WO2019138791A1 - Liquid crystal composition and liquid crystal display device - Google Patents

Abstract

The present invention provides: a liquid crystal composition satisfying at least one property among properties such as high upper-limit temperature, low lower-limit temperature, low viscosity, adequate optical anisotropy, large negative dielectric anisotropy, large specific resistance, high stability to light, and high stability to heat; and an active matrix device including said composition. The liquid crystal composition contains, as a first additive, at least one compound selected from among a compound represented by formula (S) and a compound obtained by substituting at least one hydrogen in the compound represented by formula (S) with a monovalent group, and may contain a specific compound having a large negative dielectric anisotropy as a first component, a specific compound having a high upper-limit temperature or a low viscosity as a second component, and a specific compound having a polymerizable group as a second additive.

Description

Liquid crystal composition and liquid crystal display device

The present invention relates to a liquid crystal composition, a liquid crystal display element containing the composition, and the like. In particular, the present invention relates to a liquid crystal composition having a negative dielectric anisotropy, and a liquid crystal display device containing the composition and having a mode such as IPS, VA, FFS, or FPA. The present invention also relates to a polymer supported alignment type liquid crystal display device.

In liquid crystal display devices, classification based on the operation mode of liquid crystal molecules is as follows: phase change (PC), twisted nematic (TN), super twisted nematic (STN), electrically controlled birefringence (ECB), optically compensated bend (OCB), IPS These modes are modes such as (in-plane switching), VA (vertical alignment), FFS (fringe field switching), and FPA (field-induced photo-reactive alignment). The classification based on the driving system of elements is PM (passive matrix) and AM (active matrix). PM is classified into static, multiplex, etc., and AM is classified into thin film transistor (TFT), metal insulator metal (MIM), etc. The classification of TFT is amorphous silicon and polycrystal silicon. The latter are classified into high temperature type and low temperature type according to the manufacturing process. Source based classifications are reflective based on natural light, transmissive based on back light, and semi-transmissive based on both natural light and back light.

The liquid crystal display element contains a liquid crystal composition having a nematic phase. This composition has suitable properties. By improving the properties of this composition, an AM element having good properties can be obtained. The associations in these properties are summarized in Table 1 below. The characteristics of the composition will be further described based on commercially available AM devices. The temperature range of the nematic phase is related to the usable temperature range of the device. The preferred upper temperature limit of the nematic phase is about 70 ° C. or higher, and the preferred lower temperature limit of the nematic phase is about -10 ° C. or lower. The viscosity of the composition is related to the response time of the device. Short response times are preferred for displaying motion pictures on the device. Even shorter response times of 1 millisecond are desirable. Thus, low viscosity in the composition is preferred. Small viscosities at low temperatures are more preferred.

The optical anisotropy of the composition is related to the contrast ratio of the device. Depending on the mode of the device, a large or small optical anisotropy, ie a suitable optical anisotropy, is required. The product (Δn × d) of the optical anisotropy (Δn) of the composition and the cell gap (d) of the device is designed to maximize the contrast ratio. The appropriate value of the product depends on the type of operating mode. This value is in the range of about 0.30 μm to about 0.40 μm in the VA mode device and in the range of about 0.20 μm to about 0.30 μm in the IPS mode or FFS mode device. In these cases, compositions with large optical anisotropy are preferred for small cell gap devices. The large dielectric anisotropy in the composition contributes to low threshold voltage, low power consumption and high contrast ratio in the device. Therefore, large dielectric anisotropy is preferred. The large resistivity in the composition contributes to a large voltage holding ratio and a large contrast ratio in the device. Therefore, a composition having a large specific resistance at the initial stage is preferred. After prolonged use, compositions having high specific resistance are preferred. The stability of the composition to ultraviolet light and heat is related to the lifetime of the device. When this stability is high, the lifetime of the device is long. Such characteristics are preferable for an AM element used for a liquid crystal monitor, a liquid crystal television or the like.

In a general-purpose liquid crystal display device, vertical alignment of liquid crystal molecules is achieved by a specific polyimide alignment film. In a liquid crystal display device of the polymer supported alignment (PSA) type, a polymer is combined with an alignment film. First, a composition to which a small amount of a polymerizable compound is added is injected into the device. Next, the composition is irradiated with ultraviolet light while applying a voltage between the substrates of the device. The polymerizable compound polymerizes to form a polymer network in the composition. In this composition, the polymer can control the alignment of liquid crystal molecules, thereby reducing the response time of the device and improving the image sticking. Such an effect of the polymer can be expected to devices having modes such as TN, ECB, OCB, IPS, VA, FFS, and FPA.

In an AM device having a TN mode, a composition having positive dielectric anisotropy is used. In an AM device having a VA mode, a composition having negative dielectric anisotropy is used. In an AM device having an IPS mode or an FFS mode, a composition having positive or negative dielectric anisotropy is used. A composition having positive or negative dielectric anisotropy is used in an AM element of a polymer sustained alignment (PSA) type.

JP, 2010-60981, A International Publication No. 2009/107405

One object of the present invention is: high upper limit temperature of nematic phase, lower lower limit temperature of nematic phase, small viscosity, suitable optical anisotropy, large negative dielectric anisotropy, large specific resistance, high stability to light It is an object of the present invention to provide a liquid crystal composition satisfying at least one of properties such as high stability to heat. Another object is to provide a liquid crystal composition having a proper balance between at least two of these properties. Another object is to provide a liquid crystal display device containing such a composition. Another object is to provide an AM device having characteristics such as short response time, large voltage holding ratio, low threshold voltage, large contrast ratio, and long lifetime.

The present invention provides at least one compound selected from a compound represented by the formula (S) as a first additive and a compound in which at least one hydrogen of the compound represented by the formula (S) is replaced with a monovalent group. And a liquid crystal composition having a nematic phase and negative dielectric anisotropy, and a liquid crystal display device containing the composition.

The advantages of the present invention are: high upper limit temperature of nematic phase, lower lower limit temperature of nematic phase, small viscosity, appropriate optical anisotropy, large negative dielectric anisotropy, large specific resistance, high stability to light, thermal It is to provide a liquid crystal composition satisfying at least one of the properties such as high stability to. Another advantage is to provide a liquid crystal composition having a suitable balance between at least two of these properties. Another advantage is to provide a liquid crystal display device containing such a composition. Another advantage is to provide an AM device having characteristics such as short response time, large voltage holding ratio, low threshold voltage, large contrast ratio, and long lifetime.

The usage of the terms in this specification is as follows. The terms "liquid crystal composition" and "liquid crystal display element" may be abbreviated as "composition" and "element", respectively. "Liquid crystal display element" is a generic term for liquid crystal display panels and liquid crystal display modules. The “liquid crystal compound” is a compound having a liquid crystal phase such as a nematic phase or a smectic phase and has no liquid crystal phase, but for the purpose of adjusting properties such as temperature range of the nematic phase, viscosity and dielectric anisotropy. It is a general term for compounds mixed in a composition. This compound has, for example, a six-membered ring such as 1,4-cyclohexylene or 1,4-phenylene, and its molecule (liquid crystal molecule) is rod like. The "polymerizable compound" is a compound to be added for the purpose of forming a polymer in the composition. Liquid crystal compounds having alkenyl are not classified as polymerizable compounds in that sense.

The liquid crystal composition is prepared by mixing a plurality of liquid crystal compounds. Additives such as optically active compounds and polymerizable compounds are added to the liquid crystal composition as needed. The proportion of the liquid crystal compound is represented by mass percentage (mass%) based on the mass of the liquid crystal composition not including the additive even when the additive is added. The proportion of the additive is represented by mass percentage (mass%) based on the mass of the liquid crystal composition containing no additive. That is, the proportions of the liquid crystal compound and the additive are calculated based on the total mass of the liquid crystal compound.

The “upper limit temperature of the nematic phase” may be abbreviated as the “upper limit temperature”. The “lower limit temperature of the nematic phase” may be abbreviated as the “lower limit temperature”. The expression "increase the dielectric anisotropy" means that in the case of a composition having a positive dielectric anisotropy, the value increases positively, and a composition having a negative dielectric anisotropy. In the case of goods, it means that the value increases negatively. The "high voltage holding ratio" means that the device has a large voltage holding ratio not only at room temperature but also at a temperature close to the upper limit at the initial stage, and after a long period of use it shows a large voltage not only at room temperature but also at a temperature near the upper limit. It means having a retention rate. The characteristics of the composition or the device may be examined by a time-dependent change test.

「化合物（１ｚ）」は、式（１ｚ）で表される１つの化合物、２つの化合物の混合物、または３つ以上の化合物の混合物を意味する。他の式で表される化合物についても同様である。「式（１ｚ）および式（２ｚ）で表される化合物から選択された少なくとも１つの化合物」の表現は、化合物（１ｚ）および化合物（２ｚ）の群から選択された少なくとも１つの化合物を意味する。 Formula (1z) is taken as an example. At least one compound selected from the compounds represented by formula (1z) may be abbreviated as “compound (1z)”.

The “compound (1z)” means one compound represented by the formula (1z), a mixture of two compounds, or a mixture of three or more compounds. The same applies to compounds represented by other formulas. The expression "at least one compound selected from compounds represented by the formula (1z) and the formula (2z)" means at least one compound selected from the group of the compound (1z) and the compound (2z) .

In formula (1z), the expression “Ra and Rb is alkyl, alkoxy or alkenyl” means that Ra and Rb are independently selected from the group of alkyl, alkoxy and alkenyl. That is, the group represented by Ra and the group represented by Rb may be the same or different. This rule is also applied when the symbol of Ra is used for a plurality of compounds.

In the formula (1z), symbols of α and β surrounded by a hexagon correspond to the ring α and the ring β, respectively, and represent a ring such as a 6-membered ring or a fused ring. When the index 'x' is 2, two rings α are present. The two groups represented by the two rings α may be identical or different. This rule applies to any two rings α when the index 'x' is greater than two. The oblique lines crossing one side of the ring β indicate that any hydrogen on the ring β may be replaced with a substituent (—Sp—P). The index 'y' indicates the number of substituted substituents. There is no such substitution when the index 'y' is zero. When the index 'y' is 2 or more, a plurality of substituents (-Sp-P) are present on the ring β. The rule "may be identical or different" applies also if the compounds have identical substituents.

The expression "at least one 'A'" means that the number of 'A' is arbitrary. In the expression “at least one 'A' may be replaced by 'B'”, when the number of 'A' is one, the position of 'A' is arbitrary and the number of 'A' is two Even in the case of three or more, their positions can be selected without limitation. The expression "at least one -CH _2- may be replaced by -O-" may be used. In this case, -CH ₂ -CH ₂ -CH ₂ -may be converted to -O-CH ₂ -O- by replacing non-adjacent -CH ₂ -with -O-. However, adjacent -CH _2- is not replaced by -O-. This replacement is because -OO-CH _2- (peroxide) is formed.

テトラヒドロピラン－２，５－ジイルのような二価基においても同様である。カルボニルオキシのような結合基（－ＣＯＯ－または－ＯＣＯ－）も同様である。 The alkyl of the liquid crystal compound is linear or branched and does not contain cyclic alkyl. Linear alkyls are preferred over branched alkyls. The same is true for end groups such as alkoxy and alkenyl. The configuration of 1,4-cyclohexylene is preferably trans rather than cis in order to increase the maximum temperature. Because 2-fluoro-1,4-phenylene is left-right asymmetrical, there are left (L) and right (R) orientations.

The same applies to divalent groups such as tetrahydropyran-2,5-diyl. The same applies to linking groups (-COO- or -OCO-) such as carbonyloxy.

The present invention includes the following items.

