JP2016011346A - Polymerizable compound, polymerizable composition, and liquid crystal display element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymerizable compound having high polymerization reactivity, a high conversion rate, and high solubility with a liquid crystal composition, a polymerizable composition containing the compound, a liquid crystal composite prepared from the composition, and a liquid crystal display element having the composite.SOLUTION: The polymerizable compound has at least two polymerizable groups, in which at least one polymerizable group is acryloyloxy or methacryloyloxy, and at least one polymerizable group is represented by formula (P-1). The polymerizable composition contains the above compound. The liquid crystal composite is prepared from the above composition. The liquid crystal display element includes the composite. In formula (P-1), Rrepresents an alkyl group having 2 to 15 carbon atoms, in which at least one -CHCH- is replaced by -CH=CH- or -C≡C-, and at least one hydrogen in these groups may be replaced by halogen.

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, and a liquid crystal display device.

  The liquid crystal display element utilizes the optical anisotropy, dielectric anisotropy, etc. of the liquid crystal molecules in the liquid crystal composition. The classification based on the operation mode of the liquid crystal molecules includes 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 mode liquid crystal display element in which a polymer is combined with a liquid crystal composition 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. A polymer is generated in the liquid crystal composition by irradiating ultraviolet rays with a voltage applied between the electrodes to polymerize the polymerizable compound. By this method, a liquid crystal display element with reduced response time and improved image burn-in can be obtained.

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

JP 2012-18215 A JP 2013-14538 A

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

式（Ｐ−１）において、Ｒ^１は、少なくとも１つの−ＣＨ_２ＣＨ_２−が−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられた炭素数２から１５のアルキルであり、これらの基において少なくとも１つの水素は、ハロゲンで置き換えられてもよい。 The present invention provides a polymerizable compound having at least two polymerizable groups, wherein at least one polymerizable group is acryloyloxy or methacryloyloxy, and at least one polymerizable group is represented by the formula (P-1). The present invention relates to a compound, a polymerizable composition containing the polymerizable compound and a liquid crystal composition, a liquid crystal composite prepared from the polymerizable composition, and a liquid crystal display device having the liquid crystal composite.

In Formula (P-1), R ¹ is alkyl having 2 to 15 carbons in which at least one —CH ₂ CH ₂ — is replaced by —CH═CH— or —C≡C—, and these groups In which at least one hydrogen may be replaced by a halogen.

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

  Terms used in this specification are as follows. Liquid crystalline compounds include non-polymerizable compounds having a liquid crystal phase such as a nematic phase and a smectic phase, and liquid crystal compositions having no liquid crystal phase, such as maximum temperature, minimum temperature, viscosity, and dielectric anisotropy. It is a general term for non-polymerizable compounds that are mixed for the purpose of adjusting. This compound has a six-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. The polymerizable compound is a compound added to the composition for the purpose of forming a polymer. The polymerizable composition is a composition containing a polymerizable compound, for example, a mixture of a polymerizable compound, a liquid crystal composition, an additive, and the like. The liquid crystal composite is a composite formed by polymerization of this polymerizable composition. A liquid crystal display element is a general term for a liquid crystal display panel and a liquid crystal display module. The upper limit temperature of the nematic phase is a phase transition temperature of a nematic phase to an isotropic phase in a liquid crystal composition, a polymerizable composition, or a liquid crystal composite, and may be abbreviated as an 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 polymerize. Conversion is the weight ratio of reactant consumed by a chemical reaction to reactant.

  The liquid crystal composition is prepared by mixing a liquid crystal compound. The ratio (content) of the liquid crystal compound is expressed as a percentage by weight (% by weight) based on the weight of the liquid crystal composition. Additives such as an optically active compound, an antioxidant, an ultraviolet absorber, a light stabilizer, a heat stabilizer, an antifoaming agent, a polymerization initiator, and a polymerization inhibitor are added to this composition as necessary. The ratio (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 ratio of the liquid crystal compound. Weight parts per million (ppm) may be used. The ratio of the polymerization initiator and the polymerization inhibitor is 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. Compound (1) means one compound or two or more compounds represented by 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 respectively correspond to the ring A ¹ , the ring B ¹ , the ring C ^{1, and the} like. In formula (1), the diagonal line across the circle means that the P ² —S ² group can arbitrarily select the bonding position on the ring. This rule also applies to such ^P 3 -S ³ group. This rule also applies to diagonal lines that cross a six-membered ring such as formula (1-1). In the formula (1), a subscript such as a1 represents the number of groups bonded to the ring A ¹ or the like. When a1 is 2, there are two ^P 2 -S ² group on the ring ^{A 1.} The two groups represented by the two P ² -S ² groups may be the same or different. This rule also applies when a1 is greater than 2. This rule also applies to other groups. The symbol R ¹¹ is used in a plurality of formulas such as formula (2) and formula (3). In these compounds, the two end groups represented by any two R ¹¹ may be the same or different. In equation (8), when i is 2, two symbols D ¹ exist in one equation. In this compound, the two rings represented by two symbols D ¹ may be the same or different. This rule also applies to symbols such as Z ^17.

The expression “at least one 'A' may be replaced by 'B'” means that when the number of 'A' is one, the position of 'A' is arbitrary and the number of 'A' is 2 Even more than one means that their position can be selected without limitation. The expression “at least one A may be replaced by B, C or D” means that at least one A is replaced by B, at least one A is replaced by C, and at least one A Is replaced with D, it means that a plurality of A are further 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 Alkenyl and alkenyloxyalkyl are included. Note that it is not preferable that two consecutive —CH ₂ — are replaced by —O— to form —O—O—. In alkyl and the like, it is not preferable that —CH ₂ — in the methyl moiety (—CH ₂ —H) is replaced by —O— to become —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（Ｐ−１）において、Ｒ^１は、少なくとも１つの−ＣＨ_２ＣＨ_２−が−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられた炭素数２から１５のアルキルであり、これらの基において少なくとも１つの水素は、ハロゲンで置き換えられてもよい。 Item 1. A polymerizable compound having at least two polymerizable groups, wherein at least one polymerizable group is acryloyloxy or methacryloyloxy, and at least one polymerizable group is represented by formula (P-1).

In Formula (P-1), R ¹ is alkyl having 2 to 15 carbons in which at least one —CH ₂ CH ₂ — is replaced by —CH═CH— or —C≡C—, and these groups In which at least one hydrogen may be replaced by a halogen.

式（１）において、
Ｐ^１、（ｂ１×ａ１）個のＰ^２、（ｂ２×ａ２）個のＰ^３、（ｂ３×ａ３）個のＰ^４、ａ４個のＰ^５、およびＰ^６は重合性基であり、これらの重合性基のうちの少なくとも１つは、アクリロイルオキシまたはメタクリロイルオキシであり、残りの少なくとも１つは、式（Ｐ−１）で表される重合性基であり；

式（Ｐ−１）において、Ｒ^１は炭素数２から１５のアルケニルまたは炭素数２から１５のアルキニルであり、これらの基において少なくとも１つの水素は、ハロゲンで置き換えられてもよく；
Ｓ^１、Ｓ^２、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１０のアルキレンであり、このアルキレンにおいて、少なくとも１つの−ＣＨ_２−は、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、または−ＯＣＯＯ−で置き換えられてもよく、少なくとも１つの−ＣＨ_２−ＣＨ_２−は、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、これらの基において少なくとも１つの水素は、ハロゲンで置き換えられてもよく；
ａ１、ａ２、ａ３、およびａ４は独立して、０、１、２、３、または４であり、ａ１、ａ２、ａ３、およびａ４の和は０から１０の整数であり；
環Ａ^１、環Ａ^２、環Ａ^３、および環Ａ^４は独立して、１，４−フェニレン、ピリミジン−２，５−ジイル、ピリジン−２，５−ジイル、ナフタレン−１，２−ジイル、ナフタレン−１，３−ジイル、ナフタレン−１，４−ジイル、ナフタレン−１，５−ジイル、ナフタレン−１，６−ジイル、ナフタレン−１，７−ジイル、ナフタレン−１，８−ジイル、ナフタレン−２，３−ジイル、ナフタレン−２，６−ジイル、ナフタレン−２，７−ジイル、１，４−シクロへキシレン、１，４−シクロヘキセニレン、テトラヒドロピラン−２，５−ジイル、または１，３−ジオキサン−２，５−ジイルであり、これらの環において、少なくとも１つの水素は、ハロゲンまたは炭素数１から１２のアルキルで置き換えられてもよく、このアルキルにおいて１つまたは２つの−ＣＨ_２−は、−Ｏ−で置き換えられてもよく、これらの基において少なくとも１つの水素はハロゲンで置き換えられてもよく；
Ｚ^１、Ｚ^２およびＺ^３は独立して、単結合または炭素数１から１０のアルキレンであり、このアルキレンにおいて、少なくとも１つの−ＣＨ_２−は、−Ｏ−、−ＣＯ−、−ＣＯＯ−、または−ＯＣＯ−で置き換えられてもよく、少なくとも１つの−ＣＨ_２−ＣＨ_２−は、−ＣＨ＝ＣＨ−、−Ｃ（ＣＨ_３）＝ＣＨ−、−ＣＨ＝Ｃ（ＣＨ_３）−、または−Ｃ（ＣＨ_３）＝Ｃ（ＣＨ_３）−で置き換えられてもよく、これらの基において少なくとも１つの水素は、ハロゲンで置き換えられてもよく；
ｂ１、ｂ２およびｂ３は独立して、０または１であり；
ここで、ａ１、ａ２、ａ３、およびａ４の和が２から１０の整数の場合には、−Ｓ^１−Ｐ^１および−Ｓ^６−Ｐ^６の一方または両方は、水素であってもよい。 Item 2. Item 2. The polymerizable compound according to item 1, represented by formula (1).

In equation (1),
P ¹ , (b1 × a1) P ² , (b2 × a2) P ³ , (b3 × a3) P ⁴ , a4 P ⁵ , and P ⁶ are polymerizable groups, At least one of the polymerizable groups is an acryloyloxy or methacryloyloxy, and the remaining at least one is a polymerizable group represented by the formula (P-1);

In formula (P-1), R ¹ is alkenyl having 2 to 15 carbons or alkynyl having 2 to 15 carbons, and in these groups, at least one hydrogen may be replaced by halogen;
S ¹ , S ² , S ³ , S ⁴ , S ⁵ , and S ⁶ are each independently a single bond or alkylene having 1 to 10 carbons, in which at least one —CH ₂ — is — O—, —COO—, —OCO—, or —OCOO— may be substituted, and at least one —CH ₂ —CH ₂ — may be substituted with —CH═CH— or —C≡C—. Well, in these groups at least one hydrogen may be replaced by a halogen;
a1, a2, a3, and a4 are independently 0, 1, 2, 3, or 4, and the sum of a1, a2, a3, and a4 is an integer from 0 to 10;
Ring A ¹ , Ring A ² , Ring A ³ , and Ring A ⁴ are independently 1,4-phenylene, pyrimidine-2,5-diyl, pyridine-2,5-diyl, naphthalene-1,2-diyl. , Naphthalene-1,3-diyl, naphthalene-1,4-diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene -2,3-diyl, naphthalene-2,6-diyl, naphthalene-2,7-diyl, 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, or 1 , 3-dioxane-2,5-diyl, in which at least one hydrogen may be replaced by halogen or alkyl of 1 to 12 carbons, Wherein one or two —CH ₂ — may be replaced by —O—, in which at least one hydrogen may be replaced by a halogen;
Z ¹ , Z ² and Z ³ are each independently a single bond or alkylene having 1 to 10 carbon atoms, and in this alkylene, at least one —CH ₂ — is —O—, —CO—, —COO—. is, -CH = _CH - -, - or -OCO- may be replaced by at least one _{-CH 2 -CH 2, C (CH} 3) = CH -, - CH = C (CH 3) -, or _{-C (CH 3) = C (} CH 3) - may be replaced by at least one hydrogen in these groups may be replaced by halogen;
b1, b2 and b3 are independently 0 or 1;
Here, in the case of a1, a2, a3, and the integer sum of 2 to 10 a4, one or both ^-S 1 -P ¹ and ^-S 6 -P ⁶ may be hydrogen.

式（Ｐ−２）および（Ｐ−３）において、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、およびＲ^８は水素、フッ素、塩素、または炭素数１から１０のアルキルであり、このアルキルにおいて少なくとも１つの−ＣＨ_２ＣＨ_２−は−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、これらの基において少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；
Ｓ^１、Ｓ^２、Ｓ^３、Ｓ^４、Ｓ^５、およびＳ^６が独立して、単結合または炭素数１から１０のアルキレンであり、このアルキレンにおいて、１つの−ＣＨ_２−は、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、または−ＯＣＯＯ−で置き換えられてもよく、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、フッ素または塩素で置き換えられてもよく；
ａ１、ａ２、ａ３、およびａ４が独立して、０、１、２、または３であり、ａ１、ａ２、ａ３、およびａ４の和は０から６の整数であり；
環Ａ^１、環Ａ^２、環Ａ^３、および環Ａ^４が独立して、１，４−フェニレン、ピリミジン−２，５−ジイル、ピリジン−２，５−ジイル、ナフタレン−１，４−ジイル、ナフタレン−１，５−ジイル、ナフタレン−２，６−ジイル、１，４−シクロへキシレン、テトラヒドロピラン−２，５−ジイル、または１，３−ジオキサン−２，５−ジイルであり、これらの環において、少なくとも１つの水素は、フッ素、塩素、炭素数１から３のアルキル、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から３のアルキルで置き換えられてもよく；
Ｚ^１、Ｚ^２およびＺ^３が独立して、単結合、炭素数１から５のアルキレン、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−Ｃ（ＣＨ_３）＝ＣＨ−ＣＯＯ−、−ＯＣＯ−ＣＨ＝Ｃ（ＣＨ_３）−、−ＣＨ＝Ｃ（ＣＨ_３）−ＣＯＯ−、−ＯＣＯ−（ＣＨ_３）Ｃ＝ＣＨ−、−Ｃ（ＣＨ_３）＝Ｃ（ＣＨ_３）−ＣＯＯ−、−ＯＣＯ−Ｃ（ＣＨ_３）＝Ｃ（ＣＨ_３）−、−ＣＯ−ＣＨ＝ＣＨ−、−ＣＨ＝ＣＨ−ＣＯ−、−Ｃ（ＣＨ_３）＝Ｃ（ＣＨ_３）−、−ＣＨ＝ＣＨ−ＣＨ_２Ｏ−、−ＯＣＨ_２−ＣＨ＝ＣＨ−、−ＣＨ＝ＣＨ−ＯＣＨ_２−、または−ＣＨ_２Ｏ−ＣＨ＝ＣＨ−であり；
ｂ１、ｂ２およびｂ３が独立して、０または１であり；
ここで、−Ｓ^１−Ｐ^１および−Ｓ^６−Ｐ^６の一方または両方は、水素であってもよい、項２に記載の重合性化合物。 Item 3. In Formula (1) according to Item 2, at least one of P ¹ , P ² , P ³ , P ⁴ , P ⁵ , and P ⁶ is acryloyloxy or methacryloyloxy, and the remaining at least one polymerizable group The formula (P-1) is a polymerizable group represented by the formula (P-2) or (P-3);

In the formulas (P-2) and (P-3), R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R ⁸ are hydrogen, fluorine, chlorine, or alkyl having 1 to 10 carbons And in this alkyl at least one —CH ₂ CH ₂ — may be replaced by —CH═CH— or —C≡C—, in which at least one hydrogen is replaced by fluorine or chlorine. May be;
S ¹ , S ² , S ³ , S ⁴ , S ⁵ , and S ⁶ are each independently a single bond or alkylene having 1 to 10 carbons, in which one —CH ₂ — represents —O -, - COO -, - OCO- , or -OCOO- may be replaced by one of _-CH 2 -CH ₂ - may be replaced by -CH = CH- or -C≡C-, At least one hydrogen may be replaced by fluorine or chlorine;
a1, a2, a3, and a4 are independently 0, 1, 2, or 3, and the sum of a1, a2, a3, and a4 is an integer from 0 to 6;
Ring A ¹ , Ring A ² , Ring A ³ , and Ring A ⁴ are independently 1,4-phenylene, pyrimidine-2,5-diyl, pyridine-2,5-diyl, naphthalene-1,4-diyl , Naphthalene-1,5-diyl, naphthalene-2,6-diyl, 1,4-cyclohexylene, tetrahydropyran-2,5-diyl, or 1,3-dioxane-2,5-diyl, these Wherein at least one hydrogen may be replaced by fluorine, chlorine, alkyl having 1 to 3 carbons, or alkyl having 1 to 3 carbons in which at least one hydrogen is replaced by fluorine or chlorine;
Z ¹ , Z ² and Z ³ are each independently a single bond, alkylene having 1 to 5 carbons, —CO—, —COO—, —OCO—, —CH═CH—, —CH═CH—COO—, _{-OCO-CH = CH -, -} C (CH 3) = CH-COO -, - OCO-CH = C (CH 3) -, - CH = C (CH 3) -COO -, - OCO- (CH 3 _{) C = CH -, - C} (CH 3) = C (CH 3) -COO -, - OCO-C (CH 3) = C (CH 3) -, - CO-CH = CH -, - CH = CH _{-CO -, - C (CH 3} ) = C (CH 3) -, - CH = CH-CH 2 O -, - OCH 2 -CH = CH -, - CH = CH-OCH 2 -, or -CH ₂ O—CH═CH—;
b1, b2 and b3 are independently 0 or 1;
The polymerizable compound according to Item 2, wherein one or both of -S ¹ -P ¹ and -S ⁶ -P ⁶ may be hydrogen.

