JP5135703B2 - Nematic liquid crystal composition and liquid crystal display device using the same - Google Patents
Nematic liquid crystal composition and liquid crystal display device using the same Download PDFInfo
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- 239000004973 liquid crystal related substance Substances 0.000 title claims description 42
- 239000000203 mixture Substances 0.000 title claims description 41
- 239000004988 Nematic liquid crystal Substances 0.000 title claims description 22
- 125000004432 carbon atom Chemical group C* 0.000 claims description 109
- 125000000217 alkyl group Chemical group 0.000 claims description 35
- 150000001875 compounds Chemical class 0.000 claims description 32
- 125000003342 alkenyl group Chemical group 0.000 claims description 30
- 229910052736 halogen Inorganic materials 0.000 claims description 28
- 125000003545 alkoxy group Chemical group 0.000 claims description 23
- 125000003302 alkenyloxy group Chemical group 0.000 claims description 21
- 125000005843 halogen group Chemical group 0.000 claims description 20
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 18
- 229910052731 fluorine Inorganic materials 0.000 claims description 17
- 125000001153 fluoro group Chemical group F* 0.000 claims description 15
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 13
- 150000002367 halogens Chemical class 0.000 claims description 8
- 101001053401 Arabidopsis thaliana Acid beta-fructofuranosidase 3, vacuolar Proteins 0.000 claims description 4
- 101001053395 Arabidopsis thaliana Acid beta-fructofuranosidase 4, vacuolar Proteins 0.000 claims description 4
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 125000004434 sulfur atom Chemical group 0.000 claims description 2
- 230000005611 electricity Effects 0.000 description 13
- 230000003068 static effect Effects 0.000 description 13
- 238000000034 method Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 230000005684 electric field Effects 0.000 description 4
- 230000002040 relaxant effect Effects 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000004986 Cholesteric liquid crystals (ChLC) Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000003983 crown ethers Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- NLMDJJTUQPXZFG-UHFFFAOYSA-N 1,4,10,13-tetraoxa-7,16-diazacyclooctadecane Chemical compound C1COCCOCCNCCOCCOCCN1 NLMDJJTUQPXZFG-UHFFFAOYSA-N 0.000 description 1
- 125000004955 1,4-cyclohexylene group Chemical group [H]C1([H])C([H])([H])C([H])([*:1])C([H])([H])C([H])([H])C1([H])[*:2] 0.000 description 1
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 1
- 125000005653 3,5-difluoro-1,4-phenylene group Chemical group [H]C1=C(F)C([*:2])=C(F)C([H])=C1[*:1] 0.000 description 1
- 125000005451 3-fluoro-1,4-phenylene group Chemical group [H]C1=C([*:1])C([H])=C(F)C([*:2])=C1[H] 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- -1 Pyrimidine-2,5-diyl group Chemical group 0.000 description 1
- 239000004990 Smectic liquid crystal Substances 0.000 description 1
- 229910052799 carbon Chemical group 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000002739 cryptand Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000004815 dispersion polymer Substances 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000005686 electrostatic field Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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Description
本願発明は、静電気等の一時的な電圧の印加に対する挙動を改善する効果を有するネマチック液晶組成物及び、これを用いた液晶表示素子に関する。 The present invention relates to a nematic liquid crystal composition having an effect of improving the behavior against application of a temporary voltage such as static electricity, and a liquid crystal display device using the same.
ツイストネマチック（TN）、超ねじれツイストネマチック(STN)又はアクティブマトリックスを初めとする液晶表示素子の製造工程において、液晶表示素子表面に貼られた保護フィルムを剥離した際、素子中に静電気の電場が発生する。この電場はしばしば非点灯部の液晶組成物を配向させ、すなわち点灯状態となり、電場が放電するまでその配向状態は継続する。この電場が放電するまでに要する時間は無視できず、製造工程に限らず検査工程あるいは素子表面の汚れの拭き取り作業等の出荷工程までも、その作業を中断しなければならないようになり、タクト時間の悪化を招くことになる。 In the manufacturing process of liquid crystal display elements such as twisted nematic (TN), super twisted nematic (STN) or active matrix, when the protective film affixed to the surface of the liquid crystal display element is peeled off, an electrostatic field is generated in the element. Occur. This electric field often aligns the liquid crystal composition in the non-lighted portion, i.e., is in a lit state, and the aligned state continues until the electric field is discharged. The time required for this electric field to discharge is not negligible, and the work must be interrupted not only in the manufacturing process but also in the inspection process or the shipping process such as wiping off the dirt on the element surface. Will be worsened.
