JP2005015473A - Polymerizable liquid crystalline compound having unsaturated bond and polymer thereof - Google Patents

Abstract

式中、Ｒ¹は炭素数１〜２０のアルキル、ハロゲン、−Ｚ^４−Ｐ^１などである。Ａ¹、Ａ²、Ａ³、およびＡ⁴は１，４−シクロヘキシレン、１，４−フェニレンなどである。Ｚ^１、Ｚ^２およびＺ^３は単結合、炭素数１〜２０のアルキレンなどである。Ｚ^４は任意のひとつの−ＣＨ_２−が−ＣＨ＝ＣＨ−および−Ｃ≡Ｃ−のいずれかで必ず置き換えられる炭素数１〜２０のアルキレンである。Ｐ^１は下記の基のいずれかである。

【選択図】 なし


PROBLEM TO BE SOLVED: To provide a polymerizable liquid crystalline compound having a low minimum temperature of a liquid crystal phase and excellent compatibility with other compounds, a liquid crystal composition containing the compound, transparency obtained from the liquid crystal composition, and mechanical properties Polymer excellent in strength, applicability, solubility, crystallinity, shrinkage, water permeability, water absorption, chemical resistance, etc., optical anisotropy obtained from this polymer, and liquid crystal display containing this polymer An element is provided.
A compound represented by formula (1).

In the formula, R ¹ is alkyl having 1 to 20 carbon atoms, halogen, —Z ⁴ —P ¹ or the like. A ¹ , A ² , A ³ , and A ⁴ are 1,4-cyclohexylene, 1,4-phenylene, and the like. Z ¹ , Z ² and Z ³ are a single bond, alkylene having 1 to 20 carbon atoms, and the like. Z ⁴ is alkylene having 1 to 20 carbon atoms in which any one —CH ₂ — is necessarily replaced by either —CH═CH— or —C≡C—. P ¹ is any of the following groups.

[Selection figure] None

Description

  The present invention relates to a liquid crystal compound having an unsaturated bond and having a polymerizability, a polymer obtained using this compound or a liquid crystal composition containing this compound, an optical anisotropic material obtained using this polymer, and The present invention relates to a liquid crystal display element containing this polymer.

  Terms used in the present invention will be described. The meaning of the term “liquid crystalline” is not limited to having a liquid crystal phase. Even if it does not have a liquid crystal phase itself, a characteristic that can be used as a component of a liquid crystal composition when mixed with another liquid crystal compound is also included in the meaning of liquid crystal. “Arbitrary” indicates that not only the position but also the number is arbitrary. However, the case where the number is 0 is not included. The liquid crystal compound and the liquid crystal composition may be referred to as a compound and a composition, respectively. A compound represented by the formula (1) may be referred to as a compound (1). The compounds represented by other formulas may be referred to in the same manner. The term “polymer composition” means a composition obtained by polymerizing a composition of a polymerizable liquid crystalline compound and a non-polymerizable compound having liquid crystallinity, or a liquid crystal composition and a liquid crystal composition consisting only of a polymerizable liquid crystalline compound. Means a composition obtained by polymerizing a composition of a non-polymerizable compound having

  In recent years, polymerizable liquid crystalline compounds have been used for optically anisotropic materials such as polarizing plates and retardation plates. This is because this compound exhibits optical anisotropy in a liquid crystal state, and this anisotropy is fixed by polymerization. Since the optical properties required for the optically anisotropic material vary depending on the purpose, a compound having the properties suitable for the purpose is required. This compound is generally used after being formed into a polymer. In addition to the above-mentioned anisotropy, the compound used for such a purpose is also important for the polymer-related characteristics. These properties include polymerization rate, polymer transparency, mechanical strength, applicability, solubility, crystallinity, shrinkage, water permeability, water absorption, melting point, glass transition point, clearing point, chemical resistance, etc. .

Since acrylate has high polymerization reactivity and the obtained polymer has high transparency, it is used for such purposes (Patent Documents 1 to 3).
JP-A-7-17910 JP-A-8-3111 JP-A-9-316032

  However, it is difficult to say that these acrylates sufficiently satisfy characteristics such as liquid crystallinity, compatibility with other compounds, and optical anisotropy. In addition, the polymer may not have suitable transparency, mechanical strength, applicability, solubility, crystallinity, shrinkage, water permeability, water absorption, melting point, glass transition point, clearing point, chemical resistance. . Therefore, the upper limit temperature of the liquid crystal phase is high, the lower limit temperature is low, or the temperature range of the liquid crystal phase is wide, and the compound having excellent compatibility and mechanical strength, applicability, solubility, shrinkage, water permeability, Development of a polymer having excellent properties in water absorption, melting point, glass transition point, clearing point, and chemical resistance is an urgent issue.

The first object of the present invention is to provide a liquid crystalline compound having a low minimum temperature of the liquid crystal phase, excellent compatibility with other compounds, and further having necessary characteristics such as optical anisotropy, and this compound. It is to provide a liquid crystal composition containing the same. The second purpose is weight with excellent properties such as transparency, mechanical strength, applicability, solubility, crystallinity, shrinkage, water permeability, water absorption, melting point, glass transition point, clearing point, and chemical resistance. And providing an optically anisotropic body obtained by using the polymer. A third object is to provide a liquid crystal display element containing this polymer.

  In order to achieve the above object, the present invention provides the following [1] to [37].

式中、Ｒ¹は炭素数１から２０のアルキル、水素、ハロゲン、−ＣＮ、−Ｎ＝Ｃ＝Ｏ、−Ｎ＝Ｃ＝Ｓ、または−Ｚ^４−Ｐ^１であり、このアルキルにおいて任意の−ＣＨ₂−は−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−、または−Ｃ≡Ｃ−で置き換えられてもよく、そして任意の水素はハロゲン、−ＣＦ_３または−ＣＮで置き換えられてもよい；
Ａ¹、Ａ²、Ａ³、およびＡ⁴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、ナフタレン−２，６−ジイル、テトラヒドロナフタレン−２，６−ジイル、フルオレン−２，７−ジイル、ビシクロ［２．２．２］オクタン−１，４−ジイル、ビシクロ［３．１．０］ヘキサン−３，６−ジイル、ビシクロ[４．４．０]デカンまたはＱであり、これらの環において任意の−ＣＨ_２−は−Ｏ−で置き換えられてもよく、任意の−ＣＨ＝は−Ｎ＝で置き換えられてもよく、そして任意の水素はハロゲン、炭素数１から５のアルキル、炭素数１から５のフルオロアルキル、炭素数１から５のアルコキシ、または炭素数２から５のアルケニルで置き換えられてもよく、Ｑは下記に示される２価の基のいずれかであり、

これらの２価の基において、Ｍｅはメチルであり、Ｙ^１、Ｙ^２、Ｙ^３およびＹ^４は炭素数１〜１０のアルキル、炭素数１〜１０のアルコキシ、炭素数１〜１０のフルオロアルキル、水素またはフッ素である；
Ｚ^１、Ｚ^２およびＺ^３は独立して単結合または炭素数１から２０のアルキレンであり、このアルキレンにおいて任意の−ＣＨ₂−は−Ｏ−、−Ｓ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−、または−Ｃ≡Ｃ−で置き換えられても良く、このアルキレンあるいは置換されたアルキレンにおいて任意の水素はハロゲンで置き換えられてもよい；
Ｚ^４は炭素数１から２０のアルキレンであり、このアルキレンにおいて任意のひとつの−ＣＨ_２−が−ＣＨ＝ＣＨ−および−Ｃ≡Ｃ−のいずれかでかならず置き換えられており、その他の任意の−ＣＨ₂−は−Ｏ−、−Ｓ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−、または−Ｃ≡Ｃ−で置き換えられてもよい；
Ｐ^１は（Ｐ^１−１）から（Ｐ^１−６）で示される重合能力を有する基のいずれかである；

Ｘは水素、ハロゲン、−ＣＦ_３、または炭素数１から５のアルキルである；ｍ、ｎおよびｑは独立して０、１または２である。なおｍ、ｎおよびｑが２である場合に２つある同じ記号は、独立して別の構造であってもよいし、同じであってもよい。 [1] A compound represented by formula (1).

In the formula, R ¹ is alkyl having 1 to 20 carbons, hydrogen, halogen, —CN, —N═C═O, —N═C═S, or —Z ⁴ —P ¹ . —CH ₂ — may be replaced by —O—, —S—, —CO—, —COO—, —OCO—, —CH═CH—, —CF═CF—, or —C≡C—, And any hydrogen may be replaced by halogen, —CF ₃ or —CN;
A ¹ , A ² , A ³ , and A ⁴ are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydronaphthalene-2 , 6-diyl, fluorene-2,7-diyl, bicyclo [2.2.2] octane-1,4-diyl, bicyclo [3.1.0] hexane-3,6-diyl, bicyclo [4.4 .0] decane or Q, in which any —CH ₂ — may be replaced by —O—, any —CH═ may be replaced by —N═, and any hydrogen May be replaced by halogen, alkyl having 1 to 5 carbons, fluoroalkyl having 1 to 5 carbons, alkoxy having 1 to 5 carbons, or alkenyl having 2 to 5 carbons, and Q is 2 shown below Any of the groups of valence It is in,

In these divalent groups, Me is methyl, Y ¹ , Y ² , Y ³ and Y ⁴ are alkyl having 1 to 10 carbon atoms, alkoxy having 1 to 10 carbon atoms, and fluoroalkyl having 1 to 10 carbon atoms. Hydrogen or fluorine;
Z ¹ , Z ² and Z ³ are each independently a single bond or alkylene having 1 to 20 carbon atoms, and in this alkylene, any —CH ₂ — is —O—, —S—, —COO—, —OCO—. , -CH = CH-, or -C≡C-, and in this alkylene or substituted alkylene, any hydrogen may be replaced by a halogen;
Z ⁴ is alkylene having 1 to 20 carbon atoms, and in this alkylene, any one —CH ₂ — is always replaced by either —CH═CH— or —C≡C—, and any other arbitrary —CH ₂ — may be replaced by —O—, —S—, —COO—, —OCO—, —CH═CH—, or —C≡C—;
P ¹ is any of the groups having the polymerization ability represented by (P ¹ -1) to (P ¹ -6);

X is hydrogen, halogen, —CF ₃ , or alkyl having 1 to 5 carbons; m, n and q are independently 0, 1 or 2. When m, n and q are 2, the same two symbols may be independently different structures or the same.

[2] In formula (1), R ¹ is alkyl having 1 to 10 carbons, alkoxy having 1 to 10 carbons, alkenyl having 2 to 10 carbons, hydrogen, fluorine, chlorine, —CN, —CF ₃ , —OCF ₃ , —OCHF ₂ , or —Z ⁴ —P ¹ ; P ¹ is (P ¹ -1), (P ¹ -5) or (P ¹ -6); A ¹ , A ² , A ³ And A ⁴ are independently 1,4-cyclohexylene, 1,4-phenylene, 1,4-cyclohexylene in which at least one hydrogen is replaced by halogen, 1,1 in which at least one hydrogen is replaced by halogen, 4-phenylene, naphthalene-2,6-diyl or fluorene-2,7-diyl; Z ¹ , Z ² and Z ³ are independently a single bond, — (CH ₂ ) _a —, —O (CH _{2) a -, - (CH} 2) a O -, - O _{CH 2) a O -, -} CH = CH -, - C≡C -, - COO -, - OCO -, - CH = CH-COO -, - OCO-CH = CH -, - (CH 2) a - COO—, —OCO— (CH ₂ ) _a —, —OCF ₂ —, or —CF ₂ O—, where a is an integer from 1 to 10; Z ⁴ is a straight chain having 1 to 10 carbon atoms An alkylene in which any one —CH ₂ — is always replaced by either —CH═CH— or —C≡C—, and any other —CH ₂ — is —O—, The compound according to item [1], which may be replaced by —COO—, —OCO—, —CH═CH—, or —C≡C—.

[3] In Formula (1), R ¹ is alkyl having 1 to 10 carbons, alkoxy having 1 to 10 carbons, alkenyl having 2 to 10 carbons, hydrogen, fluorine, chlorine, —CN, —CF ₃ , —OCF ₃ , —OCHF ₂ , or —Z ⁴ —P ¹ ; P ¹ is (P ¹ −1), and in (P ¹ −1), X is hydrogen, fluorine, —CF ₃ , —CH ₃ or — C ₂ H ₅ ; A ¹ , A ² , A ³ and A ⁴ are independently 1,4-cyclohexylene, 1,4-phenylene, 1, wherein at least one hydrogen is replaced by fluorine or chlorine, 4-phenylene or fluorene-2,7-diyl. However, two or more of these rings are not fluorene-2,7-diyl; Z ¹ , Z ² and Z ³ are independently a single bond, — (CH ₂ ) _a —, —O (CH _{2 ) a -, - (CH 2} ) a O -, - O (CH 2) a O -, - COO -, - OCO -, - CH = CH-COO -, - OCO-CH = CH -, - OCF 2 -, or _-CF 2 is O-, where a is the integer of 1 to 4; ^{Z 4} is _{- (CH 2) b -,} - O (CH 2) b -, - CO 2 - (CH 2 _{) b -, - OCO- (CH} 2) b -, - (CH 2) c -O- (CH 2) d -, or _{-O- (CH 2) c -O- (} CH 2) d - a is Where b is an integer from 1 to 9 and c and d are integers from 2 to 5, in which any one —CH ₂ — is necessarily —C The compound according to item [1], which is substituted with any of H═CH— and —C≡C—.

[4] In formula (1), R ¹ is alkyl having 1 to 10 carbons, alkoxy having 1 to 10 carbons, alkenyl having 2 to 10 carbons, hydrogen, fluorine, chlorine, —CN, —CF ₃ , —OCF ₃ , —OCHF ₂ , or —Z ⁴ —P ¹ ; P ¹ is (P ¹ -5) or (P ¹ -6), and in (P ¹ -6), X is hydrogen, fluorine, —CF ₃ , —CH ₃ or —C ₂ H ₅ ; A ¹ , A ² , A ³ and A ⁴ are independently 1,4-cyclohexylene, 1,4-phenylene, at least one hydrogen is fluorine or 1,4-phenylene substituted with chlorine, or fluorene-2,7-diyl. However, two or more of these rings are not fluorene-2,7-diyl; Z ¹ , Z ² and Z ³ are independently a single bond, — (CH ₂ ) _a —, —O (CH _{2 ) a -, - (CH 2} ) a O -, - O (CH 2) a O -, - COO -, - OCO -, - CH = CH-COO -, - OCO-CH = CH -, - OCF 2 -, or _-CF 2 is O-, where a is the integer of 1 to 4; ^{Z 4} is _{-O (CH 2) b -,} - CO 2 - (CH 2) b -, - OCO- ( CH ₂ ) _b —, or — (CH ₂ ) _c —O— (CH ₂ ) _d ——, where b is an integer from 1 to 9, c and d are integers from 2 to 5, of any one in these groups -CH ₂ - is always replaced by any one of -CH = CH- and -C≡C-, [1 The compound according to claim.

[5] In formula (1), R ¹ is alkyl having 1 to 10 carbons, alkoxy having 1 to 10 carbons, alkenyl having 2 to 10 carbons, hydrogen, fluorine, chlorine, —CN, —CF ₃ , —OCF ₃ , —OCHF ₂ , or —Z ⁴ —P ¹ ; P ¹ is from (P ¹ -2) to (P ¹ -4); A ¹ , A ² , A ³ and A ⁴ are independently 1,4-cyclohexylene, 1,4-phenylene, 1,4-cyclohexylene in which at least one hydrogen is replaced by halogen, 1,4-phenylene in which at least one hydrogen is replaced by halogen, naphthalene-2 , 6-diyl, or fluorene-2,7-diyl; Z ¹ , Z ² and Z ³ are each independently a single bond, — (CH ₂ ) _a —, —O (CH ₂ ) _a —, — ( _{CH 2) a O -, -} O (CH 2) a O- -CH = CH -, - C≡C - , - COO -, - OCO -, - CH = CH-COO -, - OCO-CH = CH -, - (CH 2) a -COO -, - OCO- ( CH ₂ ) _a —, —OCF ₂ —, or —CF ₂ O—, where a is an integer from 1 to 10; Z ⁴ is a linear alkylene having 1 to 10 carbons, Any one —CH ₂ — is always replaced by either —CH═CH— or —C≡C—, and any other —CH ₂ — is —O—, —COO—, —OCO—. , -CH = CH-, or -C≡C-, the compound according to item [1].

