JPWO2018168721A1 - Liquid crystal composition and liquid crystal display device - Google Patents

Abstract

Provided is a polymerizable composition containing a polymerizable compound having appropriate polymerization reactivity, high conversion, and high solubility in a liquid crystal composition, and a liquid crystal display device containing the composition. A nematic liquid crystal composition containing a maleimide compound as a first additive and having a negative dielectric anisotropy. The composition has a specific liquid crystal property having a large negative dielectric anisotropy as a first component. A compound, a specific liquid crystal compound having a high maximum temperature or a small viscosity as a second component, and a polymerizable compound having a polar group as a second additive, and a liquid crystal display device containing the composition It is.

Description

  The present invention relates to a liquid crystal composition containing a maleimide compound, a liquid crystal display device containing the composition, and the like.

  In a liquid crystal display device, classification based on the operation mode of liquid crystal molecules includes PC (phase change), TN (twisted nematic), STN (super twisted nematic), ECB (electrically controlled birefringence), OCB (optically compensated bend), and IPS. (In-plane switching), VA (vertical alignment), FFS (fringe field switching), FPA (field-induced photo-reactive alignment), and the like. The classification based on the element driving method is PM (passive matrix) and AM (active matrix). PM is classified into static, multiplex and the like, and AM is classified into TFT (thin film transistor), MIM (metal insulator metal) and the like. The classification of TFT is amorphous silicon and polycrystal silicon. The latter is classified into a high-temperature type and a low-temperature type according to the manufacturing process. The classification based on the light source is a reflection type using natural light, a transmission type using backlight, and a semi-transmission type using both natural light and backlight.

  The liquid crystal display device contains a liquid crystal composition having a nematic phase. This composition has suitable properties. By improving the characteristics of this composition, an AM device having good characteristics can be obtained. The relationship between the two characteristics is 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 temperature range in which the device can be used. The preferred upper limit temperature of the nematic phase is about 70 ° C. or higher, and the preferred lower limit temperature of the nematic phase is about −10 ° C. or lower. The viscosity of the composition is related to the response time of the device. A short response time is preferable for displaying a moving image on the element. Shorter response times are desirable even at 1 millisecond. Therefore, a small 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, large or small optical anisotropy, that is, appropriate 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 operation mode. This value ranges from about 0.30 μm to about 0.40 μm for the VA mode device, and from about 0.20 μm to about 0.30 μm for the IPS mode or FFS mode device. In these cases, a composition having a large optical anisotropy is preferable for a device having a small cell gap. The large dielectric anisotropy in the composition contributes to a low threshold voltage, small power consumption and a large contrast ratio in the device. Therefore, a large dielectric anisotropy is preferable. A large specific resistance 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 not only at room temperature but also at a temperature close to the upper limit temperature of the nematic phase is preferable. After long-term use, a composition having a large specific resistance not only at room temperature but also at a temperature close to the maximum temperature of the nematic phase is preferable. 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 device used for a liquid crystal projector, a liquid crystal television, and the like.

  In a polymer sustained alignment (PSA) type liquid crystal display device, a liquid crystal composition containing a polymer is used. First, a composition to which a small amount of a polymerizable compound is added is injected into a device. Next, the composition is irradiated with ultraviolet rays 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 alignment of the liquid crystal molecules can be controlled by the polymer, so that the response time of the device is shortened and the image sticking is improved. Such effects of the polymer can be expected for devices having modes such as TN, ECB, OCB, IPS, VA, FFS, and FPA.

  In a general-purpose liquid crystal display device, vertical alignment of liquid crystal molecules is achieved by a polyimide alignment film. On the other hand, in a liquid crystal display element having no alignment film, a liquid crystal composition containing a polymer and a polar compound is used. First, a composition containing a small amount of a polymerizable compound and a small amount of a polar compound is injected into a device. Here, the polar compound is adsorbed and arranged on the substrate surface. The liquid crystal molecules are aligned according to this arrangement. Next, the composition is irradiated with ultraviolet rays while applying a voltage between the substrates of the device. Here, the polymerizable compound is polymerized to stabilize the alignment of the liquid crystal molecules. In this composition, since the alignment of the liquid crystal molecules can be controlled by the polymer and the polar compound, the response time of the device is shortened, and the image sticking is improved. Further, in a device having no alignment film, a step of forming an alignment film is not required. Since there is no alignment film, the electric resistance of the device does not decrease due to the interaction between the alignment film and the composition. Such an effect due to the combination of the polymer and the polar compound can be expected for a device having a mode such as TN, ECB, OCB, IPS, VA, FFS, and FPA.

  In an AM device having a TN mode, a composition having a positive dielectric anisotropy is used. In an AM device having a VA mode, a composition having a negative dielectric anisotropy is used. In an AM device having the IPS mode or the FFS mode, a composition having a positive or negative dielectric anisotropy is used. A composition having a positive or negative dielectric anisotropy is used for an AM device of a polymer supported orientation type. Examples of a liquid crystal composition having a negative dielectric anisotropy are disclosed in Patent Documents 1 to 5 below. Until now, various polymerizable compounds have been developed, but the development of a compound with further improved properties described above is desired.

International Publication No. WO 2014/090362 International Publication No. WO 2014/094959 WO 2013/004372 JP 2015-168826 A International Publication No. WO 2016/015803

  A first object of the present invention is to provide a liquid crystal composition containing a maleimide compound having excellent ability to align liquid crystal molecules, appropriate polymerization reactivity, high conversion and high solubility in a liquid crystal composition. is there. The second problem is that the upper limit temperature of the nematic phase, the lower limit temperature of the nematic phase, small viscosity, appropriate optical anisotropy, large dielectric anisotropy, appropriate elastic constant, large specific resistance, appropriate pretilt, etc. The purpose of the present invention is to provide a liquid crystal composition satisfying at least one of the physical properties of: An object of the present invention is to provide a liquid crystal composition having a proper balance between at least two physical properties. A third object is to provide a liquid crystal display device having a wide temperature range in which the device can be used, a short response time, a high voltage holding ratio, a low threshold voltage, a large contrast ratio, and a long life.

式（Ａ）において、
Ｒ^１およびＲ^２は独立して、水素、ハロゲン、または炭素数１から２０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−または−Ｓ−で置き換えられてもよく、少なくとも１つの−（ＣＨ_２）_２−は−ＣＨ＝ＣＨ−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つの水素はハロゲンで置き換えられてもよい。A liquid crystal composition containing at least one compound selected from the group of compounds having a monovalent group represented by the formula (A) (maleimide compound) as a first additive, and having a negative dielectric anisotropy .

In the formula (A),
R ¹ and R ² are independently hydrogen, halogen, or alkyl having 1 to 20 carbons. In this alkyl, at least one —CH ₂ — may be replaced with —O— or —S—. well, at least one - _{(CH 2) 2} - may be replaced by -CH = CH-, in these groups, at least one hydrogen may be replaced by halogen.

  A first advantage of the present invention is to provide a liquid crystal composition containing a maleimide compound having excellent ability to align liquid crystal molecules, appropriate polymerization reactivity, high conversion and high solubility in liquid crystal compositions. is there. The second advantage is that the liquid crystal composition has a high maximum temperature of the nematic phase, a low minimum temperature of the nematic phase, a small viscosity, a suitable optical anisotropy, a large dielectric anisotropy, a suitable elastic constant, and a large specific resistance. Satisfies at least one of physical properties such as appropriate pretilt. This advantage is that the liquid crystal composition has an appropriate balance regarding at least two physical properties. A third advantage is that the liquid crystal display device has a wide temperature range in which the device can be used, a short response time, a high voltage holding ratio, a low threshold voltage, a large contrast ratio, and a long lifetime.

  The usage of 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 general term for a liquid crystal display panel and a liquid crystal display module. "Liquid crystal compound" is a compound having a liquid crystal phase such as a nematic phase or a smectic phase, or a compound having no liquid crystal phase, but having a composition for the purpose of adjusting properties such as temperature range, viscosity, and dielectric anisotropy of the nematic phase. It is a general term for compounds that are mixed with products. This compound has a six-membered ring such as 1,4-cyclohexylene and 1,4-phenylene, and has a rod-like molecular structure. The "maleimide compound" is a compound added for the purpose of functioning as an initiator, and the "polymerizable compound" is a compound added for the purpose of forming a polymer in the composition.

  The liquid crystal composition is prepared by mixing a plurality of liquid crystal compounds. Additives such as an optically active compound, an antioxidant, an ultraviolet absorber, a dye, an antifoaming agent, a polymerizable compound, a polymerization initiator, a polymerization inhibitor, and a polar compound are added to the liquid crystal composition as necessary. You. The liquid crystal compound and additives are mixed in such a procedure. The ratio (content) of the liquid crystal compound is represented by a mass percentage (% by mass) based on the mass of the liquid crystal composition containing no additive, even when an additive is added. The proportion (addition amount) of the additive is represented by a mass percentage (% by mass) based on the mass of the liquid crystal composition containing no additive. Parts per million by weight (ppm) may be used. The proportions of the polymerization initiator and the polymerization inhibitor are exceptionally expressed based on the mass of the polymerizable compound.

  The “maximum temperature of the nematic phase” may be abbreviated as “maximum temperature”. The “minimum temperature of the nematic phase” may be abbreviated as “minimum temperature”. "High specific resistance" means that the composition has a large specific resistance not only at room temperature but also at a temperature close to the upper limit temperature in the initial stage, and a large specific resistance not only at room temperature but also at a temperature close to the upper limit temperature after long-term use. Has the following meaning. "High voltage holding ratio" means that the device has a large voltage holding ratio not only at room temperature but also near the upper limit temperature in the initial stage, and a large voltage not only at room temperature but also at a temperature close to the upper limit temperature after prolonged use. It means having a retention rate. The characteristics of the composition and the device may be examined before and after the aging test (including the accelerated deterioration test). The expression "increase the dielectric anisotropy" means that when the composition has a positive dielectric anisotropy, the value increases to a positive value, and the composition has a negative dielectric anisotropy. For an object, it means that its value increases negatively.

The compound represented by the formula (1) may be abbreviated as the compound (1). At least one compound selected from the group of compounds represented by formula (1) may be abbreviated as "compound (1)." “Compound (1)” means one compound represented by the formula (1), a mixture of two compounds, or a mixture of three or more compounds. The same applies to compounds represented by other formulas. In ring A ¹ of the compound (1), a line crossing the circle, P ¹ -S ¹ groups means that can be arbitrarily selected binding position on the ring, such as six-membered rings, fused rings. This ^rule also applies to symbols such as P 2 -S ² group. The expression "at least one 'A'" means that the number of 'A' is arbitrary. The expression "at least one 'A' may be replaced by 'B'" means that when the number of 'A' is one, the position of 'A' is arbitrary and the number of 'A' is two. In more than one case, their positions can be selected without restriction. This rule also applies to the expression "at least one 'A' has been replaced by 'B'".

In the chemical formulas of the component compounds, using symbols of terminal groups R ¹ to a plurality of compounds. In these compounds, the two groups represented by any two R ¹ may be the same or different. For example, there is a case where R ^{1 of} compound (1-1-1) is ethyl and R ¹ of compound (1-1-2) is ethyl. In some cases, R ^{1 of} compound (1-1-1) is ethyl, and R ¹ of compound (1-1-2) is propyl. This rule applies to symbols such as other end groups. In the formula (1), b2 is the time of 2, two rings ^{A 2} are present. In this compound, two rings two rings A ² represents may be the same or different. This rule also applies to any two rings A2 when b2 is greater than ² . This rule also applies to other symbols.

Symbols such as A, B, C, and D surrounded by a hexagon correspond to rings such as ring A, ring B, ring C, and ring D, and represent a ring such as a six-membered ring or a condensed ring. The oblique line across this hexagon indicates that any hydrogen on the ring may be replaced by a group such as -S ¹ -P ¹ . Subscripts such as 'a1' indicate the number of replaced groups. When the subscript 'a1' is 0, there is no such replacement. When subscript 'a1' is 2 or more, there are a plurality of ^-S 1 -P ¹ is on the ring ^{A 1.} The groups represented by -S ¹ -P ¹ may be the same or different.

2-Fluoro-1,4-phenylene means the following two divalent groups. In the chemical formula, fluorine may be leftward (L) or rightward (R). This rule also applies to asymmetric divalent groups, such as tetrahydropyran-2,5-diyl, generated by removing two hydrogens from a ring. This rule also applies to divalent linking groups such as carbonyloxy (-COO- or -OCO-).

"At least one of -CH 2 _- replaced may be by -O-" expression like is used in this specification. In this _case, -CH ₂ -CH ₂ -CH ₂ - it is, -CH ₂ nonadjacent - may be converted _-O-CH 2 -O- to by is replaced by -O-. However, adjacent -CH ₂ - is not replaced by -O-. This replacement is -O-O-CH ₂ - is because (peroxide) is produced. In other words, this representation, and both _{- -} "may be replaced by -O- -CH 2 nonadjacent least two,""one -CH 2 is -O- in may be replaced" with means. This rule applies not only to replacement with -O-, but also to replacement with a divalent group such as -CH = CH- or -COO-. In the formula (A), R ¹ is alkyl having 1 to 20 carbons or the like. The carbon number of the alkyl may be increased by this type of substitution. In such a case, the maximum carbon number is 30. This rule applies to monovalent groups such as R ¹ as well as divalent groups such as alkylene.

  The alkyl of the liquid crystal compound is linear or branched and does not include cyclic alkyl. Linear alkyls are preferred over branched alkyls. The same applies to terminal groups such as alkoxy and alkenyl. The configuration of 1,4-cyclohexylene is generally preferably trans over cis. Halogen means fluorine, chlorine, bromine, iodine. Preferred halogens are fluorine or chlorine. A more preferred halogen is fluorine.

  The present invention includes the following items.

