JP2011038031A - Method for producing molded product and molded product - Google Patents
Method for producing molded product and molded product Download PDFInfo
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- 238000004519 manufacturing process Methods 0.000 title claims description 47
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- 239000000463 material Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 25
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- ZOMBKNNSYQHRCA-UHFFFAOYSA-J calcium sulfate hemihydrate Chemical compound O.[Ca+2].[Ca+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZOMBKNNSYQHRCA-UHFFFAOYSA-J 0.000 description 1
- ZHZFKLKREFECML-UHFFFAOYSA-L calcium;sulfate;hydrate Chemical class O.[Ca+2].[O-]S([O-])(=O)=O ZHZFKLKREFECML-UHFFFAOYSA-L 0.000 description 1
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
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- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
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- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 1
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- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 1
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Abstract
Description
セルロースナノファイバーのような水溶性あるいは水分散性多糖類の製造方法と成形物に関するものであり、各種バリア材料、支持体、フィルター材料、生体適合性材料などへの適合可能な材料となる成形物の製造方法と成形物に関するものである。 The present invention relates to a method for producing a water-soluble or water-dispersible polysaccharide such as cellulose nanofiber and a molded product, and is a molded product that can be adapted to various barrier materials, supports, filter materials, biocompatible materials, etc. It relates to a manufacturing method and a molded product.
近年、温暖化などによる環境の悪化や石油枯渇化が懸念されており、再生可能な天然資源を有効利用しようという流れがあらゆる分野の材料開発で起こっている。特にセルロースは植物の細胞壁などに存在し、原料としては空気中の二酸化炭素を取り込んで生合成されるため、カーボンニュートラルな材料として注目されている。現在では、セルロースを用いた様々な材料が開発されており、高機能性材料として利用されている。しかし、セルロースエステルやセルロースエーテルなど、その多くが有害な試薬や有機溶媒を用いる反応によりセルロースを化学修飾などにより改質するものが多く、生成物も各種有機溶媒に溶解するが水には溶解しないため、成形時にも有機溶媒を使用するものが多く、有機溶媒を除去するためにエネルギーを必要とし、また除去した有機溶媒を回収する設備が必要になるなどの問題があった。また、用途によっては導入した官能基が各種機能発現の阻害や、生体や環境への悪影響を及ぼす事などが懸念されている。また、これらの誘導体を用いてナノファイバーやフィルムなどを成形するには、有毒な有機溶媒を用いることが多い。水に溶解する誘導体も開発され、水を用いた成形方法も開発されているが、即座に低いエネルギーで乾燥・成形することは技術的に困難であった。 In recent years, there has been concern about environmental deterioration and oil depletion due to global warming and the like, and there has been a trend toward effective use of renewable natural resources in material development in all fields. Cellulose is particularly attracting attention as a carbon neutral material because it is present in plant cell walls and is biosynthesized by incorporating carbon dioxide in the air as a raw material. At present, various materials using cellulose have been developed and are used as highly functional materials. However, many of them, such as cellulose esters and cellulose ethers, modify cellulose by chemical modification by reaction using harmful reagents and organic solvents, and the products dissolve in various organic solvents but not in water. For this reason, many organic solvents are used even during molding, and there is a problem that energy is required to remove the organic solvent, and equipment for recovering the removed organic solvent is required. In addition, there are concerns that the introduced functional group may inhibit the expression of various functions or adversely affect the living body or the environment depending on the application. Further, in order to form nanofibers or films using these derivatives, a toxic organic solvent is often used. Derivatives that dissolve in water have been developed, and molding methods using water have also been developed. However, it has been technically difficult to immediately dry and mold with low energy.
そこで、特開２００８−１７２８のように、天然のセルロース素材を水系の処理により改質した後、解繊の処理を施すことによりナノファイバーを得る方法が知られている。この方法を用いることで、天然の構造を有効に利用しつつナノファイバ−を得ることと、水などの安全な溶媒を用いた成形が可能となった。 Therefore, as disclosed in Japanese Patent Application Laid-Open No. 2008-1728, a method of obtaining nanofibers by modifying a natural cellulose material by an aqueous treatment and then performing a defibrating treatment is known. By using this method, it was possible to obtain nanofibers while effectively utilizing the natural structure and to mold using a safe solvent such as water.
しかしながら、特許文献１のセルロースナノファイバーのような水溶性あるいは水分散性の高分子はそのナノ化機構が水などの沸点の高い極性溶媒による静電的な反発を利用した解繊を主とする分散機構からなるため、高分子の周りにある程度量の溶媒が必要となる。そのため、水溶液あるいは水分散液の中のセルロース分の濃度が薄くなってしまい、この水溶液あるいは水分散液から成形物を得るには多量の溶媒を除去する必要があった。水などの溶媒の除去には多量のエネルギーを必要とするうえ、水から成形を行った場合、成形物が水や湿度に弱く、一旦成形しても再度水や水蒸気に触れた際に膨潤・崩壊してしまうという問題があった。 However, a water-soluble or water-dispersible polymer such as cellulose nanofiber of Patent Document 1 mainly uses fibrillation utilizing electrostatic repulsion by a polar solvent having a high boiling point such as water. Due to the dispersion mechanism, a certain amount of solvent is required around the polymer. For this reason, the concentration of cellulose in the aqueous solution or aqueous dispersion becomes thin, and it was necessary to remove a large amount of solvent in order to obtain a molded product from this aqueous solution or aqueous dispersion. Removal of solvents such as water requires a large amount of energy, and when molded from water, the molded product is vulnerable to water and humidity. There was a problem of collapse.
そこで、本発明は天然資源を利用した高分子の成形体を少ないエネルギーで効率よく溶媒を除去し、成形物を形成する方法と成形物を提供することを目的としている。更に、水や湿度に強い成形物を提供することにある。 Accordingly, an object of the present invention is to provide a method and a molded product for forming a molded product by efficiently removing a solvent from a polymer molded product using natural resources with less energy. Furthermore, it is providing the molded product strong against water and humidity.
上記の課題を解決するための手段として、請求項１に記載の発明は、多孔質基材の表面に、１または２以上の溶媒と１または２以上の高分子とを含む液を接触させる工程と、前記多孔質基材により前記溶媒を除去して成形物を形成する工程とを具備することを特徴とする成形物の製造方法である。 As means for solving the above problems, the invention according to claim 1 is a step of bringing a liquid containing one or more solvents and one or more polymers into contact with the surface of the porous substrate. And a step of forming the molded product by removing the solvent with the porous base material.
