JP4041891B2 - Porous body forming material and method for producing porous body - Google Patents
Porous body forming material and method for producing porous body Download PDFInfo
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- JP4041891B2 JP4041891B2 JP2003330453A JP2003330453A JP4041891B2 JP 4041891 B2 JP4041891 B2 JP 4041891B2 JP 2003330453 A JP2003330453 A JP 2003330453A JP 2003330453 A JP2003330453 A JP 2003330453A JP 4041891 B2 JP4041891 B2 JP 4041891B2
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- 239000000463 material Substances 0.000 title claims description 35
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 83
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 41
- 239000001569 carbon dioxide Substances 0.000 claims description 41
- 229920001400 block copolymer Polymers 0.000 claims description 23
- 229920000642 polymer Polymers 0.000 claims description 21
- 239000011148 porous material Substances 0.000 claims description 20
- 229910052731 fluorine Inorganic materials 0.000 claims description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 7
- 239000011737 fluorine Substances 0.000 claims description 7
- 230000009477 glass transition Effects 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 230000008016 vaporization Effects 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- 238000000034 method Methods 0.000 description 7
- 239000004793 Polystyrene Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000005187 foaming Methods 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- -1 Perfluoroheptyl Chemical group 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000013012 foaming technology Methods 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 125000005005 perfluorohexyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 description 1
- 125000005008 perfluoropentyl group Chemical group FC(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)* 0.000 description 1
- 125000005009 perfluoropropyl group Chemical group FC(C(C(F)(F)F)(F)F)(F)* 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Description
本発明は、超臨界状態の二酸化炭素を利用して直径１００ｎｍ以下の微細な空孔を形成するために用いる材料及び該材料を用いる多孔質体の製造方法に関する。 The present invention relates to a material used for forming fine pores having a diameter of 100 nm or less using carbon dioxide in a supercritical state and a method for producing a porous body using the material.
超臨界の二酸化炭素を用いた発泡技術は既に知られた技術である。たとえば、ポリスチレンの発泡の研究としてはＭａｃｒｏｍｏｌｅｃｕｌｅｓ ３１，４６１４（１９９８）など多数報告されている。その他のポリマーについても、同様の研究例が存在している。これまでの技術の概要は以下のものである。ポリマーに超臨界二酸化炭素を含有させ飽和状態にする。その後、急激な圧力の低下・温度の上昇等で、二酸化炭素の過飽和状態を作り出し、過飽和の二酸化炭素が発泡化するのを利用するものである。しかしながら、このような従来技術では、発泡の径は１ミクロン程度までしか低下させることができなかった。例えば、特開２００１−１５１９２４号公報（特許文献１）においては、共重合体を用いて発泡により形成されるセルのサイズを小さくすることが提案されているが、その実施例にあるように、従来法よりも小さなセルサイズが得られるものの、０．５μｍ（５００ｎｍ）程度までしか低下していない。 Foaming technology using supercritical carbon dioxide is already known. For example, many studies on foaming of polystyrene have been reported such as Macromolecules 31, 4614 (1998). Similar studies exist for other polymers. The outline of the technology so far is as follows. The polymer is saturated with supercritical carbon dioxide. After that, a supersaturated state of carbon dioxide is created by a sudden pressure drop or temperature rise, and the supersaturated carbon dioxide is used for foaming. However, with such a conventional technique, the diameter of the foam could only be reduced to about 1 micron. For example, in Japanese Patent Laid-Open No. 2001-151924 (Patent Document 1), it is proposed to reduce the size of a cell formed by foaming using a copolymer. As in the examples, Although a cell size smaller than that of the conventional method can be obtained, the cell size is reduced only to about 0.5 μm (500 nm).
また、試料の表面付近では二酸化炭素の拡散・蒸発により表面から二酸化炭素が放出されるため、発泡を生じない領域が存在していた。このために、薄いフィルムなどに応用することはできなかった。これは、二酸化炭素の過飽和・発泡のプロセスを用いる場合に不可避な現象である。 Further, in the vicinity of the surface of the sample, carbon dioxide is released from the surface due to the diffusion and evaporation of carbon dioxide, so that there is a region where foaming does not occur. For this reason, it could not be applied to thin films. This is an unavoidable phenomenon when using a process of supersaturation and foaming of carbon dioxide.