式（Ａ）において、
Ｒ^１およびＲ^２は独立して、水素、ハロゲン、または炭素数１から２０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−または−Ｓ−で置き換えられてもよく、少なくとも１つの−（ＣＨ_２）_２−は−ＣＨ＝ＣＨ−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つの水素はハロゲンで置き換えられてもよい。
ここで、「これらの基において」とは、無置換の炭素数１から２０のアルキル、少なくとも１つの−ＣＨ_２−が、−Ｏ−または−Ｓ−で置き換えられた炭素数１から２０のアルキル、少なくとも１つの−（ＣＨ_２）_２−は−ＣＨ＝ＣＨ−で置き換えられた炭素数１から２０のアルキルを示す。
以下、本願明細書において、「これらの基において」または「これらの二価基において」と記載する場合は、無置換の基（アルキル、アルキレン等）のみならず、一部が他の基で置き換えられた基をも含む意味である。 Item 1. A liquid crystal composition comprising at least one compound having a monovalent group represented by the formula (A) as a first additive, and having a negative dielectric anisotropy.

In the formula (A),
R ¹ and R ² are independently hydrogen, halogen, or alkyl having 1 to 20 carbons. In this alkyl, at least one —CH ₂ — may be replaced with —O— or —S—. well, at least one - _{(CH 2) 2} - may be replaced by -CH = CH-, in these groups, at least one hydrogen may be replaced by halogen.
Here, “in these groups” refers to unsubstituted alkyl having 1 to 20 carbons, alkyl having 1 to 20 carbons in which at least one —CH ₂ — is replaced by —O— or —S—. , At least one-(CH ₂ ) ₂ -represents alkyl having 1 to 20 carbons replaced by -CH = CH-.
Hereinafter, in the specification of the present application, when "in these groups" or "in these divalent groups" is described, not only unsubstituted groups (alkyl, alkylene, etc.) but also some of them are replaced with other groups. It is meant to also include the specified groups.

式（１）において、
Ｐ^１およびＰ^２は独立して重合性基であり；
Ｓ^１およびＳ^２は独立して、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−または−Ｃ≡Ｃ−で置き換えられてもよく、これらの二価基において、少なくとも１つの水素は、ハロゲンまたは炭素数１から３のアルキルで置き換えられてもよく；
Ｒ^４およびＲ^５は独立して、水素、ハロゲン、−Ｓ^１−Ｐ^１、−Ｓ^２−Ｐ^２、または炭素数１から２０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−または−Ｓ−で置き換えられてもよく、少なくとも１つの−（ＣＨ_２）_２−は−ＣＨ＝ＣＨ−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つの水素はハロゲンで置き換えられてもよく；
ａ１およびａ２は独立して、０、１、２、３、または４であり；
−Ｓ^１−Ｐ^１および−Ｓ^２−Ｐ^２を合わせた個数は、１から８であり、そしてすべての−Ｓ^１−Ｐ^１およびすべての−Ｓ^２−Ｐ^２のうちの少なくとも１つは、式（Ａ）で表される一価基を有し、

式（Ａ）において、
Ｒ^１およびＲ^２は独立して、水素、ハロゲン、または炭素数１から２０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−または−Ｓ−で置き換えられてもよく、少なくとも１つの−（ＣＨ_２）_２−は−ＣＨ＝ＣＨ−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つの水素はハロゲンで置き換えられてもよく；
式（１）において、
環Ａ^１および環Ａ^２は独立して、炭素数３から１８の脂環式炭化水素、炭素数６から１８の芳香族炭化水素、または炭素数３から１８のヘテロ芳香族炭化水素から誘導された二価基であり、これらの二価基において、少なくとも１つの水素は、ハロゲン、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１から１２のアルケニル、または炭素数１から１２のアルケニルオキシで置き換えられてもよく、これらの一価の炭化水素基において、少なくとも１つの水素はハロゲンで置き換えられてもよく；
Ｚ^１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）−、−Ｃ（ＣＨ_３）＝Ｃ（ＣＨ_３）−、または−Ｃ≡Ｃ−で置き換えられてもよく、これらの二価基において、少なくとも１つの水素はハロゲンで置き換えられてもよく；
ｂ１は、０または１であり、
ｂ２は、０、１、２、または３である。Item 2. Item 1. The liquid crystal composition according to item 1, wherein the first additive is a compound represented by the formula (1).

In equation (1),
P ¹ and P ² are independently polymerizable groups;
S ¹ and S ² are each independently a single bond or an alkylene having 1 to 10 carbon atoms, wherein 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— or —C≡C—, and in these divalent groups, at least one hydrogen is , Halogen or alkyl having 1 to 3 carbons;
R ⁴ and R ⁵ are independently hydrogen, halogen, -S ¹ -P ¹ , -S ² -P ² , or alkyl having 1 to 20 carbons, and in this alkyl, at least one -CH _2- It may be replaced by -O- or -S-, at least one - _{(CH 2) 2} - may be replaced by -CH = CH-, in these groups, at least one hydrogen with halogen May be replaced;
a1 and a2 are independently 0, 1, 2, 3, or 4;
The combined number of -S ¹ -P ¹ and -S ² -P ² is from 1 to 8 and at least one of all -S ¹ -P ¹ and all -S ² -P ² Having a monovalent group represented by the formula (A),

In the formula (A),
R ¹ and R ² are independently hydrogen, halogen, or alkyl having 1 to 20 carbons, in which at least one —CH ₂ — may be replaced by —O— or —S—. , at least one - _{(CH 2) 2} - may be replaced by -CH = CH-, in these groups, at least one hydrogen may be replaced by halogen;
In equation (1),
Ring A ¹ and ring A ² are independently derived from an alicyclic hydrocarbon having 3 to 18 carbon atoms, an aromatic hydrocarbon having 6 to 18 carbon atoms, or a heteroaromatic hydrocarbon having 3 to 18 carbon atoms. Wherein at least one hydrogen atom is halogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 1 to 12 carbons, or 1 divalent group. From 12 to 12 alkenyloxy, and in these monovalent hydrocarbon radicals at least one hydrogen may be replaced by halogen;
Z ¹ is a single bond or an alkylene having 1 to 10 carbon atoms, in which at least one —CH ₂ — is replaced by —O—, —CO—, —COO—, or —OCO—. well, at least one _-CH 2 -CH ₂ - _{is, -CH = CH -, - C} (CH 3) = CH -, - CH = C (CH 3) -, - C (CH 3) = C (CH ₃ )-or -C≡C-; in these divalent radicals at least one hydrogen may be replaced by halogen;
b1 is 0 or 1,
b2 is 0, 1, 2, or 3.

式（１−１−１）から式（１−１−３）において、
Ｒ^１およびＲ^２は独立して、水素、ハロゲン、または炭素数１から２０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−または−Ｓ−で置き換えられてもよく、少なくとも１つの−（ＣＨ_２）_２−は−ＣＨ＝ＣＨ−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つの水素はハロゲンで置き換えられてもよく；
Ｒ^４は、水素、ハロゲン、−Ｓ^１−Ｐ^１、または炭素数１から２０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−または−Ｓ−で置き換えられてもよく、少なくとも１つの−（ＣＨ_２）_２−は−ＣＨ＝ＣＨ−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つの水素はハロゲンで置き換えられてもよく；
Ｓ^２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−または−Ｃ≡Ｃ−で置き換えられてもよく、これらの二価基において、少なくとも１つの水素は、ハロゲンまたは炭素数１から３のアルキルで置き換えられてもよく；
環Ａ^１、環Ａ^２、および環Ａ^３は独立して、炭素数３から１８の脂環式炭化水素、炭素数６から１８の芳香族炭化水素、または炭素数３から１８のヘテロ芳香族炭化水素から誘導された二価基であり、これらの二価基において、少なくとも１つの水素は、ハロゲン、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１から１２のアルケニル、または炭素数１から１２のアルケニルオキシで置き換えられてもよく、これらの一価の炭化水素基において、少なくとも１つの水素はハロゲンで置き換えられてもよく；
Ｚ^１およびＺ^２は独立して、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）−、−Ｃ（ＣＨ_３）＝Ｃ（ＣＨ_３）−、または−Ｃ≡Ｃ−で置き換えられてもよく、これらの二価基において、少なくとも１つの水素はハロゲンで置き換えられてもよい。Item 3. Item 1. The liquid crystal composition according to item 1, wherein the first additive is a compound represented by any one of formulas (1-1-1) to (1-1-3).

In the formulas (1-1-1) to (1-1-3),
R ¹ and R ² are independently hydrogen, halogen, or alkyl having 1 to 20 carbons, in which at least one —CH ₂ — may be replaced by —O— or —S—. , at least one - _{(CH 2) 2} - may be replaced by -CH = CH-, in these groups, at least one hydrogen may be replaced by halogen;
R ⁴ is hydrogen, halogen, —S ¹ —P ¹ , or alkyl having 1 to 20 carbons, wherein at least one —CH ₂ — is replaced with —O— or —S—. well, at least one - _{(CH 2) 2} - may be replaced by -CH = CH-, in these groups, at least one hydrogen may be replaced by halogen;
S ² is a single bond or an alkylene having 1 to 10 carbon atoms, in which at least one —CH ₂ — may be replaced by —O—, —CO—, —COO— or —OCO—. Often, at least one —CH ₂ —CH ₂ — may be replaced by —CH ＝ CH— or —C≡C—, and in these divalent groups, at least one hydrogen is a halogen or a carbon atom. From 3 to 3 alkyl;
Ring A ¹ , ring A ² , and ring A ³ are each independently an alicyclic hydrocarbon having 3 to 18 carbons, an aromatic hydrocarbon having 6 to 18 carbons, or a heteroaromatic having 3 to 18 carbons A divalent group derived from a hydrocarbon, in which at least one hydrogen is halogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 1 to 12 carbons Or alkenyloxy having 1 to 12 carbon atoms, and in these monovalent hydrocarbon groups, at least one hydrogen may be replaced by halogen;
Z ¹ and Z ² are each independently a single bond or alkylene having 1 to 10 carbon atoms, wherein at least one —CH ₂ — is —O—, —CO—, —COO—, or — may be replaced by OCO-, at least one _-CH 2 -CH ₂ - _{is, -CH = CH -, - C} (CH 3) = CH -, - CH = C (CH 3) -, - C ( CH ₃ ) = C (CH ₃ ) —, or —C≡C—, and in these divalent groups, at least one hydrogen may be replaced by halogen.

  Item 4. Item 4. The liquid crystal composition according to any one of Items 1 to 3, wherein a ratio of the first additive is in a range of 0.01% by mass to 10% by mass.

式（２）において、
Ｒ^２１は炭素数１から１５のアルキルであり、このＲ^２１において、少なくとも１つの−ＣＨ_２−は、−Ｏ−または−Ｓ−で置き換えられてもよく、少なくとも１つの−ＣＨ_２ＣＨ_２−は、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、少なくとも１つの水素は、ハロゲンで置き換えられてもよく；
環Ａ^２１および環Ａ^２２は独立して、１，４−シクロへキシレン、１，４−シクロヘキセニレン、１，４−フェニレン、ナフタレン−２，６−ジイル、デカヒドロナフタレン−２，６−ジイル、１，２，３，４−テトラヒドロナフタレン−２，６−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、ピリジン−２，５−ジイル、フルオレン−２，７−ジイル、フェナントレン−２，７−ジイル、アントラセン−２，６−ジイル、ペルヒドロシクロペンタ［ａ］フェナントレン−３，１７−ジイル、または２，３，４，７，８，９，１０，１１，１２，１３，１４，１５，１６，１７−テトラデカヒドロシクロペンタ［ａ］フェナントレン−３，１７−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２から１２のアルケニル、炭素数１から１１のアルコキシ、または炭素数２から１１のアルケニルオキシ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；
ａは、０、１、２、３、または４であり；
Ｚ^２１は単結合または炭素数１から６のアルキレンであり、このＺ^２１において、少なくとも１つの−ＣＨ_２−は、−Ｏ−、−ＣＯ−、−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_２ＣＨ_２−は、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、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；
Ｓｐ^２１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Ｓｐ^２１において、少なくとも１つの−ＣＨ_２−は、−Ｏ−、−ＣＯ−、−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_２ＣＨ_２−は、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、少なくとも１つの水素は、ハロゲン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、式（２ａ）で表される基から選択された基で置き換えられていてもよく；

式（２ａ）において、
Ｓｐ^２２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Ｓｐ^２２において、少なくとも１つの−ＣＨ_２−は、−Ｏ−、−ＣＯ−、−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_２ＣＨ_２−は、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、少なくとも１つの水素は、ハロゲンで置き換えられてもよく；
Ｍ^２１およびＭ^２２は独立して、水素、ハロゲン、炭素数１から５のアルキル、または少なくとも１つの水素がハロゲンで置き換えられた炭素数１から５のアルキルであり：
Ｒ^２２は炭素数１から１５のアルキルであり、このＲ^２２において、少なくとも１つの−ＣＨ_２−は、−Ｏ−または−Ｓ−で置き換えられてもよく、少なくとも１つの−ＣＨ_２ＣＨ_２−は、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、少なくとも１つの水素はハロゲンで置き換えられてもよく：
式（２）において、
Ｐ^２１は、式（２ｅ）、式（２ｆ）、式（２ｇ）、および式（２ｈ）で表される基から選択された基であり；
ただし、上記Ｓｐ^２１が取りうる基において、少なくとも１つの水素が、式（２ａ）で表される基から選択された基で置き換えられていない場合には、Ｐ^２１は、式（２ｅ）、式（２ｆ）、および式（２ｇ）で表される基から選択された基であり；

式（２ｅ）、式（２ｆ）、式（２ｇ）、および式（２ｈ）において、
Ｓｐ^２３、Ｓｐ^２４、Ｓｐ^２５は、独立して、単結合または炭素数１から１０のアルキレンであり、このＳｐ^２３、Ｓｐ^２４、Ｓｐ^２５において、少なくとも１つの−ＣＨ_２−は、−Ｏ−、−ＮＨ−、−ＣＯ−、−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_２ＣＨ_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つの水素はハロゲンで置き換えられてもよく；
Ｓ^２１は、＞ＣＨ−または＞Ｎ−であり；
Ｓ^２２は、＞Ｃ＜または＞Ｓｉ＜であり；
Ｍ^２３およびＭ^２４は独立して、水素、ハロゲン、炭素数１から５のアルキル、または少なくとも１つの水素がハロゲンで置き換えられた炭素数１から５のアルキルであり：
Ｘ^１は、−ＯＨ、−ＮＨ_２、−ＯＲ^２５、−Ｎ（Ｒ^２５）_２、式（ｘ１）、−ＣＯＯＨ、−ＳＨ、−Ｂ（ＯＨ）_２、または−Ｓｉ（Ｒ^２５）_３であり；
−ＯＲ^２５、−Ｎ（Ｒ^２５）_２、および−Ｓｉ（Ｒ^２５）_３において、
Ｒ^２５は水素または炭素数１から１０のアルキルであり、このＲ^２５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、少なくとも１つの−ＣＨ_２ＣＨ_２−は、−ＣＨ＝ＣＨ−で置き換えられてもよく、少なくとも１つの水素は、ハロゲンで置き換えられてもよく、式（ｘ１）におけるｗは１、２、３または４である。

Item 5. Item 5. The liquid crystal composition according to any one of items 1 to 4, comprising at least one polymerizable compound having a polar group represented by the formula (2) as a second additive.