[6] In the formula (1), R ¹ is alkyl having 1 to 10 carbons, alkoxy having 1 to 10 carbons, alkenyl having 2 to 10 carbons, hydrogen, fluorine, chlorine, —CN, —CF ₃ , —OCF ₃ , —OCHF ₂ , or —Z ⁴ —P ¹ , P ¹ is from (P ¹ -2) to (P ¹ -4), and A ¹ , A ² , A ³ and A ⁴ are independently 1,4-cyclohexylene, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced by fluorine or chlorine, or fluorene-2,7-diyl. However, two or more of these rings are not fluorene-2,7-diyl; Z ¹ , Z ² and Z ³ are independently a single bond, — (CH ₂ ) _a —, —O (CH _{2 ) a -, - (CH 2} ) a O -, - O (CH 2) a O -, - COO -, - OCO -, - CH = CH-COO -, - OCO-CH = CH -, - OCF 2 -, or _-CF 2 is O-, where a is the integer of 1 to 4; ^{Z 4} is _{- (CH 2) b -,} - O (CH 2) b -, - CO 2 - (CH 2 _{) b -, - OCO- (CH} 2) b -, or _{- (CH 2) c -O- (} CH 2) d - a, where b is an integer from 1 to 9, c and d are 2 from an integer of 5, any one in these groups -CH ₂ - may replace at always -CH = CH- and -C≡C- either Are, [1] A compound according to claim.

これらの式において、Ｒ¹’が炭素数１から１０のアルキル、炭素数１から１０のアルコキシ、炭素数２から１０のアルケニル、水素、フッ素、塩素、−ＣＮ、−ＣＦ_３、−ＯＣＦ_３、−ＯＣＨＦ_２、または−Ｚ^４−Ｐ^１である；Ｐ^１は式（１）におけるこれらの記号と同じ意味を示す。ただし（Ｐ^１−１）および（Ｐ^１−６）においてＸは水素、フッ素、−ＣＦ_３、−ＣＨ_３または−Ｃ_２Ｈ_５であり；Ａ^１１、Ａ^２１、Ａ^３１およびＡ^４１は独立して１，４−シクロへキシレン、１，４−フェニレン、少なくとも１つの水素がフッ素で置き換えられた１，４−シクロへキシレン、少なくとも１つの水素がフッ素で置き換えられた１，４−フェニレン、ナフタレン−２，６−ジイル、またはフルオレン−２，７−ジイルである。ただしこれらの環の２つ以上がナフタレン−２，６−ジイルまたはフルオレン−２，７−ジイルであることはない；Ｚ^１０、Ｚ^２０およびＺ^３０は独立して単結合、−（ＣＨ₂）₂−、−（ＣＨ₂）_３−、−（ＣＨ_２）_４−、−ＯＣＨ_２−、−Ｏ（ＣＨ_２）_２−、−Ｏ（ＣＨ_２）_３−、−Ｏ（ＣＨ_２）_４−、−ＣＨ_２Ｏ−、−（ＣＨ_２）_２Ｏ−、−（ＣＨ_２）_３Ｏ−、−（ＣＨ_２）_４Ｏ−、−Ｏ（ＣＨ_２）_２Ｏ−、−Ｏ（ＣＨ_２）_３Ｏ−、−Ｏ（ＣＨ_２）_４Ｏ−、−Ｏ（ＣＨ_２）_５Ｏ−、−Ｏ（ＣＨ_２）_６Ｏ−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−（ＣＨ₂）_ａ−ＣＯＯ−、−ＯＣＯ−（ＣＨ₂）_ａ−、−ＯＣＦ_２−または−ＣＦ_２Ｏ−である；ｍ、ｎおよびｑは独立して０、１または２であり、これらの合計は１〜５である；ｒは１〜６の整数であり、ｓおよびｔは独立して２または３である；Ａ^４１とＰ^１にはさまれた（ＣＨ_２）_ｒ基、（ＣＨ_２）_ｓ基または（ＣＨ_２）_ｔ基は、このうち任意のひとつの−ＣＨ_２−が−ＣＨ＝ＣＨ−および−Ｃ≡Ｃ−のいずれかでかならず置き換えられる。 [7] The compound represented by the formula (1) according to the item [1] is any one compound represented by the following formulas (1a) to (1f).

In these formulas, R ¹ ′ is alkyl having 1 to 10 carbons, alkoxy having 1 to 10 carbons, alkenyl having 2 to 10 carbons, hydrogen, fluorine, chlorine, —CN, —CF ₃ , —OCF ₃ , -OCHF _2, or by ^-Z 4 -P ^{1; P 1} has the same meaning as those in formula (1). However ^(P 1 -1) and X in ^(P 1 -6) is hydrogen, _fluorine, -CF 3, it is -CH ₃ or _{^{-C 2 H 5; A 11,}} A 21, A 31 and ^{A 41} are independently 1,4-cyclohexylene, 1,4-phenylene, 1,4-cyclohexylene in which at least one hydrogen is replaced by fluorine, 1,4-phenylene in which at least one hydrogen is replaced by fluorine, Naphthalene-2,6-diyl or fluorene-2,7-diyl. Provided that two or more of these rings are not naphthalene-2,6-diyl or fluorene-2,7-diyl; Z ¹⁰ , Z ²⁰ and Z ³⁰ are independently a single bond, — (CH ₂ ) ₂ −, — (CH ₂ ) ₃ —, — (CH ₂ ) ₄ —, —OCH ₂ —, —O (CH ₂ ) ₂ —, —O (CH ₂ ) ₃ —, —O (CH ₂ ) ₄ — , —CH ₂ O—, — (CH ₂ ) ₂ O—, — (CH ₂ ) ₃ O—, — (CH ₂ ) ₄ O—, —O (CH ₂ ) ₂ O—, —O (CH ₂ ) ₃ O—, —O (CH ₂ ) ₄ O—, —O (CH ₂ ) ₅ O—, —O (CH ₂ ) ₆ O—, —CH═CH—, —CF═CF—, —COO—, -OCO -, - CH = CH- COO -, - OCO-CH = CH -, - (CH 2) a -COO -, - OCO- (CH 2) a -, - OCF - or _-CF 2 is a O-; m, n and q are independently 0, 1 or 2, their sum is a 1 to 5; r is an integer from 1 to 6, s and t Is independently 2 or 3; the (CH ₂ ) _r group, (CH ₂ ) _s group or (CH ₂ ) _t group sandwiched between A ⁴¹ and P ¹ is any one of —CH _2- is always replaced by either -CH = CH- or -C≡C-.

[8] The compound according to item [7], which is represented by any one of formulas (1b), (1c), (1d), and (1e).

[9] In the formula (1b), (1c), (1d), and (1e) described in the item [7], m = 1 and n = q = 0, described in the item [7] or [8] Compound.

[10] In the formulas (1b), (1c), (1d), and (1e) described in the item [7], m = 1, n = q = 0, and R ¹ ′ has 1 to 10 carbon atoms. Alkyl, alkoxy having 1 to 10 carbons, alkenyl having 2 to 10 carbons, hydrogen, fluorine, chlorine, —CN, —CF ₃ , —OCF ₃ , or —OCHF ₂ ; and P ¹ is (P ¹ −1 ^{), (P} 1 -5) or be a ^(P 1 ^{-6); a 11} and ^{a 41} are each independently 1,4-cyclohexylene, 1,4-phenylene, at least one hydrogen with fluorine or chlorine 1,4-phenylene substituted; Z ¹⁰ or Z ¹¹ is a single bond, — (CH ₂ ) _a —, —O (CH ₂ ) _a —, — (CH ₂ ) _a O—, —O (CH _{2) a O -, - COO} -, - OCO -, - CH = CH-COO -, - CO-CH = CH -, - OCF 2 -, or _-CF 2 is a O-, wherein a is an integer of 1 to 4, [7] The compound according to claim.

[11] In the item [7] or [8], in the formulas (1b), (1c), (1d), and (1e) described in the item [7], m = 1, n = 1, and q = 0. The described compound.

[12] [7] Formula according to claim (1b), (1c), (1d), and in (1e) be m = 1, n = 1, q = 0; from R ¹ 'is C 1 -C 10 alkyl, alkoxy of 1 to 10 carbon atoms, alkenyl having 2 to 10 carbon atoms, hydrogen, fluorine, _{chlorine, -CN, -CF 3, -OCF 3} , -OCHF 2, -O- (CH 2) r - _{^{P 1, -CO 2 - (CH}} 2) r -P 1, -OCO- (CH 2) r -P 1, - (CH 2) s -O- (CH 2) t -P 1 or, - (CH _{2) s} -O- _{(CH 2)} a t -P ^{1, P 1} is ^(P 1 ^-1), be a ^(P 1 -5) or ^(P 1 ^{-6); a 11} and ^{a 41} is independently 1,4-cyclohexylene, 1,4-phenylene, at least one hydrogen is replaced by fluorine or chlorine It is a ^{1,4-phenylene; A 21} is in ^{2,7-diyl; Z 10} and ^{Z 20} are independently a single _{bond, - (CH 2) a -} , - O (CH 2) a —, — (CH ₂ ) _a O—, —O (CH ₂ ) _a O—, —COO—, —OCO—, —CH═CH—COO—, —OCO—CH═CH—, —OCF ₂ —, Or —CF ₂ O—, wherein a is an integer of 1 to 4;

[13] [7] Formula according to claim (1b), (1c), (1d), and in (1e) be m = 1, n = 1, q = 0; from R ¹ 'is C 1 -C 10 alkyls, C 1-10 alkoxys, C 2-10 alkenyls, hydrogen, fluorine, chlorine, —CN, —CF ₃ , —OCF ₃ , —OCHF ₂ , —O— (CH ₂ ) _r — _{^{P 1, -CO 2 - (CH}} 2) r -P 1, -OCO- (CH 2) r -P 1, - (CH 2) s -O- (CH 2) t -P 1 or, - (CH _{2) s} -O- _{(CH 2)} be t -P ^{1; P 1} is ^(P 1 ^-1), be a ^(P 1 -5) or ^{(P 1 -6); A 11} , A 21 and A ⁴¹ is independently 1,4-cyclohexylene, 1,4-phenylene, and at least one hydrogen is fluorine or chlorine. Substituted 1,4-phenylene; Z ¹⁰ , Z ²⁰ and Z ³⁰ are independently a single bond, — (CH ₂ ) _a —, —O (CH ₂ ) _a —, — (CH ₂ ) _a O _{-, - O (CH 2)} a O -, - COO -, - OCO -, - CH = CH-COO -, - OCO-CH = CH -, - OCF 2 -, or _-CF 2 is O-, Wherein a is an integer of 1 to 4, according to item [7].

[14] The item [7] or [8], wherein m = 1, n = 1, and q = 1 in the formulas (1b), (1c), (1d), and (1e) according to the item [7]. Compound described in 1.

[15] In the formulas (1b), (1c), (1d), and (1e) described in the item [7], m = 2, n = 1, and q = 1, [7] or [8] Compound described in 1.

これらの式において、Ｒ¹’が炭素数１から１０のアルキル、炭素数１から１０のアルコキシ、炭素数２から１０のアルケニル、水素、フッ素、塩素、−ＣＮ、−ＣＦ_３、−ＯＣＦ_３、−ＯＣＨＦ_２、または−Ｚ^４−Ｐ^１である；Ｐ^１は式（１）におけるこれらの記号と同じ意味を示す。ただし（Ｐ^１−１）および（Ｐ^１−６）においてＸは水素、フッ素、−ＣＦ_３、−ＣＨ_３または−Ｃ_２Ｈ_５であり；Ａ^１１、Ａ^２１、Ａ^３１およびＡ^４１は独立して、１，４−シクロへキシレン、１，４−フェニレン、少なくとも１つの水素がフッ素で置き換えられた１，４−シクロへキシレン、少なくとも１つの水素がフッ素で置き換えられた１，４−フェニレン、ナフタレン−２，６−ジイル、またはフルオレン−２，７−ジイルである。ただしこれらの環の２つ以上がナフタレン−２，６−ジイルまたはフルオレン−２，７−ジイルであることはない；ｍ、ｎおよびｑは独立して０、１または２であり、これらの合計は１〜５である；Ｚ^４０は式（Ｚ^４−１）、式（Ｚ^４−２）、式（Ｚ^４−３）、式（Ｚ^４−４）、式（Ｚ^４−５）または式（Ｚ^４−６）であり、これらの式においてｒは１〜６の整数であり、ｓおよびｔは独立して２または３であり、これらの式のそれぞれにおいて任意のひとつの−（ＣＨ_２）−が−ＣＨ＝ＣＨ−および−Ｃ≡Ｃ−のいずれかでかならず置き換えられる；Ｚ^１１、Ｚ^２１およびＺ^３１は独立して、単結合、−（ＣＨ_２）_２−、−（ＣＨ_２）_３−、−（ＣＨ_２）_４−、−ＯＣＨ_２−、−Ｏ（ＣＨ_２）_２−、−Ｏ（ＣＨ_２）_３−、−Ｏ（ＣＨ_２）_４−、−ＣＨ_２Ｏ−、−（ＣＨ_２）_２Ｏ−、−（ＣＨ_２）_３Ｏ−、−（ＣＨ_２）_４Ｏ−、−Ｏ（ＣＨ_２）_２Ｏ−、−Ｏ（ＣＨ_２）_３Ｏ−、−Ｏ（ＣＨ_２）_４Ｏ−、−Ｏ（ＣＨ_２）_５Ｏ−、−Ｏ（ＣＨ_２）_６Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−−ＣＦ＝ＣＦ−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−（ＣＨ₂）_ａ−ＣＯＯ−、または−ＯＣＯ−（ＣＨ₂）_ａ−、である；Ｚ^１２、Ｚ^２２およびＺ^３２は独立して、単結合、−（ＣＨ_２）_２−、−（ＣＨ_２）_３−、−（ＣＨ_２）_４−、−ＯＣＨ_２−、−Ｏ（ＣＨ_２）_２−、−Ｏ（ＣＨ_２）_３−、−Ｏ（ＣＨ_２）_４−、−ＣＨ_２Ｏ−、−（ＣＨ_２）_２Ｏ−、−（ＣＨ_２）_３Ｏ−、−（ＣＨ_２）_４Ｏ−、−Ｏ（ＣＨ_２）_２Ｏ−、−Ｏ（ＣＨ_２）_３Ｏ−、−Ｏ（ＣＨ_２）_４Ｏ−、−Ｏ（ＣＨ_２）_５Ｏ−、−Ｏ（ＣＨ_２）_６Ｏ−、−ＣＨ＝ＣＨ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−（ＣＨ₂）_ａ−ＣＯＯ−、−ＯＣＯ−（ＣＨ₂）_ａ−、−ＯＣＦ_２−または−ＣＦ_２Ｏ−である；Ｚ^１３、Ｚ^２３およびＺ^３３は独立して、単結合、−（ＣＨ_２）_２−、−（ＣＨ_２）_３−、−（ＣＨ_２）_４−、−ＯＣＨ_２−、−Ｏ（ＣＨ_２）_２−、−Ｏ（ＣＨ_２）_３−、−Ｏ（ＣＨ_２）_４−、−ＣＨ_２Ｏ−、−（ＣＨ_２）_２Ｏ−、−（ＣＨ_２）_３Ｏ−、−（ＣＨ_２）_４Ｏ−、−Ｏ（ＣＨ_２）_２Ｏ−、−Ｏ（ＣＨ_２）_３Ｏ−、−Ｏ（ＣＨ_２）_４Ｏ−、−Ｏ（ＣＨ_２）_５Ｏ−、−Ｏ（ＣＨ_２）_６Ｏ−、−ＣＦ＝ＣＦ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−（ＣＨ₂）_ａ−ＣＯＯ−、−ＯＣＯ−（ＣＨ₂）_ａ−、−ＯＣＦ_２−、または−ＣＦ_２Ｏ−である；Ｚ^１４、Ｚ^２４およびＺ^３４は独立して、単結合、−（ＣＨ_２）_２−、−（ＣＨ_２）_３−、−（ＣＨ_２）_４−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−、−ＯＣＦ_２−または−ＣＦ_２Ｏ−である；Ｚ^１５、Ｚ^２５およびＺ^３５は独立して、単結合、−ＯＣＨ_２−、−Ｏ（ＣＨ_２）_２−、−Ｏ（ＣＨ_２）_３−、−Ｏ（ＣＨ_２）_４−、−ＣＨ_２Ｏ−、−（ＣＨ_２）_２Ｏ−、−（ＣＨ_２）_３Ｏ−、−（ＣＨ_２）_４Ｏ−、−Ｏ（ＣＨ_２）_２Ｏ−、−Ｏ（ＣＨ_２）_３Ｏ−、−Ｏ（ＣＨ_２）_４Ｏ−、−Ｏ（ＣＨ_２）_５Ｏ−、−Ｏ（ＣＨ_２）_６Ｏ−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−（ＣＨ₂）_ａ−ＣＯＯ−、−ＯＣＯ−（ＣＨ₂）_ａ−、−ＯＣＦ_２−または−ＣＦ_２Ｏ−である。 [16] The compound represented by formula (1) according to item [1] is any one compound represented by formulas (1g) to (1k).