このような問題は、液晶組成物の比抵抗値を低下させることにより解決できることが(特許文献1)。つまり、比抵抗値の低い液晶組成物においては、静電気等の一時的な電圧の印加があっても、速やかに電圧無印加時の配向状態を復元させることができる。例えば、ネマチック液晶表示素子における液晶組成物の比抵抗値は、通常1×1011Ωcm以上であるが、これを1×1010Ωcm台まで低下させると、緩和は通常の作業が行える程度に速くなり、その効果を確認できるようになる。さらに1×109Ωcm台まで低下させると、緩和は非常に速くなり、静電気等の一時的な電圧の印加があっても、配向状態の変化は殆ど確認できないようになる。しかしながら、1×1011Ωcm以下となる液晶組成物を用いた液晶表示素子においては、しばしば消費電力の増大、さらには電気的に短絡し、文字の焼き付き等不良表示の原因となることがある。従って、適度に大きい比抵抗値を有し且つ液晶表示素子の静電気等の一時的な電圧の印加に対する挙動、すなわち静電気等の一時的な電圧の印加に対する緩和の十分速い液晶組成物の開発が求められている。 Such a problem can be solved by reducing the specific resistance value of the liquid crystal composition (Patent Document 1). That is, in the liquid crystal composition having a low specific resistance value, the alignment state when no voltage is applied can be quickly restored even when a temporary voltage such as static electricity is applied. For example, the specific resistance value of the liquid crystal composition in the nematic liquid crystal display element is usually 1 × 10 11 Ωcm or more, but if this is reduced to the 1 × 10 10 Ωcm range, the relaxation is fast enough to perform normal work. It becomes possible to confirm the effect. Furthermore, when the voltage is lowered to the 1 × 10 9 Ωcm range, the relaxation becomes very fast, and even if a temporary voltage such as static electricity is applied, almost no change in the alignment state can be confirmed. However, in a liquid crystal display device using a liquid crystal composition of 1 × 10 11 Ωcm or less, power consumption often increases, and electrical short-circuiting may cause defective display such as character burn-in. Therefore, development of a liquid crystal composition that has a reasonably large specific resistance value and that is sufficiently fast to relax against the application of a temporary voltage such as static electricity of a liquid crystal display element, that is, the application of a temporary voltage such as static electricity is required. It has been.
上述の液晶組成物における静電気等の一時的な電圧の印加を緩和させる方法として、例えば、クリプタンド(Cryptand)等のイオン性物質を添加する方法が挙げられる(特許文献2)。しかしながら、この液晶組成物中のイオン性成分は、注入口等の一部分において液晶表示素子中のポリイミド等の高分子膜に吸着されてしまい、しばしば表示ムラの原因となるという問題を有していた。 As a method for relaxing the application of a temporary voltage such as static electricity in the liquid crystal composition described above, for example, a method of adding an ionic substance such as cryptand (Patent Document 2) can be mentioned. However, the ionic component in the liquid crystal composition is adsorbed by a polymer film such as polyimide in the liquid crystal display element in a part of the injection port or the like, which often causes display unevenness. .
同様に一時的な電圧の印加を緩和させる方法として、エチレングリコール等の非イオン系界面活性剤及びこれらの共重合体を添加する方法が挙げられる(特許文献3)。しかしながら、これらは帯電防止の機構上、液晶や配向膜中のイオン量や配向状態により効果が左右されやすく、十分な帯電防止効果が得られない場合もあり、その効果を十分に得るため大量に添加すると、添加割合の増加に伴い、液晶表示素子の信頼性を示す項目の一つである、液晶組成物のネマチック−イソトロピック相転移温度が大幅に低下しまうという問題を有していた。 Similarly, as a method of relaxing application of a temporary voltage, there is a method of adding a nonionic surfactant such as ethylene glycol and a copolymer thereof (Patent Document 3). However, these effects are easily influenced by the amount of ions in the liquid crystal and the alignment film and the alignment state due to the antistatic mechanism, and there are cases where sufficient antistatic effects cannot be obtained. When added, there is a problem that the nematic-isotropic phase transition temperature of the liquid crystal composition, which is one of the items showing the reliability of the liquid crystal display element, is significantly lowered with the increase of the addition ratio.
あるいは、同様に一時的な電圧の印加を緩和させる方法として、環状ポリエーテル等いわゆるクラウンエーテルを添加する方法が挙げられる(特許文献4)。しかしながら、クラウンエーテル類は人間の皮膚あるいは目に対して著しい刺激を与える等の強い毒性があり、液晶表示素子製造等における作業環境に危険性を生じるおそれがあるという問題を有していた。 Alternatively, as a method for relaxing the temporary application of voltage, a method of adding a so-called crown ether such as a cyclic polyether can be cited (Patent Document 4). However, crown ethers have a strong toxicity such as giving significant irritation to human skin or eyes, and have a problem that there is a risk of causing a danger in a working environment in manufacturing a liquid crystal display element.
以上のように、液晶組成物における静電気等の一時的な電圧の印加を緩和させる方法として、添加剤を用いる方法では種々の問題を伴い課題の解決に至っていないのが現状であった。 As described above, as a method for relaxing application of a temporary voltage such as static electricity in the liquid crystal composition, the method using an additive has various problems and has not yet been solved.