式（１−１）において、
Ｐ^７、（ｄ１×ｃ１）個のＰ^８、（ｄ２×ｃ２）個のＰ^９、（ｄ３×ｃ３）個のＰ^１０、ｃ４個のＰ^１１、およびＰ^１２は重合性基であり、これらの重合性基の少なくとも１つは、アクリロイルオキシまたはメタクリロイルオキシであり、残りの少なくとも１つは、ビニルオキシカルボニル、１−プロペニルオキシカルボニル、２−プロペニルオキシカルボニル、２−メチル−２−プロペニルオキシカルボニル、２−ブテニルオキシカルボニル、または３−メチル−２−ブテニルオキシカルボニルであり；
Ｓ^７、Ｓ^８、Ｓ^９、Ｓ^１０、Ｓ^１１、およびＳ^１２は独立して、単結合または炭素数１から５のアルキレンであり、このアルキレンにおいて、１つの−ＣＨ_２−は、−Ｏ−、−ＣＯＯ−、または−ＯＣＯ−で置き換えられてもよく、１つの−ＣＨ_２−ＣＨ_２−は、−ＣＨ＝ＣＨ−で置き換えられてもよく；
ｃ１、ｃ２、ｃ３、およびｃ４は独立して、０、１または２であり、ｃ１、ｃ２、ｃ３、およびｃ４の和は０から５の整数であり；
環Ａ^５、環Ａ^６、環Ａ^７、および環Ａ^８は独立して、１，４−フェニレン、ピリミジン−２，５−ジイル、ピリジン−２，５−ジイル、１，４−シクロへキシレン、１，４−シクロヘキセニレン、テトラヒドロピラン−２，５−ジイル、または１，３−ジオキサン−２，５−ジイルであり、これらの環において、少なくとも１つの水素は、フッ素、塩素、炭素数１から３のアルキル、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から３のアルキルで置き換えられてもよく；
Ｚ^４、Ｚ^５およびＺ^６は独立して、単結合、炭素数１から５のアルキレン、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−Ｃ（ＣＨ_３）＝ＣＨ−ＣＯＯ−、−ＯＣＯ−ＣＨ＝Ｃ（ＣＨ_３）−、−ＣＨ＝Ｃ（ＣＨ_３）−ＣＯＯ−、−ＯＣＯ−（ＣＨ_３）Ｃ＝ＣＨ−、−Ｃ（ＣＨ_３）＝Ｃ（ＣＨ_３）−ＣＯＯ−、−ＯＣＯ−Ｃ（ＣＨ_３）＝Ｃ（ＣＨ_３）−、−ＣＯ−ＣＨ＝ＣＨ−、−ＣＨ＝ＣＨ−ＣＯ−、−Ｃ（ＣＨ_３）＝Ｃ（ＣＨ_３）−、−ＣＨ＝ＣＨ−ＣＨ_２Ｏ−、−ＯＣＨ_２−ＣＨ＝ＣＨ−、−ＣＨ＝ＣＨ−ＯＣＨ_２−、または−ＣＨ_２Ｏ−ＣＨ＝ＣＨ−であり；
ｄ１、ｄ２およびｄ３は独立して、０または１である。 Item 4. Item 4. The polymerizable compound according to any one of Items 1 to 3, represented by Formula (1-1).

In formula (1-1),
P ⁷ , (d1 × c1) P ⁸ , (d2 × c2) P ⁹ , (d3 × c3) P ¹⁰ , c4 P ¹¹ , and P ¹² are polymerizable groups, and At least one of the polymerizable groups of acryloyloxy or methacryloyloxy is vinyloxycarbonyl, 1-propenyloxycarbonyl, 2-propenyloxycarbonyl, 2-methyl-2-propenyloxycarbonyl. , 2-butenyloxycarbonyl, or 3-methyl-2-butenyloxycarbonyl;
S ⁷ , S ⁸ , S ⁹ , S ¹⁰ , S ¹¹ , and S ¹² are each independently a single bond or alkylene having 1 to 5 carbons, in which one —CH ₂ — represents —O -, - COO-, or may be replaced by -OCO-, 1 single _-CH 2 -CH ₂ -, which may be replaced by -CH = CH-;
c1, c2, c3, and c4 are independently 0, 1 or 2, and the sum of c1, c2, c3, and c4 is an integer from 0 to 5;
Ring A ⁵ , Ring A ⁶ , Ring A ⁷ , and Ring A ⁸ are independently 1,4-phenylene, pyrimidine-2,5-diyl, pyridine-2,5-diyl, 1,4-cyclohexylene. 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, or 1,3-dioxane-2,5-diyl, in which at least one hydrogen is fluorine, chlorine, carbon number 1 to 3 alkyls, or 1 to 3 alkyls in which at least one hydrogen is replaced by fluorine or chlorine may be substituted;
Z ⁴ , Z ⁵ and Z ⁶ are each independently a single bond, alkylene having 1 to 5 carbons, —CO—, —COO—, —OCO—, —CH═CH—, —CH═CH—COO—, _{-OCO-CH = CH -, -} C (CH 3) = CH-COO -, - OCO-CH = C (CH 3) -, - CH = C (CH 3) -COO -, - OCO- (CH 3 _{) C = CH -, - C} (CH 3) = C (CH 3) -COO -, - OCO-C (CH 3) = C (CH 3) -, - CO-CH = CH -, - CH = CH _{-CO -, - C (CH 3} ) = C (CH 3) -, - CH = CH-CH 2 O -, - OCH 2 -CH = CH -, - CH = CH-OCH 2 -, or -CH ₂ O—CH═CH—;
d1, d2 and d3 are independently 0 or 1.

Item 5. In formula (1-1) of item 4, P ⁷ and P ¹² are independently acryloyloxy or methacryloyloxy, and at least one of P ⁸ , P ⁹ , P ¹⁰ , and P ¹¹ is acryloyloxy or methacryloyloxy And at least one remaining is vinyloxycarbonyl, 1-propenyloxycarbonyl, 2-propenyloxycarbonyl, 2-methyl-2-propenyloxycarbonyl, 2-butenyloxycarbonyl, or 3-methyl-2-butyl Is tenyloxycarbonyl;
S ⁷ , S ⁸ , S ⁹ , S ¹⁰ , S ¹¹ , and S ¹² are single bonds;
c1, c2, c3, and c4 are independently 0 or 1, and the sum of c1, c2, c3, and c4 is an integer from 0 to 4;
Ring A ⁵ , Ring A ⁶ , Ring A ⁷ , and Ring A ⁸ are independently 1,4-phenylene, in which at least one hydrogen is fluorine, chlorine, alkyl having 1 to 3 carbons, Or at least one hydrogen may be replaced by alkyl of 1 to 3 carbons replaced by fluorine or chlorine;
Z ⁴ , Z ⁵ and Z ⁶ are single bonds;
Item 5. The polymerizable compound according to Item 4, wherein d1, d2, and d3 are each independently 0 or 1.

式（１−２）または（１−３）において、
Ｐ^１３、ｅ１個のＰ^１４、ｅ２個のＰ^１５、ｅ３個のＰ^１６、ｅ４個のＰ^１７、およびＰ^１８は重合性基であり、これらの重合性基のうちの少なくとも１つは、アクリロイルオキシまたはメタクリロイルオキシであり、残りの少なくとも１つは、ビニルオキシカルボニル、１−プロペニルオキシカルボニル、２−プロペニルオキシカルボニル、２−メチル−２−プロペニルオキシカルボニル、２−ブテニルオキシカルボニル、または３−メチル−２−ブテニルオキシカルボニルであり；
Ｓ^１３、Ｓ^１４、Ｓ^１５、Ｓ^１６、Ｓ^１７、およびＳ^１８は独立して、単結合または炭素数１から５のアルキレンであり、このアルキレンにおいて、１つの−ＣＨ_２−は、−Ｏ−、−ＣＯＯ−、または−ＯＣＯ−で置き換えられてもよく、１つの−ＣＨ_２−ＣＨ_２−は、−ＣＨ＝ＣＨ−で置き換えられてもよく；
ｅ１、ｅ２、ｅ３、およびｅ４は独立して、０、１または２であり、ｅ１、ｅ２、ｅ３、およびｅ４の和は０から３の整数であり；
環Ａ^９、環Ａ^１０、環Ａ^１１、および環Ａ^１２は１，４−フェニレンであり、この基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３のアルキル、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から３のアルキルで置き換えられてもよく；
Ｚ^７、Ｚ^８およびＺ^９は独立して、単結合、炭素数１から５のアルキレン、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−Ｃ（ＣＨ_３）＝ＣＨ−ＣＯＯ−、−ＯＣＯ−ＣＨ＝Ｃ（ＣＨ_３）−、−ＣＨ＝Ｃ（ＣＨ_３）−ＣＯＯ−、−ＯＣＯ−（ＣＨ_３）Ｃ＝ＣＨ−、−Ｃ（ＣＨ_３）＝Ｃ（ＣＨ_３）−ＣＯＯ−、−ＯＣＯ−Ｃ（ＣＨ_３）＝Ｃ（ＣＨ_３）−、−ＣＯ−ＣＨ＝ＣＨ−、−ＣＨ＝ＣＨ−ＣＯ−、−Ｃ（ＣＨ_３）＝Ｃ（ＣＨ_３）−、−ＣＨ＝ＣＨ−ＣＨ_２Ｏ−、−ＯＣＨ_２−ＣＨ＝ＣＨ−、−ＣＨ＝ＣＨ−ＯＣＨ_２−、または−ＣＨ_２Ｏ−ＣＨ＝ＣＨ−である。 Item 6. Item 5. The polymerizable compound according to any one of Items 1 to 4, which is represented by Formula (1-2) or (1-3).

In formula (1-2) or (1-3),
P ¹³ , e 1 P ¹⁴ , e 2 P ¹⁵ , e 3 P ¹⁶ , e 4 P ¹⁷ , and P ¹⁸ are polymerizable groups, and at least one of these polymerizable groups is: Acryloyloxy or methacryloyloxy, at least one of the remaining being vinyloxycarbonyl, 1-propenyloxycarbonyl, 2-propenyloxycarbonyl, 2-methyl-2-propenyloxycarbonyl, 2-butenyloxycarbonyl, or 3 -Methyl-2-butenyloxycarbonyl;
S ¹³ , S ¹⁴ , S ¹⁵ , S ¹⁶ , S ¹⁷ , and S ¹⁸ are each independently a single bond or alkylene having 1 to 5 carbons, in which one —CH ₂ — represents —O -, - COO-, or may be replaced by -OCO-, 1 single _-CH 2 -CH ₂ - may be replaced by -CH = CH-;
e1, e2, e3, and e4 are independently 0, 1 or 2, and the sum of e1, e2, e3, and e4 is an integer from 0 to 3;
Ring A ⁹ , Ring A ¹⁰ , Ring A ¹¹ , and Ring A ¹² are 1,4-phenylene, in which at least one hydrogen is fluorine, chlorine, alkyl of 1 to 3 carbons, or at least one hydrogen May be replaced by alkyl having 1 to 3 carbon atoms replaced by fluorine or chlorine;
Z ⁷ , Z ⁸ and Z ⁹ are each independently a single bond, alkylene having 1 to 5 carbons, —CO—, —COO—, —OCO—, —CH═CH—, —CH═CH—COO—, _{-OCO-CH = CH -, -} C (CH 3) = CH-COO -, - OCO-CH = C (CH 3) -, - CH = C (CH 3) -COO -, - OCO- (CH 3 _{) C = CH -, - C} (CH 3) = C (CH 3) -COO -, - OCO-C (CH 3) = C (CH 3) -, - CO-CH = CH -, - CH = CH _{-CO -, - C (CH 3} ) = C (CH 3) -, - CH = CH-CH 2 O -, - OCH 2 -CH = CH -, - CH = CH-OCH 2 -, or -CH ₂ O—CH═CH—.

式（１−４）および（１−５）において
Ｐ^１９、ｆ１個のＰ^２０、ｆ２個のＰ^２１、ｆ３個のＰ^２２、ｆ４個のＰ^２３、およびＰ^２４は重合性基であり、これらの重合性基のうちの少なくとも１つは、アクリロイルオキシまたはメタクリロイルオキシであり、残りの少なくとも１つは、ビニルオキシカルボニル、１−プロペニルオキシカルボニル、２−プロペニルオキシカルボニル、２−メチル−２−プロペニルオキシカルボニル、２−ブテニルオキシカルボニル、または３−メチル−２−ブテニルオキシカルボニルであり；
Ｓ^１９、Ｓ^２０、Ｓ^２１、Ｓ^２２、Ｓ^２３、およびＳ^２４は独立して、単結合、−ＣＨ_２−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−、−ＣＨ_２ＣＨ_２Ｏ−、−ＯＣＨ_２ＣＨ_２−、−ＣＨ＝ＣＨ−O−、または−Ｏ−ＣＨ＝ＣＨ−であり；
ｆ１、ｆ２、ｆ３、およびｆ４は独立して、０、１または２であり、ｆ１、ｆ２、ｆ３、およびｆ４の和は、０、１または２であり；
環Ａ^１３は、１，４−フェニレンであり、この基において少なくとも１つの水素はフッ素、メチル、フルオロメチル、ジフルオロメチル、またはトリフルオロメチルで置き換えられてもよく；
Ｚ^１０、Ｚ^１１およびＺ^１２は独立して、単結合、−ＣＯ−、−ＣＯＯ−、−ＣＨ＝ＣＨ−、−ＣＨ＝ＣＨ−ＣＯＯ−、−Ｃ（ＣＨ_３）＝ＣＨ−ＣＯＯ−、−ＣＨ＝Ｃ（ＣＨ_３）−ＣＯＯ−、−Ｃ（ＣＨ_３）＝Ｃ（ＣＨ_３）−ＣＯＯ−、−ＣＯＣＨ＝ＣＨ−、−Ｃ（ＣＨ_３）＝Ｃ（ＣＨ_３）−、−ＣＨ＝ＣＨ−ＣＨ_２Ｏ−、または−ＣＨ＝ＣＨ−ＯＣＨ_２−である。 Item 7. Item 5. The polymerizable compound according to any one of Items 1 to 4, which is represented by Formula (1-4) or (1-5).