In these formulas, R ¹ ′ is alkyl having 1 to 10 carbons, alkoxy having 1 to 10 carbons, alkenyl having 2 to 10 carbons, hydrogen, fluorine, chlorine, —CN, —CF ₃ , —OCF ₃ , -OCHF _2, or by ^-Z 4 -P ^{1; P 1} has the same meaning as those in formula (1). However ^(P 1 -1) and X in ^(P 1 -6) is hydrogen, _fluorine, -CF 3, it is -CH ₃ or _{^{-C 2 H 5; A 11,}} A 21, A 31 and ^{A 41} are independently 1,4-cyclohexylene, 1,4-phenylene, 1,4-cyclohexylene in which at least one hydrogen is replaced by fluorine, 1,4-phenylene in which at least one hydrogen is replaced by fluorine , Naphthalene-2,6-diyl, or fluorene-2,7-diyl. Provided that two or more of these rings are not naphthalene-2,6-diyl or fluorene-2,7-diyl; m, n and q are independently 0, 1 or 2; Z ⁴⁰ is the formula (Z ⁴ -1), formula (Z ⁴ -2), formula (Z ⁴ -3), formula (Z ⁴ -4), formula (Z ⁴ -5) or Formula (Z ^4-6 ), where r is an integer from 1 to 6, s and t are independently 2 or 3, and any one of — (CH ₂ )-must be replaced by either -CH = CH- or -C≡C-; Z ¹¹ , Z ²¹ and Z ³¹ are independently a single bond,-(CH ₂ ) ₂ -,-(CH _{2) 3 -, - (CH} 2) 4 -, - OCH 2 -, - O (CH 2) 2 -, - O (CH _{) 3 -, - O (CH} 2) 4 -, - CH 2 O -, - (CH 2) 2 O -, - (CH 2) 3 O -, - (CH 2) 4 O -, - O (CH ₂ ) ₂ O—, —O (CH ₂ ) ₃ O—, —O (CH ₂ ) ₄ O—, —O (CH ₂ ) ₅ O—, —O (CH ₂ ) ₆ O—, —COO—, —OCO—, —CH═CH—CF═CF—, —CH═CH—COO—, —OCO—CH═CH—, — (CH ₂ ) _a —COO—, or —OCO— (CH ₂ ) _a Z ¹² , Z ²² and Z ³² are independently a single bond, — (CH ₂ ) ₂ —, — (CH ₂ ) ₃ —, — (CH ₂ ) ₄ —, —OCH ₂ —, _{-O (CH 2) 2 -,} - O (CH 2) 3 -, - O (CH 2) 4 -, - CH 2 O -, - (CH 2) 2 O -, - (CH 2) 3 O- , _{(CH 2) 4 O -,} - O (CH 2) 2 O -, - O (CH 2) 3 O -, - O (CH 2) 4 O -, - O (CH 2) 5 O -, - O (CH ₂ ) ₆ O—, —CH═CH—, —COO—, —OCO—, —CH═CH—COO—, —OCO—CH═CH—, — (CH ₂ ) _a —COO—, —OCO _{- (CH 2) a -,} - OCF 2 - or _-CF 2 is ^{O-; Z 13,} Z ²³ and ^{Z 33} are independently a single _{bond, - (CH 2) 2 -} , - (CH 2) _3- , — (CH ₂ ) ₄ —, —OCH ₂ —, —O (CH ₂ ) ₂ —, —O (CH ₂ ) ₃ —, —O (CH ₂ ) ₄ —, —CH ₂ O—, — _{(CH 2) 2 O -,} - (CH 2) 3 O -, - (CH 2) 4 O -, - O (CH 2) 2 O -, - O (CH 2) 3 O -, - O (CH _{) 4 O -, - O (} CH 2) 5 O -, - O (CH 2) 6 O -, - CF = CF -, - COO -, - OCO -, - CH = CH-COO -, - OCO- CH = CH -, - (CH 2) a -COO -, - OCO- (CH 2) a -, - OCF 2 -, or _-CF 2 is ^{O-; Z 14,} Z ²⁴ and ^{Z 34} are independently Single bond, — (CH ₂ ) ₂ —, — (CH ₂ ) ₃ —, — (CH ₂ ) ₄ —, —CH═CH—, —CF═CF—, —OCF ₂ — or —CF ₂ O Z ¹⁵ , Z ²⁵ and Z ³⁵ are independently a single bond, —OCH ₂ —, —O (CH ₂ ) ₂ —, —O (CH ₂ ) ₃ —, —O (CH ₂ ) _{4. -, - CH 2 O -,} - (CH 2) 2 O -, - (CH 2) 3 O -, - (CH 2) 4 O -, - O (CH 2) 2 O _{-, - O (CH 2)} 3 O -, - O (CH 2) 4 O -, - O (CH 2) 5 O -, - O (CH 2) 6 O -, - CH = CH -, - CF ═CF—, —COO—, —OCO—, —CH═CH—COO—, —OCO—CH═CH—, — (CH ₂ ) _a —COO—, —OCO— (CH ₂ ) _a —, —OCF ₂ - or _-CF 2 is O-.

[17] In any one of formulas (1g) to (1k), Z ⁴⁰ represents formula (Z ⁴ -2), formula (Z ⁴ -3), formula (Z ⁴ -4), or formula (Z ⁴ -5). In these formulas, r is an integer of 1 to 6, s and t are independently 2 or 3, and in each of these formulas, any one — (CH ₂ ) — is —CH The compound according to item [16], which is necessarily replaced by any of ═CH— and —C≡C—.

[18] The compound according to [16] or [17], wherein m = 1 and n = q = 0 in the formulas (1g) to (1k) according to the item [16].

[19] The compound according to [16] or [17], wherein m = 1, n = 1, and q = 0 in the formulas (1g) to (1k) according to the item [16].

[20] The compound according to item [16] or [17], wherein in formulas (1g) to (1k) according to item [16], m = 1, n = 1, and q = 1.

[21] The compound according to [16] or [17], wherein m = 2, n = 1, and q = 1 in the formulas (1g) to (1k) according to the item [16].

[22] The compound according to any one of [1] to [21], which has optical activity.

[23] A liquid crystal composition containing at least one compound according to item [1].

[24] A liquid crystal composition comprising at least two polymerizable compounds, wherein at least one polymerizable compound is the compound according to item [1].

[25] The liquid crystal composition according to item [24], wherein at least two polymerizable compounds are the compound according to item [1].

[26] The liquid crystal composition according to item [24], wherein at least one polymerizable compound is the compound described in item [1] and at least one other polymerizable compound is different from the compound described in item [1]. object.

[27] A liquid crystal composition containing an optically active compound, wherein the optically active compound is selected from the group consisting of the compound described in item [22] and an optically active and polymerizable compound other than the compound described in item [22]. The liquid crystal composition according to item [23], which is at least one selected.

[28] A liquid crystal composition comprising at least one polymerizable compound according to item [1] and at least one non-polymerizable compound having liquid crystallinity.

式（２）において、Ｒ¹は炭素数１から２０のアルキル、水素、ハロゲン、−ＣＮ、−Ｎ＝Ｃ＝Ｏ、−Ｎ＝Ｃ＝Ｓ、または−Ｚ^４−Ｐ^２であり、このアルキルにおいて任意の−ＣＨ₂−は−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−、または−Ｃ≡Ｃ−で置き換えられてもよく、そして任意の水素はハロゲン、−ＣＦ_３または−ＣＮで置き換えられてもよい；Ａ¹、Ａ²、Ａ³、およびＡ⁴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、ナフタレン−２，６−ジイル、テトラヒドロナフタレン−２，６−ジイル、フルオレン−２，７−ジイル、ビシクロ［２．２．２］オクタン−１，４−ジイル、ビシクロ［３．１．０］ヘキサン−３，６−ジイル、ビシクロ[４．４．０]デカンまたはＱであり、これらの環において任意の−ＣＨ_２−は−Ｏ−で置き換えられてもよく、任意の−ＣＨ＝は−Ｎ＝で置き換えられてもよく、そして任意の水素はハロゲン、炭素数１から５のアルキル、炭素数１から５のフルオロアルキル、炭素数１から５のアルコキシ、または炭素数２から５のアルケニルの基で置き換えられてもよく、Ｑは下記に示される２価の基のいずれかであり、

これらの２価の基において、Ｍｅはメチルであり、Ｙ^１、Ｙ^２、Ｙ^３およびＹ^４は独立して、炭素数１〜１０のアルキル、炭素数１〜１０のアルコキシ、炭素数１〜１０のフルオロアルキル、水素またはフッ素である； Ｚ^１、Ｚ^２およびＺ^３は独立して単結合または炭素数１から２０のアルキレンであり、このアルキレンにおいて任意の−ＣＨ₂−は−Ｏ−、−Ｓ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−、または−Ｃ≡Ｃ−で置き換えられても良く、このアルキレンあるいは置換されたアルキレンにおいて任意の水素はハロゲンで置き換えられてもよい；Ｚ^４は炭素数１から２０のアルキレンであり、このアルキレンにおいて任意のひとつの−ＣＨ_２−が−ＣＨ＝ＣＨ−および−Ｃ≡Ｃ−のいずれかでかならず置き換えられており、その他の任意の−ＣＨ₂−は−Ｏ−、−Ｓ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−、または−Ｃ≡Ｃ−で置き換えられてもよい；Ｐ^２は（Ｐ^２−１）から（Ｐ^２−６）に示す基のいずれかである；

Ｘは水素、ハロゲン、−ＣＦ_３、または炭素数１から５のアルキル、である；ｍ、ｎおよびｑが独立して０または１である。なおｍ、ｎおよびｑが２である場合に２つある同じ記号は、独立して別の構造であってもよいし、同じであってもよい。 [29] A polymer having at least one structural unit represented by formula (2).

In the formula (2), R ¹ is alkyl having 1 to 20 carbons, hydrogen, halogen, —CN, —N═C═O, —N═C═S, or —Z ⁴ —P ^2. In the formula, any —CH ₂ — is replaced by —O—, —S—, —CO—, —COO—, —OCO—, —CH═CH—, —CF═CF—, or —C≡C—. And any hydrogen may be replaced by halogen, —CF ₃ or —CN; A ¹ , A ² , A ³ , and A ⁴ are independently 1,4-cyclohexylene, 1,4 -Cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl, fluorene-2,7-diyl, bicyclo [2.2.2] octane-1,4- Diyl, bicyclo [3.1.0] hexane-3,6-di , Bicyclo [4.4.0] decane, or Q, any -CH ₂ - in these rings - may be replaced by -O-, arbitrary -CH = may be replaced by -N = And any hydrogen may be replaced by a group of halogen, alkyl having 1 to 5 carbons, fluoroalkyl having 1 to 5 carbons, alkoxy having 1 to 5 carbons, or alkenyl having 2 to 5 carbons , Q is any of the divalent groups shown below,

In these divalent groups, Me is methyl, Y ¹ , Y ² , Y ³ and Y ⁴ are independently alkyl having 1 to 10 carbons, alkoxy having 1 to 10 carbons, 1 to C 1 10 fluoroalkyl, hydrogen or fluorine; Z ¹ , Z ² and Z ³ are each independently a single bond or alkylene having 1 to 20 carbons, in which any —CH ₂ — is —O—, -S-, -COO-, -OCO-, -CH = CH-, or -C≡C- may be substituted, and in this alkylene or substituted alkylene, any hydrogen may be replaced by halogen. ; ^{Z 4} is an alkylene having 1 to 20 carbon atoms, -CH ₂ of any one in the alkylene - is replaced always either -CH = CH- and -C≡C- Cage, other arbitrary -CH ₂ - -O -, - S -, - COO -, - OCO -, - CH = CH-, or it may be replaced by -C≡C-; ^{P 2} is ( P ² -1) to ^(is any of the groups shown in P 2 -6);

X is hydrogen, halogen, —CF ₃ , or alkyl having 1 to 5 carbons; m, n and q are independently 0 or 1. When m, n and q are 2, the same two symbols may be independently different structures or the same.

[30] The polymer according to item [29] obtained from the compound according to any one of items [2] to [22].

[31] The polymer described in the item [29], obtained by homopolymerizing one of the compounds described in any one of the items [1] to [22].

[32] The polymer according to item [29], which is obtained from the liquid crystal composition according to any one of items [23] to [27].

[33] A polymer composition containing the polymer according to the item [29] obtained from the liquid crystal composition according to the item [28].

[34] A film having optical anisotropy obtained using the polymer described in any one of [29] to [32] or the polymer composition described in [33].
[35] A molded article having optical anisotropy obtained using the polymer described in any one of [29] to [32] or the polymer composition described in [33].

[36] A liquid crystal display device containing the polymer according to any one of [29] to [32] or the polymer composition according to [33].
[37] A liquid crystal display device comprising the molded article having optical anisotropy according to the item [35].

The compound of the present invention has a liquid crystal phase in a wide temperature range, has excellent compatibility with other compounds, and further has necessary properties such as optical anisotropy and a liquid crystal containing this compound Can be used in the composition. The polymer of the present invention is excellent in properties such as mechanical strength, coatability, solubility, melting point, glass transition point and clearing point, and an optically anisotropic material can be produced from this polymer.

The polymerizable liquid crystal compound having an unsaturated bond of the present invention is represented by the formula (1).

In formula (1), Z ⁴ characterizing the present invention is alkylene having 1 to 20 carbon atoms, and in this alkylene, any one of —CH ₂ — is either —CH═CH— or —C≡C—. Any other —CH ₂ — may be replaced by —O—, —S—, —COO—, —OCO—, —CH═CH—, or —C≡C—. The alkylene preferably has 1 to 10 carbon atoms. In this alkylene, particularly preferred carbon number is 3 to 10. Preferable alkylene is specifically a group represented by any one of formulas (Z ⁴ -1) to (Z ⁴ -6).

In formulas (Z ⁴ -1) to (Z ⁴ -6), r represents an integer of 1 to 10, and s and t represent an integer of 2 to 5. In the formulas (Z ⁴ -1) to (Z ⁴ -6), the formula (Z ⁴ -2), (Z ⁴ -3), (Z ⁴ -4) or (Z ⁴ -5) is preferable. .

Ｘは水素、ハロゲン、−ＣＦ_３、または炭素数１から５のアルキルであり、好ましくは水素、フッ素、−ＣＦ_３、または炭素数１から２のアルキルである。 In the formula (1), P ¹ is any one of groups having polymerization ability represented by (P ¹ -1) to (P ¹ -6), preferably (P ¹ -1), (P ¹ -5). ) or ^(P 1 -6);

X is hydrogen, halogen, —CF ₃ , or alkyl having 1 to 5 carbons, preferably hydrogen, fluorine, —CF ₃ , or alkyl having 1 to 2 carbons.

In Formula (1), R ¹ is alkyl having 1 to 20 carbons, hydrogen, halogen, —CN, —N═C═O, —N═C═S, or —Z ⁴ —P ¹ , In alkyl, any —CH ₂ — is replaced by —O—, —S—, —CO—, —COO—, —OCO—, —CH═CH—, —CF═CF—, or —C≡C—. at best, and arbitrary hydrogen halogen, may be replaced by -CF ₃ or -CN.

Preferred examples of R ¹ include hydrogen, halogen, —CN, —CF ₃ , —CF ₂ H, —CFH ₂ , —OCF ₃ , —OCF ₂ H, straight-chain alkyl having 1 to 10 carbons, and 1 carbon. Straight chain alkoxy having from 1 to 10 carbon atoms, straight chain alkoxyalkyl having from 2 to 10 carbon atoms, straight chain alkenyl having from 2 to 10 carbon atoms, or —Z ⁴ —P ¹ ; Z ⁴ and P ¹ are as defined above Indicates.

More preferred examples of R ¹ are hydrogen, —F, —Cl, —CN, —CF ₃ , —CF ₂ H, —CFH ₂ , —OCF ₃ , —OCF ₂ H, —CH ₃ , —C ₂ H _{5. , -C 3 H 7, -C 4} H 9, -C 5 H 11, -C 6 H 13, -C 7 H 15, -C 8 H 17, -OCH 3, -OC 2 H 5, -OC 3 _{H 7, -OC 4 H 9,} -OC 5 H 11, -OC 6 H 13, -OC 7 H 15, -OC 8 H 17, -CH 2 OCH 3, -CH 2 OC 2 H 5, -CH 2 _{OC 3 H 7, -CH 2 OC} 4 H 9, -C 2 H 5 OCH 3, -C 2 H 5 OC 2 H 5, -C 2 H 5 OC 3 H 7, -C 3 H 6 OCH 3, - _{C 3 H 6 OC 2 H 5} , -C 3 H 6 OC 3 H 7, -CH 2 CH 2 F, -C 2 H 4 CH ₂ F, —CH═CH ₂ , —CH═CHCH ₃ , —CH ₂ CH═CH ₂ , allyl, —C ₂ H ₄ CH═CH ₂ , —C ₂ H ₄ CH═CHCH ₃ , or —Z ⁴ —. P ¹ etc .; Z ⁴ and P ¹ represent the aforementioned meanings.