Item 1. Containing at least one compound selected from a compound represented by the formula (S) as a first additive, and a compound in which at least one hydrogen of the compound represented by the formula (S) is replaced with a monovalent group Liquid crystal composition having a nematic phase and negative dielectric anisotropy.

式（１）において、Ｒ^１ａ、Ｒ^１ｂ、およびＲ^１ｃは、水素、炭素数１から２０のアルキル、炭素数３から２０の脂環式炭化水素基、または炭素数６から２０の芳香族炭化水素基であり、これらの基において、少なくとも１つの－ＣＨ_２－は、－Ｏ－、－ＮＨ－、－ＣＯ－、－ＣＯＯ－、または－ＯＣＯ－で置き換えられてもよく、少なくとも１つの－ＣＨ_２－ＣＨ_２－は、－ＣＨ＝ＣＨ－または－Ｃ≡Ｃ－で置き換えられてもよく、これらの基において、少なくとも１つの水素は、炭素数１から１０のアルキル、炭素数１から１０のアルコキシ、またはハロゲンで置き換えられてもよく；ｎは、１、２、３、または４である。 Item 2. Item 2. The liquid crystal composition according to item 1, containing at least one compound selected from the compounds represented by formula (1) as a first additive.

In the formula (1), R ^1a , R ^1b and R ^1c are hydrogen, alkyl having 1 to 20 carbon atoms, alicyclic hydrocarbon group having 3 to 20 carbon atoms, or aromatic carbon having 6 to 20 carbon atoms A hydrogen group, in which at least one —CH ₂ — may be replaced by —O—, —NH—, —CO—, —COO—, or —OCO—, at least one — CH ₂ —CH ₂ — may be replaced by —CH = CH— or —C≡C—, and in these groups, at least one hydrogen is an alkyl having 1 to 10 carbons, 1 to 10 carbons May be replaced by alkoxy or halogen; n is 1, 2, 3 or 4.

式（１－１）から式（１－１０）において、Ｒ^１ｄは、水素または炭素数１から１５のアルキルであり、このアルキルにおいて、少なくとも１つの－ＣＨ_２－は、－Ｏ－、－ＮＨ－、－ＣＯ－、－ＣＯＯ－、または－ＯＣＯ－で置き換えられてもよく；Ｒ^１ｅおよびＲ^１ｆは、水素、炭素数１から１５のアルキル、または炭素数１から１５のアルコキシであり；Ｒ^１ｇは、水素または炭素数１から１５のアルキルであり；Ｒ^１ｈは、水素または炭素数１から１５のアルキルであり、このアルキルにおいて、少なくとも１つの－ＣＨ_２－は、－Ｏ－、－ＮＨ－、－ＣＯ－、－ＣＯＯ－、または－ＯＣＯ－で置き換えられてもよく；Ｒ^１ｉは、炭素数１から１０のアルキル、炭素数１から１０のアルコキシ、またはハロゲンであり；Ｚ^１ａ、Ｚ^１ｂ、およびＺ^１ｃは、単結合または炭素数１から５のアルキレンであり、このアルキレンにおいて、少なくとも１つの－ＣＨ_２－は、－Ｏ－で置き換えられてもよく、これらの基において、少なくとも１つの水素は、炭素数１から５のアルキルで置き換えられてもよく；ｍは、０、１、２、３、４、または５である。 Item 3. Item 3. The liquid crystal composition according to item 1 or 2, containing at least one compound selected from compounds represented by formula (1-1) to formula (1-10) as a first additive.

In formulas (1-1) to (1-10), R ^1d is hydrogen or alkyl having 1 to 15 carbon atoms, and in this alkyl, at least one —CH ₂ — is —O—, —NH -, -CO-, -COO-, or -OCO- may be replaced; R ^1e and R ^1f are hydrogen, alkyl having 1 to 15 carbons, or alkoxy having 1 to 15 carbons; R ^{1 g} is hydrogen or alkyl having 1 to 15 carbons; R ^{1 h} is hydrogen or alkyl having 1 to 15 carbons, and in this alkyl, at least one —CH ₂ — is —O—, —NH -, - CO -, - COO- , or may be replaced by ^{-OCO-; R 1i} is alkyl of 1 to 10 carbons, there 1 -C 10 alkoxy or halogen,; ^{Z 1} , ^{Z 1b} and ^{Z 1c,} is alkylene of 5 a single bond or 1 carbon atoms, in the alkylene, at least one -CH ₂ - may be replaced by -O-, in these groups, At least one hydrogen may be replaced by alkyl having 1 to 5 carbons; m is 0, 1, 2, 3, 4 or 5.

Item 4. Item 4. The liquid crystal composition according to any one of items 1 to 3, wherein the proportion of the first additive is in the range of 0.001% by mass to 2% by mass.

式（２）において、Ｒ^２ａおよびＲ^２ｂは、水素、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、炭素数２から１２のアルケニル、炭素数２から１２のアルケニルオキシ、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から１２のアルキルであり；環Ａおよび環Ｃは、１，４－シクロヘキシレン、１，４－シクロヘキセニレン、テトラヒドロピラン－２，５－ジイル、１，４－フェニレン、少なくとも１つの水素がフッ素または塩素で置き換えられた１，４－フェニレン、ナフタレン－２，６－ジイル、少なくとも１つの水素がフッ素または塩素で置き換えられたナフタレン－２，６－ジイル、クロマン－２，６－ジイル、または少なくとも１つの水素がフッ素または塩素で置き換えられたクロマン－２，６－ジイルであり；環Ｂは、２，３－ジフルオロ－１，４－フェニレン、２－クロロ－３－フルオロ－１，４－フェニレン、２，３－ジフルオロ－５－メチル－１，４－フェニレン、３，４，５－トリフルオロナフタレン－２，６－ジイル、７，８－ジフルオロクロマン－２，６－ジイル、３，４，５，６－テトラフルオロフルオレン－２，７－ジイル、４，６－ジフルオロジベンゾフラン－３，７－ジイル、４，６－ジフルオロジベンゾチオフェン－３，７－ジイル、または１，１，６，７－テトラフルオロインダン－２，５－ジイルであり；Ｚ^２ａおよびＺ^２ｂは、単結合、エチレン、メチレンオキシ、またはカルボニルオキシであり；ａは０、１、２、または３であり、ｂは０または１であり；そしてａとｂとの和は３以下である。 Item 5. 5. The liquid crystal composition according to any one of items 1 to 4, containing at least one compound selected from the compounds represented by formula (2) as a first component.

In the formula (2), R ^2a and R ^2b are hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, alkenyloxy having 2 to 12 carbons, or at least Ring A and ring C are 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-, wherein C 1-12 alkyl in which one hydrogen is replaced by fluorine or chlorine; Diyl, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced by fluorine or chlorine, naphthalene-2,6-diyl, naphthalene-2, in which at least one hydrogen is replaced by fluorine or chlorine, 6-diyl, chroman-2, 6-diyl or a group in which at least one hydrogen is replaced by fluorine or chlorine Mann-2, 6-diyl; ring B is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5-methyl- 1,4-phenylene, 3,4,5-trifluoronaphthalene-2,6-diyl, 7,8-difluorochroman-2,6-diyl, 3,4,5,6-tetrafluorofluorene-2,7 -Diyl, 4,6-difluorodibenzofuran-3,7-diyl, 4,6-difluorodibenzothiophene-3,7-diyl, or 1,1,6,7-tetrafluoroindane-2,5-diyl Z ^2a and Z ^2b are a single bond, ethylene, methyleneoxy or carbonyloxy; a is 0, 1, 2 or 3; b is 0 or 1; and the sum of a and b Is 3 or more It is.

式（２－１）から式（２－３５）において、Ｒ^２ａおよびＲ^２ｂは、水素、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、炭素数２から１２のアルケニル、炭素数２から１２のアルケニルオキシ、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から１２のアルキルである。 Item 6. 6. The liquid crystal composition according to any one of items 1 to 5, containing at least one compound selected from compounds represented by formula (2-1) to formula (2-35) as a first component.

In formulas (2-1) to (2-35), R ^2a and R ^2b are each hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, 2 to 12 alkenyloxy, or C 1 to C 12 alkyl in which at least one hydrogen is replaced by fluorine or chlorine.

Item 7. 7. The liquid crystal composition according to item 5 or 6, wherein the proportion of the first component is in the range of 10% by mass to 90% by mass.

式（３）において、Ｒ^３ａおよびＲ^３ｂは、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、炭素数２から１２のアルケニル、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数２から１２のアルケニルであり；環Ｄおよび環Ｅは、１，４－シクロヘキシレン、１，４－フェニレン、２－フルオロ－１，４－フェニレン、または２，５－ジフルオロ－１，４－フェニレンであり；Ｚ^３ａは、単結合、エチレン、またはカルボニルオキシであり；ｃは１、２、または３である。 Item 8. 8. The liquid crystal composition according to any one of items 1 to 7, containing at least one compound selected from the compounds represented by formula (3) as a second component.

In the formula (3), R ^3a and R ^3b are alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or at least one hydrogen is replaced by fluorine or chlorine Ring C and ring E are 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene or 2,5-difluoro-1,4; Z ^3a is a single bond, ethylene or carbonyloxy; c is 1, 2 or 3.

式（３－１）から式（３－１３）において、Ｒ^３ａおよびＲ^３ｂは、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、炭素数２から１２のアルケニル、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数２から１２のアルケニルである。 Item 9. 9. The liquid crystal composition according to any one of items 1 to 8, containing at least one compound selected from the compounds represented by formulas (3-1) to (3-13) as a second component.

In formulas (3-1) to (3-13), R ^3a and R ^3b are each an alkyl of 1 to 12 carbons, an alkoxy of 1 to 12 carbons, an alkenyl of 2 to 12 carbons, or at least one of Hydrogen is alkenyl having 2 to 12 carbon atoms replaced with fluorine or chlorine.

Item 10. Item 10. The liquid crystal composition according to item 8 or 9, wherein the proportion of the second component is in the range of 10% by mass to 90% by mass.

式（４）において、環Ｆおよび環Ｉは、シクロヘキシル、シクロヘキセニル、フェニル、１－ナフチル、２－ナフチル、テトラヒドロピラン－２－イル、１，３－ジオキサン－２－イル、ピリミジン－２－イル、またはピリジン－２－イルであり、これらの環において、少なくとも１つの水素は、フッ素、塩素、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から１２のアルキルで置き換えられてもよく；環Ｇは、１，４－シクロヘキシレン、１，４－シクロヘキセニレン、１，４－フェニレン、ナフタレン－１，２－ジイル、ナフタレン－１，３－ジイル、ナフタレン－１，４－ジイル、ナフタレン－１，５－ジイル、ナフタレン－１，６－ジイル、ナフタレン－１，７－ジイル、ナフタレン－１，８－ジイル、ナフタレン－２，３－ジイル、ナフタレン－２，６－ジイル、ナフタレン－２，７－ジイル、テトラヒドロピラン－２，５－ジイル、１，３－ジオキサン－２，５－ジイル、ピリミジン－２，５－ジイル、またはピリジン－２，５－ジイルであり、これらの環において、少なくとも１つの水素は、フッ素、塩素、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から１２のアルキルで置き換えられてもよく；Ｚ^４ａおよびＺ^４ｂは、単結合または炭素数１から１０のアルキレンであり、このアルキレンにおいて、少なくとも１つの－ＣＨ_２－は、－Ｏ－、－ＣＯ－、－ＣＯＯ－、または－ＯＣＯ－で置き換えられてもよく、少なくとも１つの－ＣＨ_２－ＣＨ_２－は、－ＣＨ＝ＣＨ－、－Ｃ（ＣＨ_３）＝ＣＨ－、－ＣＨ＝Ｃ（ＣＨ_３）－、または－Ｃ（ＣＨ_３）＝Ｃ（ＣＨ_３）－で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；Ｐ^４ａ、Ｐ^４ｂ、およびＰ^４ｃは、重合性基であり；Ｓｐ^４ａ、Ｓｐ^４ｂ、およびＳｐ^４ｃは、単結合または炭素数１から１０のアルキレンであり、このアルキレンにおいて、少なくとも１つの－ＣＨ_２－は、－Ｏ－、－ＣＯＯ－、－ＯＣＯ－、または－ＯＣＯＯ－で置き換えられてもよく、少なくとも１つの－ＣＨ_２－ＣＨ_２－は、－ＣＨ＝ＣＨ－または－Ｃ≡Ｃ－で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；ｄは、０、１、または２であり；ｅ、ｆ、およびｇは、０、１、２、３、または４であり；そしてｅ、ｆ、およびｇの和は、１以上である。 Item 11. Item 11. The liquid crystal composition according to any one of items 1 to 10, containing at least one compound selected from polymerizable compounds represented by formula (4) as a second additive.

