JP2005272561A - Polymerizable liquid crystal composition and polymer of the same - Google Patents
Polymerizable liquid crystal composition and polymer of the same Download PDFInfo
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polarising Elements (AREA)
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Abstract
Description
本発明は位相差フィルム等の光学異方体を製造するのに有用な重合性液晶組成物、及びこれを用いた重合体に関する。 The present invention relates to a polymerizable liquid crystal composition useful for producing an optical anisotropic body such as a retardation film, and a polymer using the same.
重合性液晶材料を基板に塗布した後、配向させた状態で光重合させることにより位相差フィルムなどの光学異方体を製造する方法が知られている。重合性液晶材料がスメクチックA相を呈する状態で、光重合させるとスメクチック相の層構造が光学異方体中に固定化されることになりフォトニック素子等の新しい光機能素子としての応用が期待される。不必要な熱重合の誘起を抑制し、均一性に優れる光学異方体を製造するためには、室温でスメクチックA相を呈する重合性液晶材料が好ましい。このような室温でスメクチックA相を呈する重合性液晶材料は特許文献１に記載されているが、単官能液晶性アクリレートを中心に構成されているため、空気中で光重合させることは困難で、窒素置換する必要があり、製造工程において取り扱いが煩雑になり、製造コストを増大させるという問題があった。 A method for producing an optical anisotropic body such as a retardation film is known by applying a polymerizable liquid crystal material to a substrate and then photopolymerizing it in an aligned state. When photopolymerization is performed in a state where the polymerizable liquid crystal material exhibits a smectic A phase, the layer structure of the smectic phase is fixed in an optical anisotropic body, and application as a new optical functional device such as a photonic device is expected. Is done. A polymerizable liquid crystal material exhibiting a smectic A phase at room temperature is preferred in order to suppress unnecessary induction of thermal polymerization and to produce an optically anisotropic body excellent in uniformity. Such a polymerizable liquid crystal material exhibiting a smectic A phase at room temperature is described in Patent Document 1, but because it is composed mainly of a monofunctional liquid crystal acrylate, it is difficult to photopolymerize in air, Nitrogen replacement is necessary, and handling is complicated in the manufacturing process, resulting in an increase in manufacturing cost.
一方、−ＣＨ２ＣＨ２ＣＯＯ−基を連結基として有するニ官能の重合性液晶化合物は既に開示されている（特許文献２参照）。さらに、当該引用文献には−ＣＨ２ＣＨ２ＣＯＯ−基を連結基として有するニ官能の重合性液晶化合物とシアノ基を有する単官能重合性化合物を含有する重合性液晶組成物の記載もある。しかし、これらの多くの化合物の中から具体的にどの様な化合物を用いて重合性液晶組成物を構成するとスメクチックA相の発現に有効であるかの記載はない。 On the other hand, a bifunctional polymerizable liquid crystal compound having a —CH 2 CH 2 COO— group as a linking group has already been disclosed (see Patent Document 2). Further, the cited document also describes a polymerizable liquid crystal composition containing a bifunctional polymerizable liquid crystal compound having a —CH 2 CH 2 COO— group as a linking group and a monofunctional polymerizable compound having a cyano group. However, there is no description of what kind of compound among these many compounds is specifically used to constitute the polymerizable liquid crystal composition, which is effective for the development of the smectic A phase.
本発明の目的は、室温でスメクチックA相を呈する重合性液晶組成物において、窒素置換することなく光重合可能な重合性液晶材料を提供することにある。 An object of the present invention is to provide a polymerizable liquid crystal material capable of photopolymerization without substitution with nitrogen in a polymerizable liquid crystal composition exhibiting a smectic A phase at room temperature.
本発明は、上記課題を解決するために、重合性液晶化合物について検討した結果、課題を解決するに至った。
即ち、一般式（Ｉ）
As a result of studying a polymerizable liquid crystal compound in order to solve the above problems, the present invention has solved the problems.
That is, the general formula (I)
（式中、Ｗ１及びＷ２はそれぞれ独立的に単結合、−Ｏ−、−ＣＯＯ−又は−ＯＣＯ−を表し、Ｙ１及びＹ２はそれぞれ独立的に−ＣＯＯ−又は−ＯＣＯ−を表し、ｐ及びｑはそれぞれ独立的に２〜１８の整数を表し、式中に存在する３種の１，４−フェニレン基の水素原子はそれぞれ独立的に、炭素原子数１〜７のアルキル基、アルコキシ基、アルカノイル基、シアノ基又はハロゲン原子で一つ以上置換されていても良い。）で表される２官能液晶性アクリレート化合物を５０から９５％含有し、一般式（II−１）から一般式（II−４） Wherein W 1 and W 2 each independently represent a single bond, —O—, —COO— or —OCO—, and Y 1 and Y 2 each independently represent —COO— or —OCO—. , P and q each independently represent an integer of 2 to 18, and the hydrogen atoms of the three 1,4-phenylene groups present in the formula are each independently an alkyl group having 1 to 7 carbon atoms, One or more alkoxy groups, alkanoyl groups, cyano groups or halogen atoms may be substituted.) 50 to 95% of a bifunctional liquid crystalline acrylate compound represented by formula (II-1) Formula (II-4)
（式中、ｒは２〜１８の整数を表す。）で表される化合物からなる群より選ばれる少なくとも一種の単官能液晶性アクリレート化合物を５から５０％含有し、室温でスメクチックＡ相を呈することを特徴とする重合性液晶組成物及び、当該重合性液晶組成物の重合体を提供する。 (Wherein r represents an integer of 2 to 18) containing 5 to 50% of at least one monofunctional liquid crystalline acrylate compound selected from the group consisting of compounds represented by the formula, and exhibiting a smectic A phase at room temperature. A polymerizable liquid crystal composition and a polymer of the polymerizable liquid crystal composition are provided.
