JP4857543B2 - 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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- JP4857543B2 JP4857543B2 JP2004315736A JP2004315736A JP4857543B2 JP 4857543 B2 JP4857543 B2 JP 4857543B2 JP 2004315736 A JP2004315736 A JP 2004315736A JP 2004315736 A JP2004315736 A JP 2004315736A JP 4857543 B2 JP4857543 B2 JP 4857543B2
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- 239000004973 liquid crystal related substance Substances 0.000 title claims description 60
- 239000000203 mixture Substances 0.000 title claims description 58
- 239000004988 Nematic liquid crystal Substances 0.000 title claims description 23
- 125000004432 carbon atom Chemical group C* 0.000 claims description 120
- 150000001875 compounds Chemical class 0.000 claims description 96
- 125000000217 alkyl group Chemical group 0.000 claims description 61
- 125000003545 alkoxy group Chemical group 0.000 claims description 59
- 125000003342 alkenyl group Chemical group 0.000 claims description 57
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 47
- 229910052731 fluorine Inorganic materials 0.000 claims description 45
- 125000001153 fluoro group Chemical group F* 0.000 claims description 45
- 229910052801 chlorine Inorganic materials 0.000 claims description 27
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 27
- -1 naphthalene-2,6-diyl group Chemical group 0.000 claims description 15
- 125000003354 benzotriazolyl group Chemical class N1N=NC2=C1C=CC=C2* 0.000 claims description 11
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 claims description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 9
- 125000005407 trans-1,4-cyclohexylene group Chemical group [H]C1([H])C([H])([H])[C@]([H])([*:2])C([H])([H])C([H])([H])[C@@]1([H])[*:1] 0.000 claims description 9
- 239000011159 matrix material Substances 0.000 claims description 8
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 8
- 239000012071 phase Substances 0.000 claims description 5
- 230000007704 transition Effects 0.000 claims description 5
- NLCKLZIHJQEMCU-UHFFFAOYSA-N cyano prop-2-enoate Chemical group C=CC(=O)OC#N NLCKLZIHJQEMCU-UHFFFAOYSA-N 0.000 claims description 4
- 239000007791 liquid phase Substances 0.000 claims description 3
- 239000006096 absorbing agent Substances 0.000 claims 9
- 230000000052 comparative effect Effects 0.000 description 17
- 238000005259 measurement Methods 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 4
- 0 *OC(C(C#N)=C(C1CCCCC1)C1CCCCC1)=O Chemical compound *OC(C(C#N)=C(C1CCCCC1)C1CCCCC1)=O 0.000 description 3
- 239000004990 Smectic liquid crystal Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 238000002296 dynamic light scattering Methods 0.000 description 2
- 239000005262 ferroelectric liquid crystals (FLCs) Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 239000004986 Cholesteric liquid crystals (ChLC) Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
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Description
本発明は、光による電圧保持率の低下を大幅に抑制した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 in which a decrease in voltage holding ratio due to light is significantly suppressed, and a liquid crystal display device using the same.
液晶表示素子は、時計、電卓をはじめとして、家庭用各種電気機器、測定機器、自動車用パネル、ワープロ、電子手帳、プリンター、コンピューター、テレビ等に用いられており、液晶表示方式としては、その代表的なものにTN（捩れネマチック）型、STN（超捩れネマチック）型、DS（動的光散乱）型、GH（ゲスト・ホスト）型、IPS（インプレーンスイッチング）型、OCB（光学補償複屈折）型、ECB（電圧制御複屈折）型、VA（垂直配向）型、あるいはFLC（強誘電性液晶）等を挙げることができる。また駆動方式としても従来のスタティック駆動からマルチプレックス駆動が一般的になり、単純マトリックス方式、最近ではTFT（薄膜トランジスタ）やTFD（薄膜ダイオード）等により駆動されるアクティブマトリックス（AM）方式が主流となっている。 Liquid crystal display elements are used in clocks, calculators, household electric appliances, measuring instruments, automotive panels, word processors, electronic notebooks, printers, computers, televisions, etc. TN (twisted nematic) type, STN (super twisted nematic) type, DS (dynamic light scattering) type, GH (guest / host) type, IPS (in-plane switching) type, OCB (optical compensation birefringence) ) Type, ECB (voltage controlled birefringence) type, VA (vertical alignment) type, FLC (ferroelectric liquid crystal), and the like. Also, as a drive system, a multiplex drive is generally used instead of a conventional static drive, and a simple matrix system, and recently an active matrix (AM) system driven by a TFT (thin film transistor), TFD (thin film diode), etc. has become mainstream. ing.
これらの表示方式において、IPS型、OCB型、VA型等のアクティブマトリックス方式は、現在汎用となっているTN型やSTN型と異なり、電圧保持率が非常に高い液晶組成物を用いる必要がある。また、信頼性の面からの要求として、光や熱による影響を受けにくく、高い保持率を維持できるような液晶組成物が求められている。 In these display systems, active matrix systems such as IPS, OCB, and VA types need to use a liquid crystal composition that has a very high voltage holding ratio, unlike TN and STN types that are currently in general use. . Further, as a requirement from the viewpoint of reliability, there is a demand for a liquid crystal composition that is hardly affected by light and heat and can maintain a high retention rate.
今日までに、酸化防止剤や紫外線吸収剤などを液晶組成物に添加することで、その信頼性を改善することができるという報告は数多くなされている。例えば、５質量％以下の酸化防止剤を添加することで、広いネマチック温度範囲を有し、低温安定性、加熱安定性に優れ、高い電圧保持率を有する液晶組成物（特許文献１参照）が得られることが開示されており、ベンゾトリアゾールの記載もある。しかしながら、耐熱性を改善することが目的になっているため、耐光性の改善方法やその効果に関する記載がない。 To date, there have been many reports that the reliability can be improved by adding an antioxidant, an ultraviolet absorber or the like to the liquid crystal composition. For example, by adding an antioxidant of 5% by mass or less, a liquid crystal composition having a wide nematic temperature range, excellent low-temperature stability and heat stability, and a high voltage holding ratio (see Patent Document 1). It is disclosed that it can be obtained, and there is also a description of benzotriazole. However, since the purpose is to improve the heat resistance, there is no description about a method for improving the light resistance and the effect thereof.
また、紫外波長域に吸収帯をもつ添加剤を液晶組成物に添加することにより極めて良好な耐光性を確保した液晶表示素子（特許文献２参照）に関して開示されており、紫外線吸収剤としてのベンゾトリアゾールに関する記載もある。しかしながら、ＳＴＮ型に最適な液晶組成物を主眼としているため、アクティブマトリックス方式に開発された液晶組成物の耐光性改善に関する記載は無い。特に、一般的な誘電率異方性が正の液晶組成物とはその性質が大きく異なる誘電率異方性が負の液晶組成物に関して耐光性を向上させることに関しての示唆はなく、その信頼性において最も重要な測定項目である電圧保持率に関する記載もない。 Also disclosed is a liquid crystal display element (see Patent Document 2) that ensures extremely good light resistance by adding an additive having an absorption band in the ultraviolet wavelength region to the liquid crystal composition. There is also a description about triazole. However, since the main focus is on a liquid crystal composition that is optimal for the STN type, there is no description regarding the improvement in light resistance of the liquid crystal composition developed in the active matrix system. In particular, there is no suggestion for improving light resistance of a liquid crystal composition having a negative dielectric anisotropy which is significantly different from that of a general liquid crystal composition having a positive dielectric anisotropy. There is no description regarding the voltage holding ratio, which is the most important measurement item.
また、二色性色素が添加された液晶中に紫外線吸収剤を混入することで液晶の耐光性を高め寿命を長くした液晶表示素子（特許文献３参照）に関する開示がある。しかしながら、アクティブマトリックス方式に開発された液晶組成物特に誘電率異方性が負の液晶組成物の耐光性改善に関する記載がなく、その信頼性において最も重要な測定項目である電圧保持率に関する記載もない。 In addition, there is a disclosure relating to a liquid crystal display element (see Patent Document 3) in which the light resistance of the liquid crystal is increased and the lifetime is extended by mixing an ultraviolet absorber in the liquid crystal to which the dichroic dye is added. However, there is no description regarding the light resistance improvement of the liquid crystal composition developed for the active matrix method, particularly the liquid crystal composition having a negative dielectric anisotropy, and there is also a description regarding the voltage holding ratio which is the most important measurement item in the reliability. Absent.
