JP2008058374A - Liquid crystal element - Google Patents
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- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
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- G02F1/13347—Constructional arrangements; Manufacturing methods based on polymer dispersed liquid crystals, e.g. microencapsulated liquid crystals working in reverse mode, i.e. clear in the off-state and scattering in the on-state
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Abstract
【課題】 高いコントラストと電圧保持率を両立させる、負の誘電異方性を示す液晶を利用したリバースタイプの高分子分散型液晶素子を提供する。
【解決手段】 液晶材料及び高分子が相分離してなる複合層を具備し、該液晶材料が負の誘電異方性を示し、該高分子が紫外線硬化型材料の紫外線硬化により形成され、電圧無印加時には該液晶材料中の液晶分子が垂直配向する高分子分散型液晶素子において、該液晶材料の屈折率異方性が０．１０〜０．１８の範囲にある液晶素子を提供する。本願発明の表示素子は、高いコントラスト比と電圧保持率を両立できるので、TFTなどのアクティブ素子で駆動することが可能であり、優れた表示品位を有する情報ディスプレイを実現することができる。
【選択図】 なし
PROBLEM TO BE SOLVED: To provide a reverse type polymer dispersed liquid crystal element using a liquid crystal exhibiting negative dielectric anisotropy, which achieves both high contrast and voltage holding ratio.
A liquid crystal material and a composite layer formed by phase separation of a polymer are provided, the liquid crystal material exhibits negative dielectric anisotropy, and the polymer is formed by ultraviolet curing of an ultraviolet curable material. Provided is a polymer-dispersed liquid crystal element in which liquid crystal molecules in the liquid crystal material are vertically aligned when no voltage is applied, and the liquid crystal material has a refractive index anisotropy in the range of 0.10 to 0.18. Since the display element of the present invention can achieve both a high contrast ratio and a voltage holding ratio, it can be driven by an active element such as a TFT, and an information display having excellent display quality can be realized.
[Selection figure] None
Description
本発明は高分子分散型液晶素子に関する。 The present invention relates to a polymer-dispersed liquid crystal element.
液晶表示素子の一種である高分子分散型液晶素子は偏光板が必要無いために明るい表示が可能である。特許文献１は電圧を印加していない時には透明で、電圧を印加した時に光散乱するリバースモードタイプと呼ばれる高分子分散型液晶素子を開示している。これは液晶材料及び高分子が相分離してなる複合層を具備し、かつ該高分子が屈折率異方性（Δｎ）を有しており、該複合層に電圧が印加されていない状態では、液晶と高分子がほぼ揃って配向しているというものである。特に、液晶として負の誘電異方性を有する材料を用い、電圧無印加には液晶材料が垂直配向するような構成をとると、複合層を配向させるためのラビング処理が不要となり製造工程が簡素化される利点、また、紫外線に対する耐久性が向上するという利点があり、実用化が期待される。 A polymer-dispersed liquid crystal element, which is a kind of liquid crystal display element, can display brightly because it does not require a polarizing plate. Patent Document 1 discloses a polymer dispersion type liquid crystal element called a reverse mode type which is transparent when no voltage is applied and which scatters light when a voltage is applied. This includes a composite layer formed by phase separation of a liquid crystal material and a polymer, and the polymer has refractive index anisotropy (Δn), and no voltage is applied to the composite layer. The liquid crystal and the polymer are almost aligned. In particular, when a material having negative dielectric anisotropy is used as the liquid crystal and the liquid crystal material is vertically aligned when no voltage is applied, the rubbing process for aligning the composite layer is not required and the manufacturing process is simplified. And has the advantage of improving durability against ultraviolet rays, and is expected to be put to practical use.
このような液晶素子の作製方法は特許文献１に種々開示されているが、誘電異方性が負の液晶材料と紫外線硬化型材料を混合した後に、液晶セルに注入して垂直配向させた後、紫外線を照射して紫外線硬化型材料を硬化させることにより複合層を形成するのが簡素でコストや歩留まりの観点から最も有利な製造方法と考えられる。しかしながら、従来の高分子分散型液晶素子は、次のような理由からΔｎとして０．２以上比較的大きい値を有する液晶材料を用いて構成されていた。その理由として、Δｎが大きい液晶材料を用いた方が一般にコントラストを大きくすることができ、従来はΔｎが大きい材料を用いることによるコントラストの低下についての知見が不十分であったためと考えられる。 Various methods for manufacturing such a liquid crystal element are disclosed in Patent Document 1, but after a liquid crystal material having a negative dielectric anisotropy and an ultraviolet curable material are mixed and then injected into a liquid crystal cell and vertically aligned. It is considered that the formation of the composite layer by irradiating ultraviolet rays to cure the ultraviolet curable material is simple and the most advantageous production method from the viewpoint of cost and yield. However, conventional polymer dispersed liquid crystal elements have been configured using a liquid crystal material having a relatively large value of Δn of 0.2 or more for the following reason. This is probably because the use of a liquid crystal material having a large Δn can generally increase the contrast, and conventionally, the knowledge about the decrease in contrast due to the use of a material having a large Δn is insufficient.
実際に特許文献１における負の誘電異方性の材料を用いた実施例（実施例１３〜１９、２９、３０）では、Δｎとして０．２の液晶材料を用いているため、電圧保持率と表示コントラストの両立は極めて困難であった。又、該引用文献にはΔｎが大きい方がコントラストを大きくすることができるという記述のみが記載され、硬化性とのトレードオフについての記述は無く、電圧保持率との関係も考慮した、好ましいΔｎの範囲についての記述も無い。 Actually, in Examples (Examples 13 to 19, 29, and 30) using negative dielectric anisotropy material in Patent Document 1, a liquid crystal material having Δn of 0.2 is used. It has been extremely difficult to achieve both display contrast. Further, the cited document only describes that the contrast can be increased when Δn is large, and there is no description about trade-off with curability, and preferable Δn considering the relationship with the voltage holding ratio. There is no description about the range of.
今日、液晶表示素子に多大な表示情報量の表示が求められるようになってきたことから、TFT（薄膜トランジスタ）などのアクティブ素子で駆動して画素数を確保する必要があり、高い電圧保持率の確保が必須である。しかしながら、負の誘電異方性の材料を用いたリバースタイプの高分子分散型液晶素子において、高い電圧保持率とコントラストを両立することは困難であり、このような表示素子の開発がのぞまれていた。 Today, liquid crystal display elements are required to display a large amount of display information. Therefore, it is necessary to ensure the number of pixels by driving with active elements such as TFTs (thin film transistors). Securing is essential. However, it is difficult to achieve both a high voltage holding ratio and contrast in a reverse type polymer dispersed liquid crystal element using a negative dielectric anisotropy material, and development of such a display element is not desired. It was.
液晶材料及び高分子が相分離してなる複合層を具備し、該液晶材料が負の誘電異方性を示し、高分子が紫外線硬化型材料の紫外線硬化により形成され、かつ電圧無印加時には液晶材料が垂直配向する高分子分散型液晶素子において、高い電圧保持率とコントラストを両立した液晶素子を提供することにある。 A composite layer formed by phase separation of a liquid crystal material and a polymer, wherein the liquid crystal material exhibits negative dielectric anisotropy, the polymer is formed by ultraviolet curing of an ultraviolet curable material, and a liquid crystal is applied when no voltage is applied. It is an object of the present invention to provide a liquid crystal element having both high voltage holding ratio and contrast in a polymer dispersed liquid crystal element in which materials are vertically aligned.
本願発明者らは、紫外線硬化型材料及び液晶材料より構成される組成物について種々の検討を行ったところ、液晶材料のΔｎを液晶材料のΔｎを最適な範囲に設定することにより前述の課題を解決できることを見出した。すなわち、本願発明者らの知見によれば液晶材料のΔｎが大きくなるほど、紫外線硬化型材料の硬化性が悪化し、必要な紫外線照射エネルギーが増大する。製造時における紫外線照射エネルギーが大きくなると、液晶材料の劣化して電圧保持率の悪化を招く。逆に電圧保持率の悪化を防止するために、紫外線照射エネルギーを抑制すると、硬化が十分でなくなり、表示コントラストの低下を招く。液晶のΔｎが大きくなっても、紫外線硬化型材料の硬化性が変化しないものと仮定すれば、Δｎが大きくなるほど電圧印加時の光散乱が大きくなってコントラストも大きくなり好ましい。しかし、Δｎが大きい液晶は共役系が長軸方向に長くのびており、紫外波長域の吸収が大きくなる。液晶材料及び高分子が相分離してなる複合層を有する素子を得るためには、液晶及び紫外線硬化型材料の混合物を液晶セルに注入してから垂直配向させ、その状態で紫外線を照射して紫外線硬化型材料を硬化させる必要があるため、液晶自体に紫外波長域で吸収があれば、照射された紫外線が紫外線硬化型材料の硬化に有効に利用できなくなり、紫外線硬化型材料の硬化性が悪化する。硬化性が悪化するとコントラストが悪化する。このコントラスト悪化を防止しようとすると、液晶の劣化を招くほどの多量の紫外線照射が必要になってしまい、液晶が劣化すると結果として電圧保持率が悪化する。本願発明者らは種々の液晶材料を検討した結果、コントラストと電圧保持率の両立が達成できるΔｎが０．１０〜０．１８の範囲にあることを見いだし本願発明の完成に至った。 The inventors of the present application have made various studies on a composition composed of an ultraviolet curable material and a liquid crystal material. By setting Δn of the liquid crystal material to an optimal range of Δn of the liquid crystal material, the above-described problems are solved. I found out that it can be solved. That is, according to the knowledge of the present inventors, as the Δn of the liquid crystal material increases, the curability of the ultraviolet curable material deteriorates and the necessary ultraviolet irradiation energy increases. When the ultraviolet irradiation energy at the time of manufacture increases, the liquid crystal material deteriorates and the voltage holding ratio is deteriorated. Conversely, if the ultraviolet irradiation energy is suppressed in order to prevent the voltage holding ratio from deteriorating, the curing becomes insufficient and the display contrast is lowered. Assuming that the curability of the ultraviolet curable material does not change even when Δn of the liquid crystal is increased, it is preferable that Δn is increased because light scattering during voltage application is increased and contrast is increased. However, the liquid crystal having a large Δn has a long conjugated system in the major axis direction, and the absorption in the ultraviolet wavelength region increases. In order to obtain an element having a composite layer in which a liquid crystal material and a polymer are phase-separated, a mixture of a liquid crystal and an ultraviolet curable material is injected into a liquid crystal cell and vertically aligned, and then irradiated with ultraviolet rays in that state. Since it is necessary to cure the ultraviolet curable material, if the liquid crystal itself absorbs in the ultraviolet wavelength region, the irradiated ultraviolet light cannot be effectively used for curing the ultraviolet curable material, and the curability of the ultraviolet curable material is reduced. Getting worse. When curability deteriorates, contrast deteriorates. In order to prevent the deterioration of the contrast, it is necessary to irradiate a large amount of ultraviolet rays so as to cause deterioration of the liquid crystal, and when the liquid crystal deteriorates, the voltage holding ratio deteriorates as a result. As a result of studying various liquid crystal materials, the present inventors have found that Δn that can achieve both contrast and voltage holding ratio is in the range of 0.10 to 0.18, and have completed the present invention.