高分子に微細な空孔を作るその他の技術としては、ブロック共重合体のドメインをオゾンによって分解する方法、生分解による方法、熱による分解を用いる方法などが知られているが、分解物の除去などに問題があった。例えば、平２−１２７４００号公報においては、ブロックあるいはグラフト共重合体に親水性重合体を含有させ、溶媒等で除去することにより微細多孔質膜を得ることが提案されているが、セルが独立している場合などには応用できないことは容易に想像できる。 Other techniques for creating fine pores in polymers include methods of decomposing block copolymer domains with ozone, biodegradation methods, and thermal decomposition methods. There was a problem in removal. For example, in Japanese Patent Laid-Open No. 2-127400, it has been proposed that a fine porous film is obtained by adding a hydrophilic polymer to a block or graft copolymer and removing it with a solvent or the like. It can be easily imagined that it cannot be applied to such cases.
本発明は、超臨界の二酸化炭素により直径が０．１ミクロン（１００ｎｍ）以下の空孔を形成するための材料及び該材料を多孔質化するためのプロセスを提供することをその課題とする。 An object of the present invention is to provide a material for forming pores having a diameter of 0.1 microns (100 nm) or less with supercritical carbon dioxide, and a process for making the material porous.
本発明によれば、以下に示す多孔質体形成材料及び多孔質体の製造方法が提供される。 According to the present invention, the following porous body-forming material and method for producing a porous body are provided.
（１）超臨界の二酸化炭素により直径１００ｎｍ以下のみの空孔を形成するための多孔質体形成材料であって、超臨界二酸化炭素に溶解性を有する、含フッ素アルキル基を側鎖に持つポリマー鎖からなるブロック成分Ａと、超臨界二酸化炭素に溶解性を有しない、ビニル系モノマーから得られるポリマー鎖からなるブロック成分Ｂを有するブロック共重合体からなることを特徴とする多孔質体形成材料。
（２）上記（１）に記載の多孔質体形成材料に、超臨界の二酸化炭素を含浸させた後、該ブロック成分Ｂを構成するポリマー鎖の二酸化炭素含侵した状態でのガラス転移温度よりも低温に冷却した後、該材料に含浸浸されている二酸化炭素を気化させることを特徴とする、直径１００ｎｍ以下のみの空孔を有する多孔質体の製造方法。
(1) A porous material forming material for forming pores having a diameter of 100 nm or less with supercritical carbon dioxide, which is soluble in supercritical carbon dioxide and has a fluorine-containing alkyl group in the side chain A porous body-forming material comprising: a block component A comprising a chain; and a block copolymer having a block component B comprising a polymer chain obtained from a vinyl monomer that is not soluble in supercritical carbon dioxide. .
(2) From the glass transition temperature in a state where the polymer chain constituting the block component B is impregnated with carbon dioxide after impregnating the porous body-forming material according to (1) with supercritical carbon dioxide. A method for producing a porous body having pores having a diameter of not more than 100 nm, characterized by vaporizing carbon dioxide impregnated and immersed in the material after cooling to a low temperature.
本発明によれば、従来困難とされていた直径が１００ｎｍ以下の微細空孔を有する高分子多孔質体を容易に得ることができる。この多孔質体は、可視光に透明なものであり、透明な低密度材料や低誘電材料として応用することができる。
また、高強度で、低密度な材料としても応用される。連続孔を形成する場合には、フィルターとしての応用も期待される。
According to the present invention, it is possible to easily obtain a polymer porous body having fine pores having a diameter of 100 nm or less, which has been considered difficult conventionally. This porous body is transparent to visible light, and can be applied as a transparent low-density material or low-dielectric material.
It is also applied as a high-strength, low-density material. When forming continuous holes, application as a filter is also expected.