したがって、高い電圧保持率を有するアクティブマトリックス方式に適した誘電率異方性が負の液晶組成物の耐光性を改善する方法が求められていた。 Therefore, a method for improving the light resistance of a liquid crystal composition having a negative dielectric anisotropy suitable for an active matrix system having a high voltage holding ratio has been demanded.
本発明が解決しようとする課題は、絶対値の大きい誘電率異方性が負のネマチック液晶組成物において、その耐光性を改善した液晶組成物を提供することにある。 An object of the present invention is to provide, in a large dielectric anisotropy of the absolute value of a negative value matic liquid crystal composition, to provide a liquid crystal composition having improved the light fastness.
本発明は、紫外線吸収剤を含有し、絶対値が５以上である負の誘電率異方性を有する液晶化合物を少なくとも一種３％以上含有し、誘電率異方性が−２から−８であるネマチック液晶組成物であって、前記紫外線吸収剤がシアノアクリレート誘導体及び／又はベンゾトリアゾール誘導体であり、前記液晶化合物が、下記一般式（I-a）、（I-b）、（II-a）、（II-b）、（III-a）及び（III-b）で表される群から選ばれる１種又は２種以上の化合物であることを特徴とするネマチック液晶組成物提供する。
また、本発明は、上記本発明のネマチック液晶組成物を用いた液晶表示素子を提供する。
The present invention contains ultraviolet absorber, a liquid crystal compound absolute value has a negative dielectric anisotropy is 5 or more and containing at least one at least 3%, dielectric anisotropy -2 -8 Wherein the ultraviolet absorber is a cyanoacrylate derivative and / or a benzotriazole derivative, and the liquid crystal compound has the following general formulas (Ia), (Ib), (II-a), ( There is provided a nematic liquid crystal composition, which is one or more compounds selected from the group represented by II-b), (III-a) and (III-b).
The present invention also provides a liquid crystal display device using the nematic liquid crystal composition of the present invention.
本発明の絶対値が５以上である負の誘電率異方性を有する液晶化合物と紫外線吸収剤を含む液晶組成物は高い電圧保持率を有しており、なおかつ、耐光性を大幅に改善すること、すなわち、紫外線照射後の電圧保持率の低下を大幅に抑制することができた。これを用いた液晶表示素子は従来よりも耐光性が改善されたため、より長い寿命を有する。 The liquid crystal composition comprising a liquid crystal compound having a negative dielectric anisotropy having an absolute value of 5 or more and an ultraviolet absorber according to the present invention has a high voltage holding ratio and significantly improves light resistance. That is, a decrease in the voltage holding ratio after ultraviolet irradiation could be greatly suppressed. Since the liquid crystal display element using this has improved light resistance as compared with the prior art, it has a longer lifetime.
本願発明における液晶組成物において、紫外線吸収剤として、一般式(IV) In the liquid crystal composition of the present invention, as the ultraviolet absorber, the general formula (IV)
（式中、R13は炭素数1から10のアルキル基又はアルコキシル基、炭素数2から10のアルケニル基を表し、これらの基中に存在する少なくとも1個のCH2はOに置換されてもよい。環M及びNはフェニル基を表すが、それぞれ独立的に、これらの基中に存在する少なくとも1個の水素原子は炭素数1から5のアルキル基又はアルコキシル基、炭素数2から5のアルケニル基、フッ素原子、塩素原子、-CF3、-OCF3、-OH又は-NO2に置換されてもよい。）で表されるシアノアクリレート誘導体又は、一般式(V) (Wherein R 13 represents an alkyl group or alkoxyl group having 1 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms, and at least one CH 2 present in these groups may be substituted with O) Rings M and N each independently represent a phenyl group, and each of these groups independently represents at least one hydrogen atom present in an alkyl group or alkoxyl group having 1 to 5 carbon atoms, or 2 to 5 carbon atoms. An alkenyl group, a fluorine atom, a chlorine atom, -CF 3 , -OCF 3 , -OH or -NO 2 ), or a cyanoacrylate derivative represented by the general formula (V)
（式中、Y1は水素原子、炭素数1から5のアルキル基又はアルコキシル基、炭素数2から5のアルケニル基、フッ素原子、塩素原子、-CF3又は-OCF3を表し、R26及びR27はそれぞれ独立的に水素原子、炭素数1から10のアルキル基又はアルコキシル基、炭素数2から10のアルケニル基を表す。）で表されるベンゾトリアゾール誘導体を用いることが好ましく、一般式（IV）及び一般式（V）を比較した場合、一般式（IV）がより好ましい。 (Wherein Y 1 represents a hydrogen atom, an alkyl group or alkoxyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, a fluorine atom, a chlorine atom, —CF 3 or —OCF 3 , R 26 and R 27 is preferably independently a benzotriazole derivative represented by a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an alkoxyl group, and an alkenyl group having 2 to 10 carbon atoms. When comparing IV) and general formula (V), general formula (IV) is more preferred.
一般式（IV）で表される化合物は、一般式（IV-a）で表される化合物がより好ましい。 The compound represented by the general formula (IV) is more preferably a compound represented by the general formula (IV-a).
式中のR25は炭素数1から5のアルキル基又はアルコキシル基、炭素数2から5のアルケニル基であることがより好ましく、X15及びX16はそれぞれ独立的に水素原子、1から5のアルキル基又はアルコキシル基、炭素数2から5のアルケニル基、フッ素原子、塩素原子、-CF3、-OCF3に置換されていてもよい。 R 25 in the formula is more preferably an alkyl group having 1 to 5 carbon atoms or an alkoxyl group, and an alkenyl group having 2 to 5 carbon atoms, and X 15 and X 16 are each independently a hydrogen atom, An alkyl group or an alkoxyl group, an alkenyl group having 2 to 5 carbon atoms, a fluorine atom, a chlorine atom, —CF 3 , or —OCF 3 may be substituted.
一般式(V)で表される化合物は、一般式(V-a)で表される化合物がより好ましい。 The compound represented by the general formula (V) is more preferably a compound represented by the general formula (V-a).
式中、R28及びR29はそれぞれ独立的に水素原子、炭素数1から5のアルキル基又はアルコキシル基、炭素数2から5のアルケニル基を表す。
一般式（IV）又は一般式（V）で表される群から選ばれる化合物の含有率を増加すると耐光性をより改善することができるが、液晶組成物のTniを低下させるため、その含有率は0.005から0.8質量％の範囲であることがより好ましく、0.01から0.5質量％の範囲であることが特に好ましい。
In the formula, R 28 and R 29 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an alkoxyl group, and an alkenyl group having 2 to 5 carbon atoms.
Increasing the content of a compound selected from the group represented by the general formula (IV) or general formula (V) can improve the light resistance more, but decreases the Tni of the liquid crystal composition. Is more preferably in the range of 0.005 to 0.8% by mass, and particularly preferably in the range of 0.01 to 0.5% by mass.