In Formula (4), ring F and ring I are cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxane-2-yl, pyrimidin-2-yl Or pyridin-2-yl, in these rings, at least one hydrogen is fluorine, chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or at least one hydrogen is fluorine or chlorine And may be substituted by alkyl having 1 to 12 carbon atoms which is substituted with ring G: 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-1,2-diyl , Naphthalene-1,3-diyl, Naphthalene-1,4-diyl, Naphthalene-1,5-diyl, Naphthalene-1,6-diy , Naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, naphthalene-2,7-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, and in these rings, at least one hydrogen is fluorine, chlorine, carbon number 1 12 alkyl, alkoxy having 1 to 12 carbons, or alkyl having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine; Z ^4a and Z ^4b may be a single bond or carbon alkylene from C 1 10, in the alkylene, at least one of _-CH 2 -, -O -, - CO -, - COO-, or In may be replaced, at least one _-CH 2 -CH ₂ is -OCO- - _{is, -CH = CH -, - C} (CH 3) = CH -, - CH = C (CH 3) -, or _{-C (CH 3) = C (} CH 3) - may be replaced by, in these groups, at least one hydrogen may be replaced by fluorine or ^chlorine; P ^{4a, P 4b} and ^{P 4c,} Is a polymerizable group; Sp ^4a , Sp ^4b and Sp ^4c are a single bond or an alkylene having 1 to 10 carbon atoms, and in this alkylene, at least one —CH ₂ — is —O—, — COO -, - OCO-, or may be replaced by -OCOO-, at least one _-CH 2 -CH ₂ - may be replaced by -CH = CH- or -C≡C-, these Group Where at least one hydrogen may be replaced by fluorine or chlorine; d is 0, 1 or 2; e, f and g are 0, 1, 2, 3 or 4 And the sum of e, f and g is 1 or more.

式（Ｐ－１）から式（Ｐ－５）において、Ｍ^１、Ｍ^２、およびＭ^３は、水素、フッ素、炭素数１から５のアルキル、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から５のアルキルである。 Item 12. ^12. The liquid crystal composition according to item 11, wherein in formula (4), P ^4a , P ^4b and P ^4c are groups selected from the polymerizable groups represented by formulas (P-1) to (P-5) object.

In Formula (P-1) to Formula (P-5), M ¹ , M ² , and M ³ are hydrogen, fluorine, alkyl having 1 to 5 carbon atoms, or at least one hydrogen is replaced with fluorine or chlorine And alkyl having 1 to 5 carbon atoms.

式（４－１）から式（４－２９）において、Ｐ^４ｄ、Ｐ^４ｅ、およびＰ^４ｆは、式（Ｐ－１）から式（Ｐ－３）で表される基から選択された重合性基であり、ここでＭ^１、Ｍ^２、およびＭ^３は、水素、フッ素、炭素数１から５のアルキル、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から５のアルキルであり：

Ｓｐ^４ａ、Ｓｐ^４ｂ、およびＳｐ^４ｃは、単結合または炭素数１から１０のアルキレンであり、このアルキレンにおいて、少なくとも１つの－ＣＨ_２－は、－Ｏ－、－ＣＯＯ－、－ＯＣＯ－、または－ＯＣＯＯ－で置き換えられてもよく、少なくとも１つの－ＣＨ_２－ＣＨ_２－は、－ＣＨ＝ＣＨ－または－Ｃ≡Ｃ－で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよい。 Item 13. Item 13. The liquid crystal according to any one of items 1 to 12, containing at least one compound selected from polymerizable compounds represented by formula (4-1) to formula (4-29) as a second additive: Composition.

In formulas (4-1) to (4-29), P ^4d , P ^4e , and P ^4f are each selected from the groups represented by formulas (P-1) to (P-3): A group wherein M ¹ , M ² and M ³ are hydrogen, fluorine, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen is replaced by fluorine or chlorine Yes:

Sp ^4a , Sp ^4b and Sp ^4c are a single bond or alkylene having 1 to 10 carbons, and in this alkylene, at least one —CH ₂ — is —O—, —COO—, —OCO—, or -OCOO- may be replaced, and at least one -CH ₂ -CH ₂ -may be replaced by -CH = CH- or -C≡C-, and in these groups, at least one hydrogen is , Fluorine or chlorine may be substituted.

Item 14. Item 14. The liquid crystal composition according to any one of items 11 to 13, wherein the proportion of the second additive is in the range of 0.03% by mass to 10% by mass.

Item 15. Item 15. A liquid crystal display device containing the liquid crystal composition according to any one of items 1 to 14.

Item 16. The liquid crystal display element according to item 15, wherein an operation mode of the liquid crystal display element is an IPS mode, a VA mode, an FFS mode, or an FPA mode, and a driving method of the liquid crystal display element is an active matrix method.

Item 17. Item 15. A polymer supported alignment type liquid crystal display device, comprising the liquid crystal composition according to any one of items 11 to 14, wherein a polymerizable compound in the liquid crystal composition is polymerized.

Item 18. Item 15. Use of the liquid crystal composition according to any one of items 1 to 14 in a liquid crystal display device.

Item 19. Item 15. Use of the liquid crystal composition according to any one of items 11 to 14 in a polymer supported alignment type liquid crystal display device.

The present invention also includes the following items. (A) One compound, two compounds, or one compound selected from additives such as optically active compounds, antioxidants, ultraviolet light absorbers, dyes, antifoaming agents, polymerizable compounds, polymerization initiators, polymerization inhibitors A composition as described above containing three or more compounds. (B) AM element containing the above composition. (C) The above composition further containing a polymerizable compound, and an AM element of a polymer supported orientation (PSA) type containing this composition. (D) An AM element of polymer supported orientation (PSA) type containing the above composition, and the polymerizable compound in this composition is polymerized. (E) A device containing the composition described above and having a mode of PC, TN, STN, ECB, OCB, IPS, VA, FFS, or FPA. (F) A transmission type device containing the above composition. (G) Use of the above composition as a composition having a nematic phase. (H) Use as an optically active composition by adding an optically active compound to the above composition.

The composition of the present invention will be described in the following order. First, the constitutions of component compounds in the composition will be described. Second, the main properties of the component compounds and the main effects of the compounds on the composition are explained. Third, the combination of components in the composition, the preferred ratio of the components and the basis thereof will be described. Fourth, the preferred embodiments of the component compounds are described. Fifth, preferred component compounds are shown. Sixth, additives that may be added to the composition will be described. Seventh, the synthesis methods of the component compounds will be described. Finally, the application of the composition is described.

First, the composition of the composition will be described. This composition contains a plurality of liquid crystal compounds. The composition may contain an additive. The additive is an optically active compound, an antioxidant, an ultraviolet light absorber, a quencher, a pigment, an antifoaming agent, a polymerizable compound, a polymerization initiator, a polymerization inhibitor, a polar compound and the like. This composition is classified into the composition A and the composition B from the viewpoint of the liquid crystal compound. Composition A may further contain other liquid crystal compounds, additives, and the like in addition to the liquid crystal compound selected from compound (2) and compound (3). The “other liquid crystal compound” is a liquid crystal compound different from the compound (2) and the compound (3). Such compounds are mixed into the composition for the purpose of further adjusting the properties.

Composition B consists essentially of the liquid crystal compound selected from compound (2) and compound (3). "Substantially" means that composition B may contain an additive, but does not contain any other liquid crystal compound. Composition B has a smaller number of components than composition A. Composition B is preferable to composition A in terms of cost reduction. Composition A is preferable to composition B from the viewpoint that the characteristics can be further adjusted by mixing other liquid crystal compounds.

Second, the main properties of the component compounds and the main effects of the compounds on the composition and the device are explained. The main properties of the component compounds are summarized in Table 2 based on the effects of the present invention. In the symbols of Table 2, L means large or high, M medium, and S small or low. The symbols L, M, S are classifications based on qualitative comparisons among the component compounds, and 0 (zero) means smaller than S.

The main effects of the component compounds are as follows. The first additive acts as an antioxidant and contributes to high heat or light stability. Compound (1) does not affect properties such as the upper limit temperature, the optical anisotropy, and the dielectric anisotropy in many cases because the amount of addition is small. Compound (2) raises the dielectric anisotropy and lowers the lower limit temperature. The compound (3) lowers the viscosity or raises the upper limit temperature. The compound (4) is polymerizable to give a polymer by polymerization. The polymer stabilizes the orientation of the liquid crystal molecules, thereby reducing the response time of the device and improving the image sticking.

Organic compounds are degraded by light and heat energy to generate radicals. This radical acts as a chain carrier and further reacts with other organic compounds to generate a new radical, which is linked. The antioxidant preferentially reacts with radicals present in the system to capture radicals generated as the product (organic compound) degrades, thereby suppressing chain reaction, that is, the progress of degradation.
Phenolic antioxidants such as 2,6-di-tert-butyl-4-methylphenol are used as general antioxidants, donate hydrogen of phenol moiety to radical, and are themselves steric hindrance It becomes a phenoxy radical with low activity, etc. Then, the radical is trapped and stabilized. This action suppresses the increase of radicals.

The first additive of the present invention is at least one compound selected from a compound represented by the formula (S) and a compound represented by the formula (S) in which at least one hydrogen is replaced with a monovalent group. It is. When the OH group of this compound becomes a phenoxy radical, the conjugated system is expanded, and radical scavenging is performed more efficiently. For this reason, compared with the conventional antioxidant, high activity antioxidant effect | action work | functions.

Third, the combination of the components in the composition, the preferable ratio of the component compounds and the basis thereof will be described. Preferred combinations of the components in the composition are: first additive + compound (2), first additive + compound (3), first additive + compound (2) + compound (3), first additive + compound (2) + second additive, first additive + compound (3) + second additive, or first additive + compound (2) + compound (3) + second additive. A further preferable combination is the first additive + compound (2) + compound (3) or the first additive + compound (2) + compound (3) + second additive.

The preferred proportion of the first additive is about 0.001% by mass or more to increase the stability to heat or light, and about 2% by mass or less to lower the lower limit temperature. A further preferred ratio is in the range of about 0.01% by weight to about 1% by weight. An especially desirable ratio is in the range of about 0.03% by mass to about 0.5% by mass.

The preferred proportion of the compound (2) is about 10% by mass or more in order to increase the dielectric anisotropy, and about 90% by mass or less in order to lower the lower limit temperature. A further preferred ratio is in the range of about 20% by weight to about 80% by weight. An especially desirable ratio is in the range of about 30% by weight to about 70% by weight.