また、請求項２に記載の発明は、前記多孔質基材により前記溶媒を除去することで、前記液の固形分濃度を４％以上にして成形物を形成する工程を具備することを特徴とする請求項１に記載の成形物の製造方法である。 The invention according to claim 2 comprises a step of forming a molded product by removing the solvent by the porous base material so that the solid content concentration of the liquid is 4% or more. The method for producing a molded product according to claim 1.
また、請求項３に記載の発明は、形成された前記成形物を前記多孔質基材から剥離する工程を具備することを特徴とする請求項１または２に記載の成形物の製造方法である。 The invention according to claim 3 is a method for producing a molded article according to claim 1 or 2, further comprising a step of peeling the formed molded article from the porous substrate. .
また、請求項４に記載の発明は、形成された前記成形物を乾燥する工程を具備することを特徴とする請求項１から３のいずれかに記載の成形物の製造方法である。 The invention according to claim 4 is the method for producing a molded product according to any one of claims 1 to 3, further comprising a step of drying the formed molded product.
また、請求項５に記載の発明は、形成された前記成形物を洗浄する工程を具備することを特徴とする請求項１から４のいずれかに記載の成形物の製造方法である。 The invention according to claim 5 is the method for producing a molded article according to any one of claims 1 to 4, further comprising a step of washing the formed molded article.
また、請求項６に記載の発明は、前記高分子が、短軸方向が１ｎｍ以上５００ｎｍ以下、長軸方向が５００ｎｍ以上１０００μｍ以下の繊維状高分子を含むことを特徴とする請求項１から５のいずれかに記載の成形物の製造方法である。 The invention according to claim 6 is characterized in that the polymer includes a fibrous polymer having a minor axis direction of 1 nm to 500 nm and a major axis direction of 500 nm to 1000 μm. The method for producing a molded product according to any one of the above.
また、請求項７に記載の発明は、前記高分子がカルボキシル基を含むことを特徴とする請求項１から６のいずれかに記載の成形物の製造方法である。 The invention according to claim 7 is the method for producing a molded article according to any one of claims 1 to 6, wherein the polymer contains a carboxyl group.
また、請求項８に記載の発明は、前記高分子が１分子または１ファイバー中に複数のカルボキシル基を含むことを特徴とする請求項７に記載の成形物の製造方法である。 The invention according to claim 8 is the method for producing a molded product according to claim 7, wherein the polymer contains a plurality of carboxyl groups in one molecule or one fiber.
また、請求項９に記載の発明は、前記高分子が０．１ｍｍｏｌ／ｇ以上６．０ｍｍｏｌ／ｇ以下のカルボキシル基を含むことを特徴とする請求項７または８に記載の成形物の製造方法である。 The invention according to claim 9 is the method for producing a molded article according to claim 7 or 8, wherein the polymer contains a carboxyl group of 0.1 mmol / g or more and 6.0 mmol / g or less. It is.
また、請求項１０に記載の発明は、前記高分子がセルロースまたは改質セルロースであることを特徴とする請求項１から９のいずれかに記載の成形物の製造方法である。 The invention according to claim 10 is the method for producing a molded product according to any one of claims 1 to 9, wherein the polymer is cellulose or modified cellulose.
また、請求項１１に記載の発明は、前記セルロースが結晶性セルロースであることを特徴とする請求項１０に記載の成形物の製造方法である。 The invention according to claim 11 is the method for producing a molded article according to claim 10, wherein the cellulose is crystalline cellulose.
また、請求項１２に記載の発明は、前記溶媒が水であることを特徴とする請求項１から１１のいずれかに記載の成形物の製造方法である。 The invention according to claim 12 is the method for producing a molded article according to any one of claims 1 to 11, wherein the solvent is water.
また、請求項１３に記載の発明は、前記多孔質基材が水中でイオン化しうる二価以上の陽イオンを含むことを特徴とする請求項１から１２のいずれかに記載の成形物の製造方法である。 The invention according to claim 13 is the production of the molded article according to any one of claims 1 to 12, wherein the porous substrate contains a divalent or higher cation that can be ionized in water. Is the method.
また、請求項１４に記載の発明は、前記多孔質基材が石膏であることを特徴とする請求項１から１３のいずれかに記載の成形物の製造方法である。 The invention according to claim 14 is the method for producing a molded product according to any one of claims 1 to 13, wherein the porous substrate is gypsum.
また、請求項１５に記載の発明は、前記成形物を洗浄する工程が、前記成形体を０．１Ｎから１Ｎの酸に１５〜５０℃の温度で浸漬する工程であることを特徴とする請求項１３または１４に記載の成形物の製造方法である。 The invention according to claim 15 is characterized in that the step of cleaning the molded product is a step of immersing the molded product in a 0.1N to 1N acid at a temperature of 15 to 50 ° C. Item 15. A method for producing a molded article according to Item 13 or 14.
また、請求項１６に記載の発明は、前記多孔質基材が連続表面を持つことを特徴とする請求項１から１５のいずれかに記載の成形物の製造方法である。 The invention according to claim 16 is the method for producing a molded product according to any one of claims 1 to 15, wherein the porous substrate has a continuous surface.
また、請求項１７に記載の発明は、請求項１から１６のいずれかに記載の製造方法で製造された成形物である。 The invention according to claim 17 is a molded article manufactured by the manufacturing method according to any one of claims 1 to 16.
また、請求項１８に記載の発明は、ナトリウム元素濃度が３％以下であることを特徴とする請求項１７に記載の成形物である。 The invention according to claim 18 is the molded article according to claim 17, wherein the sodium element concentration is 3% or less.
また、請求項１９に記載の発明は、カルシウム元素濃度が０．０１％以上２０％以下であることを特徴とする請求項１７または１８に記載の成形物である。 The invention according to claim 19 is the molded article according to claim 17 or 18, wherein the calcium element concentration is 0.01% or more and 20% or less.
また、請求項２０に記載の発明は、短軸方向が１ｎｍ以上５００ｎｍ以下、長軸方向が５００ｎｍ以上１０００μｍ以下の繊維状セルロースを含む成形物であって、前記繊維状セルロースが０．１ｍｍｏｌ／ｇ以上６．０ｍｍｏｌ／ｇ以下のカルボキシル基を含み、ナトリウム元素濃度が３％以下であることを特徴とする成形物である。 The invention according to claim 20 is a molded article containing fibrous cellulose having a minor axis direction of 1 nm to 500 nm and a major axis direction of 500 nm to 1000 μm, wherein the fibrous cellulose is 0.1 mmol / g. The molded product is characterized by containing a carboxyl group of 6.0 mmol / g or less and a sodium element concentration of 3% or less.