即ち、本発明は液晶材料及び高分子が相分離してなる複合層を具備し、該液晶材料が負の誘電異方性を示し、該高分子が紫外線硬化型材料の紫外線硬化により形成され、電圧無印加時には該液晶材料中の液晶分子が垂直配向する高分子分散型液晶素子において、該液晶材料の屈折率異方性が０．１０〜０．１８の範囲にある液晶素子を提供する。 That is, the present invention comprises a composite layer formed by phase separation of a liquid crystal material and a polymer, the liquid crystal material exhibits negative dielectric anisotropy, and the polymer is formed by ultraviolet curing of an ultraviolet curable material, Provided is a polymer-dispersed liquid crystal element in which liquid crystal molecules in the liquid crystal material are vertically aligned when no voltage is applied, and the liquid crystal element has a refractive index anisotropy in the range of 0.10 to 0.18.
更に、誘電異方性が負であり屈折率異方性が０．１０〜０．１８の範囲にある液晶材料と紫外線硬化型材料を混合した後に、液晶セルに注入して垂直配向させた後、紫外線を照射して紫外線硬化型材料を硬化させ液晶と高分子が相分離してなる複合層を形成することによる電圧無印加時には該液晶材料中の液晶分子が垂直配向する高分子分散型液晶素子の製造方法を併せて提供する。 Further, after mixing a liquid crystal material having a negative dielectric anisotropy and a refractive index anisotropy in the range of 0.10 to 0.18 with an ultraviolet curable material, and then injecting it into the liquid crystal cell for vertical alignment A polymer dispersed liquid crystal in which the liquid crystal molecules in the liquid crystal material are vertically aligned when no voltage is applied by forming a composite layer formed by irradiating ultraviolet rays to cure the ultraviolet curable material and phase-separating the liquid crystal and the polymer. A device manufacturing method is also provided.
本発明のリバースタイプの高分子分散型液晶は、高いコントラスト比と電圧保持率を両立させたものである。TFTなどのアクティブ素子で駆動できるので画素数が多い情報ディスプレイに応用可能であり、明るい表示が可能という特徴もあるため非常に有用である。 The reverse type polymer dispersed liquid crystal of the present invention has both a high contrast ratio and a voltage holding ratio. Since it can be driven by an active element such as a TFT, it can be applied to an information display having a large number of pixels, and it is very useful because it has a feature that a bright display is possible.
紫外線硬化型材料としては、紫外線の照射により硬化する材料であれば特に制限は無いが、素子としての信頼性を確保する観点からアクリレート材料が好ましい。液晶セル中に挟持させる組成物における紫外線硬化型材料の濃度は4〜8質量%が好ましく、5〜7質量%がさらに好ましい。液晶との組成物を液晶セル中に挟持させて垂直配向させることが製造条件上重要であるので、組成物としても液晶性を示すように棒状の液晶骨格を有するものが好ましい。このような観点から、液晶性アクリレートと分類される材料を使用することが特に好ましい。液晶性アクリレートには、負の誘電異方性を示す液晶との相溶性が良く、析出しにくいものが好ましい。液晶性アクリレートの化学構造は、本発明の液晶素子の電気光学特性に大きな影響を及ぼす。液晶性アクリレートとしては一般式（I） The ultraviolet curable material is not particularly limited as long as it is a material that can be cured by irradiation with ultraviolet rays, but an acrylate material is preferable from the viewpoint of ensuring reliability as an element. The concentration of the ultraviolet curable material in the composition sandwiched in the liquid crystal cell is preferably 4 to 8% by mass, and more preferably 5 to 7% by mass. Since it is important in terms of production conditions that the composition with the liquid crystal is sandwiched in the liquid crystal cell and vertically aligned, the composition preferably has a rod-like liquid crystal skeleton so as to exhibit liquid crystallinity. From such a viewpoint, it is particularly preferable to use a material classified as a liquid crystalline acrylate. As the liquid crystalline acrylate, those having good compatibility with a liquid crystal exhibiting negative dielectric anisotropy and being difficult to precipitate are preferable. The chemical structure of the liquid crystal acrylate greatly affects the electro-optical characteristics of the liquid crystal element of the present invention. As the liquid crystalline acrylate, the general formula (I)
（式中、A、B及びCはそれぞれ独立的に、1,4-フェニレン基、1,4-シクロヘキシレン基、1,4-シクロヘキセニル基、テトラヒドロピラン-2,5-ジイル基、1,3-ジオキサン-2,5-ジイル基、テトラヒドロチオピラン-2,5-ジイル基、1,4-ビシクロ(2,2,2)オクチレン基、デカヒドロナフタレン-2,6-ジイル基、ピリジン-2,5-ジイル基、ピリミジン-2,5-ジイル基、ピラジン-2,5-ジイル基、1,2,3,4-テトラヒドロナフタレン-2,6-ジイル基、2,6-ナフチレン基、フェナントレン-2,7-ジイル基、9,10-ジヒドロフェナントレン-2,7-ジイル基、1,2,3,4,4a,9,10a-オクタヒドロフェナントレン2,7-ジイル基、フルオレン2,7-ジイル基を表し、該1,4-フェニレン基、1,2,3,4-テトラヒドロナフタレン-2,6-ジイル基、2,6-ナフチレン基、フェナントレン-2,7-ジイル基、9,10-ジヒドロフェナントレン-2,7-ジイル基、1,2,3,4,4a,9,10a-オクタヒドロフェナントレン2,7-ジイル基及びフルオレン2,7-ジイル基は非置換であるか又は置換基として１個又は２個以上のF、Cl、CF3、OCF3又はCH3を有することができ、Y1、Y2はそれぞれ独立的に、単結合、-COO-、-OCO-、-CH＝N-、-N＝CH-、-C≡C-、-CH2CH2-、-CH2CH2CH2CH2-、-CH2CH2CH2O-、-OCH2CH2CH2-、-CH2O-、-OCH2-、-CF2O-、-OCF2-、-CH＝N-N＝CH-、-CF＝CF-、-CH＝CH-、-CH2CH2CH＝CH-、-CH＝CHCH2CH2-、-CH2CH＝CHCH2-、-CH=CHCOO-、-OCOCH=CH-、-CH2CH2COO-、-OCOCH2CH2-を表し、Y3は単結合、-O-、-CO-、-COO-、-OCO-、-CH2-、-CH2O-、-OCH2-、-CONH-、-NHCO-、-CH2COO-又は-CH2OCO-を表し、Z1は炭素原子数1〜18のアルキル基、炭素原子数2〜18のアルケニル基、ハロゲン原子、CN、NCSを表し、該アルキル基又はアルケニル基は非置換であるか又は置換基として1個 又は2個以上のF、Cl、CN、CH3、又はCF3を有することができ、該アルキル基又はアルケニル基中に存在する1個 又は2個以上のCH2基は、O原子が相互に直接結合しないものとして、O、CO又はCOOで置換されていても良く、rは0又は1を表す。） (In the formula, A, B and C are each independently 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran-2,5-diyl group, 1, 3-dioxane-2,5-diyl group, tetrahydrothiopyran-2,5-diyl group, 1,4-bicyclo (2,2,2) octylene group, decahydronaphthalene-2,6-diyl group, pyridine- 2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, 2,6-naphthylene group, Phenanthrene-2,7-diyl group, 9,10-dihydrophenanthrene-2,7-diyl group, 1,2,3,4,4a, 9,10a-octahydrophenanthrene 2,7-diyl group, fluorene 2, Represents a 7-diyl group, the 1,4-phenylene group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, 2,6-naphthylene group, phenanthrene-2,7-diyl group, 9 , 10-Dihydrophenanthrene-2,7-diyl group, 1,2,3 , 4,4a, 9,10a-Octahydrophenanthrene 2,7-diyl and fluorene 2,7-diyl are unsubstituted or substituted with one or more F, Cl, CF 3 , Can have OCF 3 or CH 3 , and Y 1 and Y 2 are each independently a single bond, —COO—, —OCO—, —CH═N—, —N═CH—, —C≡C— , -CH 2 CH 2 -, - CH 2 CH 2 CH 2 CH 2 -, - CH 2 CH 2 CH 2 O -, - OCH 2 CH 2 CH 2 -, - CH 2 O -, - OCH 2 -, - CF 2 O-, -OCF 2- , -CH = NN = CH-, -CF = CF-, -CH = CH-, -CH 2 CH 2 CH = CH-, -CH = CHCH 2 CH 2 -,- CH 2 CH═CHCH 2 —, —CH═CHCOO—, —OCOCH═CH—, —CH 2 CH 2 COO—, —OCOCH 2 CH 2 —, Y 3 represents a single bond, —O—, —CO— , -COO -, - OCO -, - CH 2 -, - CH 2 O -, - OCH 2 -, - CONH -, - NHCO -, - CH 2 COO- or an -CH 2 OCO-, Z 1 is Represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a halogen atom, CN, or NCS, wherein the alkyl group or alkenyl group is unsubstituted or substituted with a substituent. One or more F Te, Cl, CN, CH 3, or CF 3 can have one or more CH 2 groups existing in said alkyl group or alkenyl group, O atoms May be substituted with O, CO or COO, and r represents 0 or 1. )
で表される化合物を含有することが好ましい。このような材料を用いると、駆動電圧及びヒステリシスを低減することが可能である。式中、A、B及びCとしては、独立的に1,4-フェニレン基、1,4-シクロヘキシレン基を選択するのが好ましく、Y1及びY2はそれぞれ独立的に、単結合、-C≡C-を選択するのが好ましく、Y3は単結合、-O-が好ましく、Z1は炭素原子数1〜5のアルキル基が好ましい。本発明の液晶素子においては、加水分解をうけるような化学構造は極力避けることが好ましい。本発明の液晶素子を、特性を均一に安定に製造するためには、負の誘電異方性を示す液晶と紫外線硬化型材料の組成物が、紫外線を照射する際の温度において結晶化しないことが重要である。この観点から、一般式（I）で表される化合物のうち、rは0が好ましく、Y3は単結合が好ましく、Z1は炭素原子数1〜5のアルキル基が好ましく、炭素原子数2〜5のアルキル基がさらに好ましく、炭素原子数3〜5のアルキル基が特に好ましい。一般式（Ｉ）の具体例を式（Ｉ−１）〜（Ｉ−１７）に挙げる。 It is preferable to contain the compound represented by these. When such a material is used, driving voltage and hysteresis can be reduced. In the formula, as A, B and C, it is preferable to independently select 1,4-phenylene group or 1,4-cyclohexylene group, and Y 1 and Y 2 are each independently a single bond,- C≡C— is preferably selected, Y 3 is preferably a single bond, —O—, and Z 1 is preferably an alkyl group having 1 to 5 carbon atoms. In the liquid crystal device of the present invention, it is preferable to avoid a chemical structure that undergoes hydrolysis as much as possible. In order to produce the liquid crystal element of the present invention uniformly and stably, the composition of the liquid crystal exhibiting negative dielectric anisotropy and the ultraviolet curable material should not crystallize at the temperature when irradiated with ultraviolet rays. is important. From this viewpoint, among the compounds represented by the general formula (I), r is preferably 0, Y 3 is preferably a single bond, Z 1 is preferably an alkyl group having 1 to 5 carbon atoms, and 2 carbon atoms. An alkyl group having ˜5 is more preferred, and an alkyl group having 3 to 5 carbon atoms is particularly preferred. Specific examples of general formula (I) are listed in formulas (I-1) to (I-17).
