JP2004059855A - Liquid crystal composition - Google Patents

Liquid crystal composition Download PDF

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JP2004059855A
JP2004059855A JP2002223302A JP2002223302A JP2004059855A JP 2004059855 A JP2004059855 A JP 2004059855A JP 2002223302 A JP2002223302 A JP 2002223302A JP 2002223302 A JP2002223302 A JP 2002223302A JP 2004059855 A JP2004059855 A JP 2004059855A
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liquid crystal
general formula
group
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JP4355993B2 (en
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Yasuo Umetsu
埼玉県北本市東間8−230−95
Kiyobumi Takeuchi
竹内 清文
Shotaro Kawakami
川上 正太郎
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DIC Corp
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Dainippon Ink and Chemicals Co Ltd
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid crystal composition having a small anisotropicity of refractive index Δn (Δn = 0.05-0.07) and a large anisotropicity of dielectric constant Δε (Δε= 4.5-8.0). <P>SOLUTION: The liquid crystal contains 5-50 mass % of one or more compounds selected from the compounds as expressed by general formulas (1), (2) and (3) (wherein, R<SP>1</SP>, R<SP>2</SP>and R<SP>3</SP>are each independently a 1-15C alkyl group, a 2-15C alkenyl group or the like; Z<SP>1</SP>, Z<SP>2</SP>and Z<SP>3</SP>are each independently -COO-, -CH<SB>2</SB>O-, -CH<SB>2</SB>CH<SB>2</SB>-, -CH=CH-, -C≡C-, -(CH<SB>2</SB>)<SB>4</SB>-, -CH<SB>2</SB>CH<SB>2</SB>-CH=CH-, a single bond or the like; X<SP>1</SP>, X<SP>2</SP>, X<SP>3</SP>and X<SP>4</SP>are each independently H, F or Cl; Q<SP>1</SP>and Q<SP>2</SP>are each independently -OCH<SB>2</SB>-, -OCF<SB>2</SB>-, -OCHF- or -CF<SB>2</SB>-; Y<SP>1</SP>, Y<SP>2</SP>and Y<SP>3</SP>are each independently -OCH<SB>2</SB>F, -OCHF<SB>2</SB>, -OCF<SB>3</SB>-CF<SB>3</SB>; and l and m are each independently 1 or 2). <P>COPYRIGHT: (C)2004,JPO

Description

【0001】
【発明の属する技術分野】
本発明は、電気光学的表示材料として有用なネマチック液晶組成物及びこれを用いた液晶表示装置に関する。
【0002】
【従来の技術】
ツイステッドネマチック液晶表示素子(TN−LCD)やスーパーツイステッドネマチック液晶表示素子(STN−LCD)においては、液晶の屈折率異方性(Δn)と液晶媒体の厚さ(d)との積であるリターデーション(R;R=Δn・d)をある一定値(TN−LCDでは0.4〜0.45に設定する場合が多い。)に設定する。
【0003】
反射型または半透過型LCDでは、光が液晶媒体に入射し、背面の反射板で反射して再度液晶媒体中を通過するため、透過型LCDと比較して実質の光路長が2倍になるため、同じリタデーション値にするためには、液晶媒体のΔnを半分程度に小さくする必要がある。
【0004】
低Δn液晶組成物は、Δn値の小さいシクロヘキサン環のみで構成されたビシクロヘキサン誘導体等の含有率を大きくすることで得ることができる。しかし、これらの化合物はスメクチック性が高く、ビシクロヘキサン系化合物の含有率を大きくした場合、ネマチック相下限温度(T−n)を低くすることが困難であり、広いネマチック温度範囲を有する液晶組成物を得ることが困難であった。また、Δnの小さい化合物は一般的にはΔεが小さく、低電圧駆動が可能なΔεが大きく、かつΔnの低い液晶組成物を得ることは困難であった。
【0005】
たとえば、特開2001−354963号には、シクロヘキシルデカヒドロナフタレン化合物とトリフルオロ化合物とを用いた液晶組成物の例が開示されているが、Δεが十分に大きくなく、しきい値電圧が高い等の問題点を抱えており、低電圧駆動の要請に最適な液晶組成物は提供されていなかった。
【0006】
【発明が解決しようとする課題】
本発明が解決しようとする課題は、小さい屈折率異方性Δn(Δn=0.05〜0.07)及び大きな誘電率異方性Δε(Δε=4.5〜8.0)を同時に有する液晶組成物を提供すること、またこの液晶組成物を使用した液晶表示素子を提供することにある。
【0007】
【課題を解決するための手段】
本発明者は、上記課題を解決するために、種々の液晶化合物を用いた液晶組成物を検討した結果、一般式(1)で表される化合物と、一般式(2)で表される化合物と、一般式(3)で表される化合物をそれぞれ特定量組み合わせることにより、極めて小さい屈折率異方性と、大きな誘電率異方性を有する液晶組成物が得られることを見いだし本発明に至った。
【0008】
すなわち本発明は、液晶組成物が、
A群:+1.5より大きい誘電率異方性を有する化合物群と、
B群:−1.5〜+1.5の誘電率異方性を有する化合物群
とから成り、A群の化合物群の第一成分として一般式(1)
【0009】
【化8】

Figure 2004059855
(式中Rは、炭素数1〜15のアルキル基又は炭素数2〜15のアルケニル基であり、この基は非置換であるか、あるいは置換基として少なくとも1個のハロゲン基を有しており、そしてこれらの基中に存在する1個又は2個以上のCH基はそれぞれ独立してO原子が相互に直接結合しないものとして−O−、−S−、−CO−、−COO−、−OCO−、−OCO−O−により置き換えられても良く、Zは、−COO−、−OCO−、−CHO−、−OCH−、−CFO−、−OCF−、−CHCH−、−CFCF−、−CH=CH−、−(CH−、−CH=CH−CHCH−、−CHCH−CH=CH− 又は単結合であり、Yは−OCHF、−OCHF、−OCF又は−CFである。)で表される化合物から選ばれる化合物を1種又は2種以上を2〜30質量%含有し、第二成分として一般式(2)