一方、光学活性化合物を液晶組成物に添加することは既に知られており、TN-LCD又はSTN-LCDの何れにも使用されている。この目的は、液晶組成物に自発的に螺旋配列性を付与するためのカイラルドーパントとして使用することにより、パネルの表示ムラを低減させることである(特許文献5)。しかしながら、特定の光学活性化合物と特定の液晶材料の選択により、前述のような添加剤を用いることなく静電気等の一時的な電圧の印加を緩和させることができることは知られていない。 On the other hand, it is already known to add an optically active compound to a liquid crystal composition, and it is used for either TN-LCD or STN-LCD. The purpose is to reduce display unevenness of the panel by using it as a chiral dopant for spontaneously imparting a helical alignment to a liquid crystal composition (Patent Document 5). However, it is not known that the application of a temporary voltage such as static electricity can be mitigated by using a specific optically active compound and a specific liquid crystal material without using the additive as described above.
本願発明の課題は、比抵抗を大幅に低下させる材料を使用することなく、適度に大きい比抵抗値を有し且つ液晶表示素子の静電気等の一時的な電圧の印加に対する挙動を改善する液晶組成物を提供することである。すなわち、本願発明は静電気等の一時的な電圧の印加に対する緩和の十分速い液晶組成物を提供する。 An object of the present invention is to provide a liquid crystal composition having a reasonably large specific resistance value and improving the behavior of a liquid crystal display element with respect to temporary application of voltage such as static electricity without using a material that greatly reduces specific resistance. Is to provide things. That is, the present invention provides a liquid crystal composition that is sufficiently fast to relax against the application of a temporary voltage such as static electricity.
本願発明者は、種々の光学活性化合物と液晶化合物を組み合わせたネマチック液晶組成物を検討した結果、本願発明を完成するに至った。
すなわち、本願発明は一般式(I)
As a result of studying a nematic liquid crystal composition in which various optically active compounds and liquid crystal compounds are combined, the present inventors have completed the present invention.
That is, the present invention relates to the general formula (I)
（式中、R1は、水素原子、炭素原子数1〜12のアルキル基、炭素原子数1〜12のアルコキシ基、炭素原子数2〜12のアルケニル基、炭素原子数2〜12のアルケニルオキシ基、ハロゲンにより置換された炭素原子数1〜12のアルキル基、ハロゲンにより置換された炭素原子数1〜12のアルコキシ基、ハロゲンにより置換された炭素原子数2〜12のアルケニル基又はハロゲンにより置換された炭素原子数2〜12のアルケニルオキシ基を表し、R2*は、光学活性基を表し、xは、0、1又は2を表す。）で表される化合物を1種以上含有し、
一般式(II)又は一般式(III)
Wherein R 1 is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an alkenyloxy having 2 to 12 carbon atoms. Group, an alkyl group having 1 to 12 carbon atoms substituted by halogen, an alkoxy group having 1 to 12 carbon atoms substituted by halogen, an alkenyl group having 2 to 12 carbon atoms substituted by halogen, or halogen The alkenyloxy group having 2 to 12 carbon atoms, R 2 * represents an optically active group, and x represents 0, 1 or 2).
General formula (II) or general formula (III)
（式中、R3は水素原子、炭素原子数1〜12のアルキル基、少なくとも一つのハロゲンにより置換された炭素原子数1〜12のアルキル基、炭素原子数2〜12のアルケニル基又は少なくとも一つのハロゲンにより置換された炭素原子数2〜12のアルケニル基を表し、これらの基中に存在する1個又は2個以上のCH2基はそれぞれ独立的にO原子が相互に直接結合しないものとして酸素原子、硫黄原子、-CO-、-COO-、-OCO-又は-OCO-O-により置き換えられてもよく、L1及びL3はそれぞれ独立的に、水素原子、フッ素原子又は-Clを表し、L2は、フッ素原子、-Cl、-CN、-CF3、-OCH2F、-OCHF2、-OCF3又は-CH2CF3を表す。）
で表される化合物を1種以上含有することを特徴とするネマチック液晶組成物及び当該化合物を用いた液晶表示素子を提供する。
Wherein R 3 is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkyl group having 1 to 12 carbon atoms substituted with at least one halogen, an alkenyl group having 2 to 12 carbon atoms, or at least one Represents an alkenyl group having 2 to 12 carbon atoms substituted by two halogens, and one or two or more CH 2 groups present in these groups are each independently defined such that O atoms are not directly bonded to each other. Oxygen atom, sulfur atom, -CO-, -COO-, -OCO- or -OCO-O- may be substituted, and L 1 and L 3 each independently represents a hydrogen atom, a fluorine atom or -Cl. L 2 represents a fluorine atom, —Cl, —CN, —CF 3 , —OCH 2 F, —OCHF 2 , —OCF 3 or —CH 2 CF 3 )
A nematic liquid crystal composition containing at least one compound represented by the formula: and a liquid crystal display device using the compound are provided.