紫外線硬化材料中における一般式（I）で表される化合物の濃度は70質量%以上が好ましく、75質量%以上がさらに好ましく、80質量%以上が特に好ましい。
この他にも液晶性アクリレートとしては、分子中に2つ以上のアクリロイルオキシ基を有するものを使用しても良い。このような化合物を利用すると、本発明の液晶素子の耐熱性を向上させることができる。
このような液晶性アクリレートの具体例を一般式（D-1）〜（D-7）に挙げる。
The concentration of the compound represented by the general formula (I) in the ultraviolet curable material is preferably 70% by mass or more, more preferably 75% by mass or more, and particularly preferably 80% by mass or more.
In addition, as the liquid crystalline acrylate, those having two or more acryloyloxy groups in the molecule may be used. When such a compound is used, the heat resistance of the liquid crystal element of the present invention can be improved.
Specific examples of such liquid crystal acrylates are listed in general formulas (D-1) to (D-7).
（式中、t及びuは独立的に2〜12の整数を表し、s及びvは独立的に0 又は1を表す。）
本発明の液晶素子の電圧印加時における光散乱を大きくし、コントラストを確保する観点から、上記式のt及びuは独立して2〜3であることが好ましい。また負の誘電異方性を示す液晶と紫外線硬化型材料の組成物が、紫外線を照射する際の温度において結晶化しないことが安定的に素子を製造するのに重要であるという観点から、化合物（D-4）は有用である。化合物（D-4）を用いると析出しにくく、有用である。
(In the formula, t and u independently represent an integer of 2 to 12, and s and v independently represent 0 or 1.)
From the viewpoint of increasing light scattering during voltage application and ensuring contrast in the liquid crystal element of the present invention, it is preferable that t and u in the above formula are independently 2 to 3. From the viewpoint that it is important for the stable production of the device that the composition of the liquid crystal exhibiting negative dielectric anisotropy and the ultraviolet curable material does not crystallize at the temperature when irradiated with ultraviolet rays. (D-4) is useful. When the compound (D-4) is used, it is difficult to precipitate and is useful.
負の誘電異方性を示す液晶としては、温度２５℃で波長５８９ｎｍにおけるΔｎが０．１０〜０．１８の範囲にあることが必要である。高い電圧保持率をより重視する場合には、Δｎとして０．１０〜０．１６５として紫外線型硬化材料の硬化に必要な紫外線照射エネルギー量を低減することが好ましく、Δｎとして０．１０〜０．１５５とするのがより好ましく、０．１０〜０．１４５とするのが特に好ましい。 As a liquid crystal exhibiting negative dielectric anisotropy, Δn at a temperature of 25 ° C. and a wavelength of 589 nm needs to be in the range of 0.10 to 0.18. In the case where higher voltage holding ratio is more important, it is preferable to reduce the amount of ultraviolet irradiation energy necessary for curing the ultraviolet curable material by setting Δn as 0.10 to 0.165, and Δn as 0.10 to 0.00. 155 is more preferable, and 0.10 to 0.145 is particularly preferable.
また、高い電圧保持率を確保する観点から、液晶にはシアノ基を有する化合物は含まない方が好ましい。負の誘電異方性を実現するための化合物としては、極性基としては分子短軸方向にF原子を有する化合物を使用することが好ましい。
このような化合物としては、一般式（II）
Further, from the viewpoint of ensuring a high voltage holding ratio, it is preferable that the liquid crystal does not contain a compound having a cyano group. As the compound for realizing negative dielectric anisotropy, it is preferable to use a compound having an F atom in the molecular minor axis direction as a polar group.
Such compounds include those represented by the general formula (II)
（式中、Rは炭素原子数1〜10のアルキル基、炭素原子数2〜10のアルケニル基、ハロゲン原子、CN又はNCSを表し、該アルキル基、アルケニル基は非置換であるうか又は置換基として1個 又は2個以上のF、Cl、CN、CH3又はCF3を有することができ、該アルキル基又はアルケニル基中に存在する1個 又は2個以上のCH2基はO原子が相互に直接結合しないものとして、O、CO又はCOOで置換されていても良く、D及びEはそれぞれ独立的に、1,4-フェニレン基、1,4-シクロヘキシレン基、1,4-シクロヘキセニル基、テトラヒドロピラン-2,5-ジイル基、1,3-ジオキサン-2,5-ジイル基、テトラヒドロチオピラン-2,5-ジイル基、1,4-ビシクロ(2,2,2)オクチレン基、デカヒドロナフタレン-2,6-ジイル基、ピリジン-2,5-ジイル基、ピリミジン-2,5-ジイル基、ピラジン-2,5-ジイル基、1,2,3,4-テトラヒドロナフタレン-2,6-ジイル基、2,6-ナフチレン基、フェナントレン-2,7-ジイル基、9,10-ジヒドロフェナントレン-2,7-ジイル基、1,2,3,4,4a,9,10a-オクタヒドロフェナントレン2,7-ジイル基又はフルオレン2,7-ジイル基を表し、該1,4-フェニレン基、1,2,3,4-テトラヒドロナフタレン-2,6-ジイル基、2,6-ナフチレン基、フェナントレン-2,7-ジイル基、9,10-ジヒドロフェナントレン-2,7-ジイル基、1,2,3,4,4a,9,10a-オクタヒドロフェナントレン2,7-ジイル基及びフルオレン2,7-ジイル基は非置換であるか又は置換基として１個又は２個以上のF、Cl、CF3、OCF3又はCH3を有することができ、Y4及びY5はそれぞれ独立的に単結合、-COO-、-OCO-、-CH＝N-、-N＝CH-、-C≡C-、-CH2CH2-、-CH2CH2CH2CH2-、-CH2CH2CH2O-、-OCH2CH2CH2-、-CH2O-、-OCH2-、-CF2O-、-OCF2-、-CH＝N-N＝CH-、-CF＝CF-、-CH＝CH-、-CH2CH2CH＝CH-、-CH＝CHCH2CH2-、-CH2CH＝CHCH2-、-CH=CHCOO-、-OCOCH=CH-、-CH2CH2COO-又は-OCOCH2CH2-を表し、Y6は単結合、-O-、-CO-、-COO-、-OCO-、-CH2-、-CH2O-、-OCH2-、-CONH-、-NHCO-、-CH2COO-又は-CH2OCO-を表し、Z1は炭素原子数1〜18のアルキル基、炭素原子数2〜18のアルケニル基、ハロゲン原子、CN又はNCSを表し、該アルキル基又はアルケニル基は非置換であるか又は置換基として1個 又は2個以上のF、Cl、CN、CH3、又はCF3を有することができ、該アルキル基又はアルケニル基中に存在する1個 又は2個以上のCH2基は、O原子が相互に直接結合しないものとして、O、CO又はCOOで置換されていても良く、qは0 又は1を表す。）で表される化合物が好ましい。 (In the formula, R represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a halogen atom, CN or NCS, and the alkyl group and alkenyl group are unsubstituted or substituted. 1 or 2 or more of F, Cl, CN, CH 3 or CF 3 , and one or two or more CH 2 groups present in the alkyl group or alkenyl group have O atoms mutually And may be substituted with O, CO or COO, and D and E are each independently 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl. Group, tetrahydropyran-2,5-diyl group, 1,3-dioxane-2,5-diyl group, tetrahydrothiopyran-2,5-diyl group, 1,4-bicyclo (2,2,2) octylene group Decahydronaphthalene-2,6-diyl group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, 1,2,3,4-teto Hydronaphthalene-2,6-diyl group, 2,6-naphthylene group, phenanthrene-2,7-diyl group, 9,10-dihydrophenanthrene-2,7-diyl group, 1,2,3,4,4a, 9,10a-octahydrophenanthrene 2,7-diyl group or fluorene 2,7-diyl group, the 1,4-phenylene group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, 2,6-naphthylene group, phenanthrene-2,7-diyl group, 9,10-dihydrophenanthrene-2,7-diyl group, 1,2,3,4,4a, 9,10a-octahydrophenanthrene 2,7 -Diyl group and fluorene 2,7-diyl group can be unsubstituted or have one or more F, Cl, CF 3 , OCF 3 or CH 3 as substituents, Y 4 and Y 5 are each independently a single bond, —COO—, —OCO—, —CH═N—, —N═CH—, —C≡C—, —CH 2 CH 2 —, —CH 2 CH 2 CH 2 CH 2- , -CH 2 CH 2 CH 2 O-, -OCH 2 CH 2 CH 2- , -CH 2 O-, -OCH 2- , -CF 2 O-, -OCF 2- , -CH = NN = CH -, -CF = CF -, -CH = CH-, -CH 2 CH 2 CH = CH-, -CH = CHCH 2 CH 2- , -CH 2 CH = CHCH 2- , -CH = CHCOO-, -OCOCH = CH-, -CH 2 CH 2 COO- or -OCOCH 2 CH 2- represents Y 6 is a single bond, -O-, -CO-, -COO-, -OCO-, -CH 2- , -CH 2 O-, -OCH 2- , -CONH-, -NHCO-, -CH 2 COO- or -CH 2 OCO-, Z 1 is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a halogen atom , CN or NCS, the alkyl group or alkenyl group may be unsubstituted or have one or more F, Cl, CN, CH 3 or CF 3 as substituents 1 or 2 or more CH2 groups present in the group or alkenyl group may be substituted with O, CO or COO, in which O atoms are not directly bonded to each other, and q represents 0 or 1 . ) Is preferred.
