JP5978938B2 - Polymerizable compound, polymerizable composition, and liquid crystal display device - Google Patents

Description

  The present invention relates to a polymerizable compound, a polymerizable composition containing the polymerizable compound and a liquid crystal composition, a liquid crystal composite prepared from the polymerizable composition, 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 2012-0823350 A US Patent No. 2011/0233464 International Publication No. 2011-074384 Pamphlet JP 2009-244433 A European Patent No. 116769

  The first object of the present invention is to provide a polymerizable compound having appropriate polymerization reactivity, high conversion rate, 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 of the present invention 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（１）において、
Ｐ^１およびＰ^２は独立して、重合性基、水素、ハロゲン、または炭素数１〜２０のアルキルであり、このアルキルにおいて、少なくとも１つの−ＣＨ_２−は−Ｏ−または−Ｓ−で置き換えられてもよく、少なくとも１つの−ＣＨ_２ＣＨ_２−は−ＣＨ＝ＣＨ−で置き換えられてもよく、これらの基において、少なくとも１つの水素はハロゲンで置き換えられてもよく、ここでＰ^１およびＰ^２の少なくとも１つは重合性基であり；
環Ａ^１、環Ａ^２、環Ａ^３、環Ａ^４、環Ａ^５、および環Ａ^６は独立して、１，４−シクロへキシレン、１，４−シクロヘキセニレン、１，４−フェニレン、ナフタレン−１，２−ジイル、ナフタレン−１，３−ジイル、ナフタレン−１，４−ジイル、ナフタレン−１，５−ジイル、ナフタレン−１，６−ジイル、ナフタレン−１，７−ジイル、ナフタレン−１，８−ジイル、ナフタレン−２，３−ジイル、ナフタレン−２，６−ジイル、ナフタレン−２，７−ジイル、テトラヒドロピラン−２，５−ジイル、１，３−ジオキサン−２，５−ジイル、ピリミジン−２，５−ジイル、またはピリジン−２，５−ジイルであり、これらの基において、少なくとも１つの水素は、ハロゲン、炭素数１〜１２のアルキル、または炭素数１〜１２のハロゲン化されたアルキルで置き換えられてもよく；
Ｚ^１およびＺ^２は独立して、単結合または炭素数１〜２０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_２ＣＨ_２−は−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、これらの基において、少なくとも１つの水素はハロゲンで置き換えられてもよく；
Ｌ^１、Ｌ^２、Ｌ^３、およびＬ^４は独立して、単結合、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＧ^１＝ＣＧ^２−ＣＯＯ−、または−ＯＣＯ−ＣＧ^２＝ＣＧ^１−であり、ここでＧ^１およびＧ^２は独立して、水素またはメチルであり；
ａ、ｂ、ｃ、およびｄは独立して、０または１であり、ａ、ｂ、ｃ、およびｄの和は、０、１または２である。 The present invention relates to a compound represented by formula (1), a polymerizable composition containing the compound and a liquid crystal composition, a liquid crystal composite prepared from the polymerizable composition, and a liquid crystal display device having the liquid crystal composite. .

In equation (1),
P ¹ and P ² are each independently a polymerizable group, hydrogen, halogen, or alkyl having 1 to 20 carbons, in which at least one —CH ₂ — is replaced by —O— or —S—. And at least one —CH ₂ CH ₂ — may be replaced by —CH═CH—, in which at least one hydrogen may be replaced by halogen, wherein P ¹ and At least one of P ² is a polymerizable group;
Ring A ¹ , Ring A ² , Ring A ³ , Ring A ⁴ , Ring A ⁵ , and Ring A ⁶ are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene. , Naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1,4-diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene -1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, naphthalene-2,7-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5- Diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, in which at least one hydrogen is halogen, alkyl having 1 to 12 carbons, or having 1 to 12 carbons It may be replaced by halogenated alkyl;
Z ¹ and Z ² are each independently a single bond or alkylene having 1 to 20 carbon atoms, in which at least one —CH ₂ — is —O—, —COO—, —OCO—, or —OCOO. - it may be replaced by at least one _-CH 2 CH ₂ - may be replaced by -CH = CH- or -C≡C-, and in the groups, at least one hydrogen is replaced by halogen May be;
L ¹ , L ² , L ³ , and L ⁴ are each independently a single bond, —COO—, —OCO—, —CH═CH—, —CF ₂ O—, —OCF ₂ —, —CH ₂ O—. , —OCH ₂ —, —CG ¹ ═CG ² —COO—, or —OCO—CG ² ═CG ¹ —, wherein G ¹ and G ² are independently hydrogen or methyl;
a, b, c, and d are each independently 0 or 1, and the sum of a, b, c, and d is 0, 1, or 2.

  The first advantage of the present invention is that the polymerizable compound has appropriate 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. Alternatively, 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. The liquid crystal compound is a general term for a compound having a liquid crystal phase such as a nematic phase or a smectic phase, and a compound having no liquid crystal phase but useful as a component of a liquid crystal composition. The liquid crystal composition is a mixture of non-polymerizable liquid crystal compounds. The polymerizable composition is 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. The polymerization reactivity represents the ease with which a polymerization initiation reaction occurs. The conversion rate indicates how much the polymerizable compound has been converted into a product that is polymerized to fix the alignment of the liquid crystal. In general, the conversion rate is determined by measuring the amount of the remaining polymerizable compound. That is, the greater the amount of the remaining polymerizable compound, the lower the conversion rate. Conversely, the smaller the amount of the remaining polymerizable compound, the higher the conversion rate.

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 formulas (1) to (15), symbols such as A ¹ , B ¹ , and C ¹ surrounded by hexagons correspond to ring A ¹ , ring B ¹ , and ring C ¹ , respectively. Symbol ring D ¹ Equation (6), is used for multiple formulas such as Formula (7). In the formula (12), when t is 2 or 3, a plurality of rings D ¹ are present in one formula. In these compounds having ring D ¹ , the two rings represented by at least one of the two symbols D ¹ may be the same or different. This rule also applies to symbols such as rings B ¹ , Z ¹¹ , X ¹¹ . A polymerizable group is also referred to as a polymerizable group.

The expression “at least one“ A ”may be replaced by“ B ”” means that when the number of “A” is one, the position of “A” is arbitrary, and the number of “A” is two. Even when there are more than two, it means that their positions can be freely 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 structural formula, fluorine may be leftward or rightward. This rule also applies to asymmetric divalent groups such as tetrahydropyran-2,5-diyl.

  The present invention includes the contents described in the following items 1 to 16.

式（１）において、
Ｐ^１およびＰ^２は独立して、重合性基、水素、ハロゲン、または炭素数１〜２０のアルキルであり、このアルキルにおいて、少なくとも１つの−ＣＨ_２−は−Ｏ−または−Ｓ−で置き換えられてもよく、少なくとも１つの−ＣＨ_２ＣＨ_２−は−ＣＨ＝ＣＨ−で置き換えられてもよく、これらの基において、少なくとも１つの水素はハロゲンで置き換えられてもよく、ここでＰ^１およびＰ^２の少なくとも１つは重合性基であり；
環Ａ^１、環Ａ^２、環Ａ^３、環Ａ^４、環Ａ^５、および環Ａ^６は独立して、１，４−シクロへキシレン、１，４−シクロヘキセニレン、１，４−フェニレン、ナフタレン−１，２−ジイル、ナフタレン−１，３−ジイル、ナフタレン−１，４−ジイル、ナフタレン−１，５−ジイル、ナフタレン−１，６−ジイル、ナフタレン−１，７−ジイル、ナフタレン−１，８−ジイル、ナフタレン−２，３−ジイル、ナフタレン−２，６−ジイル、ナフタレン−２，７−ジイル、テトラヒドロピラン−２，５−ジイル、１，３−ジオキサン−２，５−ジイル、ピリミジン−２，５−ジイル、またはピリジン−２，５−ジイルであり、これらの基において、少なくとも１つの水素は、ハロゲン、炭素数１〜１２のアルキル、または炭素数１〜１２のハロゲン化されたアルキルで置き換えられてもよく；
Ｚ^１およびＺ^２は独立して、単結合または炭素数１〜２０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_２ＣＨ_２−は−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、これらの基において、少なくとも１つの水素はハロゲンで置き換えられてもよく；
Ｌ^１、Ｌ^２、Ｌ^３、およびＬ^４は独立して、単結合、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＧ^１＝ＣＧ^２−ＣＯＯ−、または−ＯＣＯ−ＣＧ^２＝ＣＧ^１−であり、ここでＧ^１およびＧ^２は独立して、水素またはメチルであり；
ａ、ｂ、ｃ、およびｄは独立して、０または１であり、ａ、ｂ、ｃ、およびｄの和は、０、１または２である。 1. A compound represented by formula (1).

In equation (1),
P ¹ and P ² are each independently a polymerizable group, hydrogen, halogen, or alkyl having 1 to 20 carbons, in which at least one —CH ₂ — is replaced by —O— or —S—. And at least one —CH ₂ CH ₂ — may be replaced by —CH═CH—, in which at least one hydrogen may be replaced by halogen, wherein P ¹ and At least one of P ² is a polymerizable group;
Ring A ¹ , Ring A ² , Ring A ³ , Ring A ⁴ , Ring A ⁵ , and Ring A ⁶ are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene. , Naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1,4-diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene -1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, naphthalene-2,7-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5- Diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, in which at least one hydrogen is halogen, alkyl having 1 to 12 carbons, or having 1 to 12 carbons It may be replaced by halogenated alkyl;
Z ¹ and Z ² are each independently a single bond or alkylene having 1 to 20 carbon atoms, in which at least one —CH ₂ — is —O—, —COO—, —OCO—, or —OCOO. - it may be replaced by at least one _-CH 2 CH ₂ - may be replaced by -CH = CH- or -C≡C-, and in the groups, at least one hydrogen is replaced by halogen May be;
L ¹ , L ² , L ³ , and L ⁴ are each independently a single bond, —COO—, —OCO—, —CH═CH—, —CF ₂ O—, —OCF ₂ —, —CH ₂ O—. , —OCH ₂ —, —CG ¹ ═CG ² —COO—, or —OCO—CG ² ═CG ¹ —, wherein G ¹ and G ² are independently hydrogen or methyl;
a, b, c, and d are each independently 0 or 1, and the sum of a, b, c, and d is 0, 1, or 2.