絶対値が5以上である負の誘電率異方性を有する液晶化合物として一般式（I-a）及び一般式（I-b） General formula (I-a) and general formula (I-b) as liquid crystal compounds having negative dielectric anisotropy whose absolute value is 5 or more
（式中、R1、R2、R3及びR4はそれぞれ独立的に炭素数1から10のアルキル基又はアルコキシル基、炭素数2から10のアルケニル基を表し、これらの基中に存在する少なくとも1個のCH2はOに置換されてもよく、また、少なくとも1個の水素原子はフッ素原子に置換されてもよい。A、B、C及びDはそれぞれ独立的に1,4-フェニレン基、トランス-1,4-シクロヘキシレン基、ナフタレン-2,6-ジイル基、デカヒドロナフタレン-2,6-ジイル基又は1,2,3,4-テトラヒドロナフタレン-2,6-ジイル基を表し、これらの基中に存在する少なくとも1個の水素原子はフッ素原子又はメチル基に置換されてもよい。Z1、Z2、Z3及びZ4はそれぞれ独立的に-CH2CH2-、-CH=CH-、-CH(CH3)CH2-、-CH2CH(CH3)-、-CH(CH3)CH(CH3)-、-CF=CF-、-CF2CF2-、-CH2O-、-OCH2-、-CH2CH2O-、-OCH2CH2-、-OCH(CH3)-、-CH(CH3)O-、-(CH2)4-、-(CH2)3O-、-O(CH2)3-、-C≡C-、-CF2O-、-OCF2-、-COO-、-OCO-又は単結合を表す。k、l、m及びnはそれぞれ独立的に0から2を表す。X1、X2、X3、X4、X5及びX6はそれぞれ独立的にフッ素原子又は塩素原子を表す。）で表される群から選ばれる化合物を含有することが好ましいが、より好ましい例として一般式（I-A）から一般式（I-L）で表される化合物がある。 (Wherein R 1 , R 2 , R 3 and R 4 each independently represents an alkyl group or alkoxyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and exists in these groups) At least one CH 2 may be substituted with O, and at least one hydrogen atom may be substituted with a fluorine atom, and A, B, C and D are each independently 1,4-phenylene. Group, trans-1,4-cyclohexylene group, naphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group or 1,2,3,4-tetrahydronaphthalene-2,6-diyl group And at least one hydrogen atom present in these groups may be substituted with a fluorine atom or a methyl group, and Z 1 , Z 2 , Z 3 and Z 4 are each independently —CH 2 CH 2 — , -CH = CH-, -CH (CH 3 ) CH 2- , -CH 2 CH (CH 3 )-, -CH (CH 3 ) CH (CH 3 )-, -CF = CF-, -CF 2 CF 2- , -CH 2 O-, -OCH 2- , -CH 2 CH 2 O-, -OCH 2 CH 2- , -OCH (CH 3 )-, -CH (CH 3 ) O-,-(CH 2 ) 4 -,-(CH 2 ) 3 O-, -O (CH 2 ) 3- , -C≡C-, -CF 2 O-, -OCF 2- , -COO-, -OCO- or a single bond, k, l, m and n each independently represents 0 to 2. X 1 , X 2 , X 3 , X 4 , X 5 And X 6 each independently represents a fluorine atom or a chlorine atom.), But more preferred examples include those represented by general formula (IA) to general formula (IL). There are compounds represented.
式中、R14は炭素数1から5のアルキル基又はアルコキシル基、炭素数2から5のアルケニル基であることが好ましいが、炭素数1から5のアルキル基であることがより好ましい。R15は炭素数1から5のアルキル基又はアルコキシル基、炭素数2から5のアルケニル基であることが好ましいが、炭素数1から5のアルコキシル基であることがより好ましい。Z13は -CH2CH2-、-CH=CH-、-CH(CH3)CH2-、-CH2CH(CH3)-、-CH(CH3)CH(CH3)-、-CF=CF-、-CF2CF2-、-CH2O-、-OCH2-、-CH2CH2O-、-OCH2CH2-、-OCH(CH3)-、-CH(CH3)O-、-(CH2)4-、-(CH2)3O-、-O(CH2)3-、-C≡C-、-CF2O-、-OCF2-、-COO-、-OCO-又は単結合であることが好ましいが、-CH2O-、-CH2CH2O-又は-CF2O-であることがより好ましい。Z14は -CH2CH2-、-CH=CH-、-CH(CH3)CH2-、-CH2CH(CH3)-、-CH(CH3)CH(CH3)-、-CF=CF-、-CF2CF2-、-CH2O-、-OCH2-、-OCH(CH3)-、-CH(CH3)O-、-(CH2)4-、-(CH2)3O-、-O(CH2)3-、-C≡C-、-CF2O-、-OCF2-、-COO-、-OCO-又は単結合であることが好ましいが、-CH2CH2-、-CH=CH-、-COO-、-OCO-又は単結合であることがより好ましい。 In the formula, R 14 is preferably an alkyl group having 1 to 5 carbon atoms or an alkoxyl group, or an alkenyl group having 2 to 5 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms. R 15 is preferably an alkyl group having 1 to 5 carbon atoms or an alkoxyl group, and an alkenyl group having 2 to 5 carbon atoms, more preferably an alkoxyl group having 1 to 5 carbon atoms. Z 13 represents -CH 2 CH 2- , -CH = CH-, -CH (CH 3 ) CH 2- , -CH 2 CH (CH 3 )-, -CH (CH 3 ) CH (CH 3 )-,- CF = CF-, -CF 2 CF 2- , -CH 2 O-, -OCH 2- , -CH 2 CH 2 O-, -OCH 2 CH 2- , -OCH (CH 3 )-, -CH (CH 3 ) O-,-(CH 2 ) 4 -,-(CH 2 ) 3 O-, -O (CH 2 ) 3- , -C≡C-, -CF 2 O-, -OCF 2- , -COO -, -OCO- or a single bond is preferred, but -CH 2 O-, -CH 2 CH 2 O- or -CF 2 O- is more preferred. Z 14 is -CH 2 CH 2- , -CH = CH-, -CH (CH 3 ) CH 2- , -CH 2 CH (CH 3 )-, -CH (CH 3 ) CH (CH 3 )-,- CF = CF-, -CF 2 CF 2- , -CH 2 O-, -OCH 2- , -OCH (CH 3 )-, -CH (CH 3 ) O-,-(CH 2 ) 4 -,-( CH 2 ) 3 O—, —O (CH 2 ) 3 —, —C≡C—, —CF 2 O—, —OCF 2 —, —COO—, —OCO— or a single bond are preferred, It is more preferably —CH 2 CH 2 —, —CH═CH—, —COO—, —OCO— or a single bond.
一般式（I-A）から一般式（I-L）で表される群から任意に液晶化合物を選び、その具体的な構造と誘電率の測定結果を示す。なお、delta-epは25℃における誘電率異方性Δεを表すが、その値は25℃における誘電率異方性が約0である母体液晶を用意し、これに任意の液晶化合物を10質量%添加することで、外挿値として求めた。 A liquid crystal compound is arbitrarily selected from the group represented by the general formula (I-A) to the general formula (I-L), and its specific structure and measurement result of dielectric constant are shown. Note that delta-ep represents the dielectric anisotropy Δε at 25 ° C. The value is a base liquid crystal whose dielectric anisotropy at 25 ° C is about 0, and 10 mass of any liquid crystal compound is prepared. By adding%, it was determined as an extrapolated value.
一般式（I-a）又は一般式（I-b）で表される化合物の含有率は、３から６０質量％の範囲であることが好ましいが、３から５０質量％の範囲であることがより好ましく、３から４０質量％の範囲であることが特に好ましい。
The content of the compound represented by the general formula (Ia) or the general formula (Ib) is preferably in the range of 3 to 60% by mass, more preferably in the range of 3 to 50% by mass. To 40% by mass is particularly preferred.