このような化合物の中でも、Rは炭素原子数2〜6のアルキル基、炭素原子数2〜6のアルケニル基が好ましく、D及びEはそれぞれ独立的に、1,4-フェニレン基又は1,4-シクロヘキシレン基が好ましく、1,4-シクロヘキシレン基がさらに好ましく、Y4は単結合が好ましく、Y5はそれぞれ独立的に単結合、-CH2CH2-又は-CH2CH2CH2CH2-が好ましく、-CH2CH2-がさらに好ましい。Y6は単結合又は-O-が好ましく、Z1は炭素原子数1〜4のアルキル基又は炭素原子数2〜4のアルケニル基が好ましい。一般式（II）で表される化合物は、分子中に短軸方向に3つのF原子を有しており、濃度が低くても誘電異方性の絶対値を大きくすることができ、駆動電圧を有効に低減することができる。
一般式（II）で表される化合物の具体例を式（II-1）〜（II-7）に挙げる。
Among such compounds, R is preferably an alkyl group having 2 to 6 carbon atoms and an alkenyl group having 2 to 6 carbon atoms, and D and E are each independently a 1,4-phenylene group or 1,4 -Cyclohexylene group is preferred, 1,4-cyclohexylene group is more preferred, Y 4 is preferably a single bond, Y 5 is each independently a single bond, -CH 2 CH 2 -or -CH 2 CH 2 CH 2 CH 2 — is preferable, and —CH 2 CH 2 — is more preferable. Y 6 is preferably a single bond or —O—, and Z 1 is preferably an alkyl group having 1 to 4 carbon atoms or an alkenyl group having 2 to 4 carbon atoms. The compound represented by the general formula (II) has three F atoms in the minor axis direction in the molecule, and can increase the absolute value of dielectric anisotropy even when the concentration is low. Can be effectively reduced.
Specific examples of the compound represented by formula (II) are listed in formulas (II-1) to (II-7).
負の誘電異方性を有する液晶中における一般式（II）で表される化合物の濃度は40質量%以上が好ましく、45質量%以上がさらに好ましく、50質量%以上が特に好ましい。一般式（II）の濃度が高いほど、素子としての駆動電圧を低減することができる。
このような化合物としては、一般式（III）
The concentration of the compound represented by the general formula (II) in the liquid crystal having negative dielectric anisotropy is preferably 40% by mass or more, more preferably 45% by mass or more, and particularly preferably 50% by mass or more. As the concentration of the general formula (II) is higher, the driving voltage as the element can be reduced.
Such compounds include those represented by the general formula (III)
（式中、Rは炭素原子数1〜10のアルキル基、炭素原子数2〜10のアルケニル基、ハロゲン原子、CN、NCSを表し、該アルキル基、アルケニル基は非置換であるうか又は置換基として1個 又は2個以上のF、Cl、CN、CH3、CF3を有することができ、該アルキル基又はアルケニル基中に存在する1個 又は2個以上のCH2基はO原子が相互に直接結合しないものとして、O、CO、COOで置換されていても良く、F、G及びHはそれぞれ独立的に、1,4-フェニレン基、1,4-シクロヘキシレン基、1,3-ジオキサン-2,5-ジイル基、ピリミジン-2,5-ジイル基を表し、Y7、Y8及びY9はそれぞれ独立的に、単結合、-COO-、-OCO-、-C≡C-、-CH2CH2-、-CH2CH2CH2CH2-、-CH2CH2CH2O-、-OCH2CH2CH2-、-CH2O-、-OCH2-、-CF2O-、-OCF2-、-CF＝CF-、-CH＝CH-、-CH2CH2CH＝CH-、-CH＝CHCH2CH2-、-CH2CH＝CHCH2-、-CH=CHCOO-、-OCOCH=CH-、-CH2CH2COO-、-OCOCH2CH2-を表し、Y10は単結合、-O-、-CO-、-COO-、-OCO-、-CH2-、-CH2O-、-OCH2-、-CH2COO-又は-CH2OCO-を表し、Z3は炭素原子数1〜18のアルキル基、炭素原子数2〜18のアルケニル基、ハロゲン原子を表し、該アルキル基又はアルケニル基は非置換であるか又は置換基として1個 又は2個以上のF、Cl、CN、CH3、又はCF3を有することができ、該アルキル基又はアルケニル基中に存在する1個 又は2個以上のCH2基は、O原子が相互に直接結合しないものとして、O、CO又はCOOで置換されていても良く、r及びsは独立的に0 又は1を表す。）で表される化合物もまた好ましい。 (In the formula, R represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a halogen atom, CN, or NCS, and the alkyl group and alkenyl group are unsubstituted or substituted. 1 or 2 or more of F, Cl, CN, CH 3 , CF 3 , and one or two or more CH 2 groups present in the alkyl group or alkenyl group have an O atom May be substituted with O, CO, or COO, and F, G, and H are each independently 1,4-phenylene group, 1,4-cyclohexylene group, 1,3- Dioxane-2,5-diyl group, pyrimidine-2,5-diyl group, Y 7 , Y 8 and Y 9 are each independently a single bond, —COO—, —OCO—, —C≡C— , -CH 2 CH 2 -, - CH 2 CH 2 CH 2 CH 2 -, - CH 2 CH 2 CH 2 O -, - OCH 2 CH 2 CH 2 -, - CH 2 O -, - OCH 2 -, - CF 2 O -, - OCF 2 -, - CF = CF -, - CH = CH -, - CH 2 CH 2 CH = CH -, - CH = CHCH 2 CH 2 -, - CH 2 CH = CHCH 2 - -CH = CHCOO -, - OCOCH = CH -, - CH 2 CH 2 COO -, - OCOCH 2 CH 2 - represents, Y 10 is a single bond, -O -, - CO -, - COO -, - OCO- , -CH 2 -, - CH 2 O -, - OCH 2 -, - CH 2 COO- or an -CH 2 OCO-, Z 3 represents an alkyl group having 1 to 18 carbon atoms, 2 to 18 carbon atoms Represents an alkenyl group, a halogen atom, and the alkyl group or alkenyl group may be unsubstituted or have one or more F, Cl, CN, CH 3 , or CF 3 as a substituent, One or more CH 2 groups present in the alkyl group or alkenyl group may be substituted with O, CO or COO, assuming that O atoms are not directly bonded to each other, and r and s are Also preferred are compounds represented by 0 or 1 independently.
一般式（III）で表される化合物の中でも、Rは炭素原子数2〜6のアルキル基、炭素原子数2〜6のアルケニル基が好ましく、F、G及びHはそれぞれ独立的に、1,4-フェニレン基又は1,4-シクロヘキシレン基が好ましく、Y7、Y8及びY9は単結合はそれぞれ独立的に単結合、-CH2CH2-が好ましく、Y10は単結合又は-O-が好ましく、Z3は炭素原子数1〜6のアルキル基又は炭素原子数2〜6のアルケニル基が好ましい。
一般式（III）で表される化合物として具体的には、一般式（III-1）〜（III-5）の化合物を挙げることができる。
Among the compounds represented by the general formula (III), R is preferably an alkyl group having 2 to 6 carbon atoms and an alkenyl group having 2 to 6 carbon atoms, and F, G and H are each independently 1, A 4-phenylene group or a 1,4-cyclohexylene group is preferred, and Y 7 , Y 8 and Y 9 are each independently a single bond, preferably —CH 2 CH 2 —, and Y 10 is a single bond or — O- is preferred, and Z 3 is preferably an alkyl group having 1 to 6 carbon atoms or an alkenyl group having 2 to 6 carbon atoms.
Specific examples of the compound represented by the general formula (III) include compounds represented by the general formulas (III-1) to (III-5).