2. Item ^2. The compound according to item 1, wherein P ¹ and P ² in the formula (1) according to item 1 are polymerizable groups.

式（Ｐ−１）において、Ｍ^１およびＭ^２が独立して、水素、フッ素、メチル、またはトリフルオロメチルであり；
環Ａ^１、環Ａ^２、環Ａ^３、環Ａ^４、環Ａ^５、および環Ａ^６が独立して、１，４−シクロへキシレン、１，４−フェニレン、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、テトラヒドロピラン−２，５−ジイル、１，３−ジオキサン−２，５−ジイル、ピリミジン−２，５−ジイル、またはピリジン−２，５−ジイルであり、これらの基において、少なくとも１つの水素はハロゲン、炭素数１〜１２のアルキル、または炭素数１〜１２のハロゲン化されたアルキルで置き換えられてもよく；
Ｚ^１およびＺ^２が独立して、単結合または炭素数１〜１０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_２ＣＨ_２−は−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく；
Ｌ^１、Ｌ^２、Ｌ^３、およびＬ^４が独立して、単結合、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−、−ＣＧ^１＝ＣＧ^２−ＣＯＯ−、または−ＯＣＯ−ＣＧ^２＝ＣＧ^１−であり、ここでＧ^１およびＧ^２は独立して、水素またはメチルであり；
ａ、ｂ、ｃ、およびｄが独立して、０または１であり、ａ、ｂ、ｃ、およびｄの和は０または１である、項１または２に記載の化合物。 3. In the formula (1) described in item 1,
P ¹ and P ² are groups independently selected from the groups represented by formulas (P-1), (P-2) and (P-3);

In formula (P-1), M ¹ and M ² are independently hydrogen, fluorine, methyl, or trifluoromethyl;
Ring A ¹ , Ring A ² , Ring A ³ , Ring A ⁴ , Ring A ⁵ , and Ring A ⁶ are each independently 1,4-cyclohexylene, 1,4-phenylene, naphthalene-1,4-diyl , Naphthalene-1,5-diyl, naphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2 , 5-diyl, in which at least one hydrogen may be replaced by halogen, alkyl having 1 to 12 carbons, or halogenated alkyl having 1 to 12 carbons;
Z ¹ and Z ² are each independently a single bond or alkylene having 1 to 10 carbon atoms, in which at least one —CH ₂ — is —O—, —COO—, —OCO—, or —OCOO. - may be replaced by at least one _-CH 2 CH ₂ - may be replaced by -CH = CH- or -C≡C-;
L ¹ , L ² , L ³ , and L ⁴ are each independently a single bond, —COO—, —OCO—, —CH═CH—, —CG ¹ = CG ² —COO—, or —OCO—CG ^2. = CG ^1- , where G ¹ and G ² are independently hydrogen or methyl;
Item 3. The compound according to Item 1 or 2, wherein a, b, c, and d are each independently 0 or 1, and the sum of a, b, c, and d is 0 or 1.

式（１−１）、（１−２）および（１−３）において、Ｐ^１およびＰ^２は独立して、式（Ｐ−１）、（Ｐ−２）および（Ｐ−３）で表される基から選択される基であり、

式（Ｐ−１）で表される基において、Ｍ^１およびＭ^２は独立して、水素、フッ素、メチル、またはトリフルオロメチルであり；Ｚ^１およびＺ^２は独立して、単結合または炭素数１〜１０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_２ＣＨ_２−は、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく；Ｙ^１〜Ｙ^１２は独立して、水素、フッ素、メチル、またはトリフルオロメチルである。 4). Item 6. The compound according to item 1, represented by any one of formulas (1-1), (1-2), and (1-3).

In formulas (1-1), (1-2) and (1-3), P ¹ and P ² are independently represented by formulas (P-1), (P-2) and (P-3). A group selected from

In the group represented by the formula (P-1), M ¹ and M ² are independently hydrogen, fluorine, methyl, or trifluoromethyl; Z ¹ and Z ² are independently a single bond or carbon An alkylene having a number of 1 to 10, in which at least one —CH ₂ — may be replaced by —O—, —COO—, —OCO—, or —OCOO—, and at least one —CH ₂ —; ₂ CH ₂ — may be replaced by —CH═CH— or —C≡C—; Y ^{1 to} Y ¹² are independently hydrogen, fluorine, methyl, or trifluoromethyl.

5. In the formulas (1-1), (1-2), and (1-3) of item 4, P ¹ and P ² are independently CH ₂ ═CHCOO— or CH ₂ ═C (CH ₃ ) COO—. Yes; Z ¹ and Z ² are each independently a single bond or alkylene having 1 to 10 carbon atoms, in which at least one —CH ₂ — is —O—, —COO—, or —OCO—. And at least one —CH ₂ CH ₂ — may be replaced with —CH═CH— or —C≡C—; Y ^{1 to} Y ¹² are independently hydrogen or fluorine. Item 5. The compound according to Item 4.

6). In the formulas (1-1), (1-2), and (1-3) of item 4, P ¹ and P ² are independently CH ₂ ═CHCOO— or CH ₂ ═C (CH ₃ ) COO—. Yes; Z ¹ and Z ² are each independently a single bond or alkylene having 1 to 10 carbon atoms, in which at least one —CH ₂ — may be replaced by —O—, and at least 1 Item 5. The compound according to Item 4, wherein two —CH ₂ CH ₂ — may be replaced by —CH═CH—; Y ^{1 to} Y ¹² are independently hydrogen or fluorine.

式（１−１−１）〜（１−１−４）、式（１−２−１）〜（１−２−４）、および式（１−３−１）〜（１−３−４）において、Ｐ^１およびＰ^２は独立して、ＣＨ_２＝ＣＨＣＯＯ−またはＣＨ_２＝Ｃ（ＣＨ_３）ＣＯＯ−である。 7). Formulas (1-1-1) to (1-1-4), Formulas (1-2-1) to (1-2-4), and Formulas (1-3-1) to (1-3-4) The compound of claim | item 1 represented by any one of these.

Formulas (1-1-1) to (1-1-4), Formulas (1-2-1) to (1-2-4), and Formulas (1-3-1) to (1-3-4) ), P ¹ and P ² are independently CH ₂ ═CHCOO— or CH ₂ ═C (CH ₃ ) COO—.

8). Item 8. A polymerizable composition containing at least one compound according to any one of items 1 to 7.

式（２）〜（４）において、
Ｒ^１１は炭素数１〜１０のアルキルまたは炭素数２〜１０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Ｂ^１、環Ｂ^２および環Ｂ^３は独立して、１，４−シクロヘキシレン、少なくとも１つの水素がフッ素で置き換えられてもよい１，４−フェニレン、テトラヒドロピラン−２，５−ジイル、１，３−ジオキサン−２，５−ジイル、またはピリミジン−２，５−ジイルであり；
Ｚ^１１、Ｚ^１２およびＺ^１３は独立して、単結合、−ＣＨ_２ＣＨ_２−、−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−、−ＣＯＯ−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、−ＣＨ_２Ｏ−、または−（ＣＨ_２）_４−であり；
Ｌ^１１およびＬ^１２は独立して、水素またはフッ素である。 9. Item 9. The polymerizable composition according to item 8, further comprising at least one compound selected from the group of compounds represented by formulas (2) to (4).

In the formulas (2) to (4),
R ¹¹ 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 B ¹ , Ring B ² and Ring B ³ are independently 1,4-cyclohexylene, 1,4-phenylene in which at least one hydrogen may be replaced by fluorine, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl or pyrimidine-2,5-diyl;
Z ¹¹ , Z ¹² and Z ¹³ are 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（５）において、
Ｒ^１２は炭素数１〜１０のアルキルまたは炭素数２〜１０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Ｃ^１は、１，４−シクロヘキシレン、少なくとも１つの水素がフッ素で置き換えられてもよい１，４−フェニレン、テトラヒドロピラン−２，５−ジイル、１，３−ジオキサン−２，５−ジイル、またはピリミジン−２，５−ジイルであり；
Ｚ^１４は、単結合、−ＣＨ_２ＣＨ_２−、−Ｃ≡Ｃ−、−ＣＯＯ−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、または−ＣＨ_２Ｏ−であり；
Ｌ^１３およびＬ^１４は独立して、水素またはフッ素であり；
ｉは、１、２、３、または４である。 10. Item 9. The polymerizable composition according to item 8, further comprising at least one compound selected from the group of compounds represented by formula (5).

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

式（６）〜（１２）において、
Ｒ^１３およびＲ^１４は独立して、炭素数１〜１０のアルキルまたは炭素数２〜１０のアルケニルであり、このアルキルおよびアルケニルにおいて、少なくとも１つの−ＣＨ₂−は−Ｏ−で置き換えられてもよく、少なくとも１つの水素はフッ素で置き換えられてもよく；
Ｒ^１５は、水素、フッ素、炭素数１〜１０のアルキル、または炭素数２〜１０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Ｄ^１、環Ｄ^２、環Ｄ^３、および環Ｄ^４は独立して、１，４−シクロヘキシレン、１，４−シクロヘキセニレン、少なくとも１つの水素がフッ素で置き換えられてもよい１，４−フェニレン，テトラヒドロピラン−２，５−ジイル、またはデカヒドロナフタレン−２，６−ジイルであり；
環Ｄ^５および環Ｄ^６は独立して、１，４−シクロヘキシレン、１，４−シクロヘキセニレン、１，４−フェニレン，テトラヒドロピラン−２，５−ジイル、またはデカヒドロナフタレン−２，６−ジイルであり；
Ｚ^１５、Ｚ^１６、Ｚ^１７、およびＺ^１８は独立して、単結合、−ＣＨ_２ＣＨ_２−、−ＣＯＯ−、−ＣＨ_２Ｏ−、−ＯＣＦ_２−、または−ＯＣＦ_２ＣＨ_２ＣＨ_２−であり；
Ｌ^１５およびＬ^１６は独立して、フッ素または塩素であり；
Ｓ^１１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。 11 Item 9. The polymerizable composition according to item 8, further comprising at least one compound selected from the group of compounds represented by formulas (6) to (12).

