JP6088206B2 - Porous structure - Google Patents
Porous structure Download PDFInfo
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- JP6088206B2 JP6088206B2 JP2012238867A JP2012238867A JP6088206B2 JP 6088206 B2 JP6088206 B2 JP 6088206B2 JP 2012238867 A JP2012238867 A JP 2012238867A JP 2012238867 A JP2012238867 A JP 2012238867A JP 6088206 B2 JP6088206 B2 JP 6088206B2
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- Prior art keywords
- porous structure
- epoxy resin
- walled carbon
- skeleton
- carbon nanotubes
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229920000647 polyepoxide Polymers 0.000 claims description 97
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- 239000002048 multi walled nanotube Substances 0.000 claims description 72
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- 238000012360 testing method Methods 0.000 claims description 21
- 239000002270 dispersing agent Substances 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 description 34
- 239000000203 mixture Substances 0.000 description 31
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- 239000003361 porogen Substances 0.000 description 25
- 125000003118 aryl group Chemical group 0.000 description 18
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 15
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
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- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 3
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- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
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- ADRVNXBAWSRFAJ-UHFFFAOYSA-N catechin Natural products OC1Cc2cc(O)cc(O)c2OC1c3ccc(O)c(O)c3 ADRVNXBAWSRFAJ-UHFFFAOYSA-N 0.000 description 2
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- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
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- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 2
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- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
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- LMVLMHGTZULBRX-UHFFFAOYSA-N 2-[2,2,2-tris(2-hydroxyphenyl)ethyl]phenol Chemical compound OC1=CC=CC=C1CC(C=1C(=CC=CC=1)O)(C=1C(=CC=CC=1)O)C1=CC=CC=C1O LMVLMHGTZULBRX-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- XYUINKARGUCCQJ-UHFFFAOYSA-N 3-imino-n-propylpropan-1-amine Chemical compound CCCNCCC=N XYUINKARGUCCQJ-UHFFFAOYSA-N 0.000 description 1
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- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- WJYIASZWHGOTOU-UHFFFAOYSA-N Heptylamine Chemical compound CCCCCCCN WJYIASZWHGOTOU-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 102100023116 Sodium/nucleoside cotransporter 1 Human genes 0.000 description 1
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- 102100021470 Solute carrier family 28 member 3 Human genes 0.000 description 1
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Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Description
本発明は、多層カーボンナノチューブで補強したエポキシ樹脂の多孔質構造体に関する。 The present invention relates to a porous structure of an epoxy resin reinforced with multi-walled carbon nanotubes.
三次元網目構造の連続した骨格と空隙とを有する多孔質体は一般的にモノリス型多孔体と呼ばれており、主にクロマトグラフィー分野でカラムと呼ばれる分離媒体として用いられている。このような分離媒体としては、無機材料から形成されるシリカゲルと、有機材料から形成される有機ポリマーに大別される。シリカゲルの分離媒体は、溶媒による材料の膨潤が少なく、物質移動による拡散の影響が小さいことに特徴があるため、主に高性能分離媒体として用いられている。一方、有機ポリマーの分離媒体は、酸・アルカリ等のｐＨ耐久性に優れ、シリカで起こる生体系試料の非特異的吸着がないことに特徴があるため、環境や生体試料の分離に好適に用いられている。 A porous body having a continuous skeleton having three-dimensional network structure and voids is generally called a monolith type porous body, and is mainly used as a separation medium called a column in the chromatography field. Such a separation medium is roughly classified into silica gel formed from an inorganic material and organic polymer formed from an organic material. Silica gel separation media are mainly used as high-performance separation media because they are characterized by little swelling of the material by the solvent and little influence of diffusion due to mass transfer. On the other hand, organic polymer separation media are excellent in pH durability such as acid and alkali, and are characterized by the absence of non-specific adsorption of biological samples caused by silica. It has been.
これまで、有機ポリマーの三次元網目構造の研究・開発は様々なされており、各種の有機ポリマーをクロマトグラフィーの分離媒体として用いることも提案されている。 Up to now, research and development of a three-dimensional network structure of an organic polymer have been made variously, and it has also been proposed to use various organic polymers as chromatographic separation media.
例えば、エポキシ樹脂を用いた多孔体として、三次元網目状骨格と連通する空隙を有するエポキシ樹脂硬化物多孔体が提案されている（例えば、特許文献１参照）。 For example, a cured epoxy resin porous body having voids communicating with a three-dimensional network skeleton has been proposed as a porous body using an epoxy resin (see, for example, Patent Document 1).
また、エポキシ樹脂を用いた多孔体として、親水性が高くて医療用分離媒体として好適に使用することができ、しかも、分離性能や吸着性能に優れる多孔体及びその製造方法が提案されている（例えば、特許文献２参照）。この多孔体は、骨格内に１ｎｍ〜１μｍの孔径のメソポアを備えて成ることを特徴としている。 Moreover, as a porous body using an epoxy resin, a porous body that has high hydrophilicity and can be suitably used as a medical separation medium, and has excellent separation performance and adsorption performance, and a method for producing the same have been proposed ( For example, see Patent Document 2). This porous body is characterized by comprising mesopores having a pore diameter of 1 nm to 1 μm in the skeleton.
しかしながら、これらの多孔体は、粘性が高いため構造材としての用途には適していなかった。また、これらの多孔体は、変形後の復元性能に劣り、例えば８０％圧縮すると、三次元網目構造の骨格は破壊されないものの空孔が押しつぶされた圧縮状態のまま復元せず、構造材としての用途には用いることができなかった。 However, these porous bodies are not suitable for use as a structural material because of their high viscosity. In addition, these porous bodies are inferior in the restoration performance after deformation. For example, when 80% compression is performed, the skeleton of the three-dimensional network structure is not destroyed, but the pores are not restored in a compressed state, and the structure is used as a structural material. It could not be used for applications.
本発明は、骨格を多層カーボンナノチューブで補強することにより、従来のエポキシ樹脂多孔体に比べて弾性を損なうことなく粘性を下げることができるエポキシ樹脂の多孔質構造体を提供することを目的とする。 It is an object of the present invention to provide an epoxy resin porous structure capable of lowering viscosity without impairing elasticity as compared with conventional epoxy resin porous bodies by reinforcing the skeleton with multi-walled carbon nanotubes. .
本発明にかかる多孔質構造体は、エポキシ樹脂硬化物からなる三次元網目構造の骨格と、空孔とを有する多孔質構造体であって、
前記骨格及び前記空孔の共連続構造が形成され、
前記骨格内に平均直径が９ｎｍ以上１１０ｎｍ以下の多層カーボンナノチューブを０．３質量％以上１０質量％以下含み、
前記骨格内に多層カーボンナノチューブの凝集体が存在しないことを特徴とする。
また、本発明にかかる多孔質構造体は、エポキシ樹脂硬化物からなる三次元網目構造の骨格と、空孔とを有する多孔質構造体であって、
前記骨格及び前記空孔の共連続構造が形成され、
前記骨格内に平均直径が９ｎｍ以上１１０ｎｍ以下の多層カーボンナノチューブを０．３質量％以上１０質量％以下含み、
前記骨格内に分散剤を含むことを特徴とする。
The porous structure according to the present invention is a porous structure having a skeleton having a three-dimensional network structure made of a cured epoxy resin and pores,
A co-continuous structure of the skeleton and the pores is formed;
Containing 0.3 to 10% by mass of multi-walled carbon nanotubes having an average diameter of 9 to 110 nm in the skeleton,
There is no aggregate of multi-walled carbon nanotubes in the skeleton.
Further, the porous structure according to the present invention is a porous structure having a three-dimensional network structure skeleton made of a cured epoxy resin and pores,
A co-continuous structure of the skeleton and the pores is formed;
Containing 0.3 to 10% by mass of multi-walled carbon nanotubes having an average diameter of 9 to 110 nm in the skeleton,
Characterized in including that the dispersing agent in said backbone.
本発明にかかる多孔質構造体によれば、骨格内にある多層カーボンナノチューブが骨格部分を補強することにより、従来のエポキシ樹脂多孔体に比べて弾性を損なうことなく粘性を下げることができる。また、本発明にかかる多孔質構造体によれば、圧縮変形後の復元性能に優れることができる。 According to the porous structure according to the present invention, the multi-walled carbon nanotube in the skeleton reinforces the skeleton portion, so that the viscosity can be lowered without impairing the elasticity as compared with the conventional epoxy resin porous body. Moreover, according to the porous structure concerning this invention, it can be excellent in the decompression | restoration performance after compression deformation.
本発明にかかる多孔質構造体において、
前記多層カーボンナノチューブを０．４質量％以上１.０質量％以下含むことができる。
In the porous structure according to the present invention,
The multi-walled carbon nanotube may be contained in an amount of 0.4% by mass to 1.0% by mass.
本発明にかかる多孔質構造体において、
クリープ試験における粘性係数ηが１００ｍＮ・ｓｅｃ〜６５０ｍＮ・ｓｅｃであることができる。
In the porous structure according to the present invention,
The viscosity coefficient η in the creep test can be 100 mN · sec to 650 mN · sec.
本発明にかかる多孔質構造体において、
クリープ試験における遅延時間λが１ｓｅｃ〜４０ｓｅｃであることができる。
In the porous structure according to the present invention,
The delay time λ in the creep test can be 1 second to 40 seconds.