In formulas (1-4) and (1-5), P ¹⁹ , f1 P ²⁰ , f2 P ²¹ , f3 P ²² , f4 P ²³ , and P ²⁴ are polymerizable groups, At least one of these polymerizable groups is acryloyloxy or methacryloyloxy, and the remaining at least one is vinyloxycarbonyl, 1-propenyloxycarbonyl, 2-propenyloxycarbonyl, 2-methyl-2- Propenyloxycarbonyl, 2-butenyloxycarbonyl, or 3-methyl-2-butenyloxycarbonyl;
S ¹⁹ , S ²⁰ , S ²¹ , S ²² , S ²³ , and S ²⁴ are each independently a single bond, —CH ₂ —, —CH ₂ O—, —OCH ₂ —, —COO—, —OCO—, _{-CH = CH -, - C≡C -} , - CH 2 CH 2 O -, - OCH 2 CH 2 -, - CH = CH-O-, or -O-CH = CH- and is;
f1, f2, f3 and f4 are independently 0, 1 or 2, and the sum of f1, f2, f3 and f4 is 0, 1 or 2;
Ring A ¹³ is 1,4-phenylene in which at least one hydrogen may be replaced with fluorine, methyl, fluoromethyl, difluoromethyl, or trifluoromethyl;
Z ¹⁰ , Z ¹¹ and Z ¹² are each independently a single bond, —CO—, —COO—, —CH═CH—, —CH═CH—COO—, —C (CH ₃ ) ═CH—COO—, _{-CH = C (CH 3) -COO} -, - C (CH 3) = C (CH 3) -COO -, - COCH = CH -, - C (CH 3) = C (CH 3) -, - CH = _CH-CH 2 O-, or -CH = CH-OCH ₂ - it is.

Item 8. In formulas (1-4) and (1-5) of item 7, at least one of P ¹⁹ , P ²⁰ , P ²¹ , P ²² , P ²³ , and P ²⁴ is acryloyloxy or methacryloyloxy, and the rest At least one of vinyloxycarbonyl, 1-propenyloxycarbonyl, 2-propenyloxycarbonyl, 2-methyl-2-propenyloxycarbonyl, 2-butenyloxycarbonyl, or 3-methyl-2-butenyloxycarbonyl Is;
S ¹⁹ , S ²⁰ , S ²¹ , S ²² , S ²³ , and S ²⁴ are each independently a single bond, —CH ₂ —, —CH ₂ O—, —OCH ₂ —, —COO—, —OCO—, _{-CH = CH -, - C≡C -} , - CH 2 CH 2 O -, - OCH 2 CH 2 -, - CH = CH-O-, or -O-CH = CH- and is;
f1, f2, f3 and f4 are independently 0, 1 or 2, and the sum of f1, f2, f3 and f4 is 0, 1 or 2;
Ring A ¹³ is 1,4-phenylene in which at least one hydrogen may be replaced by fluorine, methyl or trifluoromethyl;
Z ¹⁰ , Z ¹¹ and Z ¹² are each independently a single bond, —CO—, —COO—, —CH═CH—, —CH═CH—COO—, —CH═CH—CH ₂ O—, or — Item 8. The polymerizable compound according to Item 7, wherein CH═CH—OCH ₂ —.

式（１−６）または（１−７）において、
Ｐ^２５、ｇ１個のＰ^２６、ｇ２個のＰ^２７、ｇ３個のＰ^２８、ｇ４個のＰ^２９、およびＰ^３０はアクリロイルオキシ、メタクリロイルオキシ、ビニルオキシカルボニル、１−プロペニルオキシカルボニル、２−プロペニルオキシカルボニル、２−メチル−２−プロペニルオキシカルボニル、２−ブテニルオキシカルボニル、または３−メチル−２−ブテニルオキシカルボニルであり、Ｐ^２５、ｇ１個のＰ^２６、ｇ２個のＰ^２７、ｇ３個のＰ^２８、ｇ４個のＰ^２９、およびＰ^３０のうちの少なくとも１つは、アクリロイルオキシまたはメタクリロイルオキシであり、残りの少なくとも１つは、ビニルオキシカルボニル、１−プロペニルオキシカルボニル、２−プロペニルオキシカルボニル、２−メチル−２−プロペニルオキシカルボニル、２−ブテニルオキシカルボニル、または３−メチル−２−ブテニルオキシカルボニルであり；
Ｓ^２５、Ｓ^２６、Ｓ^２７、Ｓ^２８、Ｓ^２９、およびＳ^３０は独立して、単結合、−ＣＨ_２−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−、−ＣＨ_２ＣＨ_２Ｏ−、−ＯＣＨ_２ＣＨ_２−、−ＣＨ＝ＣＨ−O−、または−Ｏ−ＣＨ＝ＣＨ−であり；
ｇ１、ｇ２、ｇ３およびｇ４は独立して、０、１または２であり、ｇ１、ｇ２、ｇ３およびｇ４の和は、０、１、２または３である。 Item 9 The polymerizable compound according to any one of Items 1 to 4, which is represented by the formula (1-6) or (1-7).

In formula (1-6) or (1-7),
P ²⁵ , g 1 P ²⁶ , g 2 P ²⁷ , g 3 P ²⁸ , g 4 P ²⁹ , and P ³⁰ are acryloyloxy, methacryloyloxy, vinyloxycarbonyl, 1-propenyloxycarbonyl, 2-propenyl Oxycarbonyl, 2-methyl-2-propenyloxycarbonyl, 2-butenyloxycarbonyl, or 3-methyl-2-butenyloxycarbonyl, P ²⁵ , g 1 P ²⁶ , g 2 P ²⁷ , g 3 At least one of P ²⁸ , g 4 P ²⁹ , and P ³⁰ is acryloyloxy or methacryloyloxy, and at least one of the other is vinyloxycarbonyl, 1-propenyloxycarbonyl, 2-propenyl Oxycarbonyl, 2-methyl-2-propenyloxyca Rubonyl, 2-butenyloxycarbonyl, or 3-methyl-2-butenyloxycarbonyl;
S ²⁵ , S ²⁶ , S ²⁷ , S ²⁸ , S ²⁹ , and S ³⁰ are each independently a single bond, —CH ₂ —, —CH ₂ O—, —OCH ₂ —, —COO—, —OCO—, _{-CH = CH -, - C≡C -} , - CH 2 CH 2 O -, - OCH 2 CH 2 -, - CH = CH-O-, or -O-CH = CH- and is;
g1, g2, g3 and g4 are independently 0, 1 or 2, and the sum of g1, g2, g3 and g4 is 0, 1, 2 or 3.

式（１−８）および（１−９）において、Ｐ^３１、Ｐ^３２およびＰ^３３はアクリロイルオキシ、メタクリロイルオキシ、ビニルオキシカルボニル、１−プロペニルオキシカルボニル、２−プロペニルオキシカルボニル、２−メチル−２−プロペニルオキシカルボニル、２−ブテニルオキシカルボニル、または３−メチル−２−ブテニルオキシカルボニルであり、Ｐ^３１、Ｐ^３２およびＰ^３３のうちの少なくとも１つはアクリロイルオキシまたはメタクリロイルオキシであり、残りの少なくとも１つは、ビニルオキシカルボニル、１−プロペニルオキシカルボニル、２−プロペニルオキシカルボニル、２−メチル−２−プロペニルオキシカルボニル、２−ブテニルオキシカルボニル、または３−メチル−２−ブテニルオキシカルボニルであり；ｈ１は０または１である。 Item 10. Item 10. The polymerizable compound according to item 1, represented by formula (1-8) or (1-9).

In formulas (1-8) and (1-9), P ³¹ , P ³² and P ³³ are acryloyloxy, methacryloyloxy, vinyloxycarbonyl, 1-propenyloxycarbonyl, 2-propenyloxycarbonyl, 2-methyl-2 - propenyloxy carbonyl, 2-butenyl butyloxycarbonyl or 3-methyl-2-butenyl oxy carbonyl, at least one acryloyloxy or methacryloyloxy of P ^31, P ³² and P ^33, the remaining At least one of vinyloxycarbonyl, 1-propenyloxycarbonyl, 2-propenyloxycarbonyl, 2-methyl-2-propenyloxycarbonyl, 2-butenyloxycarbonyl, or 3-methyl-2-butenyloxycarbonyl so Ri; h1 is 0 or 1.

Item 11. Item 11. A polymerizable composition containing at least one polymerizable compound according to any one of Items 1 to 10.

式（２）から（４）において、
Ｒ^１１およびＲ^１２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−ＣＨ_２−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Ｂ^１、環Ｂ^２、環Ｂ^３、および環Ｂ^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^１１、Ｚ^１２およびＺ^１３は独立して、単結合、−ＣＨ_２ＣＨ_２−、−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−、または−ＣＯＯ−である。 Item 12. Item 12. The polymerizable composition according to item 11, further comprising at least one compound selected from the group of compounds represented by formulas (2) to (4).

In the equations (2) to (4),
R ¹¹ and R ¹² are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl or alkenyl, at least one —CH ₂ — may be replaced by —O—. Well, at least one hydrogen may be replaced by fluorine;
Ring B ¹ , Ring B ² , Ring B ³ , and Ring B 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 ¹¹ , Z ¹² and Z ¹³ are each independently a single bond, —CH ₂ CH ₂ —, —CH═CH—, —C≡C—, or —COO—.

式（５）から（７）において、
Ｒ^１３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−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；
Ｘ^１１は、フッ素、塩素、−ＯＣＦ₃、−ＯＣＨＦ₂、−ＣＦ₃、−ＣＨＦ₂、−ＣＨ₂Ｆ、−ＯＣＦ₂ＣＨＦ₂、または−ＯＣＦ₂ＣＨＦＣＦ₃であり；
環Ｃ^１、環Ｃ^２および環Ｃ^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^１４、Ｚ^１５およびＺ^１６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 13. Item 13. The polymerizable composition according to Item 11 or 12, further comprising at least one compound selected from the group of compounds represented by formulas (5) to (7).

In equations (5) to (7),
R ¹³ is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, in which at least one —CH ₂ — may be replaced by —O—, and at least one hydrogen is May be replaced by fluorine;
X ¹¹ is fluorine, chlorine, —OCF ₃ , —OCHF ₂ , —CF ₃ , —CHF ₂ , —CH ₂ F, —OCF ₂ CHF ₂ , or —OCF ₂ CHFCF ₃ ;
Ring C ¹ , Ring C ² and Ring C 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 ¹⁴ , Z ¹⁵ and Z ¹⁶ are each 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（８）において、
Ｒ^１４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、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；
Ｘ^１２は−Ｃ≡Ｎまたは−Ｃ≡Ｃ−Ｃ≡Ｎであり；
環Ｄ^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^１７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 14. Item 14. The polymerizable composition according to any one of items 11 to 13, further comprising at least one compound selected from the group of compounds represented by formula (8).

In equation (8),
R ¹⁴ is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in alkyl and alkenyl, at least one —CH ₂ — may be replaced by —O—, and at least one hydrogen is fluorine. May be replaced by;
X ¹² is —C≡N or —C≡C—C≡N;
Ring ^{D 1} is 1,4-cyclohexylene, at least one hydrogen replaced by or 1,4-phenylene with fluorine, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl Or pyrimidine-2,5-diyl;
Z ¹⁷ represents 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（９）から（１５）において、
Ｒ^１５およびＲ^１６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^１７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；
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−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Ｅ^５および環Ｅ^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^１８、Ｚ^１９、Ｚ^２０、およびＺ^２１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；
Ｓ^４１は、水素またはメチルであり；
Ｘは、−ＣＨＦ−または−ＣＦ_２−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 15. Item 15. The liquid crystal composition according to any one of items 11 to 14, further comprising at least one compound selected from the group of compounds represented by formulas (9) to (15).

In the equations (9) to (15),
R ¹⁵ and R ¹⁶ are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, in which at least one —CH ₂ — may be replaced by —O—. Well, at least one hydrogen may be replaced by fluorine;
R ¹⁷ 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;
Ring E ¹ , Ring E ² , Ring E ³ , and Ring E ⁴ are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, wherein at least one hydrogen may be replaced with fluorine, 4-phenylene, tetrahydropyran-2,5-diyl, or decahydronaphthalene-2,6-diyl;
Ring E ⁵ and Ring E ⁶ are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, tetrahydropyran-2,5-diyl, or decahydronaphthalene-2,6. -Diyl;
^{Z 18, Z 19, Z 20} , and ^{Z 21} are independently a single _{bond, -CH 2 CH 2 -, -} COO -, - CH 2 O -, - OCF 2 -, or -OCF ₂ CH ₂ CH ₂ -Is;
L ¹⁵ and L ¹⁶ are independently fluorine or chlorine;
S ⁴¹ is hydrogen or methyl;
X is —CHF— or —CF ₂ —;
j, k, m, n, p, q, r, and s are independently 0 or 1, the sum of k, m, n, and p is 1 or 2, q, r, and The sum of s is 0, 1, 2, or 3, and t is 1, 2, or 3.

Item 16. Item 16. A liquid crystal composite produced by polymerization of the polymerizable composition according to any one of items 11 to 15.

Item 17. Item 16. An optical anisotropic body produced by polymerization of the polymerizable composition according to any one of Items 11 to 15.

Item 18. Item 16. A liquid crystal display device comprising the polymerizable composition according to any one of Items 11 to 15 or the liquid crystal composite according to Item 16.

Item 19. Item 16. The liquid crystal display device, selected from the group consisting of the compound according to any one of Items 1 to 10, the polymerizable composition according to any one of Items 11 to 15, and the liquid crystal composite according to Item 16. At least one use.

  The present invention also includes the following items. (A) The above polymerizability further containing at least one additive such as an optically active compound, an antioxidant, an ultraviolet absorber, a light stabilizer, a heat stabilizer, an antifoaming agent, a polymerization initiator, and a polymerization inhibitor. Composition. (B) The polymerizable composition further containing a polymerizable compound different from the compound represented by the formula (1). (C) AM device containing said polymeric composition. (D) A device containing the polymerizable composition and having a mode of PS-TN, PS-IPS, PS-FFS, PSA-VA, or PSA-OCB. (E) A transmissive device containing the polymerizable composition. (F) Use of the 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 a positive dielectric anisotropy. (I) 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 formula (5) A polymerizable composition containing at least one compound selected from the group of compounds represented by () to (7). (J) 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 formula ( A polymerizable composition containing at least one compound selected from the group of compounds represented by 8). (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), formula (5) A polymerizable composition containing at least one compound selected from the group of compounds represented by (7) and at least one compound selected from the group of compounds represented by formula (8). (L) The polymerizable composition as described above, further comprising a liquid crystalline compound having 2,3-difluorophenylene and having a negative dielectric anisotropy. (M) A liquid crystal composite produced by polymerization of the polymerizable composition. (N) Use of the polymerizable composition or the liquid crystal composite in a liquid crystal display device having a PSA mode.