本願発明のネマチック液晶組成物は、適度に大きい比抵抗値を有し、静電気等の一時的な電圧の印加に対する緩和の十分速いため帯電防止性に優れ、製造工程における電場の放電時間を短縮し液晶表示素子の効率的な製造を可能とする。 The nematic liquid crystal composition of the present invention has a reasonably large specific resistance value and is excellent in antistatic property because of sufficiently fast relaxation against application of a temporary voltage such as static electricity, and shortens the electric field discharge time in the manufacturing process. Enables efficient production of liquid crystal display elements.
以下に本願発明の一例について説明する。
本願発明において一般式(I)で表される光学活性化合物をネマチック液晶組成物に1種以上含有することで、従来の液晶組成物に比べ、液晶表示素子の静電気等の一時的な電圧の印加に対する挙動を改善することが可能であり、非常に有用である。
An example of the present invention will be described below.
In the present invention, by containing one or more optically active compounds represented by the general formula (I) in the nematic liquid crystal composition, application of a temporary voltage such as static electricity of the liquid crystal display element as compared with the conventional liquid crystal composition. It is possible to improve the behavior against and is very useful.
一般式(I)において、
R1は、水素原子、炭素原子数1〜12のアルキル基、炭素原子数1〜12のアルコキシ基、炭素原子数2〜12のアルケニル基、炭素原子数2〜12のアルケニルオキシ基、ハロゲンにより置換された炭素原子数1〜12のアルキル基、ハロゲンにより置換された炭素原子数1〜12のアルコキシ基、ハロゲンにより置換された炭素原子数2〜12のアルケニル基又はハロゲンにより置換された炭素原子数2〜12のアルケニルオキシ基を表すが、炭素原子数1〜12のアルキル基、炭素原子数1〜12のアルコキシ基、炭素原子数2〜12のアルケニル基又は炭素原子数2〜12のアルケニルオキシ基が好ましく、炭素原子数1〜7のアルキル基、炭素原子数1〜7のアルコキシ基がより好ましく、炭素原子数1〜7のアルキル基が特に好ましい、
R2は光学活性基を表し、種々の公知の光学活性基を表すが、具体的に基は以下の一般式
In general formula (I),
R 1 is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkenyloxy group having 2 to 12 carbon atoms, or halogen. Substituted alkyl group having 1 to 12 carbon atoms, alkoxy group having 1 to 12 carbon atoms substituted by halogen, alkenyl group having 2 to 12 carbon atoms substituted by halogen, or carbon atom substituted by halogen Represents an alkenyloxy group having 2 to 12 carbon atoms, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms An oxy group is preferable, an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms is more preferable, and an alkyl group having 1 to 7 carbon atoms is particularly preferable.
R 2 represents an optically active group and represents various known optically active groups. Specifically, the group has the following general formula:
（式中、Ra及びRbはそれぞれ独立的に炭素原子数1〜12のアルキル基を表し、該アルキル基は炭素原子数１〜５のアルキル基で更に置換されていても良いが、Ra及びRbは同一の置換基とはならない。）で表される置換基が好ましい。
xは、0、1又は2を表すが、1が好ましい。
一般式(I)で表される化合物はさらに具体的には一般式(I-1)
(In the formula, R a and R b each independently represents an alkyl group having 1 to 12 carbon atoms, and the alkyl group may be further substituted with an alkyl group having 1 to 5 carbon atoms. a and R b are not the same substituent).
x represents 0, 1 or 2, with 1 being preferred.
More specifically, the compound represented by the general formula (I) is represented by the general formula (I-1)
（式中、R1は、水素原子、炭素原子数1〜12のアルキル基、炭素原子数1〜12のアルコキシ基、炭素原子数2〜12のアルケニル基又は炭素原子数2〜12のアルケニルオキシ基を表し、Qは単結合又は炭素原子数1〜3のアルキレン基を表し、m及びnはそれぞれ独立的に1〜12の整数を表すが、ｍ及びｎは同じ数とはならず、xは、0、1又は2を表す。）
で表される化合物が好ましい。
(In the formula, R 1 is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an alkenyloxy having 2 to 12 carbon atoms. Q represents a single bond or an alkylene group having 1 to 3 carbon atoms, m and n each independently represents an integer of 1 to 12, but m and n are not the same number, x Represents 0, 1 or 2.)
The compound represented by these is preferable.
一般式(I-1)において、R1は、炭素原子数1〜7のアルキル基、炭素原子数1〜7のアルコシキ基、炭素原子数2〜7のアルケニル基又は炭素原子数2〜7のアルケニルオキシ基を表すことが好ましく、炭素原子数1〜7のアルキル基がさらに好ましい。
Qは単結合又はメチレン基が好ましく、単結合がより好ましい。
これら光学活性化合物の含有率は、0.01〜20質量％の範囲が好ましく、0.1〜10質量％の範囲がより好ましい。
In the general formula (I-1), R 1 is an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, or an alkyl group having 2 to 7 carbon atoms. It preferably represents an alkenyloxy group, more preferably an alkyl group having 1 to 7 carbon atoms.