When R ¹ is alkyl having an asymmetric carbon, compound (1) has optical activity. Examples of alkyl having an asymmetric carbon are 2-methylbutyl, 2-methylpentyl, 2-methylhexyl, 2-methylheptyl, 2-methyloctyl, 2-methyl-1-butenyl, 2-methyl-1-pentenyl, 2-methyl-1-hexenyl, 2-methyl-1-heptenyl, 2-methyl-1-octenyl, 2-methylbutoxy, 2-methylpentyloxy, 2-methylhexyloxy, 2-methylheptyloxy, 2-methyl Octyloxy, 2-methylbutoxycarbonyl, 2-methylpentyloxycarbonyl, 2-methylhexyloxycarbonyl, 2-methylheptyloxycarbonyl, 2-methyloctyloxycarbonyl and the like.

これらの基において、Ｍｅはメチルであり、Ｙ^１、Ｙ^２、Ｙ^３およびＹ^４は炭素数１から１０のアルキル、炭素１から１０のアルコキシ、炭素１から１０のフルオロアルキル、水素またはフッ素である。 A ¹ , A ² , A ³ , and A ⁴ in formula (1) are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6- Diyl, tetrahydronaphthalene-2,6-diyl, fluorene-2,7-diylbicyclo [2.2.2] octane-1,4-diyl, or bicyclo [3.1.0] hexane-3,6-diyl, Bicyclo [4.4.0] decane, or Q. In these rings, arbitrary —CH ₂ — may be replaced by —O—, and arbitrary —CH═ may be replaced by —N═. However, it is preferable that two adjacent —CH ₂ — are not replaced like —O—O—. Examples in which —CH ₂ — is replaced by —O— in 1,4-cyclohexylene are 1,3-dioxane-2,5-diyl and 1,4-dioxane-2,5-diyl. Examples in which —CH═ is replaced by —N═ in 1,4-phenylene are pyridine-2,5-diyl, pyrimidine-2,5-diyl and pyridazine-3,6-diyl. And any hydrogen in all cyclic groups including these rings is halogen, alkyl having 1 to 5 carbons, fluoroalkyl having 1 to 5 carbons, alkoxy having 1 to 5 carbons, or alkenyl having 2 to 5 carbons May be replaced. A preferred halogen is fluorine. Q is any of the divalent groups shown below.

In these groups, Me is methyl and Y ¹ , Y ² , Y ³ and Y ⁴ are alkyl having 1 to 10 carbons, alkoxy having 1 to 10 carbons, fluoroalkyl having 1 to 10 carbons, hydrogen or fluorine. is there.

Preferred examples of A ¹ , A ² , A ³ or A ⁴ are 1,4-cyclohexylene, 1,4-phenylene, 1,4 in which at least one hydrogen is replaced by halogen or alkyl having 1 to 5 carbons. -Phenylene, 1,3-dioxane-2,5-diyl, pyridine-2,5-diyl, 6-fluoropyridine-2,5-diyl, pyrimidine-2,5-diyl, pyridazine-3,6-diyl, Naphthalene-2,6-diyl, tetrohydronaphthalene-2,6-diyl, and fluorene-2,7-diyl. 1,4-cyclohexylene and 1,3-dioxane-2,5-diyl are preferably trans rather than cis.

More preferred examples of A ¹ , A ² , A ³ , or A ⁴ are 1,4-cyclohexylene, 1,4-phenylene, 1,4-cyclohexylene in which at least one hydrogen is replaced by halogen, at least 1 1,4-phenylene in which one hydrogen is replaced by a halogen. Most preferred examples of A ¹ , A ² , A ³ or A ⁴ are 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4. -Phenylene, 2,5-difluoro-1,4-phenylene, and 2,6-difluoro-1,4-phenylene.

In order for the compound (1) to have optical activity, A ¹ , A ² , A ³ , or A ⁴ may be any of the divalent groups shown below.

Z ¹ , Z ² and Z ³ in formula (1) are each independently a single bond or alkylene having 1 to 20 carbon atoms, and in this alkylene, any —CH ₂ — is —O—, —S—, —COO. -, -OCO-, -CH = CH-, -C≡C- may be substituted, and in this alkylene or substituted alkylene, any hydrogen may be replaced by halogen, and preferably has 1 carbon atom. To 10. Preferred examples of Z ¹ , Z ² or Z ³ are a single bond, —CH═CH—, —C≡C—, —COO—, —OCO—, — (CF ₂ ) ₂ —, —C≡C—COO. -, - OCO-C≡C -, - CH = CH- (CH 2) 2 -, - (CH 2) 2 -CH = CH -, - CF = CF -, - C≡C-HC = CH-, —CH═CH—C≡C—, —OCF ₂ —, —CF ₂ O—, or alkylene having 1 to 20 carbon atoms. More preferred alkylene has 1 to 10 carbon atoms.

More preferred examples of Z ¹ , Z ² or Z ³ are a single bond, — (CH ₂ ) ₂ —, —OCH ₂ —, —CH ₂ O—, — (CH ₂ ) _a —, —O (CH ₂ ). _{a -, - (CH 2)} a O -, - O (CH 2) a O -, - CH = CH -, - (CH 2) 4 -, - CF = CF -, - OCF 2 -, or -CF ₂ O-. Further, a compound having a smaller viscosity includes Z ¹ , Z ² or Z ³ having a single bond, — (CH ₂ ) ₂ —, —CH═CH—, —CF═CF—, —OCF ₂ —, or —CF ₂ O. -Is preferred. In these linking groups, the double bond is preferably trans rather than cis.

  In the formula (1), m, n and q are each independently 0, 1 or 2. When the sum of m, n and q is 0, the compound (1) is a compound having one ring structure, but from the viewpoint of the liquid crystal phase temperature range, the ring structure is a condensed ring composed of two or more rings. It is desirable to be. When the sum of m, n and q is 1, compound (1) is a compound having two ring structures. When the sum is 2 and 3, compound (1) is a compound having three ring structures and a compound having four ring structures, respectively. In order to set the liquid crystal phase temperature range to the low temperature side, a compound having two ring structures may be selected. When it is desired to set the liquid crystal phase temperature range to a relatively high temperature side, a compound having three ring structures or a compound having four ring structures may be selected. In order to set the liquid crystal phase temperature range to a higher temperature side, a compound in which the sum of m, n and q is 4, 5 or 6 may be selected.

また、化合物構造中のＺ^４にかならず−ＣＨ＝ＣＨ−またはＣ≡Ｃ−を有する。
これら式（１）の化合物は、通常使用される条件下において物理的および化学的に極めて安定であり、他の化合物との相溶性がよいことを特徴とする。特に重合性基Ｐ^１に不飽和結合を有するＺ^４が連結したことにより、液晶相下限温度（ＣＮ点）が低下し、液晶相温度範囲が広がるという有用な特徴を持つ。化合物（１）を構成する環、結合基または側鎖を適当に選ぶことによって、高い誘電率異方性、低い誘電率異方性、高い光学異方性、低い光学異方性、低い粘性などの物性値を調整することができる。また、化合物（１）の構造を適切に選択することで、最適な透明性、機械的強度、塗布性、溶解度、結晶化度、収縮性、透水度、吸水度、融点、ガラス転移点、透明点、耐薬品性を持つ重合体を製造することができる。 Compound (1) has 1 to 7 ring structures, but preferably 2 to 5 ring structures, and is represented by the formulas (1-A) to (1-D).

In addition, Z ⁴ in the compound structure always has —CH═CH— or C≡C—.
These compounds of the formula (1) are characterized by being physically and chemically extremely stable under the conditions usually used and having good compatibility with other compounds. In particular, since Z ⁴ having an unsaturated bond is connected to the polymerizable group P ¹ , the liquid crystal phase lower limit temperature (CN point) is lowered and the liquid crystal phase temperature range is widened. High dielectric anisotropy, low dielectric anisotropy, high optical anisotropy, low optical anisotropy, low viscosity, etc. by appropriately selecting the ring, bonding group or side chain constituting the compound (1) The physical property value can be adjusted. In addition, by appropriately selecting the structure of compound (1), optimal transparency, mechanical strength, applicability, solubility, crystallinity, shrinkage, water permeability, water absorption, melting point, glass transition point, transparency A polymer having chemical resistance can be produced.

When R ¹ is not —Z ⁴ —P ¹ , it is a monofunctional compound. When R ¹ is —Z ⁴ —P ¹ , it is a bifunctional compound having a polymerizable group at both ends of the molecule. The bifunctional compound exhibits higher polymerizability than the monofunctional compound. That is, the bifunctional compound has a higher polymerization rate, and the polymerization is completed in a shorter time, so that a polymer having a higher degree of polymerization can be obtained. The resulting polymer has higher heat resistance, lower water absorption, water permeability and gas permeability, and higher mechanical strength (particularly hardness).

Applications of the polymer in the present invention include the following.
The polymer is a thermoplastic resin or a thermosetting resin. Thermoplastic resins are used for adhesives, synthetic polymers, cosmetics, decorations, nonlinear optical materials, information storage materials, and the like. This thermoplastic resin is a linear polymer having a low degree of polymerization, and can be obtained as a polymer having a low degree of polymerization by polymerizing the liquid crystal composition of the present invention mainly composed of a monofunctional compound. Their weight average molecular weight is 500 to 1000000, preferably 1000 to 500000, more preferably 2000 to 100000.
A thermosetting resin is used for a retardation plate, a polarizing element, a liquid crystal alignment film, an antireflection film, a selective reflection film, a viewing angle compensation film, and the like, which are components of the liquid crystal display element. This thermosetting resin is a polymer having a three-dimensional network structure, and is obtained as a polymer having a high degree of polymerization by polymerizing the liquid crystal composition of the present invention mainly composed of a bifunctional compound. As the polymerization proceeds, these polymers become difficult to dissolve in the solvent and increase in hardness. The molecular weights of these polymers are difficult to measure and difficult to define, but are preferably close to infinity and large.

Furthermore, the formulas (1-A) to (1-D) can be embodied into preferable formulas such as the following examples. In the following formulas, R ¹ , Z ¹ , Z ² , Z ³ and Z ⁴ have the same meaning as these symbols in formula (1), and 1,4-cyclohexylene, 1,4-phenylene, 1, Groups representing 4-cyclohexenylene, pyridine-2,5-diyl, naphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl, and fluorene-2,7-diyl are each represented by the following formula: Represents the group

Of the above, formula (1-1) to formula (1-8), formula (1-11) to formula (1-18), or formula (1-20) to formula (1-59) are more preferred, (1-1) to Formula (1-2), Formula (1-4) to Formula (1-5), Formula (1-11) to Formula (1-16), Formula (1-30) to Formula ( 1-36) or formula (1-56) to formula (1-57) are more preferable.

In Formula (1), more preferred examples of A ¹ , A ² , A ³ , or A ⁴ are 1,4-cyclohexylene, 1,4-phenylene, and 1, wherein at least one hydrogen is replaced by halogen Since 4-cyclohexylene is 1,4-phenylene in which at least one hydrogen is replaced by a halogen, examples of formulas representing more preferred compounds in formula (1) are shown below.

In the above formulas (1-60) to (1-107), R ¹¹ is a linear alkyl having 1 to 10 carbon atoms, R ¹² is a linear alkoxyalkyl having 2 to 10 carbon atoms, and R ^{12 13} is a straight-chain alkenyl having 2 to 10 carbon atoms; A ¹¹ , A ²¹ , A ³¹ and A ⁴¹ are independently 1,4-cyclohexylene, 1,4-phenylene, and at least one hydrogen is fluorine. 1,4-cyclohexylene replaced, or 1,4-phenylene in which at least one hydrogen is replaced by fluorine; Z ¹⁰ , Z ²⁰ and Z ³⁰ are independently a single bond, — (CH ₂ ) ₂ −, — (CH ₂ ) ₃ —, — (CH ₂ ) ₄ —, —OCH ₂ —, —O (CH ₂ ) ₂ —, —O (CH ₂ ) ₃ —, —O (CH ₂ ) ₄ — _{, -CH 2 O -, - (} CH 2) 2 O-, _{(CH 2) 3 O -,} - (CH 2) 4 O -, - O (CH 2) 2 O -, - O (CH 2) 3 O -, - O (CH 2) 4 O -, - O ( CH ₂ ) ₅ O—, —O (CH ₂ ) ₆ O—, —CH═CH—, —CF═CF—, —OCF ₂ — or —CF ₂ O—; m, n and q are independently 0, 1 or 2 and the sum thereof is 1 to 5; Z ^{41 to} Z ⁴⁴ are selected from the following formulae. Z ⁴¹ is the formula (Z ⁴ -1), Z ⁴² is the formula (Z ⁴ -2), Z ⁴³ is the formula (Z ⁴ -3) or the formula (Z ⁴ -4), and Z ⁴⁴ is it is a formula ^(Z 4 -5) or formula ^(Z 4 -6). In the formula shown below, r is an integer of 1 to 6, and s and t are independently 2 or 3, any one of —CH ₂ — is —CH═CH—, —C≡C. -Must be replaced with one of-.

In the above formula (1-108) to formula (1-168), R ¹¹ is a linear alkyl having 1 to 10 carbon atoms, R ¹² is a linear alkoxyalkyl having 2 to 10 carbon atoms, and R ¹³ is a straight-chain alkenyl having 2 to 10 carbon atoms; A ¹¹ , A ²¹ , A ³¹ and A ⁴¹ are independently 1,4-cyclohexylene, 1,4-phenylene, and at least one hydrogen is fluorine. 1,4-cyclohexylene substituted with or 1,4-phenylene with at least one hydrogen replaced with fluorine; m, n and q are independently 0, 1 or 2; The sum is 1 to 5; r is an integer of 1 to 6; Z ⁴⁰ is a single bond, the above formula (Z ⁴ -1), formula (Z ⁴ -2), formula (Z ⁴ -3), wherein ^(Z 4 -4), formula ^(Z 4 -5) or formula ^{(Z 4} - 6), in these formulas, r is an integer of 1 to 6, s and t are independently 2 or 3, and any one of — (CH ₂ ) — is —CH═CH—, — It must be replaced by any of C≡C—; Z ¹¹ , Z ²¹ and Z ³¹ are independently a single bond, — (CH ₂ ) ₂ —, — (CH ₂ ) ₃ —, — (CH ₂ ) _{4. -, - OCH 2 -, -} O (CH 2) 2 -, - O (CH 2) 3 -, - O (CH 2) 4 -, - CH 2 O -, - (CH 2) 2 O -, - (CH ₂ ) ₃ O—, — (CH ₂ ) ₄ O—, —O (CH ₂ ) ₂ O—, —O (CH ₂ ) ₃ O—, —O (CH ₂ ) ₄ O—, —O ( CH ₂ ) ₅ O—, —O (CH ₂ ) ₆ O—, —CH═CH— or —CF═CF—; Z ¹² , Z ²² and Z ³² are independently , Single bond, — (CH ₂ ) ₂ —, — (CH ₂ ) ₃ —, — (CH ₂ ) ₄ —, —OCH ₂ —, —O (CH ₂ ) ₂ —, —O (CH ₂ ) ₃ — , —O (CH ₂ ) ₄ —, —CH ₂ O—, — (CH ₂ ) ₂ O—, — (CH ₂ ) ₃ O—, — (CH ₂ ) ₄ O—, —O (CH ₂ ) _{2 O -, - O (CH 2} ) 3 O -, - O (CH 2) 4 O -, - O (CH 2) 5 O -, - O (CH 2) 6 O -, - CH = CH -, - OCF ₂ — or —CF ₂ O—; Z ¹³ , Z ²³ and Z ³³ are independently a single bond, — (CH ₂ ) ₂ —, — (CH ₂ ) ₃ —, — (CH ₂ ) _{4. -, - OCH 2 -, -} O (CH 2) 2 -, - O (CH 2) 3 -, - O (CH 2) 4 -, - CH 2 O -, - (CH 2) 2 O -, - (CH ₂ ) _{3 O -, - (CH 2)} 4 O -, - O (CH 2) 2 O -, - O (CH 2) 3 O -, - O (CH 2) 4 O -, - O (CH 2) 5 O _{-, - O (CH 2)} 6 O -, - CF = CF -, - OCF 2 -, or _-CF 2 is ^{O-; Z 14,} Z ²⁴ and ^{Z 34} are independently a single bond, - ( CH ₂ ) ₂ —, — (CH ₂ ) ₃ —, — (CH ₂ ) ₄ —, —CH═CH—, —CF═CF—, —OCF ₂ — or —CF ₂ O—; Z ¹⁵ , Z ²⁵ and Z ³⁵ are independently a single bond, —OCH ₂ —, —O (CH ₂ ) ₂ —, —O (CH ₂ ) ₃ —, —O (CH ₂ ) ₄ —, —CH ₂ O—. , — (CH ₂ ) ₂ O—, — (CH ₂ ) ₃ O—, — (CH ₂ ) ₄ O—, —O (CH ₂ ) ₂ O—, —O (CH ₂ ) ₃ O—, —O ( _{H 2) 4 O -, -} O (CH 2) 5 O -, - O (CH 2) 6 O -, - CH = CH -, - CF = CF -, - OCF 2 - or _-CF 2 O-in is there.