本発明の多孔質体形成材料は、超臨界の二酸化炭素に溶解性を有する少なくとも１つのブロック成分Ａと、超臨界の二酸化炭素に溶解性を有しない少なくとも１つのブロック成分Ｂを有する。この場合、前記ＣＯ２溶解性ブロック成分Ａは、３０００ｐｓｉの圧力下、温度３５℃の超臨界二酸化炭素に対する溶解度が０．１重量％以上、好ましくは１重量％以上溶解するブロック成分であることを意味する。その溶解度の上限値は、特に制約されないが、通常、１０重量％程度である。一方、前記ＣＯ２非溶解性ブロック成分Ｂは、３０００ｐｓｉの圧力下、温度３５℃の超臨界二酸化炭素に対する溶解度が０．１重量％未満のブロック成分であることを意味する。 The porous body-forming material of the present invention has at least one block component A that is soluble in supercritical carbon dioxide and at least one block component B that is not soluble in supercritical carbon dioxide. In this case, the CO 2 soluble block component A is a block component having a solubility in supercritical carbon dioxide at a temperature of 35 ° C. under a pressure of 3000 psi of 0.1 wt% or more, preferably 1 wt% or more. means. The upper limit of its solubility is not particularly limited, usually, is about 10% by weight. On the other hand, the CO 2 non-soluble block component B means a block component having a solubility in supercritical carbon dioxide at a temperature of 35 ° C. under a pressure of 3000 psi and less than 0.1 wt%.
共重合体を形成するブロック成分Ａにおいて、そのポリマー鎖の分子量は、数平均分子量で１０００〜１０００００００、好ましくは５０００〜５０００００である。一方、ブロック成分Ｂにおいて、そのポリマー鎖の分子量は、数平均分子量で１０００〜１０００００００、好ましくは５０００〜５０００００である。共重合体中において、ブロック成分Ａの体積分率は、０．０１〜０．７、好ましくは０．０５〜０．５である。 In the block component A forming the copolymer, the molecular weight of the polymer chain is 1,000 to 10,000,000, preferably 5,000 to 500,000 in terms of number average molecular weight. On the other hand, in the block component B, the molecular weight of the polymer chain is 1000 to 10000000, preferably 5000 to 500000 in terms of number average molecular weight. In the copolymer, the volume fraction of the block component A is 0.01 to 0.7, preferably 0.05 to 0.5.
ブロック成分Ａは、フッ素原子を含むポリマー鎖から構成される。フッ素原子を含むポリマー鎖としては、含フッ素アルキル基を側鎖に持つポリマー鎖（フルオロメタクリレートポリマー鎖、フルオロアルキル基をグラフトしたポリマー鎖等）が挙げられる。The block component A is composed of a polymer chain containing fluorine atoms. Examples of the polymer chain containing a fluorine atom include polymer chains having a fluorine-containing alkyl group as a side chain (fluoromethacrylate polymer chain, polymer chain grafted with a fluoroalkyl group, etc.).
ブロック共重合体の好ましい例としては、ビニルモノマー（スチレン、オレフィン等）とパーフルオロアルキル基を有するアクリル系モノマー（メタクリレート及び／又はアクリレート）とのブロック共重合体を示すことができる。共重合が可能であれば、特に限定されない。
また、本発明で好ましく用いられるブロック共重合体は、Ｍｃｒｏｍｏｌ．Ｓｙｍｐ． １９１，１３５（２００２）に記載の方法により、アニオン重合で合成された、Ｐｏｌｙ［ｓｔｙｒｅｎｅ−ｂ−４−（３−ｐｅｒｆｌｕｏｒｏｏｃｔｙｌ）ｐｒｏｐｏｘｙｓｔｙｒｅｎ］や、Ｐｏｌｙ［ｓｔｙｒｅｎｅ−ｂ−２−（ｐｅｒｆｌｕｏｒｏｏｃｔｙｌ）ｅｔｈｙｌ ｍｅｔｈａｃｒｙｌａｔｅ］、その他のフッ素含有ブロックコポリマー、例えば、Ｐｅｒｆｌｕｏｒｏｐｒｏｐｙｌ、Ｐｅｒｆｌｕｏｒｏｐｅｎｔｙｌ、Ｐｅｒｆｌｕｏｒｏｈｅｘｙｌ、Ｐｅｒｆｌｕｏｒｏｈｅｐｔｙｌなどのパーフルオロアルキル基を側鎖に持つ、ポリマー（ポリアクリレートやポリメタクリレート等）をブロック成分として持つブロック共重合体等が挙げられる。
Preferable examples of the block copolymer include a block copolymer of a vinyl monomer (styrene, olefin, etc.) and an acrylic monomer (methacrylate and / or acrylate) having a perfluoroalkyl group. If copolymerization is possible, it will not specifically limit.
