JP2003155388A - Polymer/liquid crystal composite material and display element - Google Patents
Polymer/liquid crystal composite material and display elementInfo
- Publication number
- JP2003155388A JP2003155388A JP2002236910A JP2002236910A JP2003155388A JP 2003155388 A JP2003155388 A JP 2003155388A JP 2002236910 A JP2002236910 A JP 2002236910A JP 2002236910 A JP2002236910 A JP 2002236910A JP 2003155388 A JP2003155388 A JP 2003155388A
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- Prior art keywords
- liquid crystal
- polymer
- composite material
- carboxylic acid
- unsaturated bond
- Prior art date
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は高分子と液晶（以
下、液晶化合物または液晶組成物の総称であり、液晶化
合物には液晶性化合物をも含むものとする）を混合する
ことによって得られる高分子／液晶複合材料、およびこ
れを用いた表示素子に関する。TECHNICAL FIELD The present invention relates to a polymer obtained by mixing a polymer and a liquid crystal (hereinafter, a generic term for a liquid crystal compound or a liquid crystal composition, and the liquid crystal compound also includes a liquid crystal compound). The present invention relates to a liquid crystal composite material and a display device using the same.
【０００２】[0002]
【従来の技術】液晶／高分子複合材料による高分子分散
型液晶（ＰＤＬＣ）素子は、従来の液晶ディスプレイと
異なり偏光板や配向膜を必要とせず、セル厚の色味への
影響が相対的に少ないことから大面積ディスプレイや調
光パネル等への応用が期待されている。2. Description of the Related Art Unlike a conventional liquid crystal display, a polymer dispersed liquid crystal (PDLC) device using a liquid crystal / polymer composite material does not require a polarizing plate or an alignment film, and the cell thickness has a relative influence on the tint. It is expected to be applied to large area displays and dimming panels, etc.
【０００３】高分子分散型液晶素子は、マイクロカプセ
ルに入った誘電率異方性が正である液晶が高分子マトリ
ックス中に分散した構造（ＵＳＰ４４３５４０７）、高
分子マトリックス中に液晶が小滴あるいは連続層として
分散した構造（特開平２−５５３１８号公報）が知られ
ている。このうち後者は、液晶と高分子を溶媒に溶解し
た後、溶媒を蒸発させることによって相分離させたり
（溶媒蒸発法）、無溶媒で液晶と高分子を溶解し、冷却
することにより相分離させることで調光層を形成できる
ため、製造が簡便である。The polymer-dispersed liquid crystal device has a structure in which liquid crystals having positive dielectric constant anisotropy in microcapsules are dispersed in a polymer matrix (USP4435407). A structure in which the layers are dispersed (Japanese Patent Laid-Open No. 2-55318) is known. Of these, the latter is the one in which the liquid crystal and polymer are dissolved in a solvent and then the solvent is evaporated to cause phase separation (solvent evaporation method), or the liquid crystal and polymer are dissolved without solvent and cooled to cause phase separation. Thus, the light control layer can be formed, so that the production is simple.
【０００４】しかしこれらの相分離法で得られた液晶／
高分子複合材料は液晶含有率が低いことに起因する様々
な問題を有する。例えば駆動電圧が高いことなどであ
る。しかし、液晶含有率を高くすると液晶と高分子が複
合化しない。液晶層形成製造プロセスによっては高分子
／液晶複合膜が自己支持性を持つことが要求される場合
もある。しかし、従来の高分子／液晶複合膜において
は、液晶含有率を高くした場合、この点も十分ではな
い。なお、本明細書中で「複合化」とは、高分子が液晶
を吸収している状態を示し、「形状の自己支持性を有す
る」という語は、複合化した高分子／液晶複合材料が独
立した膜として採取できることをいう。However, the liquid crystal obtained by these phase separation methods /
Polymer composite materials have various problems due to their low liquid crystal content. For example, the driving voltage is high. However, when the liquid crystal content is increased, the liquid crystal and the polymer do not form a composite. Depending on the manufacturing process for forming the liquid crystal layer, the polymer / liquid crystal composite film may be required to have a self-supporting property. However, in the conventional polymer / liquid crystal composite film, when the liquid crystal content is increased, this point is not sufficient either. In the present specification, “composite” refers to a state in which a polymer absorbs liquid crystal, and the term “having a shape self-supporting property” means that the composite polymer / liquid crystal composite material. It means that it can be collected as an independent membrane.
【０００５】[0005]
【発明が解決しようとする課題】特開平２−１７６７１
９号公報には液晶含有率が８０重量％であるエチレン−
エチルアクリレート共重合体（エチルアクリレート含有
率１８重量％）と液晶の複合材料が開示されている。こ
の公報中には、液晶の割合が多いと高分子多孔質膜が形
成されにくい旨の記載がある。さらに、実施例には、複
合材料を透明電極付きのガラス基板で狭持した液晶セル
の飽和電圧は１２０Ｖと高いことが示されている。現在
液晶含有率が高くても、良好に複合化する材料が求めら
れており、その材料が形状の自己支持性を有しておれば
なお好ましい。また、その複合材料を用いた液晶セルの
駆動電圧を低下させることも重要な課題である。[Patent Document 1] Japanese Patent Application Laid-Open No. 2-17671
No. 9 discloses ethylene-containing liquid crystal having a content of 80% by weight.
A composite material of an ethyl acrylate copolymer (ethyl acrylate content 18% by weight) and a liquid crystal is disclosed. In this publication, there is a description that it is difficult to form a polymer porous film when the proportion of liquid crystal is high. Further, the examples show that the saturation voltage of a liquid crystal cell in which a composite material is sandwiched between glass substrates with transparent electrodes is as high as 120V. At present, there is a demand for a material that can form a good composite even if the liquid crystal content is high, and it is more preferable that the material has a shape self-supporting property. It is also an important issue to reduce the driving voltage of a liquid crystal cell using the composite material.
【０００６】本発明の第一の目的は、液晶含有率が高い
にもかかわらず、良好に複合化し、低電圧駆動が可能な
高分子／液晶複合材料を提供することである。第二の目
的は、液晶含有率が高いにも関わらず、良好に複合化
し、さらには形状の自己支持性を有する高分子／液晶複
合材料を提供することである。そして第三の目的は、こ
れらの高分子／液晶複合材料を用いた表示素子を提供す
ることである。第四の目的はこれらの高分子／液晶複合
材料を用いて、透過散乱方式を用いない表示素子を提供
することである。[0006] A first object of the present invention is to provide a polymer / liquid crystal composite material which can be well composited and can be driven at a low voltage even though the liquid crystal content is high. The second object is to provide a polymer / liquid crystal composite material which is well composited and has a shape self-supporting property even though the liquid crystal content is high. And the third object is to provide a display device using these polymer / liquid crystal composite materials. A fourth object is to provide a display device using these polymer / liquid crystal composite materials, which does not use a transmission / scattering method.