式（Ｐ−１）において、Ｒ^１は、少なくとも１つの−ＣＨ_２ＣＨ_２−が−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられた炭素数２から１５のアルキルであり、これらの基において少なくとも１つの水素は、ハロゲンで置き換えられてもよい。ハロゲンの用語は、フッ素、塩素、臭素、およびヨウ素を意味する。ハロゲンの好ましい例は、フッ素および塩素である。さらに好ましい例はフッ素である。 1. Polymerizable compound The polymerizable compound of the present invention will be described first, followed by a synthesis method, a polymerizable composition, a liquid crystal composite, and a liquid crystal display device in this order. This polymerizable compound has at least two polymerizable groups, at least one polymerizable group is acryloyloxy or methacryloyloxy, and at least one polymerizable group is represented by the formula (P-1).

In Formula (P-1), R ¹ is alkyl having 2 to 15 carbons in which at least one —CH ₂ CH ₂ — is replaced by —CH═CH— or —C≡C—, and these groups In which at least one hydrogen may be replaced by a halogen. The term halogen means fluorine, chlorine, bromine and iodine. Preferred examples of halogen are fluorine and chlorine. A more preferred example is fluorine.

第一に、化合物（１）は棒状の分子構造を有することを特徴とする。市販されている液晶表示素子に用いられる液晶組成物は、棒状の分子構造を有する液晶性化合物の混合物である。両者の分子構造は棒状という点で類似している。したがって、化合物（１）は、液晶組成物への高い溶解度を有する。第二に、化合物（１）は、高い重合性を有する基と低い重合性を有する基とを有することを特徴とする。前者はアクリロイルオキシ（−ＯＣＯ−ＣＨ＝ＣＨ_２）またはメタクリロイルオキシ（−ＯＣＯ−（ＣＨ_３）Ｃ＝ＣＨ_２）である。後者は、式（Ｐ−１）で表される重合性基である。化合物（１）は少なくとも２種類の重合性基を有する。したがって、分子の対称性が低下するので、液晶組成物への溶解度が向上すると期待される。 A typical example of this polymerizable compound is the following compound represented by the formula (1).

First, the compound (1) is characterized by having a rod-like molecular structure. A liquid crystal composition used for a commercially available liquid crystal display element is a mixture of liquid crystal compounds having a rod-like molecular structure. Their molecular structures are similar in that they are rod-shaped. Therefore, compound (1) has high solubility in the liquid crystal composition. Secondly, the compound (1) is characterized by having a group having high polymerizability and a group having low polymerizability. The former is acryloyloxy (—OCO—CH═CH ₂ ) or methacryloyloxy (—OCO— (CH ₃ ) C═CH ₂ ). The latter is a polymerizable group represented by the formula (P-1). Compound (1) has at least two kinds of polymerizable groups. Therefore, since the symmetry of the molecule is lowered, it is expected that the solubility in the liquid crystal composition is improved.

In the formula (1), at least one of P ^{1 to} P ⁶ is acryloyloxy or methacryloyloxy. At least one of the remaining P ^{1 to} P ⁶ is a polymerizable group represented by the formula (P-1). All of P ^{1 to} P ⁶ may be selected from the group of polymerizable groups represented by acryloyloxy, methacryloyloxy, and formula (P-1). At least one of P ^{1 to} P ⁶ may be another polymerizable group. The other polymerizable group means a polymerizable group different from acryloyloxy and methacryloyloxy and different from the polymerizable group represented by formula (P-1).

  Examples of other polymerizable groups are vinyl, vinyloxy, propenyloxy, oxiranyl, oxetanyl, vinylcarbonyl and the like. Examples of these are also these polymerizable groups in which at least one hydrogen has been replaced by fluorine, methyl, ethyl, propyl, butyl, pentyl, fluoromethyl, difluoromethyl, or trifluoromethyl. An example of this is also acryloyloxy (or methacryloyloxy) in which at least one hydrogen has been replaced by fluorine, methyl, ethyl, propyl, butyl, pentyl, fluoromethyl, difluoromethyl, or trifluoromethyl.

式（Ｐ−２）および（Ｐ−３）において、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、およびＲ^８は水素、ハロゲンまたは炭素数１から１０のアルキルであり、このアルキルにおいて少なくとも１つの−ＣＨ_２ＣＨ_２−は−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、これらの基において少なくとも１つの水素は、ハロゲンで置き換えられてもよい。 In formula (P-1), a preferred example of R ¹ is alkenyl having 2 to 15 carbons or alkynyl having 2 to 15 carbons, and at least one hydrogen may be replaced by halogen. A preferred example of formula (P-1) is represented by formula (P-2) or (P-3).

In formulas (P-2) and (P-3), R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R ⁸ are hydrogen, halogen, or alkyl having 1 to 10 carbons, In the alkyl, at least one —CH ₂ CH ₂ — may be replaced with —CH═CH— or —C≡C—, and in these groups at least one hydrogen may be replaced with a halogen.

Preferred examples of the polymerizable group represented by formulas (P-2) and (P-3) include vinyloxycarbonyl (—COO—CH═CH ₂ ) and 1-propenyloxycarbonyl (—COO—CH═CHCH _3). ), 2-propenyloxycarbonyl (—COO—CH ₂ CH═CH ₂ ), 2-methyl-2-propenyloxycarbonyl (—COO—CH ₂ C (CH ₃ ) ═CH ₂ ),
2-butenyloxycarbonyl (—COO—CH ₂ CH═CHCH ₃ ), 3-methyl-2-butenyloxycarbonyl (—COO—CH ₂ CH═C (CH ₃ ) ₂ ) and the like. In 1-propenyloxycarbonyl (—COO—CH═CHCH ₃ ) and 2-butenyloxycarbonyl (—COO—CH ₂ CH═CHCH ₃ ), the configuration of the double bond may be E-form. And Z body may be sufficient.

In the formula (1), S ^{1 to} S ⁶ are each independently a single bond or alkylene having 1 to 10 carbon atoms, and in the alkylene, at least one —CH ₂ — is —O—, —COO—, —OCO—, or —OCOO— may be substituted, and at least one —CH ₂ —CH ₂ — may be substituted with —CH═CH— or —C≡C—, and in these groups at least One hydrogen may be replaced with a halogen.

Preferred examples of S ^{1 to} S ⁶ are a single bond or alkylene having 1 to 5 carbon atoms, in which one —CH ₂ — is replaced by —O—, —COO—, or —OCO—. One —CH ₂ —CH ₂ — may be replaced by —CH═CH—. More preferred examples include a single _{bond, -CH 2 -, - CH 2} O -, - OCH 2 -, - COO -, - OCO -, - CH = CH -, - C≡C -, - CH 2 CH 2 O _{-, - OCH 2 CH 2 -} , - CH = CH-O-, or -O-CH = CH-. The most preferred example is a single bond.

  In the formula (1), a1 to a4 are independently 0, 1, 2, 3, or 4, and the sum of a1 to a4 is an integer of 2 to 10. Preferred examples of a1 to a4 are 0, 1 or 2. A more preferred example is 0 or 1. Further preferred examples are 0 or 2. The most preferred example is 0 or 1.

In formula (1), ring A ¹ to ring A ⁴ are independently 1,4-phenylene, pyrimidine-2,5-diyl, pyridine-2,5-diyl, naphthalene-1,2-diyl, naphthalene- 1,3-diyl, naphthalene-1,4-diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2, 3-diyl, naphthalene-2,6-diyl, naphthalene-2,7-diyl, 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, or 1,3- Dioxane-2,5-diyl. In these rings, at least one hydrogen may be replaced by halogen or alkyl having 1 to 12 carbons, and in this alkyl one or two —CH ₂ — may be replaced by —O—. In these groups, at least one hydrogen may be replaced by a halogen.

Preferred examples of ring A ¹ to ring A ⁴ include 1,4-phenylene, pyrimidine-2,5-diyl, pyridine-2,5-diyl, 1,4-cyclohexylene, 1,4-cyclohexenylene, Tetrahydropyran-2,5-diyl or 1,3-dioxane-2,5-diyl. In these rings, at least one hydrogen may be replaced by fluorine, chlorine, alkyl having 1 to 3 carbons, or alkyl having 1 to 3 carbons in which at least one hydrogen is replaced by fluorine or chlorine. A further preferred example is 1,4-phenylene, in which at least one hydrogen is fluorine, chlorine, alkyl having 1 to 3 carbon atoms, or carbon number in which at least one hydrogen is replaced by fluorine or chlorine. 1 to 3 alkyls may be substituted. In preferred examples, at least one hydrogen may be replaced with fluorine, methyl, fluoromethyl, difluoromethyl, or trifluoromethyl. The most preferred example is 1,4-phenylene. The most preferred example is also 2-fluoro-1,4-phenylene.

In the formula (1), Z ¹ , Z ² and Z ³ are each independently a single bond or alkylene having 1 to 10 carbon atoms, and in this alkylene, at least one —CH ₂ — is —O—, — CO—, —COO—, or —OCO— may be replaced, and at least one —CH ₂ —CH ₂ — is —CH═CH—, —C (CH ₃ ) ═CH—, —CH═C (CH ₃ ) —, or —C (CH ₃ ) ═C (CH ₃ ) — may be replaced, and in these groups, at least one hydrogen may be replaced with a halogen.

Preferred examples of Z ^{1 to} Z ³ include a single bond, alkylene having 1 to 5 carbon atoms, —CO—, —COO—, —OCO—, —CH═CH—, —CH═CH—COO—, —OCO—. _{CH = CH -, - C (} CH 3) = CH-COO -, - OCO-CH = C (CH 3) -, - CH = C (CH 3) -COO -, - OCO- (CH 3) C = _{CH -, - C (CH 3} ) = C (CH 3) -COO -, - OCO-C (CH 3) = C (CH 3) -, - CO-CH = CH -, - CH = CH-CO- _{, -C (CH 3) = C} (CH 3) -, - CH = CH-CH 2 O -, - OCH 2 -CH = CH -, - CH = CH-OCH 2 -, or _-CH 2 OCH = CH-. Further preferred examples are a single bond, —CO—, —COO—, —CH═CH—, —CH═CH—COO—, —C (CH ₃ ) ═CH—COO—, —CH═C (CH ₃ ). _{-COO -, - C (CH 3} ) = C (CH 3) -COO -, - COCH = CH -, - C (CH 3) = C (CH 3) -, - CH = CH-CH 2 O-, or -CH = CH-OCH ₂ - is. The most preferred example is a single bond.

  b1, b2 and b3 are independently 0 or 1. The sum of b1, b2 and b3 is 0, 1, 2 or 3. Preferred examples are 1, 2 or 3. Further preferred examples are 2 or 3. The most preferred example is 2. The most preferred example is also 3.

Preferred examples of the polymerizable group P, the linking group S, the ring A, and the bonding group Z in the compound (1) are as described above. This example also applies to the sub-formula of compound (1). With reference to the above preferred examples, a polymerizable compound having the desired physical properties can be obtained by appropriately combining these groups and rings. A preferred example of compound (1) is compound (1-1). Further preferred examples are compounds (1-2) and (1-3). Particularly preferred examples include compounds (1-4) and (1-5), compounds (1-6) and (1-57), and compounds (1-8) and (1-8). Since there is no great difference in the physical properties of the compound, the compound (1) may contain an isotope such as ² H (deuterium) and ¹³ C in an amount larger than the natural abundance.

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

2-1. Formation of Binding Group Z An example of a method for generating the bonding groups Z ^{1 to} Z ³ in the compound (1) is as shown in the following scheme. In this scheme, MSG ¹ (or MSG ² ) is a monovalent organic group having at least one ring. The monovalent organic groups represented by a plurality of MSG ¹ (or MSG ² ) may be the same or different. Compounds (1A) to (1I) correspond to compound (1). In the production of esters, a method for synthesizing a compound having -COO- was shown. A compound having —OCO— can also be synthesized by this synthesis method. The same applies to other asymmetrical linking groups.

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

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

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

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

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

(6) Formation of —CH═CH—COO— A phosphorus ylide is prepared by reacting a base such as sodium hydride with ethyl diethylphosphonoacetate, and this phosphorus ylide is reacted with an aldehyde (32) to obtain an ester (33). . Ester (33) is hydrolyzed in the presence of a base such as sodium hydroxide to give carboxylic acid (34). This compound and compound (25) are dehydrated and condensed to synthesize compound (1F).

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

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

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

2-2. Introduction of Other Polymerizable Group A method for synthesizing a compound in which the polymerizable group is —OCO— (M ¹ ) C═CH (M ² ) will be described. An example of a method for introducing this group into the ring is as shown in the following scheme. In this scheme, MSG ¹ is a monovalent organic group having at least one ring. Compound (1J) to Compound (1M) correspond to Compound (1). Note that acryloyloxy and methacryloyloxy can also be introduced into the ring by this method.

If both M ¹ and M ² are not —CF ₃ , M ¹ is fluorine and M ² is not —CF ₃ , or M ¹ is —CF ₃ and M ² is not fluorine, The carboxylic acid (41) shown in the scheme is commercially available. This carboxylic acid (41) and compound (30) are subjected to dehydration condensation in the presence of DCC and DMAP to synthesize compound (1J).

When M ¹ and M ² are both —CF ₃ , carboxylic acid (42) and compound (30) are subjected to dehydration condensation in the presence of DCC and DMAP to obtain compound (43). Compound (1K) is synthesized by reacting compound (43) with methyl 2,2-difluoro-2- (fluorosulfonyl) acetate in the presence of a copper iodide catalyst.

When M ¹ is fluorine and M ² is —CF ₃ , carboxylic acid (44) and compound (30) are subjected to dehydration condensation in the presence of DCC and DMAP to obtain compound (45). Compound (45) is fluorinated with a fluorinating agent such as DAST to obtain compound (46). Compound (1L) is synthesized by reacting compound (46) with methyl 2,2-difluoro-2- (fluorosulfonyl) acetate in the presence of a copper iodide catalyst.

When M ¹ is —CF ₃ and M ² is fluorine, compound (1M) is synthesized according to the above-described method using carboxylic acid (47) as a starting material.

2-3. Introduction of Group Represented by Formula (P-1) A method for synthesizing a compound having a polymerizable group represented by formula (P-1) will be described. An example of a method for introducing this group into the ring is as shown in the following scheme. In this scheme, MSG ¹ is a monovalent organic group having at least one ring. Compound (1N) corresponds to compound (1). R ¹ is an alkyl having 2 to 15 carbon atoms in which at least one —CH ₂ CH ₂ — is replaced by —CH═CH— or —C≡C—, in which at least one hydrogen is a halogen It may be replaced.

  A compound (1N) is synthesized by reacting a commercially available or well-known halide (48) with compound (24) in the presence of potassium carbonate or the like. Compound (1N) can also be synthesized by dehydration condensation of alcohol (49) and compound (24), which are commercially available or well-known synthesis methods, in the presence of DCC and DMAP.

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 other components such as a second component and a third component. The type of the second component depends on the intended use of the polymer. This polymerizable composition may further contain another polymerizable compound different from the compound (1) as the second component. Preferred examples of other polymerizable compounds are acrylate, methacrylate, vinyl compound, vinyloxy compound, propenyl ether, epoxy compound (oxirane, oxetane), and vinyl ketone. Further preferred examples are compounds having at least one acryloyloxy and compounds having at least one methacryloyloxy. Further preferred examples include compounds having both acryloyloxy and methacryloyloxy.

Additional examples of other polymerizable compounds are compounds (M-1) to (M-12). In 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 integers from 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 body is generated by polymerization while controlling the alignment of liquid crystal molecules. This optical anisotropic body can be used for retardation films, polarizing elements, circularly polarizing elements, elliptically polarizing elements, antireflection films, selective reflection films, color compensation films, viewing angle compensation films, and the like. An additive such as a polymerization initiator may be added to the polymerizable composition for the purpose of adjusting the physical properties of the optical anisotropic body.