【0010】
【化9】
Figure 2004059855
(式中Rは、一般式(1)のRの定義と同じであり、X、Xはそれぞれ独立してH、F又はClであり、Zは、一般式(1)のZの定義と同じであり、lは1又は2であり、Qは−OCH−、−OCF−、−OCHF−又は−CF−であり、YはF又はClである。)で表される化合物から選ばれる化合物を1種又は2種以上を5〜30質量%含有し、第三成分として一般式(3)
【0011】
【化10】
Figure 2004059855
【0012】
(式中Rは、一般式(1)のRの定義と同じであり、X、Xはそれぞれ独立してH、F又はClであり、Zは、一般式(1)のZの定義と同じであり、mは1又は2であり、Qは一般式(2)のQの定義と同じであり、YはF又はClである。)で表される化合物から選ばれる化合物を1種又は2種以上を5〜50質量%含有することを特徴とする液晶組成物を提供する。
【0013】
また、本発明は、上記液晶組成物を使用した、マトリクス状に配置された画素部にスイッチング素子が設けられているアクティブマトリクス型液晶表示素子を提供する。
【0014】
【発明の実施の形態】
一般式(1)で表される化合物(以下、化合物(1)という。)は、極めて小さな屈折率異方性Δnを有し、さらに駆動電圧の低下にも効果がある。しかしながらネマチック相下限温度を低減する効果は比較的小さい。一方、一般式(2)で表される化合物(以下、化合物(2)という。)および 一般式(3)で表される化合物(以下、化合物(3)という。)は、比較的小さなΔnを有する化合物であり、駆動電圧の低下に大きな効果がある。さらにシクロヘキサン環やベンゼン環のみからなる化合物と比べて、ネマチック相下限温度を低減する効果を有するため、スメクチック性を発現させやすい化合物(1)や後述の一般式(4)または一般式(5)で表される化合物を多量に含有しても低いネマチック相下限温度を維持することができる。
【0015】
本発明の液晶組成物は、化合物(1)と化合物(2)と化合物(3)のそれぞれの化合物から1種又は2種以上選ばれる化合物を含有する組成物である。化合物(1)と化合物(2)および化合物(3)はお互いの欠点を補うことにより、組成物として、極めて小さなΔnと低いネマチック相下限温度範囲を有し、反射型または半透過型LCD用液晶組成物として非常に有用である。
【0016】
本発明の液晶組成物は、化合物(1)から選ばれる化合物を1種〜5種の範囲で含有することが好ましく、1種〜3種の範囲で含有することが特に好ましい。また、式中Rは、炭素数1〜8のアルキル基又は炭素数2〜8のアルケニル基が好ましく、炭素数1〜5のアルキル基又は式(a)〜(e)のアルケニル基が特に好ましい。
【化11】
Figure 2004059855
(式は右端で環に結合するものとする。)
また、一般式(1)中、Zは、単結合が好ましく、YはFが好ましい。
【0017】
化合物(1)として好ましい化合物として、化合物(7)を挙げることができる。
【化12】
Figure 2004059855
【0018】
さらに好ましい化合物として以下の化合物群を挙げることができる。
【化13】
Figure 2004059855
一般式(1)から選ばれる化合物の含有量は、5質量%〜30質量%が好ましく、10質量%〜20質量%が特に好ましい。
【0019】
化合物(7)のRがデカヒドロナフタレン環側に直結した一般式(8)
【化14】
Figure 2004059855
で表される化合物(以下、化合物(8)という。) は、化合物(7)と比較して液晶性が悪くなる傾向がある。この傾向は炭素数が多くなるほど顕著である。さらに粘性においても化合物(8)の粘性は化合物(7)と比較して高く、炭素数が多くなるほど顕著である。これは炭素数が多くなると化合物(8)はデカヒドロナフタレン骨格がより中央へ位置することになるが、本発明の化合物(7)ではデカヒドロナフタレン骨格がより末端に位置することになり、液晶分子の排除体積効果が液晶の特性に影響を及ぼしていると思われる。このため化合物(7)の方がより良好な結果を示したと言える。
【0020】
化合物(2)から選ばれる化合物は1種〜5種の範囲で含有することが好ましく、1種〜3種の範囲で含有することが特に好ましい。また一般式(2)中、Rは炭素数1〜8のアルキル基又は炭素数2〜8のアルケニル基が好ましく、炭素数1〜5のアルキル基又は式(a)〜(e)のアルケニル基が特に好ましい。
式中X、Xはそれぞれ独立してH、F又はClであり、X、Xのうち少なくとも1個はFであることが好ましい。Qは単結合が好ましい。YはFが好ましい。
【0021】
化合物(2)として好ましい化合物として、以下の化合物群を挙げることができる。
【化15】
Figure 2004059855
一般式(2)から選ばれる化合物の含有量は、5質量%〜20質量%が好ましく、10質量%〜20質量%が特に好ましい。
【0022】
化合物(3)から選ばれる化合物は1種〜5種の範囲で含有することが好ましく、1種〜3種の範囲で含有することが特に好ましい。また一般式(3)中、Rは炭素数1〜8のアルキル基又は炭素数2〜8のアルケニル基が好ましく、炭素数1〜5のアルキル基又は式(a)〜(e)のアルケニル基が特に好ましい。
式中X、Xはそれぞれ独立してH、F又はClであり、X、Xのうち少なくとも1個はFであることが好ましい。Qは単結合が好ましい。YはFが好ましい。
【0023】
化合物(3)として好ましい化合物として、以下の化合物群を挙げることができる。
【化16】
Figure 2004059855
【0024】
一般式(3)から選ばれる化合物の含有量は、5質量%〜40質量%が好ましく、10質量%〜40質量%が特に好ましい。
【0025】
本発明は、デカヒドロナフタレン環を有する化合物(1)および化合物(3)とテトラヒドロナフタレン環を有する化合物(2)といったΔnが異なり、環構造も異なる2種の化合物を組み合わせることにより、低いネマチック相下限温度と小さいΔnを同時に可能とするものである。
【0026】
Δnを小さくすることは、レタデーションを一定にしたままで、セル厚を厚くできるため、パネルの量産性の向上に寄与でき有用である。本発明の液晶組成物のΔnは0.05〜0.07が好ましく、更に好ましくは0.05〜0.060である。
【0027】
ネマチック液晶相温度範囲の拡大は、最近要望の高まっている携帯端末ディスプレイ用として有用である。本発明による組成物は、特に、ネマチック相が結晶やスメクチックに転移するネマチック相下限温度に対して拡大効果があるため、本発明の液晶組成物を使用した液晶表示素子は、戸外の低温の環境でも高いコントラストでの動作が可能となる。本発明のネマチック−アイソトロピック転移温度は75℃〜120℃が好ましく、クリスタル又はスメクチック−ネマチック転移温度(℃)は−80℃〜−10℃が好ましいが、さらに好ましくはネマチック−アイソトロピック転移温度が80℃〜120℃であり、クリスタル又はスメクチック−ネマチック転移温度(℃)が−80℃〜−20℃である。
【0028】
更に、化合物(1)、化合物(2)及び化合物(3)は電流値の増加を抑制する効果を持つため、AM−LCD駆動方式による液晶素子にさらに好ましく、本発明の液晶組成物を使用した液晶表示素子は戸外の過酷な熱・太陽光・UV光の環境においても、安定で電流値増加などによる表示不良を起こしにくい。
【0029】
一般式(4)
【化17】
Figure 2004059855