絶対値が5以上である負の誘電率異方性を有する液晶化合物として一般式（II-a）及び一般式（II-b） General formula (II-a) and general formula (II-b) as liquid crystal compounds having negative dielectric anisotropy whose absolute value is 5 or more
（式中、R5、R6、R7及びR8はそれぞれ独立的に炭素数1から10のアルキル基又はアルコキシル基、炭素数2から10のアルケニル基を表し、これらの基中に存在する少なくとも1個のCH2はOに置換されてもよく、また、少なくとも1個の水素原子はフッ素原子に置換されてもよい。E、F、G及びHはそれぞれ独立的に1,4-フェニレン基、トランス-1,4-シクロヘキシレン基、ナフタレン-2,6-ジイル基、デカヒドロナフタレン-2,6-ジイル基又は1,2,3,4-テトラヒドロナフタレン-2,6-ジイル基を表し、これらの基中に存在する少なくとも1個の水素原子はフッ素原子又はメチル基に置換されてもよい。Z5、Z6、Z7及びZ8はそれぞれ独立的に-CH2CH2-、-CH=CH-、-CH(CH3)CH2-、-CH2CH(CH3)-、-CH(CH3)CH(CH3)-、-CF=CF-、-CF2CF2-、-CH2O-、-OCH2-、-CH2CH2O-、-OCH2CH2-、-OCH(CH3)-、-CH(CH3)O-、-(CH2)4-、-(CH2)3O-、-O(CH2)3-、-C≡C-、-CF2O-、-OCF2-、-COO-、-OCO-又は単結合を表す。o、p、q及びrはそれぞれ独立的に0から2を表す。X7、X8、X9及びX10はそれぞれ独立的にフッ素原子又は塩素原子を表す。）で表される群から選ばれる化合物を含有することが好ましいが、より好ましい例として一般式（II-A）からから一般式（II-H）で表される化合物がある。 (Wherein R 5 , R 6 , R 7 and R 8 each independently represents an alkyl group or alkoxyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and is present in these groups. At least one CH 2 may be substituted with O, and at least one hydrogen atom may be substituted with a fluorine atom, and E, F, G and H are each independently 1,4-phenylene. Group, trans-1,4-cyclohexylene group, naphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group or 1,2,3,4-tetrahydronaphthalene-2,6-diyl group And at least one hydrogen atom present in these groups may be substituted with a fluorine atom or a methyl group, Z 5 , Z 6 , Z 7 and Z 8 are each independently —CH 2 CH 2 — , -CH = CH-, -CH (CH 3 ) CH 2- , -CH 2 CH (CH 3 )-, -CH (CH 3 ) CH (CH 3 )-, -CF = CF-, -CF 2 CF 2- , -CH 2 O-, -OCH 2- , -CH 2 CH 2 O-, -OCH 2 CH 2- , -OCH (CH 3 )-, -CH (CH 3 ) O-,-(CH 2 ) 4 -,-(CH 2 ) 3 O-, -O (CH 2 ) 3- , -C≡C-, -CF 2 O-, -OCF 2- , -COO-, -OCO- or a single bond, o, p, q and r each independently represent 0 to 2. X 7 , X 8 , X 9 and X 10 each independently It is preferable to contain a compound selected from the group represented by general formula (II-A) to general formula (II-H). There are compounds that are
式中、R16は炭素数1から5のアルキル基又はアルコキシル基、炭素数2から5のアルケニル基であることが好ましいが、炭素数1から5のアルキル基であることがより好ましい。R17は炭素数1から5のアルキル基又はアルコキシル基、炭素数2から5のアルケニル基であることが好ましいが、炭素数1から5のアルコキシル基であることがより好ましい。R18は炭素数1から5のアルキル基又はアルコキシル基、炭素数2から5のアルケニル基であることが好ましいが、炭素数1から5のアルキル基であることがより好ましい。Z15及びZ18はそれぞれ独立的に-CH2CH2-、-CH=CH-、-CH(CH3)CH2-、-CH2CH(CH3)-、-CH(CH3)CH(CH3)-、-CF=CF-、-CF2CF2-、-CH2O-、-OCH2-、-CH2CH2O-、-OCH2CH2-、-OCH(CH3)-、-CH(CH3)O-、-(CH2)4-、-(CH2)3O-、-O(CH2)3-、-C≡C-、-CF2O-、-OCF2-、-COO-、-OCO-又は単結合であることが好ましいが、-CH2O-、-CH2CH2O-又は-CF2O-であることがより好ましい。Z16は -CH2CH2-、-CH=CH-、-CH(CH3)CH2-、-CH2CH(CH3)-、-CH(CH3)CH(CH3)-、-CF=CF-、-CF2CF2-、-CH2O-、-OCH2-、-CH2CH2O-、-OCH2CH2-、-OCH(CH3)-、-CH(CH3)O-、-(CH2)4-、-(CH2)3O-、-O(CH2)3-、-C≡C-、-CF2O-、-OCF2-、-COO-、-OCO-又は単結合であることが好ましいが、-CH2CH2-、-CH=CH-、-COO-、-OCO-又は単結合であることがより好ましい。Z17は-CH2CH2-、-CH=CH-、-CH(CH3)CH2-、-CH2CH(CH3)-、-CH(CH3)CH(CH3)-、-CF=CF-、-CF2CF2-、-CH2O-、-OCH2-、-CH2CH2O-、-OCH2CH2-、-OCH(CH3)-、-CH(CH3)O-、-(CH2)4-、-(CH2)3O-、-O(CH2)3-、-C≡C-、-CF2O-、-OCF2-、-COO-、-OCO-又は単結合であることが好ましいが、-OCH2-、-OCH2CH2-又は-OCF2-であることがより好ましい。
In the formula, R 16 is preferably an alkyl group having 1 to 5 carbon atoms or an alkoxyl group, or an alkenyl group having 2 to 5 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms. R 17 is preferably an alkyl group having 1 to 5 carbon atoms or an alkoxyl group, and an alkenyl group having 2 to 5 carbon atoms, more preferably an alkoxyl group having 1 to 5 carbon atoms. R 18 is preferably an alkyl group having 1 to 5 carbon atoms or an alkoxyl group, or an alkenyl group having 2 to 5 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms. Z 15 and Z 18 are each independently -CH 2 CH 2- , -CH = CH-, -CH (CH 3 ) CH 2- , -CH 2 CH (CH 3 )-, -CH (CH 3 ) CH (CH 3 )-, -CF = CF-, -CF 2 CF 2- , -CH 2 O-, -OCH 2- , -CH 2 CH 2 O-, -OCH 2 CH 2- , -OCH (CH 3 )-, -CH (CH 3 ) O-,-(CH 2 ) 4 -,-(CH 2 ) 3 O-, -O (CH 2 ) 3- , -C≡C-, -CF 2 O-, Although it is preferably —OCF 2 —, —COO—, —OCO— or a single bond, it is more preferably —CH 2 O—, —CH 2 CH 2 O— or —CF 2 O—. Z 16 is -CH 2 CH 2- , -CH = CH-, -CH (CH 3 ) CH 2- , -CH 2 CH (CH 3 )-, -CH (CH 3 ) CH (CH 3 )-,- CF = CF-, -CF 2 CF 2- , -CH 2 O-, -OCH 2- , -CH 2 CH 2 O-, -OCH 2 CH 2- , -OCH (CH 3 )-, -CH (CH 3 ) O-,-(CH 2 ) 4 -,-(CH 2 ) 3 O-, -O (CH 2 ) 3- , -C≡C-, -CF 2 O-, -OCF 2- , -COO -, -OCO- or a single bond is preferred, but -CH 2 CH 2- , -CH = CH-, -COO-, -OCO- or a single bond is more preferred. Z 17 is -CH 2 CH 2- , -CH = CH-, -CH (CH 3 ) CH 2- , -CH 2 CH (CH 3 )-, -CH (CH 3 ) CH (CH 3 )-,- CF = CF-, -CF 2 CF 2- , -CH 2 O-, -OCH 2- , -CH 2 CH 2 O-, -OCH 2 CH 2- , -OCH (CH 3 )-, -CH (CH 3 ) O-,-(CH 2 ) 4 -,-(CH 2 ) 3 O-, -O (CH 2 ) 3- , -C≡C-, -CF 2 O-, -OCF 2- , -COO -, -OCO- or a single bond is preferred, but -OCH 2- , -OCH 2 CH 2 -or -OCF 2- is more preferred.
一般式（II-A）から一般式（II-H）で表される群から任意に液晶化合物を選び、その具体的な構造と誘電率の測定結果を示す。なお、delta-epは25℃における誘電率異方性Δεを表す。 A liquid crystal compound is arbitrarily selected from the group represented by the general formula (II-A) to the general formula (II-H), and its specific structure and measurement result of dielectric constant are shown. Note that delta-ep represents the dielectric anisotropy Δε at 25 ° C.
なお、一般式（II-a）又は一般式（II-b）で表される化合物の含有率は、３から８０質量％の範囲が好ましいが、３から７０質量％の範囲であることがより好ましく、１０から６０質量％の範囲であることが特に好ましい。
The content of the compound represented by the general formula (II-a) or the general formula (II-b) is preferably in the range of 3 to 80% by mass, but more preferably in the range of 3 to 70% by mass. A range of 10 to 60% by mass is particularly preferable.
