JP2008266124A - Clay, clay thin film, and laminate thereof - Google Patents
Clay, clay thin film, and laminate thereof Download PDFInfo
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- JP2008266124A JP2008266124A JP2008072525A JP2008072525A JP2008266124A JP 2008266124 A JP2008266124 A JP 2008266124A JP 2008072525 A JP2008072525 A JP 2008072525A JP 2008072525 A JP2008072525 A JP 2008072525A JP 2008266124 A JP2008266124 A JP 2008266124A
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- 239000004927 clay Substances 0.000 title claims abstract description 83
- 239000010409 thin film Substances 0.000 title claims abstract description 67
- 239000003779 heat-resistant material Substances 0.000 claims abstract description 11
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 claims abstract description 7
- 125000001424 substituent group Chemical group 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- -1 stevensite Inorganic materials 0.000 claims description 13
- 229910021647 smectite Inorganic materials 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 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 description 6
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 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 description 3
- 229910000271 hectorite Inorganic materials 0.000 claims 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 description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 239000010445 mica Substances 0.000 claims description 3
- 229910052618 mica group Inorganic materials 0.000 claims description 3
- 229910000273 nontronite Inorganic materials 0.000 claims description 3
- 229910000275 saponite Inorganic materials 0.000 claims description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 3
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 claims description 3
- 229910052902 vermiculite Inorganic materials 0.000 claims description 3
- 239000010455 vermiculite Substances 0.000 claims description 3
- 235000019354 vermiculite Nutrition 0.000 claims description 3
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 239000010408 film Substances 0.000 abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 18
- 239000000758 substrate Substances 0.000 abstract description 14
- 239000010410 layer Substances 0.000 description 11
- 230000008859 change Effects 0.000 description 9
- 230000004888 barrier function Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 150000001768 cations Chemical class 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 230000035699 permeability Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 150000004693 imidazolium salts Chemical class 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- 239000004973 liquid crystal related substance Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- GWQYPLXGJIXMMV-UHFFFAOYSA-M 1-ethyl-3-methylimidazol-3-ium;bromide Chemical compound [Br-].CCN1C=C[N+](C)=C1 GWQYPLXGJIXMMV-UHFFFAOYSA-M 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229920002799 BoPET Polymers 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- KYCQOKLOSUBEJK-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;bromide Chemical compound [Br-].CCCCN1C=C[N+](C)=C1 KYCQOKLOSUBEJK-UHFFFAOYSA-M 0.000 description 1
- 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
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 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
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 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
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- DDFYFBUWEBINLX-UHFFFAOYSA-M tetramethylammonium bromide Chemical compound [Br-].C[N+](C)(C)C DDFYFBUWEBINLX-UHFFFAOYSA-M 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- SNDRYHUSDCHSDJ-UHFFFAOYSA-N tributyl(dodecyl)phosphanium Chemical compound CCCCCCCCCCCC[P+](CCCC)(CCCC)CCCC SNDRYHUSDCHSDJ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
Description
本発明はディスプレイ用途等に用いられる、薄片状耐熱材料の積層構造を有する粘土、粘土薄膜及びその積層体に関するものである。 The present invention relates to a clay having a laminated structure of flaky heat-resistant materials, a clay thin film, and a laminate thereof used for display applications and the like.
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、耐候性はもちろんのこと、耐熱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, not only the transparency and weather resistance but also the demand for heat resistance is increasing.
None of the conventional plastic substrates satisfy 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、ガスバリア性に優れ、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。しかしながら四級アンモニウムイオンに代表される疎水性陽イオンは熱分解を起こしやすく、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。
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, hydrophobic cations such as quaternary ammonium ions are prone to thermal decomposition and have the problem that the heat resistance of clay cannot be fully exhibited.
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耐熱性、耐水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、疎水性陽イオンの含有により耐水化しても耐熱性をも兼備えることができる粘土及びこれを用いて形成した粘土薄膜を提供することにある。さらに、その粘土薄膜を用いて、ガスバリア性に優れた積層体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 thin film having excellent heat resistance and water resistance. Accordingly, an object of the present invention is to provide a clay having a structure in which flaky heat-resistant materials are laminated, and having both water resistance and heat resistance due to the inclusion of hydrophobic cations, and a clay thin film formed using the clay Is to provide. Furthermore, it is providing the laminated body excellent in gas barrier property using the clay thin film.
本発明の粘土は、薄片状耐熱材料が積層された構造を有し、該積層構造の層間に下記一般式（１）で示されるイミダゾリウムイオンを含有する粘土であって、かつ、該イミダゾリウムイオンの置換基Ｒ１とＲ２の炭素数の合計が１０以下であることを特徴とする。 The clay of the present invention has a structure in which flaky heat-resistant materials are laminated, and contains a imidazolium ion represented by the following general formula (1) between layers of the laminated structure, and the imidazolium The total number of carbon atoms of the ionic substituents R1 and R2 is 10 or less.
本発明の粘土において、上記一般式（１）のＲ１、Ｒ２のどちらか一方がＣ２Ｈ５もしくはＣＨ３であると好ましい。
本発明の粘土において、上記薄片状耐熱材料が、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のうち一種以上であると好ましい。
In the clay of the present invention, it is preferable that one of R1 and R2 in the general formula (1) is C 2 H 5 or CH 3 .
In the clay of the present invention, the flaky heat-resistant material is mica, vermiculite, montmorillonite, iron montmorillonite, beidellite, saponite, hectorite, stevensite, nontronite, magadiite, isralite, kanemite, smectite and layered titanic acid. Of these, one or more are preferred.
本発明の粘土薄膜は、上記のいずれかの粘土より形成されることを特徴とする。
また、本発明の薄膜積層体は、上記粘土薄膜の片面もしくは両面に、酸化ケイ素、窒化珪素、炭化珪素の少なくとも一つを含む無機薄膜または有機薄膜のうち少なくとも一方が積層されていると好ましい。
The clay thin film of the present invention is formed from any one of the above clays.
In the thin film laminate of the present invention, it is preferable that at least one of an inorganic thin film or an organic thin film containing at least one of silicon oxide, silicon nitride, and silicon carbide is laminated on one side or both sides of the clay thin film.
本発明の粘土によれば、耐水性と耐熱性に優れたフレキシブル性を有する粘土薄膜を得ることができる。また、この粘土薄膜によれば、ガスバリア性に優れた薄膜積層体を得ることができ、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用いることが可能となる。 According to the clay of this invention, the clay thin film which has the flexibility excellent in water resistance and heat resistance can be obtained. Moreover, according to this clay thin film, the thin film laminated body excellent in gas-barrier property can be obtained, and it becomes possible to use as a film substrate for an organic EL display or a solar cell.
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を水に分散させた後、イミダゾリウム塩を添加して有機化させ、層間にイミダゾリウムイオンを含んだ本発明の粘土を得た後、該粘土を溶剤に分散させ、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。 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, dispersing a flaky heat-resistant material in water, adding an imidazolium salt to make it organic, and obtaining the clay of the present invention containing imidazolium ions between layers. Can be obtained by dispersing it in a solvent, forming it into a film or the like, and then heat-treating the film-like material from the film.
本発明においては、前記一般式（１）のイミダゾリウムイオンの置換基Ｒ１とＲ２の炭素数の合計は１０以下である。好ましくはＲ１とＲ２の炭素数の合計が５以下であることが好ましい。Ｒ１とＲ２の炭素数の合計が１０を超えると、粘土薄膜は熱分解温度が低くなり、良好な耐熱性を得ることができなくなる。前記イミダゾリウムイオンのＲ１、Ｒ２のどちらか一方がＣ２Ｈ５もしくはＣＨ３であることが好ましい。 In the present invention, the total number of carbon atoms of the substituents R1 and R2 of the imidazolium ion of the general formula (1) is 10 or less. The total number of carbon atoms of R1 and R2 is preferably 5 or less. When the total number of carbon atoms of R1 and R2 exceeds 10, the clay thin film has a low thermal decomposition temperature and cannot obtain good heat resistance. One of R1 and R2 of the imidazolium ion is preferably C 2 H 5 or CH 3 .
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。 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.
また粘土薄膜の強度を増したり、柔軟性を付与する為に、樹脂や流動物質を添加することもできる。樹脂や流動物質の添加に際しては、耐熱性の高いものを適宜選択することが出来る。例えば、樹脂としてエポキシ系樹脂、ポリイミド樹脂、シリコーン樹脂等、流動性物質としてシリコーンオイル、燐酸エステル、イオン性液体、フッ素系潤滑油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。 In addition, a resin or a fluid substance can be added to increase the strength of the clay thin film or impart flexibility. When adding a resin or a fluid substance, one having high heat resistance can be appropriately selected. For example, epoxy resin, polyimide resin, silicone resin and the like can be used as the resin, and silicone oil, phosphate ester, ionic liquid, and fluorine-based lubricating oil can be used as the fluid substance. In the present invention, there is no particular limitation.
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.
以上、本発明の粘土は、薄片状耐熱材料が積層した構造を有し、その積層構造の層間に疎水性の陽イオンであるイミダゾリウムイオンを含ませている。従って、このような粘土より得られる本発明の粘土薄膜は、耐水性及び耐熱性に優れた粘土薄膜となる。
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４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。さらに、硝子もしくはプラスチックフィルムなどの透明基材上に、上記の粘土薄膜や粘土薄膜に表面コートしたものを積層して使用することができる。
As described above, the clay of the present invention has a structure in which flaky heat-resistant materials are laminated, and imidazolium ions, which are hydrophobic cations, are included between layers of the laminated structure. Therefore, the clay thin film of the present invention obtained from such a clay is a clay thin film excellent in water resistance and heat resistance.
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 4 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. Furthermore, it is possible to use the above clay thin film or a clay thin film surface-coated on a transparent substrate such as glass or plastic film.
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.
［実施例１］
（薄片耐熱材料の有機化）
合成スメクタイト２０ｇを純水２０００ｇ中に分散させた後、イミダゾリウム塩である１−エチル−３−メチルイミダゾリウムブロミドを２ｇ投入した。スメクタイト内のナトリウムイオンとイミダゾリウムイオンのイオン交換反応により、層間に１−エチル−２−ブチルイミダゾリウムイオンを含むスメクタイトが液中に析出した。この溶液を遠心分離器で固液分離し液分を取り除き、粘土を得た。これを分散有機溶剤であるジメチルホルムアミド中に分散させ、溶剤中に膨潤した１−エチル−２−ブチルイミダゾリウムイオン含有スメクタイト溶液を得た。
[Example 1]
(Organization of heat-resistant thin-film materials)
After 20 g of synthetic smectite was dispersed in 2000 g of pure water, 2 g of 1-ethyl-3-methylimidazolium bromide, which is an imidazolium salt, was added. Smectite containing 1-ethyl-2-butylimidazolium ion between layers was deposited in the liquid by an ion exchange reaction between sodium ions and imidazolium ions in the smectite. This solution was subjected to solid-liquid separation with a centrifugal separator to remove the liquid, and clay was obtained. This was dispersed in dimethylformamide, which is a dispersed organic solvent, to obtain a 1-ethyl-2-butylimidazolium ion-containing smectite solution swollen in the solvent.
（粘土薄膜の形成）
上記により得られた溶液を、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、１２０℃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 solution obtained as described above 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 120 degreeC, the solvent content was removed, and it peeled from PET film, and obtained the clay thin film. This clay thin film was a transparent and flexible thin material having a thickness of 30 μm.
［実施例２］
実施例１において、イミダゾリウム塩を１−ブチル−３−メチルイミダゾリウムブロマイド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。
[Example 2]
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 1-butyl-3-methylimidazolium bromide was used as the imidazolium salt.
［実施例３］
実施例１において、イミダゾリウム塩を１−オクチル−３−メチルイミダゾリウムブロマイド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。
[Example 3]
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 1-octyl-3-methylimidazolium bromide was used as the imidazolium salt.
［実施例４］
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。
[Example 4]
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、１−エチル−３−メチルイミダゾリウムブロミドの代わりにテトラメチルアンモニウムブロミドを使用した以外は同様にして厚さ３０μｍの粘土薄膜を得た。
[Comparative Example 1]
A clay thin film having a thickness of 30 μm was obtained in the same manner as in Example 1, except that tetramethylammonium bromide was used instead of 1-ethyl-3-methylimidazolium bromide.