本発明の重合性液晶組成物により、スメクチックの層構造を有する光学異方体を、光重合時に窒素置換することなく製造することが可能になる。得られる光学異方体は均一性に優れており、非常に有用である。 The polymerizable liquid crystal composition of the present invention makes it possible to produce an optical anisotropic body having a smectic layer structure without nitrogen substitution during photopolymerization. The obtained optical anisotropic body has excellent uniformity and is very useful.
以下に本発明の一例について説明する。本発明の重合性液晶組成物は、紫外線または電子線などの活性エネルギー線により重合し、分子配列状態を保ったまま重合体（高分子）となる。２官能液晶性アクリレートを含有させることによって、窒素置換することなく光重合可能となった。 An example of the present invention will be described below. The polymerizable liquid crystal composition of the present invention is polymerized by active energy rays such as ultraviolet rays or electron beams, and becomes a polymer (polymer) while maintaining the molecular alignment state. By including a bifunctional liquid crystalline acrylate, photopolymerization was possible without nitrogen substitution.
本発明の目的から、２官能液晶性アクリレートは５０質量％以上、好ましくは５５質量％以上、さらに好ましくは６０質量％以上含有させることが好ましい。 For the purpose of the present invention, the bifunctional liquid crystalline acrylate is preferably contained in an amount of 50% by mass or more, preferably 55% by mass or more, and more preferably 60% by mass or more.
本発明の重合性液晶組成物は、室温でスメクチックA相を呈するように設計する必要がある。具体的には３５℃以下、このましくは３０℃以下、さらに好ましくは２５℃以下でもスメクチックA相を呈することが必要である。また、スメクチックＡ相を示す温度より高い温度域においてネマチック相を呈するように設計するのが好ましい。このようにするとネマチック相状態で配向させた後に、スメクチックＡ相に転移させることによって良好な配向状態を容易に得ることが可能になる。スメクチックＡ−ネマチック相転移温度は３５〜６０℃、好ましくは３８〜５８℃、さらに好ましくは４０〜５５℃に設定すると、良好な均一性と熱重合の抑止を両立可能である。またネマチック−等方性液体相転移温度は４１〜９０℃、好ましくは４３〜８０℃、さらに好ましくは４５〜７５℃に設定するのが好ましい。 The polymerizable liquid crystal composition of the present invention needs to be designed so as to exhibit a smectic A phase at room temperature. Specifically, it is necessary to exhibit a smectic A phase even at 35 ° C. or lower, preferably 30 ° C. or lower, more preferably 25 ° C. or lower. Moreover, it is preferable to design so that a nematic phase may be exhibited in the temperature range higher than the temperature which shows a smectic A phase. If it does in this way, after making it align in a nematic phase state, it will become possible to obtain a favorable orientation state easily by making it transfer to a smectic A phase. When the smectic A-nematic phase transition temperature is set to 35 to 60 ° C., preferably 38 to 58 ° C., more preferably 40 to 55 ° C., both good uniformity and suppression of thermal polymerization can be achieved. The nematic-isotropic liquid phase transition temperature is preferably set to 41 to 90 ° C, preferably 43 to 80 ° C, more preferably 45 to 75 ° C.
一般式（Ｉ）において、本発明の目的から、ｐ及びｑはそれぞれ独立的に３以上に設定するのが好ましい。
一般式（Ｉ）で表される化合物は具体的には、一般式（Ｉ−１）〜一般式（Ｉ―８）で表される化合物を挙げることができる。
In general formula (I), for the purposes of the present invention, it is preferable that p and q are independently set to 3 or more.
Specific examples of the compound represented by the general formula (I) include compounds represented by the general formula (I-1) to the general formula (I-8).