  The polymerizable composition may include a liquid crystal composition as the second component. When a liquid crystal display element for modes such as PS-TN, PS-IPS, PS-FFS, PSA-VA, and PSA-OCB is intended, the polymerizable composition contains compound (1) as component A, and It is preferable to further include a compound selected from the components B, C, D and E shown in FIG. Component B is compounds (2) to (4). Component C is compounds (5) to (7). Component D is compound (8). Component E is compounds (9) 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, the magnitude of dielectric anisotropy, and the like. . A polymerizable composition with appropriately selected components has a high maximum temperature, a low minimum temperature, a small viscosity, a suitable optical anisotropy (ie, a large optical anisotropy or a small optical anisotropy), positively or negatively large It has a dielectric anisotropy and an appropriate elastic constant (ie, a large elastic constant or a small elastic constant).

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

Component B is a compound in which two terminal groups are alkyl or the like. Preferred examples of component B include compounds (2-1) to (2-11), compounds (3-1) to (3-19), and compounds (4-1) to (4-7). it can. In the compound of component B, R ¹¹ and R ¹² are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, in which at least one —CH ₂ — is —O -May be replaced with at least one hydrogen may be replaced with fluorine.

  Component B is a compound close to neutrality because the absolute value of dielectric anisotropy is small. The compound (2) is mainly effective in adjusting the viscosity or the optical anisotropy. Compounds (3) and (4) are effective in expanding the temperature range of the nematic phase by increasing the maximum temperature, or adjusting the optical anisotropy.

  As the content of component B 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 element is satisfied, the content is preferably large. Therefore, when preparing a composition for a mode such as PS-IPS or PSA-VA, the content of component B is preferably 30% by weight or more, more preferably 40%, based on the weight of the liquid crystal composition. % By weight or more.

Component C is a compound having a halogen or fluorine-containing group at the right end. Preferred examples of Component C include compounds (5-1) to (5-16), compounds (6-1) to (6-113), and compounds (7-1) to (7-57). . In the compound of component C, R ¹³ is 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. X ¹¹ is fluorine, chlorine, —OCF ₃ , —OCHF ₂ , —CF ₃ , —CHF ₂ , —CH ₂ F, —OCF ₂ CHF ₂ , or —OCF ₂ CHFCF ₃ .

  Since component C has a positive dielectric anisotropy and is very stable against heat, light, etc., a composition for a mode such as PS-IPS, PS-FFS, or PSA-OCB is prepared. Used in cases. The content of Component C is suitably in the range of 1% to 99% by weight based on the weight of the liquid crystal composition, preferably in the range of 10% to 97% by weight, and more preferably in the range of 40% to 95%. % Range. When component C is added to a composition having a negative dielectric anisotropy, the content of component C is preferably 30% by weight or less based on the weight of the liquid crystal composition. By adding the component C, the elastic constant of the composition can be adjusted, and the voltage-transmittance curve of the device can be adjusted.

Component D is a compound (8) in which the right terminal group is —C≡N or —C≡C—C≡N. Preferred examples of component D include compounds (8-1) to (8-64). In the compound of component D, R ¹⁴ is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in alkyl and alkenyl, at least one —CH ₂ — may be replaced by —O—, At least one hydrogen may be replaced with fluorine. X ¹² is —C≡N or —C≡C—C≡N.

  Since component D has a positive dielectric anisotropy and a large value, it is mainly used when preparing a composition for a mode such as PS-TN. By adding this component D, the dielectric anisotropy of the composition can be increased. Component D has the effect of expanding the temperature range of the liquid crystal phase, adjusting the viscosity, or adjusting the optical anisotropy. Component D 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 D is suitably in the range of 1% to 99% by weight, preferably 10% based on the weight of the liquid crystal composition. % To 97% by weight, more preferably 40% to 95% by weight. When component D is added to a composition having a negative dielectric anisotropy, the content of component D is preferably 30% by weight or less based on the weight of the liquid crystal composition. By adding component D, the elastic constant of the composition can be adjusted, and the voltage-transmittance curve of the device can be adjusted.

Component E is compounds (9) to (15). These compounds have a benzene ring in which the lateral position is substituted with two halogens, such as 2,3-difluoro-1,4-phenylene. Preferable examples of component E include compounds (9-1) to (9-8), compounds (10-1) to (10-17), compound (11-1), compounds (12-1) to (12- 3), compounds (13-1) to (13-11), compounds (14-1) to (14-3), and compounds (15-1) to (15-3). In the compound of Component E, R ¹⁵ and R ¹⁶ are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, in which at least one —CH ₂ — is — O- may be replaced and at least one hydrogen may be replaced with fluorine. R ¹⁷ 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.

  Component E is a compound having a negative dielectric anisotropy. Component E is used when preparing a composition for a mode such as PS-IPS, PS-FFS, PSA-VA. As the content of component E is increased, the dielectric anisotropy of the composition increases negatively, but the viscosity increases. Therefore, as long as the threshold voltage requirement of the element is satisfied, the content is preferably small. Accordingly, considering that the absolute value of dielectric anisotropy is about 5, the content is preferably 40% by weight or more in order to drive sufficiently.

  Among the components E, since the compound (9) is a bicyclic compound, it is mainly effective in adjusting the viscosity, adjusting the optical anisotropy, or adjusting the dielectric anisotropy. Since the compounds (10) and (11) are tricyclic compounds, there are effects of increasing the maximum temperature, increasing the optical anisotropy, or increasing the dielectric anisotropy. Compounds (12) to (15) have the effect of increasing the dielectric anisotropy.

  When preparing a composition for a mode such as PS-IPS, PS-FFS, PSA-VA, the content of component E is preferably 40% by weight to 97% by weight based on the weight of the liquid crystal composition. More preferably, it is in the range of 50% by weight to 95% by weight. When component E is added to a composition having a positive dielectric anisotropy, the content of component E is preferably 5% by weight to 30% by weight based on the weight of the liquid crystal composition, and more preferably 5% by weight to 20%. % By weight is preferred. By adding the component E, the elastic constant of the composition can be adjusted, and the voltage-transmittance curve of the device can be adjusted.

  The polymerizable composition is prepared by a method of dissolving necessary components at a temperature higher than room temperature. Depending on the application, additives may be added to the composition. Examples of additives include optically active compounds, antioxidants, ultraviolet 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 twisting by inducing a helical structure in 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 for the purpose of adjusting the temperature dependence of the helical pitch. Preferred examples of the optically active compound include the following compounds (Op-1) to (Op-18). In 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 for maintaining a large voltage holding ratio. Preferred examples of the antioxidant include the following compounds (AO-1) and (AO-2); IRGANOX (registered trademark) 415, IRGANOX 565, IRGANOX 1010, IRGANOX 1035, IRGANOX 3114, and IRGANOX 1098 (trade names: BASF) Company). The ultraviolet absorber is effective for preventing a decrease in the maximum temperature. Preferred examples of the ultraviolet absorber include benzophenone derivatives, benzoate derivatives, triazole derivatives and the like. As specific examples, the following compounds (AO-3) and (AO-4); TINUVIN® 329, TINUVIN P, TINUVIN 326, TINUVIN 234, TINUVIN 213, TINUVIN 400, TINUVIN 328, and TINUVIN 99-2 (commercial product) Name: BASF); and 1,4-diazabicyclo [2.2.2] octane (DABCO).

  Light stabilizers such as sterically hindered amines are preferred in order to maintain a large voltage holding ratio. Preferred examples of the light stabilizer include the following compounds (AO-5) and (AO-6); TINUVIN 144, TINUVIN 765, and TINUVIN 770DF (trade name: BASF). A thermal stabilizer is also effective for maintaining a large voltage holding ratio, and a preferred example is IRGAFOS 168 (trade name: BASF). Antifoaming agents are effective for preventing foaming. Preferred examples of the antifoaming agent include dimethyl silicone oil and methylphenyl silicone oil.

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 has 1 carbon To 20 alkyls. In compounds (AO-2) and (AO-5), R ³⁰ is alkyl having 1 to 20 carbons. In the compound ^{(AO-5), R 31} is hydrogen, methyl or O ^· (oxygen radical), ring K and ring L is 1,4-cyclohexylene or 1,4-phenylene, x is 0, 1 or 2.

4). Liquid crystal composite Compound (1) has high polymerization reactivity, high conversion, and high solubility in the liquid crystal composition. A liquid crystal composite is formed by polymerizing a polymerizable composition containing the compound (1) and the liquid crystal composition. 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 performed at a temperature at which the polymerizable composition exhibits a liquid crystal phase. Polymerization occurs by heat, light, and the like. A preferred reaction is photopolymerization. The photopolymerization is preferably performed at 100 ° C. or lower in order to prevent thermal polymerization from occurring simultaneously. Polymerization may be carried out with an electric or magnetic field applied.

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

  Additional examples of photoradical 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, benzophenone / methyltriethanolamine mixture It is.

  After adding a radical photopolymerization initiator to the polymerizable composition, the polymerization can be carried out by irradiating ultraviolet rays with an electric field applied. However, the unreacted polymerization initiator or the decomposition product of the polymerization initiator may cause display defects such as image burn-in on the device. In order to avoid this, photopolymerization may be performed without adding a polymerization initiator. The preferable wavelength of the light to irradiate is in the range of 150 nm to 500 nm. A more preferable wavelength is in the range of 250 nm to 450 nm, and a most preferable wavelength is in the range of 300 nm to 400 nm.

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

5. Liquid crystal display element The effect of the polymer in a 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, the liquid crystal molecules are aligned in the direction of the electric field. According to this orientation, the molecules of the polymerizable compound are also oriented in the same direction. In this state, the composition is irradiated with ultraviolet rays to polymerize the polymerizable compound. This results in the formation of a polymer network in the polymerizable composition. Due to this network effect, the liquid crystal molecules are stabilized in the state of being aligned in the direction of the electric field. This effect is maintained even when the electric field is removed. Therefore, the response time of the element is shortened.

  The polymerization of the polymerizable composition is preferably performed in the display element. 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 the compound (1), a liquid crystal composition, an additive and the like as components is prepared. This composition is injected into the display element. The compound (1) is polymerized by irradiating ultraviolet rays while applying an electric field to the display element. A liquid crystal composite is formed by this polymerization. By this method, a liquid crystal display element having a liquid crystal composite can be easily produced. In this method, the 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 polymerizable compound is in the range of 0.1 wt% to 2 wt% based on the weight of the liquid crystal composition, a PSA mode liquid crystal display device is produced. An element 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 a reflection type, a transmission type, and a transflective type. By increasing the addition amount of the polymerizable compound, a polymer dispersed mode element can also be produced.

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

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

NMR analysis For measurement, DRX-500 manufactured by Bruker BioSpin Corporation 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. ^{For 19} F-NMR measurement, CFCl ₃ was used as an internal standard, and the number of integrations was 24. In the description of the nuclear magnetic resonance spectrum, s is a singlet, d is a doublet, t is a triplet, q is a quartet, quint is a quintet, sex is a sextet, m is a multiplet, and br is broad.

HPLC analysis For the measurement, Prominence (LC-20AD; SPD-20A) manufactured by Shimadzu Corporation was used. As the column, YMC-Pack ODS-A (length 150 mm, inner diameter 4.6 mm, particle diameter 5 μm) manufactured by YMC was used. As an eluent, acetonitrile and water were appropriately mixed and used. As a detector, a UV detector, an RI detector, a CORONA detector, or the like was appropriately used. When a UV detector was used, the detection wavelength was 254 nm. A sample was dissolved in acetonitrile to prepare a 0.1 wt% solution, and 1 μL of this solution was introduced into the sample chamber. As a recorder, C-R7 Plus manufactured by Shimadzu Corporation was used.

For the UV-Vis spectroscopic analysis, PharmaSpec UV-1700 manufactured by Shimadzu Corporation was used. The detection wavelength was 190 nm to 700 nm. The sample was dissolved in acetonitrile to prepare a 0.01 mmol / L solution, and the sample was placed in a quartz cell (optical path length 1 cm) and measured.

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, viscosity, optical anisotropy, dielectric anisotropy of the nematic phase, a mixture of a compound and a mother liquid crystal was used as a sample.

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

(1) Phase structure A sample was placed on a hot plate (Mettler FP-52 type hot stage) of a melting point measuring apparatus equipped with a polarizing microscope. While this sample was heated at a rate of 3 ° C./min, the phase state and its change were observed with a polarizing microscope to identify the type of phase.

(2) Transition temperature (° C)
For the measurement, a scanning calorimeter manufactured by Perkin Elmer, a Diamond DSC system, or a high-sensitivity differential scanning calorimeter manufactured by SSI Nanotechnology, Inc., X-DSC7000 was used. The sample was heated up and down at a rate of 3 ° C./min. The starting point of the endothermic peak or exothermic peak accompanying the phase change of the sample was obtained by extrapolation to determine the transition temperature. The melting point and polymerization initiation temperature of the compound 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 “lower limit temperature of liquid crystal phase”. The temperature at which the compound transitions from the liquid crystal phase to the liquid may be abbreviated as “clearing point”.

The crystal was represented as C. When the types of crystals can be distinguished, they are represented as C ₁ and C ₂ , respectively. The smectic phase is represented as S and the nematic phase is represented as N. In the smectic phase, when a smectic A phase, a smectic B phase, a smectic C phase, or a smectic F phase can be distinguished, 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 “C 50.0 N 100.0 I”, for example. This indicates that the transition temperature from the crystal to the nematic phase is 50.0 ° C., and the transition temperature from the nematic phase to the liquid is 100.0 ° C.

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

(4) Minimum Temperature of a Nematic Phase _{(T C;} ° C.)
A sample having a nematic phase was stored in a freezer at 0 ° C., −10 ° C., −20 ° C., −30 ° C., and −40 ° C. for 10 days, and then the liquid crystal phase was observed. For example, when the sample remained in a nematic phase at −20 ° C. and changed to a crystal or smectic phase at −30 ° C., _TC was described as ≦ −20 ° C. The lower limit temperature of the nematic phase may be abbreviated as “lower limit temperature”.

(5) Viscosity (bulk viscosity; η; measured at 20 ° C .; mPa · s)
The viscosity 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 with an Abbe refractometer using light having a wavelength of 589 nm and a polarizing plate attached to the eyepiece. After rubbing the surface of the main prism in one direction, the sample was dropped on the main prism. The refractive index (n‖) was measured when the direction of polarized light was parallel to the direction of rubbing. The refractive index (n⊥) was measured when the direction of polarized light was perpendicular to the direction of rubbing. The value of optical anisotropy (Δn) was calculated from the equation: Δn = n∥−n⊥.

(7) Specific resistance (ρ; measured at 25 ° C .; Ωcm)
1.0 mL of a sample was injected into a container equipped with an electrode. A DC voltage (10 V) was applied to the container, and the DC current after 10 seconds was measured. The specific resistance was calculated from the following equation. (Resistivity) = {(Voltage) × (Capacity of container)} / {(DC 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 (cell gap) between the two glass substrates was 5 μm. This element was sealed with an adhesive that was cured with ultraviolet rays after the sample was placed. The device was charged by applying a pulse voltage (60 microseconds at 5 V). The decaying voltage was measured for 16.7 milliseconds with a high-speed voltmeter, and the area A between the voltage curve and the horizontal axis in a unit cycle was determined. Area B was the area when it was not attenuated. The voltage holding ratio was expressed as a percentage of area A with respect to area B.

(9) Voltage holding ratio (VHR-2; measured at 80 ° C .;%)
The voltage holding ratio was measured by the above method except that the measurement was performed at 80 ° C. instead of 25 ° C. The results are indicated by the VHR-2 symbol.