The physical properties of the compound (1) are as follows. Compounds with two and three ring structures have low viscosity. A compound having three or more ring structures has a high clearing point (liquid crystal phase-phase transition temperature of isotropic liquid). Even if the compound (1) is a compound having three or more ring structures, it has good wettability when dissolved in a solvent, which is advantageous in the preparation of a composition, application on a substrate, and thinning. The compound (1) having three or more ring structures exhibits a very wide liquid crystal phase temperature region. In particular, since it has a liquid crystal phase in a high temperature region, a liquid crystal composition covered with a liquid crystal phase temperature region up to a low temperature region can be prepared by mixing with a compound having two ring structures.

For compound (1) having a large optical anisotropy, preferred examples of A ¹ , A ² , A ³ , or A ⁴ are 1,4-phenylene, pyridine-2,5-diyl optionally substituted with halogen. , Pyrimidine-2,5-diyl, pyridazine-3,6-diyl, naphthalene-2,6-diyl, tetrohydronaphthalene-2,6-diyl, and fluorene-2,7-diyl. For the compound (1) having a small optical anisotropy, preferred examples of A ¹ , A ² , A ³ or A ⁴ are 1,4-cyclohexylene, 1,4-cyclohexenylene or 1,3- Dioxane-2,5-diyl.

A compound having at least two cyclohexane rings has a high clearing point, a small optical anisotropy and a low viscosity. The compound having at least one benzene ring has a relatively large optical anisotropy and a large degree of liquid crystal alignment order (order parameter). A compound having at least two benzene rings has a particularly large optical anisotropy, a wide liquid crystal phase temperature range and a high chemical stability.

R ¹ bonded to 1,4-phenylene is —F, —CN, —CF ₃ , —OCF ₃ , or —OCF ₂ H, and ^one or both ortho positions of R ¹ are fluorine. The compound is chemically stable and has a particularly large dielectric anisotropy. A compound in which R ¹ is alkyl or alkoxy and at least one of A ¹ , A ² , A ³ and A ⁴ is 2,3-difluoro-1,4-phenylene is chemically stable and has an anisotropic dielectric constant Sex is negative.

A compound in which R ¹ has the same polymerizable moiety as P ¹ is polymerized to give a main chain type polymer (crosslinked type). The main chain polymer is more advantageous in mechanical strength.

A compound in which all of Z ¹ , Z ² and Z ³ are single bonds has a relatively high clearing point. The compound having a double bond has a wide temperature range of the liquid crystal phase. A compound having a triple bond has a particularly large optical anisotropy.
From these facts, a compound having desired physical properties can be obtained by appropriately selecting a ring, a side chain and a linking group. Even if the atom constituting the compound (1) is its isotope, it can be preferably used because it exhibits the same characteristics. Compound (1) can be produced by making full use of synthetic methods in organic chemistry described in Houben Wyle Methoden der Organischen Chemie, Organic Reactions, Organic Syntheses, and the like.

A compound having an acryloyl group can be constructed, for example, by the following method. Compound (1-a) can be produced by reacting acrylic acid in the presence of a catalyst such as p-toluenesulfonic acid and a polymerization inhibitor such as hydroquinone (3). In addition, compound (1) can be produced by allowing vinyl acrylate to act in the presence of a polymerization inhibitor such as hydroquinone and an enzyme such as lipase (3).

A vinyl ketone compound can be constructed, for example, by the following method. Compound (1-b) can be produced by synthesizing an alcohol by reacting (4) with an organometallic reagent such as a Grignard reagent and then oxidizing the alcohol by Jones oxidation or the like.

The vinyl ether compound can be constructed, for example, by the following method. Compound (1-c) can be produced by reacting (3) with n-butyl vinyl ether in the presence of a catalytic amount of palladium.

The maleimide compound can be constructed, for example, by the following method. A compound in which the double bond portion of maleimide is protected by using Diels-Alder reaction, diethyl azodicarboxylate, triphenylphosphine is allowed to act on (3), and deprotection is carried out by reverse Diels-Alder reaction. 1-d) can be produced.

The epoxy compound can be constructed, for example, by the following method. Compound (1-e) can be produced by oxidizing (5) with a peroxide such as metachloroperbenzoic acid.

An oxetane compound can be constructed, for example, by the following method. Compound (1-f) can be produced by etherification of (6) with halogenated oxetane.

The main skeleton (liquid crystal residue) of compound (1) can be constructed by the following method or by appropriately combining them. That is, with respect to an example of a method for producing the linking group Z ¹ , Z ² , Z ³ or Z ⁴ , a scheme is first shown, and then a method for producing the scheme is described. In this scheme, MSG ¹ or MSG ² is an organic group having at least one ring. A plurality of MSG ¹ (or MSG ² ) used in the scheme may be the same or different. Compounds (1A) to (1L) correspond to compound (1).

(I) Formation of a single bond A boric acid derivative (5) and a halide (6) synthesized by a known method are reacted in the presence of a catalyst such as an aqueous carbonate solution and tetrakis (triphenylphosphine) palladium. Compound (1A) is synthesized. This compound (1A) is obtained by reacting compound (7) 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. The boric acid derivative (5) can be produced by inducing the compound (7) to a Grignard reagent or a lithium reagent and acting a trialkyl borate ester.

(II) Formation of —COO— and —OCO— The compound (7) is reacted with n-butyllithium and subsequently with carbon dioxide to obtain the carboxylic acid (8). Compound (8) and phenol (9) synthesized by a known method are dehydrated in the presence of DDC (1,3-dicyclohexylcarbodiimide) and DMAP (4-dimethylaminopyridine) to have -COO- Synthesize (1B). A compound having —OCO— can also be synthesized by this method.

(III) Compound (10) is obtained by treating the product compound (1B) of —CF ₂ O— and —OCF ₂ — with a sulfurizing agent such as Lawesson's reagent. Compound (10) is fluorinated with hydrogen fluoride pyridine complex and NBS (N-bromosuccinimide) to synthesize compound (1C) having —CF ₂ O—.
See M. Kuroboshi et al., Chem. Lett., 1992, 827. Compound (1C) can also be synthesized by fluorinating compound (10) with (diethylamino) sulfur trifluoride. See William H. Bunnelle et al., J. Org. Chem. 1990, 55, 768. A compound having —OCF ₂ — can also be synthesized by this method.

(IV) Formation of —CH═CH— The compound (6) is treated with n-butyllithium and then reacted with formamide such as DMF (N, N-dimethylformamide) to obtain the aldehyde (11). Phosphoryl ylide generated by treating a phosphonium salt (12) synthesized by a known method with a base such as potassium t-butoxide is reacted with aldehyde (11) to synthesize compound (1D). Since a cis isomer is produced 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 ) ₂ — Compound (1D) is synthesized by hydrogenating compound (1D) in the presence of a catalyst such as palladium carbon.

(VI) Formation of — (CH ₂ ) ₄ — A compound having — (CH ₂ ) ₂ —CH═CH— according to the method of item (IV), using phosphonium salt (13) instead of phosphonium salt (12). obtain. This is catalytically hydrogenated to synthesize compound (1F).

(VII) Formation of —C≡C— After reacting compound (7) with 2-methyl-3-butyn-2-ol in the presence of a catalyst of dichloropalladium and copper halide, under basic conditions Deprotection yields compound (14). Compound (1G) is synthesized by reacting compound (14) with compound (6) in the presence of a catalyst of dichloropalladium and copper halide.

(VIII) Formation of —CF═CF— The compound (7) is treated with n-butyllithium and then reacted with tetrafluoroethylene to obtain the compound (15). Compound (15) is treated with n-butyllithium and then reacted with compound (6) to synthesize compound (1H).

(IX) Formation of —CH ₂ O— or —OCH ₂ — Compound (11) is reduced with a reducing agent such as sodium borohydride to obtain compound (16). This is halogenated with hydrobromic acid or the like to obtain compound (17). Compound (1J) is synthesized by reacting compound (17) with compound (9) in the presence of a base such as potassium carbonate.

_{(X) - (CH 2)} 3 O- or -O (CH _{2) 3} - by using the compound in place of the product compound (11) (18), synthesized the compound (1K) according to the method of claim (IX) To do.

_{(XI) - (CF 2)} 2 - generation of
According to the method described in J. Am. Chem. Soc., 2001, 123, 5414., diketone (21) is fluorinated with sulfur tetrafluoride in the presence of a hydrogen fluoride catalyst to give-(CF ₂ ) _2-. To obtain a compound (1L) having

Next, the liquid crystal composition will be described. This composition contains at least one compound (1). This composition may contain many kinds of compounds (1) as components. This composition may contain the compound (1) and other components. Examples of other components include liquid crystal compounds described in LiquCryst (registered trademark), which is a liquid crystal compound database sold by Fujitsu Kyushu Engineering, and polymerizable compounds described in JP-A-8-3111. It is. The content of other components is preferably such that the composition does not impair its liquid crystallinity. It is preferable that the atoms constituting the components of the composition contain more isotopes than their natural abundance because they exhibit similar properties.

The liquid crystal composition may contain an optically active compound or a dichroic dye. Since the composition containing an optically active compound exhibits a helical structure, a retardation plate having a helical structure can be produced by polymerizing the composition. If the spiral pitch is about ½ to about the same as the wavelength of light, light having that wavelength can be selectively reflected according to Bragg's law. This can be used, for example, as a circularly polarized light separating functional element. The optically active compound may be polymerizable or non-polymerizable as long as it can induce a helical structure. The direction of the helix depends on the configuration of the optically active compound. A desired spiral direction can be induced by selecting the configuration of the optically active compound as appropriate. This object can also be achieved by using the optically active compound (1). All of the compound (1) which is a component of the liquid crystal composition may be an optically active compound, or a part thereof may be an optically active compound. The liquid crystal composition of the present invention may contain an optically active compound (1) and an optically active compound other than the compound (1) as an optically active compound, or an optically active compound other than the compound (1). May contain only. Details of the optically active compound (1) will be described later. Of the optically active compounds other than the compound (1), (OP-1) to (OP-12) are non-polymerizable optically active compounds, and (OP-13) to (OP-19) are polymerizable optically active compounds. ) Is preferred. It should be noted that 1,4-cyclohexylene with a black circle in (Op-5), (Op-10) and (Op-12) indicates trans.

化合物（１）を重合することにより式（２）を構成単位とする重合体が得られる。利用できる重合法は、ラジカル重合法、アニオン重合法、カチオン重合法、配位重合法などである。化合物（１）のうちの１つを重合すると単独重合体が得られる。この重合体は式（２）で表わされる構成単位のみからなる。少なくとも２つの化合物（１）を含有する組成物を重合させると共重合体が得られる。共重合体において、式（２）で表わされる構成単位がランダム、ブロック、交互などのいずれであってもよい。 The compound (1) has any one of groups having polymerization ability represented by (P ¹ -1) to (P ¹ -6).

By polymerizing the compound (1), a polymer having the structural unit of the formula (2) is obtained. Polymerization methods that can be used include radical polymerization methods, anionic polymerization methods, cationic polymerization methods, and coordination polymerization methods. When one of the compounds (1) is polymerized, a homopolymer is obtained. This polymer consists only of the structural unit represented by the formula (2). When a composition containing at least two compounds (1) is polymerized, a copolymer is obtained. In the copolymer, the structural unit represented by the formula (2) may be any of random, block, alternating and the like.

  The compound (1) and a polymerizable compound other than the compound (1) may be copolymerized. The polymerizable compound other than the compound (1) is selected on the assumption that it is polymerizable. The polymerizable compound may be liquid crystalline or non-liquid crystalline as long as the film-forming property and mechanical strength are not lowered. For example, (meth) acrylate-based, vinyl-based, styrene-based, and vinyl ether-based polymerizable compounds are preferable.

Particularly preferred non-liquid crystalline compounds are methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, phenyl (meth) acrylate, vinyl chloride, vinyl fluoride, vinyl acetate. , Vinyl pivalate, vinyl 2,2-dimethylbutanoate, vinyl 2,2-dimethylpentanoate, vinyl 2-methyl-2-butanoate, vinyl propionate, vinyl stearate, vinyl 2-ethyl-2-methylbutanoate N-vinylacetamide, vinyl tert-butylbenzoate, vinyl N, N-dimethylaminobenzoate, vinyl benzoate, styrene, o-, m- or p-chloromethylstyrene, α-methylstyrene, ethyl vinyl ether , Hydroxybutyl monovinyl ether, t-amyl Vinyl ether, and cyclohexane dimethanol vinyl ether, tetrafluoroethylene, and hexafluoropropene.

Preferred polyfunctional acrylates are 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate, dipropylene glycol diacrylate , Tripropylene glycol diacrylate, tetraethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylol ethylene oxide addition triacrylate, pentaerythritol triacrylate, trisacryloxyethyl phosphate, bisphenol A ethylene oxide addition diacrylate, bisphenol A Glycidyl diacrylate (trade name: Biscoat 700, manufactured by Osaka Organic Chemical Co., Ltd.), and Is triethylene glycol diacrylate.

A liquid crystalline compound may be used for the purpose of controlling the temperature range of the liquid crystal phase. Particularly preferred polymerizable liquid crystal compounds are shown.

これらの式において、Ｗは水素、フッ素、塩素、または−ＣＨ_３であり、ｙは１から２０の整数である。

In these formulas, W is hydrogen, fluorine, chlorine, or —CH ₃ , and y is an integer of 1 to 20.

In order to produce a polymer, it is preferable to select a polymerization method according to the application. For example, in order to produce an optically anisotropic film such as a retardation film or a polarizing element, polymerization is performed while maintaining a liquid crystal state, and therefore, a method of irradiating energy such as ultraviolet rays or electron beams is preferable. When the polymer exhibits liquid crystallinity, it can be used for similar applications even if the polymer is formed into a thin film. Such optically anisotropic polymers are disclosed in, for example, JP-A-7-294735, JP-A-2000-131684, JP-A-2001-55573, JP-A-2001-222009, JP-A-2002-69107, WO01 / 20392A1. It can be produced by the method described in pamphlets and the like.

The polymer obtained by thermal polymerization or photopolymerization can be used for various protective films, liquid crystal alignment films, viewing angle compensation films, and the like. Polarized ultraviolet light is polymerized by aligning the polymerizable molecules in the direction of polarization, so that it can be applied to alignment films that do not require rubbing. The oriented thin film can be formed by using a spin coat method, a Langmuir blow jet method, a printing method, or the like. The film thickness of the obtained thin film is preferably 1 to 100 nm from the viewpoint of liquid crystal alignment control.

  Examples of the photo radical polymerization initiator are specific trade names, such as 1173 and 4265 from Darocur series of Ciba Specialty, 184, 369, 500, 651, 784, 819, 907 from Irgacure series. 1300, 1700, 1800, 1850, 2959, etc., but any known one can be used.

  Other examples of photo radical polymerization initiators include 4-methoxyphenyl-2,4-bis (trichloromethyl) triazine, 2- (4-butoxystyryl) -5-trichloromethyl-1,3,4-oxadiazole 9-phenylacridine, 9,10-benzphenazine, benzophenone / Michler's ketone mixture, hexaarylbiimidazole / mercaptobenzimidazole mixture, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, Benzyldimethyl ketal, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2,4-diethylxanthone / methyl p-dimethylaminobenzoate, benzophenone / methyltriethanolamine A mixture, etc. It can also be used to shift.

Examples of the photocationic polymerization initiator are specific trade names, such as U.S.C. Syracueer UVI-6990 and 6974, Asahi Denka Co., Ltd. Adekaoptomer SP-150, 152, 170 and 172, Rhodia Photoinitiator 2074 from Co., Ltd., Irgacure 250 from Ciba Specialty Co., Ltd., DTS-102 from Midori Kagaku Co., Ltd., etc. can be used.

Preferred initiators for radical polymerization by heat are benzoyl peroxide, diisopropyl peroxydicarbonate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxypivalate, di-t-butyl peroxide, t -Butyl peroxydiisobutyrate, lauroyl peroxide, dimethyl 2,2'-azobisisobutyrate, azobisisobutyronitrile, azobiscyclohexanecarbonitrile and the like. The polymerization is generally carried out at a reaction temperature of 0 to 150 ° C. for 1 to 100 hours.

  The molded article of the present invention can be produced by applying the composition of the present invention on a substrate to form a coating film, and fixing the nematic alignment formed by the composition in a liquid crystal state by light irradiation. Examples of the substrate include triacetylcellulose, diacetylcellulose, polyvinyl alcohol, polyimide, polyester, polyarylate, polyetherimide, polyethylene terephthalate, polyethylene naphthalate, and polycarbonate. Specific product names include “Arton” from JSR Corporation, “Zeonex” and “Zeonor” from Nippon Zeon Corporation, “Appel” from Mitsui Chemicals, Inc. The substrate may be a uniaxially stretched film or a biaxially stretched film. The substrate may be subjected to surface treatment such as saponification treatment, corona treatment, or plasma treatment in advance.