Q is preferably a single bond or a methylene group, and more preferably a single bond.
The content of these optically active compounds is preferably in the range of 0.01 to 20% by mass, more preferably in the range of 0.1 to 10% by mass.
本願発明のネマチック液晶組成物は、一般式(II)又は一般式(III)水素原子フッ素原子フッ素原子で表される化合物を1種以上含有するが、1〜10種含有することが好ましく、1〜5種含有することがさらに好ましい。一般式(II)及び一般式(III)において、、R3は、炭素原子数1〜7のアルキル基、炭素原子数1〜7アルコシキ基、炭素原子数2〜7のアルケニル基又は炭素原子数2〜7のアルケニルオキシ基を表すことが好ましく、炭素原子数1〜5の直鎖型アルキル基及び炭素原子数2〜5の直鎖型アルケニル基がさらに好ましい。 The nematic liquid crystal composition of the present invention contains at least one compound represented by general formula (II) or general formula (III) hydrogen atom fluorine atom fluorine atom, but preferably contains 1 to 10 types, It is more preferable to contain ~ 5 kinds. In General Formula (II) and General Formula (III), R 3 is an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, or the number of carbon atoms. It preferably represents a 2-7 alkenyloxy group, more preferably a linear alkyl group having 1-5 carbon atoms and a linear alkenyl group having 2-5 carbon atoms.
L2は、フッ素原子、-CN、-CF3又は-OCF3を表すことが好ましく、フッ素原子又は-CNがより好ましい。
一般式(II)又は（III）で表される化合物は、具体的には、一般式(II-1)、一般式(II-2)、一般式(II-3)、一般式(III-1)、一般式(III-2)及び一般式(III-3)
L 2 preferably represents a fluorine atom, —CN, —CF 3 or —OCF 3, and more preferably a fluorine atom or —CN.
Specific examples of the compound represented by the general formula (II) or (III) include the general formula (II-1), the general formula (II-2), the general formula (II-3), and the general formula (III- 1), general formula (III-2) and general formula (III-3)
（式中、R3は、炭素原子数1〜7のアルキル基、炭素原子数1〜7のアルコキシ基、炭素原子数2〜7のアルケニル基又は炭素原子数2〜7のアルケニルオキシ基を表す。）で表される化合物が好ましい。
一般式(II)及び、一般式(III)で表される化合物の含有率は3〜70質量％の範囲が好ましく、15〜50質量％の範囲がより好ましく、5〜40質量％がより好ましい。
(In the formula, R 3 represents an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, or an alkenyloxy group having 2 to 7 carbon atoms. .) Is preferred.
The content of the compound represented by the general formula (II) and the general formula (III) is preferably in the range of 3 to 70% by mass, more preferably in the range of 15 to 50% by mass, and more preferably 5 to 40% by mass. .
本願発明のネマチック液晶組成物は、一般式(V-1)、一般式(V-2)、一般式(V-3)、一般式(V-4)、一般式(V-5)、及び一般式(V-6)で表される化合物からなる群から選ばれる化合物をさらに含有することが好ましい。 The nematic liquid crystal composition of the present invention has general formula (V-1), general formula (V-2), general formula (V-3), general formula (V-4), general formula (V-5), and It is preferable to further contain a compound selected from the group consisting of compounds represented by formula (V-6).
(式中、R6は炭素原子数1〜12のアルキル基、炭素原子数1〜12のアルコキシ基、炭素原子数2〜12のアルケニル基又は炭素原子数2〜12のアルケニルオキシ基を表し、Y1及びY2はそれぞれ独立的に水素原子、フッ素原子又はメチル基を表し、L1及びL3はそれぞれ独立的に水素原子又はフッ素原子を表し、L2はフッ素原子、-CN、-CF3、-OCH2F、-OCHF2、-OCF3又は-CH2CF3を表す。)
一般式(V-1)、一般式(V-2)、一般式(V-3)、一般式(V-4)、一般式(V-5)、及び一般式(V-6)において、Y1及びY2はそれぞれ独立的に、水素原子又はフッ素原子が好ましく、水素原子がより好ましい。
一般式(V-1)、一般式(V-2)、一般式(V-3)、一般式(V-4)、一般式(V-5)、及び一般式(V-6)で表される化合物の含有率は5〜70質量％の範囲が好ましく、、10〜60質量％の範囲が好ましく、10〜50質量％がより好ましい。
(In the formula, R 6 represents an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an alkenyloxy group having 2 to 12 carbon atoms, Y 1 and Y 2 each independently represent a hydrogen atom, a fluorine atom or a methyl group, L 1 and L 3 each independently represent a hydrogen atom or a fluorine atom, and L 2 represents a fluorine atom, —CN, —CF 3 represents -OCH 2 F, -OCHF 2, -OCF 3 or -CH 2 CF 3.)
In general formula (V-1), general formula (V-2), general formula (V-3), general formula (V-4), general formula (V-5), and general formula (V-6), Y 1 and Y 2 are each independently preferably a hydrogen atom or a fluorine atom, more preferably a hydrogen atom.