また、請求項２１に記載の発明は、カルシウム元素濃度が０．０１％以上２０％以下であることを特徴とする請求項２０に記載の成形物である。 The invention according to claim 21 is the molded article according to claim 20, wherein the calcium element concentration is 0.01% or more and 20% or less.
本発明によれば、水などの安全性の高い溶媒を用いながら、少ないエネルギーで効率よく成形物を得ることができ、また、水や湿度に強い成形体を得ることが可能となった。 According to the present invention, a molded product can be efficiently obtained with less energy while using a highly safe solvent such as water, and a molded product resistant to water and humidity can be obtained.
本発明を詳細に説明する。本発明の成形物の製造方法は、多孔質基材上に溶媒に溶解或いは分散させた高分子を含む液を接触させ、液の固形分濃度を４％以上に濃縮することで、高分子の成形物を得る製造方法である。この工程を経ることで、更に乾燥工程を経ても、従来の成形方法と比べ、成形物の形成のためのエネルギーを大きく減少させることができる。逆に、濃縮工程で固形分濃度が４％より小さいと、成形物の強度を保持し難く、また、その後乾燥工程を経る場合、溶媒の除去に従来と同じく大きなエネルギーを投入することになる。 The present invention will be described in detail. In the method for producing a molded article of the present invention, a liquid containing a polymer dissolved or dispersed in a solvent is contacted on a porous substrate, and the solid content concentration of the liquid is concentrated to 4% or more, thereby This is a production method for obtaining a molded product. By passing through this process, the energy for forming a molded product can be greatly reduced even after a drying process, as compared with the conventional molding method. On the other hand, if the solid content concentration is less than 4% in the concentration step, it is difficult to maintain the strength of the molded product, and when the drying step is performed thereafter, a large amount of energy is input to the solvent as in the conventional case.
多孔質基材上に溶媒に溶解或いは分散させた高分子を含む液を接触させる方法は、公知の方法を用いることができ、具体的には、多孔質基材又はロール状多孔質基材の表面に溶媒に溶解或いは分散させた高分子を含む液をキャスト、コーティング、型押し、鋳型成形する方法などが挙げられる。 As a method of bringing a liquid containing a polymer dissolved or dispersed in a solvent into contact with a porous substrate, a known method can be used. Specifically, a porous substrate or a roll-shaped porous substrate can be used. Examples thereof include a method of casting, coating, embossing and molding a liquid containing a polymer dissolved or dispersed in a solvent on the surface.
本発明の成形物の製造方法は、多孔質基材上に形成された成形物を多孔質基材から剥離する工程を有してもよい。多孔質基材により液の固形分濃度を４％以上に濃縮して形成した成形物は、液に含まれる高分子の種類によっては、固体物としてある程度の強度を保持することができる。このため、形成した成形物は、多孔質基材から剥離することが可能であり、剥離した成形物はその物性に応じてゲル状あるいは固形状でそのままの形状あるいは更にカレンダリング、エンボス、延伸、多孔化、成形などを行うことも可能で各種用途に適用することができる。 The method for producing a molded product of the present invention may include a step of peeling the molded product formed on the porous substrate from the porous substrate. A molded product formed by concentrating the solid content concentration of the liquid to 4% or more with a porous substrate can retain a certain degree of strength as a solid depending on the type of polymer contained in the liquid. For this reason, the formed product can be peeled off from the porous substrate, and the peeled formed product is in a gel or solid form as it is or further calendered, embossed, stretched, depending on its physical properties. It can also be made porous and molded, and can be applied to various applications.
また、本発明の成形物の製造方法は、多孔質基材上に形成された成形物を乾燥する工程を有してもよい。液の固形分濃度は多孔質基材により４％以上に濃縮することができるので、それ以上に液を濃縮して固形分濃度を調整したい場合や、成形物の強度を調整したい場合に、乾燥工程を経ることで液の固形分濃度や成形物の強度を調整することができる。 Moreover, the manufacturing method of the molding of this invention may have the process of drying the molding formed on the porous base material. The solid content concentration of the liquid can be concentrated to 4% or more by the porous substrate, so if you want to adjust the solid content concentration by further concentrating the liquid, or if you want to adjust the strength of the molded product, dry By passing through the process, the solid content concentration of the liquid and the strength of the molded product can be adjusted.
また、本発明の成形物の製造方法は、形成された成形物を洗浄する工程を有してもよい。多孔質基材の材質によっては、形成された成形物の表面に異物等が付着する場合がある。このような場合に形成された成形物を洗浄する工程を経ることで、成形物の表面に付着した異物を除去することが可能である。 Moreover, the manufacturing method of the molding of this invention may have the process of wash | cleaning the formed molding. Depending on the material of the porous substrate, foreign matter or the like may adhere to the surface of the formed molded product. By passing through the step of washing the molded product formed in such a case, it is possible to remove foreign matter adhering to the surface of the molded product.
本発明の剥離工程、乾燥工程、洗浄工程は必要に応じて行えばよく、高分子の含有量の高いままのゲル状のような成形物を得る場合は、濃縮工程のみの状態をとることもでき、また、ゲルを更にアルコールなどの溶媒中に投入することで多孔質な成形物を得ることも可能である。 The peeling step, the drying step, and the washing step of the present invention may be performed as necessary. When obtaining a gel-like molded product with a high content of the polymer, it may take only the concentration step. It is also possible to obtain a porous molded article by putting the gel in a solvent such as alcohol.
剥離工程、乾燥工程、洗浄工程は、多孔質基材の表面に成形物を形成する工程を経た後であれば、どのような順序で各工程を経てもよく、形成された成形物の物性や成形物の用途に応じて適宜順序を選択することができる。 The peeling process, the drying process, and the washing process may be performed in any order as long as the process of forming a molded product on the surface of the porous substrate is performed. The order can be appropriately selected according to the use of the molded product.
本発明の多孔質基材は、主に溶媒を除去し、固形分濃度を濃縮するための基材である。多孔質基材の孔径は、溶媒が通る大きさがあれば特に限定されないが、例えば、数ｎｍから数ｍｍの無数の孔が空いている基材などを用いることができる。孔径は、大きいと目詰まりもしにくく、効率的な溶媒の除去が可能となるが、高分子物質の抜けが多くなり、成形物の表面平滑性に劣る傾向がある。また、孔径は成形物の表面形状にも影響してくる。しかし、多孔質基材と高分子間の相互作用などによっても変わってくるので、基材・高分子・溶媒の種類と量、用途に合わせて適宜選択することが可能である。 The porous substrate of the present invention is a substrate for mainly removing the solvent and concentrating the solid content concentration. The pore diameter of the porous substrate is not particularly limited as long as it has a size through which the solvent can pass. For example, a substrate having innumerable pores of several nm to several mm can be used. If the pore size is large, clogging is difficult and efficient solvent removal is possible, but there is a tendency for the polymer substance to escape more frequently and the surface smoothness of the molded product to be inferior. The hole diameter also affects the surface shape of the molded product. However, since it varies depending on the interaction between the porous substrate and the polymer, it can be appropriately selected according to the type and amount of the substrate / polymer / solvent and the application.