絶対値が５以上である負の誘電率異方性を有する液晶化合物として、一般式（III-a）及び一般式（III-b） As a liquid crystal compound having negative dielectric anisotropy having an absolute value of 5 or more, general formula (III-a) and general formula (III-b)
（式中、R9、R10、R11及びR12はそれぞれ独立的に炭素数1から10のアルキル基又はアルコキシル基、炭素数2から10のアルケニル基を表し、これらの基中に存在する少なくとも1個のCH2はOに置換されてもよく、また、少なくとも1個の水素原子はフッ素原子に置換されてもよい。環I、環J、環K及び環Lはそれぞれ独立的に1,4-フェニレン基、トランス-1,4-シクロヘキシレン基、ナフタレン-2,6-ジイル基、デカヒドロナフタレン-2,6-ジイル基又は1,2,3,4-テトラヒドロナフタレン-2,6-ジイル基を表し、これらの基中に存在する少なくとも1個の水素原子はフッ素原子又はメチル基に置換されてもよい。Z9、Z10、Z11及びZ12はそれぞれ独立的に-CH2CH2-、-CH=CH-、-CH(CH3)CH2-、-CH2CH(CH3)-、-CH(CH3)CH(CH3)-、-CF=CF-、-CF2CF2-、-CH2O-、-OCH2-、-CH2CH2O-、-OCH2CH2-、-OCH(CH3)-、-CH(CH3)O-、-(CH2)4-、-(CH2)3O-、-O(CH2)3-、-C≡C-、-CF2O-、-OCF2-、-COO-、-OCO-又は単結合を表す。s、t、u及びvはそれぞれ独立的に0から2を表す。X11、X12、X13及びX14はそれぞれ独立的にフッ素原子又は塩素原子を表す。）で表される群から選ばれる化合物を含有することが好ましいが、一般式（III-a）又は一般式（III-b）のより好ましい例として一般式（III-A）から一般式（III-L）で表される化合物がある。 (Wherein R 9 , R 10 , R 11 and R 12 each independently represents an alkyl group or alkoxyl group having 1 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms, and exists in these groups. At least one CH 2 may be substituted with O, and at least one hydrogen atom may be substituted with a fluorine atom, ring I, ring J, ring K and ring L are each independently 1 , 4-phenylene group, trans-1,4-cyclohexylene group, naphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group or 1,2,3,4-tetrahydronaphthalene-2,6 -Represents a diyl group, and at least one hydrogen atom present in these groups may be substituted with a fluorine atom or a methyl group, Z 9 , Z 10 , Z 11 and Z 12 are each independently —CH 2. 2 CH 2- , -CH = CH-, -CH (CH 3 ) CH 2- , -CH 2 CH (CH 3 )-, -CH (CH 3 ) CH (CH 3 )-, -CF = CF-, -CF 2 CF 2- , -CH 2 O-, -OCH 2- , -CH 2 CH 2 O-, -OCH 2 C H 2- , -OCH (CH 3 )-, -CH (CH 3 ) O-,-(CH 2 ) 4 -,-(CH 2 ) 3 O-, -O (CH 2 ) 3- , -C≡ C—, —CF 2 O—, —OCF 2 —, —COO—, —OCO— or a single bond, s, t, u and v each independently represents 0 to 2. X 11 , X 12 , X 13 and X 14 each independently represents a fluorine atom or a chlorine atom), but preferably contains a compound selected from the group represented by formula (III-a) or (III- More preferred examples of b) include compounds represented by general formula (III-A) to general formula (III-L).
式中、R19及びR20はそれぞれ独立的に炭素数1から5のアルキル基又はアルコキシル基、炭素数2から5のアルケニル基であることが好ましいが、炭素数1から5のアルキル基であることがより好ましい。R21は炭素数1から5のアルキル基又はアルコキシル基、炭素数2から5のアルケニル基であることが好ましいが、炭素数1から5のアルコキシル基であることがより好ましい。Z19は-CH2CH2-、-CH=CH-、-CH(CH3)CH2-、-CH2CH(CH3)-、-CH(CH3)CH(CH3)-、-CF=CF-、-CF2CF2-、-CH2O-、-OCH2-、-CH2CH2O-、-OCH2CH2-、-OCH(CH3)-、-CH(CH3)O-、-(CH2)4-、-(CH2)3O-、-O(CH2)3-、-C≡C-、-CF2O-、-OCF2-、-COO-、-OCO-又は単結合であることが好ましいが、-CH2O-、-CH2CH2O-又は-CF2O-であることがより好ましい。Z20及びZ21はそれぞれ独立的に -CH2CH2-、-CH=CH-、-CH(CH3)CH2-、-CH2CH(CH3)-、-CH(CH3)CH(CH3)-、-CF=CF-、-CF2CF2-、-CH2O-、-OCH2-、-CH2CH2O-、-OCH2CH2-、-OCH(CH3)-、-CH(CH3)O-、-(CH2)4-、-(CH2)3O-、-O(CH2)3-、-C≡C-、-CF2O-、-OCF2-、-COO-、-OCO-又は単結合であることが好ましいが、-CH2CH2-、-CH=CH-、-COO-、-OCO-又は単結合であることがより好ましい。 In the formula, each of R 19 and R 20 is preferably independently an alkyl group having 1 to 5 carbon atoms or an alkoxyl group, or an alkenyl group having 2 to 5 carbon atoms, but is an alkyl group having 1 to 5 carbon atoms. It is more preferable. R 21 is preferably an alkyl group having 1 to 5 carbon atoms or an alkoxyl group, and an alkenyl group having 2 to 5 carbon atoms, more preferably an alkoxyl group having 1 to 5 carbon atoms. Z 19 is -CH 2 CH 2- , -CH = CH-, -CH (CH 3 ) CH 2- , -CH 2 CH (CH 3 )-, -CH (CH 3 ) CH (CH 3 )-,- CF = CF-, -CF 2 CF 2- , -CH 2 O-, -OCH 2- , -CH 2 CH 2 O-, -OCH 2 CH 2- , -OCH (CH 3 )-, -CH (CH 3 ) O-,-(CH 2 ) 4 -,-(CH 2 ) 3 O-, -O (CH 2 ) 3- , -C≡C-, -CF 2 O-, -OCF 2- , -COO -, -OCO- or a single bond is preferred, but -CH 2 O-, -CH 2 CH 2 O- or -CF 2 O- is more preferred. Z 20 and Z 21 are each independently -CH 2 CH 2- , -CH = CH-, -CH (CH 3 ) CH 2- , -CH 2 CH (CH 3 )-, -CH (CH 3 ) CH (CH 3 )-, -CF = CF-, -CF 2 CF 2- , -CH 2 O-, -OCH 2- , -CH 2 CH 2 O-, -OCH 2 CH 2- , -OCH (CH 3 )-, -CH (CH 3 ) O-,-(CH 2 ) 4 -,-(CH 2 ) 3 O-, -O (CH 2 ) 3- , -C≡C-, -CF 2 O-, -OCF 2- , -COO-, -OCO- or a single bond is preferable, but -CH 2 CH 2- , -CH = CH-, -COO-, -OCO- or a single bond is more preferable. preferable.
一般式（III-A）から一般式（II-L）で表される群から任意に液晶化合物を選び、その具体的な構造と誘電率の測定結果を示す。なお、delta-epは25℃における誘電率異方性Δεを表す。 A liquid crystal compound is arbitrarily selected from the group represented by the general formula (III-A) to the general formula (II-L), and its specific structure and measurement result of dielectric constant are shown. Note that delta-ep represents the dielectric anisotropy Δε at 25 ° C.
なお、一般式（III-a）又は一般式（III-b）で表される化合物の含有率は3から50質量％の範囲であることがより好ましく、3から40質量％の範囲であることが特に好ましい。 In addition, the content of the compound represented by the general formula (III-a) or the general formula (III-b) is more preferably in the range of 3 to 50% by mass, and in the range of 3 to 40% by mass. Is particularly preferred.
更に、本発明の液晶組成物は以下に示すような絶対値が5以下の誘電率異方性を有する一般的な液晶化合物を用いても良い。 Furthermore, the liquid crystal composition of the present invention may use a general liquid crystal compound having dielectric anisotropy having an absolute value of 5 or less as shown below.
式中、R22及びR23はそれぞれ独立的に炭素数1から5のアルキル基又はアルコキシル基、炭素数2から5のアルケニル基であることが好ましい。R24は炭素数1から5のアルキル基又は炭素数2から5のアルケニル基であることが好ましい。
さらに、本発明のネマチック液晶組成物は、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などを含有してもよい。
また、本発明の液晶組成物は以下に記載するような液晶化合物の組合せが好ましい。
In the formula, each of R 22 and R 23 is preferably independently an alkyl group or alkoxyl group having 1 to 5 carbon atoms, or an alkenyl group having 2 to 5 carbon atoms. R 24 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms.
Furthermore, the nematic liquid crystal composition of the present invention may contain ordinary nematic liquid crystal, smectic liquid crystal, cholesteric liquid crystal and the like in addition to the above-mentioned compounds.
The liquid crystal composition of the present invention is preferably a combination of liquid crystal compounds as described below.