In the formulas (6) to (12),
R ¹³ and R ¹⁴ are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and alkenyl, at least one —CH ₂ — may be replaced by —O—. Well, at least one hydrogen may be replaced by fluorine;
R ¹⁵ is hydrogen, fluorine, alkyl having 1 to 10 carbons, or alkenyl having 2 to 10 carbons, and in the alkyl and alkenyl, at least one —CH ₂ — may be replaced by —O—. , At least one hydrogen may be replaced by fluorine;
Ring D ¹ , Ring D ² , Ring D ³ , and Ring D ⁴ are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, wherein at least one hydrogen may be replaced by fluorine, 4-phenylene, tetrahydropyran-2,5-diyl, or decahydronaphthalene-2,6-diyl;
Ring D ⁵ and Ring D ⁶ are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, tetrahydropyran-2,5-diyl, or decahydronaphthalene-2,6. -Diyl;
^{Z 15, Z 16, Z 17} , and ^{Z 18} are independently a single _{bond, -CH 2 CH 2 -, -} COO -, - CH 2 O -, - OCF 2 -, or -OCF ₂ CH ₂ CH ₂ -Is;
L ¹⁵ and L ¹⁶ are independently fluorine or chlorine;
S ¹¹ 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, and the sum of q, r and s Is 0, 1, 2 or 3, and t is 1, 2 or 3.

式（１３）〜（１５）において、
Ｒ^１６およびＲ^１７は独立して、炭素数１〜１０のアルキルまたは炭素数２〜１０のアルケニルであり、このアルキルまたはアルケニルにおいて、少なくとも１つの−ＣＨ₂−は−Ｏ−で置き換えられてもよく、少なくとも１つの水素はフッ素で置き換えられてもよく；
環Ｅ^１、環Ｅ^２、環Ｅ^３、および環Ｅ^４は独立して、１，４−シクロヘキシレン、１，４−フェニレン、２−フルオロ−１，４−フェニレン、２，５−ジフルオロ−１，４−フェニレン、またはピリミジン−２，５−ジイルであり；
Ｚ^１９、Ｚ^２０およびＺ^２１は独立して、単結合、−ＣＨ_２ＣＨ_２−、−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−、または−ＣＯＯ−である。 12 Item 12. The polymerizable composition according to any one of Items 9 to 11, further comprising at least one compound selected from the group of compounds represented by formulas (13) to (15).

In the formulas (13) to (15),
R ¹⁶ and R ¹⁷ are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in 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 E ¹ , Ring E ² , Ring E ³ , and Ring E ⁴ are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,5-difluoro- 1,4-phenylene or pyrimidine-2,5-diyl;
Z ¹⁹ , Z ²⁰ and Z ²¹ are each independently a single bond, —CH ₂ CH ₂ —, —CH═CH—, —C≡C—, or —COO—.

13. Item 13. A liquid crystal composite produced by polymerization of the polymerizable composition according to any one of items 8 to 12.

14 Item 13. An optically anisotropic material produced by polymerization of the polymerizable composition according to any one of items 8 to 12.

15. Item 14. A liquid crystal display device comprising the polymerizable composition according to any one of items 8 to 12 or the liquid crystal composite according to item 13.

16. Item 12. The liquid crystal display device, wherein the compound is selected from the group consisting of the compound according to any one of items 1 to 7, the polymerizable composition according to any one of items 8 to 12, and the liquid crystal composite according to item 13. At least one use.

  The present invention also includes the following items. 1) The above polymerizable composition further containing at least one optically active compound, 2) The above polymerizable composition further containing at least one antioxidant, ultraviolet absorber, and / or antifoaming agent. 3) The polymerizable composition further containing a polymerizable compound different from the compound (1), 4) Use of the compound represented by formula (1) in the liquid crystal display device having the PSA mode, 5) PSA In the liquid crystal display element having a mode, use of the compound (1-1), (1-2) or (1-3), 6) In the liquid crystal display element having a PSA mode, the compounds (1-1-1) to ( 1-1-4), use of compounds (1-2-1) to (1-2-4), or compounds (1-3-1) to (1-3-4), 7) having PSA mode In a liquid crystal display element, a small amount of the above compounds 8) Use of a polymerizable composition containing at least one, 8) Use of a liquid crystal composite produced by polymerization of the polymerizable composition in a liquid crystal display device having a PSA mode, 9) PS-TN, PS-IPS , PS-FFS, PSA-VA, or PSA-OCB mode liquid crystal display device, use of the above compound, the above polymerizable composition, or the above liquid crystal composite

  The compound (1) will be described first, and then the synthesis method, the polymerizable composition, the liquid crystal composite, and the liquid crystal display element will be described in this order.

1. Compound (1)
The compound (1) is a polymerizable compound having a β-cinnamic acid ester as a linking group and having suitable polymerization reactivity, high conversion rate, and high solubility in a liquid crystal composition.

  Preferred examples of the terminal group, ring structure and bonding group in compound (1) are as follows. This example also applies to the sub-formula of compound (1).

In Formula (1), P ¹ and P ² are each independently a polymerizable group, hydrogen, halogen, or alkyl having 1 to 20 carbon atoms, and in this alkyl, at least one —CH ₂ — is —O—. or -S- in may be replaced, at least one _-CH 2 CH ₂ - may be replaced by -CH = CH-, in these groups, at least one hydrogen may be replaced by halogen Where at least one of P ¹ and P ² is a polymerizable group.

  Preferred examples of the polymerizable group are acryloyloxy group, methacryloyloxy group, acrylamide group, methacrylamide group, vinyloxy group, vinylcarbonyl group, oxiranyl group, oxetanyl group, 3,4-epoxycyclohexyl group, and maleimide group. In these groups, at least one hydrogen may be replaced by fluorine.

式（Ｐ−１）で表される基において、Ｍ^１およびＭ^２は独立して、水素、フッ素、メチル、またはトリフルオロメチルである。−ＣＨ＝ＣＨ−の立体配置はシス型であっても、トランス型であってもよい。重合性基のさらに好ましい例は、式（Ｐ−１）で表される基である。Ｍ^１およびＭ^２の好ましい例は、水素またはメチルである。重合性基の特に好ましい例は、ＣＨ_２＝ＣＨＣＯＯ−またはＣＨ_２＝Ｃ（ＣＨ_３）ＣＯＯ−である。 A more preferred example of the polymerizable group is a group represented by the formula (P-1), (P-2) or (P-3).

In the group represented by the formula (P-1), M ¹ and M ² are independently hydrogen, fluorine, methyl, or trifluoromethyl. The configuration of —CH═CH— may be cis or trans. A more preferred example of the polymerizable group is a group represented by the formula (P-1). Preferred examples of M ¹ and M ² are hydrogen or methyl. Particularly preferred examples of the polymerizable group are CH ₂ ═CHCOO— or CH ₂ ═C (CH ₃ ) COO—.

  Halogen is fluorine, chlorine, bromine or iodine. Preferred halogens are fluorine and chlorine. A more preferred halogen is fluorine.

Examples of alkyl in which at least one —CH ₂ — (or —CH ₂ CH ₂ —) may be replaced by —O— or —S— (or —CH═CH—) are alkyl, alkoxy, alkoxyalkyl, Alkoxyalkoxy, alkylthio, alkylthioalkoxy, alkenyl, alkenyloxy, alkenyloxyalkyl, alkoxyalkenyl, and alkenylthio. These groups are linear or branched and do not include cyclic groups such as cyclohexyl. The hydrogens of these groups may be replaced by halogen, preferably fluorine or chlorine, more preferably fluorine.

In formula (1), ring A ¹ , ring A ² , ring A ³ , ring A ⁴ , ring A ⁵ , and ring A ⁶ are independently 1,4-cyclohexylene, 1,4-cyclohexenylene. 1,4-phenylene, naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1,4-diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1 , 7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, naphthalene-2,7-diyl, tetrahydropyran-2,5-diyl, 1,3- Dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, in which at least one hydrogen is halogen, alkyl having 1 to 12 carbons, or It may be replaced by alkyl halides having 1 to 12 carbon atoms. Halogenated alkyl is an alkyl in which at least one hydrogen is replaced with a halogen.

Preferred examples of ring A ¹ to ring A ⁶ include 1,4-cyclohexylene, 1,4-phenylene, naphthalene-1,4-diyl, naphthalene-1,5-diyl, naphthalene-2,6-diyl, Tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl. In these groups, at least one hydrogen may be replaced with fluorine, chlorine, methyl, or trifluoromethyl. Examples of such groups are 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2-trifluoromethyl- 1,4-phenylene, 2-fluoro-3-trifluoromethyl-1,4-phenylene, 2,3-bis (trifluoromethyl) -1,4-phenylene, and 2,3-difluoro-5-methyl- 1,4-phenylene. More preferable examples of ring A ¹ to ring A ⁶ include 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, naphthalene-1,4-diyl, Naphthalene-1,5-diyl and naphthalene-2,6-diyl. A particularly preferred example of ring A ¹ to ring A ⁶ is 1,4-phenylene.