(式中Rは、一般式(1)のRの定義と同じであり、Zは、一般式(1)のZの定義と同じであり、nは1又は2であり、Yは一般式(1)のYの定義と同じでる。)で表される化合物(以下、化合物(4)という。)は、化合物(1)と同様極めて小さな屈折率異方性Δnを有し、さらに駆動電圧の低下にも効果がある。化合物(1)、化合物(2)及び化合物(3)からなる組成物に化合物(4)を加えることにより、さらに小さなΔnを有する組成物を得ることができる。
化合物(4)から選ばれる化合物を1種〜5種の範囲で含有することが好ましく、1種〜3種の範囲で含有することが特に好ましい。また、式中Rは、炭素数1〜8のアルキル基又は炭素数2〜8のアルケニル基が好ましく、炭素数1〜5のアルキル基又は式(a)〜(e)のアルケニル基が特に好ましい。
また、一般式(4)中、Zは、−COO−、−OCO−、−(CH−、−CH=CH−CHCH−、−CHCH−CH=CH− 又は単結合が好ましく、nは1が好ましい。
【0030】
化合物(4)として好ましい化合物として、以下の化合物群を挙げることができる。
【化18】
Figure 2004059855
化合物(4)から選ばれる化合物の含有量は、5質量%〜20質量%が好ましく、5質量%〜15質量%が特に好ましい。
【0031】
一般式(5)
【化19】
Figure 2004059855
(式中R及びRは、一般式(1)のRの定義と同じであり、Zは、一般式(1)のZの定義と同じであり、oは1又は2である。)で表される化合物(以下、化合物(5)と言う。)の含有率の合計が20質量%以上の場合、通常化合物(5)に起因するスメクチック相安定性が高くなり、得られた液晶組成物のネマチック相温度範囲が狭くなるが、本発明の液晶組成物では低いネマチック相下限温度を維持することができる。化合物(5)の含有率の合計は、5〜25質量%であることが好ましく、10〜20質量%であることが特に好ましい。また、式中Rは、炭素数1〜8のアルキル基又は炭素数2〜8のアルケニル基が好ましく、炭素数1〜5のアルキル基又は式(a)〜(e)のアルケニル基が特に好ましい。
また、前記のアルケニル基の部分構造のなかでは、(a)、(b)、(c)及び(d)が特に好ましい。 一般式(5)中、Zは、単結合が好ましく、oは1が好ましい。
【0032】
本発明の液晶組成物は、さらに一般式(6)
【0033】
Figure 2004059855
(式中Rは、一般式(1)のRの定義と同じであり、Zは、−CHO−、−OCH−、−CFO−、−OCF−、−CHCH−、−CFCF−、−CH=CH−、−(CH−、−CH=CH−CHCH−、−CHCH−CH=CH− 又は単結合であり、Zは、−COO−、−OCO−、−CHO−、−OCH−、−CFO−、−OCF−、−CHCH−、−CFCF−、−CH=CH−、−(CH−、−CH=CH−CHCH−、−CHCH−CH=CH− 又は単結合であり、pは0、1又は2であり、XはH又はFである。)で表される化合物(以下、化合物(6)という。)を含有していることが好ましく、この化合物は大きなΔεを有し、駆動電圧の低下に効果がある。
【0034】
化合物(6)として好ましい化合物として、以下の化合物群を挙げることができる。
【化20】
Figure 2004059855
【0035】
一般式(6)から選ばれる化合物の含有量は、5質量%〜40質量%が好ましく、10質量%〜35質量%が特に好ましい。
本発明の液晶組成物は、従来の液晶組成物と比較して極めて小さいΔnと大きなΔεを両立させるものであり、携帯電話等に使用される反射型または半透過型LCD用液晶組成物として非常に有用なものである。
【0036】
【実施例】
以下、実施例を挙げて本発明を更に詳述するが、本発明はこれらの実施例に限定されるものではない。また、以下の実施例及び比較例の組成物における「%」は「質量%」を意味する。
実施例中、測定した特性は以下の通りである。
【0037】
Figure 2004059855
化合物の記載に下記の略号を使用する。
Figure 2004059855
【0038】
【化21】
Figure 2004059855
例えば、以下に示すように略号を用いる。
【化22】
Figure 2004059855
【0039】
(実施例1〜4)
ネマチック組成物No.1〜No.4を調整し、この組成物の諸特性を測定した結果を表1に、ネマチック組成物No.5〜No.8を調整し、この組成物の諸特性を測定した結果を表2に示す。
【0040】
【表1】
Figure 2004059855
【0041】
【表2】
Figure 2004059855
【0042】
(比較例1〜5)
特開2001−354963号記載のネマチック組成物No.9〜No.13を調整し、この組成物の諸特性を測定した結果を表3に示す。
【0043】
【表3】
Figure 2004059855
【0044】
実施例1〜4の液晶組成物No.1〜No.4と比較例1〜5の液晶組成物No.9〜No.13を比較すると、Δnが約0.06で同程度であるが、Δεは実施例が4.5〜4.8であるのに対し、比較例は3.8〜4.2である。この結果は本発明の液晶組成物が低電圧駆動に有効であることを示している。実施例5〜8の液晶組成物No.5〜No.8はΔεが5.5〜7.35で、実施例1〜4よりもさらに大きなΔεを有しており、より低電圧駆動に有効である。
【0045】
上記の実施例1〜8及び比較例1〜5の液晶組成物のΔnとΔεを図1にプロットした。比較例に比べて実施例1〜4が同程度のΔnで大きなΔεを示すことが明らかである。
【0046】
また実施例1〜8の液晶組成物のネマチック相下限温度(T−n)はいずれも−20℃以下であり、低温時の動作も良好であった。さらに実施例1〜8の液晶組成物の保持率(HR)は、測定温度80℃で99%以上の高い保持率を示し、80℃での恒温槽に500時間放置後の保持率も95%を達成しており、アクティブマトリクス型液晶表示素子用として有用なものであった。
【0047】
【発明の効果】
本発明の液晶組成物は、極めて小さい屈折率異方性Δnと、大きな誘電率異方性Δεを有し、AM−LCD方式で駆動される液晶表示素子用組成物として有用であり、高い電圧保持率を有するAM−LCD駆動液晶表示素子を提供することができる。
【図面の簡単な説明】
【図1】ΔnとΔεの関係[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a nematic liquid crystal composition useful as an electro-optical display material and a liquid crystal display using the same.
[0002]
[Prior art]
In a twisted nematic liquid crystal display (TN-LCD) and a super twisted nematic liquid crystal display (STN-LCD), the retardation is the product of the refractive index anisotropy (Δn) of the liquid crystal and the thickness (d) of the liquid crystal medium. The gradation (R; R = Δn · d) is set to a certain value (often set to 0.4 to 0.45 in a TN-LCD).
[0003]
