JP2008040135A - Manufacturing method of alignment layer and manufacturing method of porous film - Google Patents

Manufacturing method of alignment layer and manufacturing method of porous film Download PDF

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JP2008040135A
JP2008040135A JP2006214310A JP2006214310A JP2008040135A JP 2008040135 A JP2008040135 A JP 2008040135A JP 2006214310 A JP2006214310 A JP 2006214310A JP 2006214310 A JP2006214310 A JP 2006214310A JP 2008040135 A JP2008040135 A JP 2008040135A
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JP4572392B2 (en
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Masaru Yamashita
勝 山下
Tomoko Akai
智子 赤井
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National Institute of Advanced Industrial Science and Technology AIST
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a novel method capable of manufacturing: an alignment layer made of an organic-inorganic hybrid material which is prepared by aligning an organic compound in an inorganic matrix in a fixed direction and has a high alignment property; and an inorganic porous film which is excellent in alignment property and has micro pores having a satisfactory alignment property, with a simple method. <P>SOLUTION: In the manufacturing method of alignment layer, a sol solution prepared by dispersing a metal alkoxide which includes a phenyl group-containing alkoxy silane and a liquid crystal molecule having two or more benzene nuclei into a mixed solvent of highly volatile organic solvent and water is applied and gelatinized on a substrate. Further in the manufacturing method of porous film, the alignment layer is manufactured according to the above described method and, thereafter, organic compounds are removed from the alignment layer. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

本発明は、配向膜の製造方法、及び多孔膜の製造方法に関する。   The present invention relates to an alignment film manufacturing method and a porous film manufacturing method.

従来、有機高分子中に無機物をフィラーとして分散させることによって各種の機能を付与した有機−無機ハイブリッド体が製造されている。   Conventionally, an organic-inorganic hybrid body having various functions has been produced by dispersing an inorganic substance as a filler in an organic polymer.

一方、無機マトリックス中に有機物を分散させた材料の製造方法としては、例えば、金属アルコシキドを含むゾル中に液晶分子を分散させ、該ゾルに電場をかけながらゲル化させることによって配向膜を製造する方法が知られている（下記特許文献１参照）。この方法によれば、無機マトリックス中に光学特性や強度の異方性を有する液晶を導入したハイブリッド体を得ることが可能である。しかしながら、電場強度を高めるためには該ハイブリッド体に電極を近づける必要があり、また、有機分子を任意の方向に配向させるためにはハイブリッド体を任意の向きで電極間に挿入できるように電極間距離を広げる必要があり、電極間距離に比例して印加電圧を高めなければならない等の問題点がある。   On the other hand, as a method for producing a material in which an organic substance is dispersed in an inorganic matrix, for example, liquid crystal molecules are dispersed in a sol containing a metal alkoxide, and the alignment film is produced by gelation while applying an electric field to the sol. A method is known (see Patent Document 1 below). According to this method, it is possible to obtain a hybrid body in which a liquid crystal having anisotropy of optical characteristics and strength is introduced into an inorganic matrix. However, in order to increase the electric field strength, it is necessary to bring the electrodes close to the hybrid body, and in order to orient the organic molecules in any direction, the hybrid body can be inserted between the electrodes in any direction. There is a problem in that it is necessary to increase the distance and the applied voltage must be increased in proportion to the distance between the electrodes.

また無機多孔体の製造方法としては、基板上に形成したアモルファス膜を共晶分解反応が起こる条件で熱処理して、その共晶分解反応によって基板上に一次元的に成長したセラミック相とそれを取り囲むマトリック相からなる複合膜を形成し、次いで、複合膜中の一次元的に成長したセラミック相をエッチングで除去することによる一次貫通気孔を有するセラミック膜の製造方法が知られている（下記特許文献２参照）。しかしながら、この方法では、気孔の配向方向を任意に制御することができず、しかも孔径は４ｎｍ程度に過ぎない。   In addition, as a method for producing an inorganic porous material, an amorphous film formed on a substrate is heat-treated under conditions where a eutectic decomposition reaction occurs, and a ceramic phase grown on the substrate one-dimensionally by the eutectic decomposition reaction is obtained. A method of manufacturing a ceramic film having primary through-holes by forming a composite film composed of an enclosing matrix phase and then removing the one-dimensionally grown ceramic phase in the composite film by etching is known. Reference 2). However, this method cannot arbitrarily control the orientation direction of the pores, and the pore diameter is only about 4 nm.