In the formula (1), Z ¹ and Z ² are each independently a single bond or alkylene having 1 to 20 carbon atoms, and in this alkylene, at least one —CH ₂ — is —O—, —COO—, — OCO—, or —OCOO— may be replaced, and at least one —CH ₂ CH ₂ — may be replaced with —CH═CH— or —C≡C—, and in these groups, at least one Hydrogen may be replaced by halogen.

Preferred examples of Z ¹ and Z ² are a single bond, —COO—, —OCO—, —CH ₂ CH ₂ —, —CH═CH—, —C≡C—, —CH═CH—O—, —O. _{-CH = CH -, - CH 2} CH 2 CH 2 -, - CH 2 CH = CH-O -, - O-CH = CHCH 2 -, - CH = CHCH 2 -O -, - O-CH 2 _{CH = CH -, - CH 2} CH 2 CH = CH-O -, - O-CH 2 CH 2 CH = CH -, - CH 2 CH = CHCH 2 -O -, - O-CH 2 CH = CHCH 2 - _{, -CH = CHCH 2 CH 2 -O-} , and _{-O-CH = CHCH 2 CH 2} - is. More preferred examples of Z ¹ and Z ² are a single bond, —CH═CH—, —CH═CH—O—, —O—CH═CH—, —CH ₂ CH ₂ CH═CH—O—, — O—CH ₂ CH ₂ CH═CH—. Particularly preferred examples of Z ¹ and Z ² are a single bond, —CH═CH—O— or —O—CH═CH—. When Z ¹ or Z ² has —CH═CH—, the configuration thereof may be cis or trans.

In Formula (1), L ¹ , L ² , L ³ , and L ⁴ are each independently a single bond, —COO—, —OCO—, —CH═CH—, —CF ₂ O—, —OCF ₂ —. , —CH ₂ O—, —OCH ₂ —, —CG ¹ ═CG ² —COO—, or —OCO—CG ² ═CG ¹ —, wherein G ¹ and G ² are independently hydrogen or methyl It is.

Preferred examples of L ¹ ~L ⁴ is a single bond, -COO -, - OCO -, - CH = CH -, - CG 1 = CG 2 -COO-, or ^-OCO-CG 2 = CG ¹ - a and, Where G ¹ and G ² are independently hydrogen or methyl. More preferred examples of L ^{1 to} L ⁴ are a single bond or —CH═CH—. A particularly preferred example of L ^{1 to} L ⁴ is a single bond. When L ^{1 to} L ⁴ have —CH═CH—, the configuration thereof may be a cis type or a trans type.

  In formula (1), a, b, c and d are independently 0 or 1, and the sum of a, b, c and d is 0, 1 or 2. A compound in which the sum of a, b, c, and d is 0 is preferable from the viewpoint of high solubility. A compound in which the sum of a, b, c, and d is 1 is preferable from the viewpoint of having appropriate polymerizability. A compound in which the sum of a, b, c, and d is 2 is preferable from the viewpoint of a high melting point.

The target polymerizable compound can be obtained by appropriately selecting the combination of the terminal group, the ring structure and the linking group while referring to the above preferred examples. Examples of preferred compounds are compounds (1-1), (1-2) and (1-3). Examples of more preferable compounds are compounds (1-1-1) to (1-1-4), compounds (1-2-1) to (1-2-4), and compounds (1-3-1). To (1-3-4). 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. Examples of a method for generating a bonding group L ¹ ~L ⁴ in the generation compound linking group L (1) is as 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.

(I) Formation of single bond Arylboric acid (21) and 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.

(II) 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.

(III) 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.

(IV) 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.

(V) 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.

(VI) Formation of —CH═CH—COO— A base such as sodium hydride is allowed to act on ethyl diethylphosphonoacetate to prepare a phosphorus ylide. . 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).

(VII) 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 then 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).

(VIII) Formation of —CH═C (CH ₃ ) —COO— Compound (38) synthesized by a known method and 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.

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

2-2. Formation of Polymerizable Group An example of a method for generating a group represented by the polymerizable formulas (P-1), (P-2) and (P-3) in the compound (1) is as shown in the following scheme. is there. In this scheme, MSG ¹ is a monovalent organic group having at least one ring. Compounds (1J) to (1O) correspond to compound (1).

(I) Formation of group represented by formula (P-1) When M ¹ and M ² are not both —CF ₃ , M ¹ is fluorine, and M ² is not —CF ₃ , or M ¹ Is —CF ₃ and M ² is not fluorine, the carboxylic acid (41) shown in the above 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.

(II) Formation of Group Represented by Formula (P-2) Compound (1N) is synthesized by reacting compound (30) with vinyl bromide in the presence of potassium carbonate or the like.

(III) Generation of Group Represented by Formula (P-3) Vinyl compound (48) synthesized by a known method is oxidized with metachloroperbenzoic acid (mCPBA) or the like to synthesize compound (1O).

2-3. Generation of Binding Group Z An example of a method for generating the bonding groups Z ¹ and Z ² in the compound (1) is as shown in the following scheme. In this scheme, MSG ¹ is a monovalent organic group having at least one ring. Compound (1P) corresponds to compound (1).

(I) Formation of —CH ₂ O— In the presence of potassium carbonate or the like, the compound (49) synthesized by a known method is reacted with the compound (30) to obtain the compound (50). Compound (50) is reduced with a reducing agent such as lithium aluminum hydride to obtain compound (51). Compound (51) is oxidized with an oxidizing agent such as Dess-Martin reagent to obtain aldehyde (52). Phosphoryl ylide generated by treating methyltriphenylphosphonium bromide with a base such as potassium tert-butoxide is reacted with aldehyde (52) to give compound (53).

  When the group represented by the formula (P-1) is introduced into the compound (51), dehydration condensation between the compound (51) and the compound (41) is performed according to the method described above. When the group represented by the formula (P-2) is introduced into the compound (51), the compound (51) is reacted with vinyl bromide according to the method described above. When the group represented by the formula (P-3) is introduced into the compound (53), the epoxidation reaction of the compound (53) is performed according to the method described above.

(II) Formation of —CH═CH— A compound obtained by reacting phosphorus ylide generated by treating a phosphonium salt (54) synthesized by a known method with a base such as potassium tert-butoxide with aldehyde (32). (55) is obtained. When the group represented by the formula (P-1) is introduced into the compound (55), dehydration condensation between the compound (55) and the compound (41) is performed according to the method described above. When the group represented by the formula (P-2) is introduced into the compound (55), the compound (55) is reacted with vinyl bromide according to the method described above. If the compound (55) to introduce a group represented by the formula (P-3), then after converting the _-CH 2 OH to -CH = CH _2, the epoxidation reaction carried out according to the method.

  The following method may be used to introduce the formula (P-1). In the presence of potassium carbonate or the like, compound (1P) is synthesized by reacting aldehyde (56), acid anhydride (57) and sodium carboxylate (58) synthesized by a known method.

(III) Formation of —CH ₂ CH ₂ — Compound (59) is synthesized by hydrogenating compound (55) in the presence of a catalyst such as palladium carbon. The method for introducing the group represented by the formula (P-1), (P-2) or (P-3) into this alcohol is as described above.

3. Polymerizable composition The polymerizable composition contains at least one compound (1) as a first component. The type of the second component depends on the type and use of the target polymer. This polymerizable composition may further contain another polymerizable compound different from the compound (1) as the second component. Preferred examples of the other polymerizable compound are acrylate, methacrylate, vinyl compound, vinyloxy compound, propenyl ether, ethylene oxide (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 acryloyloxy and methacryloyloxy.

Additional examples of other polymerizable compounds are compounds (M-1) to (M-12).

In compounds (M-1) to (M-12), R ²¹ is hydrogen or methyl; u is 0 or 1; v and w are each independently an integer of 1 to 10; L ²¹ , L ²² , L ²³ , L ²⁴ , L ²⁵ , and L ²⁶ are independently hydrogen or fluorine.

  When the second component of the polymerizable composition is a polymerizable compound having a liquid crystal phase, an optically anisotropic material is generated by polymerization while controlling the orientation of liquid crystal molecules. This optical anisotropy 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.

  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 compound (5). Component D is compounds (6) to (12). Component E is compounds (13) to (15). When preparing such a polymerizable composition, it is preferable to select components B, C, D, and E in consideration of positive or negative dielectric anisotropy, 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 (large or small) optical anisotropy, a large positive or negative dielectric anisotropy, and a suitable Has an elastic constant (large or small).

  In the polymerizable composition including the liquid crystal composition, the amount of the compound (1), that is, the component A is in the range of 0.05% by weight to 20% by weight based on the liquid crystal composition. A more preferable addition amount is in the range of 0.1% by weight to 10% by weight. A more 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 having a halogen- or fluorine-containing group at the right end. Preferred examples of Component B include compounds (2-1) to (2-16), compounds (3-1) to (3-113), and compounds (4-1) to (4-57). .

In these compounds (component B), the definitions of R ¹¹ and X ¹¹ are the same as described above.

  Since component B has a positive dielectric anisotropy and very excellent stability to 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 B is suitably in the range of 1% to 99% by weight based on the liquid crystal composition, preferably in the range of 10% to 97% by weight, more preferably in the range of 40% to 95% by weight. It is a range. The viscosity of this composition can be adjusted by further adding the compounds (13) to (15) (component E). When component B is added to a composition having a negative dielectric anisotropy, the content of component B is preferably 30% by weight or less based on the liquid crystal composition. By adding component B, the elastic constant of the composition can be adjusted, and the voltage-transmittance curve of the device can be adjusted.

Component C is a compound (5) in which the right terminal group is —C≡N or —C≡C—C≡N. Preferable examples of component C include compounds (5-1) to (5-64).

In these compounds (component C), the definitions of R ¹² and X ¹² are the same as described above.