In equation (2),
R ²¹ is alkyl having 1 to 15 carbons, and in this R ²¹ , at least one —CH ₂ — may be replaced by —O— or —S—, and at least one —CH ₂ CH ₂ — May be replaced by -CH = CH- or -C≡C- and at least one hydrogen may be replaced by halogen;
Ring A ²¹ and ring A ²² are each independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, decahydronaphthalene-2,6- Diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine- 2,5-diyl, fluorene-2,7-diyl, phenanthrene-2,7-diyl, anthracene-2,6-diyl, perhydrocyclopenta [a] phenanthrene-3,17-diyl, or 2,3 4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydrocyclopenta [a] phenanthrene-3,17-diyl, At least one hydrogen is replaced by fluorine, chlorine, alkyl having 1 to 12 carbons, alkenyl having 2 to 12 carbons, alkoxy having 1 to 11 carbons, or alkenyloxy having 2 to 11 carbons And in these groups, at least one hydrogen may be replaced by fluorine or chlorine;
a is 0, 1, 2, 3, or 4;
Z ²¹ is a single bond or an alkylene having 1 to 6 carbon atoms, and in Z ²¹ , at least one —CH ₂ — is —O—, —CO—, —COO—, —OCO—, or —OCOO— At least one —CH ₂ CH ₂ — may be replaced by —CH ＝ CH— or —C≡C—, and at least one hydrogen may be replaced by fluorine or chlorine. Often;
Sp ²¹ is a single bond or an alkylene having 1 to 10 carbon atoms. In this Sp ²¹ , at least one —CH ₂ — is —O—, —CO—, —COO—, —OCO—, or —OCOO— At least one —CH ₂ CH ₂ — may be replaced by —CH ＝ CH— or —C≡C—, at least one hydrogen may be replaced by halogen, In these groups, at least one hydrogen may be replaced by a group selected from groups of formula (2a);

In equation (2a),
Sp ²² is alkylene of 10 a single bond or 1 carbon atoms, in the ^{Sp 22,} at least one of _-CH 2 -, -O -, - CO -, - COO -, - OCO-, or -OCOO- At least one —CH ₂ CH ₂ — may be replaced by —CH ＝ CH— or —C≡C—, and at least one hydrogen may be replaced by halogen;
M ²¹ and M ²² are independently hydrogen, halogen, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen is replaced by halogen:
R ²² is alkyl of from 1 to 15 carbon atoms, in the ^{R 22,} at least one of -CH ₂ -, -O- or -S- in may be replaced, at least one _-CH 2 CH ₂ - May be replaced by -CH = CH- or -C≡C- and at least one hydrogen may be replaced by halogen:
In equation (2),
P ²¹ is a group selected from the groups represented by formulas (2e), (2f), (2g), and (2h);
However, when at least one hydrogen is not replaced with a group selected from the group represented by the formula (2a) in the group that Sp ²¹ can take, P ²¹ is represented by the formula (2e) or the formula (2e). (2f) and a group selected from the groups represented by the formula (2g);

In the expressions (2e), (2f), (2g), and (2h),
Sp ²³ , Sp ²⁴ , and Sp ²⁵ are each independently a single bond or alkylene having 1 to 10 carbon atoms. In Sp ²³ , Sp ²⁴ , and Sp ²⁵ , at least one of —CH ₂ — is —O— , -NH -, - CO -, - COO -, - OCO-, or may be replaced by -OCOO-, at least one _-CH 2 CH ₂ - is, -CH = CH- or -C≡C- And in these groups at least one hydrogen may be replaced by halogen;
S ²¹ is> CH- or>N-;
S ²² is> C <or> Si <;
M ²³ and M ²⁴ are independently hydrogen, halogen, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen is replaced by halogen:
X ¹ is —OH, —NH ₂ , —OR ²⁵ , —N (R ²⁵ ) ₂ , formula (x1), —COOH, —SH, —B (OH) ₂ , or —Si (R ²⁵ ) ₃ . Yes;
In —OR ²⁵ , —N (R ²⁵ ) ₂ , and —Si (R ²⁵ ) ₃ ,
R ²⁵ is hydrogen or alkyl having 1 to 10 carbons. In the R ²⁵ , at least one —CH ₂ — may be replaced with —O—, and at least one —CH ₂ CH ₂ — It may be replaced by -CH = CH-, at least one hydrogen may be replaced by halogen, and w in the formula (x1) is 1, 2, 3 or 4.

式（２−２）から式（２−３８）において、
Ｒ^２１は、炭素数１から１０のアルキル、炭素数２から１０のアルケニル、または炭素数１から９のアルコキシであり、これらの基において、少なくとも１つの水素は、フッ素で置き換えられてもよく；
Ｚ^２１、Ｚ^２２、およびＺ^２３は独立して、単結合、−ＣＨ_２ＣＨ_２−、または−（ＣＨ_２）_４−であり；
Ｓｐ^２１、Ｓｐ^２２、Ｓｐ^２３、およびＳｐ^２４は独立して、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；
Ｌ^１、Ｌ^２、Ｌ^３、Ｌ^４、Ｌ^５、Ｌ^６、Ｌ^７、Ｌ^８、Ｌ^９、Ｌ^１０、Ｌ^１１、およびＬ^１２は独立して、水素、フッ素、メチル、またはエチルであり；
Ｙ^１、Ｙ^２、Ｙ^３、およびＹ^４は独立して、水素またはメチルであり；
ｌは、１、２、３、４、５、または６である。Item 6. Item 6. The liquid crystal composition according to item 5, wherein the second additive is a compound represented by any of formulas (2-2) to (2-38).

In Equations (2-2) to (2-38),
R ²¹ is alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons, or alkoxy having 1 to 9 carbons, and in these groups, at least one hydrogen may be replaced by fluorine;
Z ²¹ , Z ²² , and Z ²³ are independently a single bond, —CH ₂ CH ₂ —, or — (CH ₂ ) ₄ —;
Sp ²¹ , Sp ²² , Sp ²³ , and Sp ²⁴ are each independently a single bond or alkylene having 1 to 5 carbon atoms, in which at least one —CH ₂ — is replaced by —O—. Well;
L ¹ , L ² , L ³ , L ⁴ , L ⁵ , L ⁶ , L ⁷ , L ⁸ , L ⁹ , L ¹⁰ , L ¹¹ and L ¹² are independently hydrogen, fluorine, methyl, or ethyl. Yes;
Y ¹ , Y ² , Y ³ , and Y ⁴ are independently hydrogen or methyl;
l is 1, 2, 3, 4, 5, or 6;

  Item 7. Item 7. The liquid crystal composition according to any one of items 5 or 6, wherein the proportion of the second additive is 0.05% by mass or more and 15% by mass or less based on the mass of the liquid crystal composition.

式（３）において、Ｒ^３３およびＲ^３４は独立して、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、または炭素数２から１２のアルケニルオキシであり；環Ｃおよび環Ｅは独立して、１，４−シクロへキシレン、１，４−シクロへキセニレン、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、またはテトラヒドロピラン−２，５−ジイルであり；環Ｄ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、または７，８−ジフルオロクロマン−２，６−ジイルであり；Ｚ^３２およびＺ^３３は独立して、単結合、−ＣＨ_２ＣＨ_２−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＯＯ−、または−ＯＣＯ−であり；ｂは、１、２、または３であり、ｃは０または１であり、そしてｂとｃとの和は３以下である。Item 8. Item 8. The liquid crystal composition according to any one of items 1 to 7, wherein the liquid crystal composition contains at least one compound selected from the group of compounds represented by formula (3) as a first component.

In the formula (3), R ³³ and R ³⁴ are each independently an alkyl having 1 to 12 carbons, an alkoxy having 1 to 12 carbons, an alkenyl having 2 to 12 carbons, or an alkenyloxy having 2 to 12 carbons. Yes; Rings C and E are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 1,4-cycloalkyl in which at least one hydrogen is replaced by fluorine or chlorine Phenylene or tetrahydropyran-2,5-diyl; ring D is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro- 5-methyl-1,4-phenylene, it is a 3,4,5-trifluoro-2,6-diyl or 7,8-difluoro-chroman-2,6-diyl,; ^{Z 3} And ^{Z 33} are independently a single _{bond, -CH 2 CH 2 -, -} CH 2 O -, - OCH 2 -, - COO-, or a -OCO-; b is 1, 2 or 3, And c is 0 or 1, and the sum of b and c is 3 or less.

式（３−１）から式（３−２２）において、Ｒ^３３およびＲ^３４は独立して、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、または炭素数２から１２のアルケニルオキシである。Item 9. Item 9. The liquid crystal composition according to any one of items 1 to 8, comprising at least one compound selected from the group of compounds represented by formulas (3-1) to (3-22) as a first component. object.

In the formulas (3-1) to (3-22), R ³³ and R ³⁴ are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or It is alkenyloxy having 2 to 12 carbon atoms.

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

式（４）において、Ｒ^４５およびＲ^４６は独立して、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、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、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Ｆおよび環Ｇは独立して、１，４−シクロへキシレン、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^４４は、単結合、−ＣＨ_２ＣＨ_２−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＯＯ−、または−ＯＣＯ−であり；ｄは、１、２、または３である。Item 11. Item 11. The liquid crystal composition according to any one of items 1 to 10, comprising at least one compound selected from the group of compounds represented by formula (4) as a second component.

In the formula (4), R ⁴⁵ and R ⁴⁶ are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, and replacing at least one hydrogen with fluorine or chlorine. C 1 to C 12 alkyl, or C 2 to C 12 alkenyl in which at least one hydrogen is replaced by fluorine or chlorine; Ring F and Ring G are each independently 1,4-cyclohexylene , 1,4-phenylene, be a 2-fluoro-1,4-phenylene or ^{2,5-difluoro-1,4-phenylene,; Z 44} is a single _{bond, -CH 2 CH 2 -, -} CH 2 O —, —OCH ₂ —, —COO—, or —OCO—; d is 1, 2, or 3.

式（４−１）から式（４−１３）において、Ｒ^４５およびＲ^４６は独立して、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、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、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 12. Item 12. The liquid crystal composition according to any one of items 1 to 11, comprising at least one compound selected from the group of compounds represented by formulas (4-1) to (4-13) as a second component. object.

In the formulas (4-1) to (4-13), R ⁴⁵ and R ⁴⁶ are each independently an alkyl having 1 to 12 carbons, an alkoxy having 1 to 12 carbons, an alkenyl having 2 to 12 carbons, It is alkyl having 1 to 12 carbons in which one hydrogen is replaced by fluorine or chlorine, or alkenyl having 2 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine.

  Item 13. Item 13. The liquid crystal composition according to any one of Items 11 or 12, wherein the proportion of the second component is in the range of 10% by mass to 90% by mass based on the mass of the liquid crystal composition.

  Item 14. Item 14. A liquid crystal display device containing the liquid crystal composition according to any one of items 1 to 13.

  Item 15. Item 15. The liquid crystal display element according to item 14, 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 16. Item 14. A polymer supported alignment type liquid crystal display device comprising the liquid crystal composition according to any one of items 1 to 13, wherein a polymerizable compound in the liquid crystal composition is polymerized.

  Item 17. Item 14. A liquid crystal display device comprising the liquid crystal composition according to any one of items 1 to 13, wherein the polymerizable compound in the liquid crystal composition is polymerized, and which has no alignment film.

  Item 18. Item 14. Use of the liquid crystal composition according to any one of items 1 to 13 in a liquid crystal display device.

  Item 19. Item 14. Use of the liquid crystal composition according to any one of items 1 to 13 in a liquid crystal display device of a polymer supported alignment type.

  Item 20. Item 14. Use of the liquid crystal composition according to any one of items 1 to 13 in a liquid crystal display device having no alignment film.

  The present invention also includes the following items. (A) arranging the liquid crystal composition between two substrates, irradiating the composition with light while applying a voltage thereto, and polymerizing a polymerizable compound contained in the composition; Of manufacturing a liquid crystal display device of the invention. (B) the maximum temperature of the nematic phase is 70 ° C. or more, the optical anisotropy at a wavelength of 589 nm (measured at 25 ° C.) is 0.08 or more, and the dielectric anisotropy at a frequency of 1 kHz (measured at 25 ° C.) ) Is -2 or less.