The composition of the present invention can also be applied by dissolving in a solvent. Solvents include hexane, heptane, toluene, xylene, methoxybenzene, ethylene glycol dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone. , Cyclopentanone, cyclohexanone, methyl acetate, ethyl acetate, γ-butyrolactone, 2-pyrrolidone, N-methyl-2-pyrrolidone, dimethylformamide, chloroform, dichloromethane, dichloroethane, t-butyl alcohol, diacetone alcohol, butyl cellosolve Etc. can be used as a single solvent or a plurality of mixed solvents.
When manufacturing an alignment film, an antireflection film, a viewing angle compensation film, etc. by photopolymerization, a solution of the above composition is applied onto a substrate by spin coating, and after removing the solvent, light is irradiated. It may be polymerized.

A stabilizer may be added to the composition of the present invention to facilitate handling during use or to prevent polymerization during storage. Any known stabilizer can be used, for example, 4-ethoxyphenol, hydroquinone, 3,5-di-t-butyl-4-hydroxytoluene (BHT), and the like.

In order to mold the isolated polymer, it may be used after being dissolved in a solvent. Preferred solvents are N-methyl-2-pyrrolidone, dimethyl sulfoxide, N, N-dimethylacetamide, N, N-dimethylformamide, N, N-dimethylacetamide dimethyl acetal, tetrahydrofuran, chloroform, 1,4-dioxane, bis ( Methoxyethyl) ether, γ-butyrolactone, tetramethylurea, trifluoroacetic acid, ethyl trifluoroacetate, and hexafluoro-2-propanol, 1-methoxy-2-propanol acetate. However, the solvent is not limited thereto, and may be a mixture with a common organic solvent such as acetone, benzene, toluene, heptane, methylene chloride. Examples of a method for obtaining a uniform film thickness upon coating include a micro gravure coating method, a gravure coating method, a wire barcode method, a dip coating method, a spray coating method, and a meniscus coating method. The thickness of the optically anisotropic body is not uniform depending on the desired retardation value and the birefringence of the optically anisotropic body, but is preferably 0.05 to 50 μm, more preferably 0.1 to 20 μm, and still more preferably Is about 0.5 to 10 μm. The optically anisotropic body preferably has a haze value of 1.5% or less and a transmittance of 80% or more, more preferably a haze value of 1.0% or less and a transmittance of 85% or more. The transmittance preferably satisfies these conditions in the visible light region.

Since the polymer having the structural unit represented by the formula (2) has optical anisotropy, it can be used alone for a retardation film. By combining this polymer with other retardation films, it can be used for polarizing plates, circularly polarizing plates, elliptically polarizing plates, antireflection films, color compensation plates, viewing angle compensation plates, and the like.

Further, the compound (1) is a ferroelectric liquid crystal display element or antiferroelectric property stabilized by a polymer of the compound (1) by using it in a mixture with a ferroelectric liquid crystal and an antiferroelectric liquid crystal. A liquid crystal display element can be formed. The specific construction method of the display element itself is known in the literature (J. of Photopoly. Sci. Technol., 2000, 13 (2), 295-300, Jpn. J. Appl. Phys., 1997, 36). , 1517-1519).

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not restrict | limited at all by these Examples. The structure of the compound was confirmed by nuclear magnetic resonance (NMR) spectrum, mass (MS) spectrum, infrared absorption (IR) spectrum and the like. The unit of the phase transition temperature is ° C., C represents a crystal, N represents a nematic phase, and I represents an isotropic liquid phase. The parentheses indicate a monotropic liquid crystal phase. The phase transition temperature was observed using DSC and a polarizing microscope.

For the measurement of weight average molecular weight and number average molecular weight, Shimadzu LC-9A type gel permeation chromatograph (GPC) manufactured by Shimadzu Corporation, column Shodex GF-7M HQ manufactured by Showa Denko (developing solvent is DMF or THF, standard material is Polystyrene with a known molecular weight) was used. The pencil hardness was determined according to the method of JIS standard “JIS-K-5400 8.4 Pencil Scratch Test”.
In the following, liter, which is a unit of capacity, is represented by the symbol L.

Example 1
Production of 1,4-bis (4-((E) -8-acryloyloxy-6-octenyloxy) benzoyloxy) benzene Compound (1-1-53) was produced by the following route.

First stage Preparation of 6-chloro-1-hexanal (b) DMSO (dimethyl sulfoxide) in dichloromethane (100 mL) solution of oxalyl dichloride (11.2 g; 88.5 mmol) at −50 ° C. under nitrogen atmosphere A solution of (14.2 g; 181 mmol) in dichloromethane (20 mL) was added dropwise. Then, a solution of 6-chloro-1-hexanol (10.1 g; 74.1 mmol) in dichloromethane (50 mL) was added dropwise and stirred for 20 minutes. Triethylamine (60.5 g; 435 mmol) was added and allowed to warm to room temperature. Water was added to the reaction solution, and the mixture was extracted with dichloromethane. The organic layer was washed with saturated brine and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure to obtain crude 6-chloro-1-hexanal (b) (9.00 g).

Second Step Preparation of ethyl 8-chloro-2-octenylcarboxylate (c) To a solution of ethyl diethylphosphonoacetate (20.1 g; 89.6 mmol) in tetrahydrofuran (400 mL) was added potassium t-butoxide (11. 1 g; 98.7 mmol) was added at −40 ° C. under a nitrogen atmosphere and stirred for 30 minutes. To this was added a solution of 6-chloro-1-hexanal (b) (10.0 g; 74.3 mmol) in tetrahydrofuran (100 mL), followed by stirring at −40 ° C. for 30 minutes, and then raising to room temperature and stirring for 2 hours. did. The reaction solution was extracted with heptane, and the organic layer was washed with water and a saturated aqueous sodium chloride solution and then dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the resulting residue was purified by column chromatography (developing solvent: heptane / ethyl acetate = 9/1) to give ethyl 8-chloro-2-octenylcarboxylate (c) (7. 31 g) was obtained.

Third stage Preparation of 8-chloro-2-octenol (d) Toluene (300 mL) of ethyl 8-chloro-2-octenylcarboxylate (c) (7.31 g; 35.7 mmol) under nitrogen atmosphere To the solution, a n-hexane solution (82.4 mL; 76.6 mmol) of DIBAL-H (diisobutylaluminum hydride) was added dropwise at −70 ° C. and stirred for 3 hours. The reaction solution was extracted with toluene, the organic layer was washed with water and dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure to obtain 8-chloro-2-octenol (5.05 g).

4th stage Preparation of (8-chloro-2-octenyl) tetrahydropyran-2-yl ether (e) 8-chloro-2-octenol (d) (5.60 g; 34 g) in dichloromethane (500 mL) under nitrogen atmosphere. .4 mmol) and PPTS (pyridinium-p-toluenesulfonate) (0.97 g; 3.86 mmol) were dissolved and DHP (3,4-dihydro-2H-pyran) (6.70 g; A solution of 79.7 mmol) in dichloromethane (50 mL) was added dropwise, and the mixture was stirred at room temperature for 15 hours. The reaction solution was extracted with dichloromethane, and the organic layer was washed with water and dried over anhydrous magnesium sulfate. The solvent was distilled under reduced pressure to obtain (8-chloro-2-octenyl) tetrahydropyran-2-yl ether (e) (7.61 g).

5th stage Preparation of ethyl 4- (8- (tetrahydropyran-2-yloxy) -6-octenyloxy) benzoate (f) Under nitrogen atmosphere, ethyl 4-hydroxybenzoate (3.65 g; 22.0 mmol) ) In DMF (N, N-dimethylformamide) (300 mL) was added potassium carbonate (4.50 g; 32.6 mmol), and the mixture was stirred at room temperature for 30 minutes. Next, (8-chloro-2-octenyl) tetrahydropyranyl ether (e) (4.00 g; 16.2 mmol) was added, and the mixture was heated and stirred at 100 ° C. for 8 hours. Water was added to the reaction solution, and the mixture was extracted with toluene. The organic layer was washed with saturated sodium bicarbonate and water, and then dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by column chromatography (developing solvent: toluene / ethyl acetate = 9/1) to give 4- (8- (tetrahydropyran-2-yloxy) -6-octenyloxy). Ethyl benzoate (f) (5.62 g) was obtained.

6th stage Preparation of 4- (8- (tetrahydropyran-2-yloxy) -6-octenyloxy) benzoic acid (g) 4- (8- (tetrahydropyran-2) was added to ethanol (500 mL) under nitrogen atmosphere. -Yloxy) -6-octenyloxy) ethyl benzoate (f) (5.52 g; 14.7 mmol) and sodium hydroxide (0.88 g; 22.0 mmol) were dissolved in a minimum amount of water. The aqueous solution was added and heated to reflux for 3 hours. After returning to room temperature, water was added to the reaction solution and acidified with dilute hydrochloric acid (pH 5). The mixture was extracted with ethyl acetate, washed with a saturated aqueous sodium chloride solution, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure to obtain 4- (8- (tetrahydropyran-2-yloxy) -6-octenyloxy) benzoic acid (g) (4.44 g).

7th stage Preparation of 4- (8-hydroxy-6-octenyloxy) benzoic acid (h) 4- (8- (tetrahydropyran-2-yloxy) -6-octyl alcohol in ethanol (400 mL) under nitrogen atmosphere Tenenyloxy) benzoic acid (g) (4.44 g; 12.7 mmol) and PPTS (pyridinium-p-toluenesulfonate) (0.63 g; 2.51 mmol) were added and stirred at 50 ° C. for 19 hours. . The reaction solution was extracted with ethyl acetate, and the organic layer was washed with water and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was recrystallized from ethanol to obtain 4- (8-hydroxy-6-octenyloxy) benzoic acid (h) (2.00 g).

Step 8 Production of 4- (8-acryloyloxy-6-octenyloxy) benzoic acid (i) 4- (8-hydroxy-6-octenyloxy) benzoic acid (h) (1.53) under nitrogen atmosphere g; 5.79 mmol) in tetrahydrofuran (40 mL), vinyl acrylate (1.70 g; 17.4 mmol), lipase PS (registered trademark) (1.52 g), hydroquinone (0.008 g; 0.072 mmol) was added, and the mixture was stirred at 50 ° C. for 16 hours. The lipase was filtered off and the solvent was distilled off under reduced pressure. The obtained residue was recrystallized from ethanol to obtain 4- (8-acryloyloxy-6-octenyloxy) benzoic acid (i) (1.46 g).

Step 9 Preparation of Compound (1-13-53) 4- (8-acryloyloxy-6-octenyloxy) benzoic acid (i) (0.20 g; 0.20 g) in dichloromethane (10 mL) under nitrogen atmosphere. 628 mmol), hydroquinone (39.4 mg; 358 mmol), dicyclohexylcarbodiimide (0.17 g; 0.82 mmol), 4-dimethylaminopyridine (99.1 mg; 0.81 mmol) at room temperature. Stir for 15 hours. The insoluble material was filtered off, and the filtrate was washed successively with dilute hydrochloric acid, saturated brine, saturated aqueous sodium hydrogen carbonate solution and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by preparative thin layer chromatography (developing solvent: toluene / ethyl acetate = 8/2). As a result, 1,4-bis (4-((E) -8-acryloyl) was obtained. Oxy-6-octenyloxy) benzoyloxy) benzene (1-13-53) (0.06 g) was obtained. Phase transition temperature: C 78.5 N 138.7 I.

Example 2
Production of 4- (4-acryloyloxy-1-butynyl) benzoyloxy-4′-ethoxybiphenyl (1-1-13-11) Compound (1-13-111) was produced by the following route.

1st stage Preparation of methyl 4- (4-hydroxy-1-butynyl) benzoate (b) Under nitrogen atmosphere, methyl 4-bromobenzoate (9.37 g; 43.6 mmol), acetylpalladium (489 mg; 2.18 mmol), triphenylphosphine (1.14 g; 4.36 mmol) in diethylamine (150 mL) with copper iodide (431 mg; 4.36 mmol) and 3-butyn-1-ol ( 3.06 g; 43.6 mmol) was added and stirred for 14 hours. The solvent was distilled off from the reaction solution under reduced pressure, and the residue was washed with benzene and purified by column chromatography (toluene / ethyl acetate = 5/2). Recrystallization from heptane / benzene = 5/6 gave methyl 4- (4-hydroxy-1-butynyl) benzoate (b) (6.5 g).

Second stage Preparation of 4- (4-hydroxy-1-butynyl) benzoic acid (c) Methyl 4- (4-hydroxy-1-butynyl) benzoate (4.50 g) in methanol (50 mL) under nitrogen atmosphere. 22.0 mmol) and sodium hydroxide (1.05 g; 26.4 mmol) aqueous solution (10 mL) were added, and the mixture was heated to reflux for 1.5 hours. The reaction solution was extracted with diethyl ether, washed with saturated brine, and the solvent was evaporated under reduced pressure. The residue was washed with pentane and dried in vacuo to give 4- (4-hydroxy-1-butynyl) benzoic acid (c) (3.78 g).

Third stage Preparation of 4- (4-acryloyloxy-1-butynyl) benzoic acid (d) 4- (4-hydroxy-1-butynyl) benzoic acid (3.50 g; 18.4 mmol) under nitrogen atmosphere , P-toluenesulfonic acid (0.95 g; 5.52 mmol), acrylic acid (6.74 g; 93.6 mmol) and hydroquinone (0.21 g; 1.95 mmol) were added to toluene to generate The mixture was heated to reflux for 6 hours while removing water with a Dean-Stark tube. The reaction solution was washed with water and dried over anhydrous magnesium sulfate, and then the solvent was distilled off under reduced pressure. The residue was purified by column chromatography (developing solvent: heptane / ethyl acetate = 9/1) and recrystallized from ethanol to give 4- (4-acryloyloxy-1-butynyl) benzoic acid (d) (2.15 g ) Melting point: 151 ° C.

Fourth Stage Preparation of 4- (4-acryloyloxy-1-butynyl) benzoyloxy-4′-ethoxybiphenyl (d) 4- (4-acryloyloxy-1-butynyl) benzoic acid (d) in dichloromethane under a nitrogen atmosphere ) (200 mg; 0.82 mmol), 4-ethoxy-4′-hydroxybiphenyl (176 mg; 0.82 mmol), dicyclohexylcarbodiimide (203 mg; 0.98 mmol), 4-dimethylaminopyridine (120 mg) 0.98 mmol) and stirred at room temperature for 15 hours. The insoluble material was filtered off, and the filtrate was washed with hydrochloric acid (0.5 M), saturated brine, saturated aqueous sodium hydrogen carbonate solution and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by column chromatography (developing solvent: heptane / ethyl acetate = 9/1). As a result, 4- (4-acryloyloxy-1-butynyl) benzoyloxy-4′-ethoxy was obtained. Obtained as biphenyl (1-13-111) (364 mg).

Example 3
Production of 4- (10-vinyloxy-8-decanyloxy) benzoyloxy-4′-ethoxybiphenyl (1-13-1-10) was produced by the following route.

Stage 1 Preparation of 4- (10- (Tetrahydropyran-2-yloxy) -8-decanyloxy) benzoyloxy-4′-ethoxybiphenyl (b) 4- (10- (tetrahydropyran-2) in dichloromethane under nitrogen atmosphere -Yloxy) -6-decanyloxy) benzoic acid (a) (8.25 g; 21.9 mmol), 4-ethoxy-4'-hydroxybiphenyl (4.72 g; 22.0 mmol), dicyclohexylcarbodiimide (5 .43 g; 26.3 mmol) and 4-dimethylaminopyridine (3.24 g; 26.5 mmol) were added, and the mixture was stirred at room temperature for 15 hours. The insoluble material was filtered off, and the filtrate was washed with hydrochloric acid (0.5 M), saturated brine, saturated aqueous sodium hydrogen carbonate solution and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by column chromatography (developing solvent: heptane / ethyl acetate = 9/1). As a result, 4- (10- (tetrahydropyran-2-yloxy) -8-decanyloxy) benzoyl was obtained. Oxy-4′-ethoxybiphenyl (b) (10.0 g) was obtained. Compound (a) was synthesized according to Example 6, sixth stage.

Second stage Preparation of 4- (10-hydroxy-8-decanyloxy) benzoyloxy-4′-ethoxybiphenyl (c) 4- (10- (tetrahydropyran-2-yloxy) in ethanol (400 mL) under nitrogen atmosphere -8-decanyloxy) benzoyloxy-4'-ethoxybiphenyl (b) (6.55 g; 11.4 mmol) and PPTS (pyridinium-p-toluenesulfonate) (0.29 g; 1.15 mmol) were added. , And stirred at 50 ° C. for 19 hours. The reaction solution was extracted with ethyl acetate, and the organic layer was washed with water and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was recrystallized from ethanol to obtain 4- (10-hydroxy-8-decanyloxy) benzoyloxy-4′-ethoxybiphenyl (c) (2.81 g).