また、従来、分子オーダーで均一に混合されている系からある特定の分子を選択的に分離する分子ふるい膜として無機多孔体が製造されている（例えば、非特許文献１参照。）。しかしながら、孔径１ｎｍ程度以下という非常に小さい細孔を任意の方向に配向させた多孔膜は得られていない。
特開２００４−２９７１９号公報 特開平１０−１８２２６３号公報 「分子混合物分離のための超微細孔セラミック分離膜」，化学と工業，１９９５年，第４８巻，第８号，ｐ．９１１−９１３ Conventionally, inorganic porous materials have been produced as molecular sieve membranes that selectively separate specific molecules from a system that is uniformly mixed in the molecular order (see, for example, Non-Patent Document 1). However, a porous film in which very small pores having a pore diameter of about 1 nm or less are oriented in an arbitrary direction has not been obtained.
JP 2004-29719 A Japanese Patent Laid-Open No. 10-182263 “Ultra-fine pore ceramic separation membrane for molecular mixture separation”, Chemistry and Industry, 1995, Vol. 48, No. 8, p. 911-913

本発明の主な目的は、無機マトリックス中に有機化合物を一定方向に配向させた高い配向性を有する有機−無機ハイブリッド体からなる配向膜、及び配向性の良い細孔を有する無機多孔膜を簡単な方法で製造できる新規な方法を提供することである。   The main object of the present invention is to simplify an alignment film composed of an organic-inorganic hybrid material having a high orientation property in which an organic compound is oriented in a certain direction in an inorganic matrix, and an inorganic porous film having fine orientation pores. It is to provide a novel method that can be manufactured by a simple method.

本発明者は、上記目的を達成すべく鋭意検討を行った。その結果、高揮発性を有する有機溶媒と水との混合溶媒中にベンゼン核を２個以上含む液晶分子と金属アルコシキドを分散させたゾル溶液を調製し、該ゾル溶液を基板に塗布した後、ゲル化させる方法によれば、高揮発性有機溶媒の急激な蒸発に伴って、該液晶分子が溶媒の蒸発方向に対して平行に配向して、高い配向性を有する有機−無機ハイブリッド体が得られることを見出した。更に、得られた有機−無機ハイブリッド体から液晶分子を除去することによって、無機マトリックス中に細孔が配向した無機多孔膜が得られることを見出し、ここに本発明を完成す
るに至った。 The inventor has intensively studied to achieve the above object. As a result, after preparing a sol solution in which a liquid crystal molecule containing two or more benzene nuclei and a metal alkoxide were dispersed in a mixed solvent of an organic solvent having high volatility and water, and applying the sol solution to a substrate, According to the gelation method, with rapid evaporation of the highly volatile organic solvent, the liquid crystal molecules are aligned in parallel to the evaporation direction of the solvent to obtain an organic-inorganic hybrid having high alignment. I found out that Furthermore, it has been found that an inorganic porous film having pores oriented in an inorganic matrix can be obtained by removing liquid crystal molecules from the obtained organic-inorganic hybrid, and the present invention has been completed here.

即ち、本発明は、下記の配向膜の製造方法、および多孔膜の製造方法を提供するものである。
１． 高揮発性有機溶媒と水との混合溶媒中に、フェニル基含有アルコキシシランを含む金属アルコシキドと、ベンゼン核を２個以上有する液晶分子を分散させたゾル溶液を基板上に塗布し、ゲル化させることを特徴とする配向膜の製造方法。
２． 高揮発性有機溶媒が、２５℃における蒸気圧が１０ｋＰａ以上の親水性有機溶媒である上記項１に記載の配向膜の製造方法。
３． 高揮発性有機溶媒が、テトラヒドロフラン、アセトニトリル、アセトン及びメタノールからなる群から選ばれた少なくとも一種である上記項１又は２に記載の配向膜の製造方法。
４． 上記項１〜３のいずれかの方法によって配向膜を製造した後、該配向膜から有機化合物を除去することを特徴とする多孔膜の製造方法。
５． 有機化合物を除去する方法が、３００〜１０００℃で焼成する方法である上記項４に記載の多孔膜の製造方法。 That is, this invention provides the manufacturing method of the following oriented film and the manufacturing method of a porous film.
1. A sol solution in which a metal alkoxide containing a phenyl group-containing alkoxysilane and a liquid crystal molecule having two or more benzene nuclei is dispersed in a mixed solvent of a highly volatile organic solvent and water is applied onto a substrate and gelled. An alignment film manufacturing method characterized by the above.
2. Item 2. The method for producing an alignment film according to Item 1, wherein the highly volatile organic solvent is a hydrophilic organic solvent having a vapor pressure of 10 kPa or more at 25 ° C.
3. Item 3. The method for producing an alignment film according to Item 1 or 2, wherein the highly volatile organic solvent is at least one selected from the group consisting of tetrahydrofuran, acetonitrile, acetone, and methanol.
4). A method for producing a porous film, comprising producing an alignment film by the method according to any one of Items 1 to 3 and then removing an organic compound from the alignment film.
5. Item 5. The method for producing a porous film according to Item 4, wherein the method for removing the organic compound is a method of baking at 300 to 1000 ° C.