本発明の液晶組成物は、一般式（I-a）及び一般式（I-b）で表される化合物群の含有率が3から50質量%、一般式(IV)及び一般式(V)の含有率が0.005から0.8質量%であることがより好ましく、一般式（I-a）及び一般式（I-b）で表される化合物群の含有率が3から40質量%、一般式（IV）又は一般式（V）で表される化合物の含有率が0.01から0.5質量%であることが特に好ましい。 In the liquid crystal composition of the present invention, the content of the compound group represented by the general formula (Ia) and the general formula (Ib) is 3 to 50% by mass, the content of the general formula (IV) and the general formula (V) is More preferably from 0.005 to 0.8% by mass, the content of the compound group represented by the general formula (Ia) and the general formula (Ib) is 3 to 40% by mass, the general formula (IV) or the general formula (V) It is particularly preferable that the content of the compound represented by the formula is 0.01 to 0.5% by mass.
本発明の液晶組成物は、一般式（II-a）及び一般式（II-b）で表される化合物群の含有率が3から70質量%、一般式（IV）又は一般式（V）で表される化合物の含有率が0.005から0.8質量%であることがより好ましく、一般式（II-a）及び一般式（II-b）で表される化合物群の含有率が10から60質量%、一般式（IV）又は一般式（V）で表される化合物の含有率が0.01から0.5質量%であることが特に好ましい。
本発明の液晶組成物は、一般式（III-a）及び一般式（III-b）で表される化合物群の含有率が3から50質量%、一般式（IV）又は一般式（V）で表される化合物の含有率が0.005から0.8質量%であることがより好ましく、一般式（III-a）及び一般式（III-b）で表される化合物群の含有率が3から40質量%、一般式（IV）又は一般式（V）で表される化合物の含有率が0.01から0.5質量%であることが特に好ましい。
In the liquid crystal composition of the present invention, the content of the compound group represented by the general formula (II-a) and the general formula (II-b) is 3 to 70% by mass, the general formula (IV) or the general formula (V) The content of the compound represented by formula (II) is more preferably 0.005 to 0.8% by mass, and the content of the compound group represented by general formula (II-a) and general formula (II-b) is 10 to 60% by mass. %, The content of the compound represented by the general formula (IV) or the general formula (V) is particularly preferably 0.01 to 0.5% by mass.
In the liquid crystal composition of the present invention, the content of the compound group represented by the general formula (III-a) and the general formula (III-b) is 3 to 50% by mass, the general formula (IV) or the general formula (V) The content of the compound represented by the formula is more preferably 0.005 to 0.8% by mass, and the content of the compound group represented by the general formula (III-a) and the general formula (III-b) is 3 to 40% by mass. %, The content of the compound represented by the general formula (IV) or the general formula (V) is particularly preferably 0.01 to 0.5% by mass.
本発明の液晶組成物は、一般式（I-a）及び一般式（I-b）で表される化合物群の含有率が3から50質量%、一般式（II-a）及び一般式（II-b）で表される化合物群の含有率が3から70質量%、一般式（IV）又は一般式（V）で表される化合物の含有率が0.005から0.8質量%であることがより好ましく、一般式（I-a）及び一般式（I-b）で表される化合物群の含有率が3から40質量%、一般式（II-a）及び一般式（II-b）で表される化合物群の含有率が10から60質量%、一般式（IV）又は一般式（V）で表される化合物の含有率が0.01から0.5質量%であることが特に好ましい。 In the liquid crystal composition of the present invention, the content of the compound group represented by the general formula (Ia) and the general formula (Ib) is 3 to 50% by mass, the general formula (II-a) and the general formula (II-b) It is more preferable that the content of the compound group represented by 3 to 70 mass%, the content of the compound represented by the general formula (IV) or the general formula (V) is 0.005 to 0.8 mass%, The content of the compound group represented by (Ia) and general formula (Ib) is 3 to 40% by mass, and the content of the compound group represented by general formula (II-a) and general formula (II-b) is It is particularly preferable that the content of the compound represented by the general formula (IV) or the general formula (V) is 10 to 60% by mass and 0.01 to 0.5% by mass.
本発明の液晶組成物は、一般式（II-a）及び一般式（II-b）で表される化合物群の含有率が3から70質量%、一般式（III-a）及び一般式（III-b）で表される化合物群の含有率が3から50質量%、一般式（IV）又は一般式（V）で表される化合物の含有率が0.005から0.8質量%であることがより好ましく、一般式（II-a）及び一般式（II-b）で表される化合物群の含有率が10から60質量%、一般式（III-a）及び一般式（III-b）で表される化合物群の含有率が3から40質量%、一般式(IV)及び一般式(V)の含有率が0.01から0.5質量%であることが特に好ましい。 In the liquid crystal composition of the present invention, the content of the compound group represented by the general formula (II-a) and the general formula (II-b) is 3 to 70% by mass, the general formula (III-a) and the general formula ( More preferably, the content of the compound group represented by III-b) is 3 to 50% by mass, and the content of the compound represented by the general formula (IV) or the general formula (V) is 0.005 to 0.8% by mass. Preferably, the content of the compound group represented by the general formula (II-a) and the general formula (II-b) is 10 to 60% by mass, represented by the general formula (III-a) and the general formula (III-b). It is particularly preferable that the content of the compound group to be obtained is 3 to 40% by mass, and the content of the general formula (IV) and the general formula (V) is 0.01 to 0.5% by mass.
本発明の液晶組成物は、一般式（I-a）及び一般式（I-b）で表される化合物群の含有率が3から50質量%、一般式（III-a）及び一般式（III-b）で表される化合物群の含有率が3から50質量%、一般式（IV）又は一般式（V）で表される化合物の含有率が0.005から0.8質量%であることがより好ましく、一般式（I-a）及び一般式（I-b）で表される化合物群の含有率が3から40質量%、一般式（III-a）及び一般式（III-b）で表される化合物群の含有率が3から40質量%、一般式（IV）又は一般式（V）で表される化合物の含有率が0.01から0.5質量%であることが特に好ましい。
本発明の液晶組成物は、一般式（I-a）及び一般式（I-b）で表される化合物群の含有率が3から50質量%、一般式（II-a）及び一般式（II-b）で表される化合物群の含有率が3から70質量%、一般式（III-a）及び一般式（III-b）で表される化合物群の含有率が3から50質量%、一般式（IV）又は一般式（V）で表される化合物の含有率が0.005から0.8質量%であることがより好ましく、一般式（I-a）及び一般式（I-b）で表される化合物群の含有率が3から40質量%、一般式（II-a）及び一般式（II-b）で表される化合物群の含有率が10から60質量%、一般式（III-a）及び一般式（III-b）で表される化合物群の含有率が3から40質量%、一般式（IV）及び又は一般式（V）の含有率が0.01から0.5質量%であることが特に好ましい。
本発明の液晶組成物において、ネマチック相-等方性液体相転移温度（Tni）は80から105℃の範囲であることがより好ましく、80から95℃の範囲であることが特に好ましい。スメクチック相又は固体相-ネマチック相転移温度（Tsn）は-20℃以下であることが好ましく、-30℃以下であることがより好ましい。25℃における誘電率異方性（Δε）は-2.5から-6.5の範囲であることがより好ましく、-3.0から-5.0の範囲であることが特に好ましい。25℃における屈折率異方性（Δｎ）は0.08から0.15の範囲であることがより好ましく、0.08から0.13の範囲であることが特に好ましい。
In the liquid crystal composition of the present invention, the content of the compound group represented by the general formula (Ia) and the general formula (Ib) is 3 to 50% by mass, the general formula (III-a) and the general formula (III-b) It is more preferable that the content of the compound group represented by 3 to 50% by mass, the content of the compound represented by the general formula (IV) or the general formula (V) is 0.005 to 0.8% by mass, The content of the compound group represented by (Ia) and general formula (Ib) is 3 to 40% by mass, and the content of the compound group represented by general formula (III-a) and general formula (III-b) is It is particularly preferable that the content of the compound represented by 3 to 40% by mass and the general formula (IV) or the general formula (V) is 0.01 to 0.5% by mass.
In the liquid crystal composition of the present invention, the content of the compound group represented by the general formula (Ia) and the general formula (Ib) is 3 to 50% by mass, the general formula (II-a) and the general formula (II-b) The content of the compound group represented by the formula is 3 to 70% by mass, the content of the compound group represented by the general formula (III-a) and the general formula (III-b) is 3 to 50% by mass, More preferably, the content of the compound represented by IV) or the general formula (V) is 0.005 to 0.8% by mass, and the content of the compound group represented by the general formula (Ia) and the general formula (Ib) is 3 to 40% by mass, the content of the compound group represented by general formula (II-a) and general formula (II-b) is 10 to 60% by mass, general formula (III-a) and general formula (III- It is particularly preferable that the content of the compound group represented by b) is 3 to 40% by mass, and the content of general formula (IV) and / or general formula (V) is 0.01 to 0.5% by mass.