  The present invention also includes the following items. (C) Compounds (5) to (7) described in JP-A-2006-199941 are liquid crystal compounds having a positive dielectric anisotropy, and at least selected from the group of these compounds. A composition as described above containing one compound. (D) The above composition containing at least two of the above compounds (1). (E) The above composition further containing a polymerizable compound different from the maleimide compound (1). (F) one, two or at least three of additives such as optically active compounds, antioxidants, ultraviolet absorbers, dyes, defoamers, polymerizable compounds, polymerization initiators, polymerization inhibitors, polar compounds, etc. A composition as described above comprising: (G) An AM device containing the above composition. (H) A device containing the above composition and having a mode of TN, ECB, OCB, IPS, FFS, VA, or FPA. (I) A transmissive device containing the above composition. (J) Use of the above composition as a composition having a nematic phase. (K) 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 composition of the composition will be described. Second, the main characteristics of the component compounds and the main effects of the compounds on the composition will be described. Third, the combination of the components in the composition, the preferable ratio of the components, and the basis thereof will be described. Fourth, a preferred embodiment of the component compounds will be described. Fifth, preferred component compounds are shown. Sixth, additives that may be added to the composition will be described. Seventh, a method for synthesizing component compounds will be described. Finally, the use of the composition will be described.

  First, the composition of the composition will be described. The compositions of the present invention are classified into composition A and composition B. Composition A may further contain other liquid crystal compounds, additives, and the like, in addition to the liquid crystal compounds selected from compound (3) and compound (4). "Other liquid crystal compounds" are liquid crystal compounds different from compound (3) and compound (4). Such compounds are mixed into the composition for the purpose of further adjusting the properties. Additives include optically active compounds, antioxidants, ultraviolet absorbers, dyes, defoamers, polymerizable compounds, polymerization initiators, polymerization inhibitors, polar compounds, and the like.

  Composition B consists essentially of a liquid crystal compound selected from compound (3) and compound (4). "Substantially" means that the composition may contain additives but does not contain other liquid crystal compounds. Composition B has a smaller number of components than composition A. From the viewpoint of reducing costs, composition B is more preferable than composition A. Composition A is more preferable than composition B from the viewpoint that the properties can be further adjusted by mixing other liquid crystal compounds.

  Second, the main characteristics of the component compounds and the main effects of the compounds on the characteristics of the composition will be described. Table 2 summarizes the main characteristics of the component compounds based on the effects of the present invention. In the symbols in Table 2, L means large or high, M means medium, and S means small or low. The symbols L, M, S are classifications based on qualitative comparisons between the component compounds, and the symbol 0 means that the value is zero or close to zero.

  The main effects of the component compounds on the properties of the composition when the component compounds are mixed into the composition are as follows. Compound (1) has a function as an initiator and gives a polymer by polymerization with compound (2). This polymer stabilizes the alignment of liquid crystal molecules, thereby shortening the response time of the device and improving image burn-in. The compound (2) is adsorbed on the substrate surface by the action of the polar group, and controls the alignment of liquid crystal molecules. In order to obtain the desired effect, it is essential that the compound (2) has high compatibility with the liquid crystal compound. The compound (2) has a rod-shaped molecular structure having a six-membered ring such as 1,4-cyclohexylene and 1,4-phenylene, and has a branched structure at one end of the molecular structure. It is most suitable for this purpose because it is considered that the compatibility can be improved. Compound (2) gives a polymer by polymerization. This polymer stabilizes the orientation of liquid crystal molecules, thereby shortening the response time of the device and improving image burn-in. Compound (3) increases the dielectric anisotropy and lowers the minimum temperature. Compound (4) reduces the viscosity.

  Third, the combination of the components in the composition, the preferable ratio of the components, and the basis thereof will be described. A preferred combination of components in the composition is compound (1) + compound (2) + compound (3) + compound (4).

  The first additive, compound (1), is added to the composition for the purpose of functioning as an initiator. The desirable ratio of the compound (1) is about 0.01% by mass or more for improving the long-term reliability of the device, and about 10% by mass or less for preventing display failure of the device. A more desirable ratio is in the range of about 0.01% to about 5% by weight. A particularly desirable ratio is in the range from about 0.03% to about 1.0% by weight.

  Compound (2), which is a second additive, is added to the composition for the purpose of controlling the alignment of liquid crystal molecules. A desirable ratio of the compound (2) is about 0.05% by mass or more for aligning liquid crystal molecules, and about 15% by mass or less for preventing display failure of the device. A more desirable ratio is in the range of about 0.1% to about 10% by weight. A particularly desirable ratio is in the range from about 0.5% to about 5% by weight.

  The desirable ratio of the compound (3) as the first component is about 10% by mass or more for increasing the dielectric anisotropy and about 90% by mass or less for lowering the minimum temperature. A more desirable ratio is in the range of about 20% to about 85% by weight. A particularly desirable ratio is in the range from about 30% to about 85% by weight.

  A desirable ratio of the compound (4) as the second component is about 10% by mass or more for increasing the maximum temperature or decreasing the minimum temperature, and about 90% by mass or less for increasing the dielectric anisotropy. It is. A more desirable ratio is in the range of about 15% to about 75% by weight. A particularly desirable ratio is in the range from about 15% to about 60% by weight.

  Fourth, a preferred embodiment of the component compounds will be described.

式（Ａ）において、Ｒ^１およびＲ^２は独立して、水素、ハロゲン、または炭素数１から２０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−または−Ｓ−で置き換えられてもよく、少なくとも１つの−（ＣＨ_２）_２−は−ＣＨ＝ＣＨ−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つの水素はハロゲンで置き換えられてもよい。The composition of the present invention contains a maleimide compound having at least one monovalent group (A).

In the formula (A), R ¹ and R ² are independently hydrogen, halogen, or alkyl having 1 to 20 carbons, wherein at least one —CH ₂ — is —O— or —S—. may be replaced by at least one - (CH ₂₎ 2 _- may be replaced by -CH = CH-, in these groups, at least one hydrogen may be replaced by halogen.

  Since the compound (1) has a rod-like molecular structure similar to a liquid crystal compound, the compound (1) has high solubility in a liquid crystal composition. Therefore, compound (1) is suitable as a polymerizable compound required for a device having a PSA mode. Second, compound (1) has suitable polymerizability. Therefore, compound (1) can be stably stored. During polymerization, the speed of the photoreaction can be easily controlled. Polymerization can be performed by appropriately irradiating ultraviolet rays. Does not require excessive UV light.

In the compound (1), preferable examples of the polymerizable group P, the linking group S, the ring A, and the bonding group Z are as follows. This example also applies to compounds below compound (1). The properties of compound (1) can be arbitrarily adjusted by appropriately combining the types of these groups. Since there is no great difference in the physical properties of the compounds, the compound (1) may contain isotopes such as ² H (deuterium) and ¹³ C in an amount larger than the natural abundance.

In the formula (1), P ¹ and P ² are independently a polymerizable group. Examples of polymerizable groups are acryloyloxy, methacryloyloxy, acrylamide, methacrylamide, vinyloxy, vinylcarbonyl, oxiranyl, oxetanyl, 3,4-epoxycyclohexyl, or maleimide. In these groups, at least one hydrogen may be replaced by fluorine, methyl or trifluoromethyl. Preferred examples of polymerizable groups are acryloyloxy (P-1), vinyloxy (P-2), oxiranyl (P-3) or maleimide (A), wherein M ¹ and M ² are independently hydrogen , Fluorine, methyl, or trifluoromethyl, and R ¹ and R ² are the same as defined for the monovalent group represented by the formula (A).

In the formula (1), S ¹ and S ² are each independently a single bond or alkylene having 1 to 10 carbon atoms, and in this alkylene, at least one —CH ₂ — is —O—, —CO—, may be replaced by -COO- or -OCO-, at least one _-CH 2 -CH ₂ - may be replaced by -CH = CH- or -C≡C-, in these bivalent radical , At least one hydrogen may be replaced by halogen or alkyl having 1 to 3 carbons.

Preferred examples of S ¹ or ^{S 2} is a single _{bond, -CH 2 -, - CH 2} O -, - OCH 2 -, - COO -, - OCO -, - CH 2 CH 2 -, - CH = CH-, —C≡C—, — (CH ₂ ) ₃ —, —CH ₂ CH ₂ O—, —OCH ₂ CH ₂ —, —CH ＝ CH—O—, —O—CH ＝ CH—, —C≡C— _{O -, - O-C≡C -} , - (CH 2) 4 -, - (CH 2) 3 -O -, - O- (CH 2) 3 -, - (CH 2) 4 -, - (CH ₂ ) ₄ O— or —O (CH ₂ ) ₄ —. More preferred examples include a single _{bond, -CH 2 -, - CH 2} O -, - OCH 2 -, - COO -, - OCO -, - CH = CH -, - C≡C -, - CH 2 CH 2 O —, —OCH ₂ CH ₂ —, —CH ＝ CH—O—, or —O—CH ＝ CH—. Particularly preferred examples are a single _{bond, -CH 2 -, - CH =} CH -, - CH = CH-O -, - O-CH = CH -, - CH 2 CH 2 O-, or -OCH ₂ CH ₂ - It is. The most preferred example is a single bond. The configuration of the double bond of —CH ＝ CH— may be cis or trans. The trans form is preferred over the cis form.

In the formula (1), R ⁴ and R ⁵ are each independently hydrogen, halogen, —S ¹ —P ¹ , —S ² —P ² , or alkyl having 1 to 20 carbons. one -CH ₂ - may be replaced by -O- or -S-, at least one - _{(CH 2) 2} - may be replaced by -CH = CH-, in these groups, at least One hydrogen may be replaced by a halogen. a1 and a2 are independently 0, 1, 2, 3, or 4. -S ¹ -P ¹ or -S ² -P ² is a monovalent group involved in polymerization. The total number of -S ¹ -P ¹ and -S ² -P ² is 1 to 8. Preferred examples are 1 to 6, and more preferred examples are 1 to 3. The most preferred example is 1 or 2.

式（Ａ）において、Ｒ^１およびＲ^２は独立して、水素、ハロゲン、または炭素数１から２０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−または−Ｓ−で置き換えられてもよく、少なくとも１つの−（ＣＨ_２）_２−は−ＣＨ＝ＣＨ−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つの水素はハロゲンで置き換えられてもよい。好ましいＲ^１またはＲ^２は、メチル、エチル、または水素である。さらに好ましいＲ^１またはＲ^２は水素である。In the formula (1), at least one of all —S ¹ —P ¹ and all —S ² —P ² has a monovalent group represented by the formula (A).

In the formula (A), R ¹ and R ² are independently hydrogen, halogen, or alkyl having 1 to 20 carbons, wherein at least one —CH ₂ — is —O— or —S—. may be replaced by at least one - (CH ₂₎ 2 _- may be replaced by -CH = CH-, in these groups, at least one hydrogen may be replaced by halogen. Preferred R ¹ or R ² is methyl, ethyl, or hydrogen. More preferred R ¹ or R ² is hydrogen.

In the formula (1), ring A ¹ and ring A ² are each independently an alicyclic hydrocarbon having 3 to 18 carbon atoms, an aromatic hydrocarbon having 6 to 18 carbon atoms, or a heteroaromatic having 3 to 18 carbon atoms. A divalent group derived from an aromatic hydrocarbon by removing two hydrogens. In these divalent groups, at least one hydrogen is replaced by halogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 1 to 12 carbons, or alkenyloxy having 1 to 12 carbons. And in these monovalent hydrocarbon radicals at least one hydrogen may be replaced by halogen. Furthermore, ring ^{A 1} is the a1 hydrogens optionally replaced by ^-S 1 -P ^1, ring ^{A 2} is a2 one hydrogen is replaced by ^-S 2 -P ^2.

Examples of alicyclic hydrocarbons are cyclopropane, cyclobutane, cyclohexane, cycloheptane, cyclooctane, etc., represented by C _n H _2n . Another example is decahydronaphthalene and the like. Examples of aromatic hydrocarbons are benzene, naphthalene, anthracene, phenanthrene, fluorene, indane, indene, tetrahydronaphthalene and the like. Examples of heteroaromatic hydrocarbons are pyridine, pyrimidine, furan, pyran, thiophene, benzofuran and the like. These hydrocarbons may be substituted with monovalent groups such as fluorine, chlorine, alkyl. Preferred examples of ring A ¹ or ring A ² are benzene, fluorobenzene, naphthalene, fluorene or phenanthrene. Further preferred examples are benzene or naphthalene.

In the formula (1), Z ¹ is a single bond or an alkylene having 1 to 10 carbon atoms, in which at least one —CH ₂ — is —O—, —CO—, —COO—, or —OCO—. may be replaced by at least one _-CH 2 -CH ₂ - _{is, -CH = CH -, - C} (CH 3) = CH -, - CH = C (CH 3) -, - C (CH 3 ) = C (CH ₃ ) —, or —C≡C—, and in these divalent groups, at least one hydrogen may be replaced by halogen.

Preferred examples of Z ¹ represents a single bond, an alkylene having 1 to 4 carbon atoms _{of, -COO -, - OCO -,} - CH 2 O -, - OCH 2 -, - CF 2 O -, - OCF 2 -, - CH = CH -, - CH = CH -COO -, - OCO-CH = CH -, - C (CH 3) = CH-COO -, - OCO-CH = C (CH 3) -, - CH = C (CH _{3) -COO -, - OCO- (} CH 3) C = CH -, - C (CH 3) = C (CH 3) -COO -, - OCO-C (CH 3) = C (CH 3) -, _{-CO-CH = CH -, -} CH = CH-CO -, - C (CH 3) = C (CH 3) -, - CH = CH-CH 2 O -, - OCH 2 -CH = CH -, - CH ＝ CH—OCH ₂ —, —CH ₂ O—CH ＝ CH—, or —C≡C—. More preferred examples are a single bond, ethylene, -COO-, -OCO-, -CH = CH-, -CH = CH-COO-, -OCO-CH = CH-, or -C≡C-. The most preferred example is a single bond.