  A physical property measurement method may differ between a sample having a positive dielectric anisotropy and a negative sample. The measurement method when the dielectric anisotropy is positive is described in the items (10a) to (14a). When the dielectric anisotropy is negative, it is described in the items (10b) to (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). A sample was put in a TN device in which the twist angle was 0 degree and the distance between two glass substrates (cell gap) was 5 μm. A voltage was applied to this device in steps of 0.5 V in the range of 16 V to 19.5 V. After no application for 0.2 seconds, the 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 the transient current generated by this application were measured. The value of rotational viscosity was obtained from these measured values and the paper by M. Imai et al., Formula (8) on page 40. The value of dielectric anisotropy necessary for this calculation was determined by the method described below using the element whose rotational viscosity was measured.

(10b) Viscosity (Rotational viscosity; γ1; measured at 25 ° C .; mPa · s)
Negative dielectric anisotropy: The measurement was according to the method described in M. Imai et al., Molecular Crystals and Liquid Crystals, Vol. 259, 37 (1995). A sample was put in a VA device having a distance (cell gap) between two glass substrates of 20 μm. The device was applied stepwise by 1 volt in the range of 39 to 50 volts. After no application for 0.2 seconds, the 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 the transient current generated by this application were measured. These measurements and M.I. The value of rotational viscosity was obtained from the paper by Imai et al., Calculation formula (8) on page 40. As the dielectric anisotropy necessary for this calculation, the value measured in the following dielectric anisotropy term was used.

(11a) Dielectric anisotropy (Δε; measured at 25 ° C.)
Positive dielectric anisotropy: A sample was put 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 (10 V, 1 kHz) were applied to the device, and after 2 seconds, the dielectric constant (ε‖) in the major axis direction of the liquid crystal molecules was measured. Sine waves (0.5 V, 1 kHz) were applied to the device, and after 2 seconds, the dielectric constant (ε⊥) in the minor axis direction of the liquid crystal molecules was measured. The value of dielectric anisotropy was calculated from the equation: Δε = ε∥−ε⊥.

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

(12a) Elastic constant (K; measured at 25 ° C .; pN)
Positive dielectric anisotropy: HP4284A LCR meter made by Yokogawa Hewlett-Packard Co. was used for measurement. A sample was put in a horizontal alignment element 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 applied voltage were measured. Using the formula (2.98) and formula (2.101) on page 75 of “Liquid Crystal Device Handbook” (Nikkan Kogyo Shimbun), the values of the measured capacitance (C) and applied voltage (V) are calculated. Fitting was performed, and values of K ₁₁ and K ₃₃ were obtained from the 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 obtained.

(12b) Elastic constants (K ₁₁ and K ₃₃ ; measured at 25 ° C .; pN)
Negative dielectric anisotropy: An EC-1 type elastic constant measuring instrument manufactured by Toyo Corporation was used for measurement. A sample was put in a vertical alignment element in which the distance between two glass substrates (cell gap) was 20 μm. A 20 to 0 volt charge was applied to the device, and the capacitance and applied voltage were measured. The values of capacitance (C) and applied voltage (V) were fitted using “Liquid Crystal Device Handbook” (Nikkan Kogyo Shimbun), page 75, formulas (2.98) and (2.101). The value of the elastic constant was obtained from the formula (2.100).

(13a) Threshold voltage (Vth; measured at 25 ° C .; V)
Positive dielectric anisotropy: An LCD5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for measurement. The light source was a halogen lamp. A sample was put in a normally white mode TN device in which the distance (cell gap) between two glass substrates was 0.45 / Δn (μm) and the twist angle was 80 degrees. The voltage (32 Hz, rectangular wave) applied to this element was increased stepwise from 0V to 10V by 0.02V. At this time, the device was irradiated with light from the vertical direction, and the amount of light transmitted through the device was measured. A voltage-transmittance curve was created in which the transmittance was 100% when the light amount reached the maximum and the transmittance was 0% when the light amount was the minimum. The threshold voltage was expressed as a voltage when the transmittance reached 90%.

(13b) Threshold voltage (Vth; measured at 25 ° C .; V)
Negative dielectric anisotropy: An LCD5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for measurement. The light source was a halogen lamp. A sample is placed in a normally black mode VA element in which the distance between two glass substrates (cell gap) is 4 μm and the rubbing direction is anti-parallel, and an adhesive that cures the element with ultraviolet rays is used. And sealed. The voltage (60 Hz, rectangular wave) applied to this element was increased stepwise from 0V to 20V by 0.02V. At this time, the device was irradiated with light from the vertical direction, and the amount of light transmitted through the device was measured. A voltage-transmittance curve was created in which the transmittance was 100% when the light amount reached the maximum and the transmittance was 0% when the light amount was the minimum. The threshold voltage was expressed as a voltage when the transmittance reached 10%.

(14a) Response time (τ; measured at 25 ° C .; ms)
Positive dielectric anisotropy: An LCD5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for measurement. The light source was a halogen lamp. The low-pass filter was set to 5 kHz. A sample was put 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 the maximum, and the transmittance was 0% when the light amount was the minimum. The rise time (τr: rise time; millisecond) is the time required for the transmittance to change from 90% to 10%. The fall time (τf: fall time; millisecond) is the time required to change the transmittance from 10% to 90%. The response time was expressed as the sum of the rise time and the fall time thus obtained.

(14b) Response time (τ; measured at 25 ° C .; ms)
Negative dielectric anisotropy: An LCD5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for measurement. The light source was a halogen lamp. The low-pass filter was set to 5 kHz. A sample was put in a normally black mode PVA device in which the distance between two glass substrates (cell gap) was 3.2 μm and the rubbing direction was anti-parallel. The device was sealed using an adhesive that was cured with ultraviolet light. A voltage slightly exceeding the threshold voltage was applied to the device for 1 minute, and then 23.5 mW / cm ² of ultraviolet light 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 the maximum, and the transmittance was 0% when the light amount was the minimum. The response time was expressed as the time required to change the transmittance from 90% to 10% (fall time; millisecond).

Synthesis of compound (No. 29)

First Step Under a nitrogen atmosphere, compound (T-1) (34.1 g, 0.1 mol), compound (T-2) (44.34 g, 0.2 mol), Pd-132 (0.14 g, 0.2 mmol) ), Potassium carbonate (55.3 g, 0.4 mol), tetrabutylammonium bromide (TBAB) (16.1 g, 0.05 mol) were added to toluene (140 ml), ethanol (140 ml), and water (350 ml) for 6 hours. Heated to reflux. The reaction mixture was returned to 25 ° C., and extracted by adding water (200 ml) and toluene (100 ml). The organic layer was washed with saturated brine and dried over anhydrous magnesium sulfate. The obtained solution was concentrated under reduced pressure, and the residue was purified by recrystallization from a mixed solvent of toluene and DMF (volume ratio, toluene: DMF = 1: 1) to obtain compound (T-3) (32.85 g). 0.067 mol, 67.2%).

Step 2 Under a nitrogen atmosphere, compound (T-3) (32.85 g, 0.067 mol) was added to a mixture of sodium hydroxide (14.4 g, 0.36 mol), methanol (130 ml), and water (65 ml), Heated to reflux for 2 hours. The reaction mixture was returned to 25 ° C. and water (200 ml) was added. Subsequently, dilute hydrochloric acid (10 ml) was added and stirred well. The precipitated crystals were extracted with toluene (100 ml). The organic layer was washed with saturated brine and dried over anhydrous magnesium sulfate. The obtained solution was concentrated under reduced pressure, and the residue was purified by recrystallization from a mixed solvent of toluene and DMF (volume ratio, toluene: DMF = 1: 1), dried, and compound (T-4) ( 22.19 g, 0.047 mol, 69.8%).

Step 3 Under a nitrogen atmosphere, compound (T-4) (22.19 g, 0.047 mol) was added to DMF (220 ml). Subsequently, potassium carbonate (8.2 g, 0.059 mol) and potassium iodide (0.98 g, 5.9 mmol) were added, and finally butenyl chloride (6.65 g, 0.073 mol) was added, and then at 100 ° C. for 4 hours. Reacted. The reaction mixture was returned to 25 ° C. and water (200 ml) was added. The precipitated crystals were extracted with dichloroethane (100 ml). The organic layer was washed with saturated brine and dried over anhydrous magnesium sulfate. The obtained solution was concentrated under reduced pressure, and the residue was purified by recrystallization from toluene to obtain Compound (T-5) (16.03 g, 0.030 mol, 63.8%).

Step 4 Under a nitrogen atmosphere, Compound (T-5) (16.03 g, 0.030 mol) was added to methanol (60 ml) and THF (320 ml). Subsequently, pyridinium p-toluenesulfonate (1.5 g, 5.97 mmol) was added and stirred at room temperature for 10 hours. After completion of the reaction, water (300 ml) was added and the precipitated crystals were extracted with dichloromethane (100 ml). The organic layer was washed with saturated brine and dried over anhydrous magnesium sulfate. The obtained solution was concentrated under reduced pressure, and the residue was purified by recrystallization from toluene to obtain Compound (T-6) (9.73 g, 0.027 mol, 90.0%).

Step 5 Compound (T-6) (9.73 g, 0.027 mol) was added to dichloroethane (200 ml) under a nitrogen atmosphere. Subsequently, dicyclohexylcarbodiimide (DCC) (11.1 g, 0.054 mol) and N, N-dimethyl-4-aminopyridine (DMAP) (0.33 g, 2.70 mmol) were added. Finally, methacrylic acid (4.88 g, 0.057 mmol) was added and stirred at room temperature for 24 hours. Water (100 ml) was added after completion of the reaction. The liberated organic phase was separated, washed with saturated brine, and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure and the residue was purified by silica gel chromatography (dichloroethane). Further, recrystallization from a mixed solvent of methanol and toluene (volume ratio, 10: 1) gave Compound (No. 29) (9.2 g, 0.019 mmol, 68.6%).

¹ H-NMR (CDCl ₃ ; δ ppm): 8.03 (d, 1H), 7.74-7.72 (m, 1H), 7.68-7.65 (m, 2H), 7.45 (D, 1H), 7.41-7.36 (m, 2H), 7.25-7.22 (m, 2H), 7.19-7.17 (m, 2H), 6.38 (d , 2H), 5.79-5.78 (m, 2H), 5.68-5.62 (m, 1H), 5.40-5.30 (m, 1H), 4.52 (d, 2H) ), 2.09 (s, 6H), 1.67-1.66 (m, 3H).

  The physical properties of the compound (No. 29) were as follows. Melting point: 99.1 ° C., polymerization initiation temperature: 119.5 ° C.

Synthesis of compound (No. 30)

First Step Under a nitrogen atmosphere, compound (T-7) (50.0 g, 0.187 mol) and potassium permanganate (591 g, 3.73 mol) were added to pyridine (1000 ml), and the mixture was stirred at 80 to 90 ° C. for 22 hours. did. The reaction mixture was returned to 25 ° C., filtered, and water (500 ml) was added to the filtrate. Dilute hydrochloric acid was added slowly until the mixture was acidic. The precipitated crystals were extracted with dichloroethane (150 ml). The organic layer was washed with saturated brine and dried over anhydrous magnesium sulfate. The obtained solution was concentrated under reduced pressure, and the residue was purified by recrystallization from n-hexane to obtain Compound (T-8) (26.74 g, 0.090 mol, 48.1%).

Second Step Compound (T-8) (26.74 g, 0.090 mol) was added to methanol (120 ml) under a nitrogen atmosphere. Subsequently, concentrated sulfuric acid (4.0 g) was added and heated to reflux for 22 hours. The reaction mixture was returned to 25 ° C. and water (200 ml) was added. The liberated oil was extracted with dichloroethane (100 ml). The organic layer was washed with saturated brine and dried over anhydrous magnesium sulfate. The obtained solution was concentrated under reduced pressure, and the residue was distilled to obtain compound (T-9) (26.67 g, 0.085 mol, 95.0%).

  In the synthesis method described in Example 1, compound (No. 30) was obtained by performing the same reaction using compound (T-9) instead of compound (T-1).

¹ H-NMR (CDCl ₃ ; δ ppm): 7.98 (d, 1H), 7.64-7.63 (m, 2H), 7.37-7.34 (m, 2H), 7.27 -7.23 (m, 2H), 7.20-7.16 (m, 3H), 6.38 (d, 2H), 5.80-5.78 (m, 2H), 5.69-5 .62 (m, 1H), 5.40-5.31 (m, 1H), 4.50 (d, 2H), 2.09 (s, 6H), 1.67-1.66 (m, 3H) ).

  The physical properties of the compound (No. 30) were as follows. Melting point: 76.4 ° C., polymerization initiation temperature: 134.2 ° C.

[Comparative Example 1]
Synthesis of Comparative Compound Comparative Compound (R-1) was synthesized according to the following reaction formula to obtain colorless crystals of Comparative Compound (R-1).

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

  The physical properties of the comparative compound (R-1) were as follows. Melting point: 150.0 ° C., polymerization start temperature: 167.5 ° C.

(Comparison of solubility in liquid crystal composition)
Compound (No. 29) was added to liquid crystal composition A at a ratio of 0.3% by weight and heated at 50 ° C. for 30 minutes. The solution was left at room temperature for 2 days. Then, it was observed visually whether the crystal | crystallization precipitated. Similarly, 0.3% by weight of the compound (No. 30) was added to the liquid crystal composition A and heated at 50 ° C. for 30 minutes. The solution was left at room temperature for 2 days. Then, it was observed visually whether the crystal | crystallization precipitated. On the other hand, the comparative compound (R-1) was also observed by the same method. Table 1 shows the results. From Table 1, it can be seen that the polymerizable compound of the present invention has good solubility in the liquid crystal composition A. In addition, the component of the liquid crystal composition A and its ratio were as follows.

Table 1. Comparison of solubility in liquid crystal composition

  By referring to the experimental procedure described in Examples 1 and 2 and “2. Synthesis method”, it is possible to synthesize the compound (No. 204) from the compound (No. 1) shown below.

1-2. Example of Composition (1) The liquid crystal composition (1) of the present invention will be described in detail by way of examples. The invention is not limited by these examples. The present invention includes a mixture of the composition of Example 1 and the composition of Example 2. The invention also includes a mixture of at least two of the example compositions. The compounds in Examples were represented by symbols based on the definitions in Table 2 below. In Table 2, the configuration regarding 1,4-cyclohexylene is trans. In the examples, the number in parentheses after the symbol corresponds to the compound number. 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 are summarized. The 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． 3-HB-O2 (2-5) 10%
5-HB-CL (5-2) 10%
3-HBB (F, F) -F (6-24) 10%
3-PyB (F) -F (5-15) 10%
5-PyB (F) -F (5-15) 10%
3-PyBB-F (6-80) 10%
4-PyBB-F (6-80) 10%
5-PyBB-F (6-80) 10%
5-HBB (F) B-2 (4-5) 10%
5-HBB (F) B-3 (4-5) 10%
The following compound (No. 29) was added to the composition at a ratio of 0.3% by weight.

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

ＮＩ＝１００．５℃；Δｎ＝０．１００；Δε＝４．６；η＝１７．９ｍＰａ・ｓ． 2-HB-C (8-1) 5%
3-HB-C (8-1) 12%
3-HB-O2 (2-5) 15%
2-BTB-1 (2-10) 3%
3-HHB-F (6-1) 4%
3-HHB-1 (3-1) 8%
3-HHB-O1 (3-1) 5%
3-HHB-3 (3-1) 14%
3-HHEB-F (6-10) 4%
5-HHEB-F (6-10) 4%
2-HHB (F) -F (6-2) 7%
3-HHB (F) -F (6-2) 7%
5-HHB (F) -F (6-2) 7%
3-HHB (F, F) -F (6-3) 5%
The following compound (No. 30) was added to the composition at a ratio of 0.25% by weight.