以下、本発明の実施の形態について図面を参照しながら詳細に説明する。 Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
１．多孔質構造体
本実施の形態にかかる多孔質構造体は、エポキシ樹脂硬化物からなる三次元網目構造の骨格と、空孔とを有する多孔質構造体であって、前記骨格及び前記空孔の共連続構造が形成され、前記骨格内に平均直径が９ｎｍ以上１１０ｎｍ以下の多層カーボンナノチューブを０．３質量％以上１０質量％以下含み、前記骨格内に多層カーボンナノチューブの凝集体が存在しないことを特徴とする。また、本実施の形態にかかる多孔質構造体は、エポキシ樹脂硬化物からなる三次元網目構造の骨格と、空孔とを有する多孔質構造体であって、前記骨格及び前記空孔の共連続構造が形成され、前記骨格内に平均直径が９ｎｍ以上１１０ｎｍ以下の多層カーボンナノチューブを０．３質量％以上１０質量％以下含み、前記骨格内に分散剤を含むことを特徴とする。本実施の形態にかかる多孔質構造体によれば、骨格内にある多層カーボンナノチューブが骨格部分を補強することにより、圧縮変形後の復元性能に優れることができる。多層カーボンナノチューブが太すぎると、多孔質構造体の骨格の太さにも寄るが、骨格構造の形成を阻害する可能性がある。そこで、多孔質構造体の骨格構造の形成への影響を考慮すると、多層カーボンナノチューブの平均直径は１１０ｎｍ以下とすることができる。
1. Porous structure The porous structure according to the present embodiment is a porous structure having a skeleton having a three-dimensional network structure made of a cured epoxy resin and pores, and the skeleton and the pores. A co-continuous structure is formed, and multi-walled carbon nanotubes having an average diameter of 9 nm or more and 110 nm or less are contained in the skeleton in an amount of 0.3% by mass to 10% by mass, and there are no aggregates of the multi-walled carbon nanotubes in the skeleton. Features. The porous structure according to the present embodiment is a porous structure having a three-dimensional network structure skeleton made of a cured epoxy resin and pores, and the skeleton and the pores are co-continuous. structure is formed, the average diameter of the said skeleton a 110nm following multi-walled carbon nanotubes than 9nm comprises 0.3 wt% to 10 wt%, and wherein the including that the dispersing agent in said backbone. According to the porous structure according to the present embodiment, the multi-walled carbon nanotube in the skeleton reinforces the skeleton portion, so that the restoration performance after compression deformation can be excellent. If the multi-walled carbon nanotubes are too thick, the thickness of the skeleton of the porous structure may be reduced, but the formation of the skeleton structure may be hindered. Therefore, considering the influence on the formation of the skeleton structure of the porous structure, the average diameter of the multi-walled carbon nanotube can be 110 nm or less.
三次元網目構造を形成してなる本実施の形態にかかるエポキシ樹脂硬化物の多孔質構造体は、原料に用いるエポキシ樹脂（いわゆる主剤である）と硬化剤の特定の組み合わせによって形成される。 The porous structure of the cured epoxy resin according to the present embodiment formed with a three-dimensional network structure is formed by a specific combination of an epoxy resin (so-called main agent) used as a raw material and a curing agent.
具体的には、エポキシ樹脂と硬化剤の組み合わせが、芳香族エポキシ樹脂と非芳香族の硬化剤、特に脂環式アミンの硬化剤との組み合わせであること、又は非芳香族エポキシ樹脂と芳香族アミンの硬化剤との組み合わせ、特に脂環式エポキシ樹脂と芳香族アミンの硬化剤との組み合わせであることができる。 Specifically, the combination of the epoxy resin and the curing agent is a combination of an aromatic epoxy resin and a non-aromatic curing agent, particularly a curing agent of an alicyclic amine, or a non-aromatic epoxy resin and an aromatic. It can be a combination with an amine curing agent, particularly a combination of an alicyclic epoxy resin and an aromatic amine curing agent.
これらの組み合わせの中でも、非芳香族エポキシ樹脂として脂環式エポキシ樹脂、非芳香族硬化剤として脂環式アミンが使用された場合は、脂肪族エポキシ樹脂や脂肪族アミンが使用された場合に比して硬化物の耐熱性が高く、分離媒体用途に好適である。なお、エポキシ樹脂と硬化剤は、例えばそれぞれ１種類が使用されるが、それぞれ２種以上混在して用いることができる。しかしエポキシ樹脂又は硬化剤のいずれか一方又は両方が、芳香族と非芳香族の混合からなる場合は、得られる多孔質構造体は、非粒子凝集型網目構造と、粒子凝集体とが混在する多孔質構造体になりやすく、好ましくない。 Among these combinations, when an alicyclic epoxy resin is used as a non-aromatic epoxy resin and an alicyclic amine is used as a non-aromatic curing agent, compared to when an aliphatic epoxy resin or an aliphatic amine is used. Thus, the cured product has high heat resistance and is suitable for use as a separation medium. Note that, for example, one type of epoxy resin and one curing agent are used, but two or more types can be used in combination. However, when either one or both of the epoxy resin and the curing agent is composed of a mixture of aromatic and non-aromatic, the resulting porous structure is a mixture of non-particle aggregate type network structure and particle aggregate. It tends to be a porous structure, which is not preferable.
以下に、本発明で用いうるエポキシ樹脂及び硬化剤について例示する。 Below, the epoxy resin and hardening | curing agent which can be used by this invention are illustrated.
エポキシ樹脂のうち、芳香環由来の炭素原子を含む芳香族エポキシ樹脂としては、ビスフェノールＡ型エポキシ樹脂、臭素化ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＡＤ型エポキシ樹脂、スチルベン型エポキシ樹脂、ビフェニル型エポキシ樹脂、ビスフェノールＡノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ジアミノジフェニルメタン型エポキシ樹脂、テトラキス（ヒドロキシフェニル）エタンベースなどのポリフェニルベースエポキシ樹脂、フルオレン含有エポキシ樹脂、トリグリシジルイソシアヌレート、トリアジン環含有エポキシ樹脂等、複素芳香環を含むエポキシ樹脂などを挙げることができる。 Among the epoxy resins, aromatic epoxy resins containing aromatic ring-derived carbon atoms include bisphenol A type epoxy resins, brominated bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AD type epoxy resins, and stilbene type epoxy resins. , Biphenyl type epoxy resin, bisphenol A novolac type epoxy resin, cresol novolac type epoxy resin, diaminodiphenylmethane type epoxy resin, polyphenyl base epoxy resin such as tetrakis (hydroxyphenyl) ethane base, fluorene-containing epoxy resin, triglycidyl isocyanurate, An epoxy resin containing a heteroaromatic ring such as a triazine ring-containing epoxy resin can be used.
これらの中でも、ビスフェノールＡ型エポキシ樹脂、臭素化ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＡＤ型エポキシ樹脂、フルオレン含有エポキシ樹脂、トリグリシジルイソシアヌレートであることができ、特に、エポキシ当量が５００以下で、融点が１００℃以下である、ビスフェノールＡ型エポキシ樹脂、臭素化ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＡＤ型エポキシ樹脂、フルオレン含有エポキシ樹脂、トリグリシジルイソシアヌレートであることができる。 Among these, bisphenol A type epoxy resin, brominated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, fluorene-containing epoxy resin, triglycidyl isocyanurate can be used. A bisphenol A type epoxy resin, a brominated bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol AD type epoxy resin, a fluorene-containing epoxy resin, or a triglycidyl isocyanurate having a melting point of 500 ° C. or less and 100 ° C. or less. Can do.
また、芳香環由来の炭素原子を含まない非芳香族エポキシ樹脂として、脂肪族グリシジルエーテル型エポキシ樹脂、脂肪族グリシジルエステル型エポキシ樹脂、脂環族グリシジルエーテル型エポキシ樹脂、脂環族グリシジルエステル型エポキシ樹脂などを挙げることができる。これらの中でも、脂環族グリシジルエーテル型エポキシ樹脂、脂環族グリシジルエステル型エポキシ樹脂であることができ、特に、エポキシ当量が５００以下で、融点が１００℃以下の脂環族グリシジルエーテル型エポキシ樹脂、脂環族グリシジルエステル型エポキシ樹脂であることができる。 Non-aromatic epoxy resins containing no aromatic ring-derived carbon atoms include aliphatic glycidyl ether type epoxy resins, aliphatic glycidyl ester type epoxy resins, alicyclic glycidyl ether type epoxy resins, and alicyclic glycidyl ester type epoxies. Examples thereof include resins. Among these, an alicyclic glycidyl ether type epoxy resin and an alicyclic glycidyl ester type epoxy resin can be used, and in particular, an alicyclic glycidyl ether type epoxy resin having an epoxy equivalent of 500 or less and a melting point of 100 ° C. or less. It can be an alicyclic glycidyl ester type epoxy resin.