例えば、１ｎｍから１００μｍの範囲が高分子の抜けや濃縮の効率から見て好ましく、更には５００ｎｍから５μｍの孔径であると、高分子繊維の抜けが小さい上、目詰まりもしにくく、また濃縮の効率もよいため好ましい。 For example, the range of 1 nm to 100 μm is preferable from the viewpoint of polymer removal and concentration efficiency. Furthermore, when the pore size is 500 nm to 5 μm, the removal of polymer fibers is small and clogging is difficult, and the concentration efficiency is high. Since it is good, it is preferable.
本発明の多孔質基材による溶媒の除去方法は、孔による毛細管現象あるいは孔内の溶媒との親和性によって、溶媒が多孔質基材の孔内に取り込まれるが、外力を加えて強制的に溶媒を多孔質基材の孔内に取り込むことも可能である。例えば、多孔質基材の表側から圧力をかけて溶媒を孔内に押し込んだり、多孔質基材の裏側を陰圧にすることで溶媒を孔内に引き込んだりすることもできる。このように外力を加えて強制的に溶媒を多孔質基材の孔内に取り込むことで、短時間で液の固形分濃度を上げることができる。 The solvent removal method using the porous substrate of the present invention is that the solvent is taken into the pores of the porous substrate due to the capillary phenomenon due to the pores or the affinity with the solvent in the pores. It is also possible to incorporate the solvent into the pores of the porous substrate. For example, the solvent can be pushed into the pores by applying pressure from the front side of the porous substrate, or the solvent can be drawn into the pores by setting the back side of the porous substrate to a negative pressure. Thus, by applying an external force and forcibly taking the solvent into the pores of the porous substrate, the solid content concentration of the liquid can be increased in a short time.
また、多孔質基材の材質は、有機、無機あるいは有機無機の複合体から選ぶことが出来る。有機多孔質基材を用いる場合、基材にフレキシビリティーを持たすことが容易であるというメリットがあり、連続シート状の基材を用いて連続フィルムなどを形成することもできる。また、無機多孔質基材を用いる場合、基材の環境負荷やコストを抑えることができる。 The material of the porous substrate can be selected from organic, inorganic or organic-inorganic composites. When an organic porous substrate is used, there is a merit that it is easy to give flexibility to the substrate, and a continuous film or the like can be formed using a continuous sheet-like substrate. Moreover, when using an inorganic porous base material, the environmental load and cost of a base material can be suppressed.
特に、後述する高分子にカルボキシル基やカルボキシル基ナトリウム塩など多価の陽イオンと交換し、無数のイオン結合を形成することが出来る材料を用いた場合、多孔質基材に、カルシウム、マグネシウム、亜鉛、アルミニウム、ストロンチウム、バリウム、チタン、コバルト、シリカ、銅、銀、金、白金或いは多価アミンなどの水中でイオン化しうる二価以上の陽イオンを含むものを用いることで、更に、本発明の１つの目的でもある耐水・耐湿成形物を容易に得ることが可能である。 In particular, when using a material capable of forming a myriad of ionic bonds by exchanging with a polyvalent cation such as a carboxyl group or a carboxyl group sodium salt for the polymer described later, calcium, magnesium, By using a material containing a divalent or higher cation that can be ionized in water, such as zinc, aluminum, strontium, barium, titanium, cobalt, silica, copper, silver, gold, platinum or polyvalent amine, the present invention It is possible to easily obtain a water / moisture resistant molded product which is also one of the purposes.
有機多孔質基材の材質は、具体的には、木粉やパルプ、セルロースやセルロース誘導、キチン、キトサンなどの多糖類体、ポリテトラフルオロエチレン、ポリエチレンやポリプロピレンなどのポリオレフィン、ポリビニルアルコール、エチレンビニルアルコール共重合体、ポリアクリル酸、ポリスチレン、ポリエチレンテレフタレート、ポリ乳酸などのポリエステル、エチレンブタジエン共重合体などのエラストマー樹脂、エポキシ樹脂などを例として挙げることができる。これらの材質は単体で用いてもよく、また、複数組み合わせて用いてもよい。 Specifically, the material of the organic porous substrate is wood flour or pulp, cellulose or cellulose derivative, polysaccharides such as chitin or chitosan, polyolefin such as polytetrafluoroethylene, polyethylene or polypropylene, polyvinyl alcohol, ethylene vinyl. Examples include alcohol copolymers, polyacrylic acid, polystyrene, polyethylene terephthalate, polyesters such as polylactic acid, elastomer resins such as ethylene butadiene copolymers, and epoxy resins. These materials may be used alone or in combination.
一方、無機多孔質基材の材質は、具体的には、石膏、メソポーラスシリカ、ゼオライト、酸化チタン、アパタイトその他多孔質セラミックスなどを例として挙げることができる。安価で形状が作りやすく、吸水性が高いという点から石膏を用いるとよい。 On the other hand, specific examples of the material of the inorganic porous substrate include gypsum, mesoporous silica, zeolite, titanium oxide, apatite, and other porous ceramics. Gypsum is preferably used because it is inexpensive, easy to make, and has high water absorption.
石膏は、硫酸カルシウムの各水和物および無水物をいい、通常、型取り・鋳込み成形には硫酸カルシウム半水和物と水で反応生成した硫酸カルシウム二水和物の型が用いられている。この硫酸カルシウム二水和物は水中でカルシウムイオンを放出する。本発明のような水に分散させたセルロースナノファイバーのように、カルボキシル基のナトリウム塩などを含む物質が接触すると、カルボキシル基のナトリウム塩とカルシウム塩が交換し、理想的には２つのカルボキシル基に１つのカルシウム塩により、架橋する。こうして成形した成形物は、再度水や水蒸気と接触しても、膨潤・溶解が抑えられる。また、石膏は無数の孔が存在しており、水などの溶媒を効率的に除去することが可能となる。この濃縮の際に、通常のポリマーなどでは孔を通りぬけようとするものが多く、目詰まりの原因となる上、成形物としての収率が低くなってしまう。しかし、セルロースナノファイバーのようなものは、幅はナノオーダーで小さくても、アスペクト比があり、長さ方向は大きい。また、特にカルボキシル基を有しているため、石膏と触れた界面でカルボキシル基カルシウム塩が生成し、石膏表面に残るものが多い。 Gypsum refers to calcium sulfate hydrates and anhydrides. Usually, calcium sulfate hemihydrate and calcium sulfate dihydrate produced by reaction with water are used for molding and casting. . This calcium sulfate dihydrate releases calcium ions in water. When a substance containing a sodium salt of a carboxyl group comes into contact with a cellulose nanofiber dispersed in water as in the present invention, the sodium salt and the calcium salt of the carboxyl group are exchanged, and ideally two carboxyl groups Crosslink with one calcium salt. The molded product thus molded can be prevented from swelling / dissolving even if it comes into contact with water or water vapor again. In addition, gypsum has innumerable pores, and it is possible to efficiently remove a solvent such as water. During this concentration, many ordinary polymers or the like try to pass through the pores, causing clogging and lowering the yield as a molded product. However, a cellulose nanofiber or the like has an aspect ratio and a large length direction even if the width is small on the nano order. Moreover, since it has especially a carboxyl group, a carboxyl group calcium salt produces | generates in the interface which touched gypsum, and many remain | survive on the gypsum surface.