The preferred proportion of the compound (3) is about 10% by mass or more to raise the upper limit temperature or to lower the viscosity, and about 90% by mass or less to raise the dielectric anisotropy. A further preferred ratio is in the range of about 20% by weight to about 80% by weight. An especially desirable ratio is in the range of about 30% by weight to about 70% by weight.

The second additive is added to the composition for the purpose of being adapted to a polymer-supported oriented device. The preferred proportion of the second additive is about 0.03% by mass or more for aligning liquid crystal molecules, and about 10% by mass or less for preventing display defects of the device. A further preferred ratio is in the range of about 0.1% by weight to about 2% by weight. An especially desirable ratio is in the range of about 0.2% by mass to about 1.0% by mass.

Fourth, the preferred embodiments of the component compounds are described. In the formula (1), R ^1a , R ^1b and R ^1c are hydrogen, alkyl having 1 to 20 carbon atoms, alicyclic hydrocarbon group having 3 to 20 carbon atoms, or aromatic carbon having 6 to 20 carbon atoms A hydrogen group, in which at least one —CH ₂ — may be replaced by —O—, —NH—, —CO—, —COO—, or —OCO—, at least one — CH ₂ —CH ₂ — may be replaced by —CH = CH— or —C≡C—, and in these groups, at least one hydrogen is an alkyl having 1 to 10 carbons, 1 to 10 carbons May be replaced by alkoxy or halogen. R ^1a , R ^1b or R ^1c is preferably hydrogen, alkyl having 1 to 20 carbons, alicyclic hydrocarbon having 6 to 15 carbons, aromatic hydrocarbon having 6 to 15 carbons, at least one of them Alkyl having 1 to 20 carbon atoms in which -CH ₂ -is replaced by -O-, -CO-, -COO-, or -OCO-, at least one -CH ₂ -CH ₂ -is -CH = CH- And C 1 -C 20 alkyl substituted by or C 6 -C 15 alicyclic hydrocarbon group in which at least one —CH ₂ — is substituted by —O—. n is 1, 2, 3 or 4; Preferably n is 2 and the substitution position is preferably ortho or para to the OH group.

In formulas (1-1) to (1-10), R ^1d is hydrogen or alkyl having 1 to 15 carbon atoms, and in this alkyl, at least one —CH ₂ — is —O—, —NH -, -CO-, -COO-, or -OCO- may be substituted. Desirable R ^1d is hydrogen or alkyl having 1 to 10 carbons. R ^1e and R ^1f are hydrogen, alkyl having 1 to 15 carbons, or alkoxy having 1 to 15 carbons. Desirable R ^1e is alkyl having 1 to 15 carbons. Particularly preferred is a highly sterically hindered branched alkyl such as a tert-butyl group. Desirable R ^1f is alkyl having 1 to 10 carbons. R ^1g is hydrogen or alkyl having 1 to 15 carbons. Desirable R ^1g is alkyl having 1 to 10 carbons. R ^1h is hydrogen or alkyl having 1 to 15 carbons, and in this alkyl, at least one —CH ₂ — is —O—, —NH—, —CO—, —COO—, or —OCO— It may be replaced. Preferred R ^1h is alkyl having 1 to 10 carbons, or alkyl having 1 to 10 carbons in which at least one —CH ₂ — is replaced by —COO— or —OCO—. R ¹ⁱ is alkyl having 1 to 10 carbons, alkoxy having 1 to 10 carbons, or halogen. Desirable R ¹ⁱ is alkyl having 1 to 10 carbons. Z ^1a , Z ^1b and Z ^1c are a single bond or alkylene having 1 to 5 carbon atoms, and in this alkylene, at least one —CH ₂ — may be replaced by —O—, and these groups And at least one hydrogen may be replaced by alkyl having 1 to 5 carbon atoms. Preferred Z ^1a , Z ^1b or Z ^1c is a single bond. m is 0, 1, 2, 3, 4 or 5; Preferred m is 1, 2 or 3.

Typical specific examples of the first additive are shown below, but the present invention is not limited thereto.

In the formulas (2) and (3), R ^2a and R ^2b are hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, and 2 to 12 carbons. It is alkenyloxy or alkyl having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine. Desirable R ^2a or R ^2b is alkyl having 1 to 12 carbons to increase stability, and alkoxy having 1 to 12 carbons to increase dielectric anisotropy. R ^3a and R ^3b are alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or 2 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine It is alkenyl. Desirable R ^3a or R ^3b is alkenyl having 2 to 12 carbons to lower the viscosity, and alkyl having 1 to 12 carbons to increase the stability.

Preferred alkyl is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl. More preferred alkyl is methyl, ethyl, propyl, butyl or pentyl to lower the viscosity.

Preferred alkoxy is methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy or heptyloxy. More desirable alkoxy is methoxy or ethoxy for decreasing the viscosity.

Preferred alkenyl is vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl or 5-hexenyl. More preferred alkenyl is vinyl, 1-propenyl, 3-butenyl or 3-pentenyl to reduce viscosity. The preferred configuration of —CH = CH— in these alkenyls depends on the position of the double bond. Trans is preferable in the alkenyl such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 3-pentenyl and 3-hexenyl for decreasing the viscosity and the like. Cis is preferred for alkenyl such as 2-butenyl, 2-pentenyl and 2-hexenyl.

Preferred alkenyloxy is vinyloxy, allyloxy, 3-butenyloxy, 3-pentenyloxy or 4-pentenyloxy. More preferable alkenyloxy is allyloxy or 3-butenyloxy to lower the viscosity.

Preferred examples of the alkyl in which at least one hydrogen is replaced by fluorine or chlorine are fluoromethyl, 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl, 5-fluoropentyl, 6-fluorohexyl, 7-fluoroheptyl Or 8-fluorooctyl. Further preferred examples are 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl or 5-fluoropentyl to increase the dielectric anisotropy.

Preferred examples of the alkenyl in which at least one hydrogen is replaced by fluorine or chlorine are: 2,2-difluorovinyl, 3,3-difluoro-2-propenyl, 4,4-difluoro-3-butenyl, 5,5-difluoro -4-pentenyl or 6,6-difluoro-5-hexenyl. Further preferred examples are 2,2-difluorovinyl or 4,4-difluoro-3-butenyl for decreasing the viscosity.

または

であり、好ましくは

である。 Ring A and ring C are 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,4-phenylene, at least one hydrogen is replaced by fluorine or chlorine 1 , 4-phenylene, naphthalene-2,6-diyl, naphthalene-2,6-diyl in which at least one hydrogen is replaced by fluorine or chlorine, chroman-2,6-diyl, or at least one hydrogen is fluorine or chlorine It is chroman-2, 6-diyl replaced by. Preferred examples of "1,4-phenylene in which at least one hydrogen is replaced by fluorine or chlorine" are 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene or 2-chloro- It is 3-fluoro-1,4-phenylene. Preferred ring A or ring C is 1,4-cyclohexylene to lower viscosity, and tetrahydropyran-2,5-diyl to increase dielectric anisotropy, to increase optical anisotropy It is 1,4-phenylene. Tetrahydropyran-2,5-diyl is

Or

And preferably

It is.

好ましい環Ｂは、粘度を下げるために２，３－ジフルオロ－１，４－フェニレンであり、光学異方性を下げるために２－クロロ－３－フルオロ－１，４－フェニレンであり、誘電率異方性を上げるために７，８－ジフルオロクロマン－２，６－ジイルである。 Ring B is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5-methyl-1,4-phenylene, 3,4,4, 5-trifluoronaphthalene-2,6-diyl, 7,8-difluorochroman-2,6-diyl, 3,4,5,6-tetrafluorofluorene-2,7-diyl (FLF4), 4,6- Difluorodibenzofuran-3,7-diyl (DBFF2), 4,6-difluorodibenzothiophene-3,7-diyl (DBTF2), or 1,1,6,7-tetrafluoroindane-2,5-diyl (InF4) It is.

Preferred ring B is 2,3-difluoro-1,4-phenylene to lower the viscosity, 2-chloro-3-fluoro-1,4-phenylene to lower the optical anisotropy, and the dielectric constant 7,8-Difluorochroman-2,6-diyl to increase anisotropy.

Ring D and ring E are 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene or 2,5-difluoro-1,4-phenylene. Preferred ring D or ring E is 1,4-cyclohexylene to lower the viscosity or to raise the upper temperature limit, and 1,4-phenylene to lower the lower temperature limit.

Z ^2a and Z ^2b are a single bond, ethylene, methyleneoxy or carbonyloxy. Desirable Z ^2a or Z ^2b is a single bond to lower the viscosity, ethylene to lower the lower limit temperature, and methyleneoxy to increase the dielectric anisotropy. Z ^3a is a single bond, ethylene or carbonyloxy. Preferred Z ^3a is a single bond to lower the viscosity.

A is 0, 1, 2 or 3; b is 0 or 1; and the sum of a and b is 3 or less. Preferred a is 1 to lower the viscosity and 2 or 3 to raise the upper temperature limit. Desirable b is 0 to lower the viscosity and 1 to lower the lower limit temperature. c is 1, 2 or 3; Preferred c is 1 to lower the viscosity and 2 or 3 to raise the upper temperature limit.

In Formula (4), P ^4a , P ^4b and P ^4c are polymerizable groups. Preferable P ^4a , P ^4b or P ^4c is a polymerizable group selected from the groups represented by Formula (P-1) to Formula (P-5). Further preferred P ^4a , P ^4b or P ^4c is a group (P-1) or a group (P-2). Particularly preferred group (P-1) is —OCO—CH = CH ₂ or —OCO—C (CH ₃ ) = CH ₂ . The wavy lines in group (P-1) to group (P-5) indicate the binding site.

In groups (P-1) to (P-5), M ¹ , M ² and M ³ are hydrogen, fluorine, alkyl having 1 to 5 carbon atoms, or at least one hydrogen is replaced by fluorine or chlorine And alkyl having 1 to 5 carbon atoms. Preferred M ¹ , M ² or M ³ is hydrogen or methyl to increase the reactivity. Further preferred M ¹ is methyl and further preferred M ² or M ³ is hydrogen.

In formulas (4-1) to (4-29), P ^4d , P ^4e and P ^4f are groups represented by formulas (P-1) to (P-3). Preferred P ^4d , P ^4e or P ^4f is a group (P-1) or a group (P-2). Further preferred group (P-1) is —OCO—CH = CH ₂ or —OCO—C (CH ₃ ) = CH ₂ . The wavy lines in group (P-1) to group (P-3) indicate the binding site.

In the formula (4), Sp ^4a , Sp ^4b and Sp ^4c are a single bond or alkylene having 1 to 10 carbon atoms, and in this alkylene, at least one —CH ₂ — is —O—, —COO— , -OCO-, or -OCOO-, and at least one -CH ₂ -CH ₂ -may be replaced by -CH = CH- or -C≡C-, in these groups , At least one hydrogen may be replaced by fluorine or chlorine. Preferred Sp ^4a , Sp ^4b or Sp ^4c is a single bond, -CH ₂ CH _2- , -CH ₂ O-, -OCH _2- , -COO-, -OCO-, -CO-CH = CH-, or It is -CH = CH-CO-. Further preferred Sp ^4a , Sp ^4b or Sp ^4c is a single bond.

Ring F and ring I may be cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxane-2-yl, pyrimidin-2-yl or pyridine-2- In these rings, at least one hydrogen is fluorine, chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or the number of carbons in which at least one hydrogen is replaced by fluorine or chlorine. It may be substituted with 1 to 12 alkyl. Preferred ring F or ring I is phenyl. Ring G is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1,4-diyl, naphthalene -1,5-diyl, naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, naphthalene-2 , 7-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, in these rings, At least one hydrogen is fluorine, chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or at least one hydrogen is fluorine or chlorine. From the obtained 1 carbon atoms may be replaced by alkyl of 12. Preferred ring G is 1,4-phenylene or 2-fluoro-1,4-phenylene.