(R1及びR2は独立的に炭素原子数1〜6のアルキル基、アルコキシ基、炭素原子数2〜6のアルケニル基又はアルケニルオキシ基を表す。）
負の誘電異方性を示す液晶はネマチック相を示すことが好ましい。ネマチック相の下限温度は結晶相又は0℃以下が好ましく、-10℃以下がさらに好ましく、-20℃以下が特に好ましい。また、ネマチック相の上限温度は70℃以上が好ましく、80℃以上がさらに好ましく、90℃以上が特に好ましい。25℃における粘度は150mPa・s以下が好ましく、55mPa・s以下がさらに好ましく、35 mPa・s以下が特に好ましい。負の誘電異方性を示す液晶をセル厚5μｍの垂直配向セルに注入し、パルス幅64マイクロ秒、フレームタイム20ミリ秒で印加電圧5Vを印加した際のフレームタイム後の電圧V’と初期印加電圧V0の比に100を乗じた値を電圧保持率とした時、50℃における電圧保持率は98%以上となるような液晶を使用することが好ましい。負の誘電異方性Δεは、-3以下が好ましく、-4以下がさらに好ましく、-5以下が特に好ましい。また、負の誘電異方性を示す液晶化合物中に含有されるアルケニル基を有する化合物の濃度は40質量%以下が好ましい。含有されるアルケニル化合物の濃度が高いと、紫外線硬化型材料の硬化性が悪化する傾向がある。
(R 1 and R 2 independently represent an alkyl group having 1 to 6 carbon atoms, an alkoxy group, an alkenyl group having 2 to 6 carbon atoms, or an alkenyloxy group.)
The liquid crystal exhibiting negative dielectric anisotropy preferably exhibits a nematic phase. The lower limit temperature of the nematic phase is preferably the crystal phase or 0 ° C. or lower, more preferably −10 ° C. or lower, and particularly preferably −20 ° C. or lower. The upper limit temperature of the nematic phase is preferably 70 ° C. or higher, more preferably 80 ° C. or higher, and particularly preferably 90 ° C. or higher. The viscosity at 25 ° C. is preferably 150 mPa · s or less, more preferably 55 mPa · s or less, and particularly preferably 35 mPa · s or less. A liquid crystal exhibiting negative dielectric anisotropy is injected into a vertically aligned cell with a cell thickness of 5 μm, and the initial voltage V ′ after the frame time when an applied voltage of 5 V is applied with a pulse width of 64 microseconds and a frame time of 20 milliseconds. It is preferable to use a liquid crystal whose voltage holding ratio at 50 ° C. is 98% or more when the voltage holding ratio is a value obtained by multiplying the ratio of the applied voltage V0 by 100. The negative dielectric anisotropy Δε is preferably −3 or less, more preferably −4 or less, and particularly preferably −5 or less. The concentration of the compound having an alkenyl group contained in the liquid crystal compound exhibiting negative dielectric anisotropy is preferably 40% by mass or less. When the concentration of the alkenyl compound contained is high, the curability of the ultraviolet curable material tends to deteriorate.
負の誘電異方性を示す液晶及び紫外線硬化型材料を含有する組成物は、ネマチック液晶を示すことが好ましい。このようにすると、液晶セル中に挟持させた時に均一な垂直配向状態を得ることができる。この組成物中には、紫外線照射による紫外線硬化型材料の硬化を円滑に行うことを目的として、光重合開始剤を添加することが好ましい。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。本発明の液晶素子の保持率を確保するためには、ベンジルケタール類、もしくはアシルフォスフィンオキサイド類を使用することが好ましい。ベンジルケタール類としてはイルガキュア651（チバスペシャリティケミカルズ製）が好ましく、紫外線硬化型材料に対して1〜4質量%の濃度で添加することが好ましい。アシルフォスフィンオキサイド類としてはルシリンTPO（BASF製）が好ましく、紫外線硬化型材料に対して0.2〜１質量%の濃度で添加することが好ましい。さらに、この組成物中には、保存安定性の向上を図るために安定剤を添加しても良い。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。添加量は、紫外線硬化型材料に対して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。 The composition containing a liquid crystal exhibiting negative dielectric anisotropy and an ultraviolet curable material preferably exhibits a nematic liquid crystal. In this way, a uniform vertical alignment state can be obtained when sandwiched between liquid crystal cells. In the composition, it is preferable to add a photopolymerization initiator for the purpose of smoothly curing the ultraviolet curable material by ultraviolet irradiation. Examples of the photopolymerization initiator include benzoin ethers, benzophenones, acetophenones, benzyl ketals, and acylphosphine oxides. In order to ensure the retention of the liquid crystal element of the present invention, it is preferable to use benzyl ketals or acyl phosphine oxides. As the benzyl ketals, Irgacure 651 (manufactured by Ciba Specialty Chemicals) is preferable, and it is preferably added at a concentration of 1 to 4% by mass with respect to the ultraviolet curable material. As the acylphosphine oxides, lucillin TPO (manufactured by BASF) is preferable, and it is preferably added at a concentration of 0.2 to 1% by mass with respect to the ultraviolet curable material. Further, a stabilizer may be added to the composition in order to improve 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, nitroso compounds, and the like. . The addition amount is preferably in the range of 0.005 to 1% by mass, more preferably 0.02 to 0.5% by mass, and particularly preferably 0.03 to 0.1% by mass with respect to the ultraviolet curable material.
液晶セルはTFT（薄膜トランジスタ）などのアクティブ駆動素子が形成されているものを使用することが好ましい。セル内面に垂直配向膜を形成しておけば、負の誘電異方性を示す液晶と紫外線硬化型材料を含有する組成物を挟持させるだけで、垂直配向状態を得ることができる。垂直配向膜としては、炭素原子数4以上のアルキル基、アルキル基の水素原子がF原子により一部置換されたフルオロアルキル基を有するシランカップリング剤の薄膜や、ポリイミド系の薄膜を使用することができ、ポリイミド系の薄膜を使用するのが好ましい。 It is preferable to use a liquid crystal cell in which an active drive element such as a TFT (Thin Film Transistor) is formed. If a vertical alignment film is formed on the inner surface of the cell, a vertical alignment state can be obtained by simply sandwiching a composition containing a liquid crystal exhibiting negative dielectric anisotropy and an ultraviolet curable material. As the vertical alignment film, use should be made of an alkyl group having 4 or more carbon atoms, a silane coupling agent thin film having a fluoroalkyl group in which hydrogen atoms of the alkyl group are partially substituted by F atoms, or a polyimide-based thin film It is preferable to use a polyimide-based thin film.
セルギャップは電圧印加時において必要とする光散乱の強度によって調節するのが良いが、一般に5〜15μｍが好ましく、6〜13μｍがさらに好ましく、7〜11μｍが特に好ましい。 The cell gap may be adjusted according to the intensity of light scattering required at the time of voltage application, but is generally preferably 5 to 15 μm, more preferably 6 to 13 μm, and particularly preferably 7 to 11 μm.
本願発明の高分子分散型液晶素子の製造において、紫外線硬化型材料の硬化は紫外線の照射により行う。紫外線光源としては、高圧水銀ランプ、メタルハライドランプ等があるが、メタルハライドランプを使用するのが好ましい。好ましい光重合開始剤として上述した材料は、感度波長域がおよそ350〜380nmの領域にある。このような領域で、1〜数箇所に鋭い輝線スペクトルを有する光源よりも、幅広く、まんべんなくエネルギー強度を有する光源を使用する方が、紫外線硬化型材料の硬化性が良い傾向が得られる。紫外線照射の強度は0.5〜100mW/cm2が好ましく、1〜20mW/cm2がさらに好ましく、2〜10mW/cm2が特に好ましい。強度としては弱い方が、製造した液晶素子の駆動電圧とヒステリシスが小さくなる傾向があり好ましい。紫外線照射エネルギー量としては500〜3000mJ/cm2が好ましく、600〜2500mJ/cm2がさらに好ましく、700〜2000mJ/cm2が特に好ましい。このような範囲内で、作製した液晶素子の電圧保持率（作製した液晶素子にパルス幅64マイクロ秒、フレームタイム20ミリ秒で素子の最高印加電圧を印加した際のフレームタイム後の電圧V’と初期印加電圧V0の比に100を乗じた値）の25℃における値が98%以上となるように、紫外線照射強度とエネルギー量を調節することが好ましい。 In the production of the polymer dispersed liquid crystal element of the present invention, the ultraviolet curable material is cured by irradiation with ultraviolet rays. Examples of the ultraviolet light source include a high-pressure mercury lamp and a metal halide lamp, and it is preferable to use a metal halide lamp. The materials described above as preferred photopolymerization initiators have a sensitivity wavelength range of approximately 350 to 380 nm. In such a region, it is possible to obtain a tendency that the curability of the ultraviolet curable material is better when a light source having a wide and even energy intensity is used than a light source having a sharp emission line spectrum in one to several places. Intensity of ultraviolet radiation is preferably 0.5~100mW / cm 2, more preferably 1~20mW / cm 2, 2~10mW / cm 2 is particularly preferred. A weaker strength is preferred because the drive voltage and hysteresis of the manufactured liquid crystal element tend to be reduced. Preferably 500~3000mJ / cm 2 as ultraviolet radiation energy, more preferably 600~2500mJ / cm 2, 700~2000mJ / cm 2 is particularly preferred. Within such a range, the voltage holding ratio of the manufactured liquid crystal element (the voltage V ′ after the frame time when the maximum applied voltage of the element is applied to the manufactured liquid crystal element with a pulse width of 64 microseconds and a frame time of 20 milliseconds. It is preferable to adjust the ultraviolet irradiation intensity and the amount of energy so that the value at 25 ° C. of the value obtained by multiplying the ratio of the initial applied voltage V0 by 100) is 98% or more.
紫外線の照射は液晶セル平面に対して、片側から行っても両側から行っても良いが、液晶素子の焼き付きを防止する観点から、両側から行うのが好ましい。液晶セルの構造は、アクティブ素子やカラーフィルターの位置や有無により、両面とも照射される紫外線に対する透過率が同等では無い。実験的に、液晶セル内に挟持された紫外線硬化型材料が両面から同じ速度で硬化するように、両側の紫外線照射強度を調節するのが好ましい。片面もしくは両面からの照射のいずれにしても、紫外線強度の面内均一性は重要であり、面内における強度の最高値と最小値の差は10%以内が好ましく、5%以内がさらに好ましく、3%以内が特に好ましい。強度の均一性が良好でないと、得られる液晶素子の電気光学特性が面内でばらついてしまう危険がある。また、紫外線照射による液晶の劣化を防止する目的で、硬化に関与するも短波長の紫外線を減衰されるフィルターを使用することも好ましい。紫外線を照射する際には、液晶セルの温度を一定に制御することが好ましい。紫外線の照射に伴い温度が上昇することが重要である。温度としては10〜25℃の範囲で一定値を選択するのが好ましい。
得られた液晶素子は、光散乱フィルムなどの他の光学部材と組み合わせて使用しても良い。
Irradiation of ultraviolet rays may be performed from one side or both sides with respect to the liquid crystal cell plane, but it is preferable to perform from both sides from the viewpoint of preventing the liquid crystal element from being seized. The structure of the liquid crystal cell does not have the same transmittance for ultraviolet rays irradiated on both surfaces depending on the position and presence of active elements and color filters. Experimentally, it is preferable to adjust the ultraviolet irradiation intensity on both sides so that the ultraviolet curable material sandwiched in the liquid crystal cell is cured at the same speed from both sides. In-plane uniformity of ultraviolet intensity is important for irradiation from one side or both sides, and the difference between the maximum value and the minimum value in the plane is preferably within 10%, more preferably within 5%, Within 3% is particularly preferred. If the uniformity of strength is not good, there is a risk that the electro-optical characteristics of the obtained liquid crystal element will vary in the plane. For the purpose of preventing deterioration of the liquid crystal due to ultraviolet irradiation, it is also preferable to use a filter that is involved in curing but attenuates short-wave ultraviolet rays. When irradiating with ultraviolet rays, it is preferable to control the temperature of the liquid crystal cell to be constant. It is important that the temperature rises with the irradiation of ultraviolet rays. As the temperature, it is preferable to select a constant value in the range of 10 to 25 ° C.
The obtained liquid crystal element may be used in combination with other optical members such as a light scattering film.
（実施例１） 液晶素子の作製（１）
負の誘電異方性を示す液晶（L-1）
Example 1 Production of Liquid Crystal Element (1)
Liquid crystal exhibiting negative dielectric anisotropy (L-1)
を調製した（%は質量%を表す）。液晶（L-1）のネマチック液晶下限温度は-33℃、ネマチック上限温度は81℃、20℃における粘度は32.7mPa・s、温度25℃で波長589nmにおけるΔｎは0.135であった。またΔεは-3.7であった。この液晶（L-1)をセル厚5μｍの垂直配向セルに注入し、パルス幅64マイクロ秒、フレームタイム20ミリ秒で印加電圧5Vを印加した際のフレームタイム後の電圧V’と初期印加電圧V0の比に100を乗じた値を電圧保持率とした時、50℃における電圧保持率は98.2%であった。
紫外線硬化性材料（A-1）
(% Represents mass%). The nematic liquid crystal lower limit temperature of the liquid crystal (L-1) was −33 ° C., the nematic upper limit temperature was 81 ° C., the viscosity at 20 ° C. was 32.7 mPa · s, and the Δn at a temperature of 25 ° C. and a wavelength of 589 nm was 0.135. Δε was −3.7. This liquid crystal (L-1) is injected into a vertical alignment cell with a cell thickness of 5μm, and the voltage V 'after the frame time and the initial applied voltage when applying an applied voltage of 5V with a pulse width of 64μs and a frame time of 20ms. When the value obtained by multiplying the ratio of V0 by 100 was taken as the voltage holding ratio, the voltage holding ratio at 50 ° C. was 98.2%.
UV curable material (A-1)
を調製した（%は質量%を表す）。この（A-1）は室温でネマチック相を示した。この（A-1）に対して光重合開始剤イルガキュア651（チバスペシャリティケミカルズ製）を2質量%、4-メトキシフェノールを0.05%添加して、紫外線硬化性材料（A-1’）を調製した。
負の誘電異方性を示す液晶（L-1）が94質量%、紫外線硬化性材料（A-1’）が6質量%からなる組成物（M-1）を調製した。この組成物（M-1）は室温でネマチック相を示した。
(% Represents mass%). This (A-1) showed a nematic phase at room temperature. To this (A-1), 2% by mass of photopolymerization initiator Irgacure 651 (manufactured by Ciba Specialty Chemicals) and 0.05% of 4-methoxyphenol were added to prepare an ultraviolet curable material (A-1 ′). .
A composition (M-1) comprising 94% by mass of liquid crystal (L-1) exhibiting negative dielectric anisotropy and 6% by mass of ultraviolet curable material (A-1 ′) was prepared. This composition (M-1) exhibited a nematic phase at room temperature.
10μｍの間隔で対向する2組の透明電極上に、垂直配向膜材料JALS-204（JSR製）が約100nmの厚みで形成されたガラス製液晶セルを用意した。この液晶セルに、室温で組成物（M-1）を注入した。注入して10分後、組成物（M-1）は均一に垂直配向していることが確認できた。この液晶セルを10℃に冷却し、均一な垂直配向状態が保たれていることを確認してから、紫外線光源としてメタルハライドランプを用いて、強度5.4mW/cm2で240秒間照射した（計1296mJ/cm2のエネルギー量）。紫外線照射後、液晶セルを室温に戻して観察したところ、光散乱は観察されず、また、液晶（L-1）は垂直配向を保っていることが確認できた。 A glass liquid crystal cell in which the vertical alignment film material JALS-204 (manufactured by JSR) was formed to a thickness of about 100 nm on two sets of transparent electrodes facing each other at an interval of 10 μm was prepared. The composition (M-1) was injected into this liquid crystal cell at room temperature. Ten minutes after the injection, it was confirmed that the composition (M-1) was uniformly vertically aligned. This liquid crystal cell was cooled to 10 ° C., and after confirming that a uniform vertical alignment state was maintained, a metal halide lamp was used as an ultraviolet light source and irradiated for 240 seconds at an intensity of 5.4 mW / cm 2 (total 1296 mJ / cm 2 energy amount). When the liquid crystal cell was returned to room temperature and observed after UV irradiation, no light scattering was observed, and it was confirmed that the liquid crystal (L-1) maintained a vertical alignment.
この液晶セルに1kHzの正弦波を印加したところ、電圧の上昇に伴い、光散乱が増加していくことが確認できた。図１に印加電圧−透過率特性を示す。電圧無印加時の透過率は87%で、14V印加した時に最も光散乱が大きくなり透過率は15%となった（コントラスト比は5.8）。電圧無印加から14Vの電圧を印加した時の応答は83ミリ秒、14Vの電圧印加から電圧無印加にした時の応答は147ミリ秒であった。
作製した液晶素子の電圧保持率（液晶素子にパルス幅64マイクロ秒、フレームタイム20ミリ秒で14Vの電圧を印加した際のフレームタイム後の電圧V’と初期印加電圧V0の比に100を乗じた値）の25℃における値は98.9%であった。
（実施例２） 液晶素子の作製（２）
液晶（L-1)が94質量%、紫外線硬化性材料（A-2）
When a 1 kHz sine wave was applied to the liquid crystal cell, it was confirmed that light scattering increased as the voltage increased. FIG. 1 shows applied voltage-transmittance characteristics. When no voltage was applied, the transmittance was 87%. When 14V was applied, the light scattering was the largest and the transmittance was 15% (contrast ratio was 5.8). The response when a voltage of 14 V was applied after no voltage was applied was 83 milliseconds, and the response when a voltage of 14 V was applied and no voltage was applied was 147 milliseconds.
Voltage holding ratio of the manufactured liquid crystal element (100 times the ratio of the voltage V ′ after the frame time and the initial applied voltage V0 when a voltage of 14 V is applied to the liquid crystal element with a pulse width of 64 microseconds and a frame time of 20 milliseconds) Value) at 25 ° C. was 98.9%.
Example 2 Production of Liquid Crystal Element (2)
94% by mass of liquid crystal (L-1), UV curable material (A-2)
が5.9質量%、光重合開始剤イルガキュア651が0.1質量%からなる組成物（M-2）を調製した。この組成物（M-2）は室温でネマチック相を示した。
実施例１で使用したものと同じセルギャップが10μｍの垂直配向膜付きガラスセルに、室温で組成物（M-2）を注入した。注入して10分後、組成物（M-1）は均一に垂直配向していることが確認できた。この液晶セルを10℃に冷却し、均一な垂直配向状態が保たれていることを確認してから、紫外線光源としてメタルハライドランプを用いて、強度2.4mW/cm2で560秒間照射した（計1344mJ/cm2のエネルギー量）。紫外線照射後、液晶セルを室温に戻して観察したところ、光散乱は観察されず、また、液晶（L-1）は垂直配向を保っていることが確認できた。
この液晶セルに1kHzの正弦波を印加したところ、電圧の上昇に伴い、光散乱が増加していくことが確認できた。電圧無印加時の透過率は91%で、10V印加した時に最も光散乱が大きくなり透過率は18%となった（コントラスト比は5.1）。
A composition (M-2) comprising 5.9% by mass and 0.1% by mass of photopolymerization initiator Irgacure 651 was prepared. This composition (M-2) exhibited a nematic phase at room temperature.