多孔質基材に石膏を用いた場合、成形物の表面に石膏の粒子が付着することがある。この場合、上述した洗浄工程を経ることで成形物の表面に付着した石膏の粒子を除去することが可能であるが、特に、成形体を０．１Ｎから１Ｎの酸に１５〜５０℃の温度で浸漬することが好ましい。 When gypsum is used for the porous substrate, gypsum particles may adhere to the surface of the molded product. In this case, it is possible to remove the gypsum particles adhering to the surface of the molded product through the above-described washing step, and in particular, the molded product is made from 0.1N to 1N acid at a temperature of 15 to 50 ° C. It is preferable to immerse in.
また、多孔質基材に柔軟性があれば連続シート状の形状をとることで、あるいは多孔質基材に柔軟性がなければロール状などの形状をとることで、いずれにしても連続表面をもつ形状をとることで、成形物の連続的な形成が可能となる。これにより、連続フィルムなどの成形物を得ることができる。 Also, if the porous substrate is flexible, it can take a continuous sheet shape, or if the porous substrate is not flexible, it can take a roll shape, etc. By taking the shape, the molded product can be continuously formed. Thereby, molded articles, such as a continuous film, can be obtained.
また、成形物の成形性、密着性、離型性、表面平滑性などを付与するため、あるいは多孔質基材の表面強化などを付与するため各種表面処理を施すことが可能である。 In addition, various surface treatments can be applied to impart moldability, adhesion, mold release, surface smoothness, and the like of the molded product, or to impart surface enhancement of the porous substrate.
表面処理としては、具体的には、コロナ処理、プラズマ処理、グロ−放電処理、フレーム処理、ＵＶオゾン処理、低温プラズマ処理、エキシマレーザー光又はＡｒＦエキシマレーザー光による処理、樹脂などのコーティングなどが挙げられる。 Specific examples of the surface treatment include corona treatment, plasma treatment, glow discharge treatment, flame treatment, UV ozone treatment, low-temperature plasma treatment, treatment with excimer laser light or ArF excimer laser light, coating with resin, and the like. It is done.
次に、本発明の高分子について説明する。本発明の高分子はポリビニルアルコール、ポリオエチレンオキシド、ポリアミン、ポリアクリル酸などの合成高分子でもよいが、本発明の１つの目的である天然資源を利用した高分子であることが好ましい。また、絶対存在量の多さ、コスト、利用しやすさなどの点から澱粉やキチン・キトサン、セルロースなどの天然多糖類を原料に用いた高分子であるとより好ましい。中でも、セルロースや、再生セルロース、酢酸セルロース、カルボキシメチルセルロース、メチルセルロースなどの改質セルロース系材料が好ましい。 Next, the polymer of the present invention will be described. The polymer of the present invention may be a synthetic polymer such as polyvinyl alcohol, polyethylene oxide, polyamine, or polyacrylic acid, but is preferably a polymer utilizing natural resources, which is one object of the present invention. Moreover, it is more preferable that it is a polymer using natural polysaccharides such as starch, chitin / chitosan, and cellulose as raw materials from the standpoints of absolute abundance, cost, and ease of use. Among these, modified cellulose materials such as cellulose, regenerated cellulose, cellulose acetate, carboxymethylcellulose, and methylcellulose are preferable.
また、本発明の高分子にセルロースや改質セルロースを用いた場合、これらのセルロースは結晶性セルロースであることが好ましい。結晶性が高いと成形物表面および全体の強度や、耐水性、熱安定性が向上する。 Moreover, when cellulose or modified cellulose is used for the polymer of the present invention, these celluloses are preferably crystalline cellulose. If the crystallinity is high, the surface of the molded product and the overall strength, water resistance and thermal stability are improved.
また、本発明の高分子は、カルボキシル基を持つ多糖類がイオン交換により多価陽イオンと架橋して耐水性・耐湿性を向上させることができる点から好ましい。多糖類へのカルボキシル基導入の改質については、成形物を生体材料などに用いる場合や、より緻密な膜を形成し、ガスバリア性を向上させたい場合など、用途により、導入した官能基が機能発現の阻害要因となることがない改質処方が好ましい。このような改質処方として、Ｎ−オキシル化合物を用いた水系の酸化処理により、多糖類のピラノース環のＣ６位の水酸基のみをカルボキシル基に変換する処方を挙げることができる。このＮ−オキシル化合物を用いた酸化多糖類は安全な試薬により改質処理が行われている点、緻密な膜を形成することが出来るため、成形物の表面強度、成形のしやすさの点から好ましい。 In addition, the polymer of the present invention is preferable because a polysaccharide having a carboxyl group can be cross-linked with a polyvalent cation by ion exchange to improve water resistance and moisture resistance. Regarding the modification of the introduction of carboxyl groups into polysaccharides, the functional group introduced functions depending on the application, such as when moldings are used for biomaterials or when it is desired to form a denser film and improve gas barrier properties. A modified prescription that does not become an inhibitor of expression is preferred. As such a modified prescription, a prescription in which only the hydroxyl group at the C6 position of the pyranose ring of the polysaccharide is converted into a carboxyl group by an aqueous oxidation treatment using an N-oxyl compound can be mentioned. The oxidized polysaccharide using this N-oxyl compound is modified with a safe reagent, and can form a dense film. Therefore, the surface strength of the molded product and the ease of molding can be obtained. To preferred.