Z ^4a and Z ^4b are a single bond or alkylene having 1 to 10 carbon atoms, and in this alkylene, at least one -CH ₂ -is -O-, -CO-, -COO-, or -OCO- And at least one —CH ₂ —CH ₂ — may be replaced by —CH = CH—, —C (CH ₃ ) = CH—, —CH = C (CH ₃ ) —, or —C (CH _3). ) = C (CH ₃ )-, and in these groups, at least one hydrogen may be replaced by fluorine or chlorine. Preferred Z ^4a or Z ^4b is a single bond, -CH ₂ CH _2- , -CH ₂ O-, -OCH _2- , -COO-, or -OCO-. Further preferred Z ^4a or Z ^4b is a single bond.

D is 0, 1 or 2; Preferred d is 0 or 1. e, f and g are 0, 1, 2, 3 or 4 and the sum of e, f and g is 1 or more. Preferred e, f or g is 1 or 2.

Fifth, preferred component compounds are shown. The preferred compound (1) is the compound (1-1) to the compound (1-10) described in item 3. Among these compounds, the compound (1-2), the compound (1-3) or the compound (1-8) is preferable.

The preferred compound (2) is a compound (2-1) to a compound (2-35) described in item 6. In these compounds, at least one of the first components is a compound (2-1), a compound (2-3), a compound (2-6), a compound (2-8), a compound (2-10), a compound (2 It is preferable that it is 2-14) or the compound (2-16). At least two of the first components are the compound (2-1) and the compound (2-8), the compound (2-1) and the compound (2-14), the compound (2-3) and the compound (2-8), Compound (2-3) and Compound (2-14), Compound (2-3) and Compound (2-16), Compound (2-6) and Compound (2-8), Compound (2-6) and Compound The combination of (2-10), compound (2-6) and compound (2-16), compound (2-10) and compound (2-16) is preferred.

The preferred compound (3) is the compound (3-1) to the compound (3-13) described in item 9. In these compounds, at least one of the second components is a compound (3-1), a compound (3-3), a compound (3-5), a compound (3-6), a compound (3-8), or a compound (3-9) is preferred. At least two of the second components are the compound (3-1) and the compound (3-3), the compound (3-1) and the compound (3-5), or the compound (3-1) and the compound (3-6) It is preferable that it is a combination of

The preferred compound (4) is a compound (4-1) to a compound (4-29) described in item 13. In these compounds, at least one of the second additives is a compound (4-1), a compound (4-2), a compound (4-24), a compound (4-25), a compound (4-26), or It is preferably a compound (4-27). At least two of the second additives are the compound (4-1) and the compound (4-2), the compound (4-1) and the compound (4-18), the compound (4-2) and the compound (4-24) , Compound (4-2) and Compound (4-25), Compound (4-2) and Compound (4-26), Compound (4-25) and Compound (4-26), or Compound (4-18) It is preferable that it is a combination of and a compound (4-24).

Sixth, additives that may be added to the composition will be described. Such additives include optically active compounds, antioxidants, ultraviolet light absorbers, quenchers, dyes, antifoaming agents, polymerizable compounds, polymerization initiators, polymerization inhibitors, polar compounds and the like. An optically active compound is added to the composition for the purpose of inducing a helical structure of liquid crystal molecules to give a twist angle. Examples of such compounds are compounds (5-1) to (5-5). The preferred proportion of the optically active compound is about 5% by mass or less. A further preferred ratio is in the range of about 0.01% by weight to about 2% by weight.

In order to prevent a decrease in specific resistance due to heating in the atmosphere, or to maintain a large voltage holding ratio not only at room temperature but also at a temperature close to the upper limit temperature after the device has been used for a long time, ) To compound (6-3) may be further added to the composition.

Since the compound (6-2) has low volatility, it is effective to maintain a large voltage holding ratio not only at room temperature but also at a temperature close to the upper limit temperature after using the device for a long time. The preferred proportion of the antioxidant is about 50 ppm or more to obtain its effect, and is about 600 ppm or less so as not to lower the upper temperature limit or to raise the lower temperature limit. A further preferred ratio is in the range of about 100 ppm to about 300 ppm.

Preferred examples of the UV absorbers are benzophenone derivatives, benzoate derivatives, triazole derivatives and the like. Also preferred are light stabilizers such as sterically hindered amines. Preferred examples of the light stabilizer include compound (7-1) to compound (7-16). The preferred proportion of these absorbents and stabilizers is about 50 ppm or more to obtain the effect, and about 10000 ppm or less so as not to lower the upper temperature limit or to raise the lower temperature limit. A further preferred ratio is in the range of about 100 ppm to about 10000 ppm.

The quencher is a compound that receives the light energy absorbed by the liquid crystal compound and converts it into heat energy to prevent the decomposition of the liquid crystal compound. Preferred examples of the quencher are compound (8-1) to compound (8-7). The preferred proportion of these quenchers is about 50 ppm or more to obtain the effect, and about 20000 ppm or less in order not to raise the lower limit temperature. A further preferred ratio is in the range of about 100 ppm to about 10000 ppm.

In order to conform to a guest host (GH) mode device, a dichroic dye such as an azo dye or an anthraquinone dye is added to the composition. The preferred proportion of dye is in the range of about 0.01% by weight to about 10% by weight. In order to prevent foaming, an antifoam agent such as dimethyl silicone oil, methylphenyl silicone oil or the like is added to the composition. The preferable proportion of the antifoaming agent is about 1 ppm or more in order to obtain the effect, and is about 1000 ppm or less in order to prevent display defects. A further preferred ratio is in the range of about 1 ppm to about 500 ppm.

Polymerizable compounds are used to make them compatible with polymer-supported oriented (PSA) type devices. Compound (4) is suitable for this purpose. Along with the compound (4), a polymerizable compound different from the compound (4) may be added to the composition. Preferred examples of such polymerizable compounds are compounds such as acrylates, methacrylates, vinyl compounds, vinyloxy compounds, propenyl ethers, epoxy compounds (oxiranes, oxetanes) and vinyl ketones. Further preferred examples are derivatives of acrylate or methacrylate. The preferred proportion of the compound (4) is 10% by mass or more based on the total mass of the polymerizable compound. A further preferable ratio is 50% by mass or more. An especially desirable ratio is 80% by mass or more. The most preferable ratio is 100% by mass.

The polymerizable compound such as the compound (4) is polymerized by ultraviolet irradiation. It may be polymerized in the presence of a suitable initiator such as a photoinitiator. Appropriate conditions for polymerization, appropriate types of initiators, and appropriate amounts are known to the person skilled in the art and are described in the literature. For example, Irgacure 651 (registered trademark; BASF), Irgacure 184 (registered trademark; BASF), or Darocur 1173 (registered trademark; BASF), which are photoinitiators, are suitable for radical polymerization. The preferred proportion of the photoinitiator is in the range of about 0.1 wt% to about 5 wt% based on the total weight of the polymerizable compound. A further preferred ratio is in the range of about 1% by weight to about 3% by weight.

When storing a polymerizable compound such as compound (4), a polymerization inhibitor may be added to prevent polymerization. The polymerizable compound is usually added to the composition without removing the polymerization inhibitor. Examples of polymerization inhibitors are hydroquinone, hydroquinone derivatives such as methylhydroquinone, 4-t-butylcatechol, 4-methoxyphenol, phenothiazine and the like.

Seventh, the synthesis methods of the component compounds will be described. These compounds can be synthesized by known methods. The synthesis method is illustrated. The compound (1-2) is synthesized by the method described in JP-A-2010-120894. The compound (2-1) is synthesized by the method described in JP-A-2000-053602. The compound (3-1) is synthesized by the method described in JP-A-59-176221. The compound (4-18) is synthesized by the method described in JP-A-7-101900. Antioxidants are commercially available. Compound (6-1) can be obtained from Aldrich (Sigma-Aldrich Corporation). The compound (6-2) and the like are synthesized by the method described in US Pat. No. 3,660,505.

Compounds that did not describe the synthesis method include organic syntheses (John Wiley & Sons, Inc), Organic Reactions (John Wiley & Sons, Inc), comprehensive organic syntheses (Comprehensive Organic) It can be synthesized by the method described in the book such as Synthesis, Pergamon Press), New Experimental Chemistry Course (Maruzen). The compositions are prepared from the compounds thus obtained by known methods. For example, the component compounds are mixed and dissolved together by heating.

Finally, the application of the composition is described. The composition primarily has a lower temperature limit of about -10 ° C. or lower, an upper temperature limit of about 70 ° C. or higher, and an optical anisotropy in the range of about 0.07 to about 0.20. A composition having an optical anisotropy in the range of about 0.08 to about 0.25 may be prepared by controlling the proportions of the component compounds, or by mixing other liquid crystal compounds. By trial and error, compositions having an optical anisotropy in the range of about 0.10 to about 0.30 may be prepared. Devices containing this composition have a large voltage holding ratio. This composition is suitable for an AM device. This composition is particularly suitable for transmissive AM devices. This composition can be used as a composition having a nematic phase, or as an optically active composition by adding an optically active compound.

This composition can be used for an AM device. Furthermore, the use to PM element is also possible. This composition can be used for AM devices and PM devices having modes such as PC, TN, STN, ECB, OCB, IPS, FFS, VA, FPA. The use for an AM device having a TN, OCB, IPS mode or FFS mode is particularly preferred. In an AM device having an IPS mode or an FFS mode, the alignment of liquid crystal molecules may be parallel to or perpendicular to the glass substrate when no voltage is applied. These elements may be reflective, transmissive or semi-transmissive. Its use for transmission type devices is preferred. The use for amorphous silicon-TFT elements or polycrystalline silicon-TFT elements is also possible. The composition can be used for an element of NCAP (nematic curvilinear aligned phase) type prepared by microencapsulation or a element of PD (polymer dispersed) type in which a three-dimensional network polymer is formed in the composition.

The invention will be explained in more detail by means of examples. The invention is not limited by these examples. The present invention comprises a mixture of the composition of Example 1 and the composition of Example 2. The present invention also includes a mixture of at least two of the compositions of the Examples. The compound synthesized was identified by a method such as NMR analysis. The properties of the compounds, compositions, and devices were measured by the methods described below.

NMR analysis: For measurement, DRX-500 manufactured by Bruker Biospin Ltd. was used. ^In the measurement of ¹ H-NMR, the sample was dissolved in a deuterated solvent such as CDCl _3, and the measurement was performed at room temperature under conditions of 500 MHz and 16 integrations. Tetramethylsilane was used as an internal standard. ^{In the 19} F-NMR measurement, CFCl ₃ was used as an internal standard, and the integration was performed 24 times. In the description of nuclear magnetic resonance spectrum, s is singlet, d is doublet, t is triplet, q is quartet, quin is quintet, sex is sextet, m is multiplet, br is broad.

Gas Chromatographic Analysis: A GC-14B gas chromatograph made by Shimadzu Corporation was used for measurement. The carrier gas is helium (2 mL / min). The sample vaporization chamber was set at 280 ° C. and the detector (FID) was set at 300 ° C. For separation of the component compounds, capillary columns DB-1 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm; fixed liquid phase is dimethylpolysiloxane; nonpolar) manufactured by Agilent Technologies Inc. were used. The column was kept at 200 ° C. for 2 minutes and then heated to 280 ° C. at a rate of 5 ° C./minute. The sample was prepared in an acetone solution (0.1% by mass), and 1 μL thereof was injected into the sample vaporization chamber. The recorder is Model C-R5A Chromatopac manufactured by Shimadzu Corporation, or its equivalent. The obtained gas chromatogram showed the retention time of the peak corresponding to the component compound and the area of the peak.

As a solvent for diluting the sample, chloroform, hexane or the like may be used. The following capillary column may be used to separate the component compounds. HP-1 (30 m in length, 0.32 mm in diameter, 0.25 μm in thickness) manufactured by Agilent Technologies Inc., Rtx-1 (30 m in length, 0.32 mm in inside diameter, 0.25 μm in film thickness) manufactured by Restek Corporation, BP-1 (30 m in length, 0.32 mm in inner diameter, 0.25 μm in film thickness) manufactured by SGE International Pty. Ltd. A capillary column CBP1-M50-025 (length 50 m, inner diameter 0.25 mm, film thickness 0.25 μm) manufactured by Shimadzu Corporation may be used for the purpose of preventing overlapping of compound peaks.

The proportion of the liquid crystal compound contained in the composition may be calculated by the following method. The mixture of liquid crystalline compounds is analyzed by gas chromatography (FID). The area ratio of peaks in the gas chromatogram corresponds to the proportion of the liquid crystal compound. When the capillary column described above is used, the correction coefficient of each liquid crystal compound may be regarded as 1. Therefore, the ratio (mass%) of the liquid crystal compound can be calculated from the area ratio of the peaks.

Measurement sample: When measuring the characteristics of the composition or element, the composition was used as it was as a sample. When measuring the properties of the compound, a sample for measurement was prepared by mixing this compound (15% by mass) with the mother liquid crystal (85% by mass). The characteristic values of the compound were calculated by extrapolation from the values obtained by the measurement. (Extrapolated value) = {(measured value of sample) −0.85 × (measured value of mother liquid crystal)} / 0.15. When a smectic phase (or crystal) precipitates at 25 ° C. in this proportion, the proportion of the compound and the base liquid crystal is 10 mass%: 90 mass%, 5 mass%: 95 mass%, 1 mass%: 99 mass% in this order. changed. The values of the upper limit temperature, the optical anisotropy, the viscosity, and the dielectric anisotropy of the compound were determined by this extrapolation method.

The following mother liquid crystals were used. The proportions of the component compounds are indicated by mass%.

Measurement method: The measurement of the characteristics was performed by the following method. Many of these are the methods described in the JEITA standard (JEITA ED-2521B), which has been deliberated and enacted by the Japan Electronics and Information Technology Industries Association (JEITA), or a modified method thereof. Met. A thin film transistor (TFT) was not attached to the TN device used for the measurement.

(1) Upper limit temperature of nematic phase (NI; ° C.): The sample was placed on a hot plate of a melting point measuring apparatus equipped with a polarization microscope and heated at a rate of 1 ° C./min. The temperature was measured when part of the sample changed from the nematic phase to the isotropic liquid. The upper limit temperature of the nematic phase may be abbreviated as "upper limit temperature".

(2) Lower limit temperature of nematic phase (T _C ; ° C.): The sample having the nematic phase is put in a glass bottle, and placed in a freezer at 0 ° C., -10 ° C., -20 ° C., -30 ° C. After storage, the liquid crystal phase was observed. For example, the sample remained in the -20 ° C. in a nematic phase, when changed to -30 ° C. At crystals or a smectic phase was described as <-20 ° C. The T _C. The lower limit temperature of the nematic phase may be abbreviated as "lower limit temperature".

(3) Viscosity (bulk viscosity; ;; measured at 20 ° C .; mPa · s): For measurement, an E-type rotational viscometer manufactured by Tokyo Keiki Co., Ltd. was used.

(4) Viscosity (rotational viscosity; γ1; measured at 25 ° C .; mPa · s): For measurement, a rotational viscosity measurement system LCM-2 type manufactured by Toyo Technica Co., Ltd. was used. The sample was injected into a VA device in which the distance between two glass substrates (cell gap) was 10 μm. A rectangular wave (55 V, 1 ms) was applied to this element. The peak current and peak time of transient current generated by this application were measured. The values of rotational viscosity were obtained using these measured values and dielectric anisotropy. The dielectric anisotropy was measured by the method described in the measurement (6).

(5) Optical anisotropy (refractive index anisotropy; Δn; measured at 25 ° C.): Measurement was performed using an Abbe refractometer with a polarizing plate attached to the ocular, using light of wavelength 589 nm. After rubbing the surface of the main prism in one direction, a sample was dropped on the main prism. The refractive index n∥ was measured when the polarization direction was parallel to the rubbing direction. The refractive index n⊥ was measured when the polarization direction was perpendicular to the rubbing direction. The value of optical anisotropy was calculated from the formula of Δn = n∥−n⊥.

(6) Dielectric anisotropy (Δε; measured at 25 ° C.): The value of dielectric anisotropy was calculated from the equation of Δε = εε−ε⊥. The dielectric constants (ε∥ and ε⊥) were measured as follows.
1) Measurement of dielectric constant (ε∥): A solution of octadecyltriethoxysilane (0.16 mL) in ethanol (20 mL) was applied to a well-cleaned glass substrate. The glass substrate was rotated by a spinner and then heated at 150 ° C. for 1 hour. A sample was placed in a VA device in which the distance between two glass substrates (cell gap) was 4 μm, and this device was sealed with an adhesive cured with ultraviolet light. Sine waves (0.5 V, 1 kHz) were applied to this device, and after 2 seconds, the dielectric constant (ε∥) in the major axis direction of liquid crystal molecules was measured.
2) Measurement of dielectric constant (ε⊥): A polyimide solution was applied to a well-cleaned glass substrate. After firing the glass substrate, the obtained alignment film was rubbed. The sample was placed in a TN device in which the distance between two glass substrates (cell gap) was 9 μm and the twist angle was 80 degrees. Sine waves (0.5 V, 1 kHz) were applied to this device, and after 2 seconds, the dielectric constant (⊥) in the minor axis direction of liquid crystal molecules was measured.

(7) Threshold voltage (Vth; measured at 25 ° C .; V): An LCD-5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for measurement. The light source was a halogen lamp. A sample is placed in a normally black mode VA device in which the distance between two glass substrates (cell gap) is 4 μm and the rubbing direction is antiparallel, and an adhesive for curing this device with ultraviolet light is used. Used and sealed. The voltage (60 Hz, rectangular wave) applied to this element was gradually increased by 0.02 V from 0 V to 20 V. At this time, the device was irradiated with light from the vertical direction, and the amount of light transmitted through the device was measured. A voltage-transmittance curve was created in which the transmittance was 100% when the light amount was maximum, and the transmittance was 0% when the light amount was minimum. The threshold voltage was represented by the voltage at 10% transmittance.

(8) Voltage holding ratio (VHR-9; measured at 25 ° C .;%): The TN device used for measurement had a polyimide alignment film, and the distance between two glass substrates (cell gap) was 5 μm. . The element was sealed with an adhesive that cures with ultraviolet light after the sample was placed. The TN device was charged by applying a pulse voltage (60 microseconds at 1 V). The decaying voltage was measured with a high speed voltmeter for 166.7 milliseconds, and the area A between the voltage curve and the horizontal axis in a unit cycle was determined. The area B was the area when it did not decay. The voltage holding ratio was expressed as a percentage of the area A to the area B.

(9) Voltage holding ratio (VHR-10; measured at 60 ° C .;%): The voltage holding ratio was measured in the same manner as described above except that the measurement was performed at 60 ° C. instead of 25 ° C. The obtained value is expressed as VHR-10.

(10) Voltage holding ratio (VHR-11; measured at 60 ° C .;%): After irradiation with ultraviolet light, the voltage holding ratio was measured to evaluate the stability to ultraviolet light. The TN device used for the measurement had a polyimide alignment film, and the cell gap was 5 μm. A sample was injected into this device and irradiated with ultraviolet light of 5 mW / cm ² for 167 minutes. The light source was Blacklight manufactured by Eye Graphics Co., Ltd., F40T10 / BL (peak wavelength 369 nm), and the distance between the element and the light source was 5 mm. For the measurement of VHR-11, the decaying voltage was measured for 166.7 milliseconds. Compositions having large VHR-11 have high stability to ultraviolet light.

(11) Voltage holding ratio (VHR-12; measured at 60 ° C .;%): The TN device injected with the sample is heated in a 120 ° C. constant temperature bath for 20 hours, and then the voltage holding ratio is measured and its stability to heat Was evaluated. In the measurement of VHR-12, the decaying voltage was measured for 166.7 milliseconds. Compositions having large VHR-12 have high thermal stability.

(12) Response time (τ; measured at 25 ° C .; ms): For measurement, LCD Evaluation System Model LCD-5100 made by Otsuka Electronics Co., Ltd. was used. The light source was a halogen lamp. The low pass filter (Low-pass filter) was set to 5 kHz. The sample was placed in a normally black mode VA element in which the distance between two glass substrates (cell gap) was 4 μm and the rubbing direction was antiparallel. The device was sealed using an adhesive that cures with ultraviolet light. A rectangular wave (60 Hz, 10 V, 0.5 seconds) was applied to this element. At this time, the device was irradiated with light from the vertical direction, and the amount of light transmitted through the device was measured. It was considered that the transmittance was 100% when the light amount was maximum, and the transmittance was 0% when the light amount was minimum. The response time is represented by the time (fall time; milliseconds) taken to change from 90% transmittance to 10% transmittance.

(13) Specific resistance (ρ; measured at 25 ° C .; Ω cm): 1.0 mL of a sample was injected into a container equipped with an electrode. A direct current voltage (10 V) was applied to the container, and a direct current after 10 seconds was measured. The specific resistance was calculated from the following equation. (Specific resistance) = {(voltage) × (electric capacity of container)} / {(direct current) × (dielectric constant of vacuum)}.

Examples of compositions are given below. Component compounds are represented by symbols based on the definition of Table 3 below. In Table 3, the configuration for 1,4-cyclohexylene is trans. The number in parenthesis after the symbolized compound represents the chemical formula to which the compound belongs. The symbol (-) means other liquid crystal compounds. The proportion (percentage) of the liquid crystal compound is a mass percentage (mass%) based on the mass of the liquid crystal composition not including the additive. Finally, the characteristic values of the composition were summarized.

Comparative Example 1
3-HB (2F, 3F) -O2 (2-1) 4%
2-BB (2F, 3F)-O2 (2-6) 8%
3-BB (2F, 3F)-O2 (2-6) 8%
V2-BB (2F, 3F) -O2 (2-6) 2%
V-HHB (2F, 3F) -O1 (2-8) 4%
V-HHB (2F, 3F) -O2 (2-8) 10%
V-HHB (2F, 3F) -O4 (2-8) 4%
2-HHB (2F, 3F) -O2 (2-8) 2%
3-HHB (2F, 3F) -O2 (2-8) 4%
5-HHB (2F, 3F) -O2 (2-8) 3%
3-HH2B (2F, 3F) -O2 (2-9) 10%
3-HD h B (2F, 3F)-O2 (2-13) 10%
3-dhBB (2F, 3F) -O2 (2-16) 2%
3-HH-V (3-1) 20%
3-HHB-1 (3-5) 3%
3-HBB-2 (3-6) 6%
NI = 89.9 ° C .; Tc <−20 ° C .; Δn = 0.111; Δε = −4.1; Vth = 1.98 V; VHR-11 = 74.3%

A composition obtained by adding the compound (1-A) to the composition of Comparative Example 1 is referred to as Example 1.
Example 1
3-HB (2F, 3F) -O2 (2-1) 4%
2-BB (2F, 3F)-O2 (2-6) 8%
3-BB (2F, 3F)-O2 (2-6) 8%
V2-BB (2F, 3F) -O2 (2-6) 2%
V-HHB (2F, 3F) -O1 (2-8) 4%
V-HHB (2F, 3F) -O2 (2-8) 10%
V-HHB (2F, 3F) -O4 (2-8) 4%
2-HHB (2F, 3F) -O2 (2-8) 2%
3-HHB (2F, 3F) -O2 (2-8) 4%
5-HHB (2F, 3F) -O2 (2-8) 3%
3-HH2B (2F, 3F) -O2 (2-9) 10%
3-HD h B (2F, 3F)-O2 (2-13) 10%
3-dhBB (2F, 3F) -O2 (2-16) 2%
3-HH-V (3-1) 20%
3-HHB-1 (3-5) 3%
3-HBB-2 (3-6) 6%
Compound (1-A) was added to this composition at a rate of 0.100% by mass.
NI = 89.9 ° C .; Tc <−20 ° C .; Δn = 0.111; Δε = −4.1; Vth = 1.98 V; VHR-11 = 84.9%

Example 2
2-H1OB (2F, 3F)-O2 (2-3) 8%
3-H1OB (2F, 3F) -O2 (2-3) 9%
2-HHB (2F, 3F) -O2 (2-8) 3%
3-HHB (2F, 3F) -O2 (2-8) 4%
2-HBB (2F, 3F) -O2 (2-14) 5%
3-HBB (2F, 3F) -O2 (2-14) 11%
4-HBB (2F, 3F) -O2 (2-14) 5%
5-HBB (2F, 3F) -O2 (2-14) 10%
2-HH-3 (3-1) 20%
3-HH-4 (3-1) 4%
3-HB-O2 (3-2) 14%
3-HBB-2 (3-6) 7%
The compound (1-D) was added to the composition at a ratio of 0.050% by mass.
NI = 77.8 ° C .; Tc <−20 ° C .; Δn = 0.105; Δε = −3.4; Vth = 2.13 V; VHR-11 = 93.7%

[Example 3]
2-H1OB (2F, 3F)-O2 (2-3) 7%
3-H1OB (2F, 3F) -O2 (2-3) 7%
2-HBB (2F, 3F) -O2 (2-14) 4%
3-HBB (2F, 3F) -O2 (2-14) 8%
4-HBB (2F, 3F) -O2 (2-14) 4%
5-HBB (2F, 3F) -O2 (2-14) 7%
2-BB (2F, 3F) B-3 (2-19) 2%
2-HH-3 (3-1) 18%
3-HH-4 (3-1) 4%
3-HH-5 (3-1) 3%
3-HB-O2 (3-2) 13%
5-HB-O2 (3-2) 7%
3-HHB-3 (3-5) 2%
3-HBB-2 (3-6) 14%
Compound (1-D) was added to this composition at a rate of 0.100% by mass.
Tc <−20 ° C .; = 1 = 15.2 mPa · s; Δn = 0.107; Δε = −2.1; VHR-11 = 97.3%.

Example 4
2-H1OB (2F, 3F)-O2 (2-3) 7%
3-H1OB (2F, 3F) -O2 (2-3) 7%
3-HHB (2F, 3F) -O2 (2-8) 4%
3-HH1OB (2F, 3F) -O2 (2-10) 4%
2-HBB (2F, 3F) -O2 (2-14) 4%
3-HBB (2F, 3F) -O2 (2-14) 8%
4-HBB (2F, 3F) -O2 (2-14) 4%
5-HBB (2F, 3F) -O2 (2-14) 5%
3-dhBB (2F, 3F) -O2 (2-16) 4%
2-HH-3 (3-1) 18%
2-HH-5 (3-1) 2%
3-HH-4 (3-1) 3%
3-HH-5 (3-1) 3%
3-HB-O2 (3-2) 17%
3-HBB-2 (3-6) 10%
The compound (1-D) was added to this composition at a rate of 0.075% by mass.
Tc <−20 ° C .; = 1 = 16.1 mPa · s; Δn = 0.102; Δε = −2.8; VHR-11 = 96.4%

[Example 5]
2-H1OB (2F, 3F)-O2 (2-3) 7%
3-H1OB (2F, 3F) -O2 (2-3) 7%
3-HHB (2F, 3F) -O2 (2-8) 5%
3-HDhB (2F, 3F)-O2 (2-13) 5%
2-HBB (2F, 3F) -O2 (2-14) 4%
3-HBB (2F, 3F) -O2 (2-14) 9%
4-HBB (2F, 3F) -O2 (2-14) 4%
5-HBB (2F, 3F) -O2 (2-14) 9%
3-dhBB (2F, 3F) -O2 (2-16) 4%
2-HH-3 (3-1) 18%
3-HH-4 (3-1) 3%
3-HH-5 (3-1) 3%
3-HB-O2 (3-2) 13%
3-HBB-2 (3-6) 9%
Compound (1-D) was added to this composition at a rate of 0.100% by mass.
NI = 75.9 ° C .; = 1 = 18.4 mPa · s; Δn = 0.105; Δε = −3.4; Vth = 2.13 V; VHR-11 = 93.1%

[Example 6]
2-H1OB (2F, 3F)-O2 (2-3) 8%
3-H1OB (2F, 3F) -O2 (2-3) 8%
2O-B (2F) B (2F, 3F) -O2 (2-7) 4%
2O-B (2F) B (2F, 3F) -O 4 (2-7) 6%
3-HHB (2F, 3F) -O2 (2-8) 7%
2-HBB (2F, 3F) -O2 (2-14) 3%
3-HBB (2F, 3F) -O2 (2-14) 10%
2-HH-3 (3-1) 18%
3-HH-4 (3-1) 5%
3-HH-5 (3-1) 5%
3-HB-O2 (3-2) 7%
3-HHB-1 (3-5) 5%
3-HHB-3 (3-5) 6%
3-HBB-2 (3-6) 8%
The compound (1-D) was added to the composition at a ratio of 0.050% by mass.
NI = 74.0 ° C .; Tc <−20 ° C .; Δn = 0.098; Δε = −3.0; Vth = 2.17 V; VHR-11 = 92.5%

[Example 7]
3-HB (2F, 3F) -O2 (2-1) 13%
3-HHB (2F, 3F) -O2 (2-8) 4%
2-HBB (2F, 3F) -O2 (2-14) 4%
3-HBB (2F, 3F) -O2 (2-14) 11%
4-HBB (2F, 3F) -O2 (2-14) 5%
V-HBB (2F, 3F) -O2 (2-14) 8%
V-HBB (2F, 3F) -O4 (2-14) 8%
3-HH-V (3-1) 30%
V-HH-V (3-1) 3%
V-HH-V1 (3-1) 3%
3-HH-V1 (3-1) 5%
1-BB-3 (3-3) 6%
Compound (1-D) was added to this composition at a rate of 0.100% by mass.
NI = 74.9 ° C .; Tc <−20 ° C .; Δn = 0.106; Δε = −2.6; VHR-11 = 95.7%

[Example 8]
3-HB (2F, 3F) -O2 (2-1) 3%
2O-B (2F) B (2F, 3F) -O2 (2-7) 5%
2O-B (2F) B (2F, 3F) -O 4 (2-7) 12%
2-HHB (2F, 3F) -O2 (2-8) 4%
3-HHB (2F, 3F) -O2 (2-8) 8%
5-HBB (2F, 3F) -O2 (2-14) 8%
3-dhBB (2F, 3F) -O2 (2-16) 8%
3-HH-V (3-1) 33%
3-HH-V1 (3-1) 5%
1-BB-3 (3-3) 6%
3-HHB-1 (3-5) 8%
The compound (1-D) was added to this composition at a rate of 0.075% by mass.
NI = 74.9 ° C .; Tc <−20 ° C .; Δn = 0.106; Δε = −2.7; VHR-11 = 87.7%

[Example 9]
2O-B (2F) B (2F, 3F) -O2 (2-7) 6%
2O-B (2F) B (2F, 3F) -O 4 (2-7) 13%
2-HHB (2F, 3F) -O2 (2-8) 4%
3-HHB (2F, 3F) -O2 (2-8) 8%
3-dhBB (2F, 3F) -O2 (2-16) 5%
3-HB (2F) B (2F, 3F) -O2 (2-18) 7%
3-H2BBB (2F, 3F) -O2 (2-25) 5%
3-HH-V (3-1) 42%
3-HH-V1 (3-1) 5%
1-BB-3 (3-3) 3%
V-HHB-1 (3-5) 2%
Compound (1-D) was added to this composition at a rate of 0.100% by mass.
NI = 75.3 ° C .; Tc <−20 ° C .; Δn = 0.106; Δε = −2.7; VHR-11 = 80.1%

[Example 10]
3-H2B (2F, 3F)-O2 (2-2) 15%
5-H2B (2F, 3F)-O2 (2-2) 6%
3-HDhB (2F, 3F) -O2 (2-13) 7%
3-HBB (2F, 3F) -O2 (2-14) 10%
4-HBB (2F, 3F) -O2 (2-14) 7%
5-HBB (2F, 3F) -O2 (2-14) 7%
2-HH-3 (3-1) 18%
3-HH-4 (3-1) 8%
3-HB-O2 (3-2) 10%
5-HB-O2 (3-2) 3%
3-HHB-1 (3-5) 3%
3-HHB-3 (3-5) 3%
3-HHB-O1 (3-5) 3%
The compound (1-D) was added to the composition at a ratio of 0.050% by mass.
Tc <−20 ° C .; = 1 = 17.8 mPa · s; Δn = 0.083; Δε = −2.8; VHR-11 = 95.1%

[Example 11]
3-BB (2F, 3F)-O2 (2-6) 10%
V2-BB (2F, 3F) -O2 (2-6) 9%
V-HHB (2F, 3F) -O1 (2-8) 4%
V-HHB (2F, 3F) -O2 (2-8) 12%
V-HHB (2F, 3F) -O4 (2-8) 10%
3-HH2B (2F, 3F) -O2 (2-9) 8%
3-HH-V (3-1) 29%
3-HB-O2 (3-2) 1%
1-BB-3 (3-3) 4%
1-BB-5 (3-3) 2%
V-HHB-1 (3-5) 11%
Compound (1-D) was added to this composition at a rate of 0.100% by mass.
Tc <−20 ° C .; = 1 = 13.8 mPa · s; Δn = 0.102; Δε = −2.7; VHR-11 = 89.2%

[Example 12]
3-HB (2F, 3F) -O2 (2-1) 13%
3-HHB (2F, 3F) -1 (2-8) 2%
3-HHB (2F, 3F) -2 (2-8) 2%
2-HBB (2F, 3F) -O2 (2-14) 4%
3-HBB (2F, 3F) -O2 (2-14) 11%
4-HBB (2F, 3F) -O2 (2-14) 5%
V-HBB (2F, 3F) -O2 (2-14) 8%
V-HBB (2F, 3F) -O4 (2-14) 8%
3-HH-V (3-1) 36%
3-HH-V1 (3-1) 5%
1-BB-3 (3-3) 6%
The compound (1-D) was added to this composition at a rate of 0.075% by mass.
NI = 72.8 ° C .; Tc <−20 ° C .; Δn = 0.104; Δε = −2.4; VHR-11 = 95.6%

[Example 13]
3-HB (2F, 3F) -O2 (2-1) 3%
2O-B (2F) B (2F, 3F) -O2 (2-7) 5%
2O-B (2F) B (2F, 3F) -O 4 (2-7) 12%
2-HHB (2F, 3F) -O2 (2-8) 4%
3-HHB (2F, 3F) -O2 (2-8) 8%
5-HBB (2F, 3F) -O2 (2-14) 4%
3-dhBB (2F, 3F) -O2 (2-16) 8%
3-HB (2F, 3F) B-2 (2-17) 4%
3-HH-V (3-1) 33%
3-HH-V1 (3-1) 5%
1-BB-3 (3-3) 6%
3-HHB-1 (3-5) 6%
5-B (F) BB-2 (3-7) 2%
Compound (1-D) was added to this composition at a rate of 0.100% by mass.
NI = 71.8 ° C .; Tc <−20 ° C .; Δn = 0.105; Δε = −2.6; VHR-11 = 90.8%