In addition, block copolymers preferably used in the present invention are those described in Macromol. Symp. Poly [styrene-b-4- (3-perfluoropropyl) propoxystyren] and Poly [styrene-b-2- (perfluorooctyl) ethyl methacrylate] synthesized by anionic polymerization by the method described in 191, 135 (2002). , And other fluorine-containing block copolymers, such as block copolymers having perfluoroalkyl groups in the side chain such as Perfluoropropyl, Perfluoropentyl, Perfluorohexyl, Perfluoroheptyl, etc., and having a polymer (polyacrylate or polymethacrylate) as a block component It is done.
本発明では、前記ブロック共重合体を多孔質体形成材料として用いるが、この場合、該ブロック共重合体は、板体、シート、フィルム、成型品（容器等）等の各種の形状のものであることができる。また、該ブロック共重合体は、他の材料（ポリマー、セラミックス、金属等）との積層体・混合物等であることができる。
さらに、本発明の材料に用いるブロック共重合体は、単独で用いる必要はなく、他のポリマーとのブレンド物の形態であることができる。
In the present invention, the block copolymer is used as a porous material-forming material. In this case, the block copolymer has various shapes such as a plate, a sheet, a film, a molded product (a container, etc.). Can be. The block copolymer can be a laminate or mixture with other materials (polymer, ceramics, metal, etc.).
Furthermore, the block copolymer used for the material of the present invention does not need to be used alone, and can be in the form of a blend with other polymers.
本発明の多孔質体形成材料を用いてその多孔質体を製造するには、該材料を超臨界二酸化炭素と接触させて、該二酸化炭素を該材料に含浸させる。これにより、該二酸化炭素は、該材料を構成するブロック共重合体のブロック成分Ａ中に選択的に含浸され、ブロック成分Ｂ中には含浸されない。
この二酸化炭素含浸時間は、通常、１分〜１０時間、好ましくは１０分〜２時間である。
In order to produce the porous body using the porous body-forming material of the present invention, the material is brought into contact with supercritical carbon dioxide, and the carbon dioxide is impregnated with the material. Thereby, the carbon dioxide is selectively impregnated in the block component A of the block copolymer constituting the material, and is not impregnated in the block component B.
The carbon dioxide impregnation time is usually 1 minute to 10 hours, preferably 10 minutes to 2 hours.
次に、前記二酸化炭素含浸処理された材料を、該材料を構成するブロック共重合体のブロック成分Ｂを構成するポリマー鎖の二酸化炭素中におけるガラス転移温度（Ｔｇ）より低い温度、好ましくは該Ｔｇより１０〜５０℃程度低い温度に冷却する。
例えば、ブロック成分Ｂのポリマー鎖がポリスチレンからなる場合、ポリスチレンの二酸化炭素中におけるガラス転移温度は、３０ＭＰａにおいて４０℃程度であるので、それよりも低い温度を必要とする。例えば、０℃程度に冷却するのが好ましい。
Next, the carbon dioxide impregnated material is heated to a temperature lower than the glass transition temperature (Tg) in carbon dioxide of the polymer chain constituting the block component B of the block copolymer constituting the material, preferably the Tg. Cool to a temperature lower by about 10 to 50 ° C.
For example, when the polymer chain of the block component B is made of polystyrene, since the glass transition temperature of polystyrene in carbon dioxide is about 40 ° C. at 30 MPa, a temperature lower than that is required. For example, it is preferable to cool to about 0 ° C.