また、天然のセルロースやキチンを用いてこれらの処理を行い、続いて微細化の処理を行うことで、ナノファイバーを得ることが知られているが、このナノファイバーは原料調製の環境負荷が小さいことに加え、高い結晶性とある範囲の均一な大きさを有するため、本発明の高分子としてナノファイバーを用いることは、成形物表面および全体の強度と柔軟性、耐水性、熱安定性という点から好ましい。 In addition, it is known that nanofibers can be obtained by performing these treatments using natural cellulose or chitin, followed by miniaturization, but these nanofibers have a low environmental impact in raw material preparation. In addition, since it has high crystallinity and a uniform size within a certain range, the use of nanofibers as the polymer of the present invention means that the surface of the molded product and the overall strength and flexibility, water resistance, and heat stability. It is preferable from the point.
本発明の高分子は、短軸方向１ｎｍ以上５００ｎｍ以下、長軸方向が５００ｎｍ以上１０００μｍ以下の繊維状高分子を含むことを特徴としている。これは多くの高分子の場合、分子が単分散しているのではなく、ある単位で分子間力・水素結合・共有結合などでまとまった繊維状をしていることを意味しており、天然セルロースなどの場合、これは結晶構造をもつミクロフィブリルなどがこれにあたる。このある程度の大きさと短軸と長軸を持つことで、孔の大きさが分子や繊維の大きさより遥かに大きくても、抜けが少なく収率良く、また良好な形状の成形物を得ることができる。 The polymer of the present invention includes a fibrous polymer having a minor axis direction of 1 nm to 500 nm and a major axis direction of 500 nm to 1000 μm. This means that in many macromolecules, the molecules are not monodispersed but in a unitary fibrous form with intermolecular forces, hydrogen bonds, covalent bonds, etc. In the case of cellulose or the like, this is a microfibril having a crystal structure. By having this certain size, short axis and long axis, even if the pore size is much larger than the size of the molecule or fiber, there is little loss and good yield and a molded product with a good shape can be obtained. it can.
また、本発明の高分子は、カルボキシル基を含むことを特徴としている。カルボキシル基が導入されていることで、水などの溶液・分散液にしたときの分散性が良く、良好な表面や形状の成形が可能になる。高分子中にカルボキシル基を含むことで、イオン交換により多価陽イオンと架橋して耐水性・耐湿性を向上させることができる点から好ましい。特に、本発明の高分子は、１分子または１ファイバー中に複数のカルボキシル基を含むことが好ましい。なお、１ファイバーとは高分子が溶媒などの中で分散しうる１つの集合体・単位のことをいい、１分子でも、あるいは複数の分子が集まり集合体を成していても良い。 The polymer of the present invention is characterized by containing a carboxyl group. By introducing a carboxyl group, the dispersibility when it is made into a solution or dispersion such as water is good, and it becomes possible to form a good surface and shape. By including a carboxyl group in the polymer, it is preferable from the viewpoint that it can be cross-linked with a polyvalent cation by ion exchange to improve water resistance and moisture resistance. In particular, the polymer of the present invention preferably contains a plurality of carboxyl groups in one molecule or one fiber. One fiber means one aggregate / unit in which a polymer can be dispersed in a solvent or the like, and one molecule or a plurality of molecules may gather to form an aggregate.
本発明の高分子は、高分子に含まれるカルボキシル基の量が、０．１ｍｍｏｌ／ｇ以上６．０ｍｍｏｌ／ｇ以下であることが好ましい。０．１ｍｍｏｌ／ｇ以下であると、陽イオンと交換する点が少なく、架橋点が少なく、耐水性・耐湿性向上の効果が薄い。また、６．０ｍｍｏｌ／ｇより大きいと接触させただけでの陽イオンとの交換が不十分であるなどの理由で、交換せずに残るカルボキシル基やナトリウム塩の量が多いため、耐水性・耐湿性の向上が不十分で、成形物の水による膨潤などが大きくなってしまう。耐水性・耐湿性の向上、および成形物の形状などの観点からは、０．１ｍｍｏｌ／ｇ以上２．５ｍｍｏｌ／ｇ以下であるとより好ましく、更に耐熱性などの観点からは０．１ｍｍｏｌ／ｇ以上１．７ｍｍｏｌ／ｇ以下であるとより好ましい。 In the polymer of the present invention, the amount of carboxyl groups contained in the polymer is preferably 0.1 mmol / g or more and 6.0 mmol / g or less. When it is 0.1 mmol / g or less, there are few points to exchange with cations, there are few crosslinking points, and the effect of improving water resistance and moisture resistance is small. In addition, if the amount is larger than 6.0 mmol / g, the amount of carboxyl groups and sodium salts remaining without exchange is large due to insufficient exchange with cations just by contacting them. The improvement in moisture resistance is insufficient, and the swelling of the molded product with water increases. From the viewpoints of improvement in water resistance and moisture resistance and the shape of the molded product, it is more preferably 0.1 mmol / g or more and 2.5 mmol / g or less, and further from the viewpoint of heat resistance or the like, 0.1 mmol / g More preferably, it is 1.7 mmol / g or less.
また、本発明に用いられる溶媒は、成形際に及ぼす環境への影響を少しでも少なくするという観点、多孔質基材との接触によりイオン化しうる二価以上の陽イオンを取り込み、耐水化・耐湿化ができると言う点から、水や、水を含む溶媒であることが好ましい。 In addition, the solvent used in the present invention incorporates a divalent or higher cation that can be ionized by contact with the porous base material in order to reduce the environmental impact during molding as much as possible. From the point that it can be converted, water or a solvent containing water is preferable.
前述のＮ−オキシル化合物を用いた酸化処理と微細化により調製したセルロースナノファイバーは、カルボキシル基を有し、かつナトリウム塩を形成している。例えば、本発明の高分子としてナノファイバーを用いる場合、多孔質基材に石膏を用いて本発明の成形物の製造方法により形成した成形物は、カルボキシル基のナトリウム塩が水溶液中で石膏のカルシウム塩と置き換わり、イオン交換が起こり、カルボキシル基のカルシウム塩を形成した成形物が得られる。イオン交換は、セルロース水溶液と石膏の界面で頻繁に起こるため、石膏へのセルロースナノファイバーの浸透が抑えられ、水と交換したナトリウム塩が石膏に吸収される。濃縮の途中でも水がセルロースナノファイバーの周りに存在しているため、界面のみでなく、内部でもイオン交換が起こる。そのため、例えば３０μｍ程度のフィルムを成形したとき、フィルムの石膏面だけでなく、石膏に直接接していない面においても、ナトリウムイオンが減少していることが確認できる。 Cellulose nanofibers prepared by oxidation treatment and refinement using the aforementioned N-oxyl compound have a carboxyl group and form a sodium salt. For example, when nanofibers are used as the polymer of the present invention, the molding formed by the method of manufacturing the molding of the present invention using gypsum as the porous substrate has a sodium salt of carboxyl group in the aqueous solution of gypsum calcium. By replacing the salt, ion exchange occurs, and a molded product in which a calcium salt of a carboxyl group is formed is obtained. Since ion exchange frequently occurs at the interface between the aqueous cellulose solution and gypsum, the penetration of cellulose nanofibers into the gypsum is suppressed, and the sodium salt exchanged with water is absorbed into the gypsum. Even during concentration, water is present around the cellulose nanofibers, so that ion exchange occurs not only at the interface but also inside. Therefore, for example, when a film of about 30 μm is formed, it can be confirmed that sodium ions are reduced not only on the gypsum surface of the film but also on the surface not in direct contact with the gypsum.
本発明の成形物に含まれる元素分析法としては各種手法が適用できるが、ＩＣＰ，ＥＳＣＡ，ＥＰＭＡ（ＥＤＸ，ＷＤＸ）などの手法を用いてイオン交換されていることを確認できるが、ＥＰＭＡにおいては固体サンプルのまま簡便に測定が行える。 Although various methods can be applied as the elemental analysis method contained in the molded product of the present invention, it can be confirmed that ion exchange is performed using a method such as ICP, ESCA, EPMA (EDX, WDX). Measurements can be made simply as a solid sample.
本発明の成形物は、ナトリウム元素濃度が３％以下であることが好ましい。ナトリウム元素濃度が３％以下であることによって本発明の目的のひとつである耐水性や耐湿性が格段に向上する。また、電子部材、生態適合性材料など特殊な用途への利用が広がる。 The molded product of the present invention preferably has a sodium element concentration of 3% or less. When the sodium element concentration is 3% or less, water resistance and moisture resistance, which are one of the objects of the present invention, are remarkably improved. In addition, the use for special applications such as electronic parts and biocompatible materials will be expanded.
また、本発明の成形物は、カルシウム元素濃度が１％以上２０％以下であることが好ましい。カルシウム元素濃度が０．５％以上２０％以下であることによって、耐水性・耐湿性が向上する上、生体適合性材料・細胞培地などへの利用が期待できる。 In the molded product of the present invention, the calcium element concentration is preferably 1% or more and 20% or less. When the calcium element concentration is 0.5% or more and 20% or less, water resistance and moisture resistance are improved, and utilization to biocompatible materials and cell culture media can be expected.
なお、セルロースナノファイバーを通常の方法によりキャストし、そのＥＰＭＡを測定すると、ナトリウムが元素濃度で２から７％検出され、カルシウムは検出されない。一方、石膏を多孔質基材に用いて成形したフィルムからは０．１から１．５％のナトリウムが検出され、カルシウムは１．２から７％検出される。また、得られた成形物を洗浄した後の成形物表面からは、ナトリウムは更に減少し、カルシウムも０．５から６％に減少することが確認できる。 In addition, when cellulose nanofibers are cast by a normal method and the EPMA is measured, sodium is detected in an element concentration of 2 to 7%, and calcium is not detected. On the other hand, 0.1 to 1.5% sodium is detected and 1.2 to 7% calcium is detected from a film formed using gypsum as a porous substrate. Further, it can be confirmed that sodium is further reduced and calcium is reduced from 0.5 to 6% from the surface of the molded product after the obtained molded product is washed.
本発明の成形物は、具体的には、ゲル、フィルム、シート、多孔質シート、筒状、ボトル、針状、繊維状、リボン状などが挙げられる。 Specific examples of the molded product of the present invention include gels, films, sheets, porous sheets, cylinders, bottles, needles, fibers, and ribbons.
以下、実施例を用いて本発明を更に詳細に説明する。 Hereinafter, the present invention will be described in more detail with reference to examples.
＜製造例＞
針葉樹クラフトパルプ３０ｇを水６００ｇに浸漬し、ミキサーにて分散させた。分散後のパルプスラリーにあらかじめ水２００ｇに溶解させたＴＥＭＰＯを０．３ｇ、ＮａＢｒを３ｇ添加し、更に水で希釈し全体を１４００ｍＬとした。系内を２０℃に保ち、セルロース１ｇに対し１０ｍｍｏｌになるよう次亜塩素酸ナトリウム水溶液を計りとり、３０分で滴下した。滴下開始からｐＨは低下を始めるが、０．５Ｎ水酸化ナトリウム水溶液を用いてｐＨを１０に保つ。２時間後、０．５Ｎ水酸化ナトリウムが２．５ｍｍｏｌ／ｇになったところでエタノールを３０ｇ添加し、反応を停止させた。反応系に０．５Ｎ塩酸を添加し、ｐＨ２まで低下させた。酸化パルプをろ過し、０．０１Ｎ塩酸または水で繰返し洗浄した後、酸化パルプを得た。得られた酸化パルプを水で希釈し水酸化ナトリウム水溶液を用いてｐＨ８の１％分散液を得た。超音波ホモジナイザーで２０分間処理し、ｐＨ８の透明な１％セルロースナノファイバー水溶液を得た。
<Production example>
30 g of softwood kraft pulp was immersed in 600 g of water and dispersed with a mixer. 0.3 g of TEMPO and 3 g of NaBr previously dissolved in 200 g of water were added to the pulp slurry after dispersion, and the whole was further diluted with water to 1400 mL. The system was kept at 20 ° C., and a sodium hypochlorite aqueous solution was weighed so as to be 10 mmol with respect to 1 g of cellulose, and dropped in 30 minutes. The pH starts to decrease from the start of dropping, but the pH is kept at 10 using a 0.5N aqueous sodium hydroxide solution. Two hours later, when 0.5N sodium hydroxide reached 2.5 mmol / g, 30 g of ethanol was added to stop the reaction. 0.5N hydrochloric acid was added to the reaction system to lower the pH to 2. The oxidized pulp was filtered and washed repeatedly with 0.01N hydrochloric acid or water to obtain oxidized pulp. The obtained oxidized pulp was diluted with water to obtain a 1% dispersion having a pH of 8 using an aqueous sodium hydroxide solution. The mixture was treated with an ultrasonic homogenizer for 20 minutes to obtain a transparent 1% cellulose nanofiber aqueous solution having a pH of 8.
