JP6507404B2 - Polymerizable compound, polymerizable composition and liquid crystal display device - Google Patents

Description

  The present invention relates to a polymerizable compound, a polymerizable composition containing the polymerizable compound and a liquid crystal composition, a liquid crystal composite prepared from the polymerizable composition, a liquid crystal display element, and the like.

  The liquid crystal display element utilizes optical anisotropy, dielectric anisotropy, etc. of liquid crystal molecules in the liquid crystal composition. Classification based on the operation mode of liquid crystal molecules is PC (phase change) mode, TN (twisted nematic) mode, STN (super twisted nematic) mode, BTN (bistable twisted nematic) mode, ECB (electrically controlled birefringence) mode, OCB (Optically compensated bend) mode, IPS (in-plane switching) mode, FFS (fringe field switching) mode, VA (vertical alignment) mode, and the like.

  A liquid crystal display device of a mode in which a liquid crystal composition is combined with a polymer is known. This is, for example, a PSA (polymer sustained alignment) mode or a PS (polymer stabilized) mode. In the liquid crystal display element of this mode, a liquid crystal composition to which a polymerizable compound is added is injected into the display element. Ultraviolet rays are irradiated in a state where a voltage is applied between the electrodes to polymerize the polymerizable compound, thereby forming a polymer in the liquid crystal composition. By this method, a response time is shortened, and a liquid crystal display element with improved image sticking is obtained.

  This method can be applied to liquid crystal display devices of various operation modes, and modes such as PS-TN, PS-IPS, PS-FFS, PSA-VA, and PSA-OCB are known. The polymerizable compound used in the device of such a mode is considered to have high ability to align liquid crystal molecules, but it can not be said that the solubility in the liquid crystal composition is high. Although attempts have been made to improve the solubility in liquid crystal compositions so far, when the solubility is improved, the polymerization reactivity tends to decrease. Therefore, development of a polymerizable compound having an appropriate balance between solubility and polymerization reactivity is desired.

Chinese Patent Application Publication No. 102888231

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

式（１）において、
ａ１個のＰ^１およびａ２個のＰ^２はすべて同一に、式（Ｐ−１）、（Ｐ−２）、および（Ｐ−３）で表わされる基から選択された基であり、式（Ｐ−１）において、Ｍは、水素、フッ素、−ＣＨ_３、または−ＣＦ_３であり；

Ｓ^１およびＳ^２は独立して、単結合または炭素数１から６のアルキレンであり、このアルキレンにおいて、少なくとも１つの−ＣＨ_２−は、−Ｏ−、−ＣＯＯ−または−ＯＣＯ−で置き換えられてもよく、少なくとも１つの−ＣＨ_２−ＣＨ_２−は、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、これらの基において、少なくとも１つの水素はハロゲンで置き換えられてもよく；
ａ１およびａ２は独立して、０、１、２、３、または４であり、ａ１およびａ２の和は４であり；
環Ａ^１は、ナフタレン、アントラセン、またはフェナントレンであり、環Ａ^２は、シクロへキシル、フェニル、ナフチル、アントラセニル、またはフェナントレニルであり、これらの環において、少なくとも１つの水素は、ハロゲン、炭素数１から１０のアルキル、または少なくとも１つの水素がハロゲンで置き換えられら炭素数１から１０のアルキルで置き換えられてもよく；
Ｚ^１は、単結合、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−、−ＣＨ＝Ｃ（ＣＨ_３）−、−Ｃ（ＣＨ_３）＝ＣＨ−、−Ｃ（ＣＨ_３）＝Ｃ（ＣＨ_３）−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−Ｃ（ＣＨ_３）＝ＣＨ−ＣＯＯ−、−ＯＣＯ−ＣＨ＝ＣＨ（ＣＨ_３）−、−ＣＨ＝Ｃ（ＣＨ_３）−ＣＯＯ−、−ＯＣＯ−Ｃ（ＣＨ_３）＝ＣＨ−、−Ｃ（ＣＨ_３）＝Ｃ（ＣＨ_３）−ＣＯＯ−、−ＯＣＯ−Ｃ（ＣＨ_３）＝Ｃ（ＣＨ_３）−、−ＣＨ＝ＣＨ−ＣＯ−、−ＣＯ−ＣＨ＝ＣＨ−、−ＣＨ＝ＣＨ−ＣＨ_２Ｏ−、−ＯＣＨ_２−ＣＨ＝ＣＨ−、−ＣＨ＝ＣＨ−ＯＣＨ_２−、または−ＣＨ_２Ｏ−ＣＨ＝ＣＨ−であり；
ｂ１は０、１、２、３、または４である。 The present invention relates to a polymerizable compound represented by Formula (1), a polymerizable composition containing the compound and a liquid crystal composition, a liquid crystal composite prepared from the polymerizable composition, a liquid crystal display element, and the like.

In equation (1),
All a1 amino ^{P 1} and a2 one ^{P 2} are the same, the formula (P-1), a (P-2), and (P-3) is selected from the groups represented by the group, the formula (P in -1), M is hydrogen, fluorine, -CH ₃ or -CF _3,;

S ¹ and S ² are independently a single bond or alkylene having 1 to 6 carbon atoms, and in this alkylene, at least one —CH ₂ — is replaced by —O—, —COO— or —OCO— And at least one -CH ₂ -CH ₂ -may be replaced by -CH = CH- or -C≡C-, and in these groups, at least one hydrogen may be replaced by halogen Often;
a1 and a2 are independently 0, 1, 2, 3 or 4 and the sum of a1 and a2 is 4;
Ring A ¹ is naphthalene, anthracene or phenanthrene, ring A ² is cyclohexyl, phenyl, naphthyl, anthracenyl or phenanthrenyl, and in these rings, at least one hydrogen is a halogen, one carbon atom To 10 alkyl, or at least one hydrogen may be replaced by halogen and C1 to C10 alkyl;
Z ¹ is a single bond, -CO-, -COO-, -OCO-, -CH = CH-, -C≡C-, -CH = C (CH ₃ )-, -C (CH ₃ ) = CH- , -C (CH ₃ ) = C (CH ₃ )-, -CH = CH-COO-, -OCO-CH = CH-, -C (CH ₃ ) = CH-COO-, -OCO-CH = CH ( _{CH 3) -, - CH =} C (CH 3) -COO -, - OCO-C (CH 3) = CH -, - C (CH 3) = C (CH 3) -COO -, - OCO-C ( CH ₃ ) = C (CH ₃ )-, -CH = CH-CO-, -CO-CH = CH-, -CH = CH-CH ₂ O-, -OCH ₂ -CH = CH-, -CH = CH -OCH _2- or -CH ₂ O-CH = CH-;
b1 is 0, 1, 2, 3 or 4.

  The first advantage of the present invention is that the polymerizable compound has high polymerization reactivity, high conversion and high solubility in liquid crystal composition. The second advantage is that the liquid crystal composite has a high upper limit temperature of nematic phase, a lower lower limit temperature of nematic phase, a small viscosity, a suitable optical anisotropy, a large dielectric anisotropy, a suitable elastic constant, a large resistivity , And at least one of appropriate physical properties such as pretilt. The advantage is that the liquid crystal complex has an appropriate balance with respect to at least two physical properties. The third advantage is that the liquid crystal display device has a wide temperature range in which the device can be used, a short response time, a high voltage holding ratio, a low threshold voltage, a large contrast ratio, and a long lifetime.

  The usage of the terms in this specification is as follows. The liquid crystal compound is a non-polymerizable compound having a liquid crystal phase such as a nematic phase or a smectic phase, and physical properties of a liquid crystal composition having no liquid crystal phase but having an upper limit temperature, a lower limit temperature, a viscosity, and dielectric anisotropy. Is a generic term for non-polymerizable compounds mixed for the purpose of adjusting This compound has a 6-membered ring such as 1,4-cyclohexylene and 1,4-phenylene, and its molecular structure is rod like. The liquid crystal composition is a mixture of liquid crystal compounds. A polymerizable compound is a compound added to a composition for the purpose of forming a polymer. The polymerizable composition is a composition containing a polymerizable compound, and is, for example, a mixture of a polymerizable compound, a liquid crystal composition, an additive and the like. The liquid crystal complex is a complex formed by the polymerization of this polymerizable composition. The liquid crystal display element is a generic term for a liquid crystal display panel and a liquid crystal display module. The upper limit temperature of the nematic phase is the phase transition temperature of the nematic phase-isotropic phase in the liquid crystal composition, the polymerizable composition, or the liquid crystal composite, and may be abbreviated as the upper limit temperature. The lower limit temperature of the nematic phase may be abbreviated as the lower limit temperature. Polymerization reactivity refers to the degree of ease with which the reactants are polymerized. The conversion is the weight ratio of reactant consumed by the chemical reaction to the reactant.

  The liquid crystal composition is prepared by mixing liquid crystal compounds. The proportion (content) of the liquid crystal compound is expressed as a weight percentage (% by weight) based on the weight of the liquid crystal composition. Additives such as an optically active compound, an antioxidant, an ultraviolet light absorber, a light stabilizer, a heat stabilizer, an antifoaming agent, a polymerization initiator and a polymerization inhibitor are added to the composition as needed. The proportion (addition amount) of the additive is represented by a weight percentage (% by weight) based on the weight of the liquid crystal composition, similarly to the proportion of the liquid crystal compound. Parts per million by weight (ppm) may be used. The proportions of the polymerization initiator and the polymerization inhibitor are exceptionally expressed based on the weight of the polymerizable compound.

The compound represented by formula (1) may be abbreviated as compound (1). This abbreviation also applies to compounds represented by formula (2) and the like. The compound (1) means one compound or two or more compounds represented by the formula (1). In the formulas (1) to (15), symbols such as A ¹ , B ¹ and C ¹ surrounded by a circle or a hexagon correspond to ring A ¹ , ring B ¹ , ring C ^{1 and the} like, respectively. In the formula (1), the oblique lines crossing the circle of ring A ¹ mean that the P ¹ -S ¹ group can arbitrarily select the bonding position on the ring. This rule also applies to P ² -S ² groups and the like. This rule also applies to diagonal lines (or lines) crossing fused rings such as the naphthalene ring of formula (1-1). In the formula (1), subscript, such as a1 represents the number of groups attached to such ring A ^1. Ring A ^{1 and the} like form a group having a valence number of these bonding numbers. When a1 is 2, two S ¹ are present on ring A ¹ . The two groups represented by two S ¹ may be identical or different. This rule also applies when a1 is greater than two. This rule also applies to other groups. The symbol R ¹¹ is used in a plurality of equations such as equation (2) and equation (3). In these compounds, two terminal groups represented by any two R ¹¹ may be identical or different. In equation (5), when i is 2, two symbols C ¹ exist in one equation. In this compound, the two rings represented by the two symbols C ¹ may be identical or different. This rule also applies to symbols such as Z ^14.

In the expression “at least one 'A' may be replaced by 'B'”, when the number of 'A' is one, the position of 'A' is arbitrary and the number of 'A' is two Also in the case of three or more, it means that those positions can be selected without limitation. The expression “at least one A may be replaced by B, C or D” means that when at least one A is replaced by B, at least one A is replaced by C, and at least one When A is replaced with D, it is meant to include the case where a plurality of A are replaced with at least two of B, C and D. For example, alkyl in which at least one -CH _2- (or -CH ₂ CH _2- ) may be replaced by -O- (or -CH = CH-) includes alkyl, alkenyl, alkoxy, alkoxyalkyl, alkoxy Included are alkenyl and alkenyloxyalkyl. Note that two successive -CH ₂ - are replaced by the -O-, it is a -O-O- in such is not preferred. Alkyl such as in, -CH ₂ methyl moiety _(-CH 2 -H) - by is replaced by -O- is not preferred also be the -O-H.

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 ring divalent groups such as tetrahydropyran-2,5-diyl.

  The present invention includes the contents described in the following sections.

式（１）において、
ａ１個のＰ^１およびａ２個のＰ^２はすべて同一に、式（Ｐ−１）、（Ｐ−２）、および（Ｐ−３）で表わされる基から選択された基であり、式（Ｐ−１）において、Ｍは、水素、フッ素、−ＣＨ_３、または−ＣＦ_３であり；

Ｓ^１およびＳ^２は独立して、単結合または炭素数１から６のアルキレンであり、このアルキレンにおいて、少なくとも１つの−ＣＨ_２−は、−Ｏ−、−ＣＯＯ−または−ＯＣＯ−で置き換えられてもよく、少なくとも１つの−ＣＨ_２−ＣＨ_２−は、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、少なくとも１つの水素は、ハロゲンで置き換えられてもよく；
ａ１およびａ２は独立して、０、１、２、３、または４であり、ａ１およびａ２の和は４であり；
環Ａ^１は、ナフタレン、アントラセン、またはフェナントレンであり、環Ａ^２は、シクロへキシル、フェニル、ナフチル、アントラセニル、またはフェナントレニルであり、これらの環において、少なくとも１つの水素は、ハロゲン、炭素数１から１０のアルキル、または少なくとも１つの水素がハロゲンで置き換えられた炭素数１から１０のアルキルで置き換えられてもよく；
Ｚ^１は、単結合、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−、−ＣＨ＝Ｃ（ＣＨ_３）−、−Ｃ（ＣＨ_３）＝ＣＨ−、−Ｃ（ＣＨ_３）＝Ｃ（ＣＨ_３）−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−Ｃ（ＣＨ_３）＝ＣＨ−ＣＯＯ−、−ＯＣＯ−ＣＨ＝ＣＨ（ＣＨ_３）−、−ＣＨ＝Ｃ（ＣＨ_３）−ＣＯＯ−、−ＯＣＯ−Ｃ（ＣＨ_３）＝ＣＨ−、−Ｃ（ＣＨ_３）＝Ｃ（ＣＨ_３）−ＣＯＯ−、−ＯＣＯ−Ｃ（ＣＨ_３）＝Ｃ（ＣＨ_３）−、−ＣＨ＝ＣＨ−ＣＯ−、−ＣＯ−ＣＨ＝ＣＨ−、−ＣＨ＝ＣＨ−ＣＨ_２Ｏ−、−ＯＣＨ_２−ＣＨ＝ＣＨ−、−ＣＨ＝ＣＨ−ＯＣＨ_２−、または−ＣＨ_２Ｏ−ＣＨ＝ＣＨ−であり；
ｂ１は０、１、２、３、または４である。 Item 1. The compound represented by Formula (1).