Example 14
3-DhB (2F, 3F) -O2 (2-4) 2%
2O-B (2F) B (2F, 3F) -O2 (2-7) 5%
2O-B (2F) B (2F, 3F) -O 4 (2-7) 14%
2-HHB (2F, 3F) -O2 (2-8) 2%
3-HHB (2F, 3F) -O2 (2-8) 5%
2-HBB (2F, 3F) -O2 (2-14) 2%
3-HBB (2F, 3F) -O2 (2-14) 9%
3-HH-V (3-1) 32%
3-HH-V1 (3-1) 5%
1-BB-3 (3-3) 5%
3-HHB-1 (3-5) 2%
3-HBB-2 (3-6) 17%
The compound (1-D) was added to this composition at a rate of 0.075% by mass.
Tc <-20 ° C; Δn = 0.115; Δε = -2.1; VHR-11 = 84.1%

[Example 15]
3-HB (2F, 3F) -O2 (2-1) 12%
5-HB (2F, 3F) -O2 (2-1) 10%
3-H2B (2F, 3F)-O2 (2-2) 4%
3-BB (2F, 3F)-O2 (2-6) 6%
V-HHB (2F, 3F) -O1 (2-8) 4%
V-HHB (2F, 3F) -O2 (2-8) 10%
3-HHB (2F, 3F) -O2 (2-8) 9%
2O-DBTF2-O4 (2-34) 3%
3-HH-V (3-1) 22%
3-HBB-2 (3-6) 10%
V-HBB-2 (3-6) 10%
Compound (1-D) was added to this composition at a rate of 0.100% by mass.
NI = 75.0 ° C .; Tc <−20 ° C .; Δn = 0.106; Δε = −3.3; VHR-11 = 84.1%

The voltage holding ratio (VHR-11) after light irradiation of the composition of Comparative Example 1 was 74.3%. On the other hand, VHR-11 of the compositions of Examples 1 to 14 was in the range of 80.1% to 97.3%. Therefore, it is concluded that the liquid crystal composition of the present invention has more excellent properties.

The liquid crystal composition of the present invention can be used for a liquid crystal monitor, a liquid crystal television and the like.

Claims (19)

And at least one compound selected from the compound represented by the formula (S) and the compound represented by the formula (S) in which at least one hydrogen of the compound represented by the formula (S) is replaced with a monovalent group as the first additive; Liquid crystal composition having a nematic phase and negative dielectric anisotropy.

The liquid crystal composition according to claim 1, containing at least one compound selected from the compounds represented by formula (1) as a first additive.

In the formula (1), R ^1a , R ^1b and R ^1c are hydrogen, alkyl having 1 to 20 carbon atoms, alicyclic hydrocarbon group having 3 to 20 carbon atoms, or aromatic carbon having 6 to 20 carbon atoms A hydrogen group, in which at least one —CH ₂ — may be replaced by —O—, —NH—, —CO—, —COO—, or —OCO—, at least one — CH ₂ —CH ₂ — may be replaced by —CH = CH— or —C≡C—, and in these groups, at least one hydrogen is an alkyl having 1 to 10 carbons, 1 to 10 carbons May be replaced by alkoxy or halogen; n is 1, 2, 3 or 4. The liquid crystal composition according to claim 1, containing at least one compound selected from the compounds represented by formulas (1-1) to (1-10) as the first additive.

In formulas (1-1) to (1-10), R ^1d is hydrogen or alkyl having 1 to 15 carbon atoms, and in this alkyl, at least one —CH ₂ — is —O—, —NH -, -CO-, -COO-, or -OCO- may be replaced; R ^1e and R ^1f are hydrogen, alkyl having 1 to 15 carbons, or alkoxy having 1 to 15 carbons; R ^{1 g} is hydrogen or alkyl having 1 to 15 carbons; R ^{1 h} is hydrogen or alkyl having 1 to 15 carbons, and in this alkyl, at least one —CH ₂ — is —O—, —NH -, - CO -, - COO- , or may be replaced by ^{-OCO-; R 1i} is alkyl of 1 to 10 carbons, there 1 -C 10 alkoxy or halogen,; ^{Z 1} , ^{Z 1b} and ^{Z 1c,} is alkylene of 5 a single bond or 1 carbon atoms, in the alkylene, at least one -CH ₂ - may be replaced by -O-, in these groups, At least one hydrogen may be replaced by alkyl having 1 to 5 carbons; m is 0, 1, 2, 3, 4 or 5. The liquid crystal composition according to any one of claims 1 to 3, wherein the proportion of the first additive is in the range of 0.001% by mass to 2% by mass. The liquid crystal composition according to any one of claims 1 to 4, containing at least one compound selected from the compounds represented by formula (2) as a first component.

In the formula (2), R ^2a and R ^2b are hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, alkenyloxy having 2 to 12 carbons, or at least Ring A and ring C are 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-, wherein C 1-12 alkyl in which one hydrogen is replaced by fluorine or chlorine; Diyl, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced by fluorine or chlorine, naphthalene-2,6-diyl, naphthalene-2, in which at least one hydrogen is replaced by fluorine or chlorine, 6-diyl, chroman-2, 6-diyl or a group in which at least one hydrogen is replaced by fluorine or chlorine Mann-2, 6-diyl; ring B is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5-methyl- 1,4-phenylene, 3,4,5-trifluoronaphthalene-2,6-diyl, 7,8-difluorochroman-2,6-diyl, 3,4,5,6-tetrafluorofluorene-2,7 -Diyl, 4,6-difluorodibenzofuran-3,7-diyl, 4,6-difluorodibenzothiophene-3,7-diyl, or 1,1,6,7-tetrafluoroindane-2,5-diyl Z ^2a and Z ^2b are a single bond, ethylene, methyleneoxy or carbonyloxy; a is 0, 1, 2 or 3; b is 0 or 1; and the sum of a and b Is 3 or more It is. The liquid crystal composition according to any one of claims 1 to 5, containing at least one compound selected from compounds represented by formula (2-1) to formula (2-35) as a first component. .

In formulas (2-1) to (2-35), R ^2a and R ^2b are each hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, 2 to 12 alkenyloxy, or C 1 to C 12 alkyl in which at least one hydrogen is replaced by fluorine or chlorine. The liquid crystal composition according to claim 5 or 6, wherein the proportion of the first component is in the range of 10% by mass to 90% by mass. The liquid crystal composition according to any one of claims 1 to 7, containing at least one compound selected from the compounds represented by Formula (3) as a second component.

In the formula (3), R ^3a and R ^3b are alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or at least one hydrogen is replaced by fluorine or chlorine Ring C and ring E are 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene or 2,5-difluoro-1,4; Z ^3a is a single bond, ethylene or carbonyloxy; c is 1, 2 or 3. The liquid crystal composition according to any one of claims 1 to 8, which contains at least one compound selected from compounds represented by formulas (3-1) to (3-13) as a second component. .

In formulas (3-1) to (3-13), R ^3a and R ^3b are each an alkyl of 1 to 12 carbons, an alkoxy of 1 to 12 carbons, an alkenyl of 2 to 12 carbons, or at least one of Hydrogen is alkenyl having 2 to 12 carbon atoms replaced with fluorine or chlorine. The liquid crystal composition according to claim 8 or 9, wherein the proportion of the second component is in the range of 10% by mass to 90% by mass. The liquid crystal composition according to any one of claims 1 to 10, which contains at least one compound selected from polymerizable compounds represented by Formula (4) as a second additive.

In Formula (4), ring F and ring I are cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxane-2-yl, pyrimidin-2-yl Or pyridin-2-yl, in these rings, at least one hydrogen is fluorine, chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or at least one hydrogen is fluorine or chlorine And may be substituted by alkyl having 1 to 12 carbon atoms which is substituted with ring G: 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-1,2-diyl , Naphthalene-1,3-diyl, Naphthalene-1,4-diyl, Naphthalene-1,5-diyl, Naphthalene-1,6-diy , Naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, naphthalene-2,7-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, and in these rings, at least one hydrogen is fluorine, chlorine, carbon number 1 12 alkyl, alkoxy having 1 to 12 carbons, or alkyl having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine; Z ^4a and Z ^4b may be a single bond or carbon alkylene from C 1 10, in the alkylene, at least one of _-CH 2 -, -O -, - CO -, - COO-, or In may be replaced, at least one _-CH 2 -CH ₂ is -OCO- - _{is, -CH = CH -, - C} (CH 3) = CH -, - CH = C (CH 3) -, or _{-C (CH 3) = C (} CH 3) - may be replaced by, in these groups, at least one hydrogen may be replaced by fluorine or ^chlorine; P ^{4a, P 4b} and ^{P 4c,} Is a polymerizable group; Sp ^4a , Sp ^4b and Sp ^4c are a single bond or an alkylene having 1 to 10 carbon atoms, and in this alkylene, at least one —CH ₂ — is —O—, — COO -, - OCO-, or may be replaced by -OCOO-, at least one _-CH 2 -CH ₂ - may be replaced by -CH = CH- or -C≡C-, these Group Where at least one hydrogen may be replaced by fluorine or chlorine; d is 0, 1 or 2; e, f and g are 0, 1, 2, 3 or 4 And the sum of e, f and g is 1 or more. ^12. The liquid crystal according to claim 11, wherein in formula (4), P ^4a , P ^4b and P ^4c are groups selected from the polymerizable groups represented by formulas (P-1) to (P-5). Composition.

In Formula (P-1) to Formula (P-5), M ¹ , M ² , and M ³ are hydrogen, fluorine, alkyl having 1 to 5 carbon atoms, or at least one hydrogen is replaced with fluorine or chlorine And alkyl having 1 to 5 carbon atoms. The method according to any one of claims 1 to 12, comprising at least one compound selected from polymerizable compounds represented by Formula (4-1) to Formula (4-29) as a second additive. Liquid crystal composition.

In formulas (4-1) to (4-29), P ^4d , P ^4e , and P ^4f are each selected from the groups represented by formulas (P-1) to (P-3): A group wherein M ¹ , M ² and M ³ are hydrogen, fluorine, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen is replaced by fluorine or chlorine Yes:

Sp ^4a , Sp ^4b and Sp ^4c are a single bond or alkylene having 1 to 10 carbons, and in this alkylene, at least one —CH ₂ — is —O—, —COO—, —OCO—, or -OCOO- may be replaced, and at least one -CH ₂ -CH ₂ -may be replaced by -CH = CH- or -C≡C-, and in these groups, at least one hydrogen is , Fluorine or chlorine may be substituted. The liquid crystal composition according to any one of claims 11 to 13, wherein the proportion of the second additive is in the range of 0.03% by mass to 10% by mass. The liquid crystal display element containing the liquid crystal composition of any one of Claims 1-14. The liquid crystal display element according to claim 15, wherein an operation mode of the liquid crystal display element is an IPS mode, a VA mode, an FFS mode, or an FPA mode, and a driving method of the liquid crystal display element is an active matrix method. A polymer supported alignment type liquid crystal display device comprising the liquid crystal composition according to any one of claims 11 to 14, wherein a polymerizable compound in the liquid crystal composition is polymerized. Use of the liquid crystal composition according to any one of claims 1 to 14 in a liquid crystal display device. The use of the liquid crystal composition according to any one of claims 11 to 14 in a polymer supported alignment type liquid crystal display device.