［比較例２］
実施例１において、１−エチル−３−メチルイミダゾリウムブロミドの代わりにトリブチル−ドデシルホスホニウムを使用した以外は同様にして厚さ３０μｍの粘土薄膜を得た。
[Comparative Example 2]
A clay thin film having a thickness of 30 μm was obtained in the same manner as in Example 1 except that tributyl-dodecylphosphonium was used instead of 1-ethyl-3-methylimidazolium bromide.
［比較例３］
実施例１において、イミダゾリウム塩を１−ドデシル−３−メチルイミダゾリウムブロマイドにした以外は同様にして厚さ３０μｍの粘土薄膜を得た。
[Comparative Example 3]
A clay thin film having a thickness of 30 μm was obtained in the same manner as in Example 1 except that 1-dodecyl-3-methylimidazolium bromide was used as the imidazolium salt.
（粘土薄膜の特性評価）
上記のように得られた実施例１〜３及び比較例１〜３で作製した粘土薄膜について、それぞれの粘土薄膜を表１に記載の種々の温度に加熱したホットプレート上に３０分放置してその外観変化を観察した。結果を表１に記した。
(Characteristic evaluation of clay thin film)
About the clay thin films produced in Examples 1 to 3 and Comparative Examples 1 to 3 obtained as described above, each clay thin film was left on a hot plate heated to various temperatures described in Table 1 for 30 minutes. The appearance change was observed. The results are shown in Table 1.
（粘土の特性評価）
実施例１〜３及び比較例１〜３で作製した溶液を粘土薄膜とせず溶液のまま１２０℃にて乾燥することで粘土粉末を得、これを粘土薄膜と同様に表１に記載の種々の温度にてホットプレート上に３０分放置してその外観変化を観察した。結果を表１に記した。
(Characteristic evaluation of clay)
Clay powder was obtained by drying the solution prepared in Examples 1 to 3 and Comparative Examples 1 to 3 at 120 ° C. without using the clay thin film, and the various powders described in Table 1 were obtained. The appearance change was observed by being left on a hot plate for 30 minutes at a temperature. The results are shown in Table 1.
上記表１の結果から明らかなように、実施例１〜３の粘土薄膜は２５０℃まで外観の変化がなく、２５０℃を超える温度に対しても変化がないか、あるいは変化が小さい。これに対して、イミダゾリウムイオンを含んでいない比較例１と２の粘土薄膜は外観変化が大きく、著しく劣っている。また、イミダゾリウムイオンを含んでいても、その置換基の炭素数の合計が１０を越えて大きい比較例３の粘土薄膜は、外観変化がしやすく劣っている。この結果より、本発明で得られた粘土薄膜は耐熱性に優れていることが確認された。
また、実施例及び比較例の溶液より得られた粘土粉末は、上記粘土薄膜と同様の外観変化を示し、特に、実施例１〜３の溶液より得られた粘土粉末は、耐熱性に優れた特徴を示した。これによりこの粘土は薄膜のみならず増粘性の付与等を目的に種々の添加剤等としての利用が可能であることが分かった。
As is clear from the results in Table 1 above, the clay thin films of Examples 1 to 3 have no change in appearance up to 250 ° C, and there is no change or a small change even at temperatures exceeding 250 ° C. On the other hand, the clay thin films of Comparative Examples 1 and 2 that do not contain imidazolium ions are significantly inferior in appearance change. Moreover, even if it contains imidazolium ions, the clay thin film of Comparative Example 3 in which the total number of carbon atoms of the substituents exceeds 10 is inferior in appearance change. From this result, it was confirmed that the clay thin film obtained by this invention was excellent in heat resistance.
Moreover, the clay powder obtained from the solutions of Examples and Comparative Examples showed the same appearance change as the clay thin film, and in particular, the clay powder obtained from the solutions of Examples 1 to 3 was excellent in heat resistance. The characteristics are shown. As a result, it was found that this clay can be used not only as a thin film but also as various additives for the purpose of imparting thickening.
（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４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 4, 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４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 4 was 1 × 10 −5 g / m 2 · day or less, and it was confirmed that the clay thin film laminate was excellent in gas barrier properties.
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| JP2013123818A (en) * | 2011-12-13 | 2013-06-24 | Samsung Yokohama Research Institute Co Ltd | Laminated film and barrier film for electronic device |
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| JP2003095640A (en) * | 2001-09-21 | 2003-04-03 | Teijin Ltd | Clay organic composite |
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