In equation (1),
All a1 amino ^{P 1} and a2 one ^{P 2} are the same, the formula (P-1), a (P-2), and (P-3) is selected from the groups represented by the group, the formula (P in -1), M is hydrogen, fluorine, -CH ₃ or -CF _3,;

S ¹ and S ² are independently a single bond or alkylene having 1 to 6 carbon atoms, and in this alkylene, at least one —CH ₂ — is replaced by —O—, —COO— or —OCO— And at least one -CH ₂ -CH ₂ -may be replaced by -CH = CH- or -C≡C-, and at least one hydrogen may be replaced by halogen;
a1 and a2 are independently 0, 1, 2, 3 or 4 and the sum of a1 and a2 is 4;
Ring A ¹ is naphthalene, anthracene or phenanthrene, ring A ² is cyclohexyl, phenyl, naphthyl, anthracenyl or phenanthrenyl, and in these rings, at least one hydrogen is a halogen, one carbon atom To 10 alkyl, or at least one hydrogen may be replaced by alkyl having 1 to 10 carbons replaced by halogen;
Z ¹ is a single bond, -CO-, -COO-, -OCO-, -CH = CH-, -C≡C-, -CH = C (CH ₃ )-, -C (CH ₃ ) = CH- , -C (CH ₃ ) = C (CH ₃ )-, -CH = CH-COO-, -OCO-CH = CH-, -C (CH ₃ ) = CH-COO-, -OCO-CH = CH ( _{CH 3) -, - CH =} C (CH 3) -COO -, - OCO-C (CH 3) = CH -, - C (CH 3) = C (CH 3) -COO -, - OCO-C ( CH ₃ ) = C (CH ₃ )-, -CH = CH-CO-, -CO-CH = CH-, -CH = CH-CH ₂ O-, -OCH ₂ -CH = CH-, -CH = CH -OCH _2- or -CH ₂ O-CH = CH-;
b1 is 0, 1, 2, 3 or 4.

Ｓ^１およびＳ^２が独立して、単結合または炭素数１から６のアルキレンであり、このアルキレンにおいて、少なくとも１つの−ＣＨ_２−は、−Ｏ−、−ＣＯＯ−または−ＯＣＯ−、で置き換えられてもよく、少なくとも１つの−ＣＨ_２−ＣＨ_２−は、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、これらの基において、少なくとも１つの水素はフッ素または塩素で置き換えられてもよく；
ａ１およびａ２が独立して、０、１、２、３、または４であり、ａ１およびａ２の和が４であり；
環Ａ^１が、ナフタレン、アントラセン、またはフェナントレンであり、環Ａ^２が、フェニル、ナフチル、アントラセニル、またはフェナントレニルであり、これらの環において、少なくとも１つの水素は、フッ素、塩素、炭素数１から５のアルキル、少なくとも１つの水素がフッ素で置き換えられた炭素数１から５のアルキル、または少なくとも１つの水素がフッ素で置き換えられた炭素数１から５のアルキルで置き換えられてもよく；
Ｚ^１が、単結合、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−ＣＯ−ＣＨ＝ＣＨ−、−ＣＨ＝ＣＨ−ＣＯ−、−ＣＨ＝ＣＨ−ＣＨ_２Ｏ−、−ＯＣＨ_２−ＣＨ＝ＣＨ−、−ＣＨ＝ＣＨ−ＯＣＨ_２−、または−ＣＨ_２Ｏ−ＣＨ＝ＣＨ−であり；
ｂ１が、０、１、２または３である、項１に記載の化合物。 Item 2. In the formula (1), a1 P ¹ and a2 P ² are all the same and a group represented by the formula (P-1), and in the formula (P-1), M is hydrogen or fluorine , -CH ₃ , or -CF ₃ ;

S ¹ and S ² are independently a single bond or alkylene having 1 to 6 carbon atoms, and in this alkylene, at least one —CH ₂ — is replaced by —O—, —COO— or —OCO— And at least one of —CH ₂ —CH ₂ — may be replaced by —CHCHCH— or —C≡C—, and in these groups, at least one hydrogen is replaced by fluorine or chlorine. May be
a1 and a2 are independently 0, 1, 2, 3 or 4 and the sum of a1 and a2 is 4;
Ring A ¹ is naphthalene, anthracene or phenanthrene, and ring A ² is phenyl, naphthyl, anthracenyl or phenanthrenyl, and in these rings, at least one hydrogen is fluorine, chlorine, 1 to 5 carbon atoms And C 1 -C 5 alkyl in which at least one hydrogen is replaced by fluorine, or C 1 -C 5 alkyl in which at least one hydrogen is replaced by fluorine;
Z ¹ is a single bond, -CO-, -COO-, -OCO-, -CH = CH-, -C≡C-, -CH = CH-COO-, -OCO-CH = CH-, -CO- _{CH = CH -, - CH =} CH-CO -, - CH = CH-CH 2 O -, - OCH 2 -CH = CH -, - CH = CH-OCH 2 -, or _-CH 2 OCH = CH -And
Item 3. The compound according to item 1, wherein b1 is 0, 1, 2 or 3.

Item 3. In the formula (1), the same in all a1 amino ^{P 1} and a2 one ^{P 2,} be -OCO-HC = CH ₂ or _{-OCO- (CH 3) C = CH} 2;
S ¹ and S ² independently represent a single bond, -COO-, -OCO-, -CH _2- , -CH ₂ O-, -OCH ₂ -,-(CH ₂ ) ₂ -,-(CH ₂ ) _2— O—, —O— (CH ₂ ) ₂ —, —CH = CH—, —CH = CH—O—, —O—CH = CH—, —C≡C—, —C≡C—O— , -O-C≡C-,-(CH ₂ ) ₃ -,-(CH ₂ ) ₃ -O-, -O- (CH ₂ ) ₃ -,-(CH ₂ ) ₄ -,-(CH ₂ ) ₄ -O-, and -O- _{(CH 2) 4} - a and;
a1 and a2 are independently 0, 1, 2, 3 or 4 and the sum of a1 and a2 is 4;
Ring A ¹ is naphthalene, anthracene or phenanthrene, ring A ² is phenyl, and in these rings, at least one hydrogen is fluorine, chlorine, -CH ₃ , -CHF ₂ or -CF ₃ May be replaced;
Z ¹ is a single bond, -CH = CH-, -CH = CH-COO-, -OCO-CH = CH-, -CH = CH-CH ₂ O-, -OCH ₂ -CH = CH-, -CH = CH-OCH ₂ -, or _-CH 2 OCH = CH- and is;
Item 3. The compound according to item 1, wherein b1 is 0, 1 or 2.

式（１−１）から（１−１３）において、
Ｐ^３、Ｐ^４、Ｐ^５、およびＰ^６はすべて同一に、式（Ｐ−１）で表される基であり、式（Ｐ−１）において、Ｍは、水素、フッ素、−ＣＨ_３、または−ＣＦ_３であり；

Ｓ^３、Ｓ^４、Ｓ^５、およびＳ^６は独立して、単結合または炭素数１から６のアルキレンであり、このアルキレンにおいて、少なくとも１つの−ＣＨ_２−は、−Ｏ−、−ＣＯＯ−または−ＯＣＯ−、で置き換えられてもよく、少なくとも１つの−ＣＨ_２−ＣＨ_２−は、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；
Ｚ^５およびＺ^６は独立して、単結合、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−ＯＣＯ−Ｃ（ＣＨ_３）＝ＣＨ−、−ＣＯ−ＣＨ＝ＣＨ−、−ＣＨ＝ＣＨ−ＣＯ−、−ＣＨ＝ＣＨ−ＣＨ_２Ｏ−、−ＯＣＨ_２−ＣＨ＝ＣＨ−、−ＣＨ＝ＣＨ−ＯＣＨ_２−、または−ＣＨ_２Ｏ−ＣＨ＝ＣＨ−である。 Item 4. Item 2. The compound according to item 1, represented by any one of formulas (1-1) to (1-13).

In formulas (1-1) to (1-13),
P ³ , P ⁴ , P ⁵ and P ⁶ are all the same and a group represented by formula (P-1), and in formula (P-1), M is hydrogen, fluorine, -CH ₃ , Or -CF ₃ ;

S ³ , S ⁴ , S ⁵ and S ^{6 each} independently represent a single bond or an alkylene having 1 to 6 carbon atoms, and in this alkylene, at least one —CH ₂ — is —O—, —COO— Or -OCO-, and at least one -CH ₂ -CH ₂ -may be replaced by -CH = CH- or -C≡C-, and in these groups, at least one Hydrogen may be replaced by fluorine or chlorine;
Z ⁵ and ^{Z 6} are each independently a single bond, -CO -, - COO -, - OCO -, - CH = CH -, - C≡C -, - CH = CH-COO -, - OCO-CH = _{CH -, - OCO-C (} CH 3) = CH -, - CO-CH = CH -, - CH = CH-CO -, - CH = CH-CH 2 O -, - OCH 2 -CH = CH-, -CH = CH-OCH ₂ -, or _-CH 2 OCH = CH-.

Item 5. In formulas (1-1) to (1-13), all of P ³ , P ⁴ , P ⁵ , and P ⁶ are —OCO—HC = CH ₂ or —OCO— (CH ₃ ) C = CH ₂ The compound according to item 4, wherein S ³ , S ⁴ , S ⁵ and S ⁶ are a single bond; and Z ⁵ and Z ⁶ are a single bond.

式（１−１４）から（１−２２）において、
Ｐ^７、Ｐ^８、Ｐ^９、およびＰ^１０はすべて同一に、式（Ｐ−１）で表される基であり、式（Ｐ−１）において、Ｍは、水素、フッ素、−ＣＨ_３、または−ＣＦ_３であり；

Ｓ^７、Ｓ^８、Ｓ^９、およびＳ^１０が独立して、単結合または炭素数１から６のアルキレンであり、このアルキレンにおいて、少なくとも１つの−ＣＨ_２−は、−Ｏ−、−ＣＯＯ−または−ＯＣＯ−、で置き換えられてもよく、少なくとも１つの−ＣＨ_２−ＣＨ_２−は、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよい。 Item 6. Item 6. The compound according to item 1, represented by any one of formulas (1-14) to (1-22):

In formulas (1-14) to (1-22),
P ⁷ , P ⁸ , P ⁹ and P ¹⁰ are all the same and a group represented by formula (P-1), and in formula (P-1), M is hydrogen, fluorine, -CH ₃ , Or -CF ₃ ;

S ⁷ , S ⁸ , S ⁹ and S ¹⁰ independently represent a single bond or an alkylene having 1 to 6 carbon atoms, and in this alkylene, at least one —CH ₂ — is —O—, —COO— Or -OCO-, and at least one -CH ₂ -CH ₂ -may be replaced by -CH = CH- or -C≡C-, and in these groups, at least one Hydrogen may be replaced by fluorine or chlorine.

Item 7. In formulas (1-14) to (1-22), all of P ⁷ , P ⁸ , P ⁹ and P ¹⁰ are —OCO—HC = CH ₂ or —OCO— (CH ₃ ) C = CH ₂ 7. The compound according to item 6, wherein S ⁷ , S ⁸ , S ⁹ and S ¹⁰ are a single bond.

式（１−３−１）、（１−１４−１）または（１−１９−１）において、Ｍ^１からＭ^１２はすべて同一に、水素、フッ素、−ＣＨ_３、または−ＣＦ_３である。 Item 8. Item 3. The compound according to item 1, represented by formula (1-3-1), (1-14-1) or (1-19-1).

In formulas (1-3-1), (1-14-1) or (1-19-1), M ¹ to M ¹² are all the same and are hydrogen, fluorine, -CH ₃ or -CF ₃ .

Item 9. 9. A polymer obtained from the compound according to any one of Items 1 to 8.

Item 10. Item 9. A liquid crystal composition containing at least one selected from the group of compounds according to any one of items 1 to 8 and the polymer according to item 9.

式（２）から（４）において、
Ｒ^１１は炭素数１から１０のアルキルまたは炭素数２から１０のアルケニルであり、このアルキルおよびアルケニルにおいて、少なくとも１つの水素はフッ素で置き換えられてもよく、少なくとも１つの−ＣＨ_２−は−Ｏ−で置き換えられてもよく；
Ｘ^１１は、フッ素、塩素、−ＯＣＦ_３、−ＯＣＨＦ_２、−ＣＦ_３、−ＣＨＦ_２、−ＣＨ_２Ｆ、−ＯＣＦ_２ＣＨＦ_２、または−ＯＣＦ_２ＣＨＦＣＦ_３であり；
環Ｂ^１、環Ｂ^２および環Ｂ^３は独立して、１，４−シクロヘキシレン、少なくとも１つの水素がフッ素で置き換えられてもよい１，４−フェニレン、テトラヒドロピラン−２，５−ジイル、１，３−ジオキサン−２，５−ジイル、またはピリミジン−２，５−ジイルであり；
Ｚ^１１、Ｚ^１２およびＺ^１３は独立して、単結合、−ＣＨ_２ＣＨ_２−、−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−、−ＣＯＯ−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、−ＣＨ_２Ｏ−、または−（ＣＨ_２）_４−であり；
Ｌ^１１およびＬ^１２は独立して、水素またはフッ素である。 Item 11. Item 11. The liquid crystal composition according to item 10, further containing at least one compound selected from the group of compounds represented by formulas (2) to (4).

In equations (2) to (4),
R ¹¹ is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and alkenyl, at least one hydrogen may be replaced by fluorine, and at least one —CH ₂ — is —O May be replaced by-;
X ¹¹ represents fluorine, chlorine, -OCF ₃ , -OCHF ₂ , -CF ₃ , -CHF ₂ , -CH ₂ F, -OCF ₂ CHF ₂ , or -OCF ₂ CHFCF ₃ ;
Ring B ¹ , ring B ² and ring B ³ are independently 1,4-cyclohexylene, 1,4-phenylene in which at least one hydrogen may be replaced by fluorine, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl or pyrimidine-2,5-diyl;
Z ^{11, Z 12} and ^{Z 13} are independently a single _{bond, -CH 2 CH 2 -, -} CH = CH -, - C≡C -, - COO -, - CF 2 O -, - OCF 2 -, -CH ₂ O-, or - _{(CH 2) 4} - a and;
L ¹¹ and L ¹² are independently hydrogen or fluorine.

式（５）において、
Ｒ^１２は炭素数１から１０のアルキルまたは炭素数２から１０のアルケニルであり、このアルキルおよびアルケニルにおいて、少なくとも１つの水素はフッ素で置き換えられてもよく、少なくとも１つの−ＣＨ₂−は−Ｏ−で置き換えられてもよく；
Ｘ^１２は−Ｃ≡Ｎまたは−Ｃ≡Ｃ−Ｃ≡Ｎであり；
環Ｃ^１は、１，４−シクロヘキシレン、少なくとも１つの水素がフッ素で置き換えられてもよい１，４−フェニレン、テトラヒドロピラン−２，５−ジイル、１，３−ジオキサン−２，５−ジイル、またはピリミジン−２，５−ジイルであり；
Ｚ^１４は、単結合、−ＣＨ_２ＣＨ_２−、−Ｃ≡Ｃ−、−ＣＯＯ−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、または−ＣＨ_２Ｏ−であり；
Ｌ^１３およびＬ^１４は独立して水素またはフッ素であり；
ｉは、１、２、３または４である。 Item 12. Item 12. The liquid crystal composition according to item 10, further containing at least one compound selected from the group of compounds represented by formula (5).