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

ＮＩ＝９７．８℃；Δｎ＝０．１１６；Δε＝９．０；η＝３５．０ｍＰａ・ｓ． 3-HHB (F, F) -F (6-3) 9%
3-H2HB (F, F) -F (6-15) 8%
4-H2HB (F, F) -F (6-15) 8%
5-H2HB (F, F) -F (6-15) 8%
3-HBB (F, F) -F (6-24) 21%
5-HBB (F, F) -F (6-24) 20%
3-H2BB (F, F) -F (6-27) 10%
5-HHBB (F, F) -F (7-6) 3%
5-HHEBB-F (7-17) 2%
3-HH2BB (F, F) -F (7-15) 3%
1O1-HBBH-4 (4-1) 4%
1O1-HBBH-5 (4-1) 4%
The following compound (No. 29) was added to the composition at a ratio of 0.1% by weight.

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

ＮＩ＝８０．２℃；Δｎ＝０．１０３；Δε＝８．７；η＝２２．４ｍＰａ・ｓ． 5-HB-CL (5-2) 11%
3-HH-4 (2-1) 8%
3-HHB-1 (3-1) 5%
3-HHB (F, F) -F (6-3) 8%
3-HBB (F, F) -F (6-24) 20%
5-HBB (F, F) -F (6-24) 15%
3-HHEB (F, F) -F (6-12) 10%
4-HHEB (F, F) -F (6-12) 3%
5-HHEB (F, F) -F (6-12) 3%
2-HBEB (F, F) -F (6-39) 3%
3-HBEB (F, F) -F (6-39) 5%
5-HBEB (F, F) -F (6-39) 3%
3-HHBB (F, F) -F (7-6) 6%
The following compound (No. 30) was added to the composition at a ratio of 0.3% by weight.

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

ＮＩ＝７９．４℃；Δｎ＝０．０６４；Δε＝５．７；η＝１９．９ｍＰａ・ｓ． 5-HB-CL (5-2) 3%
7-HB (F) -F (5-3) 7%
3-HH-4 (2-1) 9%
3-HH-EMe (2-2) 23%
3-HHEB-F (6-10) 8%
5-HHEB-F (6-10) 8%
3-HHEB (F, F) -F (6-12) 10%
4-HHEB (F, F) -F (6-12) 5%
4-HGB (F, F) -F (6-103) 5%
5-HGB (F, F) -F (6-103) 6%
2-H2GB (F, F) -F (6-106) 4%
3-H2GB (F, F) -F (6-106) 5%
5-GHB (F, F) -F (6-109) 7%
The following compound (No. 29) was added to the composition at a ratio of 0.2% by weight.

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

ＮＩ＝８６．５℃；Δｎ＝０．０９０；Δε＝−３．４；η＝３５．３ｍＰａ・ｓ． 3-HB-O1 (2-5) 15%
3-HH-4 (2-1) 5%
3-HB (2F, 3F) -O2 (9-1) 12%
5-HB (2F, 3F) -O2 (9-1) 12%
2-HHB (2F, 3F) -1 (10-1) 12%
3-HHB (2F, 3F) -1 (10-1) 12%
3-HHB (2F, 3F) -O2 (10-1) 13%
5-HHB (2F, 3F) -O2 (10-1) 13%
3-HHB-1 (3-1) 6%
The following compound (No. 30) was added to the composition at a ratio of 0.4% by weight.

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

ＮＩ＝９１．５℃；Δｎ＝０．１００；Δε＝−４．１；η＝２９．２ｍＰａ・ｓ． 3-HH-4 (2-1) 8%
3-H2B (2F, 3F) -O2 (9-1) 22%
5-H2B (2F, 3F) -O2 (9-1) 22%
2-HHB (2F, 3CL) -O2 (10-12) 2%
3-HHB (2F, 3CL) -O2 (10-12) 3%
4-HHB (2F, 3CL) -O2 (10-12) 2%
5-HHB (2F, 3CL) -O2 (10-12) 2%
3-HBB (2F, 3F) -O2 (10-7) 9%
5-HBB (2F, 3F) -O2 (10-7) 9%
V-HHB-1 (3-1) 6%
3-HHB-3 (3-1) 6%
3-HHEBH-3 (4-6) 3%
3-HHEBH-4 (4-6) 3%
3-HHEBH-5 (4-6) 3%
The following compound (No. 29) was added to the composition at a ratio of 0.35% by weight.

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

ＮＩ＝７５．７℃；Δｎ＝０．０９３；Δε＝−４．１；η＝１９．２ｍＰａ・ｓ． 2-HH-5 (2-1) 3%
3-HH-4 (2-1) 15%
3-HH-5 (2-1) 4%
3-HB-O2 (2-5) 12%
3-H2B (2F, 3F) -O2 (9-4) 15%
5-H2B (2F, 3F) -O2 (9-4) 15%
3-HHB (2F, 3CL) -O2 (10-12) 5%
2-HBB (2F, 3F) -O2 (10-7) 3%
3-HBB (2F, 3F) -O2 (10-7) 9%
5-HBB (2F, 3F) -O2 (10-7) 9%
3-HHB-1 (3-1) 3%
3-HHB-3 (3-1) 4%
3-HHB-O1 (3-1) 3%
The following compound (No. 30) was added to the said composition in the ratio of 0.15 weight%.

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

ＮＩ＝７４．３℃；Δｎ＝０．０９７；Δε＝−３．２；η＝１５．３ｍＰａ・ｓ． 2-HH-3 (2-1) 21%
3-HH-4 (2-1) 9%
1-BB-3 (2-8) 9%
3-HB-O2 (2-5) 2%
3-BB (2F, 3F) -O2 (9-3) 9%
5-BB (2F, 3F) -O2 (9-3) 6%
2-HH1OB (2F, 3F) -O2 (10-5) 13%
3-HH1OB (2F, 3F) -O2 (10-5) 21%
3-HHB-1 (3-1) 5%
3-HHB-O1 (3-1) 3%
5-B (F) BB-2 (3-8) 2%
The following compound (No. 29) was added to the 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． 2-HH-3 (2-1) 16%
7-HB-1 (2-5) 10%
5-HB-O2 (2-5) 8%
3-HB (2F, 3F) -O2 (9-1) 12%
5-HB (2F, 3F) -O2 (9-1) 16%
3-HHB (2F, 3CL) -O2 (10-12) 3%
4-HHB (2F, 3CL) -O2 (10-12) 3%
5-HHB (2F, 3CL) -O2 (10-12) 2%
3-HH1OCro (7F, 8F) -5 (12-3) 5%
5-HBB (F) B-2 (4-5) 10%
5-HBB (F) B-3 (4-5) 10%
3-HDhB (2F, 3F) -O2 (10-3) 5%
The following compound (No. 30) was added to the composition at a ratio of 0.3% by weight.

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

ＮＩ＝７４．５℃；Δｎ＝０．１０６；Δε＝−３．０；η＝１４．７ｍＰａ・ｓ． 1-BB-3 (2-8) 10%
3-HH-V (2-1) 29%
3-BB (2F, 3F) -O2 (9-3) 13%
2-HH1OB (2F, 3F) -O2 (10-5) 20%
3-HH1OB (2F, 3F) -O2 (10-5) 14%
3-HHB-1 (3-1) 8%
5-B (F) BB-2 (3-8) 6%
The following compound (No. 29) was added to the composition at a ratio of 0.3% by weight.

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

ＮＩ＝８０．６℃；Δｎ＝０．１３１；Δε＝７．７；η＝１２．４ｍＰａ・ｓ． 1V2-BEB (F, F) -C (8-15) 8%
3-HB-C (8-1) 16%
2-BTB-1 (2-10) 10%
5-HH-VFF (2-1) 30%
3-HHB-1 (3-1) 4%
VFF-HHB-1 (3-1) 8%
VFF2-HHB-1 (3-1) 11%
3-H2BTB-2 (3-17) 5%
3-H2BTB-3 (3-17) 4%
3-H2BTB-4 (3-17) 4%
The following compounds (No. 29) and (No. 30) were respectively added to the composition at a ratio of 0.2% by weight.

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

ＮＩ＝８１．９℃；Δｎ＝０．１０５；Δε＝６．３；η＝１２．０ｍＰａ・ｓ． 5-HB (F) B (F, F) XB (F, F) -F (7-14) 5%
3-BB (F) B (F, F) XB (F, F) -F (7-47) 3%
4-BB (F) B (F, F) XB (F, F) -F (7-47) 7%
5-BB (F) B (F, F) XB (F, F) -F (7-47) 3%
3-HH-V (2-1) 41%
3-HH-V1 (2-1) 7%
3-HHEH-5 (3-13) 3%
3-HHB-1 (3-1) 4%
V-HHB-1 (3-1) 5%
V2-BB (F) B-1 (3-6) 5%
1V2-BB-F (2-8) 3%
3-BB (F, F) XB (F, F) -F (6-97) 11%
3-HHBB (F, F) -F (7-6) 3%
The following compound (No. 30) was added to the composition at a ratio of 0.3% by weight.

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

ＮＩ＝８１．３℃；Δｎ＝０．１０３；Δε＝７．４；η＝１２．８ｍＰａ・ｓ． 3-GB (F) B (F, F) XB (F, F) -F (7-57) 5%
3-BB (F) B (F, F) XB (F, F) -F (7-47) 3%
4-BB (F) B (F, F) XB (F, F) -F (7-47) 7%
5-BB (F) B (F, F) XB (F, F) -F (7-47) 3%
3-HH-V (2-1) 41%
3-HH-V1 (2-1) 7%
3-HHEH-5 (3-13) 3%
3-HHB-1 (3-1) 4%
V-HHB-1 (3-1) 5%
V2-BB (F) B-1 (3-6) 5%
1V2-BB-F (2-8) 3%
3-BB (F, F) XB (F, F) -F (6-97) 6%
3-GB (F, F) XB (F, F) -F (6-113) 5%
3-HHBB (F, F) -F (7-6) 3%
The following compound (No. 29) was added to the composition at a ratio of 0.3% by weight.

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

  By polymerizing a polymerizable composition containing compound (1) and a 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 for optical anisotropic bodies.

Claims (19)

A polymerizable compound having at least two polymerizable groups, wherein at least one polymerizable group is acryloyloxy or methacryloyloxy, and at least one polymerizable group is represented by formula (P-1).

In Formula (P-1), R ¹ is alkyl having 2 to 15 carbons in which at least one —CH ₂ CH ₂ — is replaced by —CH═CH— or —C≡C—, and these groups In which at least one hydrogen may be replaced by a halogen. The polymerizable compound according to claim 1 represented by formula (1).

In equation (1),
P ¹ , (b1 × a1) P ² , (b2 × a2) P ³ , (b3 × a3) P ⁴ , a4 P ⁵ , and P ⁶ are polymerizable groups, At least one of the polymerizable groups is an acryloyloxy or methacryloyloxy, and the remaining at least one is a polymerizable group represented by the formula (P-1);

In formula (P-1), R ¹ is alkenyl having 2 to 15 carbons or alkynyl having 2 to 15 carbons, and in these groups, at least one hydrogen may be replaced by halogen;
S ¹ , S ² , S ³ , S ⁴ , S ⁵ , and S ⁶ are each independently a single bond or alkylene having 1 to 10 carbons, in which at least one —CH ₂ — is — O—, —COO—, —OCO—, or —OCOO— may be substituted, and at least one —CH ₂ —CH ₂ — may be substituted with —CH═CH— or —C≡C—. Well, in these groups at least one hydrogen may be replaced by a halogen;
a1, a2, a3, and a4 are independently 0, 1, 2, 3, or 4, and the sum of a1, a2, a3, and a4 is an integer from 0 to 10;
Ring A ¹ , Ring A ² , Ring A ³ , and Ring A ⁴ are independently 1,4-phenylene, pyrimidine-2,5-diyl, pyridine-2,5-diyl, naphthalene-1,2-diyl. , Naphthalene-1,3-diyl, naphthalene-1,4-diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene -2,3-diyl, naphthalene-2,6-diyl, naphthalene-2,7-diyl, 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, or 1 , 3-dioxane-2,5-diyl, in which at least one hydrogen may be replaced by halogen or alkyl of 1 to 12 carbons, Wherein one or two —CH ₂ — may be replaced by —O—, in which at least one hydrogen may be replaced by a halogen;
Z ¹ , Z ² and Z ³ are each independently a single bond or alkylene having 1 to 10 carbon atoms, and in this alkylene, at least one —CH ₂ — is —O—, —CO—, —COO—. is, -CH = _CH - -, - or -OCO- may be replaced by at least one _{-CH 2 -CH 2, C (CH} 3) = CH -, - CH = C (CH 3) -, or _{-C (CH 3) = C (} CH 3) - may be replaced by at least one hydrogen in these groups may be replaced by halogen;
b1, b2 and b3 are independently 0 or 1;
Here, in the case of a1, a2, a3, and the integer sum of 2 to 10 a4, one or both ^-S 1 -P ¹ and ^-S 6 -P ⁶ may be hydrogen. In the formula (1) according to claim ^{2, P 1, P 2,} P 3, P 4, P 5, and at least one ^{P 6,} is acryloyloxy or methacryloyloxy, remaining at least one polymerizable Formula (P-1) which is a group is a polymerizable group represented by Formula (P-2) or (P-3);

In the formulas (P-2) and (P-3), R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R ⁸ are hydrogen, fluorine, chlorine, or alkyl having 1 to 10 carbons And in this alkyl at least one —CH ₂ CH ₂ — may be replaced by —CH═CH— or —C≡C—, in which at least one hydrogen is replaced by fluorine or chlorine. May be;
S ¹ , S ² , S ³ , S ⁴ , S ⁵ , and S ⁶ are each independently a single bond or alkylene having 1 to 10 carbons, in which one —CH ₂ — represents —O -, - COO -, - OCO- , or -OCOO- may be replaced by one of _-CH 2 -CH ₂ - may be replaced by -CH = CH- or -C≡C-, At least one hydrogen may be replaced by fluorine or chlorine;
a1, a2, a3, and a4 are independently 0, 1, 2, or 3, and the sum of a1, a2, a3, and a4 is an integer from 0 to 6;
Ring A ¹ , Ring A ² , Ring A ³ , and Ring A ⁴ are independently 1,4-phenylene, pyrimidine-2,5-diyl, pyridine-2,5-diyl, naphthalene-1,4-diyl , Naphthalene-1,5-diyl, naphthalene-2,6-diyl, 1,4-cyclohexylene, tetrahydropyran-2,5-diyl, or 1,3-dioxane-2,5-diyl, these Wherein at least one hydrogen may be replaced by fluorine, chlorine, alkyl having 1 to 3 carbons, or alkyl having 1 to 3 carbons in which at least one hydrogen is replaced by fluorine or chlorine;
Z ¹ , Z ² and Z ³ are each independently a single bond, alkylene having 1 to 5 carbons, —CO—, —COO—, —OCO—, —CH═CH—, —CH═CH—COO—, _{-OCO-CH = CH -, -} C (CH 3) = CH-COO -, - OCO-CH = C (CH 3) -, - CH = C (CH 3) -COO -, - OCO- (CH 3 _{) C = CH -, - C} (CH 3) = C (CH 3) -COO -, - OCO-C (CH 3) = C (CH 3) -, - CO-CH = CH -, - CH = CH _{-CO -, - C (CH 3} ) = C (CH 3) -, - CH = CH-CH 2 O -, - OCH 2 -CH = CH -, - CH = CH-OCH 2 -, or -CH ₂ O—CH═CH—;
b1, b2 and b3 are independently 0 or 1;
Here, the polymerizable compound according to claim 2, wherein one or both of —S ¹ —P ¹ and —S ⁶ —P ⁶ may be hydrogen. The polymerizable compound according to any one of claims 1 to 3, which is represented by the formula (1-1).