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

  When preparing a composition for a mode such as PS-TN, the content of Component C is suitably in the range of 1% by weight to 99% by weight based on the liquid crystal composition, preferably 10% by weight to It is in the range of 97% by weight, more preferably in the range of 40% to 95% by weight. This composition can adjust the temperature range, viscosity, optical anisotropy, dielectric anisotropy, etc. of the liquid crystal phase by further adding component E. 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 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 compounds (6) to (12). These compounds have a benzene ring in which the lateral position is substituted with two halogens, such as 2,3-difluoro-1,4-phenylene. As preferred examples of component D, compounds (6-1) to (6-8), compounds (7-1) to (7-17), compound (8-1), compounds (9-1) to (9- 3), compounds (10-1) to (10-11), compounds (11-1) to (11-3), and compounds (12-1) to (12-3).

In these compounds (component D), the definitions of R ¹³ , R ¹⁴ and R ¹⁵ are the same as described above.

  Component D is a compound having a negative dielectric anisotropy. Component D is used when preparing a composition for a mode such as PS-IPS, PS-FFS, PSA-VA. Increasing the content of component D increases the dielectric anisotropy of the composition negatively, but increases the viscosity. 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 D, since the compound (6) is a bicyclic compound, there is mainly an effect of adjusting the viscosity, adjusting the optical anisotropy, or adjusting the dielectric anisotropy. Since the compounds (7) and (8) are tricyclic compounds, they have the effect of increasing the maximum temperature, increasing the optical anisotropy, or increasing the dielectric anisotropy. Compounds (9) to (12) have the effect of increasing the dielectric anisotropy.

  When preparing a composition for a mode such as PS-IPS, PS-FFS, PSA-VA, the content of component D is preferably 40% by weight or more based on the liquid crystal composition, more preferably Is in the range of 50% to 95% by weight. By adding component D, the elastic constant of the composition can be adjusted, and the voltage-transmittance curve of the device can be adjusted. When component D is added to a composition having a positive dielectric anisotropy, the content of component D is preferably 30% by weight or less based on 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 a compound in which two terminal groups are alkyl or the like. Preferred examples of component E include compounds (13-1) to (13-11), compounds (14-1) to (14-19), and compounds (15-1) to (15-7). it can.

In these compounds (component E), the definitions of R ¹⁶ and R ¹⁷ are the same as described above.

  Component E is a compound close to neutrality because the absolute value of dielectric anisotropy is small. Compound (13) is mainly effective in adjusting viscosity or optical anisotropy. Compounds (14) and (15) have the effect of increasing the temperature range of the nematic phase by increasing the maximum temperature, or the effect of adjusting the optical anisotropy.

  Increasing the content of component E decreases the viscosity of the composition but decreases the dielectric anisotropy. 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 E is preferably 30% by weight or more, more preferably 40% by weight, based on the liquid crystal composition. That's it.

  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 the additive include an optically active compound, an antioxidant, an ultraviolet absorber, and an antifoaming agent. 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 (Op-18), ring J is 1,4-cyclohexylene or 1,4-phenylene, and R ²⁴ 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), (AO-2), IRGANOX 415, IRGANOX 565, IRGANOX 1010, IRGANOX 1035, IRGANOX 3114, and IRGANOX 1098 (trade name: BASF). be able to. The ultraviolet absorber is effective for preventing a decrease in the maximum temperature. Preferred examples of the ultraviolet absorber are benzophenone derivatives, benzoate derivatives, triazole derivatives and the like. Specific examples include the following compounds (AO-3), (AO-4), TINUVIN 329, TINUVIN P, TINUVIN 326, TINUVIN 234, TINUVIN 213, TINUVIN 400, TINUVIN 328, TINUVIN 99-2 (trade name: BASF), and 1,4-diazabicyclo [2.2.2] octane (DABCO) can be mentioned. 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), (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 ²⁵ is an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, —COOR ²⁶ , —CH ₂ CH ₂ COOR ²⁶ , and R ²⁶ is an alkyl group having 1 to 20 carbon atoms. In the compounds (AO-2) and (AO-5), R ²⁷ is an alkyl group having 1 to 20 carbon atoms, and in (AO-5), ring F and ring G are 1, a xylene or 1,4-phenylene 4-cyclopropyl, x is 0, 1 or ^{2,, R 28} is hydrogen, methyl or O ^·,.

4). Liquid crystal composite Compound (1) has suitable polymerization reactivity, high conversion rate, 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 proceeds by heat, light or 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 photo radical polymerization initiators are CPO Specialty Chemicals' Darocur series to TPO, 1173 and 4265, and Irgacure series to 184, 369, 500, 651, 784, 819, 907, 1300, 1700, 1800, 1850, 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, an unreacted polymerization initiator or a decomposition product of the polymerization initiator may cause display defects such as image sticking to the device. In order to prevent 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 particularly preferable wavelength is in the range of 300 nm to 400 nm.

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 polymerizable composition, liquid crystal molecules are aligned in the direction of the electric field. According to this orientation, the polymerizable compound is similarly oriented. In this state, the polymerizable composition is irradiated with ultraviolet rays to polymerize the polymerizable compound. As a result, a polymer network is formed in the liquid crystal 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 polymer is in the range of 0.1 wt% to 2 wt% based on 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 amount of polymer added, 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.

1. Example of Compound (1) Compound (1) was synthesized by the procedure 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 DRX-500 (Bruker Biospin Co., Ltd.) was used as a measuring apparatus. ^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 As a measuring apparatus, 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.

UV-Vis spectroscopic analysis PharmaSpec UV-1700 made by Shimadzu Corporation was used as a measuring apparatus. 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 methods are described in the JEITA standard (JEITA ED-2521B) established by the Japan Electronics and Information Technology Industries Association (JEITA), or It was a modified method. No thin film transistor (TFT) was attached to the TN device used for the measurement.

(1) Phase structure A sample is placed on a hot plate (Mettler FP-52 type hot stage) of a melting point measuring apparatus equipped with a polarizing microscope, and the phase state and its change are observed with a polarizing microscope while heating at a rate of 3 ° C / min. Observed and identified the type of phase.

(2) Transition temperature (° C)
The measurement was performed using a scanning calorimeter manufactured by PerkinElmer, a Diamond DSC system, or a high-sensitivity differential scanning calorimeter manufactured by SSI Nanotechnology, Inc., X-DSC7000. The temperature of the sample was raised and lowered at a rate of 3 ° C./min, the end point of the endothermic peak or exothermic peak accompanying the sample phase change was obtained by extrapolation, and the transition temperature was determined. 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 melting point and polymerization initiation temperature of the compound were also measured using this apparatus.

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 a compound and mother liquid crystals, it was indicated by the symbol _TNI . When the sample was a mixture of the compound and component B, C, D, or 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)
It measured using the E-type rotational viscometer.

(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 has a polyimide alignment film, and the distance (cell gap) between the two glass substrates is 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. The area B is an area when it is not attenuated. The voltage holding ratio is a percentage of the area A with respect to the area B.

(9) Voltage holding ratio (VHR-2; measured at 80 ° C .;%)
The result obtained by measuring similarly at 80 ° C. instead of 25 ° C. is indicated by the symbol VHR-2.

  A physical property measurement method may differ between a sample having a positive dielectric anisotropy and a negative sample. Therefore, (10-1) to (14-1) show measurement methods when the dielectric anisotropy is positive. When the dielectric anisotropy is negative, it is shown in (10-2) to (14-2).

(10-1) Viscosity (Rotational viscosity; γ1; measured at 25 ° C .; mPa · s)
The measurement followed 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.

(11-1) Dielectric anisotropy (Δε; measured at 25 ° C.)
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⊥.

(12-1) Elastic constant (K; measured at 25 ° C .; pN)
For measurement, an HP4284A LCR meter manufactured by Yokogawa Hewlett-Packard Co., Ltd. was used. 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 is an average value of K ₁₁ , K ₂₂ and K ₃₃ thus obtained.

(13-1) Threshold voltage (Vth; measured at 25 ° C .; V)
An LCD5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for the measurement. The light source is 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 is a voltage when the transmittance reaches 90%.

(14-1) Response time (τ; measured at 25 ° C .; ms)
An LCD5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for the measurement. The light source is 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. The transmittance is 100% when the light amount is maximum, and the transmittance is 0% when the light amount is 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 is the sum of the rise time and the fall time thus obtained.

(10-2) Viscosity (Rotational viscosity; γ1; measured at 25 ° C .; mPa · s)
The measurement followed 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. This element was applied stepwise in increments of 1 volt in the range of 30 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.

(11-2) Dielectric anisotropy (Δε; measured at 25 ° C.)
The value of dielectric anisotropy was calculated from the equation: Δε = ε∥−ε⊥. The dielectric constants (ε‖ and ε⊥) were measured as follows.
1) Measurement of dielectric constant (ε‖): 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.

(12-2) Elastic constant (K ₁₁ and K ₃₃ ; measured at 25 ° C .; pN)
An EC-1 type elastic constant measuring instrument manufactured by Toyo Corporation was used for the 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).

(13-2) Threshold voltage (Vth; measured at 25 ° C .; V)
An LCD5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for the measurement. The light source is 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 is a voltage when the transmittance reaches 10%.

(14-2) Response time (τ; measured at 25 ° C .; ms)
An LCD5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for the measurement. The light source is a halogen lamp. The low-pass filter was set to 5 kHz. Adhesion in which a specimen is placed in a normally black mode PVA element in which the distance between two glass substrates (cell gap) is 3.2 μm and the rubbing direction is anti-parallel, and the element is cured with ultraviolet rays. Sealed with an agent. 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. The transmittance is 100% when the light amount is maximum, and the transmittance is 0% when the light amount is minimum. The response time is the time (fall time; milliseconds) required to change the transmittance from 90% to 10%.