＜分析：カルボキシル基量測定＞
得られたナノファイバー水溶液の濃度を正確に測定した後、固形分で０．１ｇ相当を計り取り、０．２％濃度に希釈して、塩酸を添加することでｐＨ２とした後、０．１Ｎ水酸化ナトリウム水溶液を０．１ｍＬ／ｍｉｎの定速で注入しながら電導度を測定し、その変動からカルボキシル基により電導度が変動し難くなる領域を読み取り、カルボキシル基量を測定した。その結果、製造例で作成したセルロースナノファイバーのカルボキシル基量は１．６ｍｍｏｌ／ｇであった。得られたセルロースナノファイバー水溶液をスチレン容器の中で８０℃で乾燥させ、乾燥固形物を得た
<Analysis: Carboxyl group content measurement>
After accurately measuring the concentration of the obtained nanofiber aqueous solution, 0.1 g of the solid content was measured, diluted to 0.2% concentration and adjusted to pH 2 by adding hydrochloric acid, and then 0.1N The conductivity was measured while injecting an aqueous sodium hydroxide solution at a constant rate of 0.1 mL / min, and the region where the conductivity was less likely to vary due to carboxyl groups was read from the variation, and the amount of carboxyl groups was measured. As a result, the amount of carboxyl groups of the cellulose nanofiber prepared in Production Example was 1.6 mmol / g. The obtained cellulose nanofiber aqueous solution was dried in a styrene container at 80 ° C. to obtain a dry solid.
＜分析：結晶性＞
乾燥固形物のＸ線回折を測定した。セルロースナノファイバーはセルロースＩの結晶性を有することを確認した。
<Analysis: Crystallinity>
X-ray diffraction of the dried solid was measured. Cellulose nanofibers were confirmed to have cellulose I crystallinity.
＜分析：ナトリウム濃度＞
固形物のＥＰＭＡを測定した。ナトリウムが元素濃度で６．３％検出された。
<Analysis: Sodium concentration>
The EPMA of the solid was measured. Sodium was detected at an element concentration of 6.3%.
＜分析：繊維観察＞
ＳＥＭによりセルロースナノファイバーの乾燥固形物の観察を行った。繊維幅は１０ｎｍ、繊維長さは約５μｍであることが分かった。
<Analysis: Fiber observation>
The dry solid of the cellulose nanofiber was observed by SEM. It was found that the fiber width was 10 nm and the fiber length was about 5 μm.
＜実施例１＞
多孔質基材として石膏（サンエス石膏 特緑）を用いた。規定の量の水中に石膏を加え、手早くかき混ぜた後、筒状の型に流し込み石膏のロールを作成した。多孔質基材の上に製造例１の１％セルロースナノファイバー水溶液を載せ、圧力をかけてセルロースナノファイバー水溶液を濃縮させた。固形分濃度４％まで濃縮し、石膏からフィルム状の成形物を剥がした。自然乾燥により、膜厚１０μｍの実施例１の成形物を作製した。
<Example 1>
Gypsum (San-S gypsum special green) was used as the porous substrate. Gypsum was added to a specified amount of water, stirred rapidly, and then poured into a cylindrical mold to create a gypsum roll. The 1% cellulose nanofiber aqueous solution of Production Example 1 was placed on the porous substrate, and the cellulose nanofiber aqueous solution was concentrated under pressure. Concentrated to a solid content concentration of 4% and peeled off the film-like molded product from gypsum. A molded product of Example 1 having a thickness of 10 μm was produced by natural drying.
＜実施例２＞
実施例１と同様に石膏からセルロースナノファイバーフィルムを剥がし、０．１Ｎ塩酸水溶液に２５℃の温度で浸した。１０分後、取り出して８０度のオーブンで１晩乾燥させ、実施例２の成形物を作成した。
<Example 2>
In the same manner as in Example 1, the cellulose nanofiber film was peeled off from the gypsum and immersed in a 0.1N aqueous hydrochloric acid solution at a temperature of 25 ° C. After 10 minutes, the product was taken out and dried in an oven at 80 degrees overnight to produce a molded product of Example 2.
＜評価：元素濃度＞
実施例１および実施例２で作製した成形物のＥＰＭＡを測定した。実施例１は元素濃度でナトリウムが０．７％、カルシウムが３．６％であった。実施例２はナトリウムが０．１％、カルシウムが１．２％であった。
<Evaluation: Element concentration>
The EPMA of the moldings produced in Example 1 and Example 2 was measured. In Example 1, the element concentration was 0.7% for sodium and 3.6% for calcium. In Example 2, sodium was 0.1% and calcium was 1.2%.
＜評価：溶解性試験＞
製造例のセルロースナノファイバー、実施例１および実施例２で作製した成形物を、水、０．０１Ｎ水酸化ナトリウム水溶液、ｐＨ７．４の生理食塩水、０．０１Ｎ塩酸水溶液に浸漬した。３時間後形状を観察したところ、製造例のセルロースナノファイバーを単に乾燥させたものは水、水酸化ナトリウム水溶液中で崩壊あるいは溶解したが、実施例１の成形物は水あるいは水酸化ナトリウム水溶液中で膨潤したが、溶解あるいは崩壊は見られなかった。また、実施例２の成形物は水酸化ナトリウム水溶液中では膨潤したが、水、塩酸水溶液中では膨潤も見られなかった。
<Evaluation: Solubility test>
The cellulose nanofiber of Production Example, the molded product produced in Example 1 and Example 2, were immersed in water, 0.01N sodium hydroxide aqueous solution, pH 7.4 physiological saline, and 0.01N hydrochloric acid aqueous solution. When the shape was observed after 3 hours, the cellulose nanofiber of the production example was simply dried and disintegrated or dissolved in water and a sodium hydroxide aqueous solution, but the molded product of Example 1 was in water or a sodium hydroxide aqueous solution. Swelled but not dissolved or disintegrated. The molded product of Example 2 swelled in an aqueous sodium hydroxide solution, but no swelling was observed in water or an aqueous hydrochloric acid solution.
＜評価：透明性試験＞
得られた成形物の透明性を透過率により測定した。６６０ｎｍでの透過率は実施例１も実施例２も８５％以上を維持していた。
<Evaluation: Transparency test>
The transparency of the obtained molded product was measured by transmittance. The transmittance at 660 nm was maintained at 85% or more in both Example 1 and Example 2.
本発明の成形物の製造方法は、各種バリア材料、支持体、フィルター材料、生体適合性材料などへの適合可能な材料となる成形物の製造方法として用いることができる。 The method for producing a molded product of the present invention can be used as a method for producing a molded product that can be adapted to various barrier materials, supports, filter materials, biocompatible materials, and the like.
Claims (21)
前記多孔質基材により前記溶媒を除去して成形物を形成する工程と
を具備することを特徴とする成形物の製造方法。 Contacting the surface of the porous substrate with a liquid containing one or more solvents and one or more polymers,
And a step of forming the molded product by removing the solvent with the porous base material.
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