In a reflective or transflective LCD, light enters a liquid crystal medium, is reflected by a rear reflector, and passes through the liquid crystal medium again, so that the optical path length is twice as long as that of a transmissive LCD. Therefore, in order to obtain the same retardation value, it is necessary to reduce Δn of the liquid crystal medium by about half.
[0004]
A low Δn liquid crystal composition can be obtained by increasing the content of a bicyclohexane derivative or the like composed of only a cyclohexane ring having a small Δn value. However, these compounds have high smectic properties, and when the content of the bicyclohexane-based compound is increased, it is difficult to lower the minimum temperature of the nematic phase (T-n), and the liquid crystal composition has a wide nematic temperature range. Was difficult to obtain. Further, a compound having a small Δn generally has a small Δε, and it is difficult to obtain a liquid crystal composition having a large Δε that can be driven at a low voltage and a low Δn.
[0005]
For example, Japanese Patent Application Laid-Open No. 2001-354963 discloses an example of a liquid crystal composition using a cyclohexyldecahydronaphthalene compound and a trifluoro compound. However, Δε is not sufficiently large, and a threshold voltage is high. However, there has not been provided a liquid crystal composition most suitable for a request for low-voltage driving.
[0006]
[Problems to be solved by the invention]
The problem to be solved by the present invention is to simultaneously have a small refractive index anisotropy Δn (Δn = 0.05 to 0.07) and a large dielectric anisotropy Δε (Δε = 4.5 to 8.0). An object of the present invention is to provide a liquid crystal composition and a liquid crystal display device using the liquid crystal composition.
[0007]
[Means for Solving the Problems]
The present inventor has studied liquid crystal compositions using various liquid crystal compounds in order to solve the above-mentioned problems. As a result, the compound represented by the general formula (1) and the compound represented by the general formula (2) It has been found that a liquid crystal composition having an extremely small refractive index anisotropy and a large dielectric anisotropy can be obtained by combining each of the compounds represented by the general formula (3) with a specific amount. Was.
[0008]
That is, the present invention provides a liquid crystal composition,
Group A: a group of compounds having a dielectric anisotropy greater than +1.5;
Group B: a group of compounds having a dielectric anisotropy of -1.5 to +1.5, and a compound represented by the general formula (1)
[0009]
Embedded image
Figure 2004059855
(Wherein R 1 is an alkyl group having 1 to 15 carbon atoms or an alkenyl group having 2 to 15 carbon atoms, and this group is unsubstituted or has at least one halogen group as a substituent. cage, and -O as if one or more CH 2 groups are O atoms each independently present in the group not linked directly to one another -, - S -, - CO -, - COO- , -OCO -, - may be replaced by OCO-O-, Z 1 is, -COO -, - OCO -, - CH 2 O -, - OCH 2 -, - CF 2 O -, - OCF 2 - , -CH 2 CH 2 -, - CF 2 CF 2 -, - CH = CH -, - (CH 2) 4 -, - CH = CH-CH 2 CH 2 -, - CH 2 CH 2 -CH = CH- Or a single bond, and Y 1 is —OCH 2 F, —OCHF 2 , —OCF 3 or —CF 3. ) Containing 2 to 30% by mass of one or more compounds selected from the compounds represented by the general formula (2) as a second component.