In the liquid crystal composition of the present invention, the nematic phase-isotropic liquid phase transition temperature (Tni) is more preferably in the range of 80 to 105 ° C., and particularly preferably in the range of 80 to 95 ° C. The smectic phase or solid phase-nematic phase transition temperature (Tsn) is preferably −20 ° C. or lower, more preferably −30 ° C. or lower. The dielectric anisotropy (Δε) at 25 ° C. is more preferably in the range of −2.5 to −6.5, and particularly preferably in the range of −3.0 to −5.0. The refractive index anisotropy (Δn) at 25 ° C. is more preferably in the range of 0.08 to 0.15, and particularly preferably in the range of 0.08 to 0.13.
また、本発明のネマチック液晶組成物の電圧保持率VHR(INITIAL)は95%以上であることが好ましいが、98%以上であることがより好ましい。更に、紫外線照射後の電圧保持率VHR(UV)は、90%以上であることが好ましいが、95%以上であることがより好ましい。 In addition, the voltage holding ratio VHR (INITIAL) of the nematic liquid crystal composition of the present invention is preferably 95% or more, more preferably 98% or more. Furthermore, the voltage holding ratio VHR (UV) after ultraviolet irradiation is preferably 90% or more, more preferably 95% or more.
本発明のネマチック液晶組成物はVAモードのアクティブマトリクス液晶表示素子に特に有用である。
The nematic liquid crystal composition of the present invention is particularly useful for a VA mode active matrix liquid crystal display device.
以下に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。 EXAMPLES The present invention will be described in further detail with reference to examples below, but the present 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。 In the examples, the measured characteristics are as follows.
Tni：ネマチック相−等方性液体相転移温度(℃)
Tsn：スメクチック相又は固体相-ネマチック相転移温度(℃)
Δn：25℃における屈折率異方性
Δε：25℃における誘電率異方性
VHR(INITIAL) ：紫外線照射前の25℃における電圧保持率(%)
VHR(UV) ：紫外線照射後の25℃における電圧保持率(%)
なお、電圧保持率の測定条件は、印加電圧5V、フレーム時間16.5ms、パルス幅60μsecである。紫外線照射ランプには三菱電機オスラム株式会社製FL15BL-360を使用し、液晶を注入したVAモードセル（セル厚3.5um、配向膜RN-1517）に紫外線を60分間照射した。
（実施例１）
以下に記載の液晶組成物を調整した。
Tni: Nematic phase-isotropic liquid phase transition temperature (° C)
Tsn: Smectic phase or solid phase-nematic phase transition temperature (℃)
Δn: Refractive index anisotropy at 25 ° C Δε: Dielectric anisotropy at 25 ° C
VHR (INITIAL): Voltage holding ratio at 25 ° C before UV irradiation (%)
VHR (UV): Voltage holding ratio at 25 ° C after UV irradiation (%)
The measurement conditions for the voltage holding ratio are an applied voltage of 5 V, a frame time of 16.5 ms, and a pulse width of 60 μsec. FL15BL-360 manufactured by Mitsubishi Electric OSRAM Co., Ltd. was used as the ultraviolet irradiation lamp, and ultraviolet rays were irradiated to the VA mode cell (cell thickness 3.5 μm, alignment film RN-1517) into which liquid crystal was injected for 60 minutes.
Example 1
The liquid crystal composition described below was prepared.
実施例１の特性は、Tni：84℃、Tsn：-45℃、Δn：0.124、Δε：-3.2、VHR(INITIAL)：99.1%、VHR(UV)：95.3であった。
また、比較例として一般式（IV）で表される化合物を含まない比較例1を調製した。
（比較例１）
The characteristics of Example 1 were Tni: 84 ° C., Tsn: −45 ° C., Δn: 0.124, Δε: -3.2, VHR (INITIAL): 99.1%, VHR (UV): 95.3.
Further, as Comparative Example, Comparative Example 1 containing no compound represented by the general formula (IV) was prepared.
(Comparative Example 1)
比較例１の特性は、Tni：85℃、Tsn：-45℃、Δn：0.124、Δε：-3.2、VHR(INITIAL)：98.9%、VHR(UV)：70.2%であった。
実施例１の方が、紫外線照射後も高い電圧保持率を維持していることがわかる。
（実施例２）
以下に記載の液晶組成物を調整した。
The characteristics of Comparative Example 1 were Tni: 85 ° C, Tsn: -45 ° C, Δn: 0.124, Δε: -3.2, VHR (INITIAL): 98.9%, VHR (UV): 70.2%.
It can be seen that Example 1 maintains a higher voltage holding ratio even after UV irradiation.
(Example 2)
The liquid crystal composition described below was prepared.
この組成物99.5％に一般式（IV）で表される化合物である以下の化合物0.5％を加え物性値を測定した。 The following compound 0.5%, which is a compound represented by the general formula (IV), was added to 99.5% of this composition, and physical properties were measured.
実施例２の特性は、Tni：84℃、Tsn：-30℃、Δn：0.075、Δε：-2.8、VHR(INITIAL)：99.0%、VHR(UV)：95.7であった。
また、比較例として一般式（IV）で表される化合物を含まない比較例２を調製した。
（比較例２）
The characteristics of Example 2 were Tni: 84 ° C., Tsn: −30 ° C., Δn: 0.075, Δε: -2.8, VHR (INITIAL): 99.0%, and VHR (UV): 95.7.
Moreover, the comparative example 2 which does not contain the compound represented by general formula (IV) as a comparative example was prepared.
(Comparative Example 2)
比較例２の特性は、Tni：85℃、Tsn：-30℃、Δn：0.075、Δε：-2.8、VHR(INITIAL)：99.0%、VHR(UV)：68.4%であった。
（実施例３）
以下に記載の液晶組成物を調整した。
The characteristics of Comparative Example 2 were Tni: 85 ° C., Tsn: −30 ° C., Δn: 0.075, Δε: −2.8, VHR (INITIAL): 99.0%, VHR (UV): 68.4%.
(Example 3)
The liquid crystal composition described below was prepared.
この組成物99.9％に一般式（V）で表される化合物である以下の化合物0.1％を加え物性値を測定した。 The following compound 0.1%, which is a compound represented by the general formula (V), was added to 99.9% of this composition, and physical properties were measured.
実施例３の特性は、Tni：90℃、Tsn：-30℃、Δn：0.092、Δε：-3.2、VHR(INITIAL)：98.9%、VHR(UV)：93.7であった。
また、比較例として一般式（V）で表される化合物を含まない比較例３を調製した。
（比較例３）
The characteristics of Example 3 were Tni: 90 ° C., Tsn: −30 ° C., Δn: 0.092, Δε: -3.2, VHR (INITIAL): 98.9%, and VHR (UV): 93.7.
Moreover, the comparative example 3 which does not contain the compound represented by general formula (V) as a comparative example was prepared.
(Comparative Example 3)
比較例３の特性は、Tni：91℃、Tsn：-30℃、Δn：0.092、Δε：-3.2、VHR(INITIAL)：99.0%、VHR(UV)：73.4%であった。
（実施例４）
以下に記載の液晶組成物を調整した。
The characteristics of Comparative Example 3 were Tni: 91 ° C, Tsn: -30 ° C, Δn: 0.092, Δε: -3.2, VHR (INITIAL): 99.0%, VHR (UV): 73.4%.
Example 4
The liquid crystal composition described below was prepared.
この組成物99.99％に一般式（IV）で表される化合物である以下の化合物0.01％を加え物性値を測定した。 The following compound 0.01%, which is a compound represented by the general formula (IV), was added to 99.99% of this composition, and physical properties were measured.
実施例４の特性は、Tni：85℃、Tsn：-36℃、Δn：0.085、Δε：-2.5、VHR(INITIAL)：98.9%、VHR(UV)：96.7であった。
また、比較例として一般式（IV）で表される化合物を含まない比較例４を調製した。
（比較例４）
The characteristics of Example 4 were Tni: 85 ° C., Tsn: −36 ° C., Δn: 0.085, Δε: -2.5, VHR (INITIAL): 98.9%, VHR (UV): 96.7.