（式中のｐ及びｑは一般式（I）における意味と同じ）
一般式（I）で表される化合物は、本発明の組成物が安定に液晶相を発現させる目的と結晶相の析出を避ける目的から、２種以上含有させることが好ましい。これはp、qが異なる化合物でも良いし、W１、W２が異なる化合物でも良いし、1,4-フェニレン基の置換様態が異なる化合物でもよい。
一般式（I）において、Ｗ１及びＷ２が−Ｏ−を表し、Ｙ１が−ＣＯＯ−を表し、Ｙ２が−ＯＣＯ−を表し、ｐ及びｑはそれぞれ独立的に３〜１２の整数を表す化合物を２種以上混合させることが特に好ましい。例えば、ｐ＝ｑ＝６、ｐ＝ｑ＝３の化合物の混合を例示することができる。
(P and q in the formula are the same as in the general formula (I))
The compound represented by the general formula (I) is preferably contained in two or more kinds for the purpose of causing the composition of the present invention to stably develop a liquid crystal phase and avoiding precipitation of a crystal phase. This may be a compound in which p and q are different, a compound in which W 1 and W 2 are different, or a compound in which the substitution mode of the 1,4-phenylene group is different.
In General Formula (I), W 1 and W 2 represent —O—, Y 1 represents —COO—, Y 2 represents —OCO—, and p and q are each independently an integer of 3 to 12 It is particularly preferable to mix two or more compounds representing the above. For example, a mixture of compounds with p = q = 6 and p = q = 3 can be exemplified.
この他にも、２官能液晶性アクリレートとしては、一般式（ａ−１）〜一般式（ａ―１０）で表される化合物を含有させることができる。 In addition, as the bifunctional liquid crystalline acrylate, compounds represented by general formulas (a-1) to (a-10) can be contained.
（式中、u及びvはそれぞれ独立的に２〜１８の整数を表す）
ｕ及びｖは３より小さいとスメクチックA相を得るのが難しくなる傾向があり、１２より大きいと光重合して得られる重合体の耐熱性が劣化する傾向がある。そのため、ｕ及びｖはそれぞれ独立的に３〜１８を表すことが好ましく、４〜１６がより好ましく、６〜１２が特に好ましい。
(In the formula, u and v each independently represent an integer of 2 to 18)
If u and v are less than 3, it tends to be difficult to obtain a smectic A phase, and if it is greater than 12, the heat resistance of the polymer obtained by photopolymerization tends to deteriorate. Therefore, u and v each independently preferably represent 3 to 18, more preferably 4 to 16, and particularly preferably 6 to 12.
単官能液晶性アクリレートとしては、シアノ基を含有する材料を使用するのが好ましい。特に分子長軸方向にシアノ基を有する材料を用いると効果的に、室温でのスメクチックＡ相を得ることができる。これは、おそらくシアノ基同士の会合により、単官能液晶性アクリレートの分子の長さが見かけ上、長くなることに起因するものと考えられる。 As the monofunctional liquid crystal acrylate, it is preferable to use a material containing a cyano group. In particular, when a material having a cyano group in the molecular long axis direction is used, a smectic A phase at room temperature can be obtained effectively. This is probably due to the apparent lengthening of the molecular length of the monofunctional liquid crystalline acrylate due to the association of cyano groups.
分子長軸方向にシアノ基を有する材料を用いることによる別の効果は、重合性液晶組成物として正の誘電率異方性を付与することが可能になることである。一般式（I）に示されるような２官能液晶性アクリレートの誘電率異方性は、ほぼ零か若干負に傾いている。正の誘電率異方性を付与できると、光重合を行う前の状態において、電界によって液晶分子の配向状態を制御可能になるため有用である。例えば、本発明の重合性液晶組成物を基板に塗布してネマチック相を呈する状態で、電圧を印加して垂直配向させた後、スメクチックA相を呈する温度まで冷却すると、非常に良好な垂直配向状態を得ることができる。ネマチック相での垂直配向状態は不安定なため、光重合時における微少な振動や温度揺らぎで垂直配向が乱れてしまうが、スメクチックA相での垂直配向状態は安定性が高く、光重合時における外的な擾乱に影響を受けにくくなるため、良好な垂直配向状態を高分子に固定化でき非常に有用である。さらに、一般に垂直配向状態を得るためには、基板表面を界面活性剤や垂直配向膜を塗布する必要があるが、これを省略することも可能になる。 Another effect of using a material having a cyano group in the molecular long axis direction is that a positive dielectric anisotropy can be imparted to the polymerizable liquid crystal composition. The dielectric anisotropy of the bifunctional liquid crystalline acrylate as shown in the general formula (I) is almost zero or slightly negative. If a positive dielectric anisotropy can be imparted, it is useful because the alignment state of liquid crystal molecules can be controlled by an electric field in a state before photopolymerization. For example, when the polymerizable liquid crystal composition of the present invention is applied to a substrate to exhibit a nematic phase, a voltage is applied to perform vertical alignment, and then cooled to a temperature exhibiting a smectic A phase. The state can be obtained. Since the vertical alignment state in the nematic phase is unstable, the vertical alignment is disturbed by slight vibrations and temperature fluctuations during photopolymerization, but the vertical alignment state in the smectic A phase is highly stable and during photopolymerization. Since it becomes difficult to be affected by external disturbances, a good vertical alignment state can be fixed to the polymer, which is very useful. Further, in general, in order to obtain a vertical alignment state, it is necessary to apply a surfactant or a vertical alignment film to the substrate surface, but this can be omitted.