In the formula (1), b1 is 0 or 1, and b2 is 0, 1, 2, or 3. When b1 is 0 and b2 is 0, the compound has no cyclic structure. When b1 is 1 and b2 is 0, the compound has one ring represented by the ring A ^1. In this case, preferred ring A ¹ is a naphthalene, anthracene, the fused rings such as phenanthrene, a divalent group derived by removing two hydrogen. When b1 is and b2 is 1 1, the compound has a ring ^{A 1} and ring ^{A 2.} In this case, preferred ring A ¹ or ring A ² is a divalent radical derived benzene, fluorine or a benzene substituted with substituents such as methyl. When b1 is 1 and b2 is 2, the compound has three rings, ring A ¹ , ring A ² and ring A ² . Preferred ring A ¹ or ring A ² are benzene, divalent group derived from benzene substituted with substituents such as fluorine.

In the formula (2), X ¹ is a polar group. Compound (2) is preferably stable because it is added to the composition. When the compound (2) is added to the composition, the compound preferably does not lower the voltage holding ratio of the device. Compound (2) preferably has low volatility. The preferred molar mass is at least 130 g / mol. A more preferred molar mass ranges from 150 g / mol to 700 g / mol. Preferred compound (2) has a polymerizable group such as acryloyloxy (—OCO—CH ＝ CH ₂ ) and methacryloyloxy (—OCO— (CH ₃ ) C ＝ CH ₂ ).

X ¹ is a group represented by —OH, —NH ₂ , —OR ²⁵ , —N (R ²⁵ ) ₂ , formula (x1), or —Si (R ²⁵ ) ₃ , wherein R ²⁵ is , Hydrogen or alkyl having 1 to 5 carbons, wherein at least one —CH ₂ — may be replaced by —O—, and at least one —CH ₂ CH ₂ — CH- may be replaced, and in these groups at least one hydrogen may be replaced by fluorine. From the viewpoint of high solubility in the liquid crystal composition, it is particularly preferred ^{X 1} is -OH or -NH _2. -OH is preferable to -O-, -CO-, or -COO- because it has a high anchoring force. Groups having more than one heteroatom (nitrogen, oxygen) are particularly preferred. Compounds having such polar groups are effective even at low concentrations.

R ²¹ is alkyl of from 1 to 15 carbon atoms, in the ^{R 21,} at least one of -CH ₂ -, -O- or -S- in may be replaced, at least one _-CH 2 CH ₂ -May be replaced by -CH = CH- or -C≡C-, and at least one hydrogen may be replaced by halogen.
Ring A ²¹ and ring A ²² are each independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, decahydronaphthalene-2,6- Diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine- 2,5-diyl, fluorene-2,7-diyl, phenanthrene-2,7-diyl, anthracene-2,6-diyl, perhydrocyclopenta [a] phenanthrene-3,17-diyl, or 2,3 4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydrocyclopenta [a] phenanthrene-3,17-diyl, Wherein at least one hydrogen is replaced by fluorine, chlorine, alkyl having 1 to 12 carbons, alkenyl having 2 to 12 carbons, alkoxy having 1 to 11 carbons, or alkenyloxy having 2 to 11 carbons And in these groups at least one hydrogen may be replaced by fluorine or chlorine. Preferred ring A ²¹ or ring A ²² is 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, naphthalene-2,6-diyl, or 3-ethyl-1,4 -Phenylene.

Z ²¹ is a single bond or alkylene having 1 to 6 carbon atoms, and in this Z ²¹ , at least one —CH ₂ — is —O—, —CO—, —COO—, —OCO—, or —OCOO. At least one —CH ₂ CH ₂ — may be replaced by —CH ＝ CH— or —C≡C—, and at least one hydrogen may be replaced by fluorine or chlorine. Is also good. Preferred ^{Z 21} is a single _{bond, -CH 2 CH 2 -, -} CH 2 O -, - OCH 2 -, - COO-, or -OCO-. More preferred Z ²¹ is a single bond.

式（２ａ）において、
Ｓｐ^２２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Ｓｐ^２２において、少なくとも１つの−ＣＨ_２−は、−Ｏ−、−ＣＯ−、−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_２ＣＨ_２−は、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、少なくとも１つの水素は、ハロゲンで置き換えられてもよく；
Ｍ^２１およびＭ^２２は独立して、水素、ハロゲン、炭素数１から５のアルキル、または少なくとも１つの水素がハロゲンで置き換えられた炭素数１から５のアルキルであり；
Ｒ^２２は炭素数１から１５のアルキルであり、このＲ^２２において、少なくとも１つの−ＣＨ_２−は、−Ｏ−または−Ｓ−で置き換えられてもよく、少なくとも１つの−ＣＨ_２ＣＨ_２−は、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、少なくとも１つの水素はハロゲンで置き換えられてもよい。好ましいＳｐ^２１は、単結合である。
Ｐ^２１は、式（２ｅ）、式（２ｆ）、式（２ｇ）、および式（２ｈ）で表される基から選択された基であり；

式（２ｅ）、（２ｆ）、（２ｇ）、および（２ｈ）において、
Ｓｐ^２３、Ｓｐ^２４、Ｓｐ^２５は、独立して、単結合または炭素数１から１０のアルキレンであり、このＳｐ^２３、Ｓｐ^２４、Ｓｐ^２５において、少なくとも１つの−ＣＨ_２−は、−Ｏ−、−ＮＨ−、−ＣＯ−、−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_２ＣＨ_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つの水素はハロゲンで置き換えられてもよく；
Ｓ^２１は、＞ＣＨ−または＞Ｎ−であり；
Ｓ^２２は、＞Ｃ＜または＞Ｓｉ＜であり；
Ｍ^２３およびＭ^２４は独立して、水素、ハロゲン、炭素数１から５のアルキル、または少なくとも１つの水素がハロゲンで置き換えられた炭素数１から５のアルキルであり：
Ｘ^１は、−ＯＨ、−ＮＨ_２、−ＯＲ^２５、−Ｎ（Ｒ^２５）_２、式（ｘ１）、−ＣＯＯＨ、−ＳＨ、−Ｂ（ＯＨ）_２、または−Ｓｉ（Ｒ^２５）_３であり；
−ＯＲ^２５、−Ｎ（Ｒ^２５）_２、および−Ｓｉ（Ｒ^２５）_３において、
Ｒ^２５は水素または炭素数１から１０のアルキルであり、このＲ^２５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、少なくとも１つの−ＣＨ_２ＣＨ_２−は、−ＣＨ＝ＣＨ−で置き換えられてもよく、少なくとも１つの水素は、ハロゲンで置き換えられてもよく、式（ｘ１）におけるｗは１、２、３または４である。

Sp ²¹ is a single bond or an alkylene having 1 to 10 carbon atoms, and in this Sp ²¹ , at least one —CH ₂ — is —O—, —CO—, —COO—, —OCO—, or —OCOO— At least one —CH ₂ CH ₂ — may be replaced by —CH ＝ CH— or —C≡C—, at least one hydrogen may be replaced by halogen, In these groups, at least one hydrogen has been replaced by a group selected from groups of formula (2a);

In equation (2a),
Sp ²² is alkylene of 10 a single bond or 1 carbon atoms, in the ^{Sp 22,} at least one of _-CH 2 -, -O -, - CO -, - COO -, - OCO-, or -OCOO- At least one —CH ₂ CH ₂ — may be replaced by —CH ＝ CH— or —C≡C—, and at least one hydrogen may be replaced by halogen;
M ²¹ and M ²² are independently hydrogen, halogen, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen is replaced by halogen;
R ²² is alkyl of from 1 to 15 carbon atoms, in the ^{R 22,} at least one of -CH ₂ -, -O- or -S- in may be replaced, at least one _-CH 2 CH ₂ - May be replaced by -CH = CH- or -C≡C-, and at least one hydrogen may be replaced by halogen. Preferred Sp ²¹ is a single bond.
P ²¹ is a group selected from the groups represented by formulas (2e), (2f), (2g), and (2h);

In formulas (2e), (2f), (2g), and (2h),
Sp ²³ , Sp ²⁴ , and Sp ²⁵ are each independently a single bond or alkylene having 1 to 10 carbon atoms. In Sp ²³ , Sp ²⁴ , and Sp ²⁵ , at least one of —CH ₂ — is —O— , -NH -, - CO -, - COO -, - OCO-, or may be replaced by -OCOO-, at least one _-CH 2 CH ₂ - is, -CH = CH- or -C≡C- And in these groups at least one hydrogen may be replaced by halogen;
S ²¹ is> CH- or>N-;
S ²² is> C <or> Si <;
M ²³ and M ²⁴ are independently hydrogen, halogen, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen is replaced by halogen:
X ¹ is —OH, —NH ₂ , —OR ²⁵ , —N (R ²⁵ ) ₂ , formula (x1), —COOH, —SH, —B (OH) ₂ , or —Si (R ²⁵ ) ₃ . Yes;
In —OR ²⁵ , —N (R ²⁵ ) ₂ , and —Si (R ²⁵ ) ₃ ,
R ²⁵ is hydrogen or alkyl having 1 to 10 carbons. In the R ²⁵ , at least one —CH ₂ — may be replaced with —O—, and at least one —CH ₂ CH ₂ — It may be replaced by -CH = CH-, at least one hydrogen may be replaced by halogen, and w in the formula (x1) is 1, 2, 3 or 4.

  a is 0, 1, 2, 3, or 4. Preferred a is 0, 1, or 2.

In the formulas (2-2) to (2-38), R ²¹ is alkyl having 1 to 10 carbons;
Z ²¹ , Z ²² , and Z ²³ are independently a single bond, —CH ₂ CH ₂ —, or — (CH ₂ ) ₄ —;
Sp ²¹ , Sp ²² , Sp ²³ , and Sp ²⁴ are each independently a single bond or alkylene having 1 to 5 carbon atoms, in which at least one —CH ₂ — is replaced by —O—. L ¹ , L ² , L ³ , L ⁴ , L ⁵ , L ⁶ , L ⁷ , L ⁸ , L ⁹ , L ¹⁰ , L ¹¹ and L ¹² are independently hydrogen, fluorine, methyl, Or Y; Y ¹ , Y ² , Y ³ , and Y ⁴ are independently hydrogen or methyl; and l is 1, 2, 3, 4, 5, or 6.

In the formulas (3) and (4), R ³³ and R ³⁴ are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or 12 alkenyloxy. Desirable R ³³ or R ³⁴ is alkyl having 1 to 12 carbons for increasing stability, and alkoxy having 1 to 12 carbons for increasing dielectric anisotropy. R ⁴⁵ and R ⁴⁶ are each independently an alkyl having 1 to 12 carbons, an alkoxy having 1 to 12 carbons, an alkenyl having 2 to 12 carbons, 12 alkyl or alkenyl having 2 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine. Desirable R ⁴⁵ or R ⁴⁶ is alkenyl having 2 to 12 carbons for decreasing the viscosity, and alkyl having 1 to 12 carbons for increasing the stability. The alkyl of the liquid crystal compound is linear or branched and does not include cyclic alkyl. Linear alkyls are preferred over branched alkyls. The same applies to terminal groups such as alkoxy and alkenyl.

  Preferred alkyls are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, or octyl. More preferred alkyl is ethyl, propyl, butyl, pentyl, or heptyl for decreasing the viscosity.

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

  Preferred alkenyls are 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 for decreasing the viscosity. The preferred configuration of -CH = CH- in these alkenyls depends on the position of the double bond. Trans is preferable in alkenyl such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 3-pentenyl and 3-hexenyl for decreasing the viscosity. Cis is preferred in alkenyl such as 2-butenyl, 2-pentenyl and 2-hexenyl.

  Preferred alkenyloxy is vinyloxy, allyloxy, 3-butenyloxy, 3-pentenyloxy, or 4-pentenyloxy. More preferred alkenyloxy for decreasing the viscosity is allyloxy or 3-butenyloxy.

  Preferred examples of 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 for increasing the dielectric anisotropy.

  Preferred examples of alkenyl wherein 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.

Ring C and ring E are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced by fluorine or chlorine, Or tetrahydropyran-2,5-diyl. Preferred examples of "1,4-phenylene in which at least one hydrogen is replaced by fluorine or chlorine" include 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, or 2-chloro -3-fluoro-1,4-phenylene. Desirable ring C or ring E is 1,4-cyclohexylene for decreasing the viscosity, tetrahydropyran-2,5-diyl for increasing the dielectric anisotropy, and ring C or E for increasing the optical anisotropy. 1,4-phenylene. Regarding the configuration of 1,4-cyclohexylene, trans is preferable to cis for increasing the maximum temperature. Tetrahydropyran-2,5-diyl is

  Ring D 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 or 7,8-difluorochroman-2,6-diyl. Desirable ring D is 2,3-difluoro-1,4-phenylene for decreasing the viscosity, 2-chloro-3-fluoro-1,4-phenylene for decreasing the optical anisotropy, 7,8-difluorochroman-2,6-diyl for increasing anisotropy.

  Ring F and ring G are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4-phenylene. Desirable ring F or ring G is 1,4-cyclohexylene for decreasing the viscosity or increasing the maximum temperature, and 1,4-phenylene for decreasing the minimum temperature. Regarding the configuration of 1,4-cyclohexylene, trans is preferable to cis for increasing the maximum temperature.

Z ³² and ^{Z 33} are independently a single _{bond, -CH 2 CH 2 -, -} CH 2 O -, - OCH 2 -, - COO-, or -OCO-. Preferred ^{Z 32} or ^{Z 33} is a single bond for decreasing the viscosity, _-CH 2 CH ₂ for decreasing the minimum temperature - a, _-CH 2 O-or -OCH for increasing the dielectric anisotropy _2- . Z ⁴⁴ represents a single _{bond, -CH 2 CH 2 -, -} CH 2 O -, - OCH 2 -, - COO-, or -OCO-. Preferred ^{Z 44} is a single bond for decreasing the viscosity, _-CH 2 CH ₂ for decreasing the minimum temperature - and for increasing the maximum temperature -COO- or -OCO-.

  b is 1, 2, or 3, c is 0 or 1, and the sum of b and c is 3 or less. Desirable b is 1 for decreasing the viscosity, and 2 or 3 for increasing the maximum temperature. Desirable c is 0 for decreasing the viscosity, and 1 for decreasing the minimum temperature. d is 1, 2, or 3. Desirable d is 1 for decreasing the viscosity, and 2 or 3 for increasing the maximum temperature.

  Fifth, preferred component compounds are shown. Preferred compound (2) is the compound (2-2) to the compound (2-38) described in item 6. In these compounds, at least one of the second additives is compound (2-2), compound (2-3), compound (2-4), compound (2-11), compound (2-19) or compound (2-21) is preferable. It is preferable that at least two of the second additives are a combination of the compound (2-2) and the compound (2-3) or a combination of the compound (2-3) and the compound (2-4).

  Desirable compounds (3) are the compounds (3-1) to (3-22) described in item 9. In these compounds, at least one of the first components is a compound (3-1), a compound (3-3), a compound (3-4), a compound (3-6), a compound (3-8), or a compound (3-10) is preferable. At least two of the first components are compound (3-1) and compound (3-6), compound (3-1) and compound (3-10), compound (3-3) and compound (3-6), A combination of the compound (3-3) and the compound (3-10), the compound (3-4) and the compound (3-6), or the combination of the compound (3-4) and the compound (3-8) is preferable.

  Desirable compounds (4) are the compounds (4-1) to (4-13) described in item 12. In these compounds, at least one of the second components is a compound (4-1), a compound (4-3), a compound (4-5), a compound (4-6), a compound (4-8), or a compound (4-9) is preferable. At least two of the second components are the compound (4-1) and the compound (4-3), the compound (4-1) and the compound (4-5), or the compound (4-1) and the compound (4-6) A combination is preferred.

  Sixth, additives other than the first and second additives that may be added to the composition will be described. Such additives include optically active compounds, antioxidants, ultraviolet absorbers, dyes, defoamers, 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 a compound are compound (5-1) to compound (5-5). A desirable ratio of the optically active compound is about 5% by mass or less. A more desirable ratio is in the range of about 0.01% to about 2% by weight.

An antioxidant is used to prevent the specific resistance from dropping due to heating in the atmosphere, or to maintain a large voltage holding ratio not only at room temperature but also near the upper limit temperature after using the device for a long time. Added to the product. Preferred examples of the antioxidant include a compound (6) in which n is an integer of 1 to 9.

  In the compound (6), preferred n is 1, 3, 5, 7, or 9. More preferred n is 7. Since the compound (6) in which n is 7 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. A desirable ratio of the antioxidant is about 50 ppm or more to obtain the effect, and about 600 ppm or less so as not to lower the upper limit temperature or increase the lower limit temperature. A more desirable ratio is in the range of about 100 ppm to about 300 ppm.

  Preferred examples of the ultraviolet absorber include a benzophenone derivative, a benzoate derivative, and a triazole derivative. Light stabilizers such as sterically hindered amines are also preferred. A preferable ratio in these absorbents and stabilizers is about 50 ppm or more to obtain the effect, and is about 10000 ppm or less so as not to lower the upper limit temperature or increase the lower limit temperature. A more desirable ratio is in the range of about 100 ppm to about 10,000 ppm.

  A dichroic dye such as an azo dye or an anthraquinone dye is added to the composition in order to make the device compatible with a GH (guest host) mode device. The preferred proportion of dye ranges from about 0.01% to about 10% by weight. To prevent foaming, an antifoaming agent such as dimethyl silicone oil or methyl phenyl silicone oil is added to the composition. A desirable ratio of the antifoaming agent is about 1 ppm or more for obtaining the effect, and about 1000 ppm or less for preventing display defects. A more desirable ratio is in the range of about 1 ppm to about 500 ppm.

  A polymerizable compound is used in order to adapt to a device of a polymer supported alignment (PSA) type. Compound (1) and compound (2) are suitable for this purpose. In addition to the compound (1) and the compound (2), another polymerizable compound different from the compound (1) and the compound (2) may be added to the composition. Preferred examples of other polymerizable compounds are compounds such as acrylate, methacrylate, vinyl compound, vinyloxy compound, propenyl ether, epoxy compound (oxirane, oxetane), and vinyl ketone. Further preferred examples are acrylates or methacrylates. A desirable ratio of the compound (1) and the compound (2) is about 10% by mass or more based on the total mass of the polymerizable compound. A more desirable ratio is about 50% by mass or more. A particularly desirable ratio is about 80% by mass or more. A particularly desirable ratio is also 100% by mass. The reactivity of the polymerizable compound and the liquid crystal molecules can be changed by changing the types of the compound (1) and the compound (2), or by combining the compound (1) and the compound (2) with another polymerizable compound at an appropriate ratio. Can be adjusted. By optimizing the pretilt angle, a short response time of the device can be achieved. Since the alignment of the liquid crystal molecules is stabilized, a large contrast ratio and a long lifetime can be achieved.

  Polymerizable compounds such as compound (1) and compound (2) are polymerized by ultraviolet irradiation. The polymerization may be carried out in the presence of a suitable initiator such as a photopolymerization initiator. The appropriate conditions for the polymerization, the appropriate type of initiator, and the appropriate amounts are known to those skilled in the art and are described in the literature. For example, the photoinitiators Irgacure 651 (registered trademark; BASF), Irgacure 184 (registered trademark; BASF), or Darocur 1173 (registered trademark; BASF) are suitable for radical polymerization. A preferred ratio of the photopolymerization initiator ranges from about 0.1% to about 5% by weight based on the total weight of the polymerizable compound. A more desirable ratio is in the range of about 1% to about 3% by weight.

  When storing a polymerizable compound such as compound (1) and compound (2), 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 include hydroquinone, hydroquinone derivatives such as methylhydroquinone, 4-tert-butylcatechol, 4-methoxyphenol, phenothiazine and the like.

  Seventh, a method for synthesizing component compounds will be described. These compounds can be synthesized by known methods. The synthesis method is exemplified. The method for synthesizing compound (1) will be described below. Compound (2-36) and compound (2-37) are synthesized by the method described in International Publication WO 2016/129490. Compound (3-1) is synthesized by the method described in JP-T-2-503441. Compound (4-5) is synthesized by the method described in JP-A-57-165328. Some of the compounds (6) are commercially available. The compound of the formula (6) wherein n is 1 is available from Sigma-Aldrich Corporation. The compound (6) where n is 7 is synthesized by the method described in US Pat. No. 3,660,505.

  A method for synthesizing compound (1) will be described. Compound (1) can be synthesized by appropriately combining methods of synthetic organic chemistry. Methods for introducing desired end groups, rings, and linking groups into starting materials are described in Houben-Wyle, Methoden der Organische Chemie, Georg-Thieme Verlag, Stuttgart, Organic Syntheses, John Wiley & Sons, Inc.), Organic Reactions, John Wily & Sons Inc., Comprehensive Organic Synthesis, Pergamon Press, New Laboratory Chemistry Course (Maruzen), etc. Have been.

2-1. Generation of Bonding Group Z An example of a method for generating the bonding group Z in the compound (1) is as shown in the following scheme. In this scheme, MSG ¹ (or MSG ² ) is a monovalent organic group having at least one ring. The monovalent organic groups represented by a plurality of MSG ¹ (or MSG ² ) may be the same or different. Compounds (1A) to (1I) correspond to compound (1). For the production of the ester, a method for synthesizing a compound having -COO- was described. A compound having -OCO- can also be synthesized by this synthesis method. The same applies to other asymmetric bonding groups.

(1) Formation of single bond The aryl boric acid (21) is reacted with a compound (22) synthesized by a known method in an aqueous carbonate solution in the presence of a catalyst such as tetrakis (triphenylphosphine) palladium. Compound (1A) is synthesized. This compound (1A) is prepared by reacting compound (23) synthesized by a known method with n-butyllithium and then zinc chloride, and reacting compound (22) in the presence of a catalyst such as dichlorobis (triphenylphosphine) palladium. ) Can also be synthesized.

(2) Formation of —COO— Compound (23) is reacted with n-butyllithium and subsequently with carbon dioxide to obtain carboxylic acid (24). Compound (24) and phenol (25) synthesized by a known method are subjected to dehydration condensation in the presence of DCC (1,3-dicyclohexylcarbodiimide) and DMAP (N, N-dimethyl-4-aminopyridine). Compound (1B) is synthesized.

(3) Formation of —CF ₂ O— The compound (1B) is treated with a sulfurizing agent such as Lawesson's reagent to obtain a compound (26). Compound (26) is fluorinated with hydrogen fluoride pyridine complex and NBS (N-bromosuccinimide) to synthesize compound (1C). See M. Kuroboshi et al., Chem. Lett., 1992, 827. Compound (1C) is also synthesized by fluorinating compound (26) with (diethylamino) sulfur trifluoride (DAST). See WH Bunnelle et al., J. Org. Chem. 1990, 55, 768. This binding group can also be generated by the method described in Peer. Kirsch et al., Angew. Chem. Int. Ed. 2001, 40, 1480.

(4) Formation of —CH ＝ CH— The compound (22) is treated with n-butyllithium, and then reacted with a formamide such as N, N-dimethylformamide (DMF) to obtain an aldehyde (28). The compound (1D) is synthesized by reacting the phosphonium salt (27) synthesized by a known method with a base such as potassium tert-butoxide to generate phosphorus ylide with an aldehyde (28). Since a cis form is generated depending on the reaction conditions, the cis form is isomerized to a trans form by a known method, if necessary.

(5) Formation of —CH ₂ O— The compound (28) is reduced with a reducing agent such as sodium borohydride to obtain a compound (29). This is halogenated with hydrobromic acid or the like to obtain a compound (31). Compound (1E) is synthesized by reacting compound (31) with compound (30) in the presence of potassium carbonate or the like.

(6) Formation of —CH ＝ CH—COO— A phosphorus ylide is prepared by reacting a base such as sodium hydride with ethyl diethylphosphonoacetate, and the phosphorus ylide is reacted with an aldehyde (32) to obtain an ester (33). . Hydrolysis of the ester (33) in the presence of a base such as sodium hydroxide gives the carboxylic acid (34). This compound and compound (25) are subjected to dehydration condensation to synthesize compound (1F).

(7) Formation of —C (CH ₃ ) ＝ CH—COO—A base such as sodium hydride is allowed to act on ethyl diethylphosphonoacetate to prepare phosphorus ylide, and the phosphorus ylide is reacted with methyl ketone (35) to give an ester ( 36) is obtained. Next, the ester (36) is hydrolyzed in the presence of a base such as sodium hydroxide to obtain a carboxylic acid (37), and then the compound (1G) is synthesized by dehydration condensation with the compound (25).

(8) Formation of —CH ＝ C (CH ₃ ) —COO— A compound (38) synthesized by a known method and a compound (39) synthesized by a known method are combined with N, N-dicyclohexylmethylamine (Cy). ₂ NMe) a base such as, and bis (tri -tert- butylphosphine) compound are reacted in the presence of a catalyst such as palladium (1H) is synthesized.

Obtaining _{(9) -C (CH 3)} = C (CH 3) -COO- the product compound (25) with the compound by dehydration condensation of pyruvate (40). Compound (1I) is synthesized by reacting compound (40) with compound (35) in the presence of zinc and titanium tetrachloride.

この重合性基が連結基Ｓで環に結合した化合物を合成する方法の例は、下記のとおりである。まず、連結基Ｓが単結合である例を示す。2-2. Formation of Linking Group S P ¹ or P ² is a polymerizable group. Preferred examples of the polymerizable group are acryloyloxy (P-1), vinyloxy (P-2), oxiranyl (P-3) or maleimide (A). In the formula (P-1), M ¹ and M ² are independently hydrogen, fluorine, methyl, or trifluoromethyl.

An example of a method for synthesizing a compound in which the polymerizable group is bonded to the ring via the linking group S is as follows. First, an example in which the linking group S is a single bond will be described.

(1) Generation of a single bond A method of generating a single bond is as shown in the following scheme. In this scheme, MSG ¹ is a monovalent organic group having at least one ring. Compounds (1S) to (1Y) correspond to compound (1).

  The method for synthesizing the compound in which the linking group S is a single bond has been described above. Other methods for producing a linking group can be synthesized with reference to the method for synthesizing the linking group Z.

  Compound (1) has appropriate polymerization reactivity, high conversion, and high solubility in a liquid crystal composition, as compared to similar compounds. Compound (1) has an appropriate balance with respect to these at least two physical properties. Therefore, the compound (1) can be added to a PSA mode liquid crystal composition.

  Compounds for which synthesis methods were not described are described in Organic Synthesis (John Wiley & Sons, Inc.), Organic Reactions (John Wiley & Sons, Inc.) and Comprehensive Organic Synthesis (John Wiley & Sons, Inc.). Comprehensive Organic Synthesis, Pergamon Press), New Laboratory Chemistry Course (Maruzen), and the like. The composition is prepared from the compound thus obtained by a known method. For example, the component compounds are mixed and dissolved together by heating.

  Finally, the use of the composition will be described. Most compositions have a lower temperature limit of about −10 ° C. or less, an upper temperature limit of about 70 ° C. or more, 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 ratio of the component compounds or by mixing other liquid crystal compounds. Further, a composition having an optical anisotropy in the range of about 0.10 to about 0.30 may be prepared by trial and error. A device containing this composition has a large voltage holding ratio. This composition is suitable for an AM device. This composition is particularly suitable for a transmission type AM device. 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. Further, it can be used for a PM element. This composition can be used for AM devices and PM devices having modes such as PC, TN, STN, ECB, OCB, IPS, FFS, VA, and FPA. Use for an AM device having a TN, OCB, IPS mode or FFS mode is particularly preferable. In an AM device having an IPS mode or an FFS mode, when no voltage is applied, the orientation of liquid crystal molecules may be parallel to or perpendicular to the glass substrate. These elements may be of a reflective, transmissive or transflective type. Use for a transmissive element is preferred. Use for an amorphous silicon-TFT device or a polycrystalline silicon-TFT device is also possible. The composition can also be used for an NCAP (nematic curvilinear aligned phase) type device produced by microencapsulation and a PD (polymer dispersed) type device in which a three-dimensional network polymer is formed in the composition.