Synthesis of compound (No. 1)

Step 1 Under a nitrogen atmosphere, compound (T-2) (25.0 g, 183.6 mmol) and pyridinium p-toluenesulfonate (PPTS) (4.6 g, 18.4 mmol) were dissolved in dichloromethane (300 ml). It was. After cooling to 10 ° C., compound (T-1) (23.2 g, 275.4 mmol) was slowly added dropwise. The reaction mixture was returned to 25 ° C., stirred for 16 hours, and poured into water (500 ml). After the aqueous layer was extracted with dichloromethane, the combined organic layers were washed successively with water, a saturated aqueous sodium bicarbonate solution and a saturated aqueous sodium chloride solution, and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, heptane: ethyl acetate = 10: 1) to obtain compound (T-3) (31.7 g, 143.8 mmol, 78.3). %).

Second Step Under a nitrogen atmosphere, ethyl diethylphosphonoacetate (41.5 g, 215.7 mmol) was dissolved in THF (150 ml) and cooled to −40 ° C. Sodium hydride (5.2 g, 215.7 mmol) was added and stirred for 1 hour. A solution of compound (T-3) (31.7 g, 143.8 mmol) in THF (60 ml) was added dropwise in the temperature range of −40 ° C. to −30 ° C., and the mixture was further stirred for 0.5 hours. The reaction mixture was returned to 25 ° C. and then further stirred for 16 hours. The reaction mixture was then poured into water (500 ml). After extraction with toluene, the combined organic layers were washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, heptane: ethyl acetate = 10: 1) to obtain compound (T-4) (28.2 g, 97.2 mmol, 67.6). %).

Third Step Under a nitrogen atmosphere, sodium hydroxide (19.4 g, 486.0 mmol) was added to a solution of compound (T-4) (28.2 g, 97.2 mmol) in methanol (300 ml) at 25 ° C. for 16 hours. Stir. Thereafter, the reaction mixture was poured into water (500 ml) and acidified with 6N aqueous hydrochloric acid. After extraction with toluene, the combined organic layers were washed sequentially with water, a saturated aqueous sodium bicarbonate solution, and a saturated aqueous sodium chloride solution, and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by recrystallization from methanol to obtain compound (T-5) (12.2 g, 68.5 mmol, 70.5%).

Fourth Step Under a nitrogen atmosphere, methacrylic acid (6.2 g, 72.0 mmol), dicyclohexylcarbodiimide (DCC) (17.0 g, 82.2 mmol), and N, N-dimethyl-4-aminopyridine (DMAP) (0 .3 g, 2.1 mmol) was dissolved in dichloromethane (200 ml) under ice cooling. To this solution was added dropwise a solution of compound (T-5) (12.2 g, 68.5 mmol) in dichloromethane (30 ml) under ice cooling, and the mixture was stirred at 25 ° C. for 16 hours. After completion of the reaction, the insoluble matter produced was filtered, the filtrate was extracted with dichloromethane, and the combined organic layer was washed successively with water and saturated aqueous sodium chloride solution and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by recrystallization from methanol to obtain compound (T-6) (10.8 g, 43.7 mmol, 63.8%).

Step 5 Compound (T-1) (19.1 g, 227.0 mmol) and pyridinium p-toluenesulfonate (PPTS) (5.7 g, 22.7 mmol) were dissolved in dichloromethane (200 ml) under a nitrogen atmosphere. . After cooling to 10 ° C., a solution of compound (T-7) (25.0 g, 227.0 mmol) in dichloromethane (100 ml) was slowly added dropwise. The reaction mixture was returned to 25 ° C., stirred for 16 hours, and poured into water (500 ml). After the aqueous layer was extracted with dichloromethane, the combined organic layers were washed successively with water, a saturated aqueous sodium bicarbonate solution and a saturated aqueous sodium chloride solution, and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene: ethyl acetate = 5: 1) to give compound (T-8) (23.2 g, 119.7 mmol, 52.7). %).

Step 6 Under a nitrogen atmosphere, compound (T-8) (23.2 g, 119.7 mmol), methacrylic acid (10.8 g, 125.6 mmol), and N, N-dimethyl-4-aminopyridine (DMAP) ( 0.4 g, 3.6 mmol) was dissolved in dichloromethane (300 ml). To this solution, dicyclohexylcarbodiimide (DCC) (29.6 g, 143.6 mmol) was added as a solid under ice cooling, and the mixture was stirred at 25 ° C. for 16 hours. After completion of the reaction, the insoluble matter produced was filtered, the filtrate was extracted with dichloromethane, and the combined organic layer was washed successively with water and saturated aqueous sodium chloride solution and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (toluene) to obtain compound (T-9) (26.2 g, 100.0 mmol, 83.6%).

Step 7 Under a nitrogen atmosphere, compound (T-9) (26.2 g, 100.0 mmol) and p-toluenesulfonic acid (pTSA) (0.8 g, 4.1 mmol) were dissolved in methanol (400 ml). Stir at 25 ° C. for 16 hours. After completion of the reaction, the reaction mixture was poured into water (500 ml). After extraction with toluene, the combined organic layers were washed successively with water, a saturated aqueous sodium bicarbonate solution, and a saturated aqueous sodium chloride solution, and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene: ethyl acetate = 5: 1) to give compound (T-10) (15.7 g, 87.8 mmol, 87.8). %).

Step 8 Compound (T-6) (10.0 g, 40.6 mmol), Compound (T-10) (7.6 g, 42.6 mmol), and N, N-dimethyl-4-aminopyridine under nitrogen atmosphere (DMAP) (0.1 g, 1.2 mmol) was dissolved in dichloromethane (100 ml). To this solution, dicyclohexylcarbodiimide (DCC) (10.1 g, 48.7 mmol) was charged as a solid under ice-cooling and stirred at 25 ° C. for 16 hours. After completion of the reaction, the insoluble matter produced was filtered, the filtrate was extracted with dichloromethane, and the combined organic layer was washed successively with water and saturated aqueous sodium chloride solution and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene: ethyl acetate = 10: 1). The product was further purified by recrystallization from a mixed solvent of heptane and ethyl acetate (volume ratio, 9: 1) to obtain Compound (No. 1) (5.00 g, 12.3 mmol, 30.3%).

¹ H-NMR (CDCl ₃ ; δ ppm): 7.60-7.57 (m, 2H), 7.20-7.15 (m, 6H), 6.38-6.36 (m, 3H) , 5.79 (dd, 1H), 5.77 (dd, 1H), 2.64 (d, 3H), 2.08 (dd, 3H), 2.07 (dd, 3H).

The physical properties of the compound (No. 1) were as follows. Melting point: 78.2 ° C, polymerization initiation temperature: 138 ° C.
[Comparative Example 1]

For comparison, a comparative compound (R-1) was synthesized.

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 compound (R-1) were as follows. Melting point: 150 ° C., polymerization initiation temperature: 152 ° C.
[Comparative Example 2]

For comparison, a comparative compound (R-2) was synthesized.

¹ H-NMR (CDCl ₃ ; δ ppm): 7.86 (d, 1H) 7.64-7.61 (m, 2H), 7.22-7.15 (m, 6H), 6.59 ( d, 1H), 6.38-6.36 (m, 2H), 5.80 (dd, 1H), 5.77 (dd, 1H), 2.08-2.07 (m, 6H).

The physical properties of the compound (R-2) were as follows. Melting point: 160 ° C., polymerization start temperature: 162 ° C.
[Comparative Experiment 1]

Unreacted polymerizable compound Polymerizable compound (No. 1) was added to the following liquid crystal composition A in a proportion of 0.3% by weight and dissolved. This polymerizable composition was irradiated with ultraviolet rays of 11 mW / cm ² for 273 seconds. A mercury xenon lamp, EXECURE 4000-D, manufactured by HOYA CANDEO OPTRONICS Co., Ltd., was used for the irradiation of ultraviolet rays. The amount of the polymerizable compound remaining in the obtained liquid crystal composite was measured by HPLC. On the other hand, unreacted substances were similarly measured for the comparative compounds (R-2) and (R-3). The results are summarized in Table 1.

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

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

  By referring to the experimental procedure described in Example 1 and “2. Synthesis method”, it is possible to synthesize the compound (No. 306) from the compound (No. 1) shown below.

2. Examples of Polymerizable Composition The compounds in the 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＝１０９．０℃；Δｎ＝０．０８７；Δε＝３．８；η＝１８．９ｍＰａ・ｓ． 5-HB-CL (2-2) 16%
3-HH-4 (13-1) 12%
3-HH-5 (13-1) 5%
3-HHB-F (3-1) 5%
3-HHB-CL (3-1) 4%
4-HHB-CL (3-1) 4%
3-HHB (F) -F (3-2) 10%
4-HHB (F) -F (3-2) 9%
5-HHB (F) -F (3-2) 9%
7-HHB (F) -F (3-2) 8%
5-HBB (F) -F (3-23) 4%
3-HHBB (F, F) -F (4-6) 2%
4-HHBB (F, F) -F (4-6) 3%
5-HHBB (F, F) -F (4-6) 3%
3-HH2BB (F, F) -F (4-15) 3%
4-HH2BB (F, F) -F (4-15) 3%
Based on the above composition, the compound (No. 1) was added in a proportion of 0.3% by weight, and the physical properties were measured.

NI = 109.0 ° C .; Δn = 0.087; Δε = 3.8; η = 18.9 mPa · s.

3-HHB (F, F) -F (3-3) 12%
3-H2HB (F, F) -F (3-15) 8%
4-H2HB (F, F) -F (3-15) 8%
5-H2HB (F, F) -F (3-15) 8%
3-HBB (F, F) -F (3-24) 19%
5-HBB (F, F) -F (3-24) 20%
3-H2BB (F, F) -F (3-27) 9%
5-HHBB (F, F) -F (4-6) 3%
5-HHEBB-F (4-17) 2%
3-HH2BB (F, F) -F (4-15) 3%
1O1-HBBH-4 (15-1) 4%
1O1-HBBH-5 (15-1) 4%
Based on said composition, the compound (No. 2) was added in the ratio of 0.4 weight%.