[0010]
Embedded image
Figure 2004059855
(Wherein R 2 is the same as defined for R 1 in general formula (1), X 1 and X 2 are each independently H, F or Cl, and Z 2 is a group represented by general formula (1) Same as the definition of Z 1 , 1 is 1 or 2, Q 1 is —OCH 2 —, —OCF 2 —, —OCHF— or —CF 2 —, and Y 2 is F or Cl. ) Containing 5 to 30% by mass of one or more compounds selected from the compounds represented by the formula (3)
[0011]
Embedded image
Figure 2004059855
[0012]
(Wherein R 3 is the same as defined for R 1 in formula (1), X 3 and X 4 are each independently H, F or Cl, and Z 3 is a group represented by formula (1) A compound represented by the same definition as that of Z 1 , m is 1 or 2, Q 2 is the same as that of Q 1 in the general formula (2), and Y 3 is F or Cl. A liquid crystal composition comprising one or more compounds selected from the group consisting of 5 to 50% by mass.
[0013]
Further, the present invention provides an active matrix liquid crystal display device using the above liquid crystal composition, wherein a switching element is provided in a pixel portion arranged in a matrix.
[0014]
BEST MODE FOR CARRYING OUT THE INVENTION
The compound represented by the general formula (1) (hereinafter, referred to as compound (1)) has an extremely small refractive index anisotropy Δn, and is also effective in lowering the driving voltage. However, the effect of reducing the minimum temperature of the nematic phase is relatively small. On the other hand, the compound represented by the general formula (2) (hereinafter, referred to as compound (2)) and the compound represented by the general formula (3) (hereinafter, referred to as compound (3)) have a relatively small Δn. And has a significant effect on lowering the driving voltage. Furthermore, since it has an effect of lowering the minimum temperature of the nematic phase as compared with a compound consisting of only a cyclohexane ring or a benzene ring, the compound (1) which easily develops smecticity and the general formula (4) or the general formula (5) described later A low nematic phase minimum temperature can be maintained even if a large amount of the compound represented by is contained.
[0015]
The liquid crystal composition of the present invention is a composition containing one or more compounds selected from the compounds (1), (2) and (3). The compound (1), the compound (2) and the compound (3) compensate for each other's drawbacks, and as a composition, have a very small Δn and a low minimum temperature range of a nematic phase, and are a liquid crystal for a reflective or semi-transmissive LCD. Very useful as a composition.
[0016]
The liquid crystal composition of the present invention preferably contains one to five kinds of compounds selected from the compound (1), and particularly preferably one to three kinds of compounds. In the formula, R 1 is preferably an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms, particularly preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group of the formulas (a) to (e). preferable.
Embedded image
Figure 2004059855
(The formula is attached to the ring at the right end.)
In the general formula (1), Z 1 is preferably a single bond, and Y 1 is preferably F.
[0017]
Compound (7) can be mentioned as a preferred compound as compound (1).
Embedded image
Figure 2004059855
[0018]
More preferred compounds include the following compounds.
Embedded image
Figure 2004059855
The content of the compound selected from the general formula (1) is preferably 5% by mass to 30% by mass, and particularly preferably 10% by mass to 20% by mass.
[0019]
General formula (8) wherein R 8 of compound (7) is directly bonded to the decahydronaphthalene ring side
Embedded image
Figure 2004059855
(Hereinafter referred to as compound (8)) tends to have poor liquid crystallinity as compared with compound (7). This tendency becomes more remarkable as the number of carbon atoms increases. Further, the viscosity of the compound (8) is higher than that of the compound (7), and is more remarkable as the number of carbon atoms increases. This means that when the number of carbon atoms increases, the decahydronaphthalene skeleton of compound (8) is located more in the center, but in the case of compound (7) of the present invention, the decahydronaphthalene skeleton is located more at the terminal and the liquid crystal It is thought that the excluded volume effect of the molecules affects the properties of the liquid crystal. For this reason, it can be said that the compound (7) showed better results.
[0020]
The compound selected from the compounds (2) is preferably contained in one to five kinds, particularly preferably in one to three kinds. In the general formula (2), R 2 is preferably an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms, and an alkyl group having 1 to 5 carbon atoms or alkenyl of the formulas (a) to (e). Groups are particularly preferred.
In the formula, X 1 and X 2 are each independently H, F or Cl, and it is preferable that at least one of X 1 and X 2 is F. Q 1 is preferably a single bond. Y 2 is preferably F.
[0021]
Preferred examples of the compound (2) include the following compounds.
Embedded image
Figure 2004059855
The content of the compound selected from the general formula (2) is preferably 5% by mass to 20% by mass, and particularly preferably 10% by mass to 20% by mass.
[0022]
The compound selected from the compounds (3) is preferably contained in one to five kinds, particularly preferably in one to three kinds. In the general formula (3), R 3 is preferably an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms, and an alkyl group having 1 to 5 carbon atoms or an alkenyl of the formulas (a) to (e). Groups are particularly preferred.
In the formula, X 3 and X 4 are each independently H, F or Cl, and it is preferable that at least one of X 3 and X 4 is F. Q 2 is preferably a single bond. Y 3 is preferably F.
[0023]
Preferred examples of the compound (3) include the following compounds.
Embedded image
Figure 2004059855
[0024]
The content of the compound selected from the general formula (3) is preferably 5% by mass to 40% by mass, and particularly preferably 10% by mass to 40% by mass.
[0025]
The present invention provides a compound having a low nematic phase by combining two compounds having different Δn and different ring structures, such as a compound (1) having a decahydronaphthalene ring and a compound (3), and a compound (2) having a tetrahydronaphthalene ring. The lower limit temperature and a small Δn are made possible at the same time.