【０００７】[0007]
【課題を解決するための手段】上記課題は、以下に示す
本発明によって達成される。
（１） 少なくとも２つのモノマーからなる共重合体で
あって、モノマーの一方が不飽和炭化水素であり、他方
が不飽和結合を有するカルボン酸、不飽和結合を有する
カルボン酸の誘導体または不飽和結合を有するアルコー
ルのエステルである共重合体と、フッ素原子含有液晶化
合物及びシアノ基含有液晶化合物からなる群から選択さ
れた少なくとも１種の液晶化合物を含有する液晶からな
り、相分離し、複合化された高分子／液晶複合材料。The above objects can be achieved by the present invention described below. (1) A copolymer composed of at least two monomers, one of which is an unsaturated hydrocarbon and the other of which is a carboxylic acid having an unsaturated bond, a derivative of a carboxylic acid having an unsaturated bond, or an unsaturated bond. And a liquid crystal containing a liquid crystal containing at least one liquid crystal compound selected from the group consisting of a fluorine atom-containing liquid crystal compound and a cyano group-containing liquid crystal compound. Polymer / liquid crystal composite material.
【０００８】（２） 液晶がフッ素原子含有液晶化合物
を５０〜１００重量％含有する（１）項に記載の高分子
／液晶複合材料。
（３） 共重合体を構成するモノマーのうち、不飽和炭
化水素がエチレンであり、不飽和結合を有するカルボン
酸または不飽和結合を有するカルボン酸の誘導体がメタ
クリル酸またはその誘導体である、（１）項に記載の高
分子／液晶複合材料。
（４） 共重合体を構成するモノマーのうち、不飽和炭
化水素がエチレンであり、不飽和結合を有するカルボン
酸の誘導体がアクリル酸メチルである、（１）項に記載
の高分子／液晶複合材料。(2) The polymer / liquid crystal composite material according to item (1), wherein the liquid crystal contains a fluorine atom-containing liquid crystal compound in an amount of 50 to 100% by weight. (3) Among the monomers constituting the copolymer, the unsaturated hydrocarbon is ethylene, and the carboxylic acid having an unsaturated bond or the derivative of the carboxylic acid having an unsaturated bond is methacrylic acid or its derivative. The polymer / liquid crystal composite material according to the item (1). (4) The polymer / liquid crystal composite according to the item (1), wherein among the monomers constituting the copolymer, the unsaturated hydrocarbon is ethylene and the derivative of the carboxylic acid having an unsaturated bond is methyl acrylate. material.
【０００９】（５） 共重合体を構成するモノマーのう
ち、不飽和炭化水素がエチレンであり、不飽和結合を有
するアルコールのエステルがカルボン酸ビニルエステル
である、（１）項に記載の高分子／液晶複合材料。
（６） 共重合体中における、不飽和結合を有するカル
ボン酸、不飽和結合を有するカルボン酸の誘導体または
不飽和結合を有するアルコールのエステルモノマーの含
有率が５重量％から６０重量％である、（１）項に記載
の高分子／液晶複合材料。(5) The polymer according to item (1), wherein among the monomers constituting the copolymer, the unsaturated hydrocarbon is ethylene and the ester of alcohol having an unsaturated bond is carboxylic acid vinyl ester. / Liquid crystal composite material. (6) The content of the carboxylic acid having an unsaturated bond, the derivative of the carboxylic acid having an unsaturated bond or the ester monomer of the alcohol having an unsaturated bond in the copolymer is from 5% by weight to 60% by weight. The polymer / liquid crystal composite material according to item (1).
【００１０】（７） 高分子がエポキシ基を有する化合
物である（１）項に記載の高分子／液晶複合材料。
（８） 高分子がエポキシ基を有する高分子に一分子中
に複数の活性水素を有する化合物を反応させて得られる
架橋構造を有する化合物である（１）項に記載の高分子
／液晶複合材料。(7) The polymer / liquid crystal composite material according to item (1), wherein the polymer is a compound having an epoxy group. (8) The polymer / liquid crystal composite material according to item (1), wherein the polymer is a compound having a crosslinked structure, which is obtained by reacting a polymer having an epoxy group with a compound having a plurality of active hydrogens in one molecule. .
【００１１】（９） 形状の自己支持性を有する（１）
〜（８）項の何れか一項に記載の高分子／液晶複合材
料。
（１０） 液晶含有率が９０重量％をこえる、（１）〜
（９）項の何れか一項に記載の高分子／液晶複合材料。
（１１） 液晶中のシアノ基を有する化合物が、液晶全
体の１０重量％以下である、（２）項に記載の高分子／
液晶複合材料。
（１２） （１）〜（１１）の何れか一項に記載の高分
子／液晶複合材料を調光層とする表示素子。(9) Self-supporting shape (1)
~ The polymer / liquid crystal composite material according to any one of items (8) to (8). (10) Liquid crystal content exceeds 90% by weight, (1) to
The polymer / liquid crystal composite material according to any one of items (9). (11) The polymer according to item (2), wherein the compound having a cyano group in the liquid crystal is 10% by weight or less based on the whole liquid crystal.
Liquid crystal composite material. (12) A display device comprising the polymer / liquid crystal composite material according to any one of (1) to (11) as a light control layer.
【００１２】（１３） 少なくとも２つのモノマーから
なる共重合体であって、モノマーの一方が不飽和炭化水
素であり、他方が不飽和結合を有するカルボン酸、不飽
和結合を有するカルボン酸の誘導体または不飽和結合を
有するアルコールのエステルである共重合体と、液晶か
らなり、相分離し、複合化された高分子／液晶複合材料
が配向層間に挟持され、且つその複合材料を調光層とす
る表示素子。
（１４） （１）〜（１１）項の何れか一項に記載の高
分子／液晶複合材料が配向層間に挟持され、且つその複
合材料を調光層とする表示素子。(13) A copolymer composed of at least two monomers, one of which is an unsaturated hydrocarbon and the other of which is a carboxylic acid having an unsaturated bond, a derivative of a carboxylic acid having an unsaturated bond, or A polymer / liquid crystal composite material, which is composed of a liquid crystal of an alcohol ester having an unsaturated bond and a liquid crystal, and is phase-separated and composited, is sandwiched between alignment layers, and the composite material is used as a light control layer. Display element. (14) A display device in which the polymer / liquid crystal composite material according to any one of (1) to (11) is sandwiched between alignment layers, and the composite material serves as a light control layer.