3-HB-CL (2-2) 9%
3-HHB-OCF3 (3-1) 5%
3-H2HB-OCF3 (3-13) 5%
5-H4HB-OCF3 (3-19) 15%
V-HHB (F) -F (3-2) 5%
3-HHB (F) -F (3-2) 6%
5-HHB (F) -F (3-2) 6%
3-H4HB (F, F) -CF3 (3-21) 8%
5-H4HB (F, F) -CF3 (3-21) 10%
5-H2HB (F, F) -F (3-15) 5%
5-H4HB (F, F) -F (3-21) 7%
2-H2BB (F) -F (3-26) 5%
3-H2BB (F) -F (3-26) 9%
3-HBEB (F, F) -F (3-39) 5%
Based on the above composition, the compound (No. 1) was added at a ratio of 0.2% by weight, and the compound (No. 25) was further added at a ratio of 0.15% by weight.

5-HB-CL (2-2) 10%
3-HH-4 (13-1) 9%
3-HHB-1 (14-1) 4%
3-HHB (F, F) -F (3-3) 8%
3-HBB (F, F) -F (3-24) 23%
5-HBB (F, F) -F (3-24) 13%
3-HHEB (F, F) -F (3-12) 10%
4-HHEB (F, F) -F (3-12) 3%
5-HHEB (F, F) -F (3-12) 3%
2-HBEB (F, F) -F (3-39) 3%
3-HBEB (F, F) -F (3-39) 5%
5-HBEB (F, F) -F (3-39) 3%
3-HHBB (F, F) -F (4-6) 6%
Based on said composition, the compound (No. 25) was added in the ratio of 0.3 weight%.

5-HB-CL (2-2) 15%
7-HB (F, F) -F (2-4) 3%
3-HH-4 (13-1) 11%
3-HH-5 (13-1) 5%
3-HB-O2 (13-5) 14%
7-HB-1 (13-5) 2%
3-HHB-1 (14-1) 8%
3-HHB-O1 (14-1) 5%
2-HHB (F) -F (3-2) 7%
3-HHB (F) -F (3-2) 7%
5-HHB (F) -F (3-2) 7%
3-HHB (F, F) -F (3-3) 6%
3-H2HB (F, F) -F (3-15) 5%
4-H2HB (F, F) -F (3-15) 5%
Based on the above composition, Compound (No. 26) was added at a ratio of 0.4 wt%.

5-HB-CL (2-2) 3%
7-HB (F) -F (2-3) 7%
3-HH-4 (13-1) 9%
3-HH-EMe (13-2) 20%
3-HHEB-F (3-10) 9%
5-HHEB-F (3-10) 7%
3-HHEB (F, F) -F (3-12) 10%
4-HHEB (F, F) -F (3-12) 5%
4-HGB (F, F) -F (3-103) 6%
5-HGB (F, F) -F (3-103) 5%
2-H2GB (F, F) -F (3-106) 4%
3-H2GB (F, F) -F (3-106) 5%
5-GHB (F, F) -F (3-109) 10%
Based on the above composition, Compound (No. 27) was added in a proportion of 0.3% by weight.

2-HB-C (5-1) 5%
3-HB-C (5-1) 11
3-HB-O2 (13-5) 13%
2-BTB-1 (13-10) 3%
3-HHB-1 (14-1) 7%
3-HHB-F (3-1) 5%
3-HHB-O1 (14-1) 5%
3-HHB-3 (14-1) 10%
3-HHEB-F (3-10) 4%
5-HHEB-F (3-10) 4%
2-HHB (F) -F (3-2) 7%
3-HHB (F) -F (3-2) 7%
5-HHB (F) -F (3-2) 7%
3-HHB (F, F) -F (3-3) 12%
Based on the above composition, the compound (No. 27) was added at a rate of 0.2% by weight, and the compound (No. 106) was further added at a rate of 0.2% by weight.

5-HB-F (2-2) 13%
6-HB-F (2-2) 8%
7-HB-F (2-2) 8%
2-HHB-OCF3 (3-1) 7%
3-HHB-OCF3 (3-1) 6%
4-HHB-OCF3 (3-1) 6%
5-HHB-OCF3 (3-1) 7%
3-HH2B-OCF3 (3-4) 4%
5-HH2B-OCF3 (3-4) 4%
3-HHB (F, F) -OCF2H (3-3) 4%
3-HHB (F, F) -OCF3 (3-3) 4%
3-HH2B (F) -F (3-5) 3%
3-HBB (F) -F (3-23) 10%
5-HBB (F) -F (3-23) 10%
5-HBBH-3 (15-1) 3%
3-HB (F) BH-3 (15-2) 3%
Based on the above composition, Compound (No. 108) was added at a ratio of 0.35 wt%.

5-HB-CL (2-2) 15%
3-HH-4 (13-1) 13%
3-HH-5 (13-1) 5%
3-HHB-F (3-1) 5%
3-HHB-CL (3-1) 3%
4-HHB-CL (3-1) 4%
3-HHB (F) -F (3-2) 9%
4-HHB (F) -F (3-2) 9%
5-HHB (F) -F (3-2) 9%
7-HHB (F) -F (3-2) 8%
5-HBB (F) -F (3-23) 3%
1O1-HBBH-5 (15-1) 3%
3-HHBB (F, F) -F (4-6) 2%
4-HHBB (F, F) -F (4-6) 3%
5-HHBB (F, F) -F (4-6) 3%
3-HH2BB (F, F) -F (4-15) 3%
4-HH2BB (F, F) -F (4-15) 3%
Based on the above composition, the compound (No. 2) was added at a rate of 0.2% by weight, and the compound (No. 106) was further added at a rate of 0.2% by weight.

ＮＩ＝７６．４℃；Δｎ＝０．０９４；Δε＝−４．０；η＝１９．２ｍＰａ・ｓ． 2-HH-3 (13-1) 3%
2-HH-5 (13-1) 3%
3-HH-4 (13-1) 12%
3-HH-5 (13-1) 4%
3-HB-O2 (13-5) 12%
3-H2B (2F, 3F) -O2 (6-4) 14%
5-H2B (2F, 3F) -O2 (6-4) 15%
3-HHB (2F, 3CL) -O2 (7-12) 3%
2-HBB (2F, 3F) -O2 (7-7) 3%
3-HBB (2F, 3F) -O2 (7-7) 10%
5-HBB (2F, 3F) -O2 (7-7) 10%
3-HHB-1 (14-1) 4%
3-HHB-3 (14-1) 4%
3-HHB-O1 (14-1) 3%
Based on the above composition, the compound (No. 1) was added at a ratio of 0.3% by weight, and the physical properties were measured.

NI = 76.4 ° C .; Δn = 0.094; Δε = −4.0; η = 19.2 mPa · s.

2-HH-3 (13-1) 20%
3-HH-4 (13-1) 9%
1-BB-3 (13-8) 6%
3-HB-O2 (13-5) 5%
3-BB (2F, 3F) -O2 (6-3) 9%
5-BB (2F, 3F) -O2 (6-3) 6%
2-HH1OB (2F, 3F) -O2 (7-5) 13%
3-HH1OB (2F, 3F) -O2 (7-5) 20%
3-HHB-1 (14-1) 5%
3-HHB-O1 (14-1) 3%
2-BB (2F, 3F) B-3 (8-1) 4%
Based on the above composition, the compound (No. 2) was added at a ratio of 0.15 wt%, and the compound (No. 25) was further added at a ratio of 0.15 wt%.

2-HH-3 (13-1) 16%
7-HB-1 (13-5) 7%
5-HB-O2 (13-5) 8%
3-HB (2F, 3F) -O2 (6-1) 17%
5-HB (2F, 3F) -O2 (6-1) 16%
3-HHB (2F, 3CL) -O2 (7-12) 3%
4-HHB (2F, 3CL) -O2 (7-12) 3%
3-HH1OCro (7F, 8F) -5 (10-6) 5%
3-HHB-1 (14-1) 3%
5-HBB (F) B-2 (15-5) 10%
5-HBB (F) B-3 (15-5) 10%
3-HDhB (2F, 3F) -O2 (7-3) 2%
Based on the above composition, the compound (No. 1) was added at a ratio of 0.15% by weight, and the compound (No. 26) was further added at a ratio of 0.15% by weight.

2-HH-3 (13-1) 23%
3-HB-O2 (13-5) 8%
3-HB (2F, 3F) -O2 (6-1) 16%
5-HB (2F, 3F) -O2 (6-1) 16%
3-HBB (2F, 3F) -O2 (7-7) 7%
3-HH1OCro (7F, 8F) -5 (10-6) 5%
3-HHB-1 (14-1) 5%
5-HBB (F) B-2 (15-5) 8%
5-HBB (F) B-3 (15-5) 8%
3-dhBB (2F, 3F) -O2 (7-9) 4%
Based on the above composition, Compound (No. 106) was added at a ratio of 0.4% by weight.

3-HH-4 (13-1) 13%
3-HH-O1 (13-1) 6%
3-HH-O3 (13-1) 6%
3-HB-O1 (13-5) 5%
3-HB-O2 (13-5) 5%
3-HB (2F, 3F) -O2 (6-1) 10%
5-HB (2F, 3F) -O2 (6-1) 8%
3-HHB (2F, 3F) -O2 (7-1) 12%
5-HHB (2F, 3F) -O2 (7-1) 12%
3-HHB (2F, 3F) -2 (7-1) 4%
2-HHB (2F, 3F) -1 (7-1) 4%
3-HHEH-3 (14-13) 5%
3-HHEH-5 (14-13) 5%
3-HHB-1 (14-1) 5%
Based on the above composition, the compound (No. 27) was added at a ratio of 0.2% by weight, and the compound (No. 108) was further added at a ratio of 0.2% by weight.