In formula (1-1),
P ⁷ , (d1 × c1) P ⁸ , (d2 × c2) P ⁹ , (d3 × c3) P ¹⁰ , c4 P ¹¹ , and P ¹² are polymerizable groups, and At least one of the polymerizable groups of acryloyloxy or methacryloyloxy is at least one of vinyloxycarbonyl, 1-propenyloxycarbonyl, 2-propenyloxycarbonyl, 2-methyl-2-propenyl. Oxycarbonyl, 2-butenyloxycarbonyl, or 3-methyl-2-butenyloxycarbonyl;
S ⁷ , S ⁸ , S ⁹ , S ¹⁰ , S ¹¹ , and S ¹² are each independently a single bond or alkylene having 1 to 5 carbons, in which one —CH ₂ — represents —O -, - COO-, or may be replaced by -OCO-, 1 single _-CH 2 -CH ₂ -, which may be replaced by -CH = CH-;
c1, c2, c3, and c4 are independently 0, 1 or 2, and the sum of c1, c2, c3, and c4 is an integer from 0 to 5;
Ring A ⁵ , Ring A ⁶ , Ring A ⁷ , and Ring A ⁸ are independently 1,4-phenylene, pyrimidine-2,5-diyl, pyridine-2,5-diyl, 1,4-cyclohexylene. 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, or 1,3-dioxane-2,5-diyl, in which at least one hydrogen is fluorine, chlorine, carbon number 1 to 3 alkyls, or 1 to 3 alkyls in which at least one hydrogen is replaced by fluorine or chlorine may be substituted;
Z ⁴ , Z ⁵ and Z ⁶ are each independently a single bond, alkylene having 1 to 5 carbons, —CO—, —COO—, —OCO—, —CH═CH—, —CH═CH—COO—, _{-OCO-CH = CH -, -} C (CH 3) = CH-COO -, - OCO-CH = C (CH 3) -, - CH = C (CH 3) -COO -, - OCO- (CH 3 _{) C = CH -, - C} (CH 3) = C (CH 3) -COO -, - OCO-C (CH 3) = C (CH 3) -, - CO-CH = CH -, - CH = CH _{-CO -, - C (CH 3} ) = C (CH 3) -, - CH = CH-CH 2 O -, - OCH 2 -CH = CH -, - CH = CH-OCH 2 -, or -CH ₂ O—CH═CH—;
d1, d2 and d3 are independently 0 or 1. In formula (1-1) of claim 4, P ⁷ and P ¹² are independently acryloyloxy or methacryloyloxy, and at least one of P ⁸ , P ⁹ , P ¹⁰ , and P ¹¹ is acryloyloxy or methacryloyl. Oxy and at least one remaining is vinyloxycarbonyl, 1-propenyloxycarbonyl, 2-propenyloxycarbonyl, 2-methyl-2-propenyloxycarbonyl, 2-butenyloxycarbonyl, or 3-methyl-2- Butenyloxycarbonyl;
S ⁷ , S ⁸ , S ⁹ , S ¹⁰ , S ¹¹ , and S ¹² are single bonds;
c1, c2, c3, and c4 are independently 0 or 1, and the sum of c1, c2, c3, and c4 is an integer from 0 to 4;
Ring A ⁵ , Ring A ⁶ , Ring A ⁷ , and Ring A ⁸ are independently 1,4-phenylene, in which at least one hydrogen is fluorine, chlorine, alkyl having 1 to 3 carbons, Or at least one hydrogen may be replaced by alkyl of 1 to 3 carbons replaced by fluorine or chlorine;
Z ⁴ , Z ⁵ and Z ⁶ are single bonds;
The polymerizable compound according to claim 4, wherein d1, d2 and d3 are independently 0 or 1. The polymerizable compound according to any one of claims 1 to 4, which is represented by the formula (1-2) or (1-3).

In formula (1-2) or (1-3),
P ¹³ , e 1 P ¹⁴ , e 2 P ¹⁵ , e 3 P ¹⁶ , e 4 P ¹⁷ , and P ¹⁸ are polymerizable groups, and at least one of these polymerizable groups is: Acryloyloxy or methacryloyloxy, at least one of the remaining being vinyloxycarbonyl, 1-propenyloxycarbonyl, 2-propenyloxycarbonyl, 2-methyl-2-propenyloxycarbonyl, 2-butenyloxycarbonyl, or 3 -Methyl-2-butenyloxycarbonyl;
S ¹³ , S ¹⁴ , S ¹⁵ , S ¹⁶ , S ¹⁷ , and S ¹⁸ are each independently a single bond or alkylene having 1 to 5 carbons, in which one —CH ₂ — represents —O -, - COO-, or may be replaced by -OCO-, 1 single _-CH 2 -CH ₂ - may be replaced by -CH = CH-;
e1, e2, e3, and e4 are independently 0, 1 or 2, and the sum of e1, e2, e3, and e4 is an integer from 0 to 3;
Ring A ⁹ , Ring A ¹⁰ , Ring A ¹¹ , and Ring A ¹² are 1,4-phenylene, in which at least one hydrogen is fluorine, chlorine, alkyl of 1 to 3 carbons, or at least one hydrogen May be replaced by alkyl having 1 to 3 carbon atoms replaced by fluorine or chlorine;
Z ⁷ , Z ⁸ and Z ⁹ are each independently a single bond, alkylene having 1 to 5 carbons, —CO—, —COO—, —OCO—, —CH═CH—, —CH═CH—COO—, _{-OCO-CH = CH -, -} C (CH 3) = CH-COO -, - OCO-CH = C (CH 3) -, - CH = C (CH 3) -COO -, - OCO- (CH 3 _{) C = CH -, - C} (CH 3) = C (CH 3) -COO -, - OCO-C (CH 3) = C (CH 3) -, - CO-CH = CH -, - CH = CH _{-CO -, - C (CH 3} ) = C (CH 3) -, - CH = CH-CH 2 O -, - OCH 2 -CH = CH -, - CH = CH-OCH 2 -, or -CH ₂ O—CH═CH—. The polymerizable compound according to any one of claims 1 to 4, which is represented by the formula (1-4) or (1-5).

In formulas (1-4) and (1-5), P ¹⁹ , f1 P ²⁰ , f2 P ²¹ , f3 P ²² , f4 P ²³ , and P ²⁴ are polymerizable groups, At least one of these polymerizable groups is acryloyloxy or methacryloyloxy, and the remaining at least one is vinyloxycarbonyl, 1-propenyloxycarbonyl, 2-propenyloxycarbonyl, 2-methyl-2- Propenyloxycarbonyl, 2-butenyloxycarbonyl, or 3-methyl-2-butenyloxycarbonyl;
S ¹⁹ , S ²⁰ , S ²¹ , S ²² , S ²³ , and S ²⁴ are each independently a single bond, —CH ₂ —, —CH ₂ O—, —OCH ₂ —, —COO—, —OCO—, _{-CH = CH -, - C≡C -} , - CH 2 CH 2 O -, - OCH 2 CH 2 -, - CH = CH-O-, or -O-CH = CH- and is;
f1, f2, f3 and f4 are independently 0, 1 or 2, and the sum of f1, f2, f3 and f4 is 0, 1 or 2;
Ring A ¹³ is 1,4-phenylene in which at least one hydrogen may be replaced with fluorine, methyl, fluoromethyl, difluoromethyl, or trifluoromethyl;
Z ¹⁰ , Z ¹¹ and Z ¹² are each independently a single bond, —CO—, —COO—, —CH═CH—, —CH═CH—COO—, —C (CH ₃ ) ═CH—COO—, _{-CH = C (CH 3) -COO} -, - C (CH 3) = C (CH 3) -COO -, - COCH = CH -, - C (CH 3) = C (CH 3) -, - CH = _CH-CH 2 O-, or -CH = CH-OCH ₂ - it is. In formulas (1-4) and (1-5) of claim 7, at least one of P ¹⁹ , P ²⁰ , P ²¹ , P ²² , P ²³ , and P ²⁴ is acryloyloxy or methacryloyloxy, The remaining at least one is vinyloxycarbonyl, 1-propenyloxycarbonyl, 2-propenyloxycarbonyl, 2-methyl-2-propenyloxycarbonyl, 2-butenyloxycarbonyl, or 3-methyl-2-butenyloxy Is carbonyl;
S ¹⁹ , S ²⁰ , S ²¹ , S ²² , S ²³ , and S ²⁴ are each independently a single bond, —CH ₂ —, —CH ₂ O—, —OCH ₂ —, —COO—, —OCO—, _{-CH = CH -, - C≡C -} , - CH 2 CH 2 O -, - OCH 2 CH 2 -, - CH = CH-O-, or -O-CH = CH- and is;
f1, f2, f3 and f4 are independently 0, 1 or 2, and the sum of f1, f2, f3 and f4 is 0, 1 or 2;
Ring A ¹³ is 1,4-phenylene in which at least one hydrogen may be replaced by fluorine, methyl or trifluoromethyl;
Z ¹⁰ , Z ¹¹ and Z ¹² are each independently a single bond, —CO—, —COO—, —CH═CH—, —CH═CH—COO—, —CH═CH—CH ₂ O—, or — The polymerizable compound according to claim 7, wherein CH═CH—OCH ₂ —. The polymerizable compound according to any one of claims 1 to 4, which is represented by the formula (1-6) or (1-7).

In formula (1-6) or (1-7),
P ²⁵ , g 1 P ²⁶ , g 2 P ²⁷ , g 3 P ²⁸ , g 4 P ²⁹ , and P ³⁰ are acryloyloxy, methacryloyloxy, vinyloxycarbonyl, 1-propenyloxycarbonyl, 2-propenyl Oxycarbonyl, 2-methyl-2-propenyloxycarbonyl, 2-butenyloxycarbonyl, or 3-methyl-2-butenyloxycarbonyl, P ²⁵ , g 1 P ²⁶ , g 2 P ²⁷ , g 3 At least one of P ²⁸ , g 4 P ²⁹ , and P ³⁰ is acryloyloxy or methacryloyloxy, and at least one of the other is vinyloxycarbonyl, 1-propenyloxycarbonyl, 2-propenyl Oxycarbonyl, 2-methyl-2-propenyloxyca Rubonyl, 2-butenyloxycarbonyl, or 3-methyl-2-butenyloxycarbonyl;
S ²⁵ , S ²⁶ , S ²⁷ , S ²⁸ , S ²⁹ , and S ³⁰ are each independently a single bond, —CH ₂ —, —CH ₂ O—, —OCH ₂ —, —COO—, —OCO—, _{-CH = CH -, - C≡C -} , - CH 2 CH 2 O -, - OCH 2 CH 2 -, - CH = CH-O-, or -O-CH = CH- and is;
g1, g2, g3 and g4 are independently 0, 1 or 2, and the sum of g1, g2, g3 and g4 is 0, 1, 2 or 3. The polymerizable compound according to claim 1, which is represented by formula (1-8) or (1-9).

In formulas (1-8) and (1-9), P ³¹ , P ³² and P ³³ are acryloyloxy, methacryloyloxy, vinyloxycarbonyl, 1-propenyloxycarbonyl, 2-propenyloxycarbonyl, 2-methyl-2 - propenyloxy carbonyl, 2-butenyl butyloxycarbonyl or 3-methyl-2-butenyl oxy carbonyl, at least one acryloyloxy or methacryloyloxy of P ^31, P ³² and P ^33, the remaining At least one of vinyloxycarbonyl, 1-propenyloxycarbonyl, 2-propenyloxycarbonyl, 2-methyl-2-propenyloxycarbonyl, 2-butenyloxycarbonyl, or 3-methyl-2-butenyloxycarbonyl so Ri; h1 is 0 or 1.   A polymerizable composition comprising at least one of the polymerizable compounds according to claim 1. The polymerizable composition according to claim 11, further comprising at least one compound selected from the group of compounds represented by formulas (2) to (4).

In the equations (2) to (4),
R ¹¹ and R ¹² are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl or alkenyl, at least one —CH ₂ — may be replaced by —O—. Well, at least one hydrogen may be replaced by fluorine;
Ring B ¹ , Ring B ² , Ring B ³ , and Ring B 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 ¹¹ , Z ¹² and Z ¹³ are each independently a single bond, —CH ₂ CH ₂ —, —CH═CH—, —C≡C—, or —COO—. The polymerizable composition according to claim 11 or 12, further comprising at least one compound selected from the group of compounds represented by formulas (5) to (7).

In equations (5) to (7),
R ¹³ is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, in which at least one —CH ₂ — may be replaced by —O—, and at least one hydrogen is May be replaced by fluorine;
X ¹¹ is fluorine, chlorine, —OCF ₃ , —OCHF ₂ , —CF ₃ , —CHF ₂ , —CH ₂ F, —OCF ₂ CHF ₂ , or —OCF ₂ CHFCF ₃ ;
Ring C ¹ , Ring C ² and Ring C 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 ¹⁴ , Z ¹⁵ and Z ¹⁶ are each 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. The polymerizable composition according to any one of claims 11 to 13, further comprising at least one compound selected from the group of compounds represented by formula (8).

In equation (8),
R ¹⁴ is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in alkyl and alkenyl, at least one —CH ₂ — may be replaced by —O—, and at least one hydrogen is fluorine. May be replaced by;
X ¹² is —C≡N or —C≡C—C≡N;
Ring ^{D 1} is 1,4-cyclohexylene, at least one hydrogen replaced by or 1,4-phenylene with fluorine, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl Or pyrimidine-2,5-diyl;
Z ¹⁷ represents 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 claim 11, further comprising at least one compound selected from the group of compounds represented by formulas (9) to (15).

In the equations (9) to (15),
R ¹⁵ and R ¹⁶ are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, in which at least one —CH ₂ — may be replaced by —O—. Well, at least one hydrogen may be replaced by fluorine;
R ¹⁷ 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;
Ring E ¹ , Ring E ² , Ring E ³ , and Ring E ⁴ are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, wherein at least one hydrogen may be replaced with fluorine, 4-phenylene, tetrahydropyran-2,5-diyl, or decahydronaphthalene-2,6-diyl;
Ring E ⁵ and Ring E ⁶ are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, tetrahydropyran-2,5-diyl, or decahydronaphthalene-2,6. -Diyl;
^{Z 18, Z 19, Z 20} , and ^{Z 21} are independently a single _{bond, -CH 2 CH 2 -, -} COO -, - CH 2 O -, - OCF 2 -, or -OCF ₂ CH ₂ CH ₂ -Is;
L ¹⁵ and L ¹⁶ are independently fluorine or chlorine;
S ⁴¹ is hydrogen or methyl;
X is —CHF— or —CF ₂ —;
j, k, m, n, p, q, r, and s are independently 0 or 1, the sum of k, m, n, and p is 1 or 2, q, r, and The sum of s is 0, 1, 2, or 3, and t is 1, 2, or 3.   The liquid crystal composite produced | generated by superposition | polymerization of the polymeric composition of any one of Claim 11 to 15.   The optical anisotropic body produced | generated by superposition | polymerization of the polymeric composition of any one of Claim 11 to 15.   A liquid crystal display device comprising the polymerizable composition according to any one of claims 11 to 15 or the liquid crystal composite according to claim 16.   In a liquid crystal display element, selected from the group of the compound according to any one of claims 1 to 10, the polymerizable composition according to any one of claims 11 to 15, and the liquid crystal composite according to claim 16. At least one use.