Expressed by general formula (V-1), general formula (V-2), general formula (V-3), general formula (V-4), general formula (V-5), and general formula (V-6) The content of the compound to be formed is preferably in the range of 5 to 70% by mass, preferably in the range of 10 to 60% by mass, and more preferably in the range of 10 to 50% by mass.
さらに、一般式(VI-1)、一般式(VI-2)、一般式(VI-3)、一般式(VI-4)、一般式(VI-5)、一般式(VI-6)、一般式(VI-7)及び一般式(VI-8)で表される化合物からなる群から選ばれる化合物を1種以上含有することが好ましい。 Furthermore, general formula (VI-1), general formula (VI-2), general formula (VI-3), general formula (VI-4), general formula (VI-5), general formula (VI-6), It is preferable to contain one or more compounds selected from the group consisting of compounds represented by general formula (VI-7) and general formula (VI-8).
(式中、R6及びR7はそれぞれ独立的に炭素原子数1〜12のアルキル基、炭素原子数1〜12のアルコキシ基、炭素原子数2〜12のアルケニル基、炭素原子数2〜12のアルケニルオキシ基、ハロゲンにより置換された炭素原子数1〜12のアルキル基、ハロゲンにより置換された炭素原子数1〜12のアルコキシ基、ハロゲンにより置換された炭素原子数2〜12のアルケニル基又はハロゲンにより置換された炭素原子数2〜12のアルケニルオキシ基、を表し、Y1、Y2、Y3及びY4はそれぞれ独立的に水素原子、フッ素原子又はメチル基を表し、Z7は-CH2CH2-、-CH=CH-、-COO-、-OCO-、又は単結合を表し、Z8は-C≡C-、-COO-、-OCO-又は-CH=N-N=CH-を表す。)
一般式(VI-1)、一般式(VI-2)、一般式(VI-3)、一般式(VI-4)、一般式(VI-5)、一般式(VI-6)、一般式(VI-7)及び一般式(VI-8)において、R6及びR7は、それぞれ独立して炭素原子数1〜7のアルキル基、炭素原子数1〜7アルコシキ基、炭素原子数2〜7のアルケニル基又は炭素原子数2〜7のアルケニルオキシ基を表すことが好ましく、炭素原子数1〜5の直鎖型アルキル基及び炭素原子数2〜5の直鎖型アルケニル基がさらに好ましく、アルケニル基においては以下の式(a)〜(e)の構造がより好ましい。
Wherein R 6 and R 7 are each independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or 2 to 12 carbon atoms. An alkenyloxy group, an alkyl group having 1 to 12 carbon atoms substituted by halogen, an alkoxy group having 1 to 12 carbon atoms substituted by halogen, an alkenyl group having 2 to 12 carbon atoms substituted by halogen, or Represents an alkenyloxy group having 2 to 12 carbon atoms substituted by halogen, Y 1 , Y 2 , Y 3 and Y 4 each independently represents a hydrogen atom, a fluorine atom or a methyl group, and Z 7 is- CH 2 CH 2- , -CH = CH-, -COO-, -OCO-, or a single bond, Z 8 represents -C≡C-, -COO-, -OCO- or -CH = NN = CH- Represents.)
General formula (VI-1), General formula (VI-2), General formula (VI-3), General formula (VI-4), General formula (VI-5), General formula (VI-6), General formula In (VI-7) and general formula (VI-8), R 6 and R 7 are each independently an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, or 2 to 2 carbon atoms. It preferably represents a 7 alkenyl group or an alkenyloxy group having 2 to 7 carbon atoms, more preferably a linear alkyl group having 1 to 5 carbon atoms and a linear alkenyl group having 2 to 5 carbon atoms, In the alkenyl group, structures of the following formulas (a) to (e) are more preferable.
(構造式は右端で環に連結しているものとする。)
一般式(VI-1)、一般式(VI-3)、一般式(VI-6)及び一般式(VI-8)において、Z7は単結合が好ましい。
一般式(VI-4)及び一般式(VI-5)において、Z8は単結合、-C≡C-又は、-CH=N-N=CH-が好ましい。
また、上記のネマチック液晶組成物に一般式(IV-1)、一般式(IV-2)、一般式(IV-3)及び一般式(IV-4)で表される光学活性化合物をさらに1種以上含有することが好ましい。
(The structural formula shall be connected to the ring at the right end.)
In general formula (VI-1), general formula (VI-3), general formula (VI-6) and general formula (VI-8), Z 7 is preferably a single bond.
In general formula (VI-4) and general formula (VI-5), Z 8 is preferably a single bond, —C≡C— or —CH═NN═CH—.
Further, the above nematic liquid crystal composition further includes an optically active compound represented by general formula (IV-1), general formula (IV-2), general formula (IV-3) and general formula (IV-4). It is preferable to contain more than one species.