[0026]
Decreasing Δn is useful because it can increase the cell thickness while keeping the retardation constant, thereby contributing to an improvement in panel mass productivity. Δn of the liquid crystal composition of the present invention is preferably from 0.05 to 0.07, more preferably from 0.05 to 0.060.
[0027]
The expansion of the nematic liquid crystal phase temperature range is useful for a mobile terminal display that has recently been demanded. Since the composition according to the present invention has an effect of expanding the minimum temperature of the nematic phase at which the nematic phase transforms into a crystal or smectic, the liquid crystal display device using the liquid crystal composition of the present invention can be used outdoors in a low-temperature environment. However, operation with high contrast is possible. The nematic-isotropic transition temperature of the present invention is preferably from 75 ° C to 120 ° C, and the crystal or smectic-nematic transition temperature (° C) is preferably from -80 ° C to -10 ° C, more preferably the nematic-isotropic transition temperature. 80 ° C to 120 ° C, and the crystal or smectic-nematic transition temperature (° C) is -80 ° C to -20 ° C.
[0028]
Further, since the compounds (1), (2) and (3) have an effect of suppressing an increase in the current value, they are more preferable for a liquid crystal device driven by an AM-LCD, and the liquid crystal composition of the present invention was used. The liquid crystal display element is stable even in severe outdoor heat, sunlight, and UV light environments, and is unlikely to cause display defects due to an increase in current value.
[0029]
General formula (4)
Embedded image
Figure 2004059855
(Wherein R 4 has the same definition as R 1 in general formula (1); Z 4 has the same definition as Z 1 in general formula (1); n is 1 or 2; 4 is the same as the definition of Y 1 in the general formula (1) (hereinafter, referred to as compound (4)), and has a very small refractive index anisotropy Δn like compound (1). In addition, it is effective in lowering the driving voltage. By adding the compound (4) to the composition comprising the compound (1), the compound (2) and the compound (3), a composition having a smaller Δn can be obtained.
The compound selected from the compound (4) is preferably contained in one to five kinds, particularly preferably in one to three kinds. In the formula, R 4 is preferably an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms, particularly preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group of the formulas (a) to (e). preferable.
In the general formula (4), Z 4 represents —COO—, —OCO—, — (CH 2 ) 4 —, —CH = CH—CH 2 CH 2 —, —CH 2 CH 2 —CH = CH—. Alternatively, a single bond is preferable, and n is preferably 1.
[0030]
Preferred compounds as the compound (4) include the following compounds.
Embedded image
Figure 2004059855
The content of the compound selected from the compound (4) is preferably 5% by mass to 20% by mass, and particularly preferably 5% by mass to 15% by mass.
[0031]
General formula (5)
Embedded image
Figure 2004059855
(Wherein R 5 and R 6 are the same as the definition of R 1 in the general formula (1), Z 5 is the same as the definition of Z 1 in the general formula (1), and o is 1 or 2. When the total content of the compounds represented by the following formula (hereinafter, referred to as compound (5)) is 20% by mass or more, the smectic phase stability usually caused by the compound (5) is increased, and the resulting compound is obtained. Although the temperature range of the nematic phase of the liquid crystal composition is narrowed, the liquid crystal composition of the present invention can maintain a low minimum temperature of the nematic phase. The total content of the compound (5) is preferably from 5 to 25% by mass, and particularly preferably from 10 to 20% by mass. In the formula, R 5 is preferably an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms, particularly preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group of the formulas (a) to (e). preferable.
Among the partial structures of the alkenyl groups, (a), (b), (c) and (d) are particularly preferable. In the general formula (5), Z 5 is preferably a single bond, and o is preferably 1.
[0032]
The liquid crystal composition of the present invention further has the general formula (6)
[0033]
Figure 2004059855
(Wherein R 7 is the same as defined for R 1 in formula (1), and Z 6 is —CH 2 O—, —OCH 2 —, —CF 2 O—, —OCF 2 —, —CH 2 CH 2 -, - CF 2 CF 2 -, - CH = CH -, - (CH 2) 4 -, - CH = CH-CH 2 CH 2 -, - CH 2 CH 2 -CH = CH- or a single bond And Z 7 represents —COO—, —OCO—, —CH 2 O—, —OCH 2 —, —CF 2 O—, —OCF 2 —, —CH 2 CH 2 —, or —CF 2 CF 2 —. , -CH = CH -, - ( CH 2) 4 -, - CH = CH-CH 2 CH 2 -, - a CH 2 CH 2 -CH = CH- or a single bond, p is 0, 1 or 2 There, X 5 is H or F.) the compounds represented by (hereinafter, compound (6) is preferably contains a.) of this Gobutsu has a large [Delta] [epsilon], is effective in lowering the driving voltage.
[0034]
Preferred compounds as the compound (6) include the following compounds.
Embedded image
Figure 2004059855
[0035]
The content of the compound selected from the general formula (6) is preferably 5% by mass to 40% by mass, and particularly preferably 10% by mass to 35% by mass.
The liquid crystal composition of the present invention achieves both a very small Δn and a large Δε as compared with the conventional liquid crystal composition, and is very useful as a liquid crystal composition for a reflective or semi-transmissive LCD used for a mobile phone or the like. It is useful for
[0036]
【Example】
Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. Further, “%” in the compositions of the following Examples and Comparative Examples means “% by mass”.
The characteristics measured in the examples are as follows.
[0037]
Figure 2004059855
The following abbreviations are used in describing the compounds.
Figure 2004059855
[0038]
Embedded image
Figure 2004059855
For example, abbreviations are used as shown below.
Embedded image
Figure 2004059855
[0039]
(Examples 1 to 4)
Nematic composition No. 1 to No. No. 4 was adjusted, and the results of measuring various properties of this composition are shown in Table 1 in Table 1. 5-No. Table 2 shows the results obtained by adjusting No. 8 and measuring various properties of this composition.