前記冷却操作により、ブロック成分Ｂはガラス質となり、二酸化炭素とブロック共重合体からなる構造は凍結される。その結果、以下のような利点が得られる。
（１）二酸化炭素の開放に伴い、ミクロン以上の大きな孔が形成するのを防止する。
（２）ブロック共重合体のドメインサイズに近いサイズの孔を形成できる。
（３）冷却温度、及び／または、二酸化炭素圧力を調整することにより、孔の大きさを調整することを可能にする。
By the cooling operation, the block component B becomes vitreous, and the structure composed of carbon dioxide and the block copolymer is frozen. As a result, the following advantages can be obtained.
(1) The formation of large pores of micron or more with the release of carbon dioxide is prevented.
(2) A pore having a size close to the domain size of the block copolymer can be formed.
(3) It is possible to adjust the pore size by adjusting the cooling temperature and / or the carbon dioxide pressure.
前記冷却処理後には、該冷却された材料に含まれる二酸化炭素を気化させる。この場合の条件は、液体状の二酸化炭素が気化する条件であればよい。例えば、該材料の雰囲気圧を、大気圧以下にすればよい。 After the cooling treatment, carbon dioxide contained in the cooled material is vaporized. The conditions in this case should just be the conditions in which liquid carbon dioxide vaporizes. For example, the atmospheric pressure of the material may be set to atmospheric pressure or lower.
前記のようにして、該材料は多孔質化されるが、この場合の材料の多孔質化は、材料を構成するブロック共重合体のブロック成分Ａ中に含まれる二酸化炭素の気化により達成される。即ち、この多孔質化は、ブロック成分Ａにおいてのみ起り、共重合体のブロック成分Ａの部分が選択的に多孔質化される。
このように、本発明では、ブロック共重合体のブロック成分Ａの部分のみが選択的に多孔質化されることから、そのブロック成分Ａの部分に形成される多孔質体の空孔は非常に微細なものであり、その空孔径は１００ｎｍ以下となる。本発明では、ブロック共重合体の種類や多孔質化条件等を適宜選定することにより、該空孔の寸法を、２〜１００ｎｍ、特に５〜５０ｎｍの範囲に調整することができる。
As described above, the material is made porous. In this case, the material is made porous by vaporization of carbon dioxide contained in the block component A of the block copolymer constituting the material. . That is, this porosity only occurs in the block component A, and the block component A portion of the copolymer is selectively made porous.
Thus, in the present invention, since only the block component A portion of the block copolymer is selectively made porous, the pores of the porous body formed in the block component A portion are very The pore size is 100 nm or less. In the present invention, the size of the pores can be adjusted in the range of 2 to 100 nm, particularly 5 to 50 nm by appropriately selecting the type of block copolymer, the conditions for making the pores, and the like.
次に、本発明を実施例によりさらに詳述する。 Next, the present invention will be described in further detail with reference to examples.
実施例１
Ｐｏｌｙ［ｓｔｙｒｅｎｅ−ｂ−４−（３−ｐｅｒｆｌｕｏｒｏｏｃｔｙｌ）ｐｒｏｐｏｘｙｓｔｙｒｅｎ］（数平均分子量９４０００、フッ素含有ブロックＡの重量分率２８％）を使用した。ブロック共重合体は、６０℃、３０ＭＰａで２時間保持され、二酸化炭素を十分に材料の内部に浸透させた。その後、０℃、３０ＭＰａに等圧条件で急冷した。その後、毎分０．５ＭＰａの速度で圧力を開放した。得られた多孔質体の断面のＳＥＭ写真を図１に示す。５から３０ｎｍ程度の空孔が密に詰まって存在していることがわかる。
Example 1
Poly [styrene-b-4- (3-perfluorooctyl) propoxystyrene] (number average molecular weight 94,000, fluorine-containing block A weight fraction 28%) was used. The block copolymer was held at 60 ° C. and 30 MPa for 2 hours, and carbon dioxide was sufficiently infiltrated into the material. Thereafter, it was rapidly cooled to 0 ° C. and 30 MPa under an isobaric condition. Thereafter, the pressure was released at a rate of 0.5 MPa per minute. The SEM photograph of the cross section of the obtained porous body is shown in FIG. It can be seen that vacancies of about 5 to 30 nm are closely packed.