Stage 3 (1-13-1-10) Preparation Under nitrogen atmosphere, chloroform (10 mL) and 4- (10-hydroxy-8-decanyloxy) benzoyloxy-4′-ethoxybiphenyl (c) (2.81 g; 5.75 mmol), n-butyl vinyl ether (39.4 mg; 358 mmol), diacetoxy [9-10 phenanthroline] palladium (II) (0.17 g; 0.82 mmol) were added, and the mixture was stirred at 60 ° C. for 15 hours. Stir. Insolubles were filtered off, and the filtrate was extracted with chloroform, washed with water, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by column chromatography (developing solvent: heptane / ethyl acetate = 9/1) to give 4- (10-vinyloxy-8-decanyloxy) benzoyloxy-4′-ethoxybiphenyl. (1-13-10) (1.55 g) was obtained.

The following compounds are prepared according to the methods of Examples 1-3.

Example 4
The photopolymerization initiator Irgacure 9073 parts by weight was added to 100 parts by weight of the compound (1-13-53). The polymerizable compound containing the photopolymerization initiator was dissolved in 412 parts by weight of cyclopentanone to prepare a 20% strength by weight solution. This solution was applied to a glass substrate with a polyimide alignment film that had been subjected to a rubbing alignment treatment using a bar coder that gave a wet film thickness of about 12 μm. This was placed on a hot plate heated to 80 ° C. for 120 seconds to perform solvent drying and liquid crystal alignment. Further, in a state heated to 80 ° C. with a hot plate, using a 250 W / cm ultra-high pressure mercury lamp, the light of 30 mW / cm ² (center wavelength 365 nm) was irradiated for 20 seconds in a nitrogen atmosphere. And polymerized. When the optical thin film thus obtained was observed with a polarizing microscope, it was confirmed that uniform liquid crystal alignment without alignment defects was obtained. When the retardation was determined using a Berek compensator, a value of 50 nm was obtained. Further, this optical thin film was sandwiched between a crossed Nicol polarizer so that the angle formed by the rubbing direction and the absorption axis of the polarizer was 45 °, and the state of light transmission was observed on the backlight. Observation of light transmission while tilting in the rubbing direction confirmed that the change was asymmetrical from side to side with respect to the front. This suggests that the orientation vector of the liquid crystal skeleton in this optical thin film is inclined with respect to the glass substrate.

Example 5
To the polymerizable composition comprising 20 parts by weight of the compound (1-2-1), 30 parts by weight of the compound (1-1-353) and 50 parts by weight of the compound (OP-15), the above-mentioned photopolymerization initiator Irgacure 9073 was prepared. Part by weight was added. The polymerizable composition containing the photopolymerization initiator was dissolved in 412 parts by weight of cyclopentanone to prepare a 20% strength by weight solution. This solution was applied to a glass substrate with a polyimide alignment film that had been subjected to a rubbing alignment treatment using a bar coater with a wet film thickness of about 12 μm. This was placed on a hot plate heated to 70 ° C. for 120 seconds to perform solvent drying and liquid crystal alignment. Further, in a state heated to 70 ° C. with a hot plate, using a 250 W / cm ultra-high pressure mercury lamp, the light of 30 mW / cm ² (center wavelength 365 nm) was irradiated for 20 seconds in a nitrogen atmosphere. And polymerized. As a result, an optical thin film exhibiting red selective reflection was obtained.

Example 6
80 parts by weight of the compound (1-13-53) produced in Example 1, 5 parts by weight of 4- (trans-4-propylcyclohexyl) cyanobenzene, 5 parts by weight of 4- (trans-4-pentylcyclohexyl) cyanobenzene, A composition comprising 5 parts by weight of 4- (trans-4-heptylcyclohexyl) cyanobenzene and 5 parts by weight of 4 ′-(trans-4-heptylcyclohexyl) cyanobiphenyl was added to a photopolymerization initiator Irgacure 907 (trade name: 3 parts by weight of Specialty Chemicals) was added. The composition containing this photopolymerization initiator was dissolved in 412 parts by weight of cyclopentanone to prepare a 20% strength by weight solution. This solution was applied to a glass substrate with a polyimide alignment film that had been subjected to a rubbing alignment treatment using a bar coder that gave a wet film thickness of 12 μm. This was placed on a hot plate heated to 80 ° C. for 120 seconds to perform solvent drying and liquid crystal alignment. Further, in a state heated to 70 ° C. with a hot plate, using a 250 W / cm ultra-high pressure mercury lamp, the light of 30 mW / cm ² (center wavelength 365 nm) was irradiated for 20 seconds in a nitrogen atmosphere. And polymerized. When the optical thin film thus obtained was observed with a polarizing microscope, it was confirmed that uniform liquid crystal alignment without alignment defects was obtained. When the retardation was determined using a Berek compensator, a value of 55 nm was obtained. Further, this optical thin film was sandwiched between a crossed Nicol polarizer so that the angle formed by the rubbing direction and the absorption axis of the polarizer was 45 °, and the state of light transmission was observed on the backlight. Observation of light transmission while tilting in the rubbing direction confirmed that the change was asymmetrical from side to side with respect to the front. This suggests that the orientation vector of the liquid crystal skeleton in this optical thin film is inclined with respect to the glass substrate.

Example 7
The compound (1-13-53) (10 mg) prepared in Example 1, azobiscyclohexanecarbonitrile (0.1 mg), and benzene (100 μL) were placed in a glass ampule. This was cooled to −60 ° C., sufficiently deaerated with a vacuum pump, and sealed. The ampoule was heated at 110 ° C. for 24 hours. The obtained reaction mixture was reprecipitated three times from methanol (15 mL) to obtain a polymer (8.6 mg). The weight average molecular weight (M _w ) measured by GPC was 35,000. The polydispersity (Mw / Mn) was 2.16. The polymer (1.152 mg) was immersed in pure water (1 mL) and allowed to stand at 50 ° C. for 10 days. The polymer was taken out and dried well, and its weight was measured and found to be 1.155 mg. It turns out that the water absorption rate of this polymer is low.

Example 8
5 parts by weight of the polymer produced in Example 7 was dissolved in 100 parts by weight of NMP (N-methylpyrrolidone). This solution was applied to each of two glass substrates that had been thoroughly cleaned using a spin coater. These glass substrates were heated at 200 ° C. for 3 hours to remove the solvent, thereby forming a polymer thin film on the glass substrate. The surface of the polymer thin film formed on these glass substrates was rubbed in one direction with a roller equipped with a rubbing cloth and rubbed. The two glass substrates were bonded so that the polymer thin film faced each other and the rubbing directions were the same with a spacer having a thickness of 10 μm interposed therebetween to form a cell. A liquid crystal composition ZLI-1132 manufactured by Merck was injected into this cell at room temperature. The liquid crystal composition in the liquid crystal cell showed uniform homogeneous alignment.

Claims (37)

The compound represented by Formula (1).

In the formula, R ¹ is alkyl having 1 to 20 carbons, hydrogen, halogen, —CN, —N═C═O, —N═C═S, or —Z ⁴ —P ¹ . —CH ₂ — may be replaced by —O—, —S—, —CO—, —COO—, —OCO—, —CH═CH—, —CF═CF—, or —C≡C—, And any hydrogen may be replaced by halogen, —CF ₃ or —CN;
A ¹ , A ² , A ³ , and A ⁴ are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydronaphthalene-2 , 6-diyl, fluorene-2,7-diyl, bicyclo [2.2.2] octane-1,4-diyl, bicyclo [3.1.0] hexane-3,6-diyl, bicyclo [4.4 .0] decane or Q, in which any —CH ₂ — may be replaced by —O—, any —CH═ may be replaced by —N═, and any hydrogen May be replaced by halogen, alkyl having 1 to 5 carbons, fluoroalkyl having 1 to 5 carbons, alkoxy having 1 to 5 carbons, or alkenyl having 2 to 5 carbons, and Q is 2 shown below Any of the groups of valence It is in,

In these divalent groups, Me is methyl, Y ¹ , Y ² , Y ³ and Y ⁴ are alkyl having 1 to 10 carbon atoms, alkoxy having 1 to 10 carbon atoms, and fluoroalkyl having 1 to 10 carbon atoms. Hydrogen or fluorine;
Z ¹ , Z ² and Z ³ are each independently a single bond or alkylene having 1 to 20 carbon atoms, and in this alkylene, any —CH ₂ — is —O—, —S—, —COO—, —OCO—. , -CH = CH-, or -C≡C-, and in this alkylene or substituted alkylene, any hydrogen may be replaced by a halogen;
Z ⁴ is alkylene having 1 to 20 carbon atoms, and in this alkylene, any one —CH ₂ — is always replaced by either —CH═CH— or —C≡C—, and any other arbitrary —CH ₂ — may be replaced by —O—, —S—, —COO—, —OCO—, —CH═CH—, or —C≡C—;
P ¹ is any of the groups having the polymerization ability represented by (P ¹ -1) to (P ¹ -6);

X is hydrogen, halogen, —CF ₃ , or alkyl having 1 to 5 carbons; m, n and q are independently 0, 1 or 2. When m, n and q are 2, the same two symbols may be independently different structures or the same. In formula (1), R ¹ is alkyl having 1 to 10 carbons, alkoxy having 1 to 10 carbons, alkenyl having 2 to 10 carbons, hydrogen, fluorine, chlorine, —CN, —CF ₃ , —OCF ₃ , — be OCHF ₂ or ^-Z 4 -P ^{1,; P 1} is ^(P 1 ^-1), be a ^(P 1 -5) or ^{(P 1 -6); A 1} , A 2, A 3 and A ⁴ Are independently 1,4-cyclohexylene, 1,4-phenylene, 1,4-cyclohexylene in which at least one hydrogen is replaced by halogen, and 1,4-phenylene in which at least one hydrogen is replaced by halogen , Naphthalene-2,6-diyl, or fluorene-2,7-diyl; Z ¹ , Z ² and Z ³ are each independently a single bond, — (CH ₂ ) _a —, —O (CH ₂ ) _{a -, - (CH 2) a} O -, - O (CH 2 _{) A O -, - CH =} CH -, - C≡C -, - COO -, - OCO -, - CH = CH-COO -, - OCO-CH = CH -, - (CH 2) a -COO- , —OCO— (CH ₂ ) _a —, —OCF ₂ —, or —CF ₂ O—, where a is an integer from 1 to 10; Z ⁴ is a linear alkylene having 1 to 10 carbons In this alkylene, any one of —CH ₂ — is always replaced by either —CH═CH— or —C≡C—, and any other —CH ₂ — is —O— or —COO. The compound of claim 1, which may be replaced by —, —OCO—, —CH═CH—, or —C≡C—. In formula (1), R ¹ is alkyl having 1 to 10 carbons, alkoxy having 1 to 10 carbons, alkenyl having 2 to 10 carbons, hydrogen, fluorine, chlorine, —CN, —CF ₃ , —OCF ₃ , — OCHF ₂ , or —Z ⁴ —P ¹ ; P ¹ is (P ¹ −1), and in (P ¹ −1), X is hydrogen, fluorine, —CF ₃ , —CH ₃ or —C ₂ H ₅ ^{there; a 1, a 2, a} 3 and a ⁴ are independently 1,4-cyclohexylene, 1,4-phenylene, at least one hydrogen is replaced by fluorine or chlorine 1,4-phenylene Or fluorene-2,7-diyl. However, two or more of these rings are not fluorene-2,7-diyl; Z ¹ , Z ² and Z ³ are independently a single bond, — (CH ₂ ) _a —, —O (CH _{2 ) a -, - (CH 2} ) a O -, - O (CH 2) a O -, - COO -, - OCO -, - CH = CH-COO -, - OCO-CH = CH -, - OCF 2 -, or _-CF 2 is O-, where a is the integer of 1 to 4; ^{Z 4} is _{- (CH 2) b -,} - O (CH 2) b -, - CO 2 - (CH 2 _{) b -, - OCO- (CH} 2) b -, - (CH 2) c -O- (CH 2) d -, or _{-O- (CH 2) c -O- (} CH 2) d - a is Where b is an integer from 1 to 9 and c and d are integers from 2 to 5, in which any one —CH ₂ — is necessarily —C 2. A compound according to claim 1 replaced by any of H = CH- and -C≡C-. In formula (1), R ¹ is alkyl having 1 to 10 carbons, alkoxy having 1 to 10 carbons, alkenyl having 2 to 10 carbons, hydrogen, fluorine, chlorine, —CN, —CF ₃ , —OCF ₃ , — OCHF ₂ , or —Z ⁴ —P ¹ ; P ¹ is (P ¹ -5) or (P ¹ -6), and in (P ¹ -6), X is hydrogen, fluorine, —CF ₃ , — CH ₃ or —C ₂ H ₅ ; A ¹ , A ² , A ³ and A ⁴ are independently 1,4-cyclohexylene, 1,4-phenylene, at least one hydrogen is replaced by fluorine or chlorine 1,4-phenylene or fluorene-2,7-diyl. However, two or more of these rings are not fluorene-2,7-diyl; Z ¹ , Z ² and Z ³ are independently a single bond, — (CH ₂ ) _a —, —O (CH _{2 ) a -, - (CH 2} ) a O -, - O (CH 2) a O -, - COO -, - OCO -, - CH = CH-COO -, - OCO-CH = CH -, - OCF 2 -, or _-CF 2 is O-, where a is the integer of 1 to 4; ^{Z 4} is _{-O (CH 2) b -,} - CO 2 - (CH 2) b -, - OCO- ( CH ₂ ) _b —, or — (CH ₂ ) _c —O— (CH ₂ ) _d —, where b is an integer from 1 to 9, and c and d are integers from 2 to 5, -CH ₂ in the group any one of - is always replaced by any one of -CH = CH- and -C≡C-, claim The compound according to. In formula (1), R ¹ is alkyl having 1 to 10 carbons, alkoxy having 1 to 10 carbons, alkenyl having 2 to 10 carbons, hydrogen, fluorine, chlorine, —CN, —CF ₃ , —OCF ₃ , — OCHF ₂ or be a ^-Z 4 -P ^{1,; P 1} from ^(P 1 -2) be a ^{(P 1 -4); A 1} , A 2, A 3 and A ⁴ are independently 1, 4-cyclohexylene, 1,4-phenylene, 1,4-cyclohexylene in which at least one hydrogen is replaced by halogen, 1,4-phenylene in which at least one hydrogen is replaced by halogen, naphthalene-2,6- Diyl or fluorene-2,7-diyl; Z ¹ , Z ² and Z ³ are each independently a single bond, — (CH ₂ ) _a —, —O (CH ₂ ) _a —, — (CH ₂ ) _{a O -, - O (CH} 2) a O -, - C = CH -, - C≡C -, - COO -, - OCO -, - CH = CH-COO -, - OCO-CH = CH -, - (CH 2) a -COO -, - OCO- (CH 2 _{) a -, - OCF 2 -} , or _-CF 2 is a O-, wherein a is an integer from 1 to 10; ^{Z 4} is a straight-chain alkylene of 1 to 10 carbon atoms, any in the alkylene One —CH ₂ — is always replaced by either —CH═CH— or —C≡C—, and any other —CH ₂ — is —O—, —COO—, —OCO—, — The compound of claim 1, which may be replaced by CH═CH—, or —C≡C—. In formula (1), R ¹ is alkyl having 1 to 10 carbons, alkoxy having 1 to 10 carbons, alkenyl having 2 to 10 carbons, hydrogen, fluorine, chlorine, —CN, —CF ₃ , —OCF ₃ , — OCHF ₂ or be a ^-Z 4 -P ^{1,; P 1} from ^(P 1 -2) be a ^{(P 1 -4); A 1} , A 2, A 3 and A ⁴ are independently 1, 4-cyclohexylene, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced by fluorine or chlorine, or fluorene-2,7-diyl. However, two or more of these rings are not fluorene-2,7-diyl; Z ¹ , Z ² and Z ³ are independently a single bond, — (CH ₂ ) _a —, —O (CH _{2 ) a -, - (CH 2} ) a O -, - O (CH 2) a O -, - COO -, - OCO -, - CH = CH-COO -, - OCO-CH = CH -, - OCF 2 -, or _-CF 2 is O-, where a is the integer of 1 to 4; ^{Z 4} is _{- (CH 2) b -,} - O (CH 2) b -, - CO 2 - (CH 2 _{) b -, - OCO- (CH} 2) b -, or _{- (CH 2) c -O- (} CH 2) d - a, where b is an integer from 1 to 9, c and d are 2 from an integer of 5, any one in these groups -CH ₂ - may replace at always -CH = CH- and -C≡C- either It is A compound according to claim 1. The compound represented by the formula (1) according to claim 1 is any one compound represented by the following formulas (1a) to (1f).