本願発明の重合性液晶組成物は、シアノ基を有する単官能液晶性アクリレートとして、一般式（II−１）から一般式（II−４）で表される化合物が優れていることを見出したことによるものである。
一般式（II−１）から一般式（II−４）において、ｒは３〜１８が好ましく、４〜１６が好ましく、６〜１２がさらに好ましい。３より小さいとスメクチックA相を得るのが難しくなる傾向があり、１２より大きいと光重合して得られる重合体の耐熱性が劣化する傾向がある。
一般式（II−１）から一般式（II−４）で表される化合物の中でも、一般式（II−１）で表される化合物が好ましい。
The polymerizable liquid crystal composition of the present invention has found that the compounds represented by formulas (II-1) to (II-4) are excellent as monofunctional liquid crystal acrylates having a cyano group. Is due to.
In General Formula (II-1) to General Formula (II-4), r is preferably 3 to 18, preferably 4 to 16, and more preferably 6 to 12. If it is smaller than 3, it tends to be difficult to obtain a smectic A phase, and if it is larger than 12, the heat resistance of the polymer obtained by photopolymerization tends to deteriorate.
Among the compounds represented by the general formula (II-1) to the general formula (II-4), the compound represented by the general formula (II-1) is preferable.
この他に単官能液晶性材料としては、例えば一般式（ｃ−１）〜一般式（ｃ−１１）で表される化合物を含有させることができる。 In addition, as the monofunctional liquid crystalline material, for example, compounds represented by the general formula (c-1) to the general formula (c-11) can be contained.
（式中、ｔは２〜１８の整数、Yは単結合、-O-、-COO-、-OCO-又は-OCOO-を表し、Rは炭素原子数１〜１８のアルキル基又は炭素原子数２〜１８のアルケニル基を表す。）
このような化合物の中でも、ｔは３〜１８が好ましく、４〜１６が好ましく、６〜１２がさらに好ましい。３より小さいとスメクチックA相を得るのが難しくなる傾向があり、１２より大きいと光重合して得られる重合体の耐熱性が劣化する傾向がある。
(In the formula, t represents an integer of 2 to 18, Y represents a single bond, —O—, —COO—, —OCO— or —OCOO—, and R represents an alkyl group having 1 to 18 carbon atoms or the number of carbon atoms. Represents 2-18 alkenyl groups.)
Among these compounds, t is preferably from 3 to 18, preferably from 4 to 16, and more preferably from 6 to 12. If it is smaller than 3, it tends to be difficult to obtain a smectic A phase, and if it is larger than 12, the heat resistance of the polymer obtained by photopolymerization tends to deteriorate.
さらに本発明の重合性液晶組成物には、重合性官能基を有する化合物であって、液晶性を示さない化合物を添加することもできる。このような化合物としては、通常、この技術分野で高分子形成性モノマーあるいは高分子形成性オリゴマーとして認識されるものであれば特に制限なく使用することができるが、その添加量は組成物として液晶性を呈するように調整する必要がある。
本発明の重合性液晶組成物には、その重合反応性を向上させることを目的として、光重合開始剤を添加することができる。光重合開始剤としては、ベンゾインエーテル類、ベンゾフェノン類、アセトフェノン類、ベンジルケタール類、アシルフォスフィンオキサイド等が挙げられる。その添加量は、液晶組成物に対して０．０１〜５質量％が好ましく、０．０２〜１質量％がさらに好ましく、０．０３〜１質量％の範囲が特に好ましい。
Furthermore, the polymerizable liquid crystal composition of the present invention may be added with a compound having a polymerizable functional group and not exhibiting liquid crystallinity. Such a compound can be used without particular limitation as long as it is generally recognized as a polymer-forming monomer or polymer-forming oligomer in this technical field. It is necessary to adjust to exhibit sex.
A photopolymerization initiator can be added to the polymerizable liquid crystal composition of the present invention for the purpose of improving the polymerization reactivity. Examples of the photopolymerization initiator include benzoin ethers, benzophenones, acetophenones, benzyl ketals, and acylphosphine oxides. The addition amount is preferably 0.01 to 5% by mass, more preferably 0.02 to 1% by mass, and particularly preferably 0.03 to 1% by mass relative to the liquid crystal composition.
また、本発明の重合性液晶組成物には、その保存安定性を向上させるために、安定剤を添加することもできる。使用できる安定剤としては、例えば、ヒドロキノン、ヒドロキノンモノアルキルエーテル類、第三ブチルカテコール類、ピロガロール類、チオフェノール類、ニトロ化合物類、β−ナフチルアミン類、β−ナフトール類、ニトロソ化合物等が挙げられる。安定剤を使用する場合の添加量は、液晶組成物に対して０．００５〜１質量％の範囲が好ましく、０．０２〜０．５質量％がさらに好ましく、０．０３〜０．１質量％が特に好ましい。 In addition, a stabilizer can be added to the polymerizable liquid crystal composition of the present invention in order to improve its storage stability. Examples of the stabilizer that can be used include hydroquinone, hydroquinone monoalkyl ethers, tert-butylcatechols, pyrogallols, thiophenols, nitro compounds, β-naphthylamines, β-naphthols, and nitroso compounds. . When the stabilizer is used, the amount added is preferably 0.005 to 1% by mass, more preferably 0.02 to 0.5% by mass, and 0.03 to 0.1% by mass with respect to the liquid crystal composition. % Is particularly preferred.