Moreover, the comparative example 4 which does not contain the compound represented by general formula (IV) as a comparative example was prepared.
(Comparative Example 4)
比較例４の特性は、Tni：85℃、Tsn：-36℃、Δn：0.085、Δε：-2.5、VHR(INITIAL)：99.1%、VHR(UV)：74.4%であった。
The characteristics of Comparative Example 4 were Tni: 85 ° C., Tsn: −36 ° C., Δn: 0.085, Δε: -2.5, VHR (INITIAL): 99.1%, VHR (UV): 74.4%.
Claims (14)
前記紫外線吸収剤がシアノアクリレート誘導体及び／又はベンゾトリアゾール誘導体であり、
前記液晶化合物が、下記一般式（I-a）、（I-b）、（II-a）、（II-b）、（III-a）及び（III-b）で表される群から選ばれる１種又は２種以上の化合物であることを特徴とするネマチック液晶組成物。
The ultraviolet absorber is a cyanoacrylate derivative and / or a benzotriazole derivative;
The liquid crystal compound is selected from the group represented by the following general formulas (Ia), (Ib), (II-a), (II-b), (III-a) and (III-b) or A nematic liquid crystal composition comprising two or more compounds.
一般式（Ｖ）
一般式（Ｉ−ａ）及び一般式（Ｉ−ｂ）で表される化合物群の含有率が３から６０質量％であり、一般式（ＩＶ）又は一般式（Ｖ）で表される化合物の含有率が０．００１から１質量％である請求項１に記載のネマチック液晶組成物。 As UV absorber, general formula (IV)
General formula (V)
The content of the compound group represented by the general formula (Ia) and the general formula (Ib) is 3 to 60% by mass, and the compound represented by the general formula (IV) or the general formula (V) The nematic liquid crystal composition according to claim 1, wherein the content is 0.001 to 1% by mass.
一般式（Ｖ）
一般式（ＩＩ−ａ）及び一般式（ＩＩ−ｂ）で表される化合物群の含有率が３から８０質量％であり、一般式（ＩＶ）又は一般式（Ｖ）で表される化合物の含有率が０．００１から１質量％である請求項１に記載のネマチック液晶組成物。 As UV absorber, general formula (IV)
General formula (V)
The content of the compound group represented by the general formula (II-a) and the general formula (II-b) is 3 to 80% by mass, and the compound represented by the general formula (IV) or the general formula (V) The nematic liquid crystal composition according to claim 1, wherein the content is 0.001 to 1% by mass.
一般式（Ｖ）
一般式（ＩＩＩ−ａ）及び一般式（ＩＩＩ−ｂ）で表される化合物群の含有率が３から６０質量％であり、一般式（ＩＶ）又は一般式（Ｖ）で表される化合物の含有率が０．００１から１質量％である請求項１に記載のネマチック液晶組成物。 As UV absorber, general formula (IV)
General formula (V)
The content of the compound group represented by the general formula (III-a) and the general formula (III-b) is 3 to 60% by mass, and the compound represented by the general formula (IV) or the general formula (V) The nematic liquid crystal composition according to claim 1, wherein the content is 0.001 to 1% by mass.
一般式（Ｖ）
一般式（Ｉ−ａ）及び一般式（Ｉ−ｂ）で表される化合物群の含有率が３から６０質量％であり、一般式（ＩＩ−ａ）及び一般式（ＩＩ−ｂ）で表される化合物群の含有率が３から８０質量％であり、一般式（ＩＶ）又は一般式（Ｖ）で表される化合物の含有率が０．００１から１質量％である請求項１に記載のネマチック液晶組成物。 As UV absorber, general formula (IV)
General formula (V)
The content rate of the compound group represented by general formula (Ia) and general formula (Ib) is 3 to 60 mass%, and is represented by general formula (II-a) and general formula (II-b). a 80 wt% compounds of content from 3 to be, according to claim 1 formula (IV) or the content of the compound represented by the formula (V) is 1% by mass 0.001 Nematic liquid crystal composition.
一般式（Ｖ）
一般式（ＩＩ−ａ）及び一般式（ＩＩ−ｂ）で表される化合物群の含有率が３から８０質量％であり、一般式（ＩＩＩ−ａ）及び一般式（ＩＩＩ−ｂ）で表される化合物群の含有率が３から６０質量％であり、一般式（ＩＶ）又は一般式（Ｖ）で表される化合物の含有率が０．００１から１質量％である請求項１に記載のネマチック液晶組成物。 As UV absorber, general formula (IV)
General formula (V)
The content of the compound group represented by the general formula (II-a) and the general formula (II-b) is 3 to 80% by mass, and is represented by the general formula (III-a) and the general formula (III-b). a 60 wt% compounds of content from 3 to be, according to claim 1 formula (IV) or the content of the compound represented by the formula (V) is 1% by mass 0.001 Nematic liquid crystal composition.
一般式（Ｖ）
一般式（Ｉ−ａ）及び一般式（Ｉ−ｂ）で表される化合物群の含有率が３から６０質量％であり、一般式（ＩＩＩ−ａ）及び一般式（ＩＩＩ−ｂ）で表される化合物群の含有率が３から６０質量％であり、一般式（ＩＶ）又は一般式（Ｖ）で表される化合物の含有率が０．００１から１質量％である請求項１に記載のネマチック液晶組成物。 As UV absorber, general formula (IV)
General formula (V)
The content rate of the compound group represented by general formula (Ia) and general formula (Ib) is 3 to 60 mass%, and is represented by general formula (III-a) and general formula (III-b). a 60 wt% compounds of content from 3 to be, according to claim 1 formula (IV) or the content of the compound represented by the formula (V) is 1% by mass 0.001 Nematic liquid crystal composition.
一般式（Ｖ）
一般式（Ｉ−ａ）及び一般式（Ｉ−ｂ）で表される化合物群の含有率が３から６０質量％であり、一般式（ＩＩ−ａ）及び一般式（ＩＩ−ｂ）で表される化合物群の含有率が３から８０質量％であり、一般式（ＩＩＩ−ａ）及び一般式（ＩＩＩ−ｂ）で表される化合物群の含有率が３から６０質量％であり、一般式（ＩＶ）又は一般式（Ｖ）で表される化合物の含有率が０．００１から１質量％である請求項１に記載のネマチック液晶組成物。 As UV absorber, general formula (IV)
General formula (V)
The content rate of the compound group represented by general formula (Ia) and general formula (Ib) is 3 to 60 mass%, and is represented by general formula (II-a) and general formula (II-b). The content ratio of the compound group is 3 to 80 mass%, the content ratio of the compound group represented by the general formula (III-a) and the general formula (III-b) is 3 to 60 mass%, The nematic liquid crystal composition according to claim 1, wherein the content of the compound represented by the formula (IV) or the general formula (V) is 0.001 to 1% by mass.
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Families Citing this family (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63301027A (en) * | 1987-05-30 | 1988-12-08 | Canon Inc | Liquid crystal element |
| JPH08176549A (en) * | 1994-12-22 | 1996-07-09 | Matsushita Electric Ind Co Ltd | Ultraviolet resistant liquid crystal material and liquid crystal display device |
| JPH10123542A (en) * | 1996-10-15 | 1998-05-15 | Matsushita Electric Ind Co Ltd | Liquid crystal display element and its production |
| JP4691746B2 (en) * | 1999-07-28 | 2011-06-01 | Ｄｉｃ株式会社 | Nematic liquid crystal composition and liquid crystal display device using the same |
| JP2002256267A (en) * | 2000-12-27 | 2002-09-11 | Dainippon Ink & Chem Inc | Antioxidative liquid crystal composition |
| WO2004058917A1 (en) * | 2002-12-26 | 2004-07-15 | Dainippon Ink And Chemicals, Inc. | Nematic liquid-crystal composition and liquid-crystal display element employing the same |
| JP4348600B2 (en) * | 2002-12-26 | 2009-10-21 | Ｄｉｃ株式会社 | Nematic liquid crystal composition and liquid crystal display device using the same |
| JP2004256791A (en) * | 2003-02-03 | 2004-09-16 | Chisso Corp | Liquid crystal composition and liquid crystal display element |
| JP4706895B2 (en) * | 2004-03-30 | 2011-06-22 | Ｄｉｃ株式会社 | Nematic liquid crystal composition and liquid crystal display device using the same |
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