実施例２
Ｐｏｌｙ［ｓｔｙｒｅｎｅ−ｂ−２−（ｐｅｒｆｌｕｏｒｏｏｃｔｙｌ）ｅｔｈｙｌ ｍｅｔｈａｃｒｙｌａｔｅ］（数平均分子量３００００、フッ素含有ブロックＡの重量分率３５％）を使用した。ブロック共重合体は、６０℃、３０ＭＰａで２時間保持され、二酸化炭素を十分に材料の内部に浸透させた。その後、０℃、３０ＭＰａに等圧条件で急冷した。その後、毎分０．５ＭＰａの速度で圧力を開放した。得られた多孔質体の断面のＳＥＭ写真を図２に示す。５から３０ｎｍ程度の空孔が密に詰まって存在していることがわかる。
Example 2
Poly [styrene-b-2- (perfluorooctyl) ethyl methacrylate] (number average molecular weight 30000, weight fraction of fluorine-containing block A 35%) was used. The block copolymer was held at 60 ° C. and 30 MPa for 2 hours, and carbon dioxide was sufficiently infiltrated into the material. Thereafter, it was rapidly cooled to 0 ° C. and 30 MPa under an isobaric condition. Thereafter, the pressure was released at a rate of 0.5 MPa per minute. The SEM photograph of the cross section of the obtained porous body is shown in FIG. It can be seen that vacancies of about 5 to 30 nm are closely packed.
比較例１
Ｐｏｌｙ［ｓｔｙｒｅｎｅ−ｂ−４−（３−ｐｅｒｆｌｕｏｒｏｏｃｔｙｌ）ｐｒｏｐｏｘｙｓｔｙｒｅｎ］（数平均分子量９４０００、フッ素含有ブロックＡの重量分率２８％）を使用した。ブロック共重合体は、６０℃、３０ＭＰａで２時間保持され、二酸化炭素を十分に材料の内部に浸透させた。その後、急冷することなく、４０℃にて毎分０．５ＭＰａの速度で圧力を開放した。得られた試料の断面のＳＥＭ写真を観察した。目的とする１００ｎｍ以下の空孔は得られるものの、１ミクロン以上の大きさの空孔が共存し、本発明の目的とする１００ｎｍ以下の空孔のみを形成することはできなかった。また得られた試料は白濁し、透明性が失われた。
Comparative Example 1
Poly [styrene-b-4- (3-perfluorooctyl) propoxystyrene] (number average molecular weight 94,000, fluorine-containing block A weight fraction 28%) was used. The block copolymer was held at 60 ° C. and 30 MPa for 2 hours, and carbon dioxide was sufficiently infiltrated into the material. Thereafter, the pressure was released at a rate of 0.5 MPa per minute at 40 ° C. without rapid cooling. The SEM photograph of the cross section of the obtained sample was observed. Although the target pores of 100 nm or less were obtained, the pores having a size of 1 micron or more coexisted, and it was not possible to form only the target pores of 100 nm or less. Moreover, the obtained sample became cloudy and the transparency was lost.
比較例２
Ｐｏｌｙｓｔｙｒｅｎｅ（ＰＳ）分子量１０００００を使用した。このＰＳを、６０℃、３０ＭＰａで２時間保持し、二酸化炭素を十分に材料の内部に浸透させた。その後、０℃、３０ＭＰａに等圧条件で急冷した。その後、毎分０．５ＭＰａの速度で圧力を開放した。得られた試料の断面のＳＥＭ観察では、空孔の存在は確認されなかった。
Comparative Example 2
Polystyrene (PS) molecular weight 100,000 was used. This PS was held at 60 ° C. and 30 MPa for 2 hours, and carbon dioxide was sufficiently infiltrated into the material. Thereafter, it was rapidly cooled to 0 ° C. and 30 MPa under an isobaric condition. Thereafter, the pressure was released at a rate of 0.5 MPa per minute. SEM observation of the cross section of the obtained sample did not confirm the presence of pores.
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