JP2018044028A - Liquid crystal composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid crystal composition with an improved response speed, having positive dielectric anisotropy and negative dielectric anisotropy.SOLUTION: A liquid crystal composition contains a first component and a second component, the first component being at least one compound selected from a cyclohexane compound group represented by formula (1) (Rand Rindependently represent R, ROCO or RCOO; R is an alkyl group, an alkenyl group or an alkynyl group; X and Y independently represent a halogen atom or H, where both of them are not H at the same time; or, X and Y form together =O).SELECTED DRAWING: None

Description

  The present invention relates to a novel cyclohexane compound and a liquid crystal composition comprising the compound, and aims to improve the response speed of a liquid crystal display.

  Liquid crystals utilizing optical anisotropy (Δn) (hereinafter sometimes referred to as “Δn”) and dielectric anisotropy (Δε) (hereinafter also referred to as “Δε”), which are characteristics of liquid crystal compounds. Many display elements have been made so far, and have been used for watches, calculators, measuring instruments, automotive panels, word processors, electronic notebooks, mobile phones, printers, computers, TVs, and the like. The liquid crystal compound used in this liquid crystal display element has a unique liquid crystal phase, and the phase form is roughly classified into a nematic phase, a smectic phase, and a cholesteric phase. Among them, the nematic phase is most widely used. Among display methods and drive methods used in display devices, display methods such as dynamic scattering type (DS mode), guest-host type (GH mode), and twisted nematic type (TN mode) have been used so far. ), Super twisted nematic type (STN mode), thin film transistor type (TFT mode) and ferroelectric liquid crystal type (FLC) have been developed. As the driving method, a static driving method, a multiplex driving method, an active matrix driving method, a dual frequency driving method, and the like have been adopted. Recently, three types of TN type, STN type and TFT type have become mainstream. The liquid crystal material used for any display element must be stable to moisture, air, heat, light, etc., and exhibits a liquid crystal phase in the widest possible temperature range, centering on room temperature, with an appropriate anisotropic dielectric constant. Characteristics (Δε) and refractive index anisotropy (Δn), high response speed, and low voltage drive characteristics are required. In order to satisfy this characteristic, a liquid crystal having a low