本発明の配向膜の製造方法では、まず、高揮発性有機溶媒と水との混合溶媒中に、フェニル基含有アルコキシシランを含む金属アルコシキドと、ベンゼン核を２個以上含む液晶分子を分散させたゾル溶液を分散させたゾル溶液を調製する。   In the method for producing an alignment film of the present invention, first, a metal alkoxide containing a phenyl group-containing alkoxysilane and liquid crystal molecules containing two or more benzene nuclei are dispersed in a mixed solvent of a highly volatile organic solvent and water. A sol solution in which the sol solution is dispersed is prepared.

この様なゾル溶液を基板に塗布しゲル化させる方法によれば、ゲル化の際に高揮発性有機溶媒が急速に蒸発し、それに伴ってベンゼン核を２個以上含む液晶分子が一定方向に配向して、高い配向性を有する有機−無機ハイブリッド体を得ることができる。   According to such a method of applying a sol solution to a substrate and gelling, the highly volatile organic solvent rapidly evaporates during the gelation, and accordingly, liquid crystal molecules containing two or more benzene nuclei are in a certain direction. An organic-inorganic hybrid having a high orientation can be obtained by orientation.

高揮発性有機溶媒としては、特に限定的ではないが、常温における蒸気圧が高く、且つ使用する金属アルコキシドと液晶分子の溶解度が高い有機溶媒であって、水と任意の割合で混合できる親水性溶媒を用いることが好ましい。例えば、該高揮発性有機溶媒は２５℃における蒸気圧が１０ｋＰａ程度以上であることが好ましく、１１〜３５ｋＰａ程度であることがより好ましい。この様な有機溶媒の具体例としては、テトラヒドロフラン、アセトニトリル、アセトン、メタノールなどを挙げることができる。   The highly volatile organic solvent is not particularly limited, but is an organic solvent having a high vapor pressure at room temperature and a high solubility of the metal alkoxide and liquid crystal molecules to be used and can be mixed with water at an arbitrary ratio. It is preferable to use a solvent. For example, the highly volatile organic solvent preferably has a vapor pressure at 25 ° C. of about 10 kPa or more, more preferably about 11 to 35 kPa. Specific examples of such an organic solvent include tetrahydrofuran, acetonitrile, acetone, methanol and the like.

ベンゼン核を２個以上含む液晶分子は、立体配座の変化しにくい構造をもつ化合物であり、これを含むゾル溶液をゲル化させる際に、高揮発性有機溶媒の蒸発に伴って該溶媒の蒸発方向に対して平行に配向する。例えば、ゾル溶液を塗布した基板面を水平に設置してゲル化させると、溶媒は基板面に対して垂直方向に蒸発するので、液晶分子を基板面に対して垂直方向に配向させることができる。   A liquid crystal molecule containing two or more benzene nuclei is a compound having a structure whose conformation is difficult to change. When a sol solution containing this is gelled, the solvent of the solvent is evaporated along with the evaporation of the highly volatile organic solvent. Oriented parallel to the evaporation direction. For example, when the substrate surface to which the sol solution is applied is placed horizontally and gelled, the solvent evaporates in a direction perpendicular to the substrate surface, so that the liquid crystal molecules can be aligned in the direction perpendicular to the substrate surface. .