V-HB (2F, 3F) -O2 (6-1) 12%
3-HB (2F, 3F) -O4 (6-1) 12%
V-HHB (2F, 3F) -O2 (7-1) 5%
V-HBB (2F, 3F) -O2 (7-7) 5%
3-HBB (2F, 3CL) -O2 (7-13) 7%
3-HH-V1 (13-1) 8%
3-HH-V (13-1) 30%
3-HHB-1 (14-1) 4%
3-HHB-O1 (14-1) 3%
2-BB (F) B-3 (14-6) 5%
3-HHEBH-3 (15-6) 4%
5-HBB (F) B-3 (15-5) 5%
Based on the above composition, Compound (No. 74) was added in a proportion of 0.3% by weight.

ＮＩ=８０．２℃；Δｎ＝０．１０８；Δε＝７．０；η＝１２．３ｍＰａ・ｓ． 5-HB (F) B (F, F) XB (F, F) -F (4-41) 5%
3-BB (F) B (F, F) XB (F, F) -F (4-47) 3%
4-BB (F) B (F, F) XB (F, F) -F (4-47) 8%
5-BB (F) B (F, F) XB (F, F) -F (4-47) 3%
3-HH-V (13-1) 40%
3-HH-V1 (13-1) 8%
3-HHB-1 (14-1) 4%
V-HHB-1 (14-1) 5%
V2-BB (F) B-1 (14-6) 5%
1V2-BB-F (13-8) 3%
3-BB (F, F) XB (F, F) -F (3-97) 12%
3-HHBB (F, F) -F (4-6) 4%
Based on the above composition, the compound (No. 1) was added at a ratio of 0.4 wt%, and the physical properties were measured.

NI = 80.2 ° C .; Δn = 0.108; Δε = 7.0; η = 12.3 mPa · s.

3-HBB (F, F) XB (F, F) -F (4-38) 9%
4-BB (F) B (F, F) XB (F, F) -F (4-47) 8%
5-BB (F) B (F, F) XB (F, F) -F (4-47) 4%
3-HH-O1 (13-1) 5%
3-HH-V (13-1) 37%
4-HH-V1 (13-1) 6%
V-HHB-1 (14-1) 5%
1-BB (F) B-2V (14-6) 5%
5-HBB (F) B-2 (15-5) 4%
3-HXB (F, F) -F (2-13) 4%
3-HHXB (F, F) -F (3-100) 6%
3-BB (F, F) XB (F, F) -F (3-97) 7%
Based on the above composition, the compound (No. 2) was added at a rate of 0.1% by weight, and the compound (No. 25) was further added at a rate of 0.2% by weight.

3-HBBBXB (F, F) -F (4-32) 8%
4-BB (F) B (F, F) XB (F, F) -F (4-47) 8%
3-BB (F) B (F, F) XB (F) -F (4-47) 4%
3-HXB (F, F) -F (2-13) 4%
3-GB (F) B (F, F) XB (F, F) -F (4-57) 5%
3-HH-V (13-1) 38%
5-HH-V (13-1) 6%
V-HHB-1 (14-1) 5%
3-BB (F) B (F, F) -F (3-69) 5%
5-HBB (F) B-2 (15-5) 4%
3-HHXB (F, F) -F (3-100) 6%
3-BB (F, F) XB (F) -OCF3 (3-96) 7%
Based on the above composition, the compound (No. 106) was added at a ratio of 0.35 wt%.

  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 an optically anisotropic material.

Claims (14)

A compound represented by formula (1).

In equation (1),
P ¹ and P ² are groups independently selected from the groups represented by formulas (P-1), (P-2) and (P-3);

In formula (P-1), M ¹ and M ² are independently hydrogen, fluorine, methyl, or trifluoromethyl;
Ring A ¹ , Ring A ² , Ring A ³ , Ring A ⁴ , Ring A ⁵ , and Ring A ⁶ are each independently 1,4-cyclohexylene, 1,4-phenylene, naphthalene-1,4-diyl , Naphthalene-1,5-diyl, naphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2 , 5-diyl, in which at least one hydrogen may be replaced by halogen, alkyl having 1 to 12 carbons, or halogenated alkyl having 1 to 12 carbons;
Z ¹ and Z ² are each independently a single bond or alkylene having 1 to 10 carbon atoms, in which at least one —CH ₂ — is —O—, —COO—, —OCO—, or —OCOO. - may be replaced by at least one _-CH 2 CH ₂ - may be replaced by -CH = CH- or -C≡C-;
L ¹ , L ² , L ³ , and L ⁴ are each independently a single bond, —COO—, —OCO—, —CH═CH—, —CG ¹ = CG ² —COO—, or —OCO—CG ^2. = CG ^1- , where G ¹ and G ² are independently hydrogen or methyl;
a, b, c, and d are each independently 0 or 1, and the sum of a, b, c, and d is 0 or 1 . The compound according to claim 1, which is represented by any one of formulas (1-1), (1-2) and (1-3).

In formulas (1-1), (1-2) and (1-3), P ¹ and P ² are independently represented by formulas (P-1), (P-2) and (P-3). A group selected from

In Formula (P-1), M ¹ and M ² are independently hydrogen, fluorine, methyl, or trifluoromethyl; Z ¹ and Z ² are independently a single bond or a C 1-10 carbon atom. An alkylene, wherein at least one —CH ₂ — may be replaced by —O—, —COO—, —OCO—, or —OCOO—, wherein at least one —CH ₂ CH ₂ — is , —CH═CH— or —C≡C—; Y ^{1 to} Y ¹² are independently hydrogen, fluorine, methyl, or trifluoromethyl. In formulas (1-1), (1-2) and (1-3) of claim 2 , P ¹ and P ² are independently CH ₂ ═CHCOO— or CH ₂ ═C (CH ₃ ) COO—. Z ¹ and Z ² are each independently a single bond or alkylene having 1 to 10 carbons, in which at least one —CH ₂ — is —O—, —COO—, or —OCO. -At least one -CH ₂ CH ₂ -may be replaced by -CH = CH- or -C≡C-; Y ^{1 to} Y ¹² are independently hydrogen or fluorine The compound of claim 2 , wherein In formulas (1-1), (1-2) and (1-3) of claim 2 , P ¹ and P ² are independently CH ₂ ═CHCOO— or CH ₂ ═C (CH ₃ ) COO—. Z ¹ and Z ² are each independently a single bond or alkylene having 1 to 10 carbons, in which at least one —CH ₂ — may be replaced by —O—, and at least The compound of claim 2 , wherein one —CH ₂ CH ₂ — may be replaced by —CH═CH—; Y ^{1 to} Y ¹² are independently hydrogen or fluorine. Formulas (1-1-1) to (1-1-4), Formulas (1-2-1) to (1-2-4), and Formulas (1-3-1) to (1-3-4) The compound of Claim 1 represented by any one of these.

Formulas (1-1-1) to (1-1-4), Formulas (1-2-1) to (1-2-4), and Formulas (1-3-1) to (1-3-4) ), P ¹ and P ² are independently CH ₂ ═CHCOO— or CH ₂ ═C (CH ₃ ) COO—. Polymerizable composition containing at least one compound according to any one of claims 1-5. The polymerizable composition according to claim 6 , further comprising at least one compound selected from the group of compounds represented by formulas (2) to (4).

In the formulas (2) to (4),
R ¹¹ 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 B ¹ , Ring B ² and Ring B ³ are independently 1,4-cyclohexylene, 1,4-phenylene in which at least one hydrogen may be replaced by fluorine, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl or pyrimidine-2,5-diyl;
Z ¹¹ , Z ¹² and Z ¹³ are 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 claim 6 , further comprising at least one compound selected from the group of compounds represented by formula (5).

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

In the formulas (6) to (12),
R ¹³ and R ¹⁴ are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and alkenyl, at least one —CH ₂ — may be replaced by —O—. Well, at least one hydrogen may be replaced by fluorine;
R ¹⁵ is hydrogen, fluorine, alkyl having 1 to 10 carbons, or alkenyl having 2 to 10 carbons, and in the alkyl and alkenyl, at least one —CH ₂ — may be replaced by —O—. , At least one hydrogen may be replaced by fluorine;
Ring D ¹ , Ring D ² , Ring D ³ , and Ring D ⁴ are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, wherein at least one hydrogen may be replaced by fluorine, 4-phenylene, tetrahydropyran-2,5-diyl, or decahydronaphthalene-2,6-diyl;
Ring D ⁵ and Ring D ⁶ are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, tetrahydropyran-2,5-diyl, or decahydronaphthalene-2,6. -Diyl;
^{Z 15, Z 16, Z 17} , and ^{Z 18} are independently a single _{bond, -CH 2 CH 2 -, -} COO -, - CH 2 O -, - OCF 2 -, or -OCF ₂ CH ₂ CH ₂ -Is;
L ¹⁵ and L ¹⁶ are independently fluorine or chlorine;
S ¹¹ 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, and the sum of q, r and s Is 0, 1, 2 or 3, and t is 1, 2 or 3. The polymerizable composition according to any one of claims 7 to 9 , further comprising at least one compound selected from the group of compounds represented by formulas (13) to (15).

In the formulas (13) to (15),
R ¹⁶ and R ¹⁷ are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in 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 E ¹ , Ring E ² , Ring E ³ , and Ring E ⁴ are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,5-difluoro- 1,4-phenylene or pyrimidine-2,5-diyl;
Z ¹⁹ , Z ²⁰ and Z ²¹ are each independently a single bond, —CH ₂ CH ₂ —, —CH═CH—, —C≡C—, or —COO—. Liquid crystal composites produced by polymerization of a polymerizable composition according to any one of claims 6-1 0. Polymerizable optically anisotropic substance produced by polymerization of a composition according to any one of claims 6-1 0. A liquid crystal display device containing a liquid crystal composite according to the polymerizable composition or claim 1 1 according to any one of claims 6-1 0. In the liquid crystal display element, a compound according to any one of claims 1 to 5 polymerizable composition according to any one of claims 6-1 0, and the liquid crystal composite according to claim 1 1 At least one use selected from the group of: