WO2018168721A1 - Liquid-crystal composition and liquid-crystal display element - Google Patents

Abstract

Provided are: a polymerizable composition containing a polymerizable compound which has adequate polymerizability, attains a high conversion, and has high solubility in liquid-crystal compositions; and a liquid-crystal display element including the polymerizable composition. The polymerizable composition is a nematic liquid-crystal composition containing a maleimide compound as a first additive and having negative dielectric anisotropy. The polymerizable composition may contain a specific liquid-crystalline compound having a large value of negative dielectric anisotropy as a first component, a specific liquid-crystalline compound having a high upper-limit temperature or a low viscosity as a second component, and a polymerizable compound having a polar group as a second additive. The liquid-crystal display element includes the polymerizable composition.

Description

Liquid crystal composition and liquid crystal display element

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 the liquid crystal display element, the classification based on the operation mode of the liquid crystal molecules is as follows: PC (phase change), TN (twisted nematic), STN (super twisted nematic), ECB (electrically controlled birefringence), OCB (optically compensated bend), 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 drive system is PM (passive matrix) and AM (active matrix). PM is classified into static, multiplex, etc., and AM is classified into TFT (thin film insulator), MIM (metal film insulator), and the like. TFTs are classified into amorphous silicon and polycrystalline 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 includes 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 element contains a liquid crystal composition having a nematic phase. This composition has suitable properties. By improving the characteristics of the 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 a commercially available AM device. The temperature range of the nematic phase is related to the temperature range in which the device can be used. A preferred upper limit temperature of the nematic phase is about 70 ° C. or more, and a preferred lower limit temperature of the nematic phase is about −10 ° C. or less. The viscosity of the composition is related to the response time of the device. A short response time is preferred for displaying moving images on the device. A shorter response time is desirable even at 1 millisecond. Therefore, a small viscosity in the composition is preferred. A small viscosity at low temperatures is even more preferred.

 

The optical anisotropy of the composition is related to the contrast ratio of the device. Depending on the mode of the device, a large optical anisotropy or a small optical anisotropy, ie an 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 for the product depends on the type of operating mode. This value is in the range of about 0.30 μm to about 0.40 μm for the VA mode element and in the range of about 0.20 μm to about 0.30 μm for the IPS mode or FFS mode element. In these cases, a composition having a large optical anisotropy is preferable for a device having a small cell gap. A large dielectric anisotropy in the composition contributes to a low threshold voltage, a 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 not only at room temperature but also at a temperature close to the upper limit temperature of the nematic phase in the initial stage is preferable. A composition having a large specific resistance not only at room temperature but also at a temperature close to the upper limit temperature of the nematic phase after being used for a long time 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 in a liquid crystal projector, a liquid crystal television, and the like.

In a polymer-supported alignment (PSA) type liquid crystal display element, 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 the 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, since the alignment of liquid crystal molecules can be controlled by the polymer, the response time of the device is shortened, and image burn-in is improved. Such an effect of the polymer can be expected for a device having modes such as TN, ECB, OCB, IPS, VA, FFS, and FPA.

In a general-purpose liquid crystal display element, 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 to which a small amount of a polymerizable compound and a small amount of a polar compound are added is injected into the device. Here, polar compounds are 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 orientation of liquid crystal molecules can be controlled by the polymer and the polar compound, the response time of the device is shortened, and image burn-in is improved. Furthermore, in the element having no alignment film, the step of forming the alignment film is unnecessary. Since there is no alignment film, the electrical resistance of the device does not decrease due to the interaction between the alignment film and the composition. Such an effect by 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.

A composition having a positive dielectric anisotropy is used for an AM device having a TN mode. A composition having a negative dielectric anisotropy is used in an AM device having a VA mode. In an AM device having an IPS mode or an FFS mode, a composition having a positive or negative dielectric anisotropy is used. In a polymer-supported orientation type AM device, a composition having positive or negative dielectric anisotropy is used. Examples of liquid crystal compositions having negative dielectric anisotropy are disclosed in the following Patent Documents 1 to 5. Various polymerizable compounds have been developed so far, and it is desired to develop a compound that further improves the above characteristics.

International Publication No. 2014/090362 International Publication No. 2014/094959 International Publication No. 2013/004372 JP2015-168826A International Publication No. 2016/015803

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

A liquid crystal composition containing at least one compound selected from the group of compounds having a monovalent group represented by formula (A) (maleimide compound) as a first additive and having negative dielectric anisotropy .

In formula (A),
R ¹ and R ² are independently hydrogen, halogen, or alkyl having 1 to 20 carbons, and in this alkyl, at least one —CH ₂ — may be replaced by —O— or —S—. Well, at least one — (CH ₂ ) ₂ — may be replaced with —CH═CH—, in which at least one hydrogen may be replaced with a halogen.

The first advantage of the present invention is to provide a liquid crystal composition containing a maleimide compound having the ability to align excellent liquid crystal molecules, suitable polymerization reactivity, high conversion, and high solubility in the liquid crystal composition. 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, a large specific resistance. Satisfying at least one of physical properties such as an appropriate pretilt. The 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.

用語 Terms used in this specification are 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 liquid crystal display panels and liquid crystal display modules. “Liquid crystal compound” is a compound having a liquid crystal phase such as a nematic phase and a smectic phase, and a liquid crystal phase, but has a composition for the purpose of adjusting characteristics such as temperature range, viscosity, and dielectric anisotropy of the nematic phase. It is a general term for compounds mixed with products. This compound has a six-membered ring such as 1,4-cyclohexylene and 1,4-phenylene, and its molecular structure is rod-like. 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 optically active compounds, antioxidants, ultraviolet absorbers, dyes, antifoaming agents, polymerizable compounds, polymerization initiators, polymerization inhibitors, and polar compounds are added to this liquid crystal composition as necessary. The Liquid crystal compounds 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 not containing the additive even when the additive is added. The ratio (addition amount) of the additive is represented by a mass percentage (mass%) based on the mass of the liquid crystal composition not including the additive. Mass parts per million (ppm) may be used. The ratio of the polymerization initiator and the polymerization inhibitor is exceptionally expressed based on the mass of the polymerizable compound.

“The maximum temperature of the nematic phase” may be abbreviated as “the maximum temperature”. “Lower limit temperature of nematic phase” may be abbreviated as “lower limit 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. It means having. "High voltage holding ratio" means that the device has a large voltage holding ratio not only at room temperature but also at a temperature close to the upper limit 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 long-term use. It means having a retention rate. In a composition or device, characteristics may be examined before and after a aging test (including an accelerated deterioration test). The expression “increasing dielectric anisotropy” means that when the composition has a positive dielectric anisotropy, the value increases positively, and the composition having a negative dielectric anisotropy When it is a thing, it means that the value increases negatively.

The compound represented by formula (1) may be abbreviated as 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 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 the ring A ¹ of the compound (1), the line crossing the circle means that the P ¹ -S ¹ group can arbitrarily select the bonding position on the ring such as a six-membered ring or a condensed ring. This rule also applies to symbols such as P ² -S ² groups. 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 2 Even when there are more than two, their positions can be selected without restriction. This rule also applies to the expression “at least one 'A' is replaced by 'B'”.

In the chemical formulas of the component compounds, the symbol of the terminal group R ¹ is used for a plurality of compounds. In these compounds, two groups represented by two arbitrary R ¹ may be the same or different. For example, ^{R 1} of the compound (1-1-1) is ethyl, there are cases ^{wherein R 1} is ethyl of the compound (1-1-2). In some cases, R ^{1 of the} compound (1-1-1) is ethyl and R ¹ of the compound (1-1-2) is propyl. This rule also 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, the two rings represented by the two rings A ² 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 hexagons correspond to rings such as ring A, ring B, ring C, and ring D, respectively, and represent rings such as six-membered rings and condensed rings. The diagonal lines across the hexagon indicate that any hydrogen on the ring may be replaced with a group such as —S ¹ —P ¹ . Subscripts such as 'a1' indicate the number of groups replaced. When the subscript 'a1' is 0, there is no such replacement. When the subscript “a1” is 2 or more, there are a plurality of —S ¹ —P ¹ on the ring A ¹ . The plurality of 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 generated by removing two hydrogens from the ring, such as tetrahydropyran-2,5-diyl. This rule also applies to divalent linking groups such as carbonyloxy (—COO— or —OCO—).

Expressions such as “at least one —CH ₂ — may be replaced by —O—” are used herein. In this case, —CH ₂ —CH ₂ —CH ₂ — may be converted to —O—CH ₂ —O— by replacing non-adjacent —CH ₂ — with —O—. However, adjacent —CH ₂ — is not replaced by —O—. This is because —O—O—CH ₂ — (peroxide) is formed by this replacement. That is, this expression includes both “one —CH ₂ — may be replaced with —O—” and “at least two non-adjacent —CH ₂ — may be replaced with —O—”. 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. The carbon number of this alkyl may be increased by this type of replacement. In such a case, the maximum carbon number is 30. This rule applies not only to monovalent groups such as R ¹ , but also to divalent groups such as alkylene.

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

The present invention includes the following items.

Item 1. A liquid crystal composition containing at least one compound having a monovalent group represented by the formula (A) as a first additive and having negative dielectric anisotropy.

In formula (A),
R ¹ and R ² are independently hydrogen, halogen, or alkyl having 1 to 20 carbons, and in this alkyl, at least one —CH ₂ — may be replaced by —O— or —S—. Well, at least one — (CH ₂ ) ₂ — may be replaced with —CH═CH—, in which at least one hydrogen may be replaced with a halogen.
Here, “in these groups” means an unsubstituted alkyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms in which at least one —CH ₂ — is replaced by —O— or —S—. , At least one — (CH ₂ ) ₂ — represents C 1-20 alkyl substituted with —CH═CH—.
Hereinafter, in the present specification, when “in these groups” or “in these divalent groups” is described, not only an unsubstituted group (alkyl, alkylene, etc.) but also a part thereof is replaced with another group. It is also meant to include the group represented.

Item 2. Item 2. The liquid crystal composition according to item 1, wherein the first additive is a compound represented by 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 alkylene having 1 to 10 carbon atoms, in which at least one —CH ₂ — is —O—, —CO—, —COO— or —OCO. And at least one —CH ₂ —CH ₂ — may be replaced with —CH═CH— or —C≡C—, and in these divalent groups, at least one hydrogen is May be substituted with halogen or alkyl of 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, in which at least one —CH ₂ — May be replaced with —O— or —S—, and at least one — (CH ₂ ) ₂ — may be replaced with —CH═CH—, in which at least one hydrogen is a 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 1 to 8, and at least one of all -S ¹ -P ¹ and all -S ² -P ² is And having a monovalent group represented by the formula (A),

In 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 which 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. In these divalent groups, 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 1 carbon. To 12 alkenyloxy, and in these monovalent hydrocarbon groups, at least one hydrogen may be replaced with halogen;
Z ¹ is a single bond or alkylene having 1 to 10 carbon atoms, and in this alkylene, at least one —CH ₂ — may be replaced by —O—, —CO—, —COO—, or —OCO—. Well, at least one —CH ₂ —CH ₂ — may be —CH═CH—, —C (CH ₃ ) ═CH—, —CH═C (CH ₃ ) —, —C (CH ₃ ) ═C (CH ₃ ) —, or —C≡C— may be replaced, and in these divalent groups, at least one hydrogen may be replaced with a halogen;
b1 is 0 or 1,
b2 is 0, 1, 2, or 3.

Item 3. Item 2. 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 formula (1-1-1) to the formula (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 which 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, and in this alkyl, at least one —CH ₂ — may be replaced by —O— or —S—. Well, at least one — (CH ₂ ) ₂ — may be replaced by —CH═CH—, in which at least one hydrogen may be replaced by a halogen;
S ² is a single bond or alkylene having 1 to 10 carbon atoms, and in this alkylene, at least one —CH ₂ — may be replaced by —O—, —CO—, —COO— or —OCO—. Well, 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 carbon number 1 To 3 alkyls;
Ring A ¹ , Ring A ² , and Ring A ³ are independently an alicyclic hydrocarbon having 3 to 18 carbon atoms, an aromatic hydrocarbon having 6 to 18 carbon atoms, or a heteroaromatic group having 3 to 18 carbon atoms. A divalent group derived from a hydrocarbon, wherein 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, in these monovalent hydrocarbon groups, at least one hydrogen may be replaced by a halogen;
Z ¹ and Z ² are each independently a single bond or alkylene having 1 to 10 carbon atoms, in which at least one —CH ₂ — is —O—, —CO—, —COO—, or — OCO— may be substituted, and at least one —CH ₂ —CH ₂ — represents —CH═CH—, —C (CH ₃ ) ═CH—, —CH═C (CH ₃ ) —, —C ( CH ₃ ) ═C (CH ₃ ) —, or —C≡C— may be replaced, and in these divalent groups, at least one hydrogen may be replaced with a halogen.

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

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 formula (2) as the 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 with —CH═CH— or —C≡C—, and at least one hydrogen may be replaced with a halogen;
Ring A ²¹ and Ring A ²² are 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 In which 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. 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 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 with —CH═CH— or —C≡C—, and at least one hydrogen may be replaced with fluorine or chlorine. Often;
Sp ²¹ is a single bond or 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 with —CH═CH— or —C≡C—, and at least one hydrogen may be replaced with a halogen; In these groups, at least one hydrogen may be replaced with a group selected from the group represented by formula (2a);

In formula (2a):
Sp ²² is a single bond or alkylene having 1 to 10 carbon atoms, and in this Sp ²² , at least one —CH ₂ — is —O—, —CO—, —COO—, —OCO—, or —OCOO— At least one —CH ₂ CH ₂ — may be replaced with —CH═CH— or —C≡C—, and at least one hydrogen may be replaced with a 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 having 1 to 15 carbon atoms, and in this R ²² , at least one —CH ₂ — may be replaced by —O— or —S—, and at least one —CH ₂ CH ₂ — May be replaced with —CH═CH— or —C≡C—, and at least one hydrogen may be replaced with a halogen:
In equation (2),
P ²¹ is a group selected from the groups represented by formula (2e), formula (2f), formula (2g), and formula (2h);
However, in the group that Sp ²¹ can take, when at least one hydrogen is not replaced with a group selected from the group represented by formula (2a), P ²¹ is represented by formula (2e), (2f) and a group selected from the group represented by formula (2g);

In formula (2e), formula (2f), formula (2g), and formula (2h),
Sp ²³ , Sp ²⁴ and Sp ²⁵ are each independently a single bond or alkylene having 1 to 10 carbon atoms, and in this Sp ²³ , Sp ²⁴ and Sp ²⁵ , at least one —CH ₂ — is —O—. , —NH—, —CO—, —COO—, —OCO—, or —OCOO—, wherein at least one —CH ₂ CH ₂ — represents —CH═CH— or —C≡C— In which at least one hydrogen may be replaced by a halogen;
S ²¹ is> CH— or>N—;
S ²² is> C <or> Si <;
M ²³ and M ²⁴ are independently hydrogen, halogen, alkyl of 1 to 5 carbons, or alkyl of 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 carbon atoms, and in this R ²⁵ , at least one —CH ₂ — may be replaced by —O—, and at least one —CH ₂ CH ₂ — is -CH = CH- may be substituted, at least one hydrogen may be substituted with a halogen, and w in formula (x1) is 1, 2, 3 or 4.

Item 6. Item 6. The liquid crystal composition according to item 5, wherein the second additive is a compound represented by any one of formulas (2-2) to (2-38).

In the formula (2-2) to the formula (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 each 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 carbons, 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 and 6, 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.

Item 8. Item 8. The liquid crystal composition according to any one of items 1 to 7, comprising 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 independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or alkenyloxy having 2 to 12 carbons. Yes; Ring C and Ring E are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 1,4-substituted with at least one hydrogen 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, Yes, c is 0 or 1, and the sum of b and c is 3 or less.

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 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 ratio of the first component is in the range of 10% by mass to 90% by mass based on the mass of the liquid crystal composition.

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 the 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 at least one hydrogen is replaced by fluorine or chlorine Or alkyl having 1 to 12 carbon atoms, or alkenyl having 2 to 12 carbon atoms in which at least one hydrogen is replaced by fluorine or chlorine; 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; Z ⁴⁴ is a single bond, —CH ₂ CH ₂ —, —CH ₂ O —, —OCH ₂ —, —COO—, or —OCO—; d is 1, 2, or 3;

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 independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, It is alkyl having 1 to 12 carbons in which one hydrogen is replaced with fluorine or chlorine, or alkenyl having 2 to 12 carbons in which at least one hydrogen is replaced with fluorine or chlorine.

Item 13. Item 13. The liquid crystal composition according to any one of items 11 and 12, wherein the ratio 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 comprising 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 the operation mode of the liquid crystal display element is an IPS mode, a VA mode, an FFS mode, or an FPA mode, and the 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 having 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 having 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 polymer supported alignment type liquid crystal display device.

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 includes the following items. (A) The liquid crystal composition described above is placed between two substrates, light is applied to the composition while voltage is applied, and the polymerizable compound contained in the composition is polymerized, thereby Of manufacturing a liquid crystal display element. (B) The upper limit temperature of the nematic phase is 70 ° C or higher, the optical anisotropy at a wavelength of 589 nm (measured at 25 ° C) is 0.08 or higher, and the dielectric anisotropy at a frequency of 1 kHz (measured at 25 ° C) ) Is −2 or less.

The present invention includes the following items. (C) The compounds (5) to (7) described in JP-A-2006-199941 are liquid crystal compounds having positive dielectric anisotropy, but 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 compounds (1). (E) The above composition further comprising 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, antifoaming agents, polymerizable compounds, polymerization initiators, polymerization inhibitors, polar compounds A composition as described above containing one. (G) An AM device containing the above composition. (H) A device containing the above composition and having a TN, ECB, OCB, IPS, FFS, VA, or FPA mode. (I) A transmissive element containing the above composition. (J) The above composition is used 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 explained. Third, the combination of components in the composition, the preferred ratio of the components, and the basis thereof will be described. Fourth, a preferred form of the component compound 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 the component compounds will be described. Finally, the use of the composition will be described.

First, the composition of the composition will be explained. The composition of the present invention is classified into Composition A and Composition B. The composition A may further contain other liquid crystal compounds, additives and the like in addition to the liquid crystal compound selected from the compound (3) and the compound (4). The “other liquid crystal compound” is a liquid crystal compound different from the compound (3) and the 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, antifoaming agents, polymerizable compounds, polymerization initiators, polymerization inhibitors, polar compounds and the like.

Composition B consists essentially of a liquid crystalline compound selected from compound (3) and compound (4). “Substantially” means that the composition may contain an additive but no other liquid crystal compound. Composition B has fewer components than composition A. From the viewpoint of reducing the cost, the composition B is preferable to the composition A. The composition A is preferable to the composition B from the viewpoint that the characteristics 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 explained. The main characteristics of the component compounds are summarized in Table 2 based on the effects of the present invention. In the symbols in Table 2, L means large or high, M means moderate, and S means small or low. The symbols L, M, and S are classifications based on a qualitative comparison among the component compounds, and the symbol 0 means that the value is zero or close to zero.

When the component compound is mixed with the composition, the main effects of the component compound on the properties of the composition are as follows. The compound (1) has a function as an initiator and gives a polymer by polymerization with the compound (2). This polymer stabilizes the alignment of the liquid crystal molecules, thereby reducing 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 the 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. Compound (2) has a rod-like molecular structure having a six-membered ring such as 1,4-cyclohexylene and 1,4-phenylene, and a branched structure at one end of the molecular structure. It is most suitable for this purpose because it is considered that the compatibility of the cage can be improved. Compound (2) gives a polymer by polymerization. This polymer stabilizes the orientation of the liquid crystal molecules, thereby reducing the response time of the device and improving image burn-in. Compound (3) increases the dielectric anisotropy and decreases the minimum temperature. Compound (4) decreases the viscosity.

Third, the combination of components in the composition, the preferred 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).

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

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

A 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 decreasing the minimum temperature. A more desirable ratio is in the range of approximately 20% by mass to approximately 85% by mass. A particularly desirable ratio is in the range of approximately 30% by mass to approximately 85% by mass.

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

Fourth, a preferred form of the component compound will be described.

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, in which at least one —CH ₂ — is —O— or —S—. And at least one — (CH ₂ ) ₂ — may be replaced with —CH═CH—, and in these groups, at least one hydrogen may be replaced with a halogen.

Compound (1) has a rod-like molecular structure similar to a liquid crystal compound, and thus has high solubility in a liquid crystal composition. Therefore, the compound (1) is suitable as a polymerizable compound necessary for a device having a PSA mode. Secondly, the compound (1) has appropriate polymerizability. Therefore, compound (1) can be stored stably. In the polymerization, the rate 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), preferred 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 subordinate to compound (1). Compound (1) can have its physical properties arbitrarily adjusted by appropriately combining these types of groups. Since there is no great difference in the physical properties of the compound, the compound (1) may contain an isotope such as ² H (deuterium) and ¹³ C in an amount larger than the natural abundance.

In 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 with fluorine, methyl, or trifluoromethyl. Preferred examples of the polymerizable group 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 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—, —COO— or —OCO— may be substituted, and at least one —CH ₂ —CH ₂ — may be substituted with —CH═CH— or —C≡C—, and in these divalent groups , At least one hydrogen may be replaced by halogen or alkyl having 1 to 3 carbon atoms.

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 include 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 type is preferable to the cis type.

In the formula (1), 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 — may be replaced with —O— or —S—, and at least one — (CH ₂ ) ₂ — may be replaced with —CH═CH—, and in these groups, at least One hydrogen may be replaced with 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.

In formula (1), at least one of all —S ¹ —P ¹ and all —S ² —P ² has a monovalent group represented by 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 — is —O— or —S—. And at least one — (CH ₂ ) ₂ — may be replaced with —CH═CH—, and in these groups, at least one hydrogen may be replaced with a halogen. Preferred R ¹ or R ² is methyl, ethyl, or hydrogen. More preferred R ¹ or R ² is hydrogen.

In formula (1), ring A ¹ and ring A ² are 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. It is a divalent group derived by removing two hydrogens from a group hydrocarbon. In these divalent groups, at least one hydrogen is replaced with 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. In these monovalent hydrocarbon groups, at least one hydrogen may be replaced with a halogen. Further, ring A ¹ has a1 hydrogens replaced with —S ¹ —P ¹ , and ring A ² has a2 hydrogens replaced with —S ² —P ² .

Examples of the alicyclic hydrocarbon are cyclopropane, cyclobutane, cyclohexane, cycloheptane, cyclooctane and the like represented by C _n H _2n . Other examples are 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 and 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 alkylene having 1 to 10 carbon atoms, and in this alkylene, at least one —CH ₂ — is —O—, —CO—, —COO— or —OCO—. And at least one —CH ₂ —CH ₂ — may be replaced with —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 with a halogen.

Preferred examples of Z ¹ include a single bond, alkylene having 1 to 4 carbon atoms, —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—. Further 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, this compound does not have a cyclic structure. When b1 is 1 and b2 is 0, the compound has one ring represented by the ring A ^1. In this case, the preferred ring A ¹ is a divalent group derived by removing two hydrogens from a condensed ring such as naphthalene, anthracene, phenanthrene. 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 group derived from benzene substituted with a substituent such as benzene, fluorine or 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 compound (2) is added to the composition, it is preferable that this compound does not lower the voltage holding ratio of the device. The compound (2) preferably has low volatility. A preferred molar mass is 130 g / mol or more. A more preferred molar mass is in the range of 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 , where 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 — may be —CH═ CH— may be replaced, and in these groups at least one hydrogen may be replaced with fluorine. From the viewpoint of high solubility in the liquid crystal composition, X ¹ is particularly preferably —OH or —NH ₂ . —OH is preferable to —O—, —CO—, or —COO— because it has a high anchoring force. Groups having a plurality of heteroatoms (nitrogen, oxygen) are particularly preferred. The compound having such a polar group is effective even at a low concentration.

R ²¹ is alkyl having 1 to 15 carbon atoms, 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 with —CH═CH— or —C≡C—, and at least one hydrogen may be replaced with a halogen.
Ring A ²¹ and Ring A ²² are 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 In which 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. 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 Z ²¹ , at least one —CH ₂ — is —O—, —CO—, —COO—, —OCO—, or —OCOO And at least one —CH ₂ CH ₂ — may be replaced with —CH═CH— or —C≡C—, and at least one hydrogen is replaced with fluorine or chlorine. Also good. Preferred Z ²¹ is a single bond, —CH ₂ CH ₂ —, —CH ₂ O—, —OCH ₂ —, —COO—, or —OCO—. Further preferred Z ²¹ is a single bond.

Sp ²¹ is a single bond or 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 with —CH═CH— or —C≡C—, and at least one hydrogen may be replaced with a halogen; In these groups, at least one hydrogen is replaced with a group selected from the group represented by formula (2a);

In formula (2a):
Sp ²² is a single bond or alkylene having 1 to 10 carbon atoms, and in this Sp ²² , at least one —CH ₂ — is —O—, —CO—, —COO—, —OCO—, or —OCOO— At least one —CH ₂ CH ₂ — may be replaced with —CH═CH— or —C≡C—, and at least one hydrogen may be replaced with a 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 having 1 to 15 carbon atoms, and in this R ²² , at least one —CH ₂ — may be replaced by —O— or —S—, and at least one —CH ₂ CH ₂ — May be replaced with —CH═CH— or —C≡C—, and at least one hydrogen may be replaced with a halogen. Preferred Sp ²¹ is a single bond.
P ²¹ is a group selected from the groups represented by formula (2e), formula (2f), formula (2g), and formula (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, and in this Sp ²³ , Sp ²⁴ and Sp ²⁵ , at least one —CH ₂ — is —O—. , —NH—, —CO—, —COO—, —OCO—, or —OCOO—, wherein at least one —CH ₂ CH ₂ — represents —CH═CH— or —C≡C— In which at least one hydrogen may be replaced by a halogen;
S ²¹ is> CH— or>N—;
S ²² is> C <or> Si <;
M ²³ and M ²⁴ are independently hydrogen, halogen, alkyl of 1 to 5 carbons, or alkyl of 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 carbon atoms, and in this R ²⁵ , at least one —CH ₂ — may be replaced by —O—, and at least one —CH ₂ CH ₂ — is -CH = CH- may be substituted, at least one hydrogen may be substituted with a halogen, and w in formula (x1) is 1, 2, 3 or 4.

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

In formulas (2-2) to (2-38), R ²¹ is alkyl having 1 to 10 carbons;
Z ²¹ , Z ²² , and Z ²³ are each 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 carbons, 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; l is 1, 2, 3, 4, 5, or 6.

In Formula (3) and Formula (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 the stability, and alkoxy having 1 to 12 carbons for increasing the dielectric anisotropy. 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, or having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine. 12 alkyls or alkenyls 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 alkyl is preferred over branched alkyl. The same applies to terminal groups such as alkoxy and alkenyl.

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

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

Preferred alkenyl is vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, or 5-hexenyl. More desirable 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 for alkenyl such as 2-butenyl, 2-pentenyl, and 2-hexenyl.

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

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

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” are 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, or 2-chloro -3-Fluoro-1,4-phenylene. Preferred ring C or ring E is 1,4-cyclohexylene for decreasing the viscosity, tetrahydropyran-2,5-diyl for increasing the dielectric anisotropy, and increasing the optical anisotropy. 1,4-phenylene. As 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. Preferred ring D is 2,3-difluoro-1,4-phenylene for decreasing the viscosity, and 2-chloro-3-fluoro-1,4-phenylene for decreasing the optical anisotropy. In order to increase the anisotropy, 7,8-difluorochroman-2,6-diyl.

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. Preferred 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. As the configuration of 1,4-cyclohexylene, trans is preferable to cis for increasing the maximum temperature.

Z ³² and Z ³³ are each independently a single bond, —CH ₂ CH ₂ —, —CH ₂ O—, —OCH ₂ —, —COO—, or —OCO—. Desirable Z ³² or Z ³³ is a single bond for decreasing the viscosity, —CH ₂ CH ₂ — for decreasing the minimum temperature, and —CH ₂ O— or —OCH for increasing the dielectric anisotropy. _2- . Z ⁴⁴ is a single bond, —CH ₂ CH ₂ —, —CH ₂ O—, —OCH ₂ —, —COO—, or —OCO—. Desirable Z ⁴⁴ is a single bond for decreasing the viscosity, —CH ₂ CH ₂ — for decreasing the minimum temperature, and —COO— or —OCO— for increasing the maximum temperature.

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

Fifth, preferred component compounds are shown. Desirable compound (2) is the compound (2-2) to the compound (2-38) according to 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 preferred. It is preferable that at least two of the second additives are the compound (2-2) and the compound (2-3), or a combination of the compound (2-3) and the compound (2-4).

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

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

Sixth, additives other than the first additive and the second additive that may be added to the composition will be described. Such additives are optically active compounds, antioxidants, ultraviolet absorbers, dyes, antifoaming agents, polymerizable compounds, polymerization initiators, polymerization inhibitors, polar compounds and the like. An optically active compound is added to the composition for the purpose of inducing a helical structure of liquid crystal molecules to give a twist angle. Examples of such compounds are compound (5-1) to compound (5-5). A desirable ratio of the optically active compound is approximately 5% by mass or less. A more desirable ratio is in the range of approximately 0.01% by mass to approximately 2% by mass.

In order to prevent a decrease in specific resistance due to heating in the atmosphere or to maintain a large voltage holding ratio not only at room temperature but also at a temperature close to the upper limit temperature after using the device for a long time, an antioxidant is composed. Added to the product. A preferred example of the antioxidant is a compound (6) wherein n is an integer of 1 to 9.

In the compound (6), preferable n is 1, 3, 5, 7, or 9. Further preferred n is 7. Since the compound (6) in which n is 7 has low volatility, it is effective for maintaining 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 approximately 50 ppm or more for achieving its effect, and is approximately 600 ppm or less for avoiding a decrease in the maximum temperature or avoiding an increase in the minimum temperature. A more desirable ratio is in the range of approximately 100 ppm to approximately 300 ppm.

Preferred examples of the ultraviolet absorber include benzophenone derivatives, benzoate derivatives, triazole derivatives and the like. Also preferred are light stabilizers such as sterically hindered amines. A desirable ratio of these absorbers and stabilizers is approximately 50 ppm or more for achieving the effect thereof, and approximately 10,000 ppm or less for avoiding a decrease in the maximum temperature or avoiding an increase in the minimum temperature. A more desirable ratio is in the range of approximately 100 ppm to approximately 10,000 ppm.

A dichroic dye such as an azo dye or an anthraquinone dye is added to the composition in order to adapt it to a GH (guest host) mode element. A preferred ratio of the dye is in the range of approximately 0.01% by mass to approximately 10% by mass. In order to prevent foaming, an antifoaming agent such as dimethyl silicone oil or methylphenyl silicone oil is added to the composition. A desirable ratio of the antifoaming agent is approximately 1 ppm or more for obtaining the effect thereof, and approximately 1000 ppm or less for preventing a display defect. A more desirable ratio is in the range of approximately 1 ppm to approximately 500 ppm.

A polymerizable compound is used to adapt to a polymer support alignment (PSA) type device. Compound (1) and compound (2) are suitable for this purpose. Other polymerizable compounds different from the compound (1) and the compound (2) may be added to the composition together with the compound (1) and the compound (2). Preferable examples of other polymerizable compounds are compounds such as acrylate, methacrylate, vinyl compound, vinyloxy compound, propenyl ether, epoxy compound (oxirane, oxetane), vinyl ketone and the like. Further preferred examples are acrylate or methacrylate. A desirable ratio of compound (1) and compound (2) is approximately 10% by mass or more based on the total mass of the polymerizable compound. A more desirable ratio is approximately 50% by mass or more. A particularly desirable ratio is approximately 80% by mass or more. A particularly desirable ratio is also 100% by mass. By changing the types of the compound (1) and the compound (2), or by combining the compound (1) and the compound (2) with other polymerizable compounds in an appropriate ratio, the reactivity of the polymerizable compound and the liquid crystal molecules The pretilt angle can be adjusted. By optimizing the pretilt angle, a short response time of the element 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 performed in the presence of a suitable initiator such as a photopolymerization initiator. Appropriate conditions for polymerization, the appropriate type of initiator, and the appropriate amount are known to those skilled in the art and are described in the literature. For example, Irgacure 651 (registered trademark; BASF), Irgacure 184 (registered trademark; BASF), or Darocur 1173 (registered trademark; BASF), which are photoinitiators, are suitable for radical polymerization. A desirable ratio of the photopolymerization initiator is in the range of approximately 0.1% by mass to approximately 5% by mass based on the total mass of the polymerizable compound. A more desirable ratio is in the range of approximately 1% by mass to approximately 3% by mass.

When storing polymerizable compounds 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 the polymerization inhibitor include hydroquinone, hydroquinone derivatives such as methylhydroquinone, 4-t-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 illustrated. A 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 No. 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. A part of the compound (6) is commercially available. A compound of formula (6) wherein n is 1 is available from Sigma-Aldrich Corporation. Compound (6) where n is 7, and the like are synthesized by the method described in US Pat. No. 3,660,505.

The synthesis method of compound (1) will be described. Compound (1) can be synthesized by appropriately combining organic synthetic chemistry methods. Methods for introducing the desired end groups, rings, and linking groups into the starting material are as follows: Sons, Inc.), Organic Reactions, John Wilyhen & Sons Inc., Comprehensive Organic Synthesis, Pergamon Press, New Experimental Chemistry Course (Maruzen) Has 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). In the production of esters, a method for synthesizing a compound having —COO— was shown. A compound having —OCO— can also be synthesized by this synthesis method. The same applies to other asymmetrical linking groups.

 

(1) Formation of a single bond Arylboric acid (21) and a compound (22) synthesized by a known method are reacted 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 with zinc chloride, and in the presence of a catalyst such as dichlorobis (triphenylphosphine) palladium. ) Is also reacted.

(2) Formation of —COO— The compound (23) is reacted with n-butyllithium and subsequently with carbon dioxide to obtain a 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 the 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) can also be synthesized by fluorinating compound (26) with (diethylamino) sulfur trifluoride (DAST). See W. H. Bunnelle et al., J. Org. Chem. 1990, 55, 768. It is also possible to generate this linking group 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 formamide such as N, N-dimethylformamide (DMF) to obtain the aldehyde (28). A phosphoryl ylide generated by treating a phosphonium salt (27) synthesized by a known method with a base such as potassium tert-butoxide is reacted with an aldehyde (28) to synthesize a compound (1D). Since a cis isomer is generated depending on the reaction conditions, the cis isomer is isomerized to a trans isomer by a known method as necessary.

(5) Formation of —CH ₂ O— Compound (28) is obtained by reducing compound (28) with a reducing agent such as sodium borohydride. This is halogenated with hydrobromic acid or the like to obtain 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 this phosphorus ylide is reacted with an aldehyde (32) to obtain an ester (33). . Ester (33) is hydrolyzed in the presence of a base such as sodium hydroxide to give carboxylic acid (34). This compound and compound (25) are dehydrated and condensed to synthesize compound (1F).

(7) Formation of —C (CH ₃ ) ═CH—COO— A phosphorus ylide is prepared by reacting a base such as sodium hydride with ethyl diethylphosphonoacetate, and this phosphorus ylide is reacted with methyl ketone (35) to form an ester ( 36). Next, ester (36) is hydrolyzed in the presence of a base such as sodium hydroxide to obtain carboxylic acid (37), and then compound (1G) is synthesized by dehydration condensation with 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 Compound (1H) is synthesized by reaction in the presence of a base such as NMe) and a catalyst such as bis (tri-tert-butylphosphine) palladium.

(9) Formation of —C (CH ₃ ) ═C (CH ₃ ) —COO— Compound (40) is obtained by dehydration condensation of compound (25) and pyruvic acid. Compound (1I) is synthesized by reacting compound (40) with compound (35) in the presence of zinc and titanium tetrachloride.

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 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 this polymerizable group is bonded to the ring with a linking group S is as follows. First, an example in which the linking group S is a single bond is shown.

(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 synthesis method of the linking group Z.

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

Compounds that have not been described as synthetic methods include Organic Synthesis (Organic Syntheses, John Wiley & Sons, Inc.), Organic Reactions (Organic Reactions, John Wiley & Sons, Inc.), Comprehensive Organic Synthesis ( Comprehensive (Organic Synthesis, Pergamon Press) and New Experimental Chemistry Course (Maruzen). The composition is prepared from the compound thus obtained by known methods. For example, the component compounds are mixed and dissolved in each other by heating.

Finally, the use of the composition will be explained. Most compositions have a minimum temperature of about −10 ° C. or lower, a maximum temperature of about 70 ° C. or higher, and an optical anisotropy in the range of about 0.07 to about 0.20. A composition having an optical anisotropy in the range of about 0.08 to about 0.25 may be prepared by controlling the ratio of the component compounds or by mixing other liquid crystal compounds. Furthermore, a composition having 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 transmissive AM device. This composition can be used as a composition having a nematic phase, or can be used 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 PM elements. This composition can be used for an AM device and a PM device 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 alignment of liquid crystal molecules may be parallel to or perpendicular to the glass substrate. These elements may be reflective, transmissive, or transflective. Use in a transmissive element is preferred. It can also be used for an amorphous silicon-TFT device or a polycrystalline silicon-TFT device. It can also be used for an NCAP (nematic-curvilinear-aligned-phase) type device produced by microencapsulating this composition, or a PD (polymer-dispersed) type device in which a three-dimensional network polymer is formed in the composition.

An example of a method for producing 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 compound is prepared by mixing a liquid crystal compound. A polymerizable compound is added to the composition. You may add an additive further as needed. This composition is injected into the device. The device is irradiated with light with a voltage applied. Ultraviolet light is preferred. The polymerizable compound is polymerized by light irradiation. By this polymerization, a composition containing a polymer is generated. The polymer-supported orientation type element is manufactured by such a procedure.

In this procedure, when a voltage is applied, liquid crystal molecules are aligned by the action of an electric field. According to this orientation, the molecules of the polymerizable compound are also oriented. In this state, the polymerizable compound is polymerized by ultraviolet rays, so that a polymer maintaining this orientation is formed. The effect of this polymer shortens the response time of the device. Since image sticking is a malfunction of the liquid crystal molecules, the effect of this polymer also improves the image sticking. It is also possible to polymerize a polymerizable compound in the composition in advance and place the composition between the substrates of the liquid crystal display element.

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

When the compound (2), that is, a polymerizable compound having a polar group, is used as the polymerizable compound, an alignment film is not necessary on the substrate of the element. A device having no alignment film is manufactured according to the procedure described in the previous paragraph except that a substrate having no alignment film is used.

In this procedure, the 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 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 formed. The effect of this polymer additionally stabilizes the orientation of the liquid crystal molecules and shortens the response time of the device. Since image sticking is a malfunction of the liquid crystal molecules, the effect of this polymer also improves the image sticking.

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

Measurement method The characteristics were measured by the following method. Many of these are the methods described in the JEITA standard (JEITA ED-2521B) established by the Japan Electronics and Information Technology Industries Association (JEITA), or methods modified from these 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 was measured when a part of the sample changed from a nematic phase to an isotropic liquid. The upper limit temperature of the nematic phase may be abbreviated as “upper limit 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 with an Abbe refractometer using a light having a wavelength of 589 nm and a polarizing plate attached to an eyepiece. After rubbing the surface of the main prism in one direction, the 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 polarization direction was perpendicular to the rubbing direction. The value of optical anisotropy was calculated from the equation: Δn = n∥−n⊥.

(4) Dielectric anisotropy (Δε; measured at 25 ° C.): The value of dielectric anisotropy was calculated from the equation: Δε = ε∥−ε⊥. The dielectric constants (ε∥ and ε⊥) were measured as follows.
1) Measurement of dielectric constant (ε∥): An ethanol (20 mL) solution of octadecyltriethoxysilane (0.16 mL) was applied to a well-cleaned glass substrate. The glass substrate was rotated with a spinner and then heated at 150 ° C. for 1 hour. A sample was put in a VA element in which the distance between two glass substrates (cell gap) was 4 μm, and the element was sealed with an adhesive that was cured with ultraviolet rays. 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 baking this glass substrate, the obtained alignment film was rubbed. 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⊥) in the minor axis direction of the liquid crystal molecules was measured.

(5) Threshold voltage (Vth; measured at 25 ° C .; V): An LCD5100 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 element in which the distance between two glass substrates (cell gap) is 4 μm and the rubbing direction is anti-parallel, and an adhesive that cures the element with ultraviolet rays is used. And sealed. The voltage (60 Hz, rectangular wave) applied to this element was increased stepwise from 0V to 20V by 0.02V. At this time, the device was irradiated with light from the vertical direction, and the amount of light transmitted through the device was measured. A voltage-transmittance curve was created in which the transmittance was 100% when the light amount reached the maximum and the transmittance was 0% when the light amount was the minimum. The threshold voltage was expressed as a voltage when the transmittance reached 10%.

(6) Voltage holding ratio (VHR; measured at 60 ° C .;%): A pulse voltage (60 microseconds at 0.1 V) was applied to the fabricated device and charged. The decreasing voltage was measured with a high-speed voltmeter for 1666.7 milliseconds, and the area A between the voltage curve and the horizontal axis in a unit cycle was obtained. Area B was the area when it was not attenuated. The voltage holding ratio was expressed as a percentage of area A with respect to 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 regarding 1,4-cyclohexylene is trans. The number in parentheses after the symbol represents 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 mass percentage (% by mass) based on the mass of the liquid crystal composition containing no additive. Finally, the characteristic values of the composition are summarized.

Example 1 of device A composition having a maleimide compound and a polymerizable compound having a polar group added thereto was injected into an element having no raw material alignment film. After irradiating with ultraviolet rays, the vertical alignment of liquid crystal molecules in this device was examined. First, the raw materials will be explained. Raw materials are compositions (M51) to (M55), polymerizable compounds (PC-1) to (PC-5) having a polar group, maleimide compounds (MI-1) to (MI-8), and polymerizable compounds (RM-1), which 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 = 2.18 V.

Polymerizable compounds (PC-1) to (PC-5) having the following polar groups were used as the second additive.

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

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

Example 1
The polymerizable compound (PC-1) having a polar group was added to the composition (M54) in a proportion of 3% by mass, and the maleimide compound (MI-1) was further added in a proportion of 0.2% by mass. This mixture was vacuum-injected into an element having no alignment film in which the distance between two glass substrates (cell gap) was 3.5 μm. By irradiating ultraviolet rays (10 J / cm ² : 365 nm) with a UV light source of a metal halide lamp (M08-L41C: manufactured by Eye Graphics) while applying a voltage (Vp-p 18.8 V) to this element, A cell was produced. Thereafter, the VHR and the pretilt angle of this element were measured by the method described above. 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
In Examples 2 to 20 and Comparative Example 1, except that the cell preparation conditions are shown in Table 4 using a mixture prepared by adding a polymerizable compound having a polar group and a maleimide compound or other compounds to the composition shown in Table X In the same manner as in Example 1, a device having no alignment film was produced. 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, although the type of the composition and the maleimide compound and the concentration of the maleimide compound were changed, it was found that the voltage holding ratio was kept high and the pretilt angle was given. This result shows that the maleimide compound is sufficiently polymerized even when the irradiation amount of ultraviolet rays is small. On the other hand, in Comparative Example 1, the voltage holding ratio remained low. This result shows that the polymerization of the polymerizable compound did not proceed sufficiently with a small amount of ultraviolet irradiation.

By polymerizing a polymerizable composition containing the maleimide compound (1) and a liquid crystal composition, a liquid crystal display device having a mode such as PSA can be produced. 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 optical anisotropic bodies.

Claims (20)

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

   

   In formula (A),
   R ¹ and R ² are independently hydrogen, halogen, or alkyl having 1 to 20 carbons, and in this alkyl, at least one —CH ₂ — may be replaced by —O— or —S—. Well, at least one — (CH ₂ ) ₂ — may be replaced with —CH═CH—, in which at least one hydrogen may be replaced with a halogen.
2. 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 alkylene having 1 to 10 carbon atoms, in which at least one —CH ₂ — is —O—, —CO—, —COO— or —OCO. And at least one —CH ₂ —CH ₂ — may be replaced with —CH═CH— or —C≡C—, and in these divalent groups, at least one hydrogen is May be substituted with halogen or alkyl of 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, in which at least one —CH ₂ — May be replaced with —O— or —S—, and at least one — (CH ₂ ) ₂ — may be replaced with —CH═CH—, in which at least one hydrogen is a 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 1 to 8, and at least one of all -S ¹ -P ¹ and all -S ² -P ² is And having a monovalent group represented by the formula (A),
   

   

   In 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 which 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. In these divalent groups, 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 1 carbon. To 12 alkenyloxy, and in these monovalent hydrocarbon groups, at least one hydrogen may be replaced with halogen;
   Z ¹ is a single bond or alkylene having 1 to 10 carbon atoms, and in this alkylene, at least one —CH ₂ — may be replaced by —O—, —CO—, —COO—, or —OCO—. Well, at least one —CH ₂ —CH ₂ — may be —CH═CH—, —C (CH ₃ ) ═CH—, —CH═C (CH ₃ ) —, —C (CH ₃ ) ═C (CH ₃ ) —, or —C≡C— may be replaced, and in these divalent groups, at least one hydrogen may be replaced with a halogen;
   b1 is 0 or 1,
   b2 is 0, 1, 2, or 3.
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 formula (1-1-1) to the formula (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 which 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, and in this alkyl, at least one —CH ₂ — may be replaced by —O— or —S—. Well, at least one — (CH ₂ ) ₂ — may be replaced by —CH═CH—, in which at least one hydrogen may be replaced by a halogen;
   S ² is a single bond or alkylene having 1 to 10 carbon atoms, and in this alkylene, at least one —CH ₂ — may be replaced by —O—, —CO—, —COO— or —OCO—. Well, 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 carbon number 1 To 3 alkyls;
   Ring A ¹ , Ring A ² , and Ring A ³ are independently an alicyclic hydrocarbon having 3 to 18 carbon atoms, an aromatic hydrocarbon having 6 to 18 carbon atoms, or a heteroaromatic group having 3 to 18 carbon atoms. A divalent group derived from a hydrocarbon, wherein 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, in these monovalent hydrocarbon groups, at least one hydrogen may be replaced by a halogen;
   Z ¹ and Z ² are each independently a single bond or alkylene having 1 to 10 carbon atoms, in which at least one —CH ₂ — is —O—, —CO—, —COO—, or — OCO— may be substituted, and at least one —CH ₂ —CH ₂ — represents —CH═CH—, —C (CH ₃ ) ═CH—, —CH═C (CH ₃ ) —, —C ( CH ₃ ) ═C (CH ₃ ) —, or —C≡C— may be replaced, and in these divalent groups, at least one hydrogen may be replaced with a halogen.
4. The liquid crystal composition according to any one of claims 1 to 3, wherein a ratio of the first additive is in a range of 0.01% by mass to 10% by mass.
5. 5. The liquid crystal composition according to claim 1, comprising at least one polymerizable compound having a polar group represented by formula (2) as the 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 with —CH═CH— or —C≡C—, and at least one hydrogen may be replaced with a halogen;
   Ring A ²¹ and Ring A ²² are 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 In which 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. 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 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 with —CH═CH— or —C≡C—, and at least one hydrogen may be replaced with fluorine or chlorine. Often;
   Sp ²¹ is a single bond or 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 with —CH═CH— or —C≡C—, and at least one hydrogen may be replaced with a halogen; In these groups, at least one hydrogen may be replaced by a group represented by formula (2a);
   

   

   In formula (2a):
   Sp ²² is a single bond or alkylene having 1 to 10 carbon atoms, and in this Sp ²² , at least one —CH ₂ — is —O—, —CO—, —COO—, —OCO—, or —OCOO— At least one —CH ₂ CH ₂ — may be replaced with —CH═CH— or —C≡C—, and at least one hydrogen may be replaced with a 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 having 1 to 15 carbon atoms, and in this R ²² , at least one —CH ₂ — may be replaced by —O— or —S—, and at least one —CH ₂ CH ₂ — May be replaced with —CH═CH— or —C≡C—, and at least one hydrogen may be replaced with a halogen:
   In equation (2),
   P ²¹ is a group represented by formula (2e), formula (2f), formula (2g), or formula (2h);
   However, in the group that Sp ²¹ can take, when at least one hydrogen is not replaced by the group represented by formula (2a), P ²¹ is represented by formula (2e), formula (2f), or A group represented by the formula (2g);
   

   

   In formula (2e), formula (2f), formula (2g), and formula (2h),
   Sp ²³ , Sp ²⁴ and Sp ²⁵ are each independently a single bond or alkylene having 1 to 10 carbon atoms, and in this Sp ²³ , Sp ²⁴ and Sp ²⁵ , at least one —CH ₂ — is —O—. , —NH—, —CO—, —COO—, —OCO—, or —OCOO—, wherein at least one —CH ₂ CH ₂ — represents —CH═CH— or —C≡C— In which at least one hydrogen may be replaced by a halogen;
   S ²¹ is> CH— or>N—;
   S ²² is> C <or> Si <;
   M ²³ and M ²⁴ are independently hydrogen, halogen, alkyl of 1 to 5 carbons, or alkyl of 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 carbon atoms, and in this R ²⁵ , at least one —CH ₂ — may be replaced by —O—, and at least one —CH ₂ CH ₂ — is -CH = CH- may be substituted, at least one hydrogen may be substituted with a halogen, and w in formula (x1) is 1, 2, 3 or 4.
   

   
6. 6. 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 the formula (2-2) to the formula (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 each 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 carbons, 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.
7. The liquid crystal composition according to claim 5 or 6, 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.
8. The liquid crystal composition according to any one of claims 1 to 7, comprising at least one compound represented by formula (3) as a first component.
   

   

   In the formula (3), 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 alkenyloxy having 2 to 12 carbons. Yes; Ring C and Ring E are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 1,4-substituted with at least one hydrogen 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, Yes, c is 0 or 1, and the sum of b and c is 3 or less.
9. The liquid crystal according to any one of claims 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. Composition.
   

   

   

   In 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.
10. The liquid crystal composition according to claim 8 or 9, wherein the ratio of the first component is in the range of 10% by mass to 90% by mass based on the mass of the liquid crystal composition.
11. The liquid crystal composition according to any one of claims 1 to 10, comprising at least one compound 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 at least one hydrogen is replaced by fluorine or chlorine Or alkyl having 1 to 12 carbon atoms, or alkenyl having 2 to 12 carbon atoms in which at least one hydrogen is replaced by fluorine or chlorine; 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; Z ⁴⁴ is a single bond, —CH ₂ CH ₂ —, —CH ₂ O —, —OCH ₂ —, —COO—, or —OCO—; d is 1, 2, or 3;
12. 12. The liquid crystal composition according to claim 1, comprising at least one compound represented by any one 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 independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, It is alkyl having 1 to 12 carbons in which one hydrogen is replaced with fluorine or chlorine, or alkenyl having 2 to 12 carbons in which at least one hydrogen is replaced with fluorine or chlorine.
13. The liquid crystal composition according to claim 11, wherein the ratio 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.
14. A liquid crystal display element comprising the liquid crystal composition according to claim 1.
15. The liquid crystal display element according to claim 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.
16. A polymer-supported alignment type liquid crystal display element comprising the liquid crystal composition according to any one of claims 1 to 13, wherein a polymerizable compound in the liquid crystal composition is polymerized.
17. A liquid crystal display element having no alignment film, comprising the liquid crystal composition according to any one of claims 1 to 13, wherein a polymerizable compound in the liquid crystal composition is polymerized.
18. Use of the liquid crystal composition according to any one of claims 1 to 13 in a liquid crystal display device.
19. Use of the liquid crystal composition according to any one of claims 1 to 13 in a polymer supported alignment type liquid crystal display element.
20. 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.