  An example of a method for manufacturing a conventional polymer-supported orientation-type device is as follows. An element having two substrates called an array substrate and a color filter substrate is assembled. This substrate has an alignment film. At least one of the substrates has an electrode layer. A liquid crystal composition is prepared by mixing a liquid crystal compound. A polymerizable compound is added to the composition. If necessary, additives may be further added. This composition is injected into the device. Light irradiation is performed with a voltage applied to the device. Ultraviolet light is preferred. The polymerizable compound is polymerized by light irradiation. The polymerization produces a composition containing the polymer. The polymer-supported orientation-type device is manufactured by such a procedure.

  In this procedure, when a voltage is applied, the liquid crystal molecules are aligned by the action of an electric field. The molecules of the polymerizable compound are also oriented according to this orientation. In this state, the polymerizable compound is polymerized by ultraviolet rays, so that a polymer maintaining this orientation is generated. The effect of the polymer shortens the response time of the device. Since image sticking is a malfunction of liquid crystal molecules, sticking is also improved by the effect of the polymer. It should be noted that the polymerizable compound in the composition may be preliminarily polymerized, and the composition may be disposed between the substrates of the liquid crystal display device.

  Since the compound (1) has a rod-like molecular structure similar to a liquid crystal compound, the compound (1) has high solubility in a liquid crystal composition. During polymerization, the speed of the photoreaction can be easily controlled. Polymerization can be performed by appropriately irradiating ultraviolet rays. Does not require excessive UV light.

  When compound (2), that is, a polymerizable compound having a polar group, is used as the polymerizable compound, an alignment film is not required on the substrate of the device. An element without an alignment film is manufactured according to the procedure described in the preceding three paragraphs except that a substrate without an alignment film is used.

  In this procedure, compound (2) is arranged on the substrate because the polar group interacts with the substrate surface. The liquid crystal molecules are aligned according to this arrangement. When a voltage is applied, the alignment of the liquid crystal molecules is further promoted. In this state, the polymerizable group is polymerized by ultraviolet rays, so that a polymer maintaining this orientation is produced. The effect of the polymer additionally stabilizes the alignment of the liquid crystal molecules and shortens the response time of the device. Since image sticking is a malfunction of liquid crystal molecules, sticking is also improved by the effect of the polymer.

  The present invention will be described in more detail by way of examples. The invention is not limited by these examples. The present invention includes a mixture of the composition M51 and the composition M52. The invention also includes a mixture of at least two of the compositions of the examples. The characteristics of the compound, the composition and the device were measured by the following methods.

Measurement method Characteristics were measured by the following methods. Most of these methods are described in the JEITA standard (JEITA ED-2521B) established by the Japan Electronics and Information Technology Industries Association (JEITA), or modified methods thereof. Met. No thin film transistor (TFT) was attached to the TN device used for the measurement.

(1) Maximum temperature of nematic phase (NI; ° C.): A sample was placed on a hot plate of a melting point measuring apparatus equipped with a polarizing microscope and heated at a rate of 1 ° C./min. The temperature when a part of the sample changed from a nematic phase to an isotropic liquid was measured. The maximum temperature of the nematic phase may be abbreviated as “maximum temperature”.

(2) Viscosity (bulk viscosity; η; measured at 20 ° C .; mPa · s): An E-type viscometer manufactured by Tokyo Keiki Co., Ltd. was used for the measurement.

(3) Optical anisotropy (refractive index anisotropy; Δn; measured at 25 ° C.): Measurement was performed using light having a wavelength of 589 nm with an Abbe refractometer having a polarizing plate attached to an eyepiece. 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 direction of polarized light was parallel to the direction of rubbing. The refractive index n⊥ was measured when the direction of polarized light was perpendicular to the direction of rubbing. The value of the optical anisotropy was calculated from the equation: Δn = n∥−n⊥.

(4) Dielectric anisotropy (Δε; measured at 25 ° C.): The value of the dielectric anisotropy was calculated from the equation: Δε = ‖∥−⊥. 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. After rotating the glass substrate with a spinner, it was heated at 150 ° C. for 1 hour. A sample was placed in a VA device in which the distance (cell gap) between two glass substrates was 4 μm, and the device was sealed with an adhesive that cured with ultraviolet light. Sine waves (0.5 V, 1 kHz) were applied to the device, and after 2 seconds, the dielectric constant (ε‖) in the major axis direction of the liquid crystal molecules was measured.
2) Measurement of dielectric constant (ε⊥): A polyimide solution was applied to a well-cleaned glass substrate. After firing this glass substrate, a rubbing treatment was performed on the obtained alignment film. A sample was injected into 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 the device, and after 2 seconds, the dielectric constant (ε （) of the liquid crystal molecules in the minor axis direction was measured.

(5) Threshold voltage (Vth; measured at 25 ° C .; V): An LCD-5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for the 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 that cures this device with ultraviolet light is used. And sealed. The voltage (60 Hz, rectangular wave) applied to this device was increased stepwise from 0 V to 20 V in steps of 0.02 V. At this time, the device was irradiated with light from a vertical direction, and the amount of light transmitted through the device was measured. A voltage-transmittance curve was created in which the maximum light amount was 100% transmittance, and the minimum light amount was 0% transmittance. The threshold voltage was represented by a voltage when the transmittance became 10%.

(6) Voltage holding ratio (VHR; measured at 60 ° C .;%): The fabricated device was charged by applying a pulse voltage (0.1 V for 60 microseconds). The decaying voltage was measured for 1666.7 milliseconds using a high-speed voltmeter, 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 there was no attenuation. The voltage holding ratio was expressed as a percentage of the area A to the area B.

(7) Pretilt angle (degree): A spectroscopic ellipsometer M-2000U (manufactured by J.A. Woollam Co., Inc.) was used to measure the pretilt angle.

  Examples of the composition are shown below. The component compounds were represented by symbols based on the definitions in Table 3 below. In Table 3, the configuration for 1,4-cyclohexylene is trans. The number in parentheses after the symbol indicates the chemical formula to which the compound belongs. The symbol (-) means other liquid crystal compounds. The ratio (percentage) of the liquid crystal compound is a percentage by mass (% by mass) based on the mass of the liquid crystal composition containing no additive. Finally, the characteristic values of the composition were summarized.

Example 1 of device Raw Materials A composition in which a maleimide compound and a polymerizable compound having a polar group were added to an element having no alignment film was injected. After irradiation with ultraviolet light, the vertical alignment of liquid crystal molecules in this device was examined. First, the raw materials will be described. Raw materials are compositions (M51) to (M55), polymerizable compounds having polar groups (PC-1) to (PC-5), maleimide compounds (MI-1) to (MI-8), and polymerizable compounds. (RM-1), and are listed in this order.

[Composition M51]
3-HB (2F, 3F) -O2 (3-1) 9%
5-HB (2F, 3F) -O2 (3-1) 11%
2-HHB (2F, 3F) -1 (3-6) 9.5%
3-HHB (2F, 3F) -1 (3-6) 10.5%
3-HHB (2F, 3F) -O2 (3-6) 10.5%
5-HHB (2F, 3F) -O2 (3-6) 9.5%
2-HBB (2F, 3F) -O2 (3-10) 12%
3-HH-5 (4-1) 9.5%
5-HB-3 (4-2) 13.5%
5-HH-O1 (4-1) 5%
NI = 79.5 ° C .; Δn = 0.091; Δε = −3.4; Vth = 2.1 V; η = 26.3 mPa · s.

[Composition M52]
3-HB (2F, 3F) -O2 (3-1) 15.5%
3-HHB (2F, 3F) -O3 (3-6) 8%
4-HHB (2F, 3F) -O2 (3-6) 10%
2-BB (2F, 3F) B-3 (3-9) 8.75%
2-HBB (2F, 3F) -O2 (3-10) 5.5%
3-HBB (2F, 3F) -O2 (3-10) 11.5%
2-HH-3 (4-1) 24.5%
3-HH-4 (4-1) 9.25%
3-HB-O2 (4-2) 7%
NI = 76.1 ° C .; Δn = 0.097; Δε = -2.69; Vth = 2.2 V; η = 25.3 mPa · s.

[Composition M53]
3-HB (2F, 3F) -O2 (3-1) 18%
3-HHB (2F, 3F) -O2 (3-6) 9%
2-HBB (2F, 3F) -O2 (3-10) 6%
3-HBB (2F, 3F) -O2 (3-10) 10%
4-HBB (2F, 3F) -O2 (3-10) 8%
2-HH-3 (4-1) 25%
3-HH-4 (4-1) 10%
1-BB-3 (4-3) 5%
3-HBB-2 (4-6) 9%
NI = 76.1 ° C .; Δn = 0.100; Δε = −2.5; Vth = 2.4 V; η = 16.1 mPa · s.

[Composition M54]
3-HB (2F, 3F) -O2 (3-1) 12%
3-BB (2F, 3F) -O2 (3-4) 10%
5-BB (2F, 3F) -O2 (3-4) 4%
3-HDhB (2F, 3F) -O2 (3-16) 12%
3-dhBB (2F, 3F) -O2 (3-17) 8%
2-HH-3 (4-1) 20%
3-HH-4 (4-1) 6%
3-HB-O2 (4-2) 3%
3-HHB-O1 (4-5) 3%
3-HHB-1 (4-5) 6%
3-HHB-3 (4-5) 6%
3-HBB-2 (4-6) 10%
NI = 75.8 ° C .; Δn = 0.101; Δε = -2.7; Vth = 2.3 V; η = 18.3 mPa · s.

[Composition M55]
3-BB (2F, 3F) -O2 (3-4) 14%
V2-BB (2F, 3F) -O2 (3-4) 6%
V-HB (2F, 3F) -O2 (3-1) 3%
V-HHB (2F, 3F) -O2 (3-6) 13%
V-HHB (2F, 3F) -O4 (3-6) 6%
V2-HHB (2F, 3F) -O2 (3-6) 10%
V-HBB (2F, 3F) -O2 (3-10) 8%
3-HH-V (4-1) 29%
3-HH-V1 (4-1) 8%
3-HH-2V1 (4-1) 3%
NI = 74.4 ° C .; Δn = 0.100; Δε = -3.16; Vth = 2.18V.

The following polymerizable compounds (PC-1) to (PC-5) having polar groups were used as second additives.

The following maleimide compounds (MI-1) to (MI-8) were used as first additives. (RM-1) was used as a polymerizable compound for comparison.

2. VHR of liquid crystal element and pretilt angle of liquid crystal molecules

Example 1
The polymerizable compound (PC-1) having a polar group was added to the composition (M54) at a ratio of 3% by mass, and the maleimide compound (MI-1) was further added at a ratio of 0.2% by mass. This mixture was vacuum-injected into a device having no alignment film in which the distance (cell gap) between two glass substrates was 3.5 μm. The element was irradiated with ultraviolet rays (10 J / cm ² : 365 nm) using a UV light source of a metal halide lamp (M08-L41C: manufactured by Eye Graphics) while applying a voltage (Vp-p 18.8 V). A cell was prepared. Thereafter, the VHR and pretilt angle of this device were measured by the above-described method. The VHR was 90.8% and the pretilt angle was 4.7 degrees.
Light intensity measurement: Ushio Electric Co., Ltd. UV integrated light meter UIT-250

Examples 2 to 20 and Comparative Example 1
Examples 2 to 20 and Comparative Example 1 used cell mixtures prepared by adding a polymerizable compound having a polar group and a maleimide compound or other compounds to the compositions shown in Table X, except for the cell preparation conditions shown in Table 4. Produced an element having no alignment film in the same manner as in Example 1. VHR and pretilt angle were measured in the same manner as in Example 1. The results are summarized in Table 4 including Example 1.

  As can be seen from Table 4, in Examples 1 to 20, the composition, the type of the maleimide compound, and the concentration of the maleimide compound were changed, but it was found that the voltage holding ratio was kept high and the pretilt angle was given. This result indicates that the maleimide compound is sufficiently polymerized even when the irradiation amount of ultraviolet light is small. On the other hand, in Comparative Example 1, the voltage holding ratio remained low. This result indicates that the polymerization of the polymerizable compound did not sufficiently proceed with a small amount of ultraviolet irradiation.

By polymerizing the polymerizable composition containing the maleimide compound (1) and the liquid crystal composition, a liquid crystal display device having a mode such as PSA can be manufactured. This device has a wide temperature range in which the device can be used, a short response time, a high voltage holding ratio, a low threshold voltage, a large contrast ratio, and a long lifetime. Therefore, the compound (1) can be used for a liquid crystal projector, a liquid crystal television, and the like. Compound (1) can also be used as a raw material for an optically anisotropic body.

Claims (20)

A liquid crystal composition comprising at least one compound having a monovalent group represented by the formula (A) as a first additive, and having a negative dielectric anisotropy.

In the formula (A),
R ¹ and R ² are independently hydrogen, halogen, or alkyl having 1 to 20 carbons. In this alkyl, at least one —CH ₂ — may be replaced with —O— or —S—. well, at least one - _{(CH 2) 2} - may be replaced by -CH = CH-, in these groups, at least one hydrogen may be replaced by halogen. The liquid crystal composition according to claim 1, wherein the first additive is a compound represented by the formula (1).