本発明では、液晶分子としては棒状の液晶分子が好ましく、具体例としては、４（４−プロピルフェニルエチニル）シアノフェニルベンゾエート、４（４−ブチルフェニルエチニル）シアノフェニルベンゾエート、４（４−ペンチルフェニルエチニル）シアノフェニルベンゾエート、４−シアノフェニル４−エチルベンゾエート、４−シアノフェニル４−プロピルベンゾエート、４−シアノフェニル４−ヘキシルベンゾエート、４−シアノフェニル４−ノニルベンゾエート、４−エチルフェニル４−メトキシベンゾエート、４−ペンチルフェニル４−メトキシベンゾエート、４−エチルフェニル４−ペントキシベンゾエート、４−ペンチルフェニル４−ペントキシベンゾエート、４−シアノフェニル４−エトキシベンゾエート、４−シアノフェニル４−ヘキソキシベンゾエート、ペンチルシアノビフェニール、ヘキシルシアノビフェニール、ヘプチルシアノビフェニール、オクチルシアノビフェニール、ノニルシアノビフェニール等を挙げることができる。これらの液晶分子は、１種単独または２種以上組み合わせて用いることができる。   In the present invention, rod-like liquid crystal molecules are preferable as the liquid crystal molecules, and specific examples include 4 (4-propylphenylethynyl) cyanophenylbenzoate, 4 (4-butylphenylethynyl) cyanophenylbenzoate, and 4 (4-pentylphenyl). Ethynyl) cyanophenylbenzoate, 4-cyanophenyl 4-ethylbenzoate, 4-cyanophenyl 4-propylbenzoate, 4-cyanophenyl 4-hexylbenzoate, 4-cyanophenyl 4-nonylbenzoate, 4-ethylphenyl 4-methoxybenzoate 4-pentylphenyl 4-methoxybenzoate, 4-ethylphenyl 4-pentoxybenzoate, 4-pentylphenyl 4-pentoxybenzoate, 4-cyanophenyl 4-ethoxybenzoate, 4-cyanophenyl Cycloalkenyl 4 hexoxybenzoate, pentyl Lucia Bruno biphenyls, hexyl cyanobiphenyl, heptyl cyano biphenyl, octyl cyanobiphenyl, can be mentioned nonyl cyanobiphenyl like. These liquid crystal molecules can be used singly or in combination of two or more.

金属アルコキシドとしては、テトラエトキシシラン、テトラメトキシシラン、メチルトリメトキシシラン、メチルトリエトキシシラン、プロピルトリメトキシシラン、プロピルトリエトキシシラン、オクチルトリメトキシシラン、オクチルトリエトキシシラン、オクタデシルトリメトキシシラン、オクタデシルトリエトキシシラン等のアルコシキシラン化合物；チタンテトラブトキシド、チタンテトラプロポキシド等のチタンアルコキシド化合物；ジルコニウムテトラプロポキシド等のジルコニウムアルコキシド化合物等のゾル・ゲル法によって加水分解・縮合反応により無機皮膜を形成できる金属アルコキシドを用いることができる。該金属アルコシキドは、液晶分子を均一に分散させるために、フェニルトリエトキシシラン、フェニルトリメトキシシラン等のフェニル基含有アルコキシシランを含むことが必要である。フェニル基含有アルコキシシランの量は、金属アルコキシドの全量中１０〜５０モル％程度であることが好ましく、２０〜３０モル％程度であることがより好ましい。   Metal alkoxides include tetraethoxysilane, tetramethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, octadecyltrimethoxysilane, octadecyltri Alkoxysilane compounds such as ethoxysilane; Titanium alkoxide compounds such as titanium tetrabutoxide and titanium tetrapropoxide; Zirconium alkoxide compounds such as zirconium tetrapropoxide and the like. An inorganic film can be formed by hydrolysis / condensation reaction by a sol-gel method. Metal alkoxides can be used. The metal alkoxide needs to contain a phenyl group-containing alkoxysilane such as phenyltriethoxysilane or phenyltrimethoxysilane in order to uniformly disperse liquid crystal molecules. The amount of the phenyl group-containing alkoxysilane is preferably about 10 to 50 mol%, more preferably about 20 to 30 mol%, based on the total amount of the metal alkoxide.

更に、必要に応じて、金属アルコキシドの一部として、アルミニウムイソプロポキシド、アルミニウムブトキシド等のその他の金属アルコキシドを用いることができる。   Furthermore, as required, other metal alkoxides such as aluminum isopropoxide and aluminum butoxide can be used as a part of the metal alkoxide.