[0040]
[Table 1]
Figure 2004059855
[0041]
[Table 2]
Figure 2004059855
[0042]
(Comparative Examples 1 to 5)
Nematic composition No. 1 described in JP-A-2001-354963. 9-No. Table 3 shows the results obtained by adjusting the composition No. 13 and measuring various properties of this composition.
[0043]
[Table 3]
Figure 2004059855
[0044]
The liquid crystal composition Nos. 1 to No. 4 and the liquid crystal compositions Nos. 1 to 5 of Comparative Examples 1 to 5. 9-No. When 13 is compared, Δn is about 0.06, which is almost the same, but Δε is 4.5 to 4.8 in the example, while 3.8 to 4.2 in the comparative example. This result indicates that the liquid crystal composition of the present invention is effective for driving at a low voltage. The liquid crystal composition Nos. 5-No. 8 has a ΔΔ of 5.5 to 7.35, which is larger than that of Examples 1 to 4, and is effective for lower voltage driving.
[0045]
Δn and Δε of the liquid crystal compositions of Examples 1 to 8 and Comparative Examples 1 to 5 are plotted in FIG. It is clear that Examples 1-4 show a large Δε at the same Δn as compared with the comparative example.
[0046]
In addition, the liquid crystal compositions of Examples 1 to 8 all had a nematic phase minimum temperature (Tn) of -20 ° C or lower, and the operation at low temperatures was also good. Further, the retention (HR) of the liquid crystal compositions of Examples 1 to 8 showed a high retention of 99% or more at a measurement temperature of 80 ° C., and the retention after being left in a constant temperature bath at 80 ° C. for 500 hours was 95%. And was useful as an active matrix type liquid crystal display device.
[0047]
【The invention's effect】
The liquid crystal composition of the present invention has a very small refractive index anisotropy Δn and a large dielectric anisotropy Δε, is useful as a composition for a liquid crystal display element driven by an AM-LCD method, and has a high voltage. It is possible to provide an AM-LCD driven liquid crystal display device having a retention ratio.
[Brief description of the drawings]
FIG. 1. Relationship between Δn and Δε

Claims (7)

液晶組成物が、
A群:+1.5より大きい誘電率異方性を有する化合物群と、
B群:−1.5〜+1.5の誘電率異方性を有する化合物群
とから成り、A群の化合物群の第一成分として一般式(1)
Figure 2004059855
(式中Rは、炭素数1〜15のアルキル基又は炭素数2〜15のアルケニル基であり、この基は非置換であるか、あるいは置換基として少なくとも1個のハロゲン基を有しており、そしてこれらの基中に存在する1個又は2個以上のCH基はそれぞれ独立してO原子が相互に直接結合しないものとして−O−、−S−、−CO−、−COO−、−OCO−、−OCO−O−により置き換えられても良く、Zは、−COO−、−OCO−、−CHO−、−OCH−、−CFO−、−OCF−、−CHCH−、−CFCF−、−CH=CH−、−(CH−、−CH=CH−CHCH−、−CHCH−CH=CH− 又は単結合であり、Yは−OCHF、−OCHF、−OCF又は−CFである。)で表される化合物から選ばれる化合物を1種又は2種以上を2〜30質量%含有し、第二成分として一般式(2)
Figure 2004059855
(式中Rは、一般式(1)のRの定義と同じであり、X、Xはそれぞれ独立してH、F又はClであり、Zは、一般式(1)のZの定義と同じであり、lは1又は2であり、Qは−OCH−、−OCF−、−OCHF−又は−CF−であり、YはF又はClである。)で表される化合物から選ばれる化合物を1種又は2種以上を5〜30質量%含有し、第三成分として一般式(3)
Figure 2004059855
(式中Rは、一般式(1)のRの定義と同じであり、X、Xはそれぞれ独立してH、F又はClであり、Zは、一般式(1)のZの定義と同じであり、mは1又は2であり、Qは一般式(2)のQの定義と同じであり、YはF又はClである。)で表される化合物から選ばれる化合物を1種又は2種以上を5〜50質量%含有することを特徴とする液晶組成物。
The liquid crystal composition is
Group A: a group of compounds having a dielectric anisotropy greater than +1.5;
Group B: a group of compounds having a dielectric anisotropy of -1.5 to +1.5, and a compound represented by the general formula (1)
Figure 2004059855
(Wherein R 1 is an alkyl group having 1 to 15 carbon atoms or an alkenyl group having 2 to 15 carbon atoms, and this group is unsubstituted or has at least one halogen group as a substituent. cage, and -O as if one or more CH 2 groups are O atoms each independently present in the group not linked directly to one another -, - S -, - CO -, - COO- , -OCO -, - may be replaced by OCO-O-, Z 1 is, -COO -, - OCO -, - CH 2 O -, - OCH 2 -, - CF 2 O -, - OCF 2 - , -CH 2 CH 2 -, - CF 2 CF 2 -, - CH = CH -, - (CH 2) 4 -, - CH = CH-CH 2 CH 2 -, - CH 2 CH 2 -CH = CH- Or a single bond, and Y 1 is —OCH 2 F, —OCHF 2 , —OCF 3 or —CF 3. ) Containing 2 to 30% by mass of one or more compounds selected from the compounds represented by the general formula (2) as a second component.