In equation (1),
P ¹ and P ² are independently polymerizable groups;
S ¹ and S ² are each independently a single bond or an alkylene having 1 to 10 carbon atoms, wherein 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— or —C≡C—, and in these divalent groups, at least one hydrogen is , Halogen or alkyl having 1 to 3 carbons;
R ⁴ and R ⁵ are independently hydrogen, halogen, -S ¹ -P ¹ , -S ² -P ² , or alkyl having 1 to 20 carbons, and in this alkyl, at least one -CH _2- It may be replaced by -O- or -S-, at least one - _{(CH 2) 2} - may be replaced by -CH = CH-, in these groups, at least one hydrogen with halogen May be replaced;
a1 and a2 are independently 0, 1, 2, 3, or 4;
The combined number of -S ¹ -P ¹ and -S ² -P ² is from 1 to 8 and at least one of all -S ¹ -P ¹ and all -S ² -P ² Having a monovalent group represented by the formula (A),

In the formula (A),
R ¹ and R ² are independently hydrogen, halogen, or alkyl having 1 to 20 carbons, in which at least one —CH ₂ — may be replaced by —O— or —S—. , at least one - _{(CH 2) 2} - may be replaced by -CH = CH-, in these groups, at least one hydrogen may be replaced by halogen;
In equation (1),
Ring A ¹ and ring A ² are independently derived from an alicyclic hydrocarbon having 3 to 18 carbon atoms, an aromatic hydrocarbon having 6 to 18 carbon atoms, or a heteroaromatic hydrocarbon having 3 to 18 carbon atoms. Wherein at least one hydrogen atom is halogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 1 to 12 carbons, or 1 divalent group. From 12 to 12 alkenyloxy, and in these monovalent hydrocarbon radicals at least one hydrogen may be replaced by halogen;
Z ¹ is a single bond or an alkylene having 1 to 10 carbon atoms, in which at least one —CH ₂ — is replaced by —O—, —CO—, —COO—, or —OCO—. well, at least one _-CH 2 -CH ₂ - _{is, -CH = CH -, - C} (CH 3) = CH -, - CH = C (CH 3) -, - C (CH 3) = C (CH ₃ )-or -C≡C-; in these divalent radicals at least one hydrogen may be replaced by halogen;
b1 is 0 or 1,
b2 is 0, 1, 2, or 3. The liquid crystal composition according to claim 2, wherein the first additive is represented by any one of Formulas (1-1-1) to (1-1-3).

In the formulas (1-1-1) to (1-1-3),
R ¹ and R ² are independently hydrogen, halogen, or alkyl having 1 to 20 carbons, in which at least one —CH ₂ — may be replaced by —O— or —S—. , at least one - _{(CH 2) 2} - may be replaced by -CH = CH-, in these groups, at least one hydrogen may be replaced by halogen;
R ⁴ is hydrogen, halogen, —S ¹ —P ¹ , or alkyl having 1 to 20 carbons, wherein at least one —CH ₂ — is replaced with —O— or —S—. well, at least one - _{(CH 2) 2} - may be replaced by -CH = CH-, in these groups, at least one hydrogen may be replaced by halogen;
S ² is a single bond or an alkylene having 1 to 10 carbon atoms, in which at least one —CH ₂ — may be replaced by —O—, —CO—, —COO— or —OCO—. Often, at least one —CH ₂ —CH ₂ — may be replaced by —CH ＝ CH— or —C≡C—, and in these divalent groups, at least one hydrogen is a halogen or a carbon atom. From 3 to 3 alkyl;
Ring A ¹ , ring A ² , and ring A ³ are each independently an alicyclic hydrocarbon having 3 to 18 carbons, an aromatic hydrocarbon having 6 to 18 carbons, or a heteroaromatic having 3 to 18 carbons A divalent group derived from a hydrocarbon, in which at least one hydrogen is halogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 1 to 12 carbons Or alkenyloxy having 1 to 12 carbon atoms, and in these monovalent hydrocarbon groups, at least one hydrogen may be replaced by halogen;
Z ¹ and Z ² are each independently a single bond or alkylene having 1 to 10 carbon atoms, wherein at least one —CH ₂ — is —O—, —CO—, —COO—, or — may be replaced by OCO-, at least one _-CH 2 -CH ₂ - _{is, -CH = CH -, - C} (CH 3) = CH -, - CH = C (CH 3) -, - C ( CH ₃ ) = C (CH ₃ ) —, or —C≡C—, and in these divalent groups, at least one hydrogen may be replaced by halogen.   The liquid crystal composition according to any one of claims 1 to 3, wherein a ratio of the first additive is in a range from 0.01% by mass to 10% by mass. The liquid crystal composition according to any one of claims 1 to 4, further comprising at least one polymerizable compound having a polar group represented by the formula (2) as a second additive.

In equation (2),
R ²¹ is alkyl having 1 to 15 carbons, and in this R ²¹ , at least one —CH ₂ — may be replaced by —O— or —S—, and at least one —CH ₂ CH ₂ — May be replaced by -CH = CH- or -C≡C- and at least one hydrogen may be replaced by halogen;
Ring A ²¹ and ring A ²² are each independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, decahydronaphthalene-2,6- Diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine- 2,5-diyl, fluorene-2,7-diyl, phenanthrene-2,7-diyl, anthracene-2,6-diyl, perhydrocyclopenta [a] phenanthrene-3,17-diyl, or 2,3 4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydrocyclopenta [a] phenanthrene-3,17-diyl, At least one hydrogen is replaced by fluorine, chlorine, alkyl having 1 to 12 carbons, alkenyl having 2 to 12 carbons, alkoxy having 1 to 11 carbons, or alkenyloxy having 2 to 11 carbons And in these groups, at least one hydrogen may be replaced by fluorine or chlorine;
a is 0, 1, 2, 3, or 4;
Z ²¹ is a single bond or an alkylene having 1 to 6 carbon atoms, and in Z ²¹ , at least one —CH ₂ — is —O—, —CO—, —COO—, —OCO—, or —OCOO— At least one —CH ₂ CH ₂ — may be replaced by —CH ＝ CH— or —C≡C—, and at least one hydrogen may be replaced by fluorine or chlorine. Often;
Sp ²¹ is a single bond or an alkylene having 1 to 10 carbon atoms, and in this Sp ²¹ , at least one —CH ₂ — is —O—, —CO—, —COO—, —OCO—, or —OCOO— At least one —CH ₂ CH ₂ — may be replaced by —CH ＝ CH— or —C≡C—, at least one hydrogen may be replaced by halogen, In these groups, at least one hydrogen may be replaced by a group of formula (2a);

In equation (2a),
Sp ²² is alkylene of 10 a single bond or 1 carbon atoms, in the ^{Sp 22,} at least one of _-CH 2 -, -O -, - CO -, - COO -, - OCO-, or -OCOO- At least one —CH ₂ CH ₂ — may be replaced by —CH ＝ CH— or —C≡C—, and at least one hydrogen may be replaced by halogen;
M ²¹ and M ²² are independently hydrogen, halogen, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen is replaced by halogen:
R ²² is alkyl of from 1 to 15 carbon atoms, in the ^{R 22,} at least one of -CH ₂ -, -O- or -S- in may be replaced, at least one _-CH 2 CH ₂ - May be replaced by -CH = CH- or -C≡C- and at least one hydrogen may be replaced by halogen:
In equation (2),
P ²¹ is a group represented by the formula (2e), the formula (2f), the formula (2g), or the formula (2h);
However, when at least one hydrogen is not replaced with a group represented by the formula (2a) in the group that Sp ²¹ can take, P ²¹ is represented by the formula (2e), the formula (2f), or A group represented by the formula (2g):

In the expressions (2e), (2f), (2g), and (2h),
Sp ²³ , Sp ²⁴ , and Sp ²⁵ are each independently a single bond or alkylene having 1 to 10 carbon atoms. In Sp ²³ , Sp ²⁴ , and Sp ²⁵ , at least one of —CH ₂ — is —O— , -NH -, - CO -, - COO -, - OCO-, or may be replaced by -OCOO-, at least one _-CH 2 CH ₂ - is, -CH = CH- or -C≡C- And in these groups at least one hydrogen may be replaced by halogen;
S ²¹ is> CH- or>N-;
S ²² is> C <or> Si <;
M ²³ and M ²⁴ are independently hydrogen, halogen, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen is replaced by halogen:
X ¹ is —OH, —NH ₂ , —OR ²⁵ , —N (R ²⁵ ) ₂ , formula (x1), —COOH, —SH, —B (OH) ₂ , or —Si (R ²⁵ ) ₃ . Yes;
In —OR ²⁵ , —N (R ²⁵ ) ₂ , and —Si (R ²⁵ ) ₃ ,
R ²⁵ is hydrogen or alkyl having 1 to 10 carbons. In the R ²⁵ , at least one —CH ₂ — may be replaced with —O—, and at least one —CH ₂ CH ₂ — It may be replaced by -CH = CH-, at least one hydrogen may be replaced by halogen, and w in the formula (x1) is 1, 2, 3 or 4.

The liquid crystal composition according to claim 5, wherein the second additive is a compound represented by any one of formulas (2-2) to (2-38).

In Equations (2-2) to (2-38),
R ²¹ is alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons, or alkoxy having 1 to 9 carbons, and in these groups, at least one hydrogen may be replaced by fluorine;
Z ²¹ , Z ²² , and Z ²³ are independently a single bond, —CH ₂ CH ₂ —, or — (CH ₂ ) ₄ —;
Sp ²¹ , Sp ²² , Sp ²³ , and Sp ²⁴ are each independently a single bond or alkylene having 1 to 5 carbon atoms, in which at least one —CH ₂ — is replaced by —O—. Well;
L ¹ , L ² , L ³ , L ⁴ , L ⁵ , L ⁶ , L ⁷ , L ⁸ , L ⁹ , L ¹⁰ , L ¹¹ and L ¹² are independently hydrogen, fluorine, methyl, or ethyl. Yes;
Y ¹ , Y ² , Y ³ , and Y ⁴ are independently hydrogen or methyl;
l is 1, 2, 3, 4, 5, or 6;   The liquid crystal composition according to claim 5, wherein the ratio of the second additive is 0.05% by mass or more and 15% by mass or less based on the mass of the liquid crystal composition. The liquid crystal composition according to any one of claims 1 to 7, comprising at least one compound represented by the formula (3) as a first component.

In the formula (3), R ³³ and R ³⁴ are each independently an alkyl having 1 to 12 carbons, an alkoxy having 1 to 12 carbons, an alkenyl having 2 to 12 carbons, or an alkenyloxy having 2 to 12 carbons. Yes; Rings C and E are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 1,4-cycloalkyl in which at least one hydrogen is replaced by fluorine or chlorine Phenylene or tetrahydropyran-2,5-diyl; ring D is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro- 5-methyl-1,4-phenylene, it is a 3,4,5-trifluoro-2,6-diyl or 7,8-difluoro-chroman-2,6-diyl,; ^{Z 3} And ^{Z 33} are independently a single _{bond, -CH 2 CH 2 -, -} CH 2 O -, - OCH 2 -, - COO-, or a -OCO-; b is 1, 2 or 3, And c is 0 or 1, and the sum of b and c is 3 or less. The liquid crystal according to any one of claims 1 to 8, wherein the liquid crystal contains at least one compound selected from the group of compounds represented by Formulas (3-1) to (3-22) as a first component. Composition.

In the formulas (3-1) to (3-22), R ³³ and R ³⁴ are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or It is alkenyloxy having 2 to 12 carbon atoms.   The liquid crystal composition according to claim 8, wherein the proportion of the first component is in a range from 10% by mass to 90% by mass based on the mass of the liquid crystal composition. The liquid crystal composition according to any one of claims 1 to 10, further comprising at least one compound represented by the formula (4) as a second component.

In the formula (4), R ⁴⁵ and R ⁴⁶ are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, and replacing at least one hydrogen with fluorine or chlorine. C 1 to C 12 alkyl, or C 2 to C 12 alkenyl in which at least one hydrogen is replaced by fluorine or chlorine; Ring F and Ring G are each independently 1,4-cyclohexylene , 1,4-phenylene, be a 2-fluoro-1,4-phenylene or ^{2,5-difluoro-1,4-phenylene,; Z 44} is a single _{bond, -CH 2 CH 2 -, -} CH 2 O —, —OCH ₂ —, —COO—, or —OCO—; d is 1, 2, or 3. The liquid crystal composition according to any one of claims 1 to 11, further comprising at least one compound represented by any of formulas (4-1) to (4-13) as a second component.

In the formulas (4-1) to (4-13), R ⁴⁵ and R ⁴⁶ are each independently an alkyl having 1 to 12 carbons, an alkoxy having 1 to 12 carbons, an alkenyl having 2 to 12 carbons, It is alkyl having 1 to 12 carbons in which one hydrogen is replaced by fluorine or chlorine, or alkenyl having 2 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine.   The liquid crystal composition according to claim 11, wherein a ratio of the second component is in a range from 10% by mass to 90% by mass based on the mass of the liquid crystal composition.   A liquid crystal display device comprising the liquid crystal composition according to claim 1.   15. The liquid crystal display device according to claim 14, wherein an operation mode of the liquid crystal display device is one of an IPS mode, a VA mode, an FFS mode, and an FPA mode, and a driving system of the liquid crystal display device is an active matrix system.   A polymer supported alignment type liquid crystal display device, comprising the liquid crystal composition according to claim 1, wherein a polymerizable compound in the liquid crystal composition is polymerized.   A liquid crystal display device comprising the liquid crystal composition according to any one of claims 1 to 13, wherein the polymerizable compound in the liquid crystal composition is polymerized and has no alignment film.   Use of the liquid crystal composition according to any one of claims 1 to 13 in a liquid crystal display device.   Use of the liquid crystal composition according to any one of claims 1 to 13 in a polymer supported alignment type liquid crystal display device. Use of the liquid crystal composition according to any one of claims 1 to 13 in a liquid crystal display device having no alignment film.