In these formulas, R ¹ ′ is alkyl having 1 to 10 carbons, alkoxy having 1 to 10 carbons, alkenyl having 2 to 10 carbons, hydrogen, fluorine, chlorine, —CN, —CF ₃ , —OCF ₃ , -OCHF _2, or by ^-Z 4 -P ^{1; P 1} has the same meaning as those in formula (1). However ^(P 1 -1) and X in ^(P 1 -6) is hydrogen, _fluorine, -CF 3, are -CH ₃ or _{^{-C 2 H 5; A 11,}} A 21, A 31 and ^{A 41} are independently 1,4-cyclohexylene, 1,4-phenylene, 1,4-cyclohexylene in which at least one hydrogen is replaced by fluorine, 1,4-phenylene in which at least one hydrogen is replaced by fluorine, Naphthalene-2,6-diyl or fluorene-2,7-diyl. Provided that two or more of these rings are not naphthalene-2,6-diyl or fluorene-2,7-diyl; Z ¹⁰ , Z ²⁰ and Z ³⁰ are independently a single bond, — (CH ₂ ) ₂ −, — (CH ₂ ) ₃ —, — (CH ₂ ) ₄ —, —OCH ₂ —, —O (CH ₂ ) ₂ —, —O (CH ₂ ) ₃ —, —O (CH ₂ ) ₄ — , —CH ₂ O—, — (CH ₂ ) ₂ O—, — (CH ₂ ) ₃ O—, — (CH ₂ ) ₄ O—, —O (CH ₂ ) ₂ O—, —O (CH ₂ ) ₃ O—, —O (CH ₂ ) ₄ O—, —O (CH ₂ ) ₅ O—, —O (CH ₂ ) ₆ O—, —CH═CH—, —CF═CF—, —COO—, -OCO -, - CH = CH- COO -, - OCO-CH = CH -, - (CH 2) a -COO -, - OCO- (CH 2) a -, - OCF - or _-CF 2 is a O-; m, n and q are independently 0, 1 or 2, their sum is a 1 to 5; r is an integer from 1 to 6, s and t Is independently 2 or 3; the (CH ₂ ) _r group, (CH ₂ ) _s group or (CH ₂ ) _t group sandwiched between A ⁴¹ and P ¹ is any one of —CH _2- is always replaced by either -CH = CH- or -C≡C-. The compound according to claim 7, which is represented by any one of formulas (1b), (1c), (1d) and (1e). The compound according to claim 7 or 8, wherein in the formulas (1b), (1c), (1d), and (1e) according to claim 7, m = 1 and n = q = 0. In formulas (1b), (1c), (1d), and (1e) according to claim 7, m = 1, n = q = 0; R ¹ ′ is alkyl having 1 to 10 carbons, carbons 1 to 10 alkoxy, C ₂ to C 10 alkenyl, hydrogen, fluorine, chlorine, —CN, —CF ₃ , —OCF ₃ , or —OCHF ₂ ; P ¹ is (P ¹ −1), (P ¹ -5) or ^(P be a 1 ^{-6); a 11} and ^{a 41} are each independently 1,4-cyclohexylene, 1,4-phenylene, 1, at least one hydrogen is replaced by fluorine or chlorine , 4-phenylene; Z ¹⁰ or Z ¹¹ is a single bond, — (CH ₂ ) _a —, —O (CH ₂ ) _a —, — (CH ₂ ) _a O—, —O (CH ₂ ) _a O -, -COO-, -OCO-, -CH = CH-COO-, -OCO-C _{H = CH -, - OCF 2} -, or _-CF 2 is a O-, wherein a is an integer of 1 to 4, the compounds according to claim 7. The compound according to claim 7 or 8, wherein in the formulas (1b), (1c), (1d), and (1e) according to claim 7, m = 1, n = 1, and q = 0. In formulas (1b), (1c), (1d) and (1e) according to claim 7, m = 1, n = 1, q = 0; R ¹ ′ is alkyl having 1 to 10 carbons; alkoxy of 1 to 10 carbon atoms, alkenyl having 2 to 10 carbon atoms, hydrogen, fluorine, _{chlorine, -CN, -CF 3, -OCF 3} , -OCHF 2, -O- (CH 2) r -P 1, - ^{_{CO 2 - (CH 2) r}} -P 1, -OCO- (CH 2) r -P 1, - (CH 2) s -O- (CH 2) t -P 1 or, - _{(CH 2) s} - O- _{(CH 2)} be t -P ^{1; P 1} is ^(P 1 ^-1), with there ^(P 1 -5) or ^(P 1 ^{-6); A 11} and ^{A 41} is independently 1 , 4-cyclohexylene, 1,4-phenylene, 1, in which at least one hydrogen is replaced by fluorine or chlorine It is a ^{4-phenylene; A 21} is in ^{2,7-diyl; Z 10} and ^{Z 20} are independently a single _{bond, - (CH 2) a -} , - O (CH 2) a -, - ( _{CH 2) a O -, -} O (CH 2) a O -, - COO -, - OCO -, - CH = CH-COO -, - OCO-CH = CH -, - OCF 2 -, or -CF ₂ 8. A compound according to claim 7, which is O-, wherein a is an integer from 1 to 4. In formulas (1b), (1c), (1d) and (1e) according to claim 7, m = 1, n = 1, q = 0; R ¹ ′ is alkyl having 1 to 10 carbons; alkoxy of 1 to 10 carbon atoms, alkenyl having 2 to 10 carbon atoms, hydrogen, fluorine, _{chlorine, -CN, -CF 3, -OCF 3} , -OCHF 2, -O- (CH 2) r -P 1, - ^{_{CO 2 - (CH 2) r}} -P 1, -OCO- (CH 2) r -P 1, - (CH 2) s -O- (CH 2) t -P 1 or, - _{(CH 2) s} - be a ^{_{O- (CH 2) t -P 1}} ; P 1 is ^(P 1 ^-1), be a ^(P 1 -5) or ^{(P 1 -6); A 11} , A 21 and ^{A 41} are independently 1,4-cyclohexylene, 1,4-phenylene, at least one hydrogen is replaced by fluorine or chlorine Be a ^{1,4-phenylene; Z 10,} Z ²⁰ and ^{Z 30} are independently a single _{bond, - (CH 2) a -} , - O (CH 2) a -, - (CH 2) a O- , —O (CH ₂ ) _a O—, —COO—, —OCO—, —CH═CH—COO—, —OCO—CH═CH—, —OCF ₂ —, or —CF ₂ O—, The compound according to claim 7, wherein a is an integer of 1 to 4. The compound according to claim 7 or 8, wherein in formulas (1b), (1c), (1d), and (1e) according to claim 7, m = 1, n = 1, and q = 1. The compound according to claim 7 or 8, wherein in the formulas (1b), (1c), (1d), and (1e) according to claim 7, m = 2, n = 1, and q = 1. The compound represented by Formula (1) of Claim 1 is any one compound represented by Formula (1g) to (1k).

In these formulas, R ¹ ′ is alkyl having 1 to 10 carbons, alkoxy having 1 to 10 carbons, alkenyl having 2 to 10 carbons, hydrogen, fluorine, chlorine, —CN, —CF ₃ , —OCF ₃ , -OCHF _2, or by ^-Z 4 -P ^{1; P 1} has the same meaning as those in formula (1). However ^(P 1 -1) and X in ^(P 1 -6) is hydrogen, _fluorine, -CF 3, are -CH ₃ or _{^{-C 2 H 5; A 11,}} A 21, A 31 and ^{A 41} are independently 1,4-cyclohexylene, 1,4-phenylene, 1,4-cyclohexylene in which at least one hydrogen is replaced by fluorine, 1,4-phenylene in which at least one hydrogen is replaced by fluorine , Naphthalene-2,6-diyl, or fluorene-2,7-diyl. Provided that two or more of these rings are not naphthalene-2,6-diyl or fluorene-2,7-diyl; m, n and q are independently 0, 1 or 2; the total is a 1 to ^{5; Z 40} is the formula ^(Z 4 -1), wherein ^(Z 4 -2), wherein ^(Z 4 -3), wherein ^(Z 4 -4), formula ^(Z 4 -5) Or in formulas (Z ⁴ -6), in which r is an integer from 1 to 6, s and t are independently 2 or 3, and any one of-( CH ₂ ) — must be replaced by either —CH═CH— and —C≡C—; Z ¹¹ , Z ²¹ and Z ³¹ are independently a single bond, — (CH ₂ ) ₂ —, — ( _{CH 2) 3 -, - (} CH 2) 4 -, - OCH 2 -, - O (CH 2) 2 -, - O (CH ₂ ) ₃₋ , —O (CH ₂ ) ₄ —, —CH ₂ O—, — (CH ₂ ) ₂ O—, — (CH ₂ ) ₃ O—, — (CH ₂ ) ₄ O—, —O ( _{CH 2) 2 O -, -} O (CH 2) 3 O -, - O (CH 2) 4 O -, - O (CH 2) 5 O -, - O (CH 2) 6 O -, - COO- , —OCO—, —CH═CH—CF═CF—, —CH═CH—COO—, —OCO—CH═CH—, — (CH ₂ ) _a —COO—, or —OCO— (CH ₂ ) _a -, a ^is; are independently a single _bond, Z ^{12, Z 22} and ^{Z 32} is _{- (CH 2) 2 -,} - (CH 2) 3 -, - (CH 2) 4 -, - OCH 2 - _{, -O (CH 2) 2 -} , - O (CH 2) 3 -, - O (CH 2) 4 -, - CH 2 O -, - (CH 2) 2 O -, - (CH 2) 3 O − _{- (CH 2) 4 O -} , - O (CH 2) 2 O -, - O (CH 2) 3 O -, - O (CH 2) 4 O -, - O (CH 2) 5 O -, - O (CH ₂ ) ₆ O—, —CH═CH—, —COO—, —OCO—, —CH═CH—COO—, —OCO—CH═CH—, — (CH ₂ ) _a —COO—, — OCO— (CH ₂ ) _a —, —OCF ₂ — or —CF ₂ O—; Z ¹³ , Z ²³ and Z ³³ are independently a single bond, — (CH ₂ ) ₂ —, — (CH ₂ ) ₃ −, — (CH ₂ ) ₄ —, —OCH ₂ —, —O (CH ₂ ) ₂ —, —O (CH ₂ ) ₃ —, —O (CH ₂ ) ₄ —, —CH ₂ O—, _{- (CH 2) 2 O -} , - (CH 2) 3 O -, - (CH 2) 4 O -, - O (CH 2) 2 O -, - O (CH 2) 3 O -, - O ( CH ₂ ) ₄ O—, —O (CH ₂ ) ₅ O—, —O (CH ₂ ) ₆ O—, —CF═CF—, —COO—, —OCO—, —CH═CH—COO—, —OCO -CH = CH -, - (CH 2) a -COO -, - OCO- (CH 2) a -, - OCF 2 -, or _-CF 2 is ^{O-; Z 14,} Z ²⁴ and ^{Z 34} are independently a single _{bond, - (CH 2) 2 -} , - (CH 2) 3 -, - (CH 2) 4 -, - CH = CH -, - CF = CF -, - OCF 2 - or -CF ₂ Z ¹⁵ , Z ²⁵ and Z ³⁵ are each independently a single bond, —OCH ₂ —, —O (CH ₂ ) ₂ —, —O (CH ₂ ) ₃ —, —O (CH ₂ ). _{4 -, - CH 2 O -} , - (CH 2) 2 O -, - (CH 2) 3 O -, - (CH 2) 4 O -, - O (CH 2) 2 _{O -, - O (CH 2} ) 3 O -, - O (CH 2) 4 O -, - O (CH 2) 5 O -, - O (CH 2) 6 O -, - CH = CH -, - CF═CF—, —COO—, —OCO—, —CH═CH—COO—, —OCO—CH═CH—, — (CH ₂ ) _a —COO—, —OCO— (CH ₂ ) _a —, — OCF ₂ — or —CF ₂ O—. In any one of formulas (1g) to (1k), Z ⁴⁰ is formula (Z ⁴ -2), formula (Z ⁴ -3), formula (Z ⁴ -4), or formula (Z ⁴ -5). In these formulas, r is an integer of 1 to 6, s and t are independently 2 or 3, and in each of these formulas, any one — (CH ₂ ) — is —CH═CH— 17. A compound according to claim 16, which is always replaced by either-and -C≡C-. The compound according to claim 16 or 17, wherein in the formulas (1g) to (1k) according to claim 16, m = 1 and n = q = 0. The compound according to claim 16 or 17, wherein in the formulas (1g) to (1k) according to claim 16, m = 1, n = 1, q = 0. The compound according to claim 16 or 17, wherein in the formulas (1g) to (1k) according to claim 16, m = 1, n = 1, q = 1. The compound according to claim 16 or 17, wherein in the formulas (1g) to (1k) according to claim 16, m = 2, n = 1, and q = 1. The compound according to any one of claims 1 to 21, which has optical activity. A liquid crystal composition comprising at least one compound according to claim 1. A liquid crystal composition comprising at least two polymerizable compounds, wherein at least one polymerizable compound is the compound according to claim 1. The liquid crystal composition according to claim 24, wherein the at least two polymerizable compounds are the compounds according to claim 1. The liquid crystal composition according to claim 24, wherein at least one polymerizable compound is the compound according to claim 1, and at least the other polymerizable compound is different from the compound according to claim 1. A liquid crystal composition containing an optically active compound, wherein the optically active compound is at least one selected from the group consisting of the compound according to claim 22 and an optically active and polymerizable compound other than the compound according to claim 22. The liquid crystal composition according to claim 23, wherein A liquid crystal composition comprising at least one polymerizable compound according to claim 1 and at least one non-polymerizable compound having liquid crystallinity. A polymer having at least one structural unit represented by formula (2).

In the formula (2), R ¹ is alkyl having 1 to 20 carbons, hydrogen, halogen, —CN, —N═C═O, —N═C═S, or —Z ⁴ —P ^2. In the formula, any —CH ₂ — is replaced by —O—, —S—, —CO—, —COO—, —OCO—, —CH═CH—, —CF═CF—, or —C≡C—. And any hydrogen may be replaced by halogen, —CF ₃ or —CN; A ¹ , A ² , A ³ , and A ⁴ are independently 1,4-cyclohexylene, 1,4 -Cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl, fluorene-2,7-diyl, bicyclo [2.2.2] octane-1,4- Diyl, bicyclo [3.1.0] hexane-3,6-di , Bicyclo [4.4.0] decane, or Q, any -CH ₂ - in these rings - may be replaced by -O-, arbitrary -CH = may be replaced by -N = And any hydrogen may be replaced by a group of halogen, alkyl having 1 to 5 carbons, fluoroalkyl having 1 to 5 carbons, alkoxy having 1 to 5 carbons, or alkenyl having 2 to 5 carbons , Q is any of the divalent groups shown below,

In these divalent groups, Me is methyl, Y ¹ , Y ² , Y ³ and Y ⁴ are independently alkyl having 1 to 10 carbons, alkoxy having 1 to 10 carbons, 1 to C 1 10 fluoroalkyl, hydrogen or fluorine; Z ¹ , Z ² and Z ³ are each independently a single bond or alkylene having 1 to 20 carbons, in which any —CH ₂ — is —O—, -S-, -COO-, -OCO-, -CH = CH-, or -C≡C- may be substituted, and in this alkylene or substituted alkylene, any hydrogen may be replaced by halogen. ; ^{Z 4} is an alkylene having 1 to 20 carbon atoms, -CH ₂ of any one in the alkylene - is replaced always either -CH = CH- and -C≡C- Cage, other arbitrary -CH ₂ - -O -, - S -, - COO -, - OCO -, - CH = CH -, - it may be replaced by C≡C-; ^{P 2} is (P ² -1) to ^(is any of the groups shown in P 2 -6);

X is hydrogen, halogen, —CF ₃ , or alkyl having 1 to 5 carbons; m, n and q are independently 0 or 1. When m, n and q are 2, the same two symbols may be independently different structures or the same. 30. A polymer according to claim 29 obtained from the compound according to any one of claims 2 to 22. The polymer according to claim 29, which is obtained by homopolymerizing one of the compounds according to any one of claims 1 to 22. 30. The polymer according to claim 29, which is obtained from the liquid crystal composition according to any one of claims 23 to 27. A polymer composition containing the polymer according to claim 29, obtained from the liquid crystal composition according to claim 28. A film having optical anisotropy obtained by using the polymer according to any one of claims 29 to 32 or the polymer composition according to claim 33. A molded article having optical anisotropy obtained by using the polymer according to any one of claims 29 to 32 or the polymer composition according to claim 33. A liquid crystal display device comprising the polymer according to any one of claims 29 to 32 or the polymer composition according to claim 33. 36. A liquid crystal display element comprising the molded article having optical anisotropy according to claim 35.