（式中、R4は、水素原子、ヒドロキシル基、炭素原子数1〜12のアルキル基、炭素原子数1〜12のアルコキシ基、炭素原子数2〜12のアルケニル基、炭素原子数2〜12のアルケニルオキシ基、ハロゲンにより置換された炭素原子数1〜12のアルキル基、ハロゲンにより置換された炭素原子数1〜12のアルコキシ基、ハロゲンにより置換された炭素原子数2〜12のアルケニル基又はハロゲンにより置換された炭素原子数2〜12のアルケニルオキシ基、-CNを表し、R5*は、光学活性基を表す。）
一般式(IV-1)、一般式(IV-2)、一般式(IV-3)及び一般式(IV-4)において、R5*は、次の一般式で表される置換基が好ましい。
(In the formula, R 4 is a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or 2 to 12 carbon atoms. An alkenyloxy group, an alkyl group having 1 to 12 carbon atoms substituted by halogen, an alkoxy group having 1 to 12 carbon atoms substituted by halogen, an alkenyl group having 2 to 12 carbon atoms substituted by halogen, or (Represents an alkenyloxy group having 2 to 12 carbon atoms substituted by halogen, —CN, and R 5 * represents an optically active group.)
In general formula (IV-1), general formula (IV-2), general formula (IV-3) and general formula (IV-4), R 5 * is preferably a substituent represented by the following general formula: .
（式中、m及びnはそれぞれ独立的に1〜12の整数を表すが、ｍ及びｎは同じ数とはならない。）
本願発明の液晶組成物は比抵抗値が1.0×1013Ωcm以下であることが好ましく、1.0×1012Ωcm以下がより好ましく、比抵抗値が1.0×1011Ωcm以下が特に好ましい。ネマチック相上限温度は60℃以上であることが好ましく、80℃以上がより好ましく、90℃以上が特に好ましい。屈折率異方性(Δn)は0.06〜0.30の範囲であることが好ましく、0.07〜0.18が更に好ましい範囲であり、0.07〜0.16の範囲がTN-LCDのセル厚の設計に特に好ましく、0.12〜0.18の範囲がSTN-LCDのセル厚の設計に特に好ましい。
(In the formula, m and n each independently represent an integer of 1 to 12, but m and n are not the same number.)
The liquid crystal composition of the present invention preferably has a specific resistance value of 1.0 × 10 13 Ωcm or less, more preferably 1.0 × 10 12 Ωcm or less, and particularly preferably a specific resistance value of 1.0 × 10 11 Ωcm or less. The upper limit temperature of the nematic phase is preferably 60 ° C or higher, more preferably 80 ° C or higher, and particularly preferably 90 ° C or higher. The refractive index anisotropy (Δn) is preferably in the range of 0.06 to 0.30, more preferably in the range of 0.07 to 0.18, and the range of 0.07 to 0.16 is particularly preferable for the design of the cell thickness of the TN-LCD, and 0.12 to A range of 0.18 is particularly preferred for STN-LCD cell thickness design.
本願発明の液晶組成物は、上記の化合物以外に、通常のネマチック液晶、スメクチック液晶、コレステリック液晶、2色性色素などを含有していてもよい。
上記ネマチック液晶組成物はTN-LCD、STN-LCD、OCB-LCD、高分子分散型液晶表示素子、フェーズチェンジ型コレステリック液晶表示素子に有用であるが、TN-LCD、STN-LCDに特に有用である。また、透過型あるいは反射型の液晶表示素子に用いることができる。
The liquid crystal composition of the present invention may contain a normal nematic liquid crystal, a smectic liquid crystal, a cholesteric liquid crystal, a dichroic dye and the like in addition to the above compounds.
The nematic liquid crystal composition is useful for TN-LCD, STN-LCD, OCB-LCD, polymer dispersion type liquid crystal display element, phase change type cholesteric liquid crystal display element, but is particularly useful for TN-LCD and STN-LCD. is there. Further, it can be used for a transmissive or reflective liquid crystal display element.
本願発明のTN液晶表示素子は目的に応じて、ねじり角を80°から130°の範囲で選択することができ、85°から110°が好ましい。本願発明のSTN液晶表示素子は目的に応じて、ねじり角を180°から270°の範囲で選択することができ、180°から250°が好ましい。
本願発明の液晶組成物を使用することにより、適度に大きい比抵抗値を有し、かつ液晶表示素子に対して一時的に静電気で印加された電圧が十分速い時間で緩和することができる。
In the TN liquid crystal display element of the present invention, the twist angle can be selected in the range of 80 ° to 130 ° according to the purpose, and 85 ° to 110 ° is preferable. In the STN liquid crystal display element of the present invention, the twist angle can be selected in the range of 180 ° to 270 ° according to the purpose, and 180 ° to 250 ° is preferable.
By using the liquid crystal composition of the present invention, the voltage having a reasonably large specific resistance and temporarily applied to the liquid crystal display element by static electricity can be relaxed in a sufficiently fast time.
