲルが収縮し、重量が初期の約３５％になった。 When this gel was immersed in water at 20 ° C. for 165 hours, the gel swelled and its weight was about 400% of the initial value. Further, when this swollen gel was immersed in water at 50 ° C. for 24 hours, the gel contracted and the weight became about 35% of the initial value.
（実施例３）
［水溶性のアクリル系モノマー（ａ）、水膨潤性粘土鉱物（ｂ）、水媒体（ｃ）を含む反応溶液の調製］
水溶性のアクリル系モノマー（ａ）としてアクリル酸２−メトキシエチル（和光純薬工業株式会社製）２．６ｇ、粘土鉱物（ｃ）としてLaponite XLG（Rockwood Additives Ltd.社製）１．６ｇ、水媒体（ｃ）として水２０ｇ、を均一に混合して反応溶液（３）を調製した。
(Example 3)
[Preparation of reaction solution containing water-soluble acrylic monomer (a), water-swellable clay mineral (b), aqueous medium (c)]
2.6 g of 2-methoxyethyl acrylate (manufactured by Wako Pure Chemical Industries, Ltd.) as the water-soluble acrylic monomer (a), 1.6 g of Laponite XLG (manufactured by Rockwood Additives Ltd.) as the clay mineral (c), water 20 g of water as a medium (c) was uniformly mixed to prepare a reaction solution (3).
［重合開始剤（ｄ）を溶媒（ｅ）に溶解させた溶液］
溶媒（ｅ）として、Ｎ，Ｎ−ジメチルアセトアミド（和光純薬工業株式会社製）９５ｇ、重合開始剤（ｄ）として１−ヒドロキシシクロヘキシルフェニルケトン「イルガキュアー１８４」（チバガイギー社製）５ｇを、均一に混合して溶液（３）を調製した。
[Solution of polymerization initiator (d) in solvent (e)]
95 g of N, N-dimethylacetamide (manufactured by Wako Pure Chemical Industries, Ltd.) as the solvent (e) and 5 g of 1-hydroxycyclohexyl phenyl ketone “Irgacure 184” (manufactured by Ciba Geigy) as the polymerization initiator (d) To prepare a solution (3).
［有機無機複合ヒドロゲルの作製］
上記反応溶液（３）全量に、溶液（３）を８０μｌ入れ、超音波分散機で、均一に分散させた後、バーコーターを用いて厚み１５０μｍになるようにガラス板に塗布し、３６５ｎｍにおける紫外線強度が４０ｍＷ／ｃｍ２の紫外線を１２０秒照射しアクリル酸２−メトキシエチルを重合させて、薄膜状の有機無機複合ヒドロゲル（Ｍ−ＮＣ１０−Ｍ１）を作製した。得られたゲルは、目視で無色透明であった。
[Preparation of organic-inorganic composite hydrogel]
80 μl of the solution (3) is added to the total amount of the reaction solution (3), dispersed uniformly with an ultrasonic disperser, and then applied to a glass plate to a thickness of 150 μm using a bar coater, and ultraviolet light at 365 nm. Ultraviolet rays having an intensity of 40 mW / cm 2 were irradiated for 120 seconds to polymerize 2-methoxyethyl acrylate, thereby preparing a thin-film organic-inorganic composite hydrogel (M-NC10-M1). The obtained gel was colorless and transparent visually.
（実施例４）
［水溶性のアクリル系モノマー（ａ）、水膨潤性粘土鉱物（ｂ）水媒体（ｃ）を含む反応溶液の調製］
水溶性のアクリル系モノマー（ａ）として４−アクリロイルモルホリン（和光純薬工業株式会社製）２．８ｇ、粘土鉱物（ｃ）としてLaponite XLG（Rockwood Additives Ltd.社製）１．６ｇ、水媒体（ｃ）として水２０ｇ、を均一に混合して反応溶液（４）を調製した。
Example 4
[Preparation of reaction solution containing water-soluble acrylic monomer (a), water-swellable clay mineral (b) aqueous medium (c)]
2.8 g of 4-acryloylmorpholine (manufactured by Wako Pure Chemical Industries, Ltd.) as the water-soluble acrylic monomer (a), 1.6 g of Laponite XLG (manufactured by Rockwood Additives Ltd.) as the clay mineral (c), C) 20 g of water was uniformly mixed to prepare a reaction solution (4).
［重合開始剤（ｄ）を溶媒（ｅ）に溶解させた溶液］
溶媒（ｅ）として、ポリオキシプロピレン モノアクリレート「ブレンマーＡＰ−４００」（日本油脂株式会社製）９２ｇ、重合開始剤（ｄ）として１−ヒドロキシシクロヘキシルフェニルケトン「イルガキュアー１８４」（チバガイギー社製）８ｇを、均一に混合して溶液（４）を調製した。
[Solution of polymerization initiator (d) in solvent (e)]
As a solvent (e), polyoxypropylene monoacrylate “Blenmer AP-400” (manufactured by NOF Corporation) 92 g, and as a polymerization initiator (d) 1-hydroxycyclohexyl phenyl ketone “Irgacure 184” (manufactured by Ciba Geigy) 8 g Were mixed uniformly to prepare a solution (4).
［有機無機複合ヒドロゲルの作製］
上記反応溶液（４）全量に、溶液（４）を８０μｌ入れ、ミキサーで溶液を均一に混合した後、バーコーターを用いて厚み２００μｍになるようにガラス板に塗布し、（線幅約２００μｍ、長さ約５ｃｍの黒線が描かれている）ポリエチレンテレフタレート（ＰＥＴ）製マスクを介して、３６５ｎｍにおける紫外線強度が４０ｍＷ／ｃｍ２の紫外線を１２０秒照射し４−アクリロイルモルホリンを部分重合させて、未硬化の（黒線）部分を水洗で除いて、マスクの黒線部分と同じ形状の溝を持つ薄膜状の有機無機複合ヒドロゲル（ＡＣＭＯ−ＮＣ１０−Ｍ１）を作製した。
[Preparation of organic-inorganic composite hydrogel]
80 μl of the solution (4) is added to the total amount of the reaction solution (4), and the solution is uniformly mixed with a mixer, and then applied to a glass plate to a thickness of 200 μm using a bar coater (line width of about 200 μm, Through a polyethylene terephthalate (PET) mask (a black line having a length of about 5 cm is drawn), ultraviolet light having an ultraviolet intensity at 365 nm of 40 mW / cm 2 is irradiated for 120 seconds to partially polymerize 4-acryloylmorpholine, The uncured (black line) part was removed by washing with water to prepare a thin-film organic-inorganic composite hydrogel (ACMO-NC10-M1) having a groove having the same shape as the black line part of the mask.
［ゲルの物性］
上記作製したゲルは、目視で無色透明であった。
また、光学顕微鏡で溝を観察したところ、溝の幅は約２００μｍであった。
[Physical properties of gel]
The prepared gel was colorless and transparent visually.
Further, when the grooves were observed with an optical microscope, the width of the grooves was about 200 μm.
（比較例１）
［水溶性のアクリル系モノマー（ａ）、水膨潤性粘土鉱物（ｂ）、水溶性重合開始剤、水媒体（ｃ）を含む反応溶液の調製］
水溶性のアクリル系モノマー（ａ）としてＮ，Ｎージメチルアクリルアミド（株式会社興人製）２ｇ、粘土鉱物（ｂ）としてLaponite XLG（Rockwood Additives Ltd.社製）０．８ｇ、水溶性重合開始剤（過酸化物）としてペルオキソ二硫酸カリウム（和光純薬工業株式会社製）０．０２ｇ、水媒体（ｃ）として水２０ｇ、を、酸素を遮断しない空気中で均一に混合して反応溶液（１’）を調製した。
(Comparative Example 1)
[Preparation of reaction solution containing water-soluble acrylic monomer (a), water-swellable clay mineral (b), water-soluble polymerization initiator, and aqueous medium (c)]
2 g of N, N-dimethylacrylamide (manufactured by Kojin Co., Ltd.) as the water-soluble acrylic monomer (a), 0.8 g of Laponite XLG (manufactured by Rockwood Additives Ltd.) as the clay mineral (b), water-soluble polymerization initiator 0.02 g of potassium peroxodisulfate (manufactured by Wako Pure Chemical Industries, Ltd.) as the (peroxide) and 20 g of water as the aqueous medium (c) were mixed uniformly in the air without blocking oxygen to obtain a reaction solution (1 ') Was prepared.
［有機無機複合ヒドロゲルの作製］
上記反応溶液（１’）を、酸素を遮断しない空気中で内径５．５ｍｍのガラス管に封入し、２０℃の水槽中で１５時間静置（重合）した。しかし、上記すべての操作が酸素を遮断しなかったため、溶液が少し粘稠になっただけで、ゲルは得られなかった。
[Preparation of organic-inorganic composite hydrogel]
The reaction solution (1 ′) was sealed in a glass tube having an inner diameter of 5.5 mm in air that does not block oxygen, and left standing (polymerization) in a 20 ° C. water bath for 15 hours. However, since all the above operations did not block oxygen, the solution only became slightly viscous and no gel was obtained.
（比較例２）
［水溶性のアクリル系モノマー（ａ）、水膨潤性粘土鉱物（ｂ）、水溶性重合開始剤、水媒体（ｃ）を含む反応溶液の調製］
水溶性のアクリル系モノマー（ａ）としてＮーイソプロピルアクリルアミド（株式会社興人製）２．３ｇ、粘土鉱物（ｃ）としてLaponite XLG（Rockwood Additives Ltd.社製）０．８ｇ、水溶性重合開始剤として-２−ヒドロキシー１−［４−（２−ヒドロキシエトキシ）フェニル］−１−プロパン「イルガキュアー２９５９」（チバガイギー社製）０．２ｇ、水媒体（ｃ）として水２０ｇ、を均一に混合して反応溶液（２’）を調製した。
(Comparative Example 2)
[Preparation of reaction solution containing water-soluble acrylic monomer (a), water-swellable clay mineral (b), water-soluble polymerization initiator, and aqueous medium (c)]
2.3 g of N-isopropylacrylamide (manufactured by Kojin Co., Ltd.) as the water-soluble acrylic monomer (a), 0.8 g of Laponite XLG (manufactured by Rockwood Additives Ltd.) as the clay mineral (c), water-soluble polymerization initiator 2-hydroxy-1- [4- (2-hydroxyethoxy) phenyl] -1-propane “Irgacure 2959” (manufactured by Ciba Geigy) and 20 g of water as the aqueous medium (c) were uniformly mixed. Thus, a reaction solution (2 ′) was prepared.
［有機無機複合ヒドロゲルの作製］
上記反応溶液（２’）を内径５．５ｍｍのガラス管に封入し、３６５ｎｍにおける紫外線強度が４０ｍＷ／ｃｍ２の紫外線を１２０秒照射しＮーイソプロピルアクリルアミドを重合させた。
[Preparation of organic-inorganic composite hydrogel]
The reaction solution (2 ′) was sealed in a glass tube having an inner diameter of 5.5 mm, and irradiated with ultraviolet rays having an ultraviolet intensity of 40 mW / cm 2 at 365 nm for 120 seconds to polymerize N-isopropylacrylamide.
［ゲルの物性］
上記作製したゲルは、目視で乳白色で不透明なものであった。引っ張り試験機（ＡＧＳ−Ｈ型、島津製作所製）を用いて、測定を試みたが、該ゲルの強度が弱すぎて測定不能であった。
[Physical properties of gel]
The prepared gel was visually milky white and opaque. Measurement was attempted using a tensile tester (AGS-H type, manufactured by Shimadzu Corporation), but the gel was too weak to measure.
上記実施例及び比較例から、本発明の製造方法によれば酸素を除去することなく極短時間で、広い範囲の粘土鉱物含有率において、粘土鉱物が有機高分子中に均一に分散し、優れた力学物性や柔軟性及び透明性などを示す有機無機複合ヒドロゲルを製造できることが明らかであった。
From the above examples and comparative examples, according to the production method of the present invention, the clay mineral is uniformly dispersed in the organic polymer in an extremely short time without removing oxygen, and in a wide range of clay mineral content. It was clear that organic-inorganic composite hydrogels exhibiting mechanical properties, flexibility, transparency and the like can be produced.
Claims (14)
から選ばれる少なくとも一種の水溶性のアクリル系モノマー（ａ）をエネルギー線の照射により反応させることからなる有機無機複合ヒドロゲルの製造方法。 A water-insoluble polymerization initiator (d) that is acetophenones, benzophenones, ketones, benzoin ethers, α-hydroxy ketones, phenylglyoxylates or metallocenes was dispersed in an aqueous medium (c). In the solution, in the presence of the water-swellable clay mineral (b), the following formulas (1) to (6)
A method for producing an organic-inorganic composite hydrogel comprising reacting at least one water-soluble acrylic monomer (a) selected from energy rays by irradiation with energy rays.
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| DE602005021915T DE602005021915D1 (en) | 2004-12-14 | 2005-12-13 | HEM HYBRIDHYDROGEL, THIS COMPREHENSIVE CELL CULTURE SUPPLY AND ANTI-FIXING MATERIAL, COMPREHENSIVE DRIED PRODUCT THEREOF |
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