また、本発明の重合性液晶組成物を偏光フィルムや配向膜の原料、又は印刷インキ及び塗料、保護膜等の用途に利用する場合には、その目的に応じて金属、金属錯体、染料、顔料、色素、蛍光材料、燐光材料、界面活性剤、レベリング剤、チキソ剤、ゲル化剤、多糖類、紫外線吸収剤、赤外線吸収剤、抗酸化剤、イオン交換樹脂、酸化チタン等の金属酸化物等を添加することもできる。 In addition, when the polymerizable liquid crystal composition of the present invention is used for a raw material for a polarizing film or an alignment film, a printing ink, a paint, a protective film, or the like, a metal, a metal complex, a dye, or a pigment is used depending on the purpose. , Dyes, fluorescent materials, phosphorescent materials, surfactants, leveling agents, thixotropic agents, gelling agents, polysaccharides, ultraviolet absorbers, infrared absorbers, antioxidants, ion exchange resins, metal oxides such as titanium oxide, etc. Can also be added.
次に本発明の重合体について説明する。本発明の重合性液晶化合物または重合性液晶組成物を重合させることによって製造される重合体は種々の用途に利用できる。例えば、本発明の重合性液晶組成物を、配向させない状態で重合させた場合、光散乱板、偏光解消板、モアレ縞防止板として利用可能である。また、本発明の重合性液晶化合物または重合性液晶組成物を配向させた状態において、重合させることにより製造された重合体は、物理的性質に異方性を有しており、有用である。このような重合体は、例えば、本発明の重合性液晶化合物又は重合性液晶組成物表面を、布等でラビング処理した基板、もしくは有機薄膜を形成した基板表面を布等でラビング処理した基板、あるいはＳｉＯ２を斜方蒸着した配向膜を有する基板上に担持させるか、基板間に挟持させた後、本発明の液晶を重合させることによって製造することができる。 Next, the polymer of the present invention will be described. The polymer produced by polymerizing the polymerizable liquid crystal compound or polymerizable liquid crystal composition of the present invention can be used for various applications. For example, when the polymerizable liquid crystal composition of the present invention is polymerized without being oriented, it can be used as a light scattering plate, a depolarizing plate, or a moire fringe prevention plate. In addition, the polymer produced by polymerizing the polymerizable liquid crystal compound or the polymerizable liquid crystal composition of the present invention is useful because it has anisotropy in physical properties. Such a polymer is, for example, a substrate obtained by rubbing the surface of the polymerizable liquid crystal compound or polymerizable liquid crystal composition of the present invention with a cloth or the like, or a substrate obtained by rubbing a substrate surface on which an organic thin film is formed with a cloth or the like, Alternatively, it can be produced by polymerizing the liquid crystal of the present invention after it is supported on a substrate having an orientation film on which SiO 2 is obliquely deposited or sandwiched between the substrates.
重合性液晶化合物または重合性液晶組成物を基板上に担持させる際の方法としては、スピンコーティング、ダイコーティング、エクストルージョンコーティング、ロールコーティング、ワイヤーバーコーティング、グラビアコーティング、スプレーコーティング、ディッピング、プリント法等を挙げることができる。またコーティングの際、重合性液晶組成物に有機溶媒を添加しても良い。有機溶媒としては、酢酸エチル、テトラヒドロフラン、トルエン、ヘキサン、メタノール、エタノール、ジメチルホルムアミド、塩化メチレン、イソプロパノール、アセトン、メチルエチルケトン、アセトニトリル、セロソルブ類を挙げることができる。これらは単独でも、組み合わせて用いても良く、その蒸気圧と重合性液晶組成物の溶解性を考慮し、適宜選択すれば良い。また、その添加量は９０重量％以下が好ましい。添加した有機溶媒を揮発させる方法としては、自然乾燥、加熱乾燥、減圧乾燥、減圧加熱乾燥を用いることができる。重合性液晶材料の塗布性をさらに向上させるためには、基板上にポリイミド薄膜等の中間層を設けることや、重合性液晶材料にレベリング剤を添加するのも有効である。基板上にポリイミド薄膜等の中間層を設けるのは、重合性液晶材料を重合させて得られる重合体と基板の密着性が良くない場合に、密着性を向上させる手段としても有効である。 Methods for supporting a polymerizable liquid crystal compound or polymerizable liquid crystal composition on a substrate include spin coating, die coating, extrusion coating, roll coating, wire bar coating, gravure coating, spray coating, dipping, printing method, etc. Can be mentioned. Further, an organic solvent may be added to the polymerizable liquid crystal composition during coating. Examples of the organic solvent include ethyl acetate, tetrahydrofuran, toluene, hexane, methanol, ethanol, dimethylformamide, methylene chloride, isopropanol, acetone, methyl ethyl ketone, acetonitrile, and cellosolves. These may be used alone or in combination, and may be appropriately selected in consideration of the vapor pressure and the solubility of the polymerizable liquid crystal composition. The amount added is preferably 90% by weight or less. As a method for volatilizing the added organic solvent, natural drying, heat drying, reduced pressure drying, or reduced pressure heat drying can be used. In order to further improve the applicability of the polymerizable liquid crystal material, it is also effective to provide an intermediate layer such as a polyimide thin film on the substrate or to add a leveling agent to the polymerizable liquid crystal material. Providing an intermediate layer such as a polyimide thin film on the substrate is also effective as a means for improving the adhesion when the polymer obtained by polymerizing the polymerizable liquid crystal material and the substrate are not good in adhesion.