以下、実施例を挙げて本願発明を更に詳述するが、本願発明はこれらの実施例に限定されるものではない。又、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。 EXAMPLES Hereinafter, although an Example is given and this invention is further explained in full detail, this invention is not limited to these Examples. Further, “%” in the compositions of the following Examples and Comparative Examples means “% by mass”.
実施例中、測定した特性は以下の通りである。
TNI ：ネマチック相−等方性液体相転移温度(℃)
Δε ：誘電率異方性(25℃)
Δn ：複屈折率(25℃)
ρ ：比抵抗値（Ω・cm）
帯電時間：液晶組成物をセルに注入し、静電気ガンを用いて点灯状態にした
後、元の電圧無印加状態に戻るまでの時間（秒）
化合物記載に下記の略号を使用する。
-n 数字 ：-CnH2n+1 (アルキル側鎖は数字、代表するときはRとする。)
-On ：-OCnH2n+1
-ndm ：-(CnH2n+1-CH=CH-(CH2)m-1)
ndm- ：CnH2n+1-CH=CH-(CH2)m-1-
-Od(m)n ：-O(CnH2n+1-CH=CH-(CH2)m-2)
d(m)nO- ：CnH2n+1-CH=CH-(CH2)m-2O-
連結基
-VO- ：-COO- T- ：-C≡C- -2- ：-CH2CH2-
置換基
-CN ：-C≡N -F ：-F
環
Ph ：1,4-フェニレン基 Ph1：3-フルオロ-1,4-フェニレン基
Ph2：3,5-ジフルオロ-1,4-フェニレン基
Ma ：ピリミジン-2,5-ジイル基 Cy ：1,4-シクロヘキシレン基
In the examples, the measured characteristics are as follows.
T NI : Nematic phase-isotropic liquid phase transition temperature (° C)
Δε: Dielectric anisotropy (25 ° C)
Δn: Birefringence (25 ° C)
ρ: Specific resistance (Ω · cm)
Charging time: Liquid crystal composition was injected into the cell and turned on using an electrostatic gun.
After that, it takes time (seconds) to return to the original no voltage application state.
The following abbreviations are used in compound descriptions.
-n number: -C n H 2n + 1 (the alkyl side chain is a number, and R is representative for representation)
-On: -OC n H 2n + 1
-ndm :-( C n H 2n + 1 -CH = CH- (CH 2) m-1)
ndm-: C n H 2n + 1 -CH = CH- (CH 2 ) m-1-
-Od (m) n: -O ( C n H 2n + 1 -CH = CH- (CH 2) m-2)
d (m) nO-: C n H 2n + 1 -CH = CH- (CH 2 ) m-2 O-
Linking group
-VO-: -COO- T-: -C≡C- -2-: -CH 2 CH 2 -
Substituent
-CN: -C≡N -F: -F
ring
Ph: 1,4-phenylene group Ph1: 3-fluoro-1,4-phenylene group
Ph2: 3,5-difluoro-1,4-phenylene group
Ma: Pyrimidine-2,5-diyl group Cy: 1,4-cyclohexylene group
（実施例１、比較例１）
以下に示すような光学活性化合物CD-1又はCD-2を含むネマチック液晶組成物(LC1、LC2、LC3)を調製し、その物性値を測定し、その結果を比較例1とともに表1に示す。
(Example 1, Comparative Example 1)
A nematic liquid crystal composition (LC1, LC2, LC3) containing the optically active compound CD-1 or CD-2 as shown below was prepared, its physical properties were measured, and the results are shown in Table 1 together with Comparative Example 1. .
それらの比抵抗値ならびに6.0μmのTNセルに注入したときの帯電特性を測定し、その結果を表２に示す。 Their specific resistance values and charging characteristics when injected into a 6.0 μm TN cell were measured, and the results are shown in Table 2.
比較例1と比べ、3-Ma-Ph2-CN、3-Cy-Ph2-CN、3-Cy-Ph1-CN、CD-1を含有するネマチック液晶組成物LC1、LC2及びLC3は、比較例1と比較し比抵抗値を低下させることなく帯電時間を大幅に短縮することができた。
Compared with Comparative Example 1, nematic liquid crystal compositions LC1, LC2, and LC3 containing 3-Ma-Ph2-CN, 3-Cy-Ph2-CN, 3-Cy-Ph1-CN, and CD-1 are Comparative Example 1. The charging time can be greatly shortened without lowering the specific resistance value.
Claims (9)
一般式(II)又は一般式(III)
で表される化合物を1種以上含有することを特徴とするネマチック液晶組成物。 Formula (I-1)
General formula (II) or general formula (III)
A nematic liquid crystal composition comprising at least one compound represented by the formula:
で表される化合物からなる群から選ばれる化合物を1種以上含有する請求項１に記載のネマチック液晶組成物。 General formula (II-1), general formula (II-2), general formula (II-3), general formula (III-1), general formula (III-2) and general formula (III-3)
The nematic liquid crystal composition according to claim 1, comprising at least one compound selected from the group consisting of compounds represented by:
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