JP2008239410A - Clay thin film and its laminate - Google Patents
Clay thin film and its laminate Download PDFInfo
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- JP2008239410A JP2008239410A JP2007082963A JP2007082963A JP2008239410A JP 2008239410 A JP2008239410 A JP 2008239410A JP 2007082963 A JP2007082963 A JP 2007082963A JP 2007082963 A JP2007082963 A JP 2007082963A JP 2008239410 A JP2008239410 A JP 2008239410A
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- 239000004927 clay Substances 0.000 title claims abstract description 80
- 239000010409 thin film Substances 0.000 title claims abstract description 65
- 239000002608 ionic liquid Substances 0.000 claims abstract description 22
- 239000003779 heat-resistant material Substances 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 13
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052901 montmorillonite Inorganic materials 0.000 claims abstract description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000004693 imidazolium salts Chemical class 0.000 claims abstract description 6
- -1 stevensite Inorganic materials 0.000 claims abstract description 6
- 229910021647 smectite Inorganic materials 0.000 claims abstract description 4
- VNSBYDPZHCQWNB-UHFFFAOYSA-N calcium;aluminum;dioxido(oxo)silane;sodium;hydrate Chemical compound O.[Na].[Al].[Ca+2].[O-][Si]([O-])=O VNSBYDPZHCQWNB-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910000271 hectorite Inorganic materials 0.000 claims abstract description 3
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 claims abstract description 3
- 229910052742 iron Inorganic materials 0.000 claims abstract description 3
- 239000010445 mica Substances 0.000 claims abstract description 3
- 229910052618 mica group Inorganic materials 0.000 claims abstract description 3
- 229910000273 nontronite Inorganic materials 0.000 claims abstract description 3
- 229910000275 saponite Inorganic materials 0.000 claims abstract description 3
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 claims abstract description 3
- 229910052902 vermiculite Inorganic materials 0.000 claims abstract description 3
- 239000010455 vermiculite Substances 0.000 claims abstract description 3
- 235000019354 vermiculite Nutrition 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims description 13
- 230000002209 hydrophobic effect Effects 0.000 claims description 6
- 125000002091 cationic group Chemical group 0.000 claims description 4
- 150000004714 phosphonium salts Chemical group 0.000 claims description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 2
- 239000010408 film Substances 0.000 abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 17
- 239000000758 substrate Substances 0.000 abstract description 12
- 239000010410 layer Substances 0.000 description 12
- 150000001768 cations Chemical class 0.000 description 9
- 230000004888 barrier function Effects 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 230000035699 permeability Effects 0.000 description 6
- KYCQOKLOSUBEJK-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;bromide Chemical compound [Br-].CCCCN1C=C[N+](C)=C1 KYCQOKLOSUBEJK-UHFFFAOYSA-M 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 239000004973 liquid crystal related substance Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
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- QWLSTCVUGYAKLE-UHFFFAOYSA-M 1-dodecyl-3-methylimidazol-3-ium;bromide Chemical compound [Br-].CCCCCCCCCCCC[N+]=1C=CN(C)C=1 QWLSTCVUGYAKLE-UHFFFAOYSA-M 0.000 description 1
- URVSXZLUUCVGQM-UHFFFAOYSA-M 1-methyl-3-octylimidazol-1-ium;bromide Chemical compound [Br-].CCCCCCCCN1C=C[N+](C)=C1 URVSXZLUUCVGQM-UHFFFAOYSA-M 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical group N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- WXMVWUBWIHZLMQ-UHFFFAOYSA-N 3-methyl-1-octylimidazolium Chemical compound CCCCCCCCN1C=C[N+](C)=C1 WXMVWUBWIHZLMQ-UHFFFAOYSA-N 0.000 description 1
- QUJHOIQSCPTTSO-UHFFFAOYSA-N CCCCCCCCCCCCCCCCCCNC(=C)CCCCCCCCCCCCCCCCC=C Chemical class CCCCCCCCCCCCCCCCCCNC(=C)CCCCCCCCCCCCCCCCC=C QUJHOIQSCPTTSO-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
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- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
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- 239000012454 non-polar solvent Substances 0.000 description 1
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- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 238000005546 reactive sputtering Methods 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
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- PDSVZUAJOIQXRK-UHFFFAOYSA-N trimethyl(octadecyl)azanium Chemical class CCCCCCCCCCCCCCCCCC[N+](C)(C)C PDSVZUAJOIQXRK-UHFFFAOYSA-N 0.000 description 1
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- Laminated Bodies (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
Description
本発明は薄片状耐熱材料が積層した構造を有し、イオン性液体を含む粘土薄膜に関するものである。 The present invention relates to a clay thin film having a structure in which flaky heat-resistant materials are laminated and containing an ionic liquid.