上記した液晶分子の使用量は、フェニル基含有アルコシキシラン１００重量部に対して５〜８０重量部程度であることが好ましく、１０〜５０重量部程度であることがより好ましい。   The amount of the liquid crystal molecules used is preferably about 5 to 80 parts by weight and more preferably about 10 to 50 parts by weight with respect to 100 parts by weight of the phenyl group-containing alkoxysilane.

混合溶媒おける各溶媒の使用量は、金属アルコキシド１モルに対して、高揮発性有機溶媒２〜２０モル程度と水１〜８モル程度とすることが好ましく、金属アルコキシドがテトラエトキシシランである場合には、高揮発性有機溶媒５〜１５モル程度と水２〜４モル程度とすることが好ましい。   The amount of each solvent used in the mixed solvent is preferably about 2 to 20 mol of highly volatile organic solvent and about 1 to 8 mol of water with respect to 1 mol of the metal alkoxide, and the metal alkoxide is tetraethoxysilane. It is preferable that the highly volatile organic solvent is about 5 to 15 mol and water is about 2 to 4 mol.

更に、水と高揮発性有機溶媒の混合溶媒中には、金属アルコキシドの加水分解・縮合反応を進行させるために触媒として酸を添加することが適切である。酸としては、特に限定されないが、硝酸、塩酸、硫酸、リン酸、酢酸等を用いることができる。酸の使用量は、金属アルコキシド１モルに対して、０．００５〜０．１モル程度とすることが好ましく、金属アルコキシドがテトラエトキシシランである場合には０．００５〜０．０１モル程度とすることが好ましい。   Furthermore, it is appropriate to add an acid as a catalyst in the mixed solvent of water and a highly volatile organic solvent in order to advance the hydrolysis / condensation reaction of the metal alkoxide. Although it does not specifically limit as an acid, Nitric acid, hydrochloric acid, a sulfuric acid, phosphoric acid, an acetic acid etc. can be used. The amount of acid used is preferably about 0.005 to 0.1 mol per 1 mol of metal alkoxide, and about 0.005 to 0.01 mol when the metal alkoxide is tetraethoxysilane. It is preferable to do.

金属アルコキシドと液晶分子を含むゾル溶液は、該ゾル溶液を塗布した際に液晶分子の均一な分散状態を維持できるように、塗布前に金属アルコキシドを一部加水分解、縮合させておくことが好ましい。この際の金属アルコキシドの加水分解反応は、使用する金属アルコシキドの加水分解反応の容易さなどによって異なるが、通常６０〜９０℃程度の加熱下で行うことが好ましい。これにより、縮合生成物のネットワークが形成され易くなる。加水分解・縮合を進行させる程度については特に限定的ではなく、使用する、金属アルコキシド、液晶分子等の種類に応じて、液晶分子の均一な分散状態を維持でき、且つ、該ゾル溶液を塗布する際に均一に塗布できる程度の粘度とすればよい。   The sol solution containing the metal alkoxide and the liquid crystal molecules is preferably partially hydrolyzed and condensed before the application so that the uniform dispersion state of the liquid crystal molecules can be maintained when the sol solution is applied. . The hydrolysis reaction of the metal alkoxide at this time varies depending on the ease of the hydrolysis reaction of the metal alkoxide used, but is usually preferably performed under heating at about 60 to 90 ° C. This facilitates the formation of a condensation product network. The degree to which hydrolysis / condensation proceeds is not particularly limited, and it is possible to maintain a uniform dispersion state of liquid crystal molecules according to the type of metal alkoxide, liquid crystal molecules, etc. used, and to apply the sol solution. The viscosity may be such that it can be uniformly applied.