硬化剤のうち、芳香環由来の炭素原子を含む芳香族硬化剤としては、メタフェニレンジアミン、ジアミノジフェニルメタン、ジアミノジフェニルスルホン、ベンジルジメチルアミン、ジメチルアミノメチルベンゼン等の芳香族アミン、無水フタル酸、無水トリメリット酸、無水ピロメリット酸などの芳香族酸無水物、フェノール樹脂、フェノールノボラック樹脂、トリアジン環などの複素芳香環を有するアミンなどを挙げることできる。これらの中でも、分子内に一級アミンを２以上有する芳香族アミン化合物であることができ、特に、メタフェニレンジアミン、ジアミノジフェニルメタン、ジアミノジフェニルスルホンであることができる。 Among the curing agents, aromatic curing agents containing carbon atoms derived from aromatic rings include aromatic amines such as metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, benzyldimethylamine, dimethylaminomethylbenzene, phthalic anhydride, anhydrous Examples thereof include aromatic acid anhydrides such as trimellitic acid and pyromellitic anhydride, phenol resins, phenol novolac resins, and amines having a heteroaromatic ring such as a triazine ring. Among these, aromatic amine compounds having two or more primary amines in the molecule can be used, and in particular, metaphenylenediamine, diaminodiphenylmethane, and diaminodiphenylsulfone can be used.
また芳香環由来の炭素原子を含まない非芳香族硬化剤としては、エチレンジアミン、ジ
エチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、イミノビスプロピルアミン、ビス（ヘキサメチレン）トリアミン、１，３，６−トリスアミノメチルヘキサン、ポリメチレンジアミン、トリメチルヘキサメチレンジアミン、ポリエーテルジアミン等の脂肪族アミン類、イソホロンジアミン、メンタンジアミン、Ｎ−アミノエチルピペラジン、３，９−ビス（３−アミノプロピル）２，４，８，１０−テトラオキサスピロ（５，５）ウンデカンアダクト、ビス（４−アミノ−３−メチルシクロヘキシル）メタン、ビス（４−アミノシクロヘキシル）メタンやこれらの変性品等の脂環族ポリアミン類、その他ポリアミン類とダイマー酸からなる脂肪族ポリアミドアミン類などを挙げることができる。これらの中でも、分子内に一級アミンを２以上有する脂環族アミン化合物であることができ、特に、ビス（４−アミノ−３−メチルシクロヘキシル）メタン、ビス（４−アミノシクロヘキシル）などであることができる。
Non-aromatic curing agents containing no aromatic carbon atoms include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, iminobispropylamine, bis (hexamethylene) triamine, 1,3,6-tris. Aliphatic amines such as aminomethylhexane, polymethylenediamine, trimethylhexamethylenediamine, and polyetherdiamine, isophoronediamine, menthanediamine, N-aminoethylpiperazine, 3,9-bis (3-aminopropyl) 2,4, Alicyclic polyamines such as 8,10-tetraoxaspiro (5,5) undecane adduct, bis (4-amino-3-methylcyclohexyl) methane, bis (4-aminocyclohexyl) methane and their modified products, etc. Polyamines and dimers And aliphatic polyamidoamines consisting acid. Among these, it can be an alicyclic amine compound having two or more primary amines in the molecule, and in particular, bis (4-amino-3-methylcyclohexyl) methane, bis (4-aminocyclohexyl) and the like. Can do.
本実施の形態に用いられるポロゲンとは、エポキシ樹脂及び硬化剤を溶かすことができ、且つエポキシ樹脂と硬化剤が重合した後、反応誘起相分離を生ぜしめることが可能な溶剤をいい、例えばメチルセロソルブ、エチルセロソルブなどのセロソルブ類、エチレングリコールモノメチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテートなどエステル類、又はポリエチレングリコール、ポリプロピレングリコールなどのグリコール類などを挙げることができる。これらの中でも、分子量６００以下のポリエチレングリコール、メチルセロソルブ、エチルセロソルブ、エチレングリコールモノメチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテートであることができ、特に分子量２００以下のポリエチレングリコール、プロピレングリコールモノメチルエーテルアセテートであることができる。 The porogen used in the present embodiment refers to a solvent that can dissolve the epoxy resin and the curing agent, and can cause reaction-induced phase separation after the epoxy resin and the curing agent are polymerized. Examples include cellosolves such as cellosolve and ethyl cellosolve, esters such as ethylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate, and glycols such as polyethylene glycol and polypropylene glycol. Among these, polyethylene glycol, methyl cellosolve, ethyl cellosolve, ethylene glycol monomethyl ether acetate, and propylene glycol monomethyl ether acetate having a molecular weight of 600 or less, particularly polyethylene glycol and propylene glycol monomethyl ether acetate having a molecular weight of 200 or less. Can do.
また、個々のエポキシ樹脂又は硬化剤と常温で不溶又は難溶であっても、エポキシ樹脂と硬化剤をアダクト化することにより可溶となるような溶剤もポロゲンとして使用可能である。 Moreover, even if it is insoluble or hardly soluble at room temperature with individual epoxy resins or curing agents, a solvent that becomes soluble by adducting the epoxy resin and the curing agent can also be used as the porogen.
本実施の形態においては、エポキシ樹脂硬化物の多孔質構造体を構成する全炭素原子に占める芳香環由来の炭素原子比率が０．１０〜０．６５の範囲になるように、エポキシ樹脂及び硬化剤の種類と量を決定することが必要である。 In the present embodiment, the epoxy resin and the curing are performed so that the carbon atom ratio derived from the aromatic ring in the total carbon atoms constituting the porous structure of the cured epoxy resin is in the range of 0.10 to 0.65. It is necessary to determine the type and amount of agent.
芳香環由来の炭素原子比率が全炭素原子の０．１０未満である場合は、該多孔質構造体による分離媒体は平面分子構造認識性が低下する。また全炭素原子に占める芳香環由来の炭素原子比率が０．６５を超すと、柱状のエポキシ樹脂硬化物の三次元分岐網目状骨格からなる、非粒子凝集型の多孔質構造体を得ることが困難となる。 When the ratio of carbon atoms derived from the aromatic ring is less than 0.10 of the total carbon atoms, the planar medium structure recognition property of the separation medium using the porous structure is lowered. Further, when the ratio of carbon atoms derived from aromatic rings to all carbon atoms exceeds 0.65, a non-particle-aggregated porous structure composed of a three-dimensional branched network skeleton of a cured epoxy resin can be obtained. It becomes difficult.
エポキシ樹脂と硬化剤の添加割合は、上記の全炭素原子に占める芳香環由来の炭素原子比率を満足する範囲のなかで、エポキシ基１当量に対して、硬化剤当量が０．６〜１．５の範囲になるように調整することができる。硬化剤当量比が０．６より少ない場合は硬化物の架橋密度が低くなり、耐熱性、耐溶剤性などが低下する場合がある。また１．５より多くなると、未反応の官能基が多くなり、未反応のまま硬化物中に残留したり、あるいは架橋密度向上を阻害する要因となり好ましくない。 The addition ratio of the epoxy resin and the curing agent is such that the curing agent equivalent is 0.6 to 1. with respect to 1 equivalent of the epoxy group, within the range satisfying the carbon atom ratio derived from the aromatic ring in the total carbon atoms. It can be adjusted to be in the range of 5. When the curing agent equivalent ratio is less than 0.6, the crosslink density of the cured product is lowered, and heat resistance, solvent resistance, and the like may be lowered. On the other hand, if it exceeds 1.5, the number of unreacted functional groups increases, and it remains unreacted in the cured product or becomes a factor that hinders the improvement of the crosslinking density.
本実施の形態に用いられる多層カーボンナノチューブは、平均直径が９ｎｍ以上１１０ｎｍ以下である。ここでいう平均直径は、繊維径の平均値である。さらに、多層カーボンナノチューブは、９ｎｍ以上２０ｎｍ以下または４０ｎｍ以上１１０ｎｍ以下であることができる。多層カーボンナノチューブは、その平均直径が比較的細いため、比表面積が大きく、マトリックスであるエポキシ樹脂との表面反応性が高く、多層カーボンナノチューブを解繊し、三次元網目構造の骨格内に分散させることができると、エポキシ樹脂を多層カーボンナノチューブによって少量でも効果的に補強することができる。平均直径が９ｎ
ｍ以上である多層カーボンナノチューブを用いることで、エポキシ樹脂中に比較的分散させやすい。また、平均直径が１１０ｎｍ以下の多層カーボンナノチューブを用いることによって、エポキシ樹脂の骨格を少量の多層カーボンナノチューブで補強することができる。多層カーボンナノチューブは、その表面におけるエポキシ樹脂との反応性を向上させるために、表面改質として、例えば酸化処理することもできる。なお、本発明の詳細な説明において多層カーボンナノチューブの平均直径及び平均長さは、電子顕微鏡による例えば５，０００倍の撮像（カーボンナノチューブのサイズによって適宜倍率は変更できる）から２００箇所以上の直径及び長さを計測し、その算術平均値として計算して得ることができる。
The multi-walled carbon nanotube used in the present embodiment has an average diameter of 9 nm to 110 nm. The average diameter here is an average value of fiber diameters. Furthermore, the multi-walled carbon nanotubes can be 9 nm to 20 nm or 40 nm to 110 nm. Multi-walled carbon nanotubes have a relatively small average diameter, so they have a large specific surface area and high surface reactivity with the epoxy resin that is the matrix. The multi-walled carbon nanotubes are defibrated and dispersed in the skeleton of the three-dimensional network structure. If it is possible, the epoxy resin can be effectively reinforced by the multi-walled carbon nanotubes even in a small amount. Average diameter is 9n
By using multi-walled carbon nanotubes of m or more, it is relatively easy to disperse in the epoxy resin. Further, by using multi-walled carbon nanotubes having an average diameter of 110 nm or less, the epoxy resin skeleton can be reinforced with a small amount of multi-walled carbon nanotubes. Multi-walled carbon nanotubes can be subjected to, for example, oxidation treatment as surface modification in order to improve the reactivity with the epoxy resin on the surface. In the detailed description of the present invention, the average diameter and the average length of the multi-walled carbon nanotubes are, for example, from 5,000 times imaging with an electron microscope (the magnification can be changed appropriately depending on the size of the carbon nanotubes) It can be obtained by measuring the length and calculating it as its arithmetic mean.
多層カーボンナノチューブは、炭素六角網面のグラファイトの１枚面（グラフェンシート）を巻いて筒状にした形状を有する。また、部分的にカーボンナノチューブの構造を有する炭素材料も使用することができる。なお、多層カーボンナノチューブという名称の他にグラファイトフィブリルナノチューブ、気相成長炭素繊維、ナノカーボンといった名称で称されることもある。 The multi-walled carbon nanotube has a cylindrical shape formed by winding one surface (graphene sheet) of graphite having a carbon hexagonal mesh surface. A carbon material partially having a carbon nanotube structure can also be used. In addition to the name of multi-walled carbon nanotube, it may be referred to as a name such as graphite fibril nanotube, vapor-grown carbon fiber, or nanocarbon.
多層カーボンナノチューブは、気相成長法によって得ることができる。気相成長法は、触媒気相合成法（Catalytic Chemical Vapor Deposition：ＣＣＶＤ）とも呼ばれ、炭化水素等のガスを金属系触媒の存在下で気相熱分解させて多層カーボンナノチューブを製造する方法である。より詳細に気相成長法を説明すると、例えば、ベンゼン、トルエン等の有機化合物を原料とし、フェロセン、ニッケルセン等の有機遷移金属化合物を金属系触媒として用い、これらをキャリアーガスとともに高温例えば４００℃以上１０００℃以下の反応温度に設定された反応炉に導入し、浮遊状態あるいは反応炉壁に第１の多層カーボンナノチューブを生成させる浮遊流動反応法（Floating Reaction Method）や、あらかじめアルミナ、酸化マグネシウム等のセラミックス上に担持された金属含有粒子を炭素含有化合物と高温で接触させて多層カーボンナノチューブを基板上に生成させる触媒担持反応法（Substrate Reaction Method）等を用いることができる。例えば、平均直径が９ｎｍ以上２０ｎｍ以下の多層カーボンナノチューブは触媒担持反応法によって得ることができ、平均直径が６０ｎｍ以上１１０ｎｍ以下の多層カーボンナノチューブは浮遊流動反応法によって得ることができる。多層カーボンナノチューブの直径は、例えば金属含有粒子の大きさや反応時間などで調節することができる。平均直径が９ｎｍ以上２０ｎｍ以下の多層カーボンナノチューブは、窒素吸着比表面積が１０ｍ２／ｇ以上５００ｍ２／ｇ以下であることができ、さらに１００ｍ２／ｇ以上３５０ｍ２／ｇ以下であることができ、特に、１５０ｍ２／ｇ以上３００ｍ２／ｇ以下であることができる。 Multi-walled carbon nanotubes can be obtained by vapor phase growth. Vapor growth is also called catalytic chemical vapor deposition (CCVD), which is a method of producing multi-walled carbon nanotubes by gas phase pyrolysis of hydrocarbon gas in the presence of metal catalyst. is there. The vapor phase growth method will be described in more detail. For example, an organic compound such as benzene or toluene is used as a raw material, an organic transition metal compound such as ferrocene or nickelcene is used as a metal catalyst, and these are used together with a carrier gas at a high temperature such as 400 ° C. Floating reaction method (Floating Reaction Method) that introduces the first multi-walled carbon nanotubes in a floating state or on the reaction furnace wall, alumina, magnesium oxide, etc. A catalyst-supporting reaction method (Substrate Reaction Method) in which metal-containing particles supported on the ceramics are brought into contact with a carbon-containing compound at a high temperature to produce multi-walled carbon nanotubes on a substrate can be used. For example, multi-wall carbon nanotubes having an average diameter of 9 nm to 20 nm can be obtained by a catalyst-supporting reaction method, and multi-wall carbon nanotubes having an average diameter of 60 nm to 110 nm can be obtained by a floating flow reaction method. The diameter of the multi-walled carbon nanotube can be adjusted by, for example, the size of the metal-containing particles and the reaction time. Average diameter 20nm following multi-walled carbon nanotubes than 9nm a nitrogen adsorption specific surface area of 10 m 2 / g or more 500 meters 2 / g can be less, can even not greater than 100 m 2 / g or more 350 meters 2 / g In particular, it may be 150 m 2 / g or more and 300 m 2 / g or less.
多孔質構造体は、多層カーボンナノチューブを０．３質量％以上１０質量％以下含む。さらに、多孔質構造体は、多層カーボンナノチューブを０．４質量％以上１.０質量％以下含むことができる。多孔質構造体における多層カーボンナノチューブの含有量は、比較的少量であっても補強することができる。多孔質構造体における多層カーボンナノチューブの含有量が０．３質量％以上１０質量％以下であれば多孔質構造体の弾性を維持しながら粘性を下げることができる。多孔質構造体における多層カーボンナノチューブの含有量が１０質量％以下であれば重合前の混合物の溶液における粘度が高くなりすぎないため、多層カーボンナノチューブを分散させることができ、多孔質構造体を製造することができる。多孔質構造体における多層カーボンナノチューブの含有量が０．３質量％以上であれば、多層カーボンナノチューブの補強効果を得ることができる。 The porous structure contains 0.3% by mass or more and 10% by mass or less of multi-walled carbon nanotubes . Furthermore, the porous structure can contain 0.4 to 1.0 mass% of multi-walled carbon nanotubes. Even if the content of the multi-walled carbon nanotube in the porous structure is relatively small, it can be reinforced. When the content of the multi-walled carbon nanotube in the porous structure is 0.3 mass% or more and 10 mass% or less, the viscosity can be lowered while maintaining the elasticity of the porous structure. If the content of the multi-walled carbon nanotube in the porous structure is 10% by mass or less, the viscosity in the solution of the mixture before polymerization does not become too high, so that the multi-walled carbon nanotube can be dispersed and a porous structure is produced. can do. When the content of the multi-walled carbon nanotube in the porous structure is 0.3% by mass or more, the reinforcing effect of the multi-walled carbon nanotube can be obtained.
多孔質構造体は、クリープ試験における粘性係数ηが１００ｍＮ・ｓｅｃ〜６５０ｍＮ・ｓｅｃであることができ、さらに、３００ｍＮ・ｓｅｃ〜６５０ｍＮ・ｓｅｃであることができる。また、多孔質構造体は、クリープ試験における遅延時間λが１ｓｅｃ〜４０ｓｅｃであることができ、さらに、２０ｓｅｃ〜４０ｓｅｃであることができる。クリー
プ試験による粘弾性特性の測定は、試験片の大きさなどの諸条件によって、例えば、ＪＩＳ Ｋ６２５３のＭ法に基づく国際ゴム硬さ試験（ＩＲＨＤ）、熱機械分析試験（ＴＭＡ）などの試験方法から適宜選択して行うことができる。
The porous structure may have a viscosity coefficient η in a creep test of 100 mN · sec to 650 mN · sec, and further may be 300 mN · sec to 650 mN · sec. The porous structure can have a delay time λ in a creep test of 1 sec to 40 sec, and further can be 20 sec to 40 sec. The measurement of the viscoelastic property by the creep test is performed according to various conditions such as the size of the test piece, for example, a test method such as an international rubber hardness test (IRHD) or a thermomechanical analysis test (TMA) based on the JIS K6253 method M. Can be selected as appropriate.
ＪＩＳ Ｋ６２５３のＭ法に基づく国際ゴム硬さ試験（ＩＲＨＤ）は、架橋ゴムの硬度を測定する方法であって、例えば、図１に示すように、多孔質構造体をＯリング形状に成形した架橋サンプル２０に先端に鋼球を有するインデンタ（押針）１０を定荷重（一次荷重０．８５ｇ、二次荷重１４．８ｇ）、３０秒間押し付けたときの変位から硬度を算出することができる。ここで、国際ゴム硬さ試験（ＩＲＨＤ）の結果（硬度を測定するときよりも長時間測定する）を定圧粘弾性試験の時間−歪み曲線（クリープ曲線）としてとらえて、図２に示すような２つのバネ３０，４０と１つのダッシュポット５０を組み合わせたいわゆる三要素フォークトモデルに当てはめて、バネ定数Ｋ１，Ｋ２、粘性係数η及び遅延時間λを計算することができる。具体的には、国際ゴム硬さ試験（ＩＲＨＤ）にて力を加えた瞬間のひずみ量ε０と６００秒後のひずみ量ε（６００）を測定する。ε０=σ／Ｋ１（ここでσ＝１５３．３ｍＮ）より、Ｋ１を計算する。ε（６００）＝σ／Ｋ２としてＫ２を計算する。ｔ＝λの時を遅延時間とするので、下記式（１）より、ε(t)=ε０＋ε（６００）（１−１／ｅ）となるときの時間tを抽出する。下記式（２）よりηを計算する。 The International Rubber Hardness Test (IRHD) based on JIS K6253 method M is a method for measuring the hardness of a crosslinked rubber. For example, as shown in FIG. 1, a crosslinked structure formed into an O-ring shape is crosslinked. The hardness can be calculated from the displacement when the indenter (push needle) 10 having a steel ball at the tip is pressed against the sample 20 at a constant load (primary load 0.85 g, secondary load 14.8 g) for 30 seconds. Here, the result of the international rubber hardness test (IRHD) (measured for a longer time than when measuring hardness) is taken as a time-strain curve (creep curve) of a constant pressure viscoelasticity test, as shown in FIG. By applying a so-called three-element forked model in which two springs 30 and 40 and one dashpot 50 are combined, the spring constants K1 and K2, the viscosity coefficient η, and the delay time λ can be calculated. Specifically, the strain amount ε 0 at the moment when force is applied in the International Rubber Hardness Test (IRHD) and the strain amount ε (600) after 600 seconds are measured. K1 is calculated from ε 0 = σ / K1 (where σ = 153.3 mN). K2 is calculated as ε (600) = σ / K2. Since the delay time is t = λ, the time t when ε (t) = ε 0 + ε (600) (1-1 / e) is extracted from the following equation (1). Η is calculated from the following equation (2).
ε（ｔ）＝ε０＋σ／Ｋ２［１−ｅｘｐ（−ｔ／λ）］ （１）
λ＝η／Ｋ２ （２）
また、熱機械分析試験（ＴＭＡ）による場合には、例えば、幅２ｍｍ×厚み１ｍｍ×長さ１０ｍｍの短冊試料を用いて、室温２５℃、５００ｋＰａにて測定し、時間−歪み曲線を得て、ＩＲＨＤと同様にしてバネ定数Ｋ１，Ｋ２、粘性係数η及び遅延時間λを計算することができる。
ε (t) = ε 0 + σ / K2 [1-exp (−t / λ)] (1)
λ = η / K2 (2)
In the case of a thermomechanical analysis test (TMA), for example, using a strip sample having a width of 2 mm, a thickness of 1 mm, and a length of 10 mm, measurement is performed at room temperature of 25 ° C. and 500 kPa, and a time-strain curve is obtained. The spring constants K1, K2, the viscosity coefficient η, and the delay time λ can be calculated in the same manner as IRHD.
多孔質構造体は、多層カーボンナノチューブによる骨格の補強によって、エポキシ樹脂単体の多孔質構造体に比べて、圧縮試験前後の復元率（％）に優れることができる。 The porous structure can be excellent in the restoration rate (%) before and after the compression test as compared with the porous structure of the epoxy resin alone by reinforcing the skeleton with the multi-walled carbon nanotubes.
２．多孔質構造体の製造方法
本実施の形態にかかる多孔質構造体を製造する方法は、例えば、エポキシ樹脂と硬化剤とポロゲンと多層カーボンナノチューブと分散剤とを含む混合物を、加熱してエポキシ樹脂を重合させながらエポキシ樹脂の重合物とポロゲンとをスピノーダル相分離させて硬化物を得る第１の工程と、前記第１の工程で得られた前記硬化物からポロゲンを除去して多孔質構造体を得る第２の工程と、を含むことができる。
2. Method for producing porous structure The method for producing a porous structure according to the present embodiment includes, for example, heating a mixture containing an epoxy resin, a curing agent, a porogen, a multi-walled carbon nanotube, and a dispersing agent to epoxy resin. The first step of obtaining a cured product by spinodal phase separation of the epoxy resin polymer and porogen while polymerizing the resin, and removing the porogen from the cured product obtained in the first step to form a porous structure A second step of obtaining
第１の工程は、まず、エポキシ樹脂と硬化剤とポロゲンと多層カーボンナノチューブを含む混合物を作成することができる。第１の工程は、エポキシ樹脂と硬化剤とを混合して第１の混合物を得る工程と、ポロゲンと多層カーボンナノチューブとを混合して第２の混合物を得る工程と、第１の混合物と第２の混合物とを混合して混合物を得る工程と、を含むことができる。 In the first step, first, a mixture containing an epoxy resin, a curing agent, a porogen, and multi-walled carbon nanotubes can be created. The first step is a step of mixing an epoxy resin and a curing agent to obtain a first mixture, a step of mixing a porogen and multi-walled carbon nanotubes to obtain a second mixture, a first mixture and a first mixture Mixing the two mixtures to obtain a mixture.
混合物は、さらに多層カーボンナノチューブを解繊させる分散剤を含むことができる。例えば、第２の混合物を得る工程は、多層カーボンナノチューブを解繊させる分散剤を添加したポロゲンに多層カーボンナノチューブを混合することができる。このとき、ポロゲンを撹拌しながら多層カーボンナノチューブを添加することができる。分散剤は、凝集しやすい多層カーボンナノチューブをポロゲン中で解繊し、ポロゲン中に分散させるためのものである。分散剤としては、多層カーボンナノチューブを分散することができる公知の分散剤を用いることができる。分散剤としては、例えば、カテキンなどのポリフェノール含有水溶液、アニオン系界面活性剤、カチオン系界面活性剤、ノニオン系界面活性剤等の
界面活性剤などを用いることができる。
The mixture can further include a dispersant that defibrates the multi-walled carbon nanotubes. For example, in the step of obtaining the second mixture, the multi-walled carbon nanotubes can be mixed with a porogen to which a dispersant for defibrating the multi-walled carbon nanotubes is added. At this time, the multi-walled carbon nanotube can be added while stirring the porogen. The dispersant is for defibrating multi-walled carbon nanotubes that are easily aggregated in a porogen and dispersing them in the porogen. As the dispersant, a known dispersant capable of dispersing the multi-walled carbon nanotubes can be used. As the dispersant, for example, surfactants such as polyphenol-containing aqueous solutions such as catechin, anionic surfactants, cationic surfactants, nonionic surfactants, and the like can be used.
第１の工程は、超音波を照射して混合物を撹拌する工程を含むことができる。例えば、混合物を得る工程は、２種類の液体（第１の混合物と第２の混合物）を機械的に撹拌混合し、超音波を照射してさらに撹拌することもできる。第１の工程では、第１の混合物のエポキシ樹脂と硬化剤に対して非反応性であり、かつそれらを溶解可能なポロゲンに常温で又は加温して溶解し、ポロゲン中に添加された多層カーボンナノチューブを混合物中に分散させる。 The first step may include a step of stirring the mixture by irradiating ultrasonic waves. For example, in the step of obtaining a mixture, two types of liquids (first mixture and second mixture) can be mechanically stirred and mixed, and further stirred by irradiation with ultrasonic waves. In the first step, a multilayer which is non-reactive with the epoxy resin and the curing agent of the first mixture and is dissolved in a porogen capable of dissolving them at room temperature or heated and added into the porogen. Carbon nanotubes are dispersed in the mixture.
第１の工程は、さらに、混合物を加熱重合し、重合物とポロゲンがスピノーダル相分離後、相分離が進展して共連続構造が消滅する前に、架橋反応によって構造を凍結固定させて硬化物を得ることができる。 In the first step, the mixture is further polymerized by heating, and after the spinodal phase separation of the polymer and porogen, the structure is frozen and fixed by a crosslinking reaction before the phase separation progresses and the co-continuous structure disappears. Can be obtained.
第２の工程は、第１の工程で得られた硬化物からポロゲンを除去して多孔質構造体を得る。この場合、目的とする多孔構造が得られない場合は、硬化促進剤を添加することが効果的である場合もある。硬化促進剤としては、公知の物を使用することができる。例えば、トリエチルアミン、トリブチルアミン等の三級アミン、２−フェノール−４−メチルイミダゾール、２−エチル−４−メチルイミダゾール、２−フェノール−４，５−ジヒドロキシメチルイミダゾールなどのイミダゾール類などが挙げられる。 In the second step, the porogen is removed from the cured product obtained in the first step to obtain a porous structure. In this case, it may be effective to add a curing accelerator if the intended porous structure cannot be obtained. A well-known thing can be used as a hardening accelerator. Examples thereof include tertiary amines such as triethylamine and tributylamine, and imidazoles such as 2-phenol-4-methylimidazole, 2-ethyl-4-methylimidazole and 2-phenol-4,5-dihydroxymethylimidazole.
なお、例えば、第１の工程として、エポキシ樹脂と多層カーボンナノチューブとを最初に混合した後に、ポロゲンを混合すると、エポキシ樹脂の粘度が高すぎて多層カーボンナノチューブが分散不良を起こす傾向があり、望ましくない。 For example, as a first step, if the porogen is mixed after the epoxy resin and the multi-walled carbon nanotube are first mixed, the viscosity of the epoxy resin tends to be too high and the multi-walled carbon nanotube tends to cause poor dispersion, which is desirable. Absent.
本実施の形態にかかる多孔質構造体を得るには、重合開始から構造凍結まで、遅くとも１２０分で終了することができる。また相分離による曇点発生から三次元架橋による構造の凍結まで、３０分以内であることができ、こうした条件を目安に重合温度を設定することができる。 In order to obtain the porous structure according to the present embodiment, the polymerization can be completed in 120 minutes at the latest from the start of the polymerization to the freezing of the structure. Also, the time from cloud point generation due to phase separation to freezing of the structure due to three-dimensional crosslinking can be within 30 minutes, and the polymerization temperature can be set based on these conditions.
例えば、上記のごとく、全炭素原子に占める芳香環由来の炭素原子比率を満足する範囲の中で、エポキシ基１当量に対して、硬化剤当量が０．６〜１．５の範囲になるようにエポキシ樹脂と硬化剤を選択した後、それぞれの原材料を反応容器に投入して第１の混合物を得て、多層カーボンナノチューブを含むポロゲンを添加する。添加されたポロゲンにエポキシ樹脂と硬化剤を溶解する。この時、エポキシ樹脂が常温で固形の場合、粉砕した樹脂を１００℃以下に加熱したポロゲンに投入して溶解した後、硬化剤を添加溶解し、直ちに所定の重合温度に加熱し重合を行うこともできる。加熱重合後、重合が進行し、ポリマー成分が増大すると、スピノーダル相分離が起こり、共連続構造が発現するが、相分離が更に進行し、共連続構造が消滅する前にエポキシ樹脂の架橋反応を進行させることにより構造が凍結固定されて、所望の三次元網目構造が得られる。しかし、この現象を目視で確認することは不可能であるため、あらかじめ試験的に硬化剤（必要に応じて硬化促進剤も含む）の種類と量、ポロゲンの量を変化させながら電子顕微鏡等で構造確認をしながら最適温度プロファイルを決定して制御を行う。具体的な条件は、後述の実施例中に記載される。 For example, as described above, the curing agent equivalent is in the range of 0.6 to 1.5 with respect to 1 equivalent of the epoxy group in the range satisfying the carbon atom ratio derived from the aromatic ring in the total carbon atoms. After selecting an epoxy resin and a curing agent, the respective raw materials are put into a reaction vessel to obtain a first mixture, and a porogen containing multi-walled carbon nanotubes is added. An epoxy resin and a curing agent are dissolved in the added porogen. At this time, if the epoxy resin is solid at room temperature, the pulverized resin is poured into a porogen heated to 100 ° C. or lower and dissolved, and then a curing agent is added and dissolved, and immediately heated to a predetermined polymerization temperature for polymerization. You can also. When the polymerization proceeds and the polymer component increases after heat polymerization, spinodal phase separation occurs and a co-continuous structure develops, but the phase separation further proceeds and the epoxy resin undergoes a crosslinking reaction before the co-continuous structure disappears. By proceeding, the structure is frozen and fixed, and a desired three-dimensional network structure is obtained. However, since it is impossible to visually confirm this phenomenon, an electron microscope or the like is used in advance while experimentally changing the type and amount of a curing agent (including a curing accelerator if necessary) and the amount of porogen. The optimal temperature profile is determined and controlled while checking the structure. Specific conditions are described in the examples described later.
本実施の形態では硬化物の架橋を十分に行うために構造凍結後、更にアフターキュアーを実施することができる。ポロゲンを除去した後にアフターキュアーを実施すると、収縮が発生して多孔構造に変化を生じることがあるので、ポロゲンを除去せずに行うことができる。使用したポロゲンが低沸点溶剤の場合は、高沸点溶剤に置換した後アフターキュアーを行うなどの方法を採ることができる。架橋が不十分な多孔質構造体を液体クロマト分離媒体として使用すると理論段数が低下するため、十分な架橋反応を行う必要がある。 In this embodiment, in order to sufficiently crosslink the cured product, after-curing can be further performed after the structure is frozen. When after-curing is performed after removing the porogen, shrinkage may occur and the porous structure may change, so that the porogen can be removed without removal. When the porogen used is a low-boiling solvent, a method such as after-curing after replacing with a high-boiling solvent can be employed. When a porous structure with insufficient crosslinking is used as a liquid chromatographic separation medium, the number of theoretical plates is reduced, and therefore a sufficient crosslinking reaction must be performed.
多層カーボンナノチューブは、溶液の混合物中において、０．３質量％以上１０質量％以下であることができ、さらに、０．４質量％以上１．０質量％以下であることができる。多層カーボンナノチューブの配合量が０．３質量％以上であると多孔質構造体の骨格構造の補強効果を得ることができ、１０質量％以下であるとスピノーダル分解相分離に影響が少なく、いわゆるモノリス構造の多孔質構造体を得ることができる。 The multi-walled carbon nanotube can be 0.3% by mass or more and 10% by mass or less, and can be 0.4% by mass or more and 1.0% by mass or less in the mixture of the solutions. When the compounding amount of the multi-walled carbon nanotube is 0.3% by mass or more, the effect of reinforcing the skeleton structure of the porous structure can be obtained, and when it is 10% by mass or less, there is little influence on the spinodal decomposition phase separation, so-called monolith. A porous structure having a structure can be obtained.
本実施の形態にかかるエポキシ樹脂硬化物の多孔質構造体において、空孔率は２０％〜８０％であることができる。空孔率が２０％未満では、空孔率が低すぎてソリッドのエポキシ樹脂構造体との差が得にくくモノリス特有の柔軟性が低下する。また空孔率が８０％を超すと、多孔質構造体の強度が低下する。 In the porous structure of the cured epoxy resin according to the present embodiment, the porosity can be 20% to 80%. If the porosity is less than 20%, the porosity is too low to obtain a difference from the solid epoxy resin structure, and the flexibility unique to the monolith decreases. On the other hand, when the porosity exceeds 80%, the strength of the porous structure decreases.
また、本実施の形態にかかるエポキシ樹脂硬化物の多孔質構造体は、平均孔径が０．５μｍ以上５０μｍ以下であることができる。 Moreover, the porous structure of the cured epoxy resin according to the present embodiment can have an average pore diameter of 0.5 μm or more and 50 μm or less.
また、本実施の形態にかかるエポキシ樹脂硬化物の多孔質構造体は、水銀圧入法で測定される微分細孔分布の最大値の１／４の高さにおける対数分布幅が０．７以下であることができる。微分細孔分布の最大値の１／４の高さにおける対数分布幅とは、細孔分布の広がりを示す一つの指標であり、細孔分布の最大値の１／４の高さにおける対数分布の幅を対数にて表示したものである。最大値の１／４の高さにおける対数分布幅が、０．７を超えると分離媒体としての理論段数が低下する傾向がある。 The porous structure of the cured epoxy resin according to the present embodiment has a logarithmic distribution width of 0.7 or less at the height of 1/4 of the maximum value of the differential pore distribution measured by the mercury intrusion method. Can be. The logarithmic distribution width at the height of 1/4 of the maximum value of the differential pore distribution is one index indicating the spread of the pore distribution, and the logarithmic distribution at the height of 1/4 of the maximum value of the pore distribution. Is a logarithmic width. When the logarithmic distribution width at the height of ¼ of the maximum value exceeds 0.7, the number of theoretical plates as a separation medium tends to decrease.
多孔質構造体の空孔率、孔径、孔径分布などは、使用されるエポキシ樹脂、エポキシ硬化剤、ポロゲンなど原料の種類や比率、又は温度、攪拌、圧力などの反応条件により変化するため、目的とする多孔質構造体としての空孔率、孔径、及び孔径を得るためには、系の相図を作成し最適な条件を選択することが好ましい。相分離は経時的に変化するが、樹脂とポロゲンの共連続構造を特定の状態で固定し安定した多孔質構造を形成させるには、相分離時におけるエポキシ樹脂重合物の分子量、分子量分布、系の粘度、架橋反応速度などが厳密にコントロールすることが一般的に行われる。 The porosity, pore size, pore size distribution, etc. of the porous structure vary depending on the type and ratio of raw materials such as epoxy resin, epoxy curing agent, porogen used, or reaction conditions such as temperature, stirring, pressure, etc. In order to obtain the porosity, the pore diameter, and the pore diameter as the porous structure, it is preferable to create a phase diagram of the system and select optimum conditions. Although phase separation changes with time, in order to fix the co-continuous structure of the resin and porogen in a specific state and form a stable porous structure, the molecular weight, molecular weight distribution, and system of the epoxy resin polymer during phase separation In general, the viscosity, crosslinking reaction rate, and the like are strictly controlled.
本実施の形態にかかるエポキシ樹脂硬化物の多孔質構造体は、骨格内にある多層カーボンナノチューブが骨格部分を補強することにより、従来のエポキシ樹脂多孔体に比べて弾性を損なうことなく粘性を下げることができる。また、本発明にかかる多孔質構造体によれば、圧縮変形後の復元性能に優れることができる。そのため、従来の液体クロマトグラフィー用の分離媒体以外の、例えば、構造材としての用途にも採用が期待できる。また、多孔質構造体は、シート状、棒状、筒状など任意の形状を採ることができるため、その用途に応じて使い分けることが可能である。さらに、例えば、多孔質構造体は、液体クロマトグラフィー用のカラム用充填媒体として、大きな径のカラムからキャピラリーカラムまで使用できる。 In the porous structure of the cured epoxy resin according to the present embodiment, the multi-walled carbon nanotube in the skeleton reinforces the skeleton portion, thereby lowering the viscosity without impairing elasticity compared to the conventional epoxy resin porous body. be able to. Moreover, according to the porous structure concerning this invention, it can be excellent in the decompression | restoration performance after compression deformation. Therefore, it can be expected to be used in applications other than conventional separation media for liquid chromatography, for example, as a structural material. Moreover, since the porous structure can take an arbitrary shape such as a sheet shape, a rod shape, or a cylindrical shape, it can be properly used depending on its application. Furthermore, for example, the porous structure can be used from a large-diameter column to a capillary column as a packing medium for a column for liquid chromatography.
もちろん該多孔質構造体は、エポキシ樹脂硬化物であることから、表面に官能基を有しており、グラフト反応等で目的に応じた表面修飾を行うことが可能である。 Of course, since the porous structure is a cured epoxy resin, it has a functional group on the surface and can be subjected to surface modification according to the purpose by graft reaction or the like.
本発明にかかる多孔質構造体のエポキシ樹脂硬化物は三次元架橋されており、耐薬品性、耐熱性に優れていることから、過酷な環境下でも使用可能である。 Since the cured epoxy resin of the porous structure according to the present invention is three-dimensionally cross-linked and has excellent chemical resistance and heat resistance, it can be used even in harsh environments.
上記のように、本発明の実施形態について詳細に説明したが、本発明の新規事項及び効果から実体的に逸脱しない多くの変形が可能であることは当業者には容易に理解できよう。したがって、このような変形例はすべて、本発明の範囲に含まれるものとする。 Although the embodiments of the present invention have been described in detail as described above, those skilled in the art can easily understand that many modifications can be made without departing from the novel matters and effects of the present invention. Accordingly, all such modifications are intended to be included in the scope of the present invention.
以下、本発明の実施例について述べるが、本発明はこれらに限定されるものではない。 Examples of the present invention will be described below, but the present invention is not limited thereto.
Ａ．サンプルの作製
Ａ−１．第１の工程
エポキシ樹脂（三菱ガス化学社製、商品名「ＴＥＴＲＡＤ−Ｃ（「テトラ−ド／ＴＥＴＲＡＤ」は三菱ガス化学社の登録商標）」、ビスフェノールＡ型エポキシ樹脂、エポキシ当量９５〜１１０（表では「Ａ剤」））１．００ｇと、硬化剤（ＳＡＮＨＯ ＣＨＥＭＩＣＡＬ社製、商品名「トーマイド２４５−Ｓ（「トーマイド／ＴＯＨＭＩＤＥ」はティーアンドケイ東華社の登録商標）」、ポリアミノアミン、２５℃における粘度１０００〜２５００ｍＰａ・ｓ、アミン価５２０〜５５０ｍｍｏｌ／ｇ（表では「Ｂ剤」））１．００ｇと、をスクリュー管瓶中で室温において混合し、第１の混合物を得た。
A. Preparation of sample A-1. First Step Epoxy Resin (Mitsubishi Gas Chemical Co., Ltd., trade name “TETRAD-C (“ Tetrad / TETRAD ”is a registered trademark of Mitsubishi Gas Chemical Company)”, bisphenol A type epoxy resin, epoxy equivalent 95-110 ( 1.00 g in the table) and a curing agent (manufactured by SANHO CHEMICAL, trade name “Tomide 245-S (“ Tomide / TOHMIDE ”is a registered trademark of T & K Toka)”, polyaminoamine, 25 A viscosity of 1000 to 2500 mPa · s at ℃ and an amine value of 520 to 550 mmol / g (“B agent” in the table) 1.00 g were mixed in a screw tube bottle at room temperature to obtain a first mixture.
また、ポリエチレングリコール（和光純薬工業社製、分子量２００（表では「ＰＥＧ」））５．００ｇに表１〜表３に示す量の多層カーボンナノチューブと分散剤とをスクリュー管瓶中で室温において撹拌混合し、さらに超音波（出力３００Ｗ）を照射して第２の混合物を得た。なお、表１〜表３における配合割合は、上段が多孔質構造体の固体成分中の配合質量割合（ｗｔ％）であり、下段が製造工程で用いる溶液成分（多孔質構造体に残らない成分）中の配合質量割合（ｗｔ％）である。 In addition, 5.00 g of polyethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd., molecular weight 200 (“PEG” in the table)) in the amount of multi-walled carbon nanotubes and dispersant shown in Tables 1 to 3 at room temperature in a screw tube bottle. The mixture was stirred and mixed, and further irradiated with ultrasonic waves (output 300 W) to obtain a second mixture. The blending ratios in Tables 1 to 3 are blending mass ratios (wt%) in the solid component of the porous structure in the upper stage, and solution components (components not remaining in the porous structure) used in the manufacturing process in the lower stage. ) In the blended mass ratio (wt%).
次に、第１の混合物と第２の混合物とをスクリュー管瓶中で室温において撹拌混合し、さらに超音波（出力３００Ｗ）を照射して混合物の溶液とした。この混合物の溶液を７０℃で３０分間重合し、多孔質構造体を調製した。その後、１００℃条件で３時間キュアを行い、室温まで冷却して取り出した。 Next, the first mixture and the second mixture were stirred and mixed in a screw tube bottle at room temperature, and further irradiated with ultrasonic waves (output 300 W) to obtain a solution of the mixture. A solution of this mixture was polymerized at 70 ° C. for 30 minutes to prepare a porous structure. Thereafter, curing was performed at 100 ° C. for 3 hours, and the mixture was cooled to room temperature and taken out.
なお、比較例６，７として、多層カーボンナノチューブの代わりにシングルウォールカーボンナノチューブとダブルウォールカーボンナノチューブを用いて実施例と同様にして多孔質構造体を製造しようとしたが、第２の混合物の段階でカーボンナノチューブが分散しなかったため、多孔質構造体を製造しなかった。 In Comparative Examples 6 and 7, an attempt was made to produce a porous structure in the same manner as in Example using single wall carbon nanotubes and double wall carbon nanotubes instead of multi-walled carbon nanotubes. Since the carbon nanotubes were not dispersed, a porous structure was not manufactured.
Ａ−２．第２の工程
第１の工程で得られた多孔質構造体を水で洗浄してポリエチレングリコールを除去し、乾燥し、実施例１〜７及び比較例２〜５の多孔質構造体サンプルを得た。
A-2. Second Step The porous structure obtained in the first step is washed with water to remove polyethylene glycol and dried to obtain porous structure samples of Examples 1 to 7 and Comparative Examples 2 to 5. It was.
なお、比較例１は多層カーボンナノチューブ及び分散剤を配合せずにほぼ同様に作成した純粋なエポキシ樹脂硬化物モノリスの多孔質構造体サンプルであった。 Comparative Example 1 was a pure epoxy resin monolithic porous structure sample prepared in the same manner without blending multi-walled carbon nanotubes and a dispersant.
また、サンプル作成に用いた多層カーボンナノチューブは、「ＣＮＴ−１」、「ＣＮＴ−２」、及び「ＣＮＴ−３」が平均直径が約１５ｎｍの多層カーボンナノチューブであって、製造メーカが異なるものであり、「ＣＮＴ−４」が平均直径が約７０ｎｍの多層カーボンナノチューブであった。また、分散剤は、「分散剤Ａ」がドデシルベンゼンスルホン酸ナトリウム、「分散剤Ｂ」が多種類の界面活性剤が混合された台所用洗剤、「分散剤Ｃ」がカテキン水溶液であった。表１〜表３の配合欄における多層カーボンナノチューブの配合量及び分散剤の配合量は、第１の工程で得られた混合物における配合量であった。 The multi-walled carbon nanotubes used for sample preparation are “CNT-1”, “CNT-2”, and “CNT-3”, which are multi-walled carbon nanotubes having an average diameter of about 15 nm, with different manufacturers. “CNT-4” was a multi-walled carbon nanotube having an average diameter of about 70 nm. In addition, as for the dispersant, “dispersant A” was sodium dodecylbenzenesulfonate, “dispersant B” was a kitchen detergent in which various types of surfactants were mixed, and “dispersant C” was an aqueous catechin solution. The blending amount of the multi-walled carbon nanotubes and the blending amount of the dispersant in the blending columns of Tables 1 to 3 were blending amounts in the mixture obtained in the first step.
表１〜表３の多孔質構造体の欄に、多孔質構造体サンプルにおける多層カーボンナノチューブの質量百分率（質量％）を示し、多孔質構造体サンプルの密度（ｇ／ｃｍ３）を示した。 In the column of the porous structure in Tables 1 to 3, the mass percentage (% by mass) of the multi-walled carbon nanotubes in the porous structure sample is shown, and the density (g / cm 3 ) of the porous structure sample is shown.
Ｂ．測定及び観察
Ｂ−１．クリープ試験
サンプルが薄いため、ここでは、クリープ試験として、ＪＩＳ Ｋ６２５３のＭ法に基づく国際ゴム硬さ試験（ＩＲＨＤ）に従って、図１に示す多孔質構造体をＯリング形状に成形した架橋サンプル２０に先端に鋼球を有するインデンタ（押針）１０を定荷重（一次荷重０．８５ｇ、二次荷重１４．８ｇ）、６００秒間押し付けたときの変位を測定し、その結果を定圧粘弾性試験の時間−歪み曲線（クリープ曲線）としてグラフにして遅延時間λを測定した。そして、図２に示すような２つのバネ３０，４０と１つのダッシュポット５０を組み合わせたいわゆる三要素フォークトモデルに当てはめて、バネ定数Ｋ１，Ｋ２、粘性係数η及び遅延時間λを計算した。具体的には、国際ゴム硬さ試験（ＩＲＨＤ）にて力を加えた瞬間のひずみ量ε０と６００秒後のひずみ量ε（６００）を測定した。まず、ε０=σ／Ｋ１（ここでσ＝１５３．３ｍＮ）より、Ｋ１を計算し、ε（６００）＝σ／Ｋ２としてＫ２を計算した。さらに、ｔ＝λの時を遅延時間とするので、下記式（１）より、ε(t)=ε０＋ε（６００）（１−１／ｅ）となるときの時間tを抽出し、下記式（２）よりηを計算した。
B. Measurement and observation B-1. Since the creep test sample is thin, here, as the creep test, in accordance with the international rubber hardness test (IRHD) based on the JIS K6253 method M, the cross-linked sample 20 in which the porous structure shown in FIG. Displacement when indenter (push needle) 10 having a steel ball at the tip is pressed for 600 seconds under constant load (primary load 0.85 g, secondary load 14.8 g) is measured, and the result is the time for constant pressure viscoelasticity test. -The delay time λ was measured in the form of a graph as a strain curve (creep curve). Then, by applying a so-called three-element forked model in which two springs 30 and 40 and one dashpot 50 as shown in FIG. 2 are combined, the spring constants K1 and K2, the viscosity coefficient η, and the delay time λ are calculated. Specifically, the strain amount ε 0 at the moment when force was applied in the international rubber hardness test (IRHD) and the strain amount ε (600) after 600 seconds were measured. First, K1 was calculated from ε 0 = σ / K1 (where σ = 153.3 mN), and K2 was calculated as ε (600) = σ / K2. Further, since the delay time is t = λ, the time t when ε (t) = ε 0 + ε (600) (1-1 / e) is extracted from the following equation (1). Η was calculated from equation (2).
ε（ｔ）＝ε０＋σ／Ｋ２［１−ｅｘｐ（−ｔ／λ）］ （１）
λ＝η／Ｋ２ （２）
時間−歪み曲線（クリープ曲線）の一例として、実施例２の時間−歪み曲線（クリープ曲線）を図３に示した。各サンプルのバネ定数Ｋ１，Ｋ２、粘性係数η、遅延時間λを表１〜表３に示した。
ε (t) = ε 0 + σ / K2 [1-exp (−t / λ)] (1)
λ = η / K2 (2)
As an example of the time-strain curve (creep curve), the time-strain curve (creep curve) of Example 2 is shown in FIG. Tables 1 to 3 show the spring constants K1 and K2, the viscosity coefficient η, and the delay time λ of each sample.
各実施例の多孔質構造体サンプルは、骨格内にある多層カーボンナノチューブが骨格部分を補強することにより、比較例１の多孔質構造体サンプルに比べて弾性Ｋ１，Ｋ２を損なうことなく粘性η及び遅延時間λを下げることができた。 The porous structure sample of each example has a viscosity η and a loss of elasticity K1 and K2 as compared with the porous structure sample of Comparative Example 1 because the multi-walled carbon nanotubes in the skeleton reinforce the skeleton portion. The delay time λ could be lowered.
Ｂ−２．圧縮試験前後の観察
実施例１及び比較例１の多孔質構造体サンプル
（８０％圧縮試験していないサンプル）を走査型電子顕微鏡で観察した。実施例１の多孔質構造体サンプルの電子顕微鏡写真を図４に示した。比較例１の多孔質構造体サンプルの電子顕微鏡写真を図６に示した。
B-2. Observation before and after the compression test The porous structure samples of Example 1 and Comparative Example 1 (samples not subjected to the 80% compression test) were observed with a scanning electron microscope. An electron micrograph of the porous structure sample of Example 1 is shown in FIG. An electron micrograph of the porous structure sample of Comparative Example 1 is shown in FIG.
次に、多孔質構造体サンプルを８０％圧縮試験した。８０％圧縮試験は、多孔質構造体サンプルの圧縮試験前の高さの２０％の高さまで圧縮した後、荷重から解放した。 Next, the porous structure sample was subjected to an 80% compression test. The 80% compression test was released from the load after compressing the porous structure sample to a height of 20% of the height before the compression test.
その８０％圧縮試験後の多孔質構造体サンプルを電子顕微鏡で観察した。実施例１の多孔質構造体サンプルの８０％圧縮試験した後の電子顕微鏡写真を図５に示した。比較例１の多孔質構造体サンプルの８０％圧縮試験後の電子顕微鏡写真を図７に示した。圧縮方向は、写真の上下方向であった。 The porous structure sample after the 80% compression test was observed with an electron microscope. The electron micrograph after the 80% compression test of the porous structure sample of Example 1 is shown in FIG. The electron micrograph after the 80% compression test of the porous structure sample of Comparative Example 1 is shown in FIG. The compression direction was the vertical direction of the photograph.
図４及び図５を比較すると、実施例１の多孔質構造体サンプルは圧縮後に上下方向に大きく復元したことがわかった。これに対し、図６及び図７を比較すると、比較例１の多孔質構造体サンプルは圧縮された状態で骨格構造が塑性変形したままあまり復元せず、空孔も押しつぶされて小さくなっていた。 4 and 5 were compared, it was found that the porous structure sample of Example 1 was greatly restored in the vertical direction after compression. On the other hand, comparing FIG. 6 and FIG. 7, the porous structure sample of Comparative Example 1 was not restored much while the skeleton structure was plastically deformed in a compressed state, and the pores were also crushed and became smaller. .
Ｂ−３．電子顕微鏡の観察
多孔質構造体サンプルの破断面を透過型電子顕微鏡で観察した。実施例３の骨格部分を走査型電子顕微鏡で撮影した写真を図８及び図９に示した。
B-3. Observation with an electron microscope The fracture surface of the porous structure sample was observed with a transmission electron microscope. The photograph which image | photographed the frame | skeleton part of Example 3 with the scanning electron microscope was shown in FIG.8 and FIG.9.
各実施例のサンプルの電子顕微鏡観察の結果、三次元網目構造の骨格と、空孔とを有する多孔質構造体であって、骨格及び空孔の共連続構造が形成されていることが観察された。また、各実施例のサンプルは、骨格内に多層カーボンナノチューブが解繊した状態で分散し骨格と濡れていることが観察された。比較例３，４の分散剤を用いていない多孔質構造体は、骨格内に多層カーボンナノチューブが存在するものの分散しておらず、凝集体のまま骨格内に存在していた。 As a result of observing the sample of each example with an electron microscope, it was observed that the porous structure had a three-dimensional network structure and pores, and a co-continuous structure of the framework and pores was formed. It was. In addition, it was observed that the samples of each example were dispersed and wetted with the skeleton in a state where the multi-walled carbon nanotubes were defibrated in the skeleton. The porous structures not using the dispersant of Comparative Examples 3 and 4 were not dispersed although multi-walled carbon nanotubes existed in the skeleton, and existed in the skeleton as aggregates.
１０ インデンタ（押針）、２０ Ｏリング型の架橋サンプル、Ｋ１，Ｋ２ バネ定数、η 粘性係数 10 Indenter, 20 O-ring type cross-linked sample, K1, K2 spring constant, η viscosity coefficient
Claims (5)
前記骨格及び前記空孔の共連続構造が形成され、
前記骨格内に平均直径が９ｎｍ以上１１０ｎｍ以下の多層カーボンナノチューブを０．３質量％以上１０質量％以下含み、
前記骨格内に多層カーボンナノチューブの凝集体が存在しない、多孔質構造体。 A porous structure having a three-dimensional network structure skeleton made of a cured epoxy resin and pores,
A co-continuous structure of the skeleton and the pores is formed;
Containing 0.3 to 10% by mass of multi-walled carbon nanotubes having an average diameter of 9 to 110 nm in the skeleton,
A porous structure having no aggregate of multi-walled carbon nanotubes in the skeleton.
前記骨格及び前記空孔の共連続構造が形成され、
前記骨格内に平均直径が９ｎｍ以上１１０ｎｍ以下の多層カーボンナノチューブを０．３質量％以上１０質量％以下含み、
前記骨格内に分散剤を含む、多孔質構造体。 A porous structure having a three-dimensional network structure skeleton made of a cured epoxy resin and pores,
A co-continuous structure of the skeleton and the pores is formed;
Containing 0.3 to 10% by mass of multi-walled carbon nanotubes having an average diameter of 9 to 110 nm in the skeleton,
Including, porous structure of the dispersing agent in said backbone.
前記多層カーボンナノチューブを０．４質量％以上１.０質量％以下含む、多孔質構造
体。 In claim 1 or 2,
A porous structure containing the multi-walled carbon nanotubes in an amount of 0.4% by mass to 1.0% by mass.
クリープ試験における粘性係数ηが１００ｍＮ・ｓｅｃ〜６５０ｍＮ・ｓｅｃである、多孔質構造体。 In any one of Claims 1-3,
A porous structure having a viscosity coefficient η in a creep test of 100 mN · sec to 650 mN · sec.
クリープ試験における遅延時間λが１ｓｅｃ〜４０ｓｅｃである、多孔質構造体。 In any one of Claims 1-4,
A porous structure having a delay time λ in a creep test of 1 sec to 40 sec.
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