【００１３】[0013]
【発明の実施の形態】以下本発明を詳細に説明する。本
発明の複合材料の成分の一つである液晶は、単一の液晶
化合物でも液晶組成物でもよい。液晶は、電気光学素子
の駆動部分に用いる場合には棒状化合物で構成されたサ
ーモトロピック液晶が好ましく、さらに室温においてネ
マチック相あるいはコレステリック相を有し、誘電率異
方性値が２以上あるいは−２以下であるものが好まし
い。また、室温においてカイラルスメクチックＣ相また
はカイラルスメクチックＣA相を呈し、自発分極値が０.
１以上であるものが好ましい。BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. The liquid crystal which is one of the components of the composite material of the present invention may be a single liquid crystal compound or a liquid crystal composition. The liquid crystal is preferably a thermotropic liquid crystal composed of a rod-shaped compound when it is used for a driving part of an electro-optical element, and has a nematic phase or a cholesteric phase at room temperature and has a dielectric anisotropy value of 2 or more or -2. The following are preferable. Further, it exhibits a chiral smectic C phase or a chiral smectic C A phase at room temperature, and has a spontaneous polarization value of 0.
It is preferably 1 or more.
【００１４】ネマチック相あるいはコレステリック相を
有する液晶の誘電率異方性は、芳香環の水素原子の一部
をフッ素原子で置換された基、トリフルオロメチル基、
ジフルオロメチル基、トリフルオロメトキシ基、ジフル
オロメトキシ基、トリフルオロアセトキシ基、若しくは
トリフルオロアセチル基等のフッ素原子を含有する基、
あるいはシアノ基などの電子吸引性基によって発現す
る。したがって、誘電率異方性の絶対値の大きい化合
物、具体的には誘電率異方性値が２以上あるいは−２以
下の液晶を得るためには、これら官能基の何れかを有す
る化合物が必須となる。The dielectric anisotropy of a liquid crystal having a nematic phase or a cholesteric phase is determined by a group in which a part of hydrogen atoms of an aromatic ring is replaced with a fluorine atom, a trifluoromethyl group,
A group containing a fluorine atom such as a difluoromethyl group, a trifluoromethoxy group, a difluoromethoxy group, a trifluoroacetoxy group, or a trifluoroacetyl group,
Alternatively, it is expressed by an electron-withdrawing group such as a cyano group. Therefore, in order to obtain a compound having a large absolute value of dielectric anisotropy, specifically a liquid crystal having a dielectric anisotropy value of 2 or more or -2 or less, a compound having any of these functional groups is essential. Becomes
【００１５】しかし、シアノ基を有する液晶化合物、あ
るいはシアノ基を有する化合物のみで構成された液晶組
成物は、液晶含有率が高い場合には複合化されにくい傾
向がある。その様な場合、シアノ基を有する液晶化合物
の含有率が５０重量％以下である液晶組成物を用いるこ
とが好ましい。より好ましくは３０重量％以下、更によ
り好ましくは１０重量％以下である。However, a liquid crystal compound having a cyano group or a liquid crystal composition composed only of a compound having a cyano group tends to be difficult to form a composite when the liquid crystal content is high. In such a case, it is preferable to use a liquid crystal composition containing 50% by weight or less of the liquid crystal compound having a cyano group. It is more preferably 30% by weight or less, and even more preferably 10% by weight or less.
【００１６】本発明の目的である液晶高含量の高分子／
液晶複合材料を得るためには、液晶として上述したフッ
素原子を含有する基を有する液晶化合物を使用すること
が必須の条件である。液晶含有率が９０重量％を越える
複合材料を得るためにはフッ素原子を含有する基を有す
る液晶化合物を全液晶の５０〜１００重量％添加するこ
とが好ましい。Polymers with high liquid crystal content, which is the object of the present invention,
In order to obtain a liquid crystal composite material, it is an essential condition to use the above-mentioned liquid crystal compound having a group containing a fluorine atom as liquid crystal. In order to obtain a composite material having a liquid crystal content of more than 90% by weight, it is preferable to add a liquid crystal compound having a group containing a fluorine atom in an amount of 50 to 100% by weight of all liquid crystals.
【００１７】本発明ではフッ素原子を含有する基を有す
る液晶化合物及びシアノ基含有液晶化合物以外に、更に
その他の液晶化合物を添加することもできる。しかし、
液晶高含量の高分子／液晶複合材料を得るためには、フ
ッ素原子を含有する基を有する液晶化合物以外に合計５
０重量％以下のシアノ基含有液晶化合物及び／又はその
他の液晶化合物を添加することができる。更にフッ素原
子を含有する基を有する液晶化合物のみからなる液晶が
液晶含有率が大きい複合材料を得るためには最も好まし
い。このように液晶材料の成分を選択することによって
初めて良好に複合化した高分子／液晶複合材料を調製す
ることができる。In the present invention, in addition to the liquid crystal compound having a fluorine atom-containing group and the cyano group-containing liquid crystal compound, other liquid crystal compounds may be added. But,
In order to obtain a polymer / liquid crystal composite material with a high content of liquid crystal, a total of 5 other than the liquid crystal compound having a group containing a fluorine atom.
0% by weight or less of a cyano group-containing liquid crystal compound and / or other liquid crystal compound can be added. Further, a liquid crystal composed of only a liquid crystal compound having a group containing a fluorine atom is most preferable for obtaining a composite material having a large liquid crystal content. By selecting the components of the liquid crystal material in this way, it is possible to prepare a polymer / liquid crystal composite material that is well composited.
【００１８】本発明の複合材料の共重合体の重合性モノ
マーである不飽和炭化水素としては、エチレン、プロピ
レン、イソプレン、ブタジエン等を挙げることができ
る。また他の重合性モノマーとして、不飽和結合を有す
るカルボン酸、不飽和結合を有するカルボン酸の誘導体
または不飽和結合を有するアルコールのエステル誘導体
を挙げることができる。不飽和カルボン酸、不飽和結合
を有するカルボン酸の誘導体または不飽和結合を有する
アルコールのエステル誘導体としては、液晶と良好に複
合化する点から不飽和カルボン酸エステルが好ましく、
この中でも高分子／液晶複合材料としたときに形状の自
己支持性に優れているという点で特に好ましいものは不
飽和カルボン酸メチルエステルである。Examples of the unsaturated hydrocarbon which is a polymerizable monomer of the copolymer of the composite material of the present invention include ethylene, propylene, isoprene and butadiene. Examples of the other polymerizable monomer include a carboxylic acid having an unsaturated bond, a derivative of a carboxylic acid having an unsaturated bond, and an ester derivative of an alcohol having an unsaturated bond. As the unsaturated carboxylic acid, the derivative of the carboxylic acid having an unsaturated bond or the ester derivative of the alcohol having an unsaturated bond, an unsaturated carboxylic acid ester is preferable from the viewpoint of good complexation with liquid crystal,
Among them, unsaturated carboxylic acid methyl ester is particularly preferable in that it is excellent in shape self-supporting property when formed into a polymer / liquid crystal composite material.
【００１９】不飽和結合を有するカルボン酸の誘導体と
してはアクリル酸エステル、メタクリル酸エステルが好
ましく、具体的にはメチルアクリレート、メチルメタク
リレート、アクリル酸メチルを挙げることができる。不
飽和結合を有するアルコールのエステル誘導体としては
カルボン酸ビニルエステルが好ましく、具体的には酢酸
ビニル、プロピオン酸ビニルを挙げることができる。ま
た本発明の複合材料の共重合体は、上記の不飽和炭化水
素と、不飽和結合を有するカルボン酸、不飽和結合を有
するカルボン酸の誘導体または不飽和結合を有するアル
コールのエステル誘導体の他に、さらに第三のモノマー
成分としてこれら以外の重合性モノマーを用いた共重合
体であってもよい。The carboxylic acid derivative having an unsaturated bond is preferably an acrylic acid ester or a methacrylic acid ester, and specific examples thereof include methyl acrylate, methyl methacrylate and methyl acrylate. As the ester derivative of the alcohol having an unsaturated bond, vinyl carboxylate is preferable, and specific examples thereof include vinyl acetate and vinyl propionate. Further, the copolymer of the composite material of the present invention includes the above unsaturated hydrocarbon, a carboxylic acid having an unsaturated bond, a derivative of a carboxylic acid having an unsaturated bond, or an ester derivative of an alcohol having an unsaturated bond. Further, it may be a copolymer using a polymerizable monomer other than these as the third monomer component.
【００２０】本発明の複合材料の共重合体はランダム共
重合体でも、ブロック共重合体でもよい。不飽和結合を
有するカルボン酸、不飽和結合を有するカルボン酸の誘
導体または不飽和結合を有するアルコールのエステル
の、共重合体中における含有率は５〜６０重量％が好ま
しい。５重量％以上であると、飽和電圧下における透過
率が高くなり、６０重量％以下であると液晶含有率を高
くした場合でも形状の自己支持性を保ちやすい。より好
ましくは８〜４０重量％である。上記の第三のモノマー
成分は２０重量％以下が好ましい。The copolymer of the composite material of the present invention may be a random copolymer or a block copolymer. The content of a carboxylic acid having an unsaturated bond, a carboxylic acid derivative having an unsaturated bond or an ester of an alcohol having an unsaturated bond in the copolymer is preferably 5 to 60% by weight. When it is 5% by weight or more, the transmittance under a saturation voltage becomes high, and when it is 60% by weight or less, the self-supporting property of the shape is easily maintained even when the liquid crystal content is increased. It is more preferably 8 to 40% by weight. The content of the third monomer component is preferably 20% by weight or less.
【００２１】本発明の複合材料の自己支持性をより向上
させるためには、用いられる高分子が架橋構造を有して
いる化合物であることが好ましい。架橋構造の形成法と
しては、エポキシ基を有する高分子と一分子中に複数の
活性水素を有する化合物（低分子、高分子を問わず）を
反応させることにより得られる。エポキシ基を有する高
分子としては不飽和基を有するカルボン酸の誘導体とし
て、グリシジルアクリレート、グリシジルメタクリレー
ト等の不飽和基を有するグリシジルエステルをコモノマ
ーとして得られる共重合体を挙げることができる。In order to further improve the self-supporting property of the composite material of the present invention, the polymer used is preferably a compound having a crosslinked structure. The method for forming the crosslinked structure can be obtained by reacting a polymer having an epoxy group with a compound having a plurality of active hydrogens in one molecule (whether a low molecule or a polymer). Examples of the polymer having an epoxy group include copolymers obtained by using a glycidyl ester having an unsaturated group such as glycidyl acrylate and glycidyl methacrylate as a comonomer, as a derivative of a carboxylic acid having an unsaturated group.
【００２２】活性水素を有する化合物としてカルボキシ
ル基、ヒドロキシル基あるいはアミノ基を有する化合物
である。これらのうちではカルボキシル基を有する化合
物が最も好ましい。ヒドロキシル基は反応が遅く、アミ
ノ基は副反応が多いからである。これらは低分子量化合
物でも高分子でもよい。具体例としてポリセバシン酸無
水物のようにカルボン酸が縮合して高分子化した化合
物、あるいはアジピン酸、ピロメリット酸、トリメリッ
ト酸、３,３′,４,４′−ベンゾフェノンテトラカルボ
ン酸等の低分子量多価カルボン酸であって、エポキシ硬
化剤である化合物を挙げることができる。The compound having active hydrogen is a compound having a carboxyl group, a hydroxyl group or an amino group. Of these, compounds having a carboxyl group are most preferable. This is because the hydroxyl group has a slow reaction and the amino group has many side reactions. These may be low molecular weight compounds or polymers. Specific examples include compounds obtained by polymerizing condensation of carboxylic acids such as polysebacic anhydride, or adipic acid, pyromellitic acid, trimellitic acid, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid, etc. The compound which is a low molecular weight polycarboxylic acid and is an epoxy curing agent can be mentioned.
【００２３】本発明の液晶／高分子複合材料の液晶含有
率は、好ましくは８０〜９９％重量であり、低電圧駆動
という点でより好ましくは９０重量％を越え、かつ９９
重量％以下である。９０重量％以下では低電圧駆動が不
十分であり、９９重量％を越えると形状を保つことが困
難であるからである。さらに好ましくは９５〜９９重量
％である。形状の自己支持性をも維持するためには９０
重量％を越え９５重量％以下が好ましい。The liquid crystal content of the liquid crystal / polymer composite material of the present invention is preferably 80 to 99% by weight, more preferably more than 90% by weight in view of low voltage driving, and 99% by weight.
It is less than or equal to wt. This is because low voltage driving is insufficient at 90% by weight or less, and it is difficult to maintain the shape at 99% by weight or more. More preferably, it is 95 to 99% by weight. 90 to maintain self-supporting shape
It is preferably more than 95% by weight and less than 95% by weight.
【００２４】本発明の複合材料のなかにはゲル状となり
流動性が消失するものもあるが、複合化していれば、流
動性の有無は問わない。本発明の液晶／高分子複合材料
は溶媒蒸発法にて作成してもよく、無溶媒で液晶と高分
子を加熱溶解し、冷却することで作成してもよい。Some of the composite materials of the present invention are in the form of gel and lose the fluidity, but the fluidity does not matter as long as they are composite. The liquid crystal / polymer composite material of the present invention may be prepared by a solvent evaporation method, or may be prepared by heating and dissolving a liquid crystal and a polymer without a solvent, and then cooling.
【００２５】本発明の表示素子としては、本発明の高分
子／液晶複合材料を調光層とし、これを電極を有する少
なくとも一方が透明な基板で挟持させてなるものを挙げ
ることができる。この液晶表示素子は電界のオンとオフ
の切り替えにより、可視光の透過状態と散乱状態あるい
は散乱状態と透過状態を切り替える透過散乱方式により
表示が可能である。さらに通常用いられる配向層を電極
上に有する少なくとも一方が透明な２枚の基板間に、本
発明の高分子／液晶複合材料を挟持してなるものを挙げ
ることができる。この表示素子は少なくとも１枚の偏光
板と組み合わせることにより、電界による高分子／液晶
複合材料の複屈折制御を行うことで表示が可能である。
ＴＮモード、ＳＴＮモード、ＩＰＳモード、ＶＡモード
といった現行ＬＣＤはいずれも液晶の複屈折を電界で制
御して、表示を実現しており、コントラストや解像度が
高いという特徴を有する。Examples of the display device of the present invention include those in which the polymer / liquid crystal composite material of the present invention is used as a light control layer, and this is sandwiched between transparent substrates having at least one having electrodes. This liquid crystal display element can perform display by a transmission / scattering method in which a visible light transmission state and a scattering state or a scattering state and a transmission state are switched by switching an electric field on and off. Further, there may be mentioned one in which the polymer / liquid crystal composite material of the present invention is sandwiched between two substrates, at least one of which has a commonly used alignment layer on an electrode and which is transparent. By combining this display element with at least one polarizing plate, it is possible to display by controlling the birefringence of the polymer / liquid crystal composite material by the electric field.
Current LCDs such as TN mode, STN mode, IPS mode, and VA mode all realize the display by controlling the birefringence of the liquid crystal by an electric field, and are characterized by high contrast and resolution.
【００２６】また本発明の高分子／液晶複合材料に二色
性色素を添加し、これを電極を有する少なくとも一方が
透明な２枚の基板で挟持させてなるものを挙げることが
できる。この表示素子は一般にゲスト・ホスト方式と称
される方式において表示できる。すなわち電界のオンと
オフの切り替えにより、二色性色素の配向状態が変化
し、着色状態と無色状態、無色状態と着色状態を切り替
えることができる。本発明の表示素子は液晶含有率が高
いため、低電圧駆動が可能であるという優れた利点を有
する。Another example is a polymer / liquid crystal composite material of the present invention to which a dichroic dye is added and which is sandwiched between two substrates having electrodes and at least one of which is transparent. This display element can display in a system generally called a guest-host system. That is, the orientation state of the dichroic dye is changed by switching the electric field on and off, and the colored state and the colorless state and the colorless state and the colored state can be switched. Since the display element of the present invention has a high liquid crystal content, it has an excellent advantage that it can be driven at a low voltage.
【００２７】[0027]
【実施例】以下実施例により本発明を具体的に説明す
る。
実施例１
住友化学(株)製アクリフトＷＫ３０７（メチルメタクリ
レート含有率２５重量％）と４−ペンチル−４′−シア
ノビフェニル（５ＣＢ）が１／９の重量比である複合材
料Ａを加熱溶解により調製した。この溶液をスライドガ
ラス上に滴下した後冷却すると白濁した膜ができた。得
られた高分子／液晶複合材料からなる膜は形状の自己支
持性を有した。複合材料Ａに６.８μｍのスペーサーを
加熱攪拌して混合し、これを等方相状態でインジウム−
スズ酸化物（ＩＴＯ）電極付ガラス基板上に滴下し、も
う一方のガラス基板を張り合わせ、室温まで冷却し、表
示素子を作成した。この表示素子のしきい値電圧は３Ｖ
以下であり、飽和電圧は約３０Ｖであった。The present invention will be described in detail with reference to the following examples. Example 1 Sumitomo Chemical Co., Ltd. Acryft WK307 (methyl methacrylate content 25% by weight) and 4-pentyl-4'-cyanobiphenyl (5CB) in a weight ratio of 1/9 were prepared by heating and melting. did. When this solution was dropped on a slide glass and then cooled, a white turbid film was formed. The obtained film composed of the polymer / liquid crystal composite material had a shape self-supporting property. A 6.8 μm spacer was heated and mixed with the composite material A, and the mixture was mixed with indium in the isotropic phase state.
It was dropped on a glass substrate with a tin oxide (ITO) electrode, the other glass substrate was laminated, and cooled to room temperature to prepare a display element. The threshold voltage of this display element is 3V
Below, the saturation voltage was about 30V.
【００２８】実施例２
高分子として住友化学(株)製アクリフトＷＨ２０６（メ
チルメタクリレート含有率２０％）を用いた以外は、実
施例１の方法に準じて複合材料Ｂを調整し、さらにこれ
を用いて表示素子を作成した。得られた複合材料Ｂは形
状の自己支持性を有した。また、この表示素子のしきい
値電圧は３Ｖ以下であり、飽和電圧は約３０Ｖであっ
た。Example 2 A composite material B was prepared in the same manner as in Example 1 except that Acryft WH206 manufactured by Sumitomo Chemical Co., Ltd. (methyl methacrylate content: 20%) was used as the polymer. A display element was created. The resulting composite material B had a shape self-supporting property. The threshold voltage of this display element was 3 V or less, and the saturation voltage was about 30 V.
【００２９】実施例３
高分子としてアルドリッチ社製エチレン−メチルアクリ
レート共重合体（メチルアクリレート含有率２１.５
％）を用いた以外は、実施例１の方法に準じて複合材料
Ｄを調整し、さらにこれを用いて表示素子を作成した。
得られた複合材料Ｄは形状の自己支持性を有した。ま
た、この表示素子のしきい値電圧は３Ｖ以下であり、飽
和電圧は約３０Ｖであった。Example 3 As a polymer, an ethylene-methyl acrylate copolymer manufactured by Aldrich (methyl acrylate content 21.5) was used.
%) Was used to prepare the composite material D in accordance with the method of Example 1, and the composite material D was used to prepare a display element.
The obtained composite material D had a shape self-supporting property. The threshold voltage of this display element was 3 V or less, and the saturation voltage was about 30 V.
【００３０】実施例４
高分子としてアルドリッチ社製エチレン−酢酸ビニル共
重合体（酢酸ビニル含有率２５％）を用いた以外は、実
施例１の方法に準じて複合材料Ｅを調整し、さらにこれ
を用いて表示素子を作成した。得られた複合材料Ｅは形
状の自己支持性を有した。また、この表示素子のしきい
値電圧は３Ｖ以下であり、飽和電圧は約３０Ｖであっ
た。Example 4 A composite material E was prepared in the same manner as in Example 1 except that an ethylene-vinyl acetate copolymer (vinyl acetate content 25%) manufactured by Aldrich was used as the polymer. A display element was prepared using. The obtained composite material E had a shape self-supporting property. The threshold voltage of this display element was 3 V or less, and the saturation voltage was about 30 V.
【００３１】実施例５
２０μｍのスペーサーを用いた以外は実施例１の方法に
準じて表示素子を得た。この表示素子の飽和電圧は約６
０Ｖであった。Example 5 A display device was obtained according to the method of Example 1 except that a 20 μm spacer was used. The saturation voltage of this display element is about 6
It was 0V.
【００３２】実施例６
以下の組成からなる液晶組成物Ａを調製した。濃度は重
量％を示す。Example 6 A liquid crystal composition A having the following composition was prepared. The concentration is% by weight.
【化１】 [Chemical 1]
【００３３】液晶組成物ＡはＮ−Ｉ転移点７１.５℃、
誘電率異方性値１１.１、屈折率異方性値０.０９９であ
った。高分子／液晶複合材料として住友化学(株)製アク
リフトＷＨ２０６（メチルメタクリレート含有率２０
％）と液晶組成物Ａの重量比が３／９７である複合材料
Ｆを加熱溶解により調製し、さらに実施例１の方法に準
じて表示素子を作成した。本複合材料Ｆは良好に複合化
し、流動性が消失していた。この表示素子のしきい値電
圧は３Ｖ以下であり飽和電圧は約１５Ｖであった。The liquid crystal composition A has an NI transition point of 71.5 ° C.
The dielectric anisotropy value was 11.1 and the refractive index anisotropy value was 0.099. Sumitomo Chemical Co., Ltd. Acryft WH206 (methyl methacrylate content 20 as a polymer / liquid crystal composite material)
%) And the liquid crystal composition A in a weight ratio of 3/97, a composite material F was prepared by heating and melting, and a display element was prepared according to the method of Example 1. This composite material F was well composited and the fluidity was lost. The threshold voltage of this display element was 3 V or less and the saturation voltage was about 15 V.
【００３４】実施例７
高分子としてアルドリッチ社製エチレン−メチルアクリ
レート（メチルアクリレート含有率２１.５％）共重合
体を用いた以外は実施例７と同様にして複合材料Ｇを調
整し、さらにこれを用いて表示素子を作成した。得られ
た複合材料Ｇは良好に複合化した。また、この表示素子
のしきい値電圧は３Ｖ以下であり飽和電圧は約１５Ｖで
あった。Example 7 A composite material G was prepared in the same manner as in Example 7 except that an ethylene-methyl acrylate (Methyl acrylate content 21.5%) copolymer manufactured by Aldrich was used as the polymer. A display element was prepared using. The obtained composite material G was well composited. The threshold voltage of this display element was 3 V or less and the saturation voltage was about 15 V.
【００３５】実施例８
高分子として住友化学(株)製アクリフトＷＫ３０７（メ
チルメタクリレート含有率２５％）を用い、液晶として
チッソ(株)製ＪＣ−１０１３（シアノ系液晶組成物）を
用い、高分子と液晶の重量比を１７／８３とした以外は
実施例１の方法に準じて高分子／液晶複合材料Ｊおよび
表示素子を得た。本複合材料Ｊは形状の自己支持性を有
した。また、この表示素子の飽和電圧は約６０Ｖであっ
た。Example 8 Acryft WK307 (25% methyl methacrylate content) manufactured by Sumitomo Chemical Co., Ltd. was used as the polymer, and JC-1013 (cyano liquid crystal composition) manufactured by Chisso Corporation was used as the liquid crystal. A polymer / liquid crystal composite material J and a display element were obtained according to the method of Example 1 except that the weight ratio of the liquid crystal and the liquid crystal was 17/83. This composite material J had a shape self-supporting property. The saturation voltage of this display element was about 60V.
【００３６】実施例９
高分子として住友化学(株)製アクリフトＷＫ３０７（メ
チルメタクリレート含有率２５％）を用い、液晶として
液晶組成物Ａとチッソ(株)製ＪＣ−１０１３の重量比１
／１混合物（フッ素原子を含有する基を有する液晶化合
物５０重量％）を用い、高分子と液晶の重量比を３／９
７とした以外は実施例１の方法に準じて複合材料Ｋを調
製した。この複合材料Ｋは良好に複合化した。得られた
複合材料Ｋをポリイミド配向膜を有するＩＴＯ付ガラス
基板に、液晶層厚９.７μｍ、ラビング角８０°となる
ように挟持し、アニールすることにより表示素子を作成
した。クロスニコルに配置した偏光板間において、複合
材料Ｋが配向していることが確認された。この表示素子
のしきい値電圧は３.３Ｖ、飽和電圧は９.９Ｖであっ
た。Example 9 Acryft WK307 (25% methyl methacrylate content) manufactured by Sumitomo Chemical Co., Ltd. was used as a polymer, and the liquid crystal composition A was used as a liquid crystal and the weight ratio of JC-1013 manufactured by Chisso Corporation was 1
/ 1 mixture (50% by weight of a liquid crystal compound having a group containing a fluorine atom), and the weight ratio of the polymer to the liquid crystal is 3/9.
Composite material K was prepared according to the method of Example 1 except that No. 7 was used. This composite material K was well composited. The obtained composite material K was sandwiched between a glass substrate with ITO having a polyimide alignment film so as to have a liquid crystal layer thickness of 9.7 μm and a rubbing angle of 80 °, and annealed to prepare a display element. It was confirmed that the composite material K was oriented between the polarizing plates arranged in crossed Nicols. This display device had a threshold voltage of 3.3V and a saturation voltage of 9.9V.
【００３７】実施例１０
液晶組成物Ａ／下式液晶化合物Ｃ＝７／３（重量比）の
液晶組成物Ｂを調製した。Example 10 A liquid crystal composition B of liquid crystal composition A / lower liquid crystal compound C = 7/3 (weight ratio) was prepared.
【化２】 [Chemical 2]
【００３８】アルドリッチ社製エチレン−メチルアクリ
レート−グリシジルメタクリレートの共重合体０.２５
ｇと液晶組成物Ｂ１.６ｇを加熱溶解し、これにアルド
リッチ社製ポリセバシン酸無水物０.０５ｇを加え、加
熱溶解して複合材料Ｌを得た。複合材料Ｌをガラスプレ
ート上に展開し、１５０℃で９０分加熱したところ、ゴ
ム状となり、形状の自己支持性が確認された。複合材料
Ｌを層厚７μｍでＩＴＯ付ガラス基板間に挟持し、１５
０℃で９０分加熱し、室温まで冷却して表示素子を得
た。この表示素子の飽和電圧は１７Ｖであった。Ethylene-methyl acrylate-glycidyl methacrylate copolymer manufactured by Aldrich 0.25
g and liquid crystal composition B (1.6 g) were heated and dissolved, and polysebacic acid anhydride (0.05 g, manufactured by Aldrich Co., Ltd.) was added, and the mixture was heated and dissolved to obtain a composite material L. When the composite material L was spread on a glass plate and heated at 150 ° C. for 90 minutes, it became rubber-like, and the self-supporting property of the shape was confirmed. Composite material L is sandwiched between glass substrates with ITO with a layer thickness of 7 μm,
It heated at 0 degreeC for 90 minutes, and cooled to room temperature, and the display element was obtained. The saturation voltage of this display element was 17V.
【００３９】実施例１１
アルドリッチ社製エチレン−メチルアクリレート−グリ
シジルメタクリレートの共重合体０.２５ｇと液晶組成
物Ｂ２.３ｇを加熱溶解し、複合材料Ｍを得た。得られ
た複合材料Ｍをポリイミド配向膜を有するＩＴＯ付ガラ
ス基板に、液晶層厚５μｍ、ラビング角１８０°となる
ように挟持し、アニールすることにより表示素子を作成
した。クロスニコルに配置した偏光板間において、複合
材料Ｍが配向していることが確認された。この表示素子
の飽和電圧は約７Ｖであった。Example 11 A composite material M was obtained by heating and dissolving 0.25 g of a copolymer of ethylene-methyl acrylate-glycidyl methacrylate manufactured by Aldrich and 2.3 g of liquid crystal composition B. The resulting composite material M was sandwiched between a glass substrate with ITO having a polyimide alignment film so as to have a liquid crystal layer thickness of 5 μm and a rubbing angle of 180 °, and annealed to prepare a display element. It was confirmed that the composite material M was oriented between the polarizing plates arranged in crossed Nicols. The saturation voltage of this display element was about 7V.
【００４０】[0040]
【発明の効果】本発明によって、液晶含有率が非常に高
くとも、良好に複合化した高分子／液晶複合材料を調製
することができ、この高分子／液晶複合材料によって低
電圧駆動が可能な表示素子、更には透過散乱方式以外の
方式で駆動する表示素子を提供することができる。また
液晶含有率が非常に高いにもかかわらず、形状の自己支
持性を有する高分子／液晶複合材料は、ロールプロセス
や転写プロセスによって調光層を形成できる可能性があ
り、また架橋構造を有する高分子／液晶複合材料は曲げ
折り曲げに強い表示体を形成することができる。Industrial Applicability According to the present invention, it is possible to prepare a polymer / liquid crystal composite material that is well composited even if the liquid crystal content is very high, and this polymer / liquid crystal composite material can be driven at a low voltage. It is possible to provide a display element and further a display element driven by a method other than the transmission / scattering method. In addition, although the liquid crystal content is very high, the polymer / liquid crystal composite material having a shape self-supporting property has a possibility of forming a light control layer by a roll process or a transfer process, and has a crosslinked structure. The polymer / liquid crystal composite material can form a display body that is resistant to bending and bending.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｇ０２Ｆ 1/1334 Ｇ０２Ｆ 1/1334 Ｆターム(参考） 2H089 HA04 KA07 QA16 RA04 4H027 BA01 BB11 BD04 BD07 BD09 CM04 CP04 CQ04 CR04 CS04 CT04 CU04 DH04 4J002 BB071 BB081 BB141 BF031 BL001 EB116 EH146 EL106 ET006 GP00 ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 7 Identification code FI theme code (reference) G02F 1/1334 G02F 1/1334 F term (reference) 2H089 HA04 KA07 QA16 RA04 4H027 BA01 BB11 BD04 BD07 BD09 CM04 CP04 CQ04 CR04 CS04 CT04 CU04 DH04 4J002 BB071 BB081 BB141 BF031 BL001 EB116 EH146 EL106 ET006 GP00
Claims (14)
合体であって、モノマーの一方が不飽和炭化水素であ
り、他方が不飽和結合を有するカルボン酸、不飽和結合
を有するカルボン酸の誘導体または不飽和結合を有する
アルコールのエステルである共重合体と、フッ素原子含
有液晶化合物及びシアノ基含有液晶化合物からなる群か
ら選択された少なくとも１種の液晶化合物を含有する液
晶からなり、相分離し、複合化された高分子／液晶複合
材料。1. A copolymer composed of at least two monomers, one of which is an unsaturated hydrocarbon and the other of which is a carboxylic acid having an unsaturated bond, a derivative of a carboxylic acid having an unsaturated bond or an unsaturated bond. It is composed of a copolymer, which is an ester of alcohol having a saturated bond, and a liquid crystal containing at least one liquid crystal compound selected from the group consisting of a fluorine atom-containing liquid crystal compound and a cyano group-containing liquid crystal compound. Polymerized / liquid crystal composite material.
〜１００重量％含有する請求項１に記載の高分子／液晶
複合材料。2. The liquid crystal comprises a fluorine atom-containing liquid crystal compound.
The polymer / liquid crystal composite material according to claim 1, which is contained in an amount of ˜100% by weight.
飽和炭化水素がエチレンであり、不飽和結合を有するカ
ルボン酸または不飽和結合を有するカルボン酸の誘導体
がメタクリル酸またはその誘導体である、請求項１に記
載の高分子／液晶複合材料。3. Among the monomers constituting the copolymer, the unsaturated hydrocarbon is ethylene, and the carboxylic acid having an unsaturated bond or the derivative of a carboxylic acid having an unsaturated bond is methacrylic acid or a derivative thereof. The polymer / liquid crystal composite material according to claim 1.
飽和炭化水素がエチレンであり、不飽和結合を有するカ
ルボン酸の誘導体がアクリル酸メチルである、請求項１
に記載の高分子／液晶複合材料。4. The monomer which constitutes the copolymer, wherein the unsaturated hydrocarbon is ethylene, and the derivative of the carboxylic acid having an unsaturated bond is methyl acrylate.
The polymer / liquid crystal composite material according to item 1.
飽和炭化水素がエチレンであり、不飽和結合を有するア
ルコールのエステルがカルボン酸ビニルエステルであ
る、請求項１に記載の高分子／液晶複合材料。5. The polymer / liquid crystal according to claim 1, wherein among the monomers constituting the copolymer, the unsaturated hydrocarbon is ethylene and the ester of an alcohol having an unsaturated bond is a carboxylic acid vinyl ester. Composite material.
るカルボン酸、不飽和結合を有するカルボン酸の誘導体
または不飽和結合を有するアルコールのエステルモノマ
ーの含有率が５重量％から６０重量％である、請求項１
に記載の高分子／液晶複合材料。6. The content of a carboxylic acid having an unsaturated bond, a derivative of a carboxylic acid having an unsaturated bond or an ester monomer of an alcohol having an unsaturated bond in the copolymer is from 5% by weight to 60% by weight. Yes, claim 1
The polymer / liquid crystal composite material according to item 1.
る請求項１に記載の高分子／液晶複合材料。7. The polymer / liquid crystal composite material according to claim 1, wherein the polymer is a compound having an epoxy group.
分子中に複数の活性水素を有する化合物を反応させて得
られる架橋構造を有する化合物である請求項１に記載の
高分子／液晶複合材料。8. The polymer / liquid crystal composite according to claim 1, wherein the polymer is a compound having a crosslinked structure, which is obtained by reacting a polymer having an epoxy group with a compound having a plurality of active hydrogens in one molecule. material.
の何れか一項に記載の高分子／液晶複合材料。9. A shape-self-supporting material having a self-supporting property.
The polymer / liquid crystal composite material according to any one of 1.
求項１〜９の何れか一項に記載の高分子／液晶複合材
料。10. The polymer / liquid crystal composite material according to claim 1, which has a liquid crystal content of more than 90% by weight.
液晶全体の１０重量％以下である、請求項２に記載の高
分子／液晶複合材料。11. A compound having a cyano group in liquid crystal,
The polymer / liquid crystal composite material according to claim 2, which is 10% by weight or less of the entire liquid crystal.
高分子／液晶複合材料を調光層とする表示素子。12. A display device comprising the polymer / liquid crystal composite material according to claim 1 as a light control layer.
重合体であって、モノマーの一方が不飽和炭化水素であ
り、他方が不飽和結合を有するカルボン酸、不飽和結合
を有するカルボン酸の誘導体または不飽和結合を有する
アルコールのエステルである共重合体と、液晶からな
り、相分離し、複合化された高分子／液晶複合材料が配
向層間に挟持され、且つその複合材料を調光層とする表
示素子。13. A copolymer composed of at least two monomers, one of which is an unsaturated hydrocarbon and the other of which is a carboxylic acid having an unsaturated bond, a derivative of a carboxylic acid having an unsaturated bond or an unsaturated carboxylic acid. A display in which a polymer / liquid crystal composite material, which is composed of a liquid crystal of a copolymer of an alcohol ester having a saturated bond and a liquid crystal, is phase-separated and is sandwiched between alignment layers, and uses the composite material as a light control layer element.
高分子／液晶複合材料が配向層間に挟持され、且つその
複合材料を調光層とする表示素子。14. A display device in which the polymer / liquid crystal composite material according to claim 1 is sandwiched between alignment layers, and the composite material serves as a light control layer.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003313556A (en) * | 2002-04-19 | 2003-11-06 | Chisso Corp | Polymer/liquid crystal composite material excellent in light transmission property |
| JP2010001353A (en) * | 2008-06-19 | 2010-01-07 | Kawamura Inst Of Chem Res | Organic/inorganic composite material including liquid crystalline compound |
| JP2011525553A (en) * | 2008-06-27 | 2011-09-22 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツング | Liquid crystal media |
| US10254576B2 (en) | 2014-09-30 | 2019-04-09 | Seiko Electric Co., Ltd. | Light control device and method for manufacturing the same |
-
2002
- 2002-08-15 JP JP2002236910A patent/JP3915627B2/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003313556A (en) * | 2002-04-19 | 2003-11-06 | Chisso Corp | Polymer/liquid crystal composite material excellent in light transmission property |
| JP2010001353A (en) * | 2008-06-19 | 2010-01-07 | Kawamura Inst Of Chem Res | Organic/inorganic composite material including liquid crystalline compound |
| JP2011525553A (en) * | 2008-06-27 | 2011-09-22 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツング | Liquid crystal media |
| US8956550B2 (en) | 2008-06-27 | 2015-02-17 | Merck Patent Gmbh | Liquid-crystalline medium |
| US8956549B2 (en) | 2008-06-27 | 2015-02-17 | Merck Patent Gmbh | Liquid-crystalline medium |
| US8974693B2 (en) | 2008-06-27 | 2015-03-10 | Merck Patent Gmbh | Liquid-crystalline medium |
| JP2017061705A (en) * | 2008-06-27 | 2017-03-30 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツングＭｅｒｃｋ Ｐａｔｅｎｔ Ｇｅｓｅｌｌｓｃｈａｆｔ ｍｉｔ ｂｅｓｃｈｒａｅｎｋｔｅｒ Ｈａｆｔｕｎｇ | Liquid-crystalline medium |
| US10254576B2 (en) | 2014-09-30 | 2019-04-09 | Seiko Electric Co., Ltd. | Light control device and method for manufacturing the same |
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