本発明の配向膜の製造方法では、上記した金属アルコキシド及び液晶分子を含むゾル溶液を基板に塗布しゲル化させることによって、高揮発性有機溶媒の蒸発方向に対して平行に液晶分子を配向させることができる。これによって、無機マトリックス中に液晶分子が一定方向に配向した有機−無機ハイブリッド体からなる配向膜を得ることができる。ゾル溶液を基板に塗布する方法については特に限定的ではないが、特に、ディップコーティング法によって塗布する場合には、基板に対してゾル溶液を均一に塗布することができ、迅速に有機溶媒を揮発させることが可能となる。   In the method for producing an alignment film of the present invention, the sol solution containing the metal alkoxide and the liquid crystal molecules described above is applied to a substrate and gelled, thereby aligning the liquid crystal molecules in parallel with the evaporation direction of the highly volatile organic solvent. be able to. Thus, an alignment film made of an organic-inorganic hybrid in which liquid crystal molecules are aligned in a certain direction in an inorganic matrix can be obtained. The method for applying the sol solution to the substrate is not particularly limited, but in particular, when applying by the dip coating method, the sol solution can be uniformly applied to the substrate, and the organic solvent is volatilized quickly. It becomes possible to make it.

基板としては、特に限定はなく、配向膜の使用目的に応じて適宜選択すればよく、例えば、ガラス、シリコン、セラミックス、非磁性の金属等を用いることができ、さらに多孔体を形成させる場合にはこれらの多孔質基材等も用いることができる。   The substrate is not particularly limited and may be appropriately selected depending on the purpose of use of the alignment film. For example, glass, silicon, ceramics, non-magnetic metal, etc. can be used, and further when a porous body is formed. These porous substrates can also be used.

ゾル溶液の塗布量については、特に限定的ではないが、例えば、乾燥後の膜厚が０．０５〜２μｍ程度になる量とすればよい。   The application amount of the sol solution is not particularly limited, but may be an amount that causes the film thickness after drying to be about 0.05 to 2 μm, for example.

基板上に塗布したゾル溶液をゲル化させるには、室温で放置しても良く、或いは、ゲル化反応を迅速に進行させるためには加熱してもよい。ゲル化に要する時間は、ゲル化させる際の温度によって異なり、例えば、室温では１日程度以上保持すればよく、４０〜６０℃程度に加熱した場合には、３時間程度以上保持すればよい。   In order to gel the sol solution applied on the substrate, it may be left at room temperature, or may be heated in order to cause the gelation reaction to proceed rapidly. The time required for gelation varies depending on the temperature at the time of gelation. For example, it may be maintained at room temperature for about 1 day or more, and when heated to about 40 to 60 ° C., it may be maintained for about 3 hours or more.

上記した方法によって、金属アルコキシドが加水分解・縮合して形成される無機マトリックス中に液晶分子が配向した状態の有機−無機複合体からなる配向膜を得ることができる。得られる配向膜は、無機マトリックス中において液晶分子が一定方向に均一に分散した状態であり、高い強度を有するものとなる。また、偏光作用のある液晶分子を用いる場合には、該液晶分子の配向状態を制御した状態で均一に分散させているため、偏光膜として使用可能である。   By the above-described method, an alignment film made of an organic-inorganic composite in a state where liquid crystal molecules are aligned in an inorganic matrix formed by hydrolysis and condensation of metal alkoxide can be obtained. The resulting alignment film is in a state where liquid crystal molecules are uniformly dispersed in a certain direction in the inorganic matrix and has high strength. In the case of using liquid crystal molecules having a polarizing action, the liquid crystal molecules can be used as a polarizing film because they are uniformly dispersed in a state in which the alignment state of the liquid crystal molecules is controlled.

上記した方法によって得られる配向膜は、更に、該配向膜から液晶分子を除去することによって、任意の方向に配向した細孔を有する多孔膜とすることができる。   The alignment film obtained by the above-described method can be made into a porous film having pores aligned in an arbitrary direction by further removing liquid crystal molecules from the alignment film.

上記配向膜から液晶分子を除去する方法としては、例えば、焼成、溶媒抽出等の方法を採用することができる。   As a method for removing liquid crystal molecules from the alignment film, for example, a method such as baking or solvent extraction can be employed.

焼成によって液晶分子を除去するには、使用している液晶分子の種類に応じて、該液晶分子を分解除去できる温度とすればよい。通常は、３００〜１０００℃程度、好ましくは５００〜７００℃程度で、１〜７時間程度、好ましくは１．５〜３時間程度焼成すればよい。   In order to remove the liquid crystal molecules by firing, the temperature may be set at a temperature at which the liquid crystal molecules can be decomposed and removed according to the type of liquid crystal molecules used. Usually, it may be fired at about 300 to 1000 ° C., preferably about 500 to 700 ° C. for about 1 to 7 hours, preferably about 1.5 to 3 hours.

上記方法によって配向膜から液晶分子を除去することによって、該液晶分子と同一の配向方向であって、該液晶分子と同様の径である０．４〜０．７ｎｍの細孔を有する多孔膜を得ることができる。この様にして得られる多孔膜では、細孔が多孔膜を透通する場合には、該多孔膜は分子ふるいやガス分離用フィルターとして有効に使用できる。   By removing the liquid crystal molecules from the alignment film by the above method, a porous film having the same orientation direction as the liquid crystal molecules and having pores of 0.4 to 0.7 nm having the same diameter as the liquid crystal molecules is obtained. Obtainable. In the porous membrane thus obtained, when the pores penetrate the porous membrane, the porous membrane can be effectively used as a molecular sieve or a gas separation filter.

本発明の配向膜の製造方法によれば、ベンゼン核を２個以上含む液晶分子を分散させた高揮発性有機溶媒を含むゾル溶液を基板に塗布してゲル化させることによって、該液晶分子の配向方向を高揮発性有機溶媒の蒸発方向に大して平行方向に制御することができる。その結果、無機マトリックス中に液晶分子が一定方向に配向した有機−無機ハイブリッド体からなる配向膜を得ることができる。得られる配向膜は、無機骨格中で液晶分子が配向して均一に分散しているので、強度が大きく、偏光膜としての使用が可能である。   According to the method for producing an alignment film of the present invention, a sol solution containing a highly volatile organic solvent in which liquid crystal molecules containing two or more benzene nuclei are dispersed is applied to a substrate and gelled. The orientation direction can be controlled to be parallel to the evaporation direction of the highly volatile organic solvent. As a result, an alignment film composed of an organic-inorganic hybrid in which liquid crystal molecules are aligned in a certain direction in an inorganic matrix can be obtained. The obtained alignment film has high strength because the liquid crystal molecules are aligned and uniformly dispersed in the inorganic skeleton, and can be used as a polarizing film.

また、本発明の多孔膜の製造方法によれば、上記配向膜を形成した後、液晶分子を除去するという簡単な方法によって、非常に径の小さい細孔を有する多孔膜を得ることができる。この方法によれば、配向性良く任意の方向に細孔を配向させることが可能であり、例えば、高い透過率および選択性を示す多孔膜を得ることができる。   Further, according to the method for producing a porous film of the present invention, a porous film having pores having a very small diameter can be obtained by a simple method of removing liquid crystal molecules after forming the alignment film. According to this method, it is possible to orient the pores in any direction with good orientation, and for example, it is possible to obtain a porous membrane exhibiting high transmittance and selectivity.

以下、実施例を挙げて本発明を更に詳細に説明する。   Hereinafter, the present invention will be described in more detail with reference to examples.

実施例１
テトラエトキシシラン：フェニルトリエトキシシラン：テトラヒドロフラン：水：硝酸の割合がモル比で０．８：０．２：１０：３：０．００７５となるように配合し、さらに４（４−プロピルフェニルエチニル）シアノフェニルベンゾエートをフェニルトリエトキシシラン１００重量部に対して１０重量部（金属アルコキシドの合計量１００重量部に対して２．２重量部）配合し、テトラヒドロフランの沸点温度で二晩還流することによりゾルを製造した。 Example 1
It was formulated so that the ratio of tetraethoxysilane: phenyltriethoxysilane: tetrahydrofuran: water: nitric acid was 0.8: 0.2: 10: 3: 0.0075 in molar ratio, and 4 (4-propylphenylethynyl) ) By blending 10 parts by weight of cyanophenylbenzoate with respect to 100 parts by weight of phenyltriethoxysilane (2.2 parts by weight with respect to 100 parts by weight of the total amount of metal alkoxide) and refluxing at the boiling point of tetrahydrofuran overnight. A sol was produced.

得られたゾルは透明で均質であった。このゾルをディップコート法によって室温でシリコン基板に塗布し、基板をそのまま吊り下げて、室温で１日放置してゲル化させて配向膜を得た。   The obtained sol was transparent and homogeneous. This sol was applied to a silicon substrate at room temperature by a dip coating method, the substrate was suspended as it was, and allowed to gel at room temperature for 1 day to obtain an alignment film.

得られた配向膜は、ほぼ透明で均質な厚さ約０．１μｍの膜であり、液晶分子が均一に分散していた。赤外分光光度計で液晶中のシアノ基の吸収を偏光を用いて測定したところ、シアノ基は基板と垂直方向に配向しており、配向率は８０％であった。   The obtained alignment film was a substantially transparent and homogeneous film having a thickness of about 0.1 μm, and liquid crystal molecules were uniformly dispersed. When the absorption of the cyano group in the liquid crystal was measured using polarized light with an infrared spectrophotometer, the cyano group was aligned in the direction perpendicular to the substrate, and the orientation ratio was 80%.

比較例１
溶媒としてエタノール（沸点：７８℃）を用い、テトラエトキシシラン：フェニルトリエトキシシラン：エタノール：水：硝酸の割合がモル比で０．８：０．２：１０：３：０．００７５となるように配合し、さらに４−シアノフェニル４−ノニルベンゾエートをフェニルトリエトキシシラン１００重量部に対して１０重量部（金属アルコキシドの合計量１００重量部に対して２．２重量部）配合し、エタノールの沸点温度で二晩還流することによりゾルを製造した。 Comparative Example 1
Ethanol (boiling point: 78 ° C.) is used as a solvent, and the ratio of tetraethoxysilane: phenyltriethoxysilane: ethanol: water: nitric acid is 0.8: 0.2: 10: 3: 0.0075 in molar ratio. In addition, 10 parts by weight of 4-cyanophenyl 4-nonylbenzoate is added to 100 parts by weight of phenyltriethoxysilane (2.2 parts by weight based on 100 parts by weight of the total amount of metal alkoxide). A sol was prepared by refluxing at the boiling temperature overnight.

得られたゾルは透明で均質であった。このゾルをディップコート法によって室温でシリコン基板に塗布し、基板を水平に設置して、室温で１日放置してゲル化させて配向膜を得た。   The obtained sol was transparent and homogeneous. This sol was applied to a silicon substrate by a dip coating method at room temperature, the substrate was placed horizontally, and allowed to gel at room temperature for 1 day to obtain an alignment film.

得られた膜は、ほぼ透明で均質であり、液晶分子が均一に分散していたが、液晶中のシアノ基は配向していなかった。   The obtained film was almost transparent and homogeneous, and liquid crystal molecules were uniformly dispersed, but the cyano group in the liquid crystal was not oriented.

Claims (5)

高揮発性有機溶媒と水との混合溶媒中に、フェニル基含有アルコキシシランを含む金属アルコシキドと、ベンゼン核を２個以上有する液晶分子を分散させたゾル溶液を基板上に塗布し、ゲル化させることを特徴とする配向膜の製造方法。 A sol solution in which a metal alkoxide containing a phenyl group-containing alkoxysilane and a liquid crystal molecule having two or more benzene nuclei is dispersed in a mixed solvent of a highly volatile organic solvent and water is applied onto a substrate and gelled. An alignment film manufacturing method characterized by the above. 高揮発性有機溶媒が、２５℃における蒸気圧が１０ｋＰａ以上の親水性有機溶媒である請求項１に記載の配向膜の製造方法。 The method for producing an alignment film according to claim 1, wherein the highly volatile organic solvent is a hydrophilic organic solvent having a vapor pressure at 25 ° C. of 10 kPa or more. 高揮発性有機溶媒が、テトラヒドロフラン、アセトニトリル、アセトン及びメタノールからなる群から選ばれた少なくとも一種である請求項１又は２に記載の配向膜の製造方法。 The method for producing an alignment film according to claim 1, wherein the highly volatile organic solvent is at least one selected from the group consisting of tetrahydrofuran, acetonitrile, acetone, and methanol. 請求項１〜３のいずれかの方法によって配向膜を製造した後、該配向膜から有機化合物を除去することを特徴とする多孔膜の製造方法。 A method for producing a porous film, comprising: producing an alignment film by the method according to claim 1, and then removing an organic compound from the alignment film. 有機化合物を除去する方法が、３００〜１０００℃で焼成する方法である請求項４に記載の多孔膜の製造方法。 The method for producing a porous film according to claim 4, wherein the method of removing the organic compound is a method of baking at 300 to 1000 ° C.
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CN111061092A (en) * 2020-01-20 2020-04-24 Tcl华星光电技术有限公司 Liquid crystal display panel

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WO2011052657A1 (en) * 2009-10-27 2011-05-05 株式会社 アルバック Precursor composition for porous film and method for forming porous film
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