Figure 2004059855
(Wherein R 2 is the same as defined for R 1 in general formula (1), X 1 and X 2 are each independently H, F or Cl, and Z 2 is a group represented by general formula (1) Same as the definition of Z 1 , 1 is 1 or 2, Q 1 is —OCH 2 —, —OCF 2 —, —OCHF— or —CF 2 —, and Y 2 is F or Cl. ) Containing 5 to 30% by mass of one or more compounds selected from the compounds represented by the formula (3)
Figure 2004059855
(Wherein R 3 is the same as defined for R 1 in formula (1), X 3 and X 4 are each independently H, F or Cl, and Z 3 is a group represented by formula (1) A compound represented by the same definition as that of Z 1 , m is 1 or 2, Q 2 is the same as that of Q 1 in the general formula (2), and Y 3 is F or Cl. A liquid crystal composition comprising 5 to 50% by mass of one or more compounds selected from the group consisting of:
ネマチック−アイソトロピック転移温度が75℃〜120℃であり、クリスタル又はスメクチック−ネマチック転移温度(℃)が−80℃〜−10℃であり、屈折率の異方性が0.05〜0.07であり、誘電率の異方性が4.5〜8.0であることを特徴とする請求項1記載の液晶組成物。The nematic-isotropic transition temperature is from 75 ° C to 120 ° C, the crystal or smectic-nematic transition temperature (° C) is from -80 ° C to -10 ° C, and the anisotropy of the refractive index is from 0.05 to 0.07. The liquid crystal composition according to claim 1, wherein the anisotropy of the dielectric constant is 4.5 to 8.0. 前記A群の第四成分として一般式(4)
Figure 2004059855
(式中Rは、一般式(1)のRの定義と同じであり、Zは、一般式(1)のZの定義と同じであり、nは1又は2であり、Yは一般式(1)のYの定義と同じでる。)で表される化合物から選ばれる化合物を1種又は2種以上を含有する請求項1又は2に記載の液晶組成物。
General formula (4) as a fourth component of the group A
Figure 2004059855
(Wherein R 4 has the same definition as R 1 in general formula (1); Z 4 has the same definition as Z 1 in general formula (1); n is 1 or 2; 4 is the same as the definition of Y 1 in formula (1).) The liquid crystal composition according to claim 1, comprising one or more compounds selected from compounds represented by the formula:
前記B群の化合物として一般式(5)
Figure 2004059855
(式中R及びRは、一般式(1)のRの定義と同じであり、Zは、一般式(1)のZの定義と同じであり、oは1又は2である。)で表される化合物から選ばれる化合物を1種もしくは2種以上を含有する請求項1〜3のいずれかに記載の液晶組成物。
The compound of the group B is represented by the general formula (5)
Figure 2004059855
(Wherein R 5 and R 6 are the same as the definition of R 1 in the general formula (1), Z 5 is the same as the definition of Z 1 in the general formula (1), and o is 1 or 2. The liquid crystal composition according to any one of claims 1 to 3, comprising one or more compounds selected from the compounds represented by the formula (1).
前記A群の第五成分として一般式(6)
Figure 2004059855
(式中Rは、一般式(1)のRの定義と同じであり、Zは、−CHO−、−OCH−、−CFO−、−OCF−、−CHCH−、−CFCF−、−CH=CH−、−(CH−、−CH=CH−CHCH−、−CHCH−CH=CH− 又は単結合であり、Zは、−COO−、−OCO−、−CHO−、−OCH−、−CFO−、−OCF−、−CHCH−、−CFCF−、−CH=CH−、−(CH−、−CH=CH−CHCH−、−CHCH−CH=CH− 又は単結合であり、pは0、1又は2であり、XはH又はFである。)で表される化合物から選ばれる化合物を1種もしくは2種以上を含有する請求項1〜4のいずれかに記載の液晶組成物。
General formula (6) as a fifth component of the group A
Figure 2004059855
(Wherein R 7 is the same as defined for R 1 in formula (1), and Z 6 is —CH 2 O—, —OCH 2 —, —CF 2 O—, —OCF 2 —, —CH 2 CH 2 -, - CF 2 CF 2 -, - CH = CH -, - (CH 2) 4 -, - CH = CH-CH 2 CH 2 -, - CH 2 CH 2 -CH = CH- or a single bond And Z 7 represents —COO—, —OCO—, —CH 2 O—, —OCH 2 —, —CF 2 O—, —OCF 2 —, —CH 2 CH 2 —, or —CF 2 CF 2 —. , -CH = CH -, - ( CH 2) 4 -, - CH = CH-CH 2 CH 2 -, - a CH 2 CH 2 -CH = CH- or a single bond, p is 0, 1 or 2 There, X 5 is H or F. the compound selected from compounds represented by) containing more than one or two of claims 1 to 4 The liquid crystal composition according to any misalignment.
一般式(1)の化合物として、Zが単結合である一般式(7)
Figure 2004059855
(式中Rは、一般式(1)のRの定義と同じであり、Yは一般式(1)のYの定義と同じである。)から選ばれる1種もしくは2種以上の化合物を含有する請求項1〜5のいずれかに記載の液晶組成物。
As the compound of the general formula (1), the general formula (7) wherein Z 1 is a single bond
Figure 2004059855
(In the formula, R 8 is the same as the definition of R 1 in the general formula (1), and Y 5 is the same as the definition of Y 1 in the general formula (1).) The liquid crystal composition according to any one of claims 1 to 5, comprising a compound of the formula:
請求項1〜6のいずれかに記載の液晶組成物を用いたアクティブマトリクス型液晶表示素子。An active matrix liquid crystal display device using the liquid crystal composition according to claim 1.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006037005A (en) * 2004-07-29 2006-02-09 Dainippon Ink & Chem Inc Nematic liquid crystal composition
JP2020164784A (en) * 2019-03-26 2020-10-08 Jnc株式会社 Liquid crystal composition and liquid crystal display element

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006037005A (en) * 2004-07-29 2006-02-09 Dainippon Ink & Chem Inc Nematic liquid crystal composition
JP2020164784A (en) * 2019-03-26 2020-10-08 Jnc株式会社 Liquid crystal composition and liquid crystal display element
CN111748358A (en) * 2019-03-26 2020-10-09 捷恩智株式会社 Liquid crystal composition and liquid crystal display element

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