The composition (M-2) was injected at room temperature into a glass cell with a vertical alignment film having the same cell gap of 10 μm as used in Example 1. Ten minutes after the injection, it was confirmed that the composition (M-1) was uniformly vertically aligned. This liquid crystal cell was cooled to 10 ° C., and after confirming that a uniform vertical alignment state was maintained, a metal halide lamp was used as an ultraviolet light source, and irradiation was performed for 560 seconds at an intensity of 2.4 mW / cm 2 (total 1344 mJ / cm 2 energy amount). When the liquid crystal cell was returned to room temperature and observed after UV irradiation, no light scattering was observed, and it was confirmed that the liquid crystal (L-1) maintained a vertical alignment.
When a 1 kHz sine wave was applied to the liquid crystal cell, it was confirmed that light scattering increased as the voltage increased. When no voltage was applied, the transmittance was 91%. When 10V was applied, the light scattering was the largest and the transmittance was 18% (contrast ratio was 5.1).
作製した液晶素子の電圧保持率（液晶素子にパルス幅64マイクロ秒、フレームタイム20ミリ秒で10Vの電圧を印加した際のフレームタイム後の電圧V’と初期印加電圧V0の比に100を乗じた値）の25℃における値は99.0%であった。
（実施例３） 液晶素子の作製（３）
負の誘電異方性を示す液晶（L-2）
Voltage holding ratio of the manufactured liquid crystal element (100 times the ratio of the voltage V ′ after the frame time and the initial applied voltage V0 when a voltage of 10 V is applied to the liquid crystal element with a pulse width of 64 microseconds and a frame time of 20 milliseconds) Value) at 25 ° C. was 99.0%.
Example 3 Production of Liquid Crystal Element (3)
Liquid crystal exhibiting negative dielectric anisotropy (L-2)
を調製した（%は質量%を表す）。液晶（L-2）の温度25℃で波長589nmにおけるΔｎは0.157であった。
この液晶（L-2）をセル厚5μｍの垂直配向セルに注入し、パルス幅64マイクロ秒、フレームタイム20ミリ秒で印加電圧5Vを印加した際のフレームタイム後の電圧V’と初期印加電圧V0の比に100を乗じた値を電圧保持率とした時、50℃における電圧保持率は98.2%であった。
(% Represents mass%). Δn of the liquid crystal (L-2) at a temperature of 25 ° C. and a wavelength of 589 nm was 0.157.
This liquid crystal (L-2) is injected into a vertical alignment cell with a cell thickness of 5 μm, and the voltage V ′ after the frame time and the initial applied voltage when applying an applied voltage of 5 V with a pulse width of 64 microseconds and a frame time of 20 milliseconds. When the value obtained by multiplying the ratio of V0 by 100 was taken as the voltage holding ratio, the voltage holding ratio at 50 ° C. was 98.2%.
負の誘電異方性を示す液晶（L-2）が94質量%、紫外線硬化性材料（A-1’）が6質量%からなる組成物（M-3）を調製した。この組成物（M-3）は室温でネマチック相を示した。
実施例１で使用したものと同じセルギャップが10μｍの垂直配向膜付きガラスセルに、室温で組成物（M-3）を注入した。注入して10分後、組成物（M-3）は均一に垂直配向していることが確認できた。この液晶セルを10℃に冷却し、均一な垂直配向状態が保たれていることを確認してから、紫外線光源としてメタルハライドランプを用いて、強度5.4mW/cm2で240秒間照射した（計1296mJ/cm2のエネルギー量）。紫外線照射後、液晶セルを室温に戻して観察したところ、光散乱は観察されず、また、液晶（L-2）は垂直配向を保っていることが確認できた。
この液晶セルに1kHzの正弦波を印加したところ、電圧の上昇に伴い、光散乱が増加していくことが確認できた。電圧無印加時の透過率は86%で、16V印加した時に最も光散乱が大きくなり透過率は15%となった（コントラスト比は5.7）。
A composition (M-3) comprising 94% by mass of liquid crystal (L-2) exhibiting negative dielectric anisotropy and 6% by mass of ultraviolet curable material (A-1 ′) was prepared. This composition (M-3) exhibited a nematic phase at room temperature.
The composition (M-3) was injected at room temperature into a glass cell with a vertical alignment film having the same cell gap of 10 μm as used in Example 1. Ten minutes after the injection, it was confirmed that the composition (M-3) was uniformly vertically aligned. This liquid crystal cell was cooled to 10 ° C., and after confirming that a uniform vertical alignment state was maintained, a metal halide lamp was used as an ultraviolet light source and irradiated for 240 seconds at an intensity of 5.4 mW / cm 2 (total 1296 mJ / cm 2 energy amount). When the liquid crystal cell was returned to room temperature and observed after UV irradiation, no light scattering was observed, and it was confirmed that the liquid crystal (L-2) maintained a vertical alignment.
When a 1 kHz sine wave was applied to the liquid crystal cell, it was confirmed that light scattering increased as the voltage increased. When no voltage was applied, the transmittance was 86%. When 16V was applied, the light scattering was the largest and the transmittance was 15% (contrast ratio was 5.7).
作製した液晶素子の電圧保持率（液晶素子にパルス幅64マイクロ秒、フレームタイム20ミリ秒で16Vの電圧を印加した際のフレームタイム後の電圧V’と初期印加電圧V0の比に100を乗じた値）の25℃における値は98.6%であった。
（比較例１） 液晶素子の作製（４）
液晶（L-1)が94質量%、紫外線硬化性材料（HX-220）（日本化薬株式会社製）
Voltage holding ratio of the manufactured liquid crystal element (100 times the ratio of the voltage V 'after the frame time and the initial applied voltage V0 when a voltage of 16 V is applied to the liquid crystal element with a pulse width of 64 microseconds and a frame time of 20 milliseconds) Value) at 25 ° C. was 98.6%.
Comparative Example 1 Production of Liquid Crystal Element (4)
94% by mass of liquid crystal (L-1), UV curable material (HX-220) (manufactured by Nippon Kayaku Co., Ltd.)
実施例１で使用したものと同じセルギャップが10μｍの垂直配向膜付きガラスセルに、室温で組成物（M-4）を注入した。注入して10分後、組成物（M-1）はほぼ均一に垂直配向していることが確認できた。この液晶セルを10℃に冷却し、ほぼ均一な垂直配向状態が保たれていることを確認してから、紫外線光源としてメタルハライドランプを用いて、強度2.4mW/cm2で560秒間照射した（計1344mJ/cm2のエネルギー量）。紫外線照射後、液晶セルを室温に戻して観察したところ、光散乱は観察されず、また、液晶（L-1）は、ほぼ均一な垂直配向を保っていることが確認できた。
この液晶セルに1kHzの正弦波を印加したところ、電圧の上昇に伴い、光散乱が増加していくことが確認できた。電圧無印加時の透過率は85%で、14V印加した時に最も光散乱が大きくなり透過率は41%となった（コントラスト比は2.1）。
The composition (M-4) was injected at room temperature into a glass cell with a vertical alignment film having the same cell gap of 10 μm as used in Example 1. Ten minutes after the injection, it was confirmed that the composition (M-1) was almost uniformly vertically aligned. The liquid crystal cell was cooled to 10 ° C., and after confirming that a substantially uniform vertical alignment state was maintained, a metal halide lamp was used as an ultraviolet light source, and irradiation was performed for 560 seconds at an intensity of 2.4 mW / cm 2 (total) 1344mJ / cm 2 energy). When the liquid crystal cell was returned to room temperature and observed after UV irradiation, no light scattering was observed, and it was confirmed that the liquid crystal (L-1) maintained almost uniform vertical alignment.
When a 1 kHz sine wave was applied to the liquid crystal cell, it was confirmed that light scattering increased as the voltage increased. When no voltage was applied, the transmittance was 85%. When 14V was applied, the light scattering was the largest and the transmittance was 41% (contrast ratio was 2.1).
作製した液晶素子の電圧保持率（液晶素子にパルス幅64マイクロ秒、フレームタイム20ミリ秒で14Vの電圧を印加した際のフレームタイム後の電圧V’と初期印加電圧V0の比に100を乗じた値）の25℃における値は98.7%であった。 Voltage holding ratio of the manufactured liquid crystal element (100 times the ratio of the voltage V ′ after the frame time and the initial applied voltage V0 when a voltage of 14 V is applied to the liquid crystal element with a pulse width of 64 microseconds and a frame time of 20 milliseconds) Value) at 25 ° C. was 98.7%.
本比較例から、紫外線硬化性材料として液晶性アクリレートで無いものを使用すると、配向の均一性が悪化すること、液晶素子としての電圧保持率は高いものの、コントラストが大幅に悪化してしまうことがわかる。
（比較例２） 液晶素子の作製（５）
負の誘電異方性を示す液晶（L-3）
From this comparative example, when a material that is not a liquid crystal acrylate is used as the ultraviolet curable material, the uniformity of alignment is deteriorated, and the voltage holding ratio as a liquid crystal element is high, but the contrast is greatly deteriorated. Recognize.
(Comparative Example 2) Production of liquid crystal element (5)
Liquid crystal with negative dielectric anisotropy (L-3)
を調製した（%は質量%を表す）。液晶（L-3）の温度25℃で波長589nmにおけるΔｎは0.08であった。
この液晶（L-3）をセル厚5μｍの垂直配向セルに注入し、パルス幅64マイクロ秒、フレームタイム20ミリ秒で印加電圧5Vを印加した際のフレームタイム後の電圧V’と初期印加電圧V0の比に100を乗じた値を電圧保持率とした時、50℃における電圧保持率は98.9%であった。
(% Represents mass%). The Δn of the liquid crystal (L-3) at a temperature of 25 ° C. and a wavelength of 589 nm was 0.08.
This liquid crystal (L-3) is injected into a vertical alignment cell with a cell thickness of 5μm, and the voltage V 'after the frame time and the initial applied voltage when an applied voltage of 5V is applied with a pulse width of 64 microseconds and a frame time of 20 milliseconds. When the value obtained by multiplying the ratio of V0 by 100 was defined as the voltage holding ratio, the voltage holding ratio at 50 ° C. was 98.9%.
負の誘電異方性を示す液晶（L-3）が94質量%、紫外線硬化性材料（A-1’）が6質量%からなる組成物（M-5）を調製した。この組成物（M-5）は室温でネマチック相を示した。
実施例１で使用したものと同じセルギャップが10μｍの垂直配向膜付きガラスセルに、室温で組成物（M-5）を注入した。注入して10分後、組成物（M-4）は均一に垂直配向していることが確認できた。この液晶セルを10℃に冷却し、均一な垂直配向状態が保たれていることを確認してから、紫外線光源としてメタルハライドランプを用いて、強度5.4mW/cm2で240秒間照射した（計1296mJ/cm2のエネルギー量）。紫外線照射後、液晶セルを室温に戻して観察したところ、光散乱は観察されず、また、液晶（L-3）は垂直配向を保っていることが確認できた。
この液晶セルに1kHzの正弦波を印加したところ、電圧の上昇に伴い、光散乱が増加していくことが確認できた。電圧無印加時の透過率は88%で、15V印加した時に最も光散乱が大きくなり透過率は21%となった（コントラスト比は4.2）。
A composition (M-5) comprising 94% by mass of liquid crystal (L-3) exhibiting negative dielectric anisotropy and 6% by mass of ultraviolet curable material (A-1 ′) was prepared. This composition (M-5) exhibited a nematic phase at room temperature.
The composition (M-5) was injected into a glass cell with a vertical alignment film having the same cell gap of 10 μm as that used in Example 1 at room temperature. Ten minutes after the injection, it was confirmed that the composition (M-4) was uniformly vertically aligned. This liquid crystal cell was cooled to 10 ° C., and after confirming that a uniform vertical alignment state was maintained, a metal halide lamp was used as an ultraviolet light source and irradiated for 240 seconds at an intensity of 5.4 mW / cm 2 (total 1296 mJ / cm 2 energy amount). When the liquid crystal cell was returned to room temperature and observed after UV irradiation, no light scattering was observed, and it was confirmed that the liquid crystal (L-3) maintained a vertical alignment.
When a 1 kHz sine wave was applied to the liquid crystal cell, it was confirmed that light scattering increased as the voltage increased. When no voltage was applied, the transmittance was 88%. When 15V was applied, the light scattering was the largest and the transmittance was 21% (contrast ratio was 4.2).
作製した液晶素子の電圧保持率（液晶素子にパルス幅64マイクロ秒、フレームタイム20ミリ秒で15Vの電圧を印加した際のフレームタイム後の電圧V’と初期印加電圧V0の比に100を乗じた値）の25℃における値は98.8%であった。 Voltage holding ratio of the manufactured liquid crystal element (100 times the ratio of the voltage V 'after the frame time and the initial applied voltage V0 when a voltage of 15 V is applied to the liquid crystal element with a pulse width of 64 microseconds and a frame time of 20 milliseconds) Value) at 25 ° C. was 98.8%.
本比較例から、液晶のΔｎが0.13以下になると、液晶素子としての電圧保持率は高いものの、コントラストが悪化してしまうことがわかる。
（比較例３） 液晶素子の作製（６）
負の誘電異方性を示す液晶（L-4）
From this comparative example, it can be seen that when Δn of the liquid crystal is 0.13 or less, the voltage holding ratio as the liquid crystal element is high, but the contrast is deteriorated.
(Comparative Example 3) Production of liquid crystal element (6)
Liquid crystal exhibiting negative dielectric anisotropy (L-4)
を調製した（%は質量%を表す）。液晶（L-4）の温度25℃で波長589nmにおけるΔｎは0.20であった。
この液晶（L-4）をセル厚5μｍの垂直配向セルに注入し、パルス幅64マイクロ秒、フレームタイム20ミリ秒で印加電圧5Vを印加した際のフレームタイム後の電圧V’と初期印加電圧V0の比に100を乗じた値を電圧保持率とした時、50℃における電圧保持率は98.0%であった。
(% Represents mass%). The Δn of the liquid crystal (L-4) at a temperature of 25 ° C. and a wavelength of 589 nm was 0.20.
This liquid crystal (L-4) is injected into a 5μm thick vertical alignment cell, and the voltage V 'after the frame time and the initial applied voltage when the applied voltage 5V is applied with a pulse width of 64 microseconds and a frame time of 20 milliseconds. When the value obtained by multiplying the ratio of V0 by 100 was defined as the voltage holding ratio, the voltage holding ratio at 50 ° C. was 98.0%.
負の誘電異方性を示す液晶（L-4）が94質量%、紫外線硬化性材料（A-1’）が6質量%からなる組成物（M-6）を調製した。この組成物（M-6）は室温でネマチック相を示した。
実施例１で使用したものと同じセルギャップが10μｍの垂直配向膜付きガラスセルに、室温で組成物（M-6）を注入した。注入して10分後、組成物（M-6）は均一に垂直配向していることが確認できた。この液晶セルを10℃に冷却し、均一な垂直配向状態が保たれていることを確認してから、紫外線光源としてメタルハライドランプを用いて、強度5.4mW/cm2で240秒間照射した（計1296mJ/cm2のエネルギー量）。紫外線照射後、液晶セルを室温に戻して観察したところ、光散乱は観察されず、また、液晶（L-4）は垂直配向を保っていることが確認できた。
この液晶セルに1kHzの正弦波を印加したところ、電圧の上昇に伴い、光散乱が増加していくことが確認できた。電圧無印加時の透過率は87%で、14V印加した時に最も光散乱が大きくなり透過率は56%となった（コントラスト比は1.6）。
A composition (M-6) comprising 94% by mass of liquid crystal (L-4) exhibiting negative dielectric anisotropy and 6% by mass of ultraviolet curable material (A-1 ′) was prepared. This composition (M-6) exhibited a nematic phase at room temperature.
The composition (M-6) was injected at room temperature into a glass cell with a vertical alignment film having the same cell gap of 10 μm as used in Example 1. Ten minutes after the injection, it was confirmed that the composition (M-6) was uniformly vertically aligned. This liquid crystal cell was cooled to 10 ° C., and after confirming that a uniform vertical alignment state was maintained, a metal halide lamp was used as an ultraviolet light source and irradiated for 240 seconds at an intensity of 5.4 mW / cm 2 (total 1296 mJ / cm 2 energy amount). When the liquid crystal cell was returned to room temperature and observed after UV irradiation, no light scattering was observed, and it was confirmed that the liquid crystal (L-4) maintained vertical alignment.
When a 1 kHz sine wave was applied to the liquid crystal cell, it was confirmed that light scattering increased as the voltage increased. When no voltage was applied, the transmittance was 87%. When 14V was applied, the light scattering was greatest and the transmittance was 56% (contrast ratio was 1.6).
作製した液晶素子の電圧保持率（液晶素子にパルス幅64マイクロ秒、フレームタイム20ミリ秒で14Vの電圧を印加した際のフレームタイム後の電圧V’と初期印加電圧V0の比に100を乗じた値）の25℃における値は98.2%であった。
本比較例から、液晶のΔｎが0.16以上になると、紫外線硬化型材料の硬化性が悪化して、コントラストの低下を招くことがわかる。
Voltage holding ratio of the manufactured liquid crystal element (100 times the ratio of the voltage V ′ after the frame time and the initial applied voltage V0 when a voltage of 14 V is applied to the liquid crystal element with a pulse width of 64 microseconds and a frame time of 20 milliseconds) Value) at 25 ° C. was 98.2%.
From this comparative example, it can be seen that when Δn of the liquid crystal is 0.16 or more, the curability of the ultraviolet curable material is deteriorated and the contrast is lowered.
（比較例４） 液晶素子の作製（７）
、強度5.4mW/cm2で3600秒間照射した（計19440mJ/cm2のエネルギー量）以外は、比較例３と同様にして液晶素子を作製した。この液晶セルに1kHzの正弦波を印加したところ、電圧の上昇に伴い、光散乱が増加していくことが確認できた。電圧無印加時の透過率は87%で、19V印加した時に最も光散乱が大きくなり透過率は20%となった（コントラスト比は4.4）。
Comparative Example 4 Production of liquid crystal element (7)
A liquid crystal device was produced in the same manner as in Comparative Example 3 except that irradiation was performed for 3600 seconds at an intensity of 5.4 mW / cm 2 (total energy amount of 19440 mJ / cm 2 ). When a 1 kHz sine wave was applied to the liquid crystal cell, it was confirmed that light scattering increased as the voltage increased. When no voltage was applied, the transmittance was 87%. When 19V was applied, the light scattering was the largest and the transmittance was 20% (contrast ratio 4.4).
作製した液晶素子の電圧保持率（液晶素子にパルス幅64マイクロ秒、フレームタイム20ミリ秒で19Vの電圧を印加した際のフレームタイム後の電圧V’と初期印加電圧V0の比に100を乗じた値）の25℃における値は86.5%であった。 Voltage holding ratio of the manufactured liquid crystal element (100 times the ratio of the voltage V 'after the frame time and the initial applied voltage V0 when a voltage of 19 V is applied to the liquid crystal element with a pulse width of 64 microseconds and a frame time of 20 milliseconds) Value) at 25 ° C. was 86.5%.
本比較例から、液晶のΔｎが0.16以上になると、紫外線硬化型材料の硬化性が悪化するため、コントラストを確保しようとすると、多大な紫外線エネルギー照射量が必要になることがわかる。これにより、液晶が劣化し、液晶素子の保持率が悪化してしまうことがわかる。 From this comparative example, it can be seen that when Δn of the liquid crystal is 0.16 or more, the curability of the ultraviolet curable material is deteriorated, so that it is necessary to irradiate a large amount of ultraviolet energy when attempting to ensure contrast. Thereby, it turns out that a liquid crystal deteriorates and the retention of a liquid crystal element will deteriorate.
Claims (7)
The method according to claim 6, wherein the ultraviolet curable material is cured using a metal halide lamp as an ultraviolet light source.
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| JP2006231997A Active JP5017963B2 (en) | 2006-08-29 | 2006-08-29 | Liquid crystal element |
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