重合性液晶化合物または重合性液晶組成物を基板間に挟持させる方法としては、毛細管現象を利用した注入法が挙げられる。基板間に形成された空間を減圧し、その後、重合性液晶材料を注入する手段も有効である。 Examples of a method for sandwiching the polymerizable liquid crystal compound or the polymerizable liquid crystal composition between the substrates include an injection method using a capillary phenomenon. It is also effective to depressurize the space formed between the substrates and then inject a polymerizable liquid crystal material.
ラビング処理、あるいはＳｉＯ２の斜方蒸着以外の配向処理としては、液晶材料の流動配向の利用や、電場又は磁場の利用を挙げることができる。これらの配向手段は単独で用いても、また組み合わせて用いても良い。さらに、ラビングに代わる配向処理方法として、光配向法を用いることもできる。この方法は、例えば、ポリビニルシンナメート等の分子内に光二量化反応する官能基を有する有機薄膜、光で異性化する官能基を有する有機薄膜又はポリイミド等の有機薄膜に、偏光した光、好ましくは偏光した紫外線を照射することによって、配向膜を形成するものである。この光配向法に光マスクを適用することにより配向のパターン化が容易に達成できるので、重合体内部の分子配向も精密に制御することが可能となる。 Examples of the alignment treatment other than the rubbing treatment or the oblique deposition of SiO 2 include the use of fluid orientation of a liquid crystal material and the use of an electric field or a magnetic field. These orientation means may be used alone or in combination. Furthermore, a photo-alignment method can be used as an alignment treatment method instead of rubbing. This method can be applied to, for example, an organic thin film having a functional group that undergoes photodimerization reaction in a molecule such as polyvinyl cinnamate, an organic thin film having a functional group that is isomerized by light, or an organic thin film such as polyimide. An alignment film is formed by irradiating polarized ultraviolet rays. By applying an optical mask to this photo-alignment method, the patterning of the alignment can be easily achieved, so that the molecular orientation inside the polymer can be precisely controlled.
基板の形状としては、平板の他に、曲面を構成部分として有していても良い。基板を構成する材料は、有機材料、無機材料を問わずに用いることができる。基板の材料となる有機材料としては、例えば、ポリエチレンテレフタレート、ポリカーボネート、ポリイミド、ポリアミド、ポリメタクリル酸メチル、ポリスチレン、ポリ塩化ビニル、ポリテトラフルオロエチレン、ポリクロロトリフルオロエチレン、ポリアリレート、ポリスルホン、トリアセチルセルロース、セルロース、ポリエーテルエーテルケトン等が挙げられ、また、無機材料としては、例えば、シリコン、ガラス、方解石等が挙げられる。 As a shape of the substrate, in addition to a flat plate, a curved surface may be included as a constituent part. The material which comprises a board | substrate can be used regardless of an organic material and an inorganic material. Examples of the organic material used as the substrate material include polyethylene terephthalate, polycarbonate, polyimide, polyamide, polymethyl methacrylate, polystyrene, polyvinyl chloride, polytetrafluoroethylene, polychlorotrifluoroethylene, polyarylate, polysulfone, and triacetyl. Cellulose, cellulose, polyetheretherketone and the like can be mentioned, and examples of the inorganic material include silicon, glass and calcite.
これらの基板を布等でラビングすることによって適当な配向性を得られない場合、公知の方法に従ってポリイミド薄膜又はポリビニルアルコール薄膜等の有機薄膜を基板表面に形成し、これを布等でラビングしても良い。また、通常のツイステッド・ネマチック（ＴＮ）素子又はスーパー・ツイステッド・ネマチック（ＳＴＮ）素子で使用されているプレチルト角を与えるポリイミド薄膜は、重合体内部の分子配向構造を更に精密に制御することができることから、特に好ましい。 When appropriate orientation cannot be obtained by rubbing these substrates with a cloth or the like, an organic thin film such as a polyimide thin film or a polyvinyl alcohol thin film is formed on the substrate surface according to a known method, and this is rubbed with a cloth or the like. Also good. In addition, the polyimide thin film that gives a pretilt angle used in a normal twisted nematic (TN) element or a super twisted nematic (STN) element can control the molecular orientation structure inside the polymer more precisely. Are particularly preferred.
また、電場によって配向状態を制御する場合には、電極層を有する基板を使用する。この場合、電極上に前述のポリイミド薄膜等の有機薄膜を形成するのが好ましい。 In the case where the alignment state is controlled by an electric field, a substrate having an electrode layer is used. In this case, it is preferable to form an organic thin film such as the aforementioned polyimide thin film on the electrode.
本発明の重合性液晶化合物または重合性液晶組成物を重合させる方法としては、迅速な重合の進行が望ましいので、紫外線又は電子線等の活性エネルギー線を照射することによって重合させる方法が好ましい。紫外線を使用する場合、偏光光源を用いても良いし、非偏光光源を用いても良い。また、液晶組成物を２枚の基板間に挟持させて状態で重合を行う場合には、少なくとも照射面側の基板は活性エネルギー線に対して適当な透明性が与えられていなければならない。また、光照射時にマスクを用いて特定の部分のみを重合させた後、電場や磁場または温度等の条件を変化させることにより、未重合部分の配向状態を変化させて、さらに活性エネルギー線を照射して重合させるという手段を用いても良い。また、照射時の温度は、本発明の液晶組成物の液晶状態が保持される温度範囲内であることが好ましい。特に、光重合によって重合体を製造しようとする場合には、意図しない熱重合の誘起を避ける意味からも可能な限り室温に近い温度、即ち、典型的には２５℃での温度で重合させることが好ましい。活性エネルギー線の強度は、０．１ｍＷ／ｃｍ２〜２Ｗ／ｃｍ２が好ましい。強度が０．１ｍＷ／ｃｍ２以下の場合、光重合を完了させるのに多大な時間が必要になり生産性が悪化してしまい、２Ｗ／ｃｍ２以上の場合、重合性液晶化合物または重合性液晶組成物が劣化してしまう危険がある。 As a method for polymerizing the polymerizable liquid crystal compound or the polymerizable liquid crystal composition of the present invention, since rapid progress of polymerization is desirable, a method of polymerizing by irradiating active energy rays such as ultraviolet rays or electron beams is preferable. When ultraviolet rays are used, a polarized light source or a non-polarized light source may be used. Further, when the polymerization is carried out with the liquid crystal composition sandwiched between two substrates, at least the substrate on the irradiation surface side must be given appropriate transparency to the active energy rays. Moreover, after polymerizing only a specific part using a mask during light irradiation, the orientation state of the unpolymerized part is changed by changing conditions such as electric field, magnetic field or temperature, and further irradiation with active energy rays is performed. Then, it is possible to use a means for polymerization. Moreover, it is preferable that the temperature at the time of irradiation is in the temperature range in which the liquid crystal state of the liquid crystal composition of the present invention is maintained. In particular, when a polymer is to be produced by photopolymerization, the polymerization should be performed at a temperature as close to room temperature as possible from the viewpoint of avoiding unintentional thermal polymerization, that is, typically at a temperature of 25 ° C. Is preferred. The intensity of the active energy ray is preferably 0.1 mW / cm 2 to 2 W / cm 2 . When the intensity is 0.1 mW / cm 2 or less, a great amount of time is required to complete the photopolymerization, and the productivity is deteriorated. When the intensity is 2 W / cm 2 or more, the polymerizable liquid crystal compound or the polymerizable liquid crystal is used. There is a risk that the composition will deteriorate.
重合によって得られた本発明の重合体は、初期の特性変化を軽減し、安定的な特性発現を図ることを目的として熱処理を施すこともできる。熱処理の温度は５０〜２５０℃の範囲で、また熱処理時間は３０秒〜１２時間の範囲が好ましい。 The polymer of the present invention obtained by polymerization can be subjected to heat treatment for the purpose of reducing initial characteristic changes and achieving stable characteristic expression. The heat treatment temperature is preferably in the range of 50 to 250 ° C., and the heat treatment time is preferably in the range of 30 seconds to 12 hours.
このような方法によって製造される本発明の重合体は、基板から剥離して単体で用いても、剥離せずに用いても良い。また、得られた重合体を積層しても、他の基板に貼り合わせて用いてもよい。 The polymer of the present invention produced by such a method may be peeled off from the substrate and used alone or without peeling. Further, the obtained polymer may be laminated or bonded to another substrate for use.
以下、実施例を挙げて本発明を更に詳述するが、本発明はこれらの実施例に限定されるものではない。また、以下の実施例及び比較例の組成物における「%」は『質量%』を意味する。
（実施例１）
化合物（I-1-a） 40％
EXAMPLES Hereinafter, although an Example is given and this invention is further explained in full detail, this invention is not limited to these Examples. Further, “%” in the compositions of the following examples and comparative examples means “mass%”.