In equation (5),
R ¹² is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and alkenyl, at least one hydrogen may be replaced by fluorine, and at least one —CH ₂ — is —O May be replaced by-;
X ¹² is —C≡N or —C≡C—C≡N;
Ring C ¹ is 1,4-cyclohexylene, 1,4-phenylene in which at least one hydrogen may be replaced by fluorine, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl Or pyrimidine-2,5-diyl;
Z ¹⁴ is a single _{bond, -CH 2 CH 2 -, -} C≡C -, - COO -, - CF 2 O -, - OCF 2 -, or _-CH 2 O-;
L ¹³ and L ¹⁴ are independently hydrogen or fluorine;
i is 1, 2, 3 or 4;

式（６）から（１２）において、
Ｒ^１３およびＲ^１４は独立して、炭素数１から１０のアルキルまたは炭素数２から１０のアルケニルであり、このアルキルおよびアルケニルにおいて、少なくとも１つの−ＣＨ₂−は−Ｏ−で置き換えられてもよく、少なくとも１つの水素はフッ素で置き換えられてもよく；
Ｒ^１５は、水素、フッ素、炭素数１から１０のアルキル、または炭素数２から１０のアルケニルであり、このアルキルおよびアルケニルにおいて、少なくとも１つの−ＣＨ₂−は−Ｏ−で置き換えられてもよく、少なくとも１つの水素はフッ素で置き換えられてもよく；
Ｓ^１１は水素またはメチルであり；
Ｘは、−ＣＦ_２−、−Ｏ−、または−ＣＨＦ−であり；
環Ｄ^１、環Ｄ^２、環Ｄ^３、および環Ｄ^４は独立して、１，４−シクロヘキシレン、１，４−シクロヘキセニレン、少なくとも１つの水素がフッ素で置き換えられてもよい１，４−フェニレン、テトラヒドロピラン−２，５−ジイル、またはデカヒドロナフタレン−２，６−ジイルであり；
環Ｄ^５および環Ｄ^６は独立して、１，４−シクロヘキシレン、１，４−シクロヘキセニレン、１，４−フェニレン，テトラヒドロピラン−２，５−ジイル、またはデカヒドロナフタレン−２，６−ジイルであり；
Ｚ^１５、Ｚ^１６、Ｚ^１７、およびＺ^１８は独立して、単結合、−ＣＨ_２ＣＨ_２−、−ＣＯＯ−、−ＣＨ_２Ｏ−、−ＯＣＦ_２−、または−ＯＣＦ_２ＣＨ_２ＣＨ_２−であり；
Ｌ^１５およびＬ^１６は独立して、フッ素または塩素であり；
ｊ、ｋ、ｍ、ｎ、ｐ、ｑ、ｒ、およびｓは独立して、０または１であり、ｋ、ｍ、ｎおよびｐの和は、１または２であり、ｑ、ｒおよびｓの和は、０、１、２または３であり、ｔは、１、２または３である。 Item 13. Item 13. The liquid crystal composition according to any one of items 10 to 12, further containing at least one compound selected from the group of compounds represented by formulas (6) to (12).

In equations (6) to (12),
R ¹³ and R ¹⁴ are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and alkenyl, at least one —CH ₂ — may be replaced by —O— Well, at least one hydrogen may be replaced by fluorine;
R ¹⁵ is hydrogen, fluorine, alkyl having 1 to 10 carbons, or alkenyl having 2 to 10 carbons, and in the alkyl and alkenyl, at least one —CH ₂ — may be replaced by —O— , At least one hydrogen may be replaced by fluorine;
S ¹¹ is hydrogen or methyl;
X is -CF _2- , -O-, or -CHF-;
Ring D ¹ , ring D ² , ring D ³ , and ring D ⁴ are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, or at least one hydrogen optionally substituted by fluorine 1, 4-phenylene, tetrahydropyran-2,5-diyl, or decahydronaphthalene-2,6-diyl;
Ring ^{D 5} and ring ^{D 6} are each independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, tetrahydropyran-2,5-diyl or decahydronaphthalene, 2,6 -Diyl;
^{Z 15, Z 16, Z 17} , and ^{Z 18} are independently a single _{bond, -CH 2 CH 2 -, -} COO -, - CH 2 O -, - OCF 2 -, or -OCF ₂ CH ₂ CH ₂ -And
L ¹⁵ and L ¹⁶ are independently fluorine or chlorine;
j, k, m, n, p, q, r and s are independently 0 or 1, and the sum of k, m, n and p is 1 or 2, q, r and s The sum is 0, 1, 2 or 3 and t is 1, 2 or 3.

式（１３）から（１５）において、
Ｒ^１６およびＲ^１７は独立して、炭素数１から１０のアルキルまたは炭素数２から１０のアルケニルであり、このアルキルまたはアルケニルにおいて、少なくとも１つの−ＣＨ₂−は−Ｏ−で置き換えられてもよく、少なくとも１つの水素はフッ素で置き換えられてもよく；
環Ｅ^１、環Ｅ^２、環Ｅ^３および環Ｅ^４は独立して、１，４−シクロヘキシレン、１，４−フェニレン、２−フルオロ−１，４−フェニレン、２，５−ジフルオロ−１，４−フェニレン、またはピリミジン−２，５−ジイルであり；
Ｚ^１９、Ｚ^２０およびＺ^２１は独立して、単結合、−ＣＨ_２ＣＨ_２−、−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−、または−ＣＯＯ−である。 Item 14. Item 14. The liquid crystal composition according to any one of items 10 to 13, further containing at least one compound selected from the group of compounds represented by formulas (13) to (15).

In equations (13) to (15),
R ¹⁶ and R ¹⁷ are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in this alkyl or alkenyl, at least one —CH ₂ — may be replaced by —O— Well, at least one hydrogen may be replaced by fluorine;
Ring E ¹ , ring E ² , ring E ³ and ring E ⁴ are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,5-difluoro-1 , 4-phenylene, or pyrimidine-2,5-diyl;
Z ^{19, Z 20} and ^{Z 21} are independently a single _{bond, -CH 2 CH 2 -, -} CH = CH -, - C≡C-, or -COO-.

Item 15. Item 15. The method according to item 10, further comprising at least one of a polymerizable compound, an optically active compound, an antioxidant, an ultraviolet light absorber, a light stabilizer, a heat stabilizer, an antifoamer, a polymerization initiator, and a polymerization inhibitor The liquid crystal composition according to any one of the above.

Item 16. Item 20. A liquid crystal display device containing the liquid crystal composition according to any one of items 10 to 15.

  The present invention also includes the following items. (A) The above-mentioned polymerizability further containing at least one of additives such as an optically active compound, an antioxidant, an ultraviolet light absorber, a light stabilizer, a heat stabilizer, an antifoaming agent, a polymerization initiator and a polymerization inhibitor Composition. (B) The polymerizable composition as described above which further contains a polymerizable compound different from the compound represented by the formula (1). (C) An AM element containing the above-described polymerizable composition. (D) A device containing the above-described polymerizable composition and having a PS-TN, PS-IPS, PS-FFS, PSA-VA, or PSA-OCB mode. (E) A transmission-type device containing the above-described polymerizable composition. (F) Use of the above-mentioned polymerizable composition as a composition having a nematic phase. (G) Use as an optically active composition by adding an optically active compound to the above composition.

  The present invention also includes the following items. (H) A polymerizable composition containing at least one compound selected from the group of compounds represented by formula (1) and having positive dielectric anisotropy. (I) Polymerizability comprising at least one compound selected from the group of compounds represented by formula (1) and at least one compound selected from the group of compounds represented by formulas (2) to (4) Composition. (J) A polymerizable composition comprising at least one compound selected from the group of compounds represented by formula (1) and at least one compound selected from the group of compounds represented by formula (5). (K) at least one compound selected from the group of compounds represented by formula (1), at least one compound selected from the group of compounds represented by formulas (2) to (4), and A polymerizable composition containing at least one compound selected from the group of compounds represented by).

  The present invention also includes the following items. (L) A polymerizable composition containing at least one compound selected from the group of compounds represented by formula (1) and having negative dielectric anisotropy. (M) Polymerizable including at least one compound selected from the group of compounds represented by formula (1) and at least one compound selected from the group of compounds represented by formulas (6) to (12) Composition. (N) at least one compound selected from the group of compounds represented by formula (1), at least one compound selected from the group of compounds represented by formulas (6) to (12), and A polymerizable composition containing at least one compound selected from the group of compounds represented by (4) to (4). (O) A liquid crystal complex produced by the polymerization of the above-mentioned polymerizable composition. (P) Use of the above polymerizable composition or the above liquid crystal composite in a liquid crystal display device having a PSA mode.

1. Polymerizable Compound The polymerizable compound (1) of the present invention will be described first, and thereafter, the synthetic method, the polymerizable composition, the liquid crystal composite, and the liquid crystal display device will be described in the order. The first feature of the compound (1) is that it has a condensed ring such as naphthalene, anthracene and phenanthrene and four polymerizable groups. The polymerizable group may be directly bonded to the fused ring, or may be indirectly linked to the fused ring via a bivalent group such as phenylene or naphthalenediyl. The second feature of the compound (1) is that it has molecular symmetry (or partial symmetry). The backbone of this molecule is a fused ring, which has symmetry. Symmetry of the whole molecule can be achieved by arranging four polymerizable groups directly or indirectly in a well-balanced manner in this fused ring. The third feature of the compound (1) is that the four polymerizable groups are identical. This feature is excellent as it can contribute to molecular symmetry. Symmetry means mirror symmetry or rotational symmetry.

  Due to the symmetry of the molecule, compound (1) is expected to have the following advantages. The first point is that the synthesis of the polymerizable compound is easy. A naphthalene will be described as an example. The reactivity at the 1 and 8 (peri position) of naphthalene is equivalent since the two positions are symmetrical. Likewise, the reactivity at positions 2, 3 and 6 (pros position) of naphthalene is equivalent. Therefore, it is considered easier to introduce a plurality of functional groups at symmetrical positions of naphthalene than it is to introduce at asymmetric positions. Since the compound (1) is symmetrical, its synthesis is presumed to be relatively easy.

  The second point is that when the compound is added to the liquid crystal composition, the decrease in the order parameter (degree of order of the liquid crystal) of the liquid crystal is small. The compound (1) forms a polymer network between liquid crystal molecules by being added to the liquid crystal composition and then polymerized. In the PSA mode, this polymer is used to control liquid crystal molecules. When a polymerizable compound is added to the liquid crystal composition, the order parameter of the liquid crystal decreases. Since the compound (1) has molecular symmetry or partial symmetry, it is presumed that the decrease in order parameter is small.

The compound (No. 1) is a compound of the present invention in which four polymerizable groups are identical. The compound (III) is a compound disclosed in Chinese Patent Publication No. 102888231 specification in which one of four polymerizable groups is not identical. These compounds were compared by molecular model. As a result, it was found that the compound (No. 1) had a more elongated oval shape than the compound (III). Therefore, it is presumed that the compound (No. 1) is difficult to reduce the order parameter when added to rod-like liquid crystal molecules.

化合物（１）の重合性基Ｐ^１およびＰ^２、連結基Ｓ^１およびＳ^２、環Ａ^１およびＡ^２、または結合基Ｚ^１の好ましい例は、化合物（１）の下位式にも適用される。化合物の物性に大きな差異がないので、化合物（１）は、^２Ｈ（重水素）、^１３Ｃなどの同位体を天然存在比の量より多く含んでもよい。 Preferred examples of the compound (1) will be described.

Preferred examples of the polymerizable groups P ¹ and P ² , the linking groups S ¹ and S ² , the rings A ¹ and A ² , or the linking group Z ¹ of the compound (1) also apply to the subformula of the compound (1) Ru. Compound (1) may contain isotopes such as ² H (deuterium) and ¹³ C in an amount larger than the natural abundance ratio, because there is no large difference in the physical properties of the compounds.

そして、ａ１個のＰ^１およびａ２個のＰ^２はすべて同じである。 In Formula (1), P ¹ and P ² are groups selected from the groups represented by Formulas (P-1), (P-2), and (P-3), and Formula (P-1) in, M is hydrogen, fluorine, -CH ₃ or -CF _3,.

Then, a1 one of ^{P 1} and a2 one of ^{P 2} are all the same.

Preferred examples of P ¹ and P ² are the groups (P-1) and (P-2). A further preferred example is a group (P-1). In group (P-1), preferred M is hydrogen, fluorine or -CH _3. More preferably M is hydrogen or -CH _3. Particularly preferred examples of P ¹ and P ² are acryloyloxy (—OCO—HC = CH ₂ ) and methacryloyloxy (—OCO— (CH ₃ ) C = CH ₂ ). A particularly preferred example is methacryloyloxy.

In the formula (1), S ¹ and S ² independently represent a single bond or an alkylene having 1 to 6 carbon atoms, and in this alkylene, at least one —CH ₂ — is —O—, —COO— or -OCO- may be replaced, and at least one -CH ₂ -CH ₂ -may be replaced by -CH = CH- or -C≡C-, and in these groups, at least one hydrogen is , May be replaced by halogen. Preferred examples of halogen are fluorine or chlorine. A further preferred example is fluorine.

Preferred examples of S ¹ or S ² include single bond, -COO-, -OCO-, -CH _2- , -CH ₂ O-, -OCH ₂ -,-(CH ₂ ) _2- and-(CH ₂ ) _2— O—, —O— (CH ₂ ) ₂ —, —CH = CH—, —CH = CH—O—, —O—CH = CH—, —C≡C—, —C≡C—O— , -O-C≡C-,-(CH ₂ ) ₃ -,-(CH ₂ ) ₃ -O-, -O- (CH ₂ ) ₃ -,-(CH ₂ ) ₄ -,-(CH ₂ ) ₄ -O-, or -O- _{(CH 2) 4} - a. Further preferred examples are single bond, -CH ₂ -,-(CH ₂ ) ₂ -O-, -O- (CH ₂ ) _2- , -CH = CH-, -CH = CH-O-, and -O. -CH = CH-. The most preferred example is a single bond.

  In formula (1), a1 and a2 are independently 0, 1, 2, 3 or 4 and the sum of a1 and a2 is 4.

  Preferred combinations of a1 and a2 are (a1 = 4, a2 = 0), (a1 = 2, a2 = 2) or (a1 = 0, a2 = 4). A further preferred combination is (a1 = 4, a2 = 0) or (a1 = 2, a2 = 2). A particularly preferred combination is (a1 = 4, a2 = 0).

In the formula (1), the ring A ¹ is naphthalene, anthracene or phenanthrene, which is exactly the (a1 + b1) -valent group derived from these rings. Ring A ² is cyclohexyl, phenyl, naphthyl, anthracenyl or phenanthrenyl, and in these rings, at least one hydrogen is halogen, alkyl having 1 to 10 carbons, or at least one hydrogen is replaced by halogen It may be substituted by alkyl having 1 to 10 carbon atoms.

  Preferred examples of halogen are fluorine or chlorine. A further preferred example is fluorine. Preferred examples of alkyl in which at least one hydrogen is replaced by halogen are fluoromethyl, difluoromethyl and trifluoromethyl.

Preferred examples of ring A ¹ are naphthalene, anthracene, phenanthrene, 1-methylnaphthalene, 1-fluoronaphthalene, 1-trifluoromethylnaphthalene, 1-fluoroanthracene or phenanthrene. Further preferred examples are naphthalene, anthracene and phenanthrene. Preferred examples of ring A ² are cyclohexyl, phenyl, naphthyl, anthracenyl, phenanthrenyl, 4-methylphenyl and 1-fluoro-2-naphthyl. Further preferred examples are phenyl, naphthyl, anthracenyl and phenanthrenyl.

In formula (1), Z ¹ is a single bond, -CO-, -COO-, -OCO-, -CH = CH-, -C≡C-, -CH = C (CH ₃ )-, -C ( _{CH 3) = CH -, -} C (CH 3) = C (CH 3) -, - CH = CH-COO -, - OCO-CH = CH -, - C (CH 3) = CH-COO -, - _{OCO-CH = CH (CH 3} ) -, - CH = C (CH 3) -COO -, - OCO-C (CH 3) = CH -, - C (CH 3) = C (CH 3) -COO- , -OCO-C (CH ₃ ) = C (CH ₃ )-, -CH = CH-CO-, -CO-CH = CH-, -CH = CH-CH ₂ O-, -OCH ₂ -CH = CH -, - CH = CH-OCH 2 -, or _-CH 2 OCH = CH-.

Preferred examples of Z ¹ include a single bond, -CO-, -COO-, -OCO-, -CH = CH-, -C≡C-, -C (CH ₃ ) = CH-, -CH = CH-COO -, - OCO-CH = CH -, - CH = CH-CO -, - CO-CH = CH -, - CH = CH-CH 2 O -, - OCH 2 -CH = CH -, - CH = CH- OCH ₂ -, and _-CH 2 OCH = a CH-. Further preferred examples are a single bond or -CH = CH-. The most preferred example is a single bond.

  In formula (1), b1 is 0, 1, 2, 3, or 4. Preferred examples of b1 are 0, 2 and 4 from the viewpoint of molecular symmetry. Further preferred examples are 0 and 2. Examples of compounds in which b1 is 0 are compounds (1-14) to (1-22). Examples of compounds in which b1 is 2 are compounds (1-1) to (1-13). A particularly preferred example is 0.

Incidentally, the element S ¹ to bind to P ¹ is oxygen is not preferred. This is because a divalent group such as -COO-O- or -O-O- is formed. This rule also applies to such binding of P ² and S ^2.

  The preferable example of a compound (1) is compound (1-1)-(1-22) as described in claim 4 or 5. Further preferred examples are compounds (1-1), (1-4), and (1-14) to (1-22) from the viewpoint of molecular symmetry. Preferred examples from the viewpoint of partial symmetry are compounds (1-2), (1-3), (1-5), (1-7), (1-9), and (1-13) is there. Particularly preferred examples are compounds (1-14) to (1-22). The preferable specific compound of a compound (1) is a compound (1-3-1), (1-14-1), or (1-19-1) described in item 8.

2. Synthetic Method A synthetic method of compound (1) will be described. The compound (1) can be synthesized by appropriately combining the methods of synthetic organic chemistry. Houben-Wyle, Methoden der Organische Chemie, Georg-Thieme Verlag, Stuttgart, Organic method for introducing the desired polymerizable group P, linking group S, ring A or linking group Z into the starting material Syntheses (Organic Syntheses, John Wily & Sons, Inc.), Organic Reactions (Organic Reactions, John Wily & Sons Inc.), Comprehensive Organic Synthesis (Comprehensive Organic Synthesis, Pergamon Press), New Experimental Chemistry Course ( Maruzen) and others.

2-1. Formation of Bonding Group Z An example of a method of generating the bonding group Z in the compound (1) is as the scheme below. 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 identical or different. Compounds (1A) to (1R) correspond to compound (1). In formation of ester, the synthesis method of the compound which has -COO- was shown. Compounds having -OCO- can also be synthesized by this synthetic method. The same applies to other asymmetric linking groups.

(1) Formation of Single Bond: Arylboric acid (21) is reacted with a compound (22) synthesized by a known method in an aqueous carbonate solution in the presence of a catalyst such as tetrakis (triphenylphosphine) palladium. Compound (1A) is synthesized. Compound (1A) is prepared by reacting compound (23) synthesized by a known method with n-butyllithium and then with zinc chloride, and reacting compound (22) in the presence of a catalyst such as dichlorobis (triphenylphosphine) palladium. It is also synthesized by reacting.

(2) Formation of -COO- Compound (23) is reacted with n-butyllithium and then carbon dioxide to obtain carboxylic acid (24). This 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). Thus, the compound (1B) is synthesized.

(3) Formation of —CH = CH— Compound (23) is treated with n-butyllithium and then reacted with formamide such as N, N-dimethylformamide (DMF) to obtain aldehyde (28). The compound (1D) is synthesized by reacting a phosphorylide generated by treating a phosphonium salt (27) synthesized by a known method with a base such as potassium tert-butoxide, with an aldehyde (28). Depending on the reaction conditions, a cis form is formed, and if necessary, the cis form is isomerized to a trans form by a known method.

(4) Formation of-(CH ₂ ) _2- Compound (1E) is synthesized by hydrogenating compound (1D) in the presence of a catalyst such as palladium carbon.

(5) Formation of (CH ₂ ) _4-Using phosphonium salt (29) in place of phosphonium salt (27), the reaction is carried out according to the method of item (III), and-(CH ₂ ) ₂ -CH = CH- To obtain a compound having The compound is catalytically hydrogenated to synthesize a compound (1F).

(6) Formation of -C≡C- After reacting compound (23) with 2-methyl-3-butyn-2-ol in the presence of a catalyst of dichloropalladium and copper halide, under basic conditions Deprotection provides compound (30). Compound (30) is reacted with compound (22) in the presence of a catalyst of dichloropalladium and copper halide to synthesize compound (1G).

(7) Formation of —CH ₂ O— Compound (28) is reduced with a reducing agent such as sodium borohydride to give compound (32). This is halogenated with hydrobromic acid or the like to obtain a compound (33). Compound (33) is reacted with compound (31) in the presence of potassium carbonate or the like to synthesize compound (1J).

(8) Production of (CH ₂ ) ₃ -O- Using Compound (34) in place of Compound (28), Compound (1K) is synthesized according to the method of Item (VII).

(9) Production of -COCH = CH- A compound (1 L) is synthesized by reacting the compound (37) with the compound (28) in the presence of barium hydroxide.

(10) Formation of —C (CH ₃ ) = C (CH ₃ ) — The compound (1M) is synthesized by reacting the compound (37) and the compound (38) in the presence of zinc and titanium tetrachloride.

(11) Formation of -CH = CH-COO- A base such as sodium hydride is allowed to act on diethyl phosphonoacetate to prepare a phosphorus ylide, which is reacted with an aldehyde (39) to obtain an ester (40) . The ester (40) is hydrolyzed in the presence of a base such as sodium hydroxide to give the carboxylic acid (41). The compound and alcohol (25) are dehydrated and condensed to synthesize a compound (1N).

(12) Formation of —C (CH ₃ ) = CH—COO— A base such as sodium hydride is allowed to act on diethylphosphonoethyl acetate to prepare a phosphorus ylide, which is reacted with a methyl ketone (37) to give an ester ( 42). The ester (42) is hydrolyzed in the presence of a base such as sodium hydroxide to give the carboxylic acid (43). The compound is dehydrated and condensed with an alcohol (25) to obtain a compound (1P).

(13) to obtain the alcohol (44) by -CH = _CH-CH 2 O- generate ester (47) is reduced by diisobutylaluminum hydride (DIBAL). The reaction of alcohol (44) with N-bromosuccinimide (NBS) in the presence of triphenylphosphine gives bromide (45). This compound and compound (25) are dehydrated and condensed to obtain compound (1Q).

(14) Formation of -CO- Compound (23) is reacted with n-butyllithium and then aldehyde (38) to give alcohol (46). Compound (1R) is synthesized by reacting alcohol (46) with an oxidizing agent such as Jones reagent.

2-2. Formation of Polymerizable Group P An example of a method of generating the following polymerizable group 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 (1X) correspond to compound (1).

(1) Generation of M ² CH = CM ¹ -COO- When M ¹ and M ² are not both —CF ₃ , M ¹ is fluorine and M ² is not —CF ₃ or M ¹ is — When it is CF ₃ and M ² is not fluorine, the carboxylic acid (51) shown in the above scheme is commercially available. The carboxylic acid (51) and the compound (31) are dehydrated and condensed in the presence of DCC and DMAP to synthesize a compound (1S).

When M ¹ and M ² are both —CF ₃ , the carboxylic acid (52) and the compound (31) are dehydrated and condensed in the presence of DCC and DMAP to obtain a compound (53). The compound (53) is reacted with methyl 2,2-difluoro-2- (fluorosulfonyl) acetate in the presence of a catalytic amount of copper iodide to synthesize a compound (1T).

When M ¹ is fluorine and M ² is —CF ₃ , the carboxylic acid (54) and the compound (31) are dehydrated and condensed in the presence of DCC and DMAP to obtain a compound (55). Compound (55) is fluorinated with a fluorinating agent such as DAST to give compound (56). The compound (56) is reacted with methyl 2,2-difluoro-2- (fluorosulfonyl) acetate in the presence of a catalytic amount of copper iodide to synthesize a compound (1 U).

When M ¹ is —CF ₃ and M ² is fluorine, carboxylic acid (57) is used as a starting material, and compound (1V) is synthesized according to the method described above.

(2) Formation of vinyloxy group In the presence of potassium carbonate or the like, compound (31) and vinyl bromide are reacted to synthesize compound (1W).

(3) Formation of Epoxy Group A vinyl compound (58) synthesized by a known method is oxidized with metachloroperbenzoic acid (mCPBA) or the like to synthesize a compound (1X).

2-3. Generation of Linking Group S An example of a method for generating a linking group S in compound (1) is as shown in the following scheme. In this scheme, MSG ¹ is a monovalent organic group having at least one ring. The compound (1Y) corresponds to the compound (1).

(1) Formation of —CH ₂ O— In the presence of potassium carbonate or the like, a compound (59) synthesized by a known method is reacted with a compound (31) to obtain a compound (60). Compound (60) is reduced with a reducing agent such as lithium aluminum hydride to give compound (61). Compound (61) is oxidized with an oxidizing agent such as Dess-Martin reagent to give aldehyde (62). The phosphorus ylide generated by treating methyltriphenylphosphonium bromide with a base such as potassium tert-butoxide is reacted with an aldehyde (62) to give a compound (63).

When M ² CH = CM ¹ -COO- is introduced into the compound (61), dehydration condensation of the compound (61) and the compound (51) is performed according to the method described above. When a vinyloxy group is introduced into compound (61), the reaction of compound (61) with vinyl bromide is carried out according to the method described above. When an epoxy group is introduced into the compound (63), the epoxidation reaction of the compound (63) is performed according to the method described above.

(2) Formation of -CH = CH- A compound obtained by reacting a phosphorylide generated by treating a phosphonium salt (64) synthesized by a known method with a base such as potassium tert-butoxide with an aldehyde (38) Get (65). When M ² CH = CM ¹ -COO- is introduced into the compound (65), dehydration condensation of the compound (65) and the compound (51) is performed according to the method described above. When a vinyloxy group is introduced into compound (65), the reaction of compound (65) with vinyl bromide is carried out according to the method described above. When an epoxy group is introduced into compound (65), epoxidation reaction is carried out after converting -CH ₂ OH to -CH = CH ₂ according to the method described above.

The introduction of M ² CH = CM ¹ -COO- may be by the following method. Compound (1Y) is synthesized by reacting aldehyde (66), acid anhydride (67) and sodium carboxylate (68) synthesized by a known method in the presence of potassium carbonate and the like.

(3) Formation of —CH ₂ CH ₂ — Compound (69) is synthesized by hydrogenating compound (65) in the presence of a catalyst such as palladium carbon. The method of introduce | transducing M < ² > CH = CM < ¹ > -COO-, a vinyloxy group, or an epoxy group into this alcohol is as above-mentioned.

2-4. Formation of Ring A Ring A ¹ is naphthalene, anthracene and the like, and ring A ² is cyclohexyl, phenyl, naphthyl and the like. Hydroxy derivatives of compounds such as naphthalene and anthracene which are required as starting materials when synthesizing compound (1) are commercially available. Monovalent groups such as cyclohexyl, phenyl, naphthyl can be used in the synthesis by selecting hydroxy compounds as starting materials.

3. Polymerizable Composition The polymerizable composition contains at least one of the compounds (1) as a first component. The component of the composition may be only the first component. The composition may include a second component, a third component, and the like. The type of the second component and the like depends on the type and application of the target polymer. The polymerizable composition may further contain, as a second component, another polymerizable compound different from the compound (1). Preferred examples of other polymerizable compounds are acrylates, methacrylates, vinyl compounds, vinyloxy compounds, propenyl ethers, ethylene oxide (oxiranes, oxetanes), and vinyl ketones. Further preferred examples are compounds having at least one acryloyloxy and compounds having at least one methacryloyloxy. Further preferred examples also include compounds having acryloyloxy and methacryloyloxy.

Additional examples of the other polymerizable compound are compounds (M-1) to (M-12). In the compounds (M-1) to (M-12), R ²⁵ , R ²⁶ and R ²⁷ are independently hydrogen or methyl; u, x and y are independently 0 or 1; v And w are independently an integer of 1 to 10; L ²¹ , L ²² , L ²³ , L ²⁴ , L ²⁵ and L ²⁶ are independently hydrogen or fluorine.

  When the second component of the polymerizable composition is a polymerizable compound having a liquid crystal phase, an optical anisotropic substance is formed by polymerization while controlling the alignment of liquid crystal molecules. This optically anisotropic substance can be used for a retardation film, a polarization element, a circular polarization element, an elliptical polarization element, an antireflection film, a selective reflection film, a color compensation film, a viewing angle compensation film, and the like. Additives such as a polymerization initiator may be added to the polymerizable composition for the purpose of adjusting the physical properties of the optically anisotropic substance.

  The polymerizable composition may contain a liquid crystal composition as a second component. When aiming at a liquid crystal display device for modes such as PS-TN, PS-IPS, PS-FFS, PSA-VA, PSA-OCB, the polymerizable composition contains Compound (1) as Component A, and It is preferred to further include a compound selected from components B, C, D and E shown in Component B is compounds (2) to (4). Component C is a compound (5). Component D is compounds (6) to (12). Component E is compounds (13) to (15). When preparing such a polymerizable composition, it is preferable to select components B, C, D, and E in consideration of positive or negative dielectric anisotropy, magnitude of dielectric anisotropy, etc. . Polymerizable compositions with appropriately selected components have a high upper temperature limit, a low lower temperature limit, a low viscosity, a suitable (ie large or small) optical anisotropy, a positive or negative large dielectric anisotropy, and Have a large (or small) elastic constant.

  The polymerizable composition is prepared by adding the compound (1) to the liquid crystal composition. In such composition, the addition amount of the compound (1), that is, the component A is in the range of 0.05% by weight to 20% by weight based on the liquid crystal composition. A more preferable addition amount is in the range of 0.1% by weight to 10% by weight. A further preferable addition amount is in the range of 0.2% by weight to 1% by weight. At least one other polymerizable compound different from compound (1) may be further added. In this case, the total added amount of the compound (1) and the other polymerizable compound is preferably within the above range. The physical properties of the resulting polymer can be adjusted by appropriately selecting other polymerizable compounds. Examples of other polymerizable compounds are acrylates, methacrylates and the like as described above. Compounds (M-1) to (M-12) are also included in this example.

Component B is a compound having a halogen or fluorine-containing group at the right end. Preferred examples of component B include compounds (2-1) to (2-16), compounds (3-1) to (3-113), and compounds (4-1) to (4-57). it can. In the compounds of component B, the definitions of R ¹¹ and X ¹¹ are the same as in item 11.

  Component B has a positive dielectric anisotropy and is very excellent in stability to heat, light and the like, so it prepares a composition for a mode such as PS-IPS, PS-FFS and PSA-OCB. It is used in the case. The content of component B is suitably in the range of 1% by weight to 99% by weight based on the liquid crystal composition, preferably in the range of 10% by weight to 97% by weight, more preferably 40% by weight to 95% by weight It is a range. This composition can adjust a viscosity by further adding compound (13)-(15) (component E). When component B is added to a composition having negative dielectric anisotropy, the content of component B is preferably 30% by weight or less based on the liquid crystal composition. By adding the component B, it is possible to adjust the elastic constant of the composition and adjust the voltage-transmittance curve of the device.

Component C is a compound (5) in which the right terminal group is -C≡N or -C≡C-C≡N. As preferable examples of component C, compounds (5-1) to (5-64) can be mentioned. In the compounds of component C, the definitions of R ¹² and X ¹² are the same as in item 12.

  Component C is mainly used when preparing a composition for a mode such as PS-TN since the dielectric anisotropy is positive and the value thereof is large. By adding this component C, the dielectric anisotropy of the composition can be increased. Component C has the effect of widening the temperature range of the liquid crystal phase, adjusting the viscosity, or adjusting the optical anisotropy. Component C is also useful for adjusting the voltage-transmittance curve of the device.

  When preparing a composition for a mode such as PS-TN, the content of component C is suitably in the range of 1% by weight to 99% by weight based on the liquid crystal composition, preferably 10% by weight It is in the range of 97% by weight, more preferably in the range of 40% to 95% by weight. This composition can adjust the temperature range of the liquid crystal phase, viscosity, optical anisotropy, dielectric anisotropy and the like by further adding the component E. When component C is added to a composition having negative dielectric anisotropy, the content of component C is preferably 30% by weight or less based on the liquid crystal composition. By adding the component C, it is possible to adjust the elastic constant of the composition and adjust the voltage-transmittance curve of the device.

Component D is compounds (6) to (12). These compounds, like 2,3-difluoro-1,4-phenylene, have a benzene ring in which the lateral position is substituted with two halogens. Preferred examples of component D include compounds (6-1) to (6-8), compounds (7-1) to (7-17), compounds (8-1), and compounds (9-1) to (9-). 3), compounds (10-1) to (10-11), compounds (11-1) to (11-3), and compounds (12-1) to (12-3). In the compounds of component D, the definitions of R ¹³ , R ¹⁴ and R ¹⁵ are the same as in item 13 above.

  Component D is a compound having negative dielectric anisotropy. Component D is used when preparing the composition for modes, such as PS-IPS, PS-FFS, PSA-VA. Increasing the content of component D negatively increases the dielectric anisotropy of the composition but increases the viscosity. Therefore, the smaller the content, the better, as long as the required value of the threshold voltage of the device is satisfied. Therefore, in consideration of the fact that the absolute value of the dielectric anisotropy is about 5, it is preferable that the content be 40% by weight or more in order to perform sufficient voltage driving.

  Among the component D, since the compound (6) is a bicyclic compound, it is mainly effective in adjusting the viscosity, adjusting the optical anisotropy, or adjusting the dielectric anisotropy. Since the compounds (7) and (8) are tricyclic compounds, they have the effect of increasing the upper limit temperature, increasing the optical anisotropy, or increasing the dielectric anisotropy. Compounds (9) to (12) have the effect of increasing the dielectric anisotropy.

  When preparing a composition for modes such as PS-IPS, PS-FFS, PSA-VA, the content of component D is preferably 40% by weight or more based on the liquid crystal composition, and more preferably Is in the range of 50% by weight to 95% by weight. By adding the component D, it is possible to adjust the elastic constant of the composition and adjust the voltage-transmittance curve of the device. When component D is added to a composition having positive dielectric anisotropy, the content of component D is preferably 30% by weight or less based on the liquid crystal composition. By adding the component D, it is possible to adjust the elastic constant of the composition and adjust the voltage-transmittance curve of the device.

Component E is a compound in which the two end groups are alkyl or the like. Preferred examples of component E include compounds (13-1) to (13-11), compounds (14-1) to (14-19), and compounds (15-1) to (15-7). it can. In the compound of component E, the definitions of R ¹⁶ and R ¹⁷ are the same as in item 14.

  Component E is a compound close to neutrality because the absolute value of dielectric anisotropy is small. The compound (13) mainly has an effect of adjusting viscosity or adjusting optical anisotropy. Compounds (14) and (15) have the effect of extending the temperature range of the nematic phase by raising the upper limit temperature, or the effect of adjusting the optical anisotropy.

  When the content of component E is increased, the viscosity of the composition decreases but the dielectric anisotropy decreases. Therefore, as long as the required value of the threshold voltage of the device is satisfied, it is preferable that the content be as high as possible. Therefore, when preparing a composition for a mode such as PS-IPS, PSA-VA, the content of component E is preferably 30% by weight or more, more preferably 40% by weight based on the liquid crystal composition. It is above.

  The preparation of the polymerizable composition is performed by a method such as dissolving the necessary components at a temperature higher than room temperature. Depending on the application, additives may be added to the composition. Examples of the additives are optically active compounds, antioxidants, ultraviolet light absorbers, light stabilizers, heat stabilizers, antifoaming agents, polymerization initiators, polymerization inhibitors and the like. Such additives are well known to those skilled in the art and are described in the literature.

The optically active compound has an effect of preventing reverse twist by inducing a helical structure to liquid crystal molecules to give a necessary twist angle. The helical pitch can be adjusted by adding an optically active compound. Two or more optically active compounds may be added in order to adjust the temperature dependency of the helical pitch. The following compounds (Op-1) to (Op-18) can be mentioned as preferable examples of the optically active compound. In the compound (Op-18), ring J is 1,4-cyclohexylene or 1,4-phenylene, and R ²⁸ is alkyl having 1 to 10 carbons.

  Antioxidants are effective to maintain a large voltage holding ratio. Preferred examples of the antioxidant include the following compounds (AO-1) and (AO-2), IRGANOX 415, IRGANOX 565, IRGANOX 1010, IRGANOX 1035, IRGANOX 3114, and IRGANOX 1098 (trade name: BASF Corporation) be able to. UV absorbers are effective to prevent the lowering of the upper limit temperature. Preferred examples of UV absorbers are benzophenone derivatives, benzoate derivatives, triazole derivatives and the like, and specific examples include the following compounds (AO-3) and (AO-4), TINUVIN 329, TINUVIN P, TINUVIN 326, TINUVIN 234, Mention may be made of TINUVIN 213, TINUVIN 400, TINUVIN 328, TINUVIN 99-2 (trade name: BASF), and 1,4-diazabicyclo [2.2.2] octane (DABCO). Light stabilizers such as sterically hindered amines are preferred to maintain high voltage holding rates. The following compounds (AO-5) and (AO-6), TINUVIN 144, TINUVIN 765, and TINUVIN 770DF (brand name: BASF company) can be mentioned as a preferable example of a light stabilizer. In addition, a heat stabilizer is also effective for maintaining a large voltage holding ratio, and IRGAFOS 168 (trade name: BASF Corporation) can be mentioned as a preferable example. Defoamers are effective to prevent foaming. Preferred examples of the antifoaming agent are dimethyl silicone oil, methylphenyl silicone oil and the like.

In the compound (AO-1), R ²⁹ is alkyl having 1 to 20 carbons, alkoxy having 1 to 20 carbons, -COOR ³² , or -CH ₂ CH ₂ COOR ³² , wherein R ³² is 1 carbon To 20 alkyl. In compounds (AO-2) and (AO-5), R ³⁰ is alkyl having 1 to 20 carbons. In compound (AO-5), R ³¹ is hydrogen, methyl or O ^· (oxygen radical), ring K and ring L are 1,4-cyclohexylene or 1,4-phenylene, x is 0, 1 or 2

4. Liquid Crystal Complex Compound (1) has high polymerization reactivity, high conversion, and high solubility in liquid crystal composition. A liquid crystal composite is formed by polymerizing a polymerizable composition containing the compound (1) and the liquid crystal composition. The compound (1) forms a polymer in the liquid crystal composition by polymerization. This polymer has an effect of causing a pretilt in liquid crystal molecules. The polymerization is preferably carried out at a temperature at which the polymerizable composition exhibits a liquid crystal phase. Polymerization proceeds by heat, light and the like. The preferred reaction is photopolymerization. The photopolymerization is preferably carried out at 100 ° C. or less in order to prevent thermal polymerization from occurring. The polymerization may be performed in the state where an electric field or a magnetic field is applied.

  The polymerization reactivity and conversion of the compound (1) can be adjusted. The compound (1) is suitable for radical polymerization. By optimizing the reaction temperature, the amount of the remaining compound (1) can be reduced. The compound (1) can be rapidly polymerized by adding a polymerization initiator. Examples of photo radical polymerization initiators are TPO, 1173 and 4265 from Darrocure series of Ciba Specialty Chemicals, Inc., 184, 369, 500, 651, 784, 819, 907, 1300, from Irgacure series. 1700, 1800, 1850, and 2959.

  Additional examples of photo radical polymerization initiators include 4-methoxyphenyl-2,4-bis (trichloromethyl) triazine, 2- (4-butoxystyryl) -5-trichloromethyl-1,3,4-oxadiazole, 9-phenylacridine, 9,10-benzphenazine, benzophenone / Michler's ketone mixture, hexaarylbiimidazole / mercaptobenzimidazole mixture, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, benzyl Dimethyl ketal, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2,4-diethylxanthone / methyl p-dimethylaminobenzoate mixture, benzophenone / methyltriethanolamine mixture It is.

  After adding a photo-radical polymerization initiator to the polymerizable composition, polymerization can be carried out by irradiating ultraviolet light in a state where an electric field is applied. However, unreacted polymerization initiator or decomposition products of the polymerization initiator may cause display defects such as burn-in to the device. In order to prevent this, photopolymerization may be carried out without adding a polymerization initiator. The preferred wavelength of the light to be irradiated is in the range of 150 nm to 500 nm. The more preferred wavelength is in the range of 250 nm to 450 nm, and the most preferred wavelength is in the range of 300 nm to 400 nm.

  When storing the polymerizable compound, a polymerization inhibitor may be added to prevent polymerization. The polymerizable compound is usually added to the composition without removing the polymerization inhibitor. Examples of polymerization inhibitors are hydroquinone, hydroquinone derivatives such as methyl hydroquinone, 4-tert-butyl catechol, 4-methoxyphenol, phenothiazine and the like.

5. Liquid Crystal Display Element The effect of the polymer in the liquid crystal display element is interpreted as follows. The polymerizable composition is a mixture of a liquid crystal compound, a polymerizable compound and the like. By applying an electric field to this composition, liquid crystal molecules are aligned in the direction of the electric field. The polymerizable compound is also oriented according to this orientation. The composition is irradiated with ultraviolet light, and the polymerizable compound is polymerized while maintaining the orientation to form a three-dimensional network structure. Even when the electric field is removed, the orientation of the polymer is maintained. The liquid crystal molecules are stabilized in the state of being oriented in the direction of the electric field by the effect of the polymer. Therefore, the response time of the device is shortened.

  The polymerization of the polymerizable composition is preferably carried out in a display device. An example is as follows. A display element having two glass substrates provided with a transparent electrode and an alignment film is prepared. A polymerizable composition containing a compound (1), a liquid crystal composition, an additive and the like as components is prepared. This composition is injected into the display element. The display element is irradiated with ultraviolet light while applying an electric field to polymerize the compound (1). This polymerization produces a liquid crystal complex. A liquid crystal display device having a liquid crystal composite can be easily manufactured by this method. In this method, rubbing treatment of the alignment film may be omitted. Note that a method of stabilizing liquid crystal molecules in the absence of an electric field may be employed.

  When the addition amount of the polymer is in the range of 0.1% by weight to 2% by weight based on the weight of the liquid crystal composition, a liquid crystal display element of PSA mode is produced. The elements in the PSA mode can be driven by a driving method such as AM (active matrix) or PM (passive matrix). Such an element can be applied to any of reflective, transmissive and semi-transmissive types. By increasing the amount of polymer added, a device in the polymer dispersed mode can also be produced.

  The invention will be explained in more detail by means of examples. The invention is not limited by these examples.

1. Examples of Compound (1) Compound (1) was synthesized by the procedure shown in Example 1 and the like. The compound synthesized was identified by a method such as NMR analysis. Physical properties of the compounds were measured by the methods described below.

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

HPLC analysis The measuring apparatus used Shimadzu Prominence (LC-20AD; SPD-20A). As a column, YMC YMC-Pack ODS-A (length 150 mm, inner diameter 4.6 mm, particle diameter 5 μm) was used. The eluate was used by appropriately mixing acetonitrile and water. As a detector, a UV detector, an RI detector, a CORONA detector, etc. were used suitably. When a UV detector was used, the detection wavelength was 254 nm. The sample was dissolved in acetonitrile to prepare a 0.1% by weight solution, and 1 μL of this solution was introduced into the sample chamber. As a recorder, C-R7Aplus made by Shimadzu Corporation was used.

Ultraviolet-visible spectral analysis As a measurement apparatus, PharmaSpec UV-1700 manufactured by Shimadzu Corporation was used. The detection wavelength was from 190 nm to 700 nm. The sample was dissolved in acetonitrile to prepare a solution of 0.01 mmol / L, and placed in a quartz cell (optical path length: 1 cm) for measurement.

Measurement sample When measuring the phase structure and transition temperature (clearing point, melting point, polymerization initiation temperature, etc.), the compound itself was used as a sample. When measuring physical properties such as the upper limit temperature of the nematic phase, viscosity, optical anisotropy, dielectric anisotropy and the like, a mixture of the compound and the base liquid crystal was used as a sample.

Measurement Method Measurement of physical properties was performed by the following method. Many of these are described in the JEITA standard (JEITA · ED-2521 B), which is deliberately enacted by the Japan Electronics and Information Technology Industries Association (JEITA), or a modified method thereof. there were. A thin film transistor (TFT) was not attached to the TN device used for the measurement.

(1) Phase structure Place the sample on a hot plate (Motler FP-52 hot stage) of a melting point measuring apparatus equipped with a polarized light microscope, and heat the phase state and its changes while heating at a rate of 3 ° C / min. It observed and specified the kind of phase.

(2) Transition temperature (° C)
It was measured using a Perkin Elmer scanning calorimeter, a Diamond DSC system or a high sensitivity differential scanning calorimeter, X-DSC7000 manufactured by SSI Nano Technology. The temperature of the sample was raised and lowered at a rate of 3 ° C./min, and the transition point was determined by extrapolating the start point of the endothermic peak or exothermic peak associated with the phase change of the sample. The melting point of the compound and the polymerization initiation temperature were also measured using this apparatus. The temperature at which a compound transitions from a solid to a liquid crystal phase such as a smectic phase or a nematic phase may be abbreviated as "the lower limit temperature of the liquid crystal phase". The temperature at which a compound transitions from liquid crystal phase to liquid may be abbreviated as the "clearing point".

The crystal is designated C. When the types of crystals can be distinguished, they are represented as C ₁ and C ₂ respectively. The smectic phase is represented by S and the nematic phase is represented by N. When a smectic A phase, a smectic B phase, a smectic C phase, or a smectic F phase can be distinguished among the smectic phases, they are represented as S _A , S _B , S _C or S _F , respectively. The liquid (isotropic) was designated as I. The transition temperature is expressed as, for example, "C 50.0 N 100.0 I". This indicates that the transition temperature from crystal to nematic phase is 50.0 ° C., and the transition temperature from nematic phase to liquid is 100.0 ° C.

(3) Maximum temperature of nematic phase (T _NI or NI; ° C.)
The sample was placed on the hot plate of a melting point apparatus equipped with a polarizing microscope and heated at a rate of 1 ° C./min. The temperature was measured when part of the sample changed from the nematic phase to the isotropic liquid. The upper limit temperature of the nematic phase may be abbreviated as "upper limit temperature". When the sample is a mixture of a compound and a mother liquid crystal, it is indicated by the symbol _TNI . When the sample is a mixture of the compound and component B, C, D or E, it is indicated by the symbol NI.

(4) Lower limit temperature of nematic phase (T _c ; ° C.)
The liquid crystal phase was observed after storing the sample which has a nematic phase in the freezer of 0 degreeC, -10 degreeC, -20 degreeC, -30 degreeC, and -40 degreeC for 10 days. For example, the sample remained in the -20 ° C. in a nematic phase, when changed to -30 ° C. At crystals or a smectic phase was described as ≦ -20 ° C. The T _C. The lower limit temperature of the nematic phase may be abbreviated as "lower limit temperature".

(5) Viscosity (bulk viscosity; ;; measured at 20 ° C .; mPa · s)
It was measured using an E-type rotational viscometer manufactured by Tokyo Keiki Co., Ltd.

(6) Optical anisotropy (refractive index anisotropy; measured at 25 ° C .; Δn)
The measurement was performed using an Abbe refractometer with a polarizing plate attached to the eyepiece, using light at a wavelength of 589 nm. After rubbing the surface of the main prism in one direction, a sample was dropped on the main prism. The refractive index (n‖) was measured when the direction of polarization 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 (Δn) was calculated from the equation of Δn = n‖-n⊥.

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

(8) Voltage holding ratio (VHR-1; measured at 25 ° C;%)
The TN device used for the measurement had a polyimide alignment film, and the distance between two glass substrates (cell gap) was 5 μm. The element was sealed with an adhesive that cures with ultraviolet light after the sample was placed. A pulse voltage (60 microseconds at 5 V) was applied to this element to charge it. The decaying voltage was measured with a high-speed voltmeter for 16.7 milliseconds, and the area A between the voltage curve and the horizontal axis in a unit cycle was determined. The area B was the area when it did not decay. The voltage holding ratio was expressed as a percentage of the area A to the area B.

(9) Voltage holding ratio (VHR-2; measured at 80 ° C;%)
The voltage holding ratio was measured in the same manner as described above except that the measurement was performed at 80 ° C. instead of at 25 ° C. The obtained result is indicated by the symbol VHR-2.

  The measurement method of physical properties may be different between a sample with positive dielectric anisotropy and a sample with negative dielectric anisotropy. The measuring methods when the dielectric anisotropy is positive are described in the items (10a) to (14a). When dielectric anisotropy is negative, it describes in term (10b)-(14b).

(10a) Viscosity (rotational viscosity; γ1; measured at 25 ° C .; mPa · s)
Positive dielectric anisotropy: The measurement was according to the method described in M. Imai et al., Molecular Crystals and Liquid Crystals, Vol. 259, 37 (1995). The sample was placed in a TN device having a twist angle of 0 degree and a distance between two glass substrates (cell gap) of 5 μm. The device was applied stepwise in steps of 0.5 V in the range of 16 V to 19.5 V. After 0.2 seconds of no application, application was repeated under the condition of only one rectangular wave (rectangular pulse; 0.2 seconds) and no application (2 seconds). The peak current and peak time of transient current generated by this application were measured. These measurements and M. The rotational viscosity was obtained from the paper of Imai et al., Calculation formula (8) on page 40. The value of dielectric anisotropy required for this calculation was determined by the method described below using the device for which this rotational viscosity was measured.

(10b) Viscosity (rotational viscosity; γ1; measured at 25 ° C .; mPa · s)
Negative dielectric anisotropy: Measurement was according to the method described in M. Imai et al., Molecular Crystals and Liquid Crystals, Vol. 259, 37 (1995). A sample was placed in a VA device in which the distance between two glass substrates (cell gap) was 20 μm. The device was applied stepwise in the range of 39 to 50 volts in increments of 1 volt. After 0.2 seconds of no application, application was repeated under the condition of only one rectangular wave (rectangular pulse; 0.2 seconds) and no application (2 seconds). The peak current and peak time of transient current generated by this application were measured. These measurements and M. The rotational viscosity was obtained from the paper of Imai et al., Calculation formula (8) on page 40. The dielectric anisotropy required for this calculation was the value measured in the section of dielectric anisotropy described below.

(11a) Dielectric anisotropy (Δε; measured at 25 ° C.)
Positive dielectric anisotropy: A sample was placed in a TN device in which the distance between two glass substrates (cell gap) is 9 μm and the twist angle is 80 degrees. Sine waves (10 V, 1 kHz) were applied to this device, and after 2 seconds, the dielectric constant (‖) in the major axis direction of liquid crystal molecules was measured. Sine waves (0.5 V, 1 kHz) were applied to this device, and after 2 seconds, the dielectric constant (⊥) in the minor axis direction of liquid crystal molecules was measured. The value of dielectric anisotropy was calculated from the equation of Δε = ε‖−ε⊥.

(11b) dielectric anisotropy (Δε; measured at 25 ° C.)
Negative dielectric anisotropy: The value of dielectric anisotropy was calculated from the equation of Δε = ε‖−ε⊥. The dielectric constants (ε‖ and ε⊥) were measured as follows.
1) Measurement of dielectric constant (‖): A solution of octadecyltriethoxysilane (0.16 mL) in ethanol (20 mL) was applied to a well-cleaned glass substrate. The glass substrate was rotated by a spinner and then heated at 150 ° C. for 1 hour. A sample was placed in a VA device in which the distance between two glass substrates (cell gap) was 4 μm, and this device was sealed with an adhesive cured with ultraviolet light. Sine waves (0.5 V, 1 kHz) were applied to this device, and after 2 seconds, the dielectric constant (‖) in the major axis direction of liquid crystal molecules was measured.
2) Measurement of dielectric constant (ε⊥): A polyimide solution was applied to a well-cleaned glass substrate. After firing the glass substrate, the obtained alignment film was rubbed. The sample was placed in a TN device in which the distance between two glass substrates (cell gap) was 9 μm and the twist angle was 80 degrees. Sine waves (0.5 V, 1 kHz) were applied to this device, and after 2 seconds, the dielectric constant (⊥) in the minor axis direction of liquid crystal molecules was measured.

(12a) elastic constant (K; measured at 25 ° C .; pN)
Positive dielectric anisotropy: An HP4284A LCR meter manufactured by Yokogawa-Hewlett-Packard Co. was used for measurement. The sample was placed in a horizontal alignment device in which the distance between two glass substrates (cell gap) was 20 μm. A charge of 0 to 20 volts was applied to the device, and the capacitance and the applied voltage were measured. The values of the measured capacitance (C) and the applied voltage (V) are calculated using the formula (2.98) and formula (2.101) on page 75 of “Liquid Crystal Device Handbook” (Nippon Kogyo Shimbun) Fitting was performed to obtain values of K ₁₁ and K ₃₃ from equation (2.99). Then the equation (3.18) on page 171, to calculate the _{K 22} using the values of _{K 11} and _{K 33} was determined previously. The elastic constant K was represented by the average value of K ₁₁ , K ₂₂ and K ₃₃ thus determined.

(12b) elastic constant (K ₁₁ and K ₃₃ ; measured at 25 ° C .; pN)
Negative dielectric anisotropy: For measurement, an EC-1 elastic modulus measuring device manufactured by Toyo Corporation was used. The sample was placed in a vertical alignment device in which the distance between two glass substrates (cell gap) was 20 μm. A charge of 20 volts to 0 volts was applied to the device, and the capacitance and the applied voltage were measured. The values of capacitance (C) and applied voltage (V) are fitted using the formula (2.98) and formula (2.101) shown on page 75 of “Liquid Crystal Device Handbook” (Nippon Kogyo Shimbun Ltd.) The value of the elastic constant was obtained from the equation (2.100).

(13a) Threshold voltage (Vth; measured at 25 ° C .; V)
Positive dielectric anisotropy: For measurement, an LCD 5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used. The light source was a halogen lamp. The sample was placed in a normally white mode TN device in which the distance between two glass substrates (cell gap) is 0.45 / Δn (μm) and the twist angle is 80 degrees. The voltage (32 Hz, rectangular wave) applied to this element was gradually increased by 0.02 V from 0 V to 10 V. At this time, the device was irradiated with light from the vertical direction, and the amount of light transmitted through the device was measured. A voltage-transmittance curve was created in which the transmittance was 100% when the light amount was maximum, and the transmittance was 0% when the light amount was minimum. The threshold voltage was represented by the voltage at 90% transmittance.

(13b) Threshold voltage (Vth; measured at 25 ° C .; V)
Negative dielectric anisotropy: For measurement, an LCD 5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used. The light source was a halogen lamp. A sample is placed in a normally black mode VA device in which the distance between two glass substrates (cell gap) is 4 μm and the rubbing direction is antiparallel, and an adhesive for curing this device with ultraviolet light is used. Used and sealed. The voltage (60 Hz, rectangular wave) applied to this element was gradually increased by 0.02 V from 0 V to 20 V. At this time, the device was irradiated with light from the vertical direction, and the amount of light transmitted through the device was measured. A voltage-transmittance curve was created in which the transmittance was 100% when the light amount was maximum, and the transmittance was 0% when the light amount was minimum. The threshold voltage was represented by the voltage at 10% transmittance.

(14a) Response time (τ; measured at 25 ° C; ms)
Positive dielectric anisotropy: For measurement, an LCD 5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used. The light source was a halogen lamp. The low pass filter (Low-pass filter) was set to 5 kHz. The sample was placed in a normally white mode TN device in which the distance between two glass substrates (cell gap) was 5.0 μm and the twist angle was 80 degrees. A rectangular wave (60 Hz, 5 V, 0.5 seconds) was applied to this element. At this time, the device was irradiated with light from the vertical direction, and the amount of light transmitted through the device was measured. It was considered that the transmittance was 100% when the light amount was maximum, and the transmittance was 0% when the light amount was minimum. The rise time (τr: millisecond) is the time taken for the transmittance to change from 90% to 10%. The fall time (τf: milliseconds) is the time taken to change from 10% transmission to 90% transmission. The response time is represented by the sum of the rise time and the fall time obtained in this manner.

(14b) Response time (τ; measured at 25 ° C; ms)
Negative dielectric anisotropy: For measurement, an LCD 5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used. The light source was a halogen lamp. The low pass filter (Low-pass filter) was set to 5 kHz. A sample is placed in a normally black mode PVA element in which the distance between two glass substrates (cell gap) is 3.2 μm and the rubbing direction is antiparallel, and the element is cured with ultraviolet light Sealed with an agent. A voltage slightly higher than the threshold voltage was applied to the device for 1 minute, and then ultraviolet light of 23.5 mW / cm ² was applied for 8 minutes while applying a voltage of 5.6 V. A rectangular wave (60 Hz, 10 V, 0.5 seconds) was applied to this element. At this time, the device was irradiated with light from the vertical direction, and the amount of light transmitted through the device was measured. It was considered that the transmittance was 100% when the light amount was maximum, and the transmittance was 0% when the light amount was minimum. The response time is represented by the time (fall time; milliseconds) taken to change from 90% transmittance to 10% transmittance.

Example 1
Synthesis of Compound (No. 1)

Step 1 Under nitrogen atmosphere, compound (T-1) (10.0 g, 40.3 mmol) and tetrabutylammonium bromide (TBAB) (0.2 g, 18.4 mmol) in concentrated hydrobromic acid (100 ml) In addition, it was heated to reflux for 1 hour. The reaction mixture was allowed to warm to 25 ° C. and poured into ice water (100 ml). After adding zinc powder, filtration was performed. The filtrate was concentrated to give compound (T-2) (7.7 g, 40.3 mmol, 100.0%).

Second Step Methacrylic acid (15.3 g, 177.2 mmol), dicyclohexylcarbodiimide (DCC) (36.6 g, 177.2 mmol), and N, N-dimethyl-4-aminopyridine (DMAP) (4) under nitrogen atmosphere .9 g (40.3 mmol) was dissolved in toluene (200 ml) under ice-cooling. To this solution was added dropwise a solution of compound (T-2) (7.7 g, 40.3 mmol) in toluene (30 ml) under ice-cooling, and the mixture was stirred at 25 ° C. for 16 hours. After completion of the reaction, the resulting insolubles were filtered, the filtrate was extracted with toluene, and the combined organic layer was washed successively with water and saturated aqueous sodium chloride solution, and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene: ethyl acetate = 10: 1). Further, purification was conducted by recrystallization from a mixed solvent of heptane and ethyl acetate (volume ratio, 9: 1) to obtain a compound (No. 1) (11.8 g, 25.5 mmol, 63.2%).

¹ H-NMR (CDCl ₃ ; δ ppm): 7.84 (d, 2 H), 7.48 (m, 2 H), 6.50 (d, 2 H), 6.35 (d, 2 H), 5. 88-5.87 (m, 2H), 5.78-5.77 (m, 2H), 2.13 (s, 6H), 2.06 (s, 6H).

  Physical properties of compound (No. 1) were as described below. Melting point: 160.4 ° C., polymerization initiation temperature: 167 ° C.

Example 2
Synthesis of Compound (No. 51)

Step 1 Under nitrogen atmosphere, the compound (T-3) (5.0 g, 27.7 mmol) was dissolved in dioxane (60 ml). Thereto was added 12 M hydrochloric acid (90 ml). After stirring for 1 hour at 25 ° C., the reaction mixture is poured into water (100 ml). After filtering the precipitate, the filtrate was extracted with dimethyl ether. The combined organic layer was washed successively with water, saturated aqueous sodium hydrogen carbonate solution and saturated aqueous sodium chloride solution, and dried over anhydrous magnesium sulfate. The solution is concentrated under reduced pressure, and the residue is purified by silica gel chromatography (volume ratio, heptane: ethyl acetate = 7: 3) to give compound (T-4) (3.4 g, 10.6 mmol, 76.3) %) Got.

Second Step Under a nitrogen atmosphere, compound (T-4) (3.4 g, 10.6 mmol) was dissolved in dichloromethane (35 ml). After cooling to −60 ° C., boron tribromide (11.9 g, 47.7 mmol) was added dropwise at a temperature range of −60 ° C. to −50 ° C., and stirred for an additional hour. The reaction mixture was allowed to warm to 25 ° C. and then stirred for additional 16 hours. The reaction mixture was then poured into water (100 ml). After extraction with ethyl acetate, the combined organic layers were washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure to give compound (T-5) (2.8 g, 10.3 mmol, 97.2%).

Third Step Methacrylic acid (3.9 g, 45.3 mmol), dicyclohexylcarbodiimide (DCC) (9.4 g, 45.3 mmol), and N, N-dimethyl-4-aminopyridine (DMAP) (1 under nitrogen atmosphere) .3 g (10.3 mmol) was dissolved in toluene (100 ml) under ice-cooling. To this solution was added dropwise a solution of compound (T-5) (2.8 g, 10.3 mmol) in toluene (20 ml) under ice-cooling, and the mixture was stirred at 25 ° C. for 16 hours. After completion of the reaction, the resulting insolubles were filtered, the filtrate was extracted with toluene, and the combined organic layer was washed successively with water and saturated aqueous sodium chloride solution, and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene: ethyl acetate = 10: 1). Furthermore, purification by recrystallization from a mixed solvent of heptane and ethyl acetate (volume ratio, 9: 1) gave a compound (No. 51) (3.9 g, 7.3 mmol, 70.6%).

¹ H-NMR (CDCl ₃ ; δ ppm): 7.87 (d, 1 H), 7.80 (s, 1 H), 7.65 (d, 1 H), 7.52 to 7.49 (m, 1 H) ), 7.46-7.42 (m, 1 H), 7.37-7. 35 (m, 1 H), 7. 28-7. 24 (m, 2 H), 6.32 (s, 2 H), 6.28 (s, 1 H), 6.08 (s, 1 H), 5.75-5.74 (m, 2 H), 5.72 (m, 1 H), 5.59 (m, 1 H), 2 .04 (s, 3 H), 2.03 (s, 3 H), 2.00 (s, 3 H), 1.86 (s, 3 H).

  Physical properties of compound (No. 51) were as described below. Liquid at normal temperature, polymerization initiation temperature: 248 ° C.

[Example 3]
Synthesis of Compound (No. 151)

Step 1 Compound (T-6) (5.0 g, 30.8 mmol), Compound (T-7) (9.0 g, 33.9 mmol), triethylamine (9.4 g, 92.5 mmol) under a nitrogen atmosphere Copper iodide (0.6 g, 3.1 mmol), bistriphenylphosphine palladium dichloride (1.1 g, 1.5 mmol) were dissolved in DMF (60 ml). The reaction mixture was heated to 81 ° C. and stirred for 16 hours. The reaction mixture was allowed to return to 25 ° C. and then poured into water (100 ml). After extraction with dichloromethane, the combined organic layer was washed successively with aqueous ammonium chloride solution and water, and dried over anhydrous magnesium sulfate. The solution is concentrated under reduced pressure, and the residue is purified by silica gel chromatography (volume ratio, cyclohexane: ethyl acetate = 5: 1) to give compound (T-8) (7.6 g, 25.5 mmol, 82.6) %) Got.

Second Step Under a nitrogen atmosphere, compound (T-8) (7.6 g, 25.5 mmol) was dissolved in a mixed solvent of toluene (40 ml) and IPA (40 ml). Further, Pd / C (0.40 g) was added, and the mixture was stirred at room temperature under a hydrogen atmosphere until hydrogen was not absorbed. After completion of the reaction, Pd / C was removed and the solvent was distilled off. The residue was purified by silica gel chromatography (volume ratio, cyclohexane: ethyl acetate = 5: 1) to give compound (T-9) (7.7 g, 25.4 mmol, 99.8%).

Third Step In a nitrogen atmosphere, bistrifluoroacetoxyiodobenzene (13.1 g, 30.5 mmol) and boron trifluoride diethyl ether complex (8.3 g, 58.4 mmol) were dissolved in dichloromethane (200 ml). After cooling to −20 ° C., a dichloromethane solution (50 ml) of compound (T-9) (7.7 g, 25.4 mmol) was added dropwise at a temperature range of −20 ° C. to −15 ° C., and stirred for further 40 minutes. The reaction mixture was allowed to return to 25 ° C. and then poured into water (200 ml). After extraction with dichloromethane, the combined organic layers were washed with water and dried over anhydrous magnesium sulfate. The solution is concentrated under reduced pressure, and the residue is purified by recrystallization from a mixed solvent of heptane and ethyl acetate (volume ratio, 9: 1) to give compound (T-10) (6.0 g, 20.0 mmol , 78.9%).

Step 4 Under nitrogen atmosphere, the compound (T-10) (6.0 g, 20.0 mmol) was dissolved in dichloromethane (60 ml). After cooling to −60 ° C., boron tribromide (22.5 g, 90.0 mmol) was added dropwise at a temperature range of −60 ° C. to −50 ° C. and stirred for an additional hour. The reaction mixture was allowed to warm to 25 ° C. and then stirred for additional 16 hours. The reaction mixture was then poured into water (200 ml). After extraction with ethyl acetate, the combined organic layers were washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure to give compound (T-11) (4.8 g, 19.7 mmol, 98.5%).

Step 5 Methacrylic acid (7.5 g, 86.7 mmol), dicyclohexylcarbodiimide (DCC) (17.9 g, 86.7 mmol), and N, N-dimethyl-4-aminopyridine (DMAP) (2 0.2 g (19.7 mmol) was dissolved in toluene (200 ml) under ice-cooling. To this solution was added dropwise a solution of compound (T-11) (4.8 g, 19.7 mmol) in toluene (20 ml) under ice-cooling, and the mixture was stirred at 25 ° C. for 16 hours. After completion of the reaction, the resulting insolubles were filtered, the filtrate was extracted with toluene, and the combined organic layer was washed successively with water and saturated aqueous sodium chloride solution, and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene: ethyl acetate = 10: 1). Furthermore, purification by recrystallization from a mixed solvent of heptane and ethyl acetate (volume ratio, 9: 1) gave a compound (No. 151) (6.5 g, 12.5 mmol, 63.7%).

¹ H-NMR (CDCl ₃ ; δ ppm): 8.40 (s, 2 H), 7.80 (s, 2 H), 7.71 (s, 2 H), 6.36 (d, 4 H), 5. 79-5.77 (m, 4H), 2.07-2.06 (m, 12H).

Physical properties of compound (No. 151) were as described below. Melting point: 134.1 ° C., polymerization initiation temperature: 148 ° C.
Comparative Example 1

A comparison compound (R-1) was synthesized for comparison.

¹ H-NMR (DMSO-d; δ ppm): 7.24 (d, 4 H), 6.96 (d, 4 H), 6.41 (d, 2 H), 6.26 (d, 2 H), 1 .98 (s, 6H).

  Physical properties of compound (R-1) were as described below. Melting point: 150 ° C., polymerization initiation temperature: 152 ° C.

Example 4
Comparative Experiment 1-Unreacted Polymerizable Compound To a liquid crystal composition A described below, a polymerizable compound (No. 1) was added at a ratio of 0.3% by weight and dissolved. The polymerizable composition was irradiated with 75 mW / cm ² of ultraviolet light for 200 seconds (15,000 mJ). For irradiation with ultraviolet light, a mercury xenon lamp, EXECURE 4000-D manufactured by Hoya Candeo OPTRONICS Co., Ltd. was used. The amount of the polymerizable compound remaining in the obtained liquid crystal composite was measured by HPLC. The results of irradiation with ultraviolet light for 400 seconds (30,000 mJ) are also summarized in Table 1. On the other hand, the unreacted substance was similarly measured also about the comparison compound (R-2). The results are summarized in Table 1.

The components of the liquid crystal composition A were as follows.

  From Table 1, it can be seen that the amount of unreacted material remaining in the liquid crystal composite is small in the case of the compound (No. 1). Therefore, it is concluded that the polymerizable compound of the present invention has a higher conversion than conventional compounds.

[Example 5]
By referring to the experimental procedures described in Example 1 and “2. Synthesis method”, it is possible to synthesize a compound (No. 199) from the compound (No. 1) shown below.

2. Examples of Polymerizable Compositions The compounds in the examples are represented by symbols based on the definition of Table 2 below. In Table 2, the configuration for 1,4-cyclohexylene is trans. The numbers in parentheses after the symbols in the examples correspond to the numbers of the compounds. The symbol (-) means other liquid crystal compounds. The content (percentage) of the liquid crystal compound is a weight percentage (% by weight) based on the liquid crystal composition. Finally, the physical property values of the polymerizable composition were summarized. Physical properties were measured according to the method described above, and the measured values were described as they were (without extrapolation).

ＮＩ＝１００．８℃；Δｎ＝０．１９２；Δε＝８．２；η＝４１．０ｍＰａ・ｓ． [Example 6]
3-HB-O2 (13-5) 10%
5-HB-CL (2-2) 10%
3-HBB (F, F)-F (3-24) 10%
3-PyB (F) -F (2-15) 10%
5-PyB (F) -F (2-15) 10%
3-PyBB-F (3-80) 10%
4-PyBB-F (3-80) 10%
5-PyBB-F (3-80) 10%
5-HBB (F) B-2 (15-5) 10%
5-HBB (F) B-3 (15-5) 10%
The following compound (No. 1) was added to the above composition at a ratio of 0.3% by weight.

NI = 100.8 ° C .; Δn = 0.192; Δε = 8.2; = 4 = 41.0 mPa · s.

ＮＩ＝１００．５℃；Δｎ＝０．１００；Δε＝４．６；η＝１７．９ｍＰａ・ｓ． [Example 7]
2-HB-C (5-1) 5%
3-HB-C (5-1) 12%
3-HB-O2 (13-5) 15%
2-BTB-1 (13-10) 3%
3-HHB-F (3-1) 4%
3-HHB-1 (14-1) 8%
3-HHB-O1 (14-1) 5%
3-HHB-3 (14-1) 14%
3-HHEB-F (3-10) 4%
5-HHEB-F (3-10) 4%
2-HHB (F)-F (3-2) 7%
3-HHB (F) -F (3-2) 7%
5-HHB (F) -F (3-2) 7%
3-HHB (F, F)-F (3-3) 5%
The following compound (No. 51) was added to the above composition at a ratio of 0.25% by weight.

NI = 100.5 ° C .; Δn = 0.100; Δε = 4.6; = 1 = 17.9 mPa · s.

ＮＩ＝９７．８℃；Δｎ＝０．１１６；Δε＝９．０；η＝３５．０ｍＰａ・ｓ． [Example 8]
3-HHB (F, F)-F (3-3) 9%
3-H2HB (F, F) -F (3-15) 8%
4-H2HB (F, F)-F (3-15) 8%
5-H2HB (F, F) -F (3-15) 8%
3-HBB (F, F)-F (3-24) 21%
5-HBB (F, F)-F (3-24) 20%
3-H 2 BB (F, F)-F (3-27) 10%
5-HBBB (F, F)-F (4-6) 3%
5-HHEBB-F (4-17) 2%
3-HH2BB (F, F) -F (4-15) 3%
1O1-HBBH-4 (15-1) 4%
1O1-HBBH-5 (15-1) 4%
The following compound (No. 151) was added to the above composition at a ratio of 0.1% by weight.

NI = 97.8 ° C .; Δn = 0.116; Δε = 9.0; = 3 = 35.0 mPa · s.

ＮＩ＝８０．２℃；Δｎ＝０．１０３；Δε＝８．７；η＝２２．４ｍＰａ・ｓ． [Example 9]
5-HB-CL (2-2) 11%
3-HH-4 (13-1) 8%
3-HHB-1 (14-1) 5%
3-HHB (F, F)-F (3-3) 8%
3-HBB (F, F)-F (3-24) 20%
5-HBB (F, F)-F (3-24) 15%
3-HHEB (F, F)-F (3-12) 10%
4-HHEB (F, F)-F (3-12) 3%
5-HHEB (F, F)-F (3-12) 3%
2-HBEB (F, F)-F (3-39) 3%
3-HBEB (F, F)-F (3-39) 5%
5-HBEB (F, F)-F (3-39) 3%
3-HBBB (F, F)-F (4-6) 6%
The following compound (No. 102) was added to the above composition at a ratio of 0.3% by weight.

NI = 80.2 ° C .; Δn = 0.103; Δε = 8.7; = 2 = 22.4 mPa · s.

ＮＩ＝７９．４℃；Δｎ＝０．０６４；Δε＝５．７；η＝１９．９ｍＰａ・ｓ． [Example 10]
5-HB-CL (2-2) 3%
7-HB (F) -F (2-3) 7%
3-HH-4 (13-1) 9%
3-HH-EMe (13-2) 23%
3-HHEB-F (3-10) 8%
5-HHEB-F (3-10) 8%
3-HHEB (F, F)-F (3-12) 10%
4-HHEB (F, F)-F (3-12) 5%
4-HGB (F, F)-F (3-103) 5%
5-HGB (F, F)-F (3-103) 6%
2-H 2 GB (F, F)-F (3-106) 4%
3-H 2 GB (F, F)-F (3-106) 5%
5-GHB (F, F)-F (3-109) 7%
The following compound (No. 1) was added to the above composition at a ratio of 0.2% by weight.

NI = 79.4 ° C .; Δn = 0.064; Δε = 5.7; = 1 = 19.9 mPa · s.

ＮＩ＝８６．５℃；Δｎ＝０．０９０；Δε＝−３．４；η＝３５．３ｍＰａ・ｓ． [Example 11]
3-HB-O1 (13-5) 15%
3-HH-4 (13-1) 5%
3-HB (2F, 3F) -O2 (6-1) 12%
5-HB (2F, 3F)-O2 (6-1) 12%
2-HHB (2F, 3F) -1 (7-1) 12%
3-HHB (2F, 3F) -1 (7-1) 12%
3-HHB (2F, 3F) -O2 (7-1) 13%
5-HHB (2F, 3F) -O2 (7-1) 13%
3-HHB-1 (14-1) 6%
The following compound (No. 51) was added to the above composition at a ratio of 0.4% by weight.

NI = 86.5 ° C .; Δn = 0.090; Δε = −3.4; = 3 = 35.3 mPa · s.

ＮＩ＝９１．５℃；Δｎ＝０．１００；Δε＝−４．１；η＝２９．２ｍＰａ・ｓ． [Example 12]
3-HH-4 (13-1) 8%
3-H 2 B (2F, 3F) -O 2 (6-4) 22%
5-H2B (2F, 3F) -O2 (6-4) 22%
2-HHB (2F, 3CL) -O2 (7-12) 2%
3-HHB (2F, 3CL) -O2 (7-12) 3%
4-HHB (2F, 3CL) -O2 (7-12) 2%
5-HHB (2F, 3CL) -O2 (7-12) 2%
3-HBB (2F, 3F) -O2 (7-7) 9%
5-HBB (2F, 3F) -O2 (7-7) 9%
V-HHB-1 (14-1) 6%
3-HHB-3 (14-1) 6%
3-HHEBH-3 (15-6) 3%
3-HHEBH-4 (15-6) 3%
3-HHEBH-5 (15-6) 3%
The following compound (No. 151) was added to the above composition at a ratio of 0.35% by weight.

NI = 91.5 ° C .; Δn = 0.100; Δε = −4.1; = 2 = 29.2 mPa · s.

ＮＩ＝７５．７℃；Δｎ＝０．０９３；Δε＝−４．１；η＝１９．２ｍＰａ・ｓ． [Example 13]
2-HH-5 (13-1) 3%
3-HH-4 (13-1) 15%
3-HH-5 (13-1) 4%
3-HB-O2 (13-5) 12%
3-H 2 B (2F, 3F) -O 2 (6-4) 15%
5-H2B (2F, 3F) -O2 (6-4) 15%
3-HHB (2F, 3CL) -O2 (7-12) 5%
2-HBB (2F, 3F) -O2 (7-7) 3%
3-HBB (2F, 3F) -O2 (7-7) 9%
5-HBB (2F, 3F) -O2 (7-7) 9%
3-HHB-1 (14-1) 3%
3-HHB-3 (14-1) 4%
3-HHB-O1 (14-1) 3%
The following compound (No. 102) was added to the above composition at a rate of 0.15% by weight.

NI = 75.7 ° C .; Δn = 0.093; Δε = −4.1; = 1 = 19.2 mPa · s.

ＮＩ＝７４．３℃；Δｎ＝０．０９７；Δε＝−３．２；η＝１５．３ｍＰａ・ｓ． Example 14
2-HH-3 (13-1) 21%
3-HH-4 (13-1) 9%
1-BB-3 (13-8) 9%
3-HB-O2 (13-5) 2%
3-BB (2F, 3F) -O2 (6-3) 9%
5-BB (2F, 3F)-O2 (6-3) 6%
2-HH1OB (2F, 3F) -O2 (7-5) 13%
3-HH1OB (2F, 3F) -O2 (7-5) 21%
3-HHB-1 (14-1) 5%
3-HHB-O1 (14-1) 3%
5-B (F) BB-2 (14-6) 2%
The following compound (No. 1) was added to the above composition at a ratio of 0.25% by weight.

NI = 74.3 ° C; Δn = 0.097; Δε = -3.2; η = 15.3 mPa · s.

ＮＩ＝８２．０℃；Δｎ＝０．１０６；Δε＝−２．６；η＝２４．８ｍＰａ・ｓ． [Example 15]
2-HH-3 (13-1) 16%
7-HB-1 (13-5) 10%
5-HB-O2 (13-5) 8%
3-HB (2F, 3F) -O2 (6-1) 12%
5-HB (2F, 3F)-O2 (6-1) 16%
3-HHB (2F, 3CL) -O2 (7-12) 3%
4-HHB (2F, 3CL) -O2 (7-12) 3%
5-HHB (2F, 3CL) -O2 (7-12) 2%
3-HH1OCro (7F, 8F) -5 (9-3) 5%
5-HBB (F) B-2 (15-5) 10%
5-HBB (F) B-3 (15-5) 10%
3-HD h B (2F, 3F)-O2 (7-3) 5%
The following compound (No. 51) was added to the above composition at a ratio of 0.3% by weight.

NI = 82.0 ° C .; Δn = 0.106; Δε = −2.6; = 2 = 24.8 mPa · s.

ＮＩ＝７４．５℃；Δｎ＝０．１０６；Δε＝−３．０；η＝１４．７ｍＰａ・ｓ． [Example 16]
1-BB-3 (13-8) 10%
3-HH-V (13-1) 29%
3-BB (2F, 3F)-O2 (6-3) 13%
2-HH1OB (2F, 3F) -O2 (7-5) 20%
3-HH1OB (2F, 3F) -O2 (7-5) 14%
3-HHB-1 (14-1) 8%
5-B (F) BB-2 (14-8) 6%
The following compound (No. 151) was added to the above composition at a ratio of 0.3% by weight.

NI = 74.5 ° C .; Δn = 0.106; Δε = −3.0; = 1 = 14.7 mPa · s.

ＮＩ＝８０．６℃；Δｎ＝０．１３１；Δε＝７．７；η＝１２．４ｍＰａ・ｓ． [Example 17]
1V2-BEB (F, F) -C (5-13) 8%
3-HB-C (5-1) 16%
2-BTB-1 (13-10) 10%
5-HH-VFF (13-1) 30%
3-HHB-1 (14-1) 4%
VFF-HHB-1 (14-1) 8%
VFF2-HHB-1 (14-1) 11%
3-H 2 BTB-2 (14-17) 5%
3-H 2 BTB-3 (14-17) 4%
3-H2BTB-4 (14-17) 4%
The following compounds (No. 1) and (No. 102) were each added to the above composition at a ratio of 0.2% by weight.

NI = 80.6 ° C .; Δn = 0.131; Δε = 7.7; = 1 = 12.4 mPa · s.

ＮＩ＝８１．９℃；Δｎ＝０．１０５；Δε＝６．３；η＝１２．０ｍＰａ・ｓ． [Example 18]
5-HB (F) B (F, F) X B (F, F)-F (4-41) 5%
3-BB (F) B (F, F) X B (F, F)-F (4-47) 3%
4-BB (F) B (F, F) X B (F, F)-F (4-47) 7%
5-BB (F) B (F, F) X B (F, F)-F (4-47) 3%
3-HH-V (13-1) 41%
3-HH-V1 (13-1) 7%
3-HHEH-5 (14-13) 3%
3-HHB-1 (14-1) 4%
V-HHB-1 (14-1) 5%
V2-BB (F) B-1 (14-6) 5%
1V2-BB-F (2-1) 3%
3-BB (F, F) XB (F, F) -F (3-97) 11%
3-HBBB (F, F)-F (4-6) 3%
The following compound (No. 51) was added to the above composition at a ratio of 0.3% by weight.

NI = 81.9 ° C .; Δn = 0.105; Δε = 6.3; = 1 = 12.0 mPa · s.

ＮＩ＝８１．３℃；Δｎ＝０．１０３；Δε＝７．４；η＝１２．８ｍＰａ・ｓ． [Example 19]
3-GB (F) B (F, F) XB (F, F)-F (4-57) 5%
3-BB (F) B (F, F) X B (F, F)-F (4-47) 3%
4-BB (F) B (F, F) X B (F, F)-F (4-47) 7%
5-BB (F) B (F, F) X B (F, F)-F (4-47) 3%
3-HH-V (13-1) 41%
3-HH-V1 (13-1) 7%
3-HHEH-5 (14-13) 3%
3-HHB-1 (14-1) 4%
V-HHB-1 (14-1) 5%
V2-BB (F) B-1 (14-6) 5%
1V2-BB-F (2-1) 3%
3-BB (F, F) XB (F, F) -F (3-97) 6%
3-GB (F, F) XB (F, F)-F (3-113) 5%
3-HBBB (F, F)-F (4-6) 3%
The following compound (No. 151) was added to the above composition at a ratio of 0.3% by weight.

NI = 81.3 ° C .; Δn = 0.103; Δε = 7.4; = 1 = 12.8 mPa · s.

  By polymerizing the polymerizable composition containing the compound (1) and the liquid crystal composition, a liquid crystal display device having a mode such as PSA can be produced. This polymerizable compound can also be used as a raw material of an optical anisotropic body.

Claims (11)

Equation (1-1) to (1-13) either one at a represented Ru of compounds of.

In formulas (1-1) to (1-13),
P ³ , P ⁴ , P ⁵ and P ⁶ are all the same and a group represented by formula (P-1), and in formula (P-1), M is hydrogen, fluorine, -CH ₃ , Or -CF ₃ ;

S ³ , S ⁴ , S ⁵ and S ^{6 each} independently represent a single bond or an alkylene having 1 to 6 carbon atoms, and in this alkylene, at least one —CH ₂ — is —O—, —COO— Or -OCO-, at least one -CH ₂ -CH ₂ -may be replaced by -CH = CH- or -C≡C-, and at least one hydrogen is fluorine or May be replaced by chlorine;
Z ⁵ and ^{Z 6} are each independently a single bond, -CO -, - COO -, - OCO -, - CH = CH -, - C≡C -, - CH = CH-COO -, - OCO-CH = _{CH -, - OCO-C (} CH 3) = CH -, - CO-CH = CH -, - CH = CH-CO -, - CH = CH-CH 2 O -, - OCH 2 -CH = CH-, -CH = CH-OCH ₂ -, or _-CH 2 OCH = CH-. In formulas (1-1) to (1-13), all of P ³ , P ⁴ , P ⁵ , and P ⁶ are —OCO—HC = CH ₂ or —OCO— (CH ₃ ) C = CH ₂ The compound according to claim 1 , wherein S ³ , S ⁴ , S ⁵ and S ⁶ are a single bond; and Z ⁵ and Z ⁶ are a single bond. The compound of Claim 1 represented by Formula (1-3-1 ) .

Oite the formula (1-3-1), all M ⁴ is the same from ^{M 1,} hydrogen, fluorine, -CH ₃ or -CF _3,. A polymer obtained from the compound according to any one of claims 1 to 3 . A liquid crystal composition comprising at least one selected from the group of polymers according to claim 4 . The liquid crystal composition according to claim 5 , further comprising at least one compound selected from the group of compounds represented by formulas (2) to (4).

In equations (2) to (4),
R ¹¹ is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and alkenyl, at least one hydrogen may be replaced by fluorine, and at least one —CH ₂ — is —O May be replaced by-;
X ¹¹ represents fluorine, chlorine, -OCF ₃ , -OCHF ₂ , -CF ₃ , -CHF ₂ , -CH ₂ F, -OCF ₂ CHF ₂ , or -OCF ₂ CHFCF ₃ ;
Ring B ¹ , ring B ² and ring B ³ are independently 1,4-cyclohexylene, 1,4-phenylene in which at least one hydrogen may be replaced by fluorine, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl or pyrimidine-2,5-diyl;
Z ^{11, Z 12} and ^{Z 13} are independently a single _{bond, -CH 2 CH 2 -, -} CH = CH -, - C≡C -, - COO -, - CF 2 O -, - OCF 2 -, -CH ₂ O-, or - _{(CH 2) 4} - a and;
L ¹¹ and L ¹² are independently hydrogen or fluorine. Further comprising at least one compound selected from the group of compounds represented by formula (5), the liquid crystal composition according to claim 5 or 6.

In equation (5),
R ¹² is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and alkenyl, at least one hydrogen may be replaced by fluorine, and at least one —CH ₂ — is —O May be replaced by-;
X ¹² is —C≡N or —C≡C—C≡N;
Ring C ¹ is 1,4-cyclohexylene, 1,4-phenylene in which at least one hydrogen may be replaced by fluorine, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl Or pyrimidine-2,5-diyl;
Z ¹⁴ is a single _{bond, -CH 2 CH 2 -, -} C≡C -, - COO -, - CF 2 O -, - OCF 2 -, or _-CH 2 O-;
L ¹³ and L ¹⁴ are independently hydrogen or fluorine;
i is 1, 2, 3 or 4; The liquid crystal composition according to any one of claims 5 to 7 , further comprising at least one compound selected from the group of compounds represented by formulas (6) to (12).

In equations (6) to (12),
R ¹³ and R ¹⁴ are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and alkenyl, at least one —CH ₂ — may be replaced by —O— Well, at least one hydrogen may be replaced by fluorine;
R ¹⁵ is hydrogen, fluorine, alkyl having 1 to 10 carbons, or alkenyl having 2 to 10 carbons, and in the alkyl and alkenyl, at least one —CH ₂ — may be replaced by —O— , At least one hydrogen may be replaced by fluorine;
S ¹¹ is hydrogen or methyl;
X is -CF _2- , -O-, or -CHF-;
Ring D ¹ , ring D ² , ring D ³ and ring D ⁴ are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4 in which at least one hydrogen may be replaced by fluorine -Phenylene, tetrahydropyran-2,5-diyl, or decahydronaphthalene-2,6-diyl;
Ring ^{D 5} and ring ^{D 6} are each independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, tetrahydropyran-2,5-diyl or decahydronaphthalene, 2,6 -Diyl;
^{Z 15, Z 16, Z 17} , and ^{Z 18} are independently a single _{bond, -CH 2 CH 2 -, -} COO -, - CH 2 O -, - OCF 2 -, or -OCF ₂ CH ₂ CH ₂ -And
L ¹⁵ and L ¹⁶ are independently fluorine or chlorine;
j, k, m, n, p, q, r and s are independently 0 or 1, and the sum of k, m, n and p is 1 or 2, q, r and s The sum of is 0, 1, 2 or 3 and t is 1, 2 or 3. The liquid crystal composition according to any one of claims 5 to 8 , further comprising at least one compound selected from the group of compounds represented by formulas (13) to (15).

In equations (13) to (15),
R ¹⁶ and R ¹⁷ are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in this alkyl or alkenyl, at least one —CH ₂ — may be replaced by —O— Well, at least one hydrogen may be replaced by fluorine;
Ring E ¹ , ring E ² , ring E ³ and ring E ⁴ are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,5-difluoro- 1,4-phenylene, or pyrimidine-2,5-diyl;
Z ^{19, Z 20} and ^{Z 21} are independently a single _{bond, -CH 2 CH 2 -, -} CH = CH -, - C≡C-, or -COO-. The composition according to any one of claims 5 to 9 , further comprising at least one of a polymerizable compound, an optically active compound, an antioxidant, an ultraviolet light absorber, a light stabilizer, a heat stabilizer, an antifoaming agent, a polymerization initiator, and a polymerization inhibitor. The liquid crystal composition according to any one of the above. A liquid crystal display device comprising the liquid crystal composition according to any one of claims 5 to 10 .