ディスプレイは、モバイル性や省スペースの面より、従来のブラウン管方式から液晶方式（ＬＣＤ）に急激に変わりつつある。更に次世代ディスプレイとして、自発光デバイスであり、明るさ、鮮やかさ、消費電力の点でも優れた有機ＥＬ方式のものが生産され始めている。これらは従来のブラウン管方式のものと比べればモバイル性や省スペースの面で格段に優れているが、基板としてガラスが使用されているために、比較的重量があり、また、割れるという問題も有している。
これらの問題点を解決するため、一部の液晶方式のものではフィルム基板（プラセルと呼ばれている）が使用されている。しかしながら、次世代ディスプレイとして脚光を浴びている有機ＥＬディスプレイの場合、低抵抗な透明導電膜が必要とされており、この為２５０℃を超える熱処理が不可欠である。
また、太陽電池パネルにもガラス基板から軽くて、割れにくいフィルム基板の利用が注目されている。この場合、透明性、耐熱性、耐候性はもちろんのこと、難燃性の要求も高まってきている。
従来のプラスチック基板ではこのような特性をすべて両立して満足するものが無い。これらの要求を満たし得る材料としては粘土薄膜が注目されている。
The display is rapidly changing from a conventional cathode ray tube system to a liquid crystal system (LCD) in terms of mobility and space saving. Furthermore, as a next-generation display, a self-luminous device that is excellent in terms of brightness, vividness, and power consumption is being produced. These are far superior in terms of mobility and space saving compared to the conventional CRT type, but because of the use of glass as a substrate, they are relatively heavy and have the problem of cracking. is doing.
In order to solve these problems, a film substrate (referred to as a “placel”) is used in some liquid crystal type devices. However, in the case of an organic EL display that has been in the spotlight as a next-generation display, a low-resistance transparent conductive film is required, and thus heat treatment exceeding 250 ° C. is indispensable.
In addition, the use of a film substrate that is light from a glass substrate and difficult to break is also attracting attention for solar cell panels. In this case, in addition to transparency, heat resistance, and weather resistance, there is an increasing demand for flame retardancy.
No conventional plastic substrate satisfies all of these characteristics. As a material that can satisfy these requirements, a clay thin film has attracted attention.
粘土薄膜は、透明性をもち優れたフレキシビリティーを有し、粒子が層状に緻密に配向している構造を有しているので、気体バリア性に優れ、主成分が無機物である為に非常に耐熱性に優れた材料である（特許文献１参照）。しかしながら、液晶や有機ＥＬディスプレイ用のフィルム基板として使用する場合、いくつかの問題が存在する。
一つは耐水性の問題である。一般的に用いられる粘土は層間に親水性の陽イオンを含んでおり、吸湿性の高い物質である。このため、水分による劣化が懸念される有機ＥＬディスプレイ用のフィルム基板としては適さない。耐水性を上げる対策の一つとして層間への撥水剤添加が考えられるが、吸水性を制御した場合、全く水分がなくなると膜が柔軟性を喪失してしまい、柔軟性を保つ程度の水分を保持しようとすると、急激な過熱による水分の沸騰の為膜を破壊する結果となってしまう。もう一つの耐水化の方法として粘土層間に含まれる親水性陽イオンを疎水性陽イオンに交換する方法がある。しかしながら粘土膜に柔軟性を与える為には熱に弱い樹脂分を多量に粘土層間に挿入する必要があり、粘土が有する耐熱性を十分に発揮することができないという問題を有していた。
また、粘土自体は無機物であるために不燃である。しかし、柔軟性を与える為に添加する樹脂分が有機物であるために、その有機物が燃える為に粘土膜は燃焼するという問題も有していた。
One is the problem of water resistance. Commonly used clay contains a hydrophilic cation between layers, and is a highly hygroscopic substance. For this reason, it is not suitable as a film substrate for an organic EL display in which deterioration due to moisture is a concern. One measure to increase water resistance is to add a water-repellent agent between the layers. However, when water absorption is controlled, the film loses its flexibility when it loses water at all, so that it retains flexibility. If an attempt is made to hold the film, the film will be destroyed due to the boiling of water due to rapid overheating. As another water resistance method, there is a method of exchanging hydrophilic cations contained between clay layers with hydrophobic cations. However, in order to give flexibility to the clay film, it is necessary to insert a large amount of heat-sensitive resin between the clay layers, and there is a problem that the heat resistance of clay cannot be fully exhibited.
Moreover, since clay itself is an inorganic substance, it is nonflammable. However, since the resin component added to give flexibility is an organic material, the clay film also has a problem of burning because the organic material burns.
上記したように、粘土薄膜を有機ＥＬディスプレイや太陽電池用のフィルム基板として利用するために透明性、耐熱性、耐水性、難燃性に優れたフレキシブル性を有する薄膜を提供する必要がある。したがって、本発明の目的は、薄片状耐熱材料が積層した構造を有し、イオン性液体を含ませることにより耐熱性、耐水性、柔軟性、難燃性を両立し、且つ環境に配慮した、優れた粘土薄膜を提供することにある。 As described above, in order to use a clay thin film as a film substrate for an organic EL display or a solar cell, it is necessary to provide a flexible thin film having excellent transparency, heat resistance, water resistance, and flame retardancy. Accordingly, the object of the present invention is to have a structure in which flaky heat-resistant materials are laminated, and by including an ionic liquid, it has both heat resistance, water resistance, flexibility, flame retardancy, and is environmentally friendly. The object is to provide an excellent clay thin film.
本発明の粘土薄膜は、薄片状耐熱材料とイオン性液体とを含むことを特徴とする。
本発明でいう粘土薄膜とは、薄片状耐熱材料が配向して積層した構造を有する膜厚１〜３０００μｍの膜状物のことである。本発明の粘土薄膜は、例えば薄片状耐熱材料及びイオン性液体を溶剤に分散させ、これをフィルムなどに膜状化して形成し、その後該膜状物を熱処理後、フィルムから剥離することにより得ることができる。
前記薄片状耐熱材料としては、雲母、バーミキュライト、モンモリロナイト、鉄モンモリロナイト、バイデライト、サポナイト、ヘクトライト、スチーブンサイト、ノントロナイト、マガディアイト、アイラライト、カネマイト、スメクタイト及び層状チタン酸などを挙げることができる。これらは一種以上を粘土薄膜に用いることができる。
The clay thin film of the present invention includes a flaky heat-resistant material and an ionic liquid.
The clay thin film referred to in the present invention is a film-like material having a thickness of 1 to 3000 μm having a structure in which flaky heat-resistant materials are oriented and laminated. The clay thin film of the present invention is obtained by, for example, forming a flaky heat-resistant material and an ionic liquid in a solvent, forming the film into a film, and then peeling the film from the film after heat treatment. be able to.
Examples of the flaky heat-resistant material include mica, vermiculite, montmorillonite, iron montmorillonite, beidellite, saponite, hectorite, stevensite, nontronite, magadiite, ilarite, kanemite, smectite, and layered titanic acid. . One or more of these can be used for the clay thin film.
イオン性液体とは、陽イオンと陰イオンの特殊な組み合わせで、２５℃の常温でも液状状態でかつ安定した塩のことを言い、難燃性・不揮発性・高極性・高イオン伝導性・高耐熱性などの性質を有している。イオン性液体は、上述した性質を有しているために、粘土薄膜に含有させた際に、膜に柔軟性と難燃性の両方を付与することを可能とするのである。具体的には、下記の化１に示す四級アンモニウム塩、四級ホスホニウム塩、イミダゾリウム塩等においてＲ１〜Ｒ１１を適正なものにすることにより、常温で液状状態となるイオン性液体を用いることができる。 An ionic liquid is a special combination of a cation and an anion, which is a salt that is in a liquid state and stable even at room temperature of 25 ° C. It is flame retardant, non-volatile, highly polar, highly ionic conductive, high It has properties such as heat resistance. Since the ionic liquid has the above-described properties, it is possible to impart both flexibility and flame retardancy to the film when it is contained in the clay thin film. Specifically, using an ionic liquid that is in a liquid state at room temperature by making R1 to R11 appropriate in the quaternary ammonium salt, quaternary phosphonium salt, imidazolium salt, etc. shown in Chemical Formula 1 below. Can do.
本発明においては、イオン性液体として２５℃で液状のイミダゾリウム塩が好ましく用いられる。これは他のイオン性液体に比べ熱分解温度が高いからである。これらのイオン性液体は、重量比で粘土薄膜全体の１〜６０％であることが好ましい。１％未満の場合では、粘土に柔軟性を付与することが困難であり、６０％を超えると膜として自立しにくくなる。 In the present invention, an imidazolium salt that is liquid at 25 ° C. is preferably used as the ionic liquid. This is because the thermal decomposition temperature is higher than that of other ionic liquids. These ionic liquids are preferably 1 to 60% of the entire clay thin film by weight ratio. If it is less than 1%, it is difficult to impart flexibility to the clay, and if it exceeds 60%, it becomes difficult to stand alone as a film.
また粘土薄膜の強度を増すために、樹脂を添加することもできる。樹脂に関しては、耐熱性の高い樹脂を適宜選択することが出来る。例えば、エポキシ系樹脂、ポリイミド樹脂、シリコーン樹脂等をあげることが出来る。本発明においては、特に限定されるものではない。 A resin can also be added to increase the strength of the clay thin film. As for the resin, a resin having high heat resistance can be appropriately selected. For example, an epoxy resin, a polyimide resin, a silicone resin, and the like can be given. In the present invention, there is no particular limitation.
また、本発明の粘土薄膜を構成する薄片状耐熱材料の層間には、疎水性を有する陽イオン物質を含むことが好ましく、これにより粘土層間に上記イオン性液体が含有されやすくなる。一般に粘土は層間に親水性の交換性陽イオンを含んでいる。本発明においては粘土である薄片状耐熱材料の層間に有する親水性の交換性陽イオンを疎水性の陽イオン物質に交換し有機化させることが好ましい。疎水性の陽イオン物質としては例えば、ジメリルジステアリルアンモニウム塩やトリメチルステアリルアンモニウム塩などの第４級アンモニウム塩や、ベンジル基やポリオキシエチレン基を有するアンモニウム塩を用いたり、ホスホニウム塩やピリジニウム塩やイミダゾリウム塩を用い、粘土のイオン交換性、例えば、モンモリロナイトの陽イオン交換性を利用して有機化することができる。これにより、薄片状耐熱材料の有機溶剤への分散が容易になり、また、イオン性液体を添加した際に粘土薄膜への含有が容易となる。 Moreover, it is preferable to include a cationic substance having hydrophobicity between the layers of the flaky heat-resistant material constituting the clay thin film of the present invention, whereby the ionic liquid is easily contained between the clay layers. In general, clay contains hydrophilic exchangeable cations between layers. In the present invention, it is preferable that the hydrophilic exchangeable cation possessed between the layers of the flaky heat-resistant material, which is clay, is exchanged with a hydrophobic cation substance for organic formation. Examples of hydrophobic cationic substances include quaternary ammonium salts such as dimethylyl distearyl ammonium salt and trimethyl stearyl ammonium salt, ammonium salts having a benzyl group and a polyoxyethylene group, phosphonium salts and pyridinium salts. And imidazolium salts can be used to organically utilize the ion exchange properties of clay, for example, the cation exchange properties of montmorillonite. This facilitates dispersion of the flaky heat-resistant material in the organic solvent, and facilitates inclusion in the clay thin film when an ionic liquid is added.
本発明の粘土薄膜は、単独でも自立膜として利用可能であるが、より高いガスバリア性、耐薬品性、表面平滑性を得るために粘土薄膜の片面または両面に無機薄膜または有機薄膜のうち少なくとも一方を単層または複数層形成することが可能である。積層膜種は特に限定しないが、用途により最適なものを選択できる。例えば酸化珪素もしくは酸化窒化珪素をスパッタ法もしくはプラズマＣＶＤ法により製膜を行うことにより高いガスバリア性及び耐薬品性を付与することができる。更には有機ポリマーを塗布することにより表面に平坦性を持たせることができる。例えば、ハードコート層を積層して、ハードコート性を付与することもできる。これらの無機及び有機の表面コートを積層することにより粘土薄膜単独では持ち得ない特性を付与することができる。
また、本発明の粘土薄膜を作製する際に、硬化助剤、酸化防止剤、界面活性剤、顔料、レベリング剤等の一般的な添加剤を種々添加することができる。
The clay thin film of the present invention can be used alone as a free-standing film, but at least one of an inorganic thin film and an organic thin film on one or both sides of the clay thin film in order to obtain higher gas barrier properties, chemical resistance, and surface smoothness. It is possible to form a single layer or a plurality of layers. There are no particular limitations on the type of laminated film, but an optimum film can be selected depending on the application. For example, high gas barrier properties and chemical resistance can be imparted by forming silicon oxide or silicon oxynitride by sputtering or plasma CVD. Furthermore, the surface can be made flat by applying an organic polymer. For example, a hard coat layer can be laminated to impart hard coat properties. By laminating these inorganic and organic surface coats, it is possible to impart properties that cannot be obtained with a clay thin film alone.
Moreover, when producing the clay thin film of this invention, various general additives, such as a hardening adjuvant, antioxidant, surfactant, a pigment, and a leveling agent, can be added.
本発明の粘土薄膜は、薄片状耐熱材料が積層した構造を有し、イオン性液体を含ませることにより耐熱性、耐水性、柔軟性、透明性、難燃性を両立した、優れた薄膜である。
また、本発明の粘土薄膜は、それがもつ上記特性により、多くの製品に利用することができる。例えば電子ペーパー用基板、電子デバイス用封止フィルム、レンズフィルム、導光板用フィルム、プリズムフィルム、位相差板・偏光板用フィルム、視野角補正フィルム、ＰＤＰ用フィルム、ＬＥＤ用フィルム、光通信用部材、タッチパネル用フィルム、各種機能性フィルムの基板、内部が透けて見える構造の電子機器用フィルム、ビデオディスク・ＣＤ／ＣＤ−Ｒ／ＣＤ−ＲＷ／ＤＶＤ／ＭＯ／ＭＤ・相変化ディスク・光カードを含む光記録メディア用フィルム、燃料電池用封止フィルム、太陽電池用フィルム等に使用することができる。
また、下記実施例５に示すように表面コートにより付加機能をつけると高いガスバリア性を実現でき、液晶や有機ＥＬディスプレイ用のフィルム基板として好適に使用することができる。
The clay thin film of the present invention has a structure in which flaky heat-resistant materials are laminated, and is an excellent thin film that combines heat resistance, water resistance, flexibility, transparency, and flame retardancy by including an ionic liquid. is there.
In addition, the clay thin film of the present invention can be used for many products due to the above properties. For example, electronic paper substrate, electronic device sealing film, lens film, light guide plate film, prism film, retardation plate / polarizing plate film, viewing angle correction film, PDP film, LED film, optical communication member Film for touch panels, substrates for various functional films, films for electronic devices with a transparent structure, video discs, CD / CD-R / CD-RW / DVD / MO / MD, phase change discs, optical cards It can be used for the film for optical recording media containing, the sealing film for fuel cells, the film for solar cells, etc.
Moreover, as shown in Example 5 below, when an additional function is provided by surface coating, a high gas barrier property can be realized, and it can be suitably used as a film substrate for liquid crystal and organic EL displays.
以下、本発明を実施するための最良の形態を実施例に基づいて説明するが、本発明はこれら実施例に限定されるものではない。 Hereinafter, the best mode for carrying out the present invention will be described based on examples, but the present invention is not limited to these examples.
（粘土の有機化）
１−ドデシル−３−メチルイミダゾリウムブロマイド５ｇを純水５０ｇ中に分散させた後、合成スメクタイト（クニミネ工業社製、商品名：スメクトンＳＡ）５ｇ投入し十分に分散膨潤させた。この溶液を遠心分離器で固液分離し液分を取り除いた後、更に純水５０ｇを投入し分散、固液分離を行った。この分散・固液分離を発泡がなくなるまで繰り返したのち、乾燥機で水分を完全に除去した。これにより粘土に含まれる親水性の交換性陽イオンと疎水性の陽イオン物質である１−ドデシル−３−メチルイミダゾリウムイオンが交換され、無極性溶剤であるトルエン対し膨潤性を持つ有機化粘土を得た。
(Organization of clay)
After 5 g of 1-dodecyl-3-methylimidazolium bromide was dispersed in 50 g of pure water, 5 g of synthetic smectite (Kunimine Kogyo Co., Ltd., trade name: Smecton SA) was added and sufficiently dispersed and swollen. This solution was subjected to solid-liquid separation with a centrifugal separator to remove the liquid component, and then 50 g of pure water was added to perform dispersion and solid-liquid separation. This dispersion / solid-liquid separation was repeated until no foaming occurred, and then the moisture was completely removed with a dryer. As a result, the hydrophilic exchangeable cation contained in the clay and the hydrophobic cation substance 1-dodecyl-3-methylimidazolium ion are exchanged, and the organic clay has swelling properties with respect to toluene which is a nonpolar solvent. Got.
（粘土薄膜の形成）
上記により得られた有機化粘土を粉砕し、有機化粘土１０ｇをトルエン１００ｇ中に分散・膨潤させ、イオン性液体として、２５℃で液状の１−ブチル−３−メチルイミダゾリウムブロマイドを２．５ｇを添加し分散を行った。得られた溶液をアプリケーターで離けい処理したポリエチレンテレフタレートフィルム（以下、ＰＥＴフィルムという）上に塗布して製膜した。その後、１００℃の乾燥機に投入し、溶剤分を除去し、ＰＥＴフィルムから剥がして本発明の粘土薄膜を得た。
この粘土薄膜は、透明で柔軟性のある厚さ３０μｍの薄状物であった。
(Formation of clay thin film)
The organic clay obtained above is pulverized, 10 g of the organic clay is dispersed and swollen in 100 g of toluene, and 2.5 g of 1-butyl-3-methylimidazolium bromide liquid at 25 ° C. is used as the ionic liquid. Was added and dispersed. The obtained solution was applied onto a polyethylene terephthalate film (hereinafter referred to as PET film) that had been treated with an applicator to form a film. Then, it put into the dryer of 100 degreeC, the solvent content was removed, and it peeled from PET film, and obtained the clay thin film of this invention.
This clay thin film was a transparent and flexible thin material having a thickness of 30 μm.
実施例１において、１−ブチル−３−メチルイミダゾリウムブロマイドの添加量を０．５ｇにした以外は同様にして厚さ３０μｍの本発明の粘土薄膜を得た。 A clay thin film of the present invention having a thickness of 30 μm was obtained in the same manner as in Example 1, except that the amount of 1-butyl-3-methylimidazolium bromide added was changed to 0.5 g.
実施例１において、１−ブチル−３−メチルイミダゾリウムブロマイドの添加量を１０ｇにした以外は同様にして厚さ３０μｍの本発明の粘土薄膜を得た。 A clay thin film of the present invention having a thickness of 30 μm was obtained in the same manner as in Example 1 except that the amount of 1-butyl-3-methylimidazolium bromide added was changed to 10 g.
実施例１において、イオン性液体として、１−ブチル−３−メチルイミダゾリウムブロマイドの代わりに、２５℃で液状の１−オクチル−３−メチルイミダゾリウムを用いた以外は同様にして厚さ３０μｍの本発明の粘土薄膜を得た。 In Example 1, a 30 μm-thickness was similarly obtained except that 1-octyl-3-methylimidazolium liquid at 25 ° C. was used as the ionic liquid instead of 1-butyl-3-methylimidazolium bromide. A clay thin film of the present invention was obtained.
実施例１にて作製した粘土薄膜の表裏面に、反応性スパッタリングにて無機層であるＳｉＯｘ膜を厚さ６０ｎｍ積層し、本発明の粘土薄膜積層体を得た。
この粘土薄膜積層体は、実施例１で得られた粘土薄膜の透明性と柔軟性を維持していた。
On the front and back surfaces of the clay thin film produced in Example 1, a Si O x film, which is an inorganic layer, was laminated by a thickness of 60 nm by reactive sputtering to obtain a clay thin film laminate of the present invention.
This clay thin film laminate maintained the transparency and flexibility of the clay thin film obtained in Example 1.
［比較例１］
実施例１において、イオン性液体の代わりに、液状物質ではあるが、難燃性の無い非イオン性のジメチルシリコンオイル（信越化学工業社製 ＫＦ９６）を用いた以外は同様にして厚さ３０μｍの粘土薄膜を得た。
[Comparative Example 1]
In Example 1, a 30 μm-thickness was similarly used except that nonionic dimethyl silicone oil (KF96 manufactured by Shin-Etsu Chemical Co., Ltd.), which is a liquid substance but has no flame retardancy, was used instead of the ionic liquid. A clay thin film was obtained.
［比較例２］
実施例１において、粘土薄膜の形成工程で、添加剤を添加せずに有機化粘土のみで粘土薄膜を形成した。
[Comparative Example 2]
In Example 1, in the clay thin film forming step, the clay thin film was formed using only the organized clay without adding an additive.
（粘土薄膜の特性評価）
上記のように得られた実施例１〜４及び比較例１、２で作製した粘土薄膜について、下記の特性を測定しその結果を表１に記した。
〔燃焼試験〕
粘土薄膜を１２５×１３ｍｍに切り出し、長い方を高さ方向にしてつるす。
下から炎を近づけて、粘土薄膜に火を５秒接炎する。その後炎を粘土薄膜より離して、炎が燃焼していくのかどうか確認した。
評価として、×：燃焼（燃え広がる）、△：若干の燃焼（燃え広がるが、ある程度の燃焼後に自己消火）、○：即自己消火（火はつくが、燃え広がらずにすぐに自己消火）、◎：不燃（火がつかない）
の５段階評価を行った。
〔柔軟性〕
粘土薄膜を１００×５０ｍｍに切り出し、両手で短い方の辺（５０ｍｍ）を持ち、お互いの辺がくっつくまで折り曲げ、その後反対方向に折り曲げ同様にお互いの辺がくっつくようにする屈曲運度を５０回行い粘土薄膜を屈曲させる。
屈曲させた後の粘土膜の状態に応じて以下の３段階の評価を行った。○：屈曲後も変化無し、△：一部亀裂が発生、×：屈曲途中で割れる。
(Characteristic evaluation of clay thin film)
For the clay thin films prepared in Examples 1 to 4 and Comparative Examples 1 and 2 obtained as described above, the following characteristics were measured and the results are shown in Table 1.
[Combustion test]
A clay thin film is cut out to 125 × 13 mm, and the long one is suspended in the height direction.
Bring the flame closer from the bottom and touch the clay thin film for 5 seconds. After that, the flame was separated from the clay thin film, and it was confirmed whether the flame would burn.
Evaluation: x: combustion (flame spreads), △: slight combustion (flame spreads, self-extinguishes after a certain amount of combustion), ○: self-extinguish immediately (fires, but self-extinguishes immediately without spreading), ◎: Nonflammable (cannot catch fire)
A five-step evaluation was performed.
[Flexibility]
Cut the clay thin film into 100x50mm, hold the shorter side (50mm) with both hands, bend until each side sticks, and then bend in the opposite direction, as well as bend each other like 50 times. Bend the clay thin film.
The following three stages of evaluation were performed according to the state of the clay film after bending. ○: No change after bending, Δ: Some cracks occurred, ×: Cracking during bending.
＊ＯＭＩ−Ｂｒ：１−オクチル−３−メチルイミダゾリウムブロマイド
上記表１の結果から明らかなように、実施例１〜４において、粘土薄膜に常温で液状状態であって、かつ、難燃性も有しているイオン性液体が含有されているために、粘土薄膜の柔軟性および難燃性の両立が達成されていることが分かる。一方、難燃性のない液状物質を含有した粘土膜（比較例１）は燃焼試験で燃焼し、添加物を添加しない粘土のみの膜（比較例２）では柔軟性に欠けていることが分かる。 As is clear from the results of Table 1 above, in Examples 1 to 4, the clay thin film contains an ionic liquid that is in a liquid state at room temperature and also has flame retardancy. It can be seen that both the flexibility and flame retardancy of the clay thin film are achieved. On the other hand, the clay film containing the non-flammable liquid material (Comparative Example 1) burns in the combustion test, and the clay-only film without the additive (Comparative Example 2) is found to lack flexibility. .
（粘土薄膜積層体の特性評価）
実施例１で得られた粘土薄膜および実施例５で得られた粘土薄膜積層体について、ガスバリア性の評価として、下記の方法にて水蒸気透過率の特性を測定した。
〔水蒸気透過率〕
ＪＩＳ Ｋ ７１２６ Ａ法（差圧法）に準じた差圧式のガスクロ法により、ガス・蒸気等の透過率・透湿度の測定が可能なＧＴＲテック社製のガス・蒸気透過率測定装置を用いて、温度４０℃／湿度９０％ＲＨの条件における水蒸気透過率の測定を行った。
(Characteristic evaluation of clay thin film laminate)
For the clay thin film obtained in Example 1 and the clay thin film laminate obtained in Example 5, the water vapor permeability was measured by the following method as an evaluation of gas barrier properties.
(Water vapor transmission rate)
Using a gas / vapor permeability measuring device manufactured by GTR Tech Co., which is capable of measuring the permeability / moisture permeability of gas / vapor, etc., by a differential pressure type gas chromatography method according to JIS K 7126 A method (differential pressure method) The water vapor transmission rate was measured at a temperature of 40 ° C./humidity of 90% RH.
上記の測定の結果、実施例１の粘土薄膜の水蒸気透過率は０．９ｇ／ｍ２・ｄａｙであり、ガスバリア性は良好であった。実施例５の粘土薄膜積層体の水蒸気透過率は１×１０−５ｇ／ｍ２・ｄａｙ以下であり、さらにガスバリア性に優れたものであることが確認された。 As a result of the above measurement, the water vapor permeability of the clay thin film of Example 1 was 0.9 g / m 2 · day, and the gas barrier property was good. The water vapor permeability of the clay thin film laminate of Example 5 was 1 × 10 −5 g / m 2 · day or less, and it was confirmed that the gas barrier property was excellent.
Claims (7)
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| JPN6012036493; ＫＩＭ，Ｎ．Ｈ． ｅｔ ａｌ: 'Ｍｏｄｉｆｉｃａｔｉｏｎ ｏｆ ｃａｔｉｏｎｉｃ ｎａｎｏｃｌａｙｓ ｗｉｔｈ ｉｏｎｉｃ ｌｉｑｕｉｄｓ' Ｍｉｃｒｏｐｏｒｏｕｓ Ｍｅｓｏｐｏｒｏｕｓ Ｍａｔｅｒ Ｖｏｌ．９６， Ｎｏ．１-３, 20061126, ｐ．２９-３５ * |
| JPN6012036495; ＢＹＲＮＥ，Ｃ． ｅｔ ａｌ: 'Ｉｏｎｉｃ Ｌｉｑｕｉｄ Ｍｏｄｉｆｉｃａｔｉｏｎ ｏｆ Ｌａｙｅｒｅｄ Ｓｉｌｉｃａｔｅｓ ｆｏｒ Ｅｎｈａｎｃｅｄ Ｔｈｅｒｍａｌ Ｓｔａｂｉｌｉｔｙ．' Ｍａｃｒｏｍｏｌ Ｒａｐｉｄ Ｃｏｍｍｕｎ Ｖｏｌ．２８， Ｎｏ．６, 20070316, ｐ．７８０-７８４ * |
| JPN6012036497; ＦＯＸ，Ｄ．Ｍ． ｅｔ ａｌ: 'ＡＰＰＬＩＣＡＴＩＯＮ ＯＦ ＴＲＩＡＬＫＹＬＩＭＩＤＡＺＯＬＩＵＭ ＬＩＱＵＩＤＳ ＡＮＤ ＳＡＬＴＳ ＴＯ ＴＨＥ ＰＲＥＰＡＲＡＴＩＯＮ ＯＦ ＰＯＬＹＭＥＲ-ＬＡＹＥＲＥＤ ＳＩＬＩＣＡＴＥ' Ｐｏｌｙｍ Ｐｒｅｐｒ Ｖｏｌ．４５， Ｎｏ．１, 200403, ｐ．３１１-３１２ * |
| JPN6012036499; 相宮拓司他: 'モンモリロナイトによるイオン性液体のゲル化：ナノコンポジットへの応用' 高分子学会予稿集（ＣＤ-ＲＯＭ） Ｖｏｌ．５３， Ｎｏ．２， Ｄｉｓｋ１, 20040901, Ｐ．１Ｊ１０ * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016199428A (en) * | 2015-04-10 | 2016-12-01 | 国立大学法人東京農工大学 | Composition having ionic conductivity |
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