(Example 1)
Compound (I-1-a) 40%
（実施例２）
化合物（I-1-a） 35％
(Example 2)
Compound (I-1-a) 35%
（実施例３）
実施例１で調製した組成物（A’）を濃度が30%となるようにキシレンに溶解させた。ラビングしたポリイミド配向膜付きガラス基板（２×３センチ角）に、組成物（A’）キシレン溶液を滴下してスピンコーター（３０００回転／分で30秒回転）で塗布した。塗布厚は約１μｍであった。塗布後、60℃に加熱した後、室温まで冷却することにより、ガラス基板上に塗布された組成物（A’）がスメクチックA相を呈する状態にした。この状態で、高圧水銀ランプを光源とする４０mW/cm2の強度の紫外線を2分間照射すると、組成物（A’）は硬化してポリマー化した。ポリマー中にはスメクチックA相の構造が固定化されているのが顕微鏡で確認できた。また均一性も優れていた。
実施例３の重合性液晶組成物は空気中で光重合を行うことができた。
(Example 3)
The composition (A ′) prepared in Example 1 was dissolved in xylene so as to have a concentration of 30%. A composition (A ′) xylene solution was dropped onto a rubbed glass substrate with a polyimide alignment film (2 × 3 cm square) and applied with a spin coater (3000 rotations / minute for 30 seconds). The coating thickness was about 1 μm. After the application, the composition was heated to 60 ° C. and then cooled to room temperature, so that the composition (A ′) applied on the glass substrate exhibited a smectic A phase. In this state, when an ultraviolet ray having an intensity of 40 mW / cm 2 using a high-pressure mercury lamp as a light source was irradiated for 2 minutes, the composition (A ′) was cured and polymerized. It was confirmed with a microscope that the structure of the smectic A phase was fixed in the polymer. Also, the uniformity was excellent.
The polymerizable liquid crystal composition of Example 3 could be photopolymerized in air.
（実施例４）
実施例２で調製した組成物（B’）を濃度が30%となるようにキシレンに溶解させた。ラビングしたポリイミド配向膜付きガラス基板（２×３センチ角）に、組成物（A’）キシレン溶液を滴下してスピンコーター（３０００回転／分で30秒回転）で塗布した。塗布厚は約１μｍであった。塗布後、60℃に加熱した後、室温まで冷却することにより、ガラス基板上に塗布された組成物（B’）がスメクチックA相を呈する状態にした。この状態で、高圧水銀ランプを光源とする４０mW/cm2の強度の紫外線を2分間照射すると、組成物（B’）は硬化してポリマー化した。ポリマー中にはスメクチックA相の構造が固定化されているのが顕微鏡で確認できた。また均一性も優れていた。
実施例４の重合性液晶組成物もまた空気中で光重合を行うことができた。
Example 4
The composition (B ′) prepared in Example 2 was dissolved in xylene so as to have a concentration of 30%. A composition (A ′) xylene solution was dropped onto a rubbed glass substrate with a polyimide alignment film (2 × 3 cm square) and applied with a spin coater (3000 rotations / minute for 30 seconds). The coating thickness was about 1 μm. After coating, the composition was heated to 60 ° C. and then cooled to room temperature, so that the composition (B ′) coated on the glass substrate exhibited a smectic A phase. In this state, when an ultraviolet ray having an intensity of 40 mW / cm 2 using a high pressure mercury lamp as a light source was irradiated for 2 minutes, the composition (B ′) was cured and polymerized. It was confirmed with a microscope that the structure of the smectic A phase was fixed in the polymer. Also, the uniformity was excellent.
The polymerizable liquid crystal composition of Example 4 could also be photopolymerized in air.
（比較例）
化合物（d-1） 33.3%
(Comparative example)
Compound (d-1) 33.3%
調製した組成物（C’）を濃度が30%となるようにキシレンに溶解させた。ラビングしたポリイミド配向膜付きガラス基板（２×３センチ角）に、組成物（A’）キシレン溶液を滴下してスピンコーター（３０００回転／分で30秒回転）で塗布した。塗布厚は約１μｍであった。塗布後、60℃に加熱した後、室温まで冷却することにより、ガラス基板上に塗布された組成物（C’）がスメクチックA相を呈する状態にした。この状態で、高圧水銀ランプを光源とする４０mW/cm2の強度の紫外線を2分間照射しても、組成物（C’）は硬化せずポリマーにならず、空気中では光重合をすることはできなかった。
The prepared composition (C ′) was dissolved in xylene so as to have a concentration of 30%. A composition (A ′) xylene solution was dropped onto a rubbed glass substrate with a polyimide alignment film (2 × 3 cm square) and applied with a spin coater (3000 rotations / minute for 30 seconds). The coating thickness was about 1 μm. After the application, the composition was heated to 60 ° C. and then cooled to room temperature, so that the composition (C ′) applied on the glass substrate exhibited a smectic A phase. In this state, the composition (C ') does not cure and does not become a polymer even when irradiated with UV light of 40 mW / cm 2 for 2 minutes using a high-pressure mercury lamp as the light source. I couldn't.
Claims (5)
A polymer of the polymerizable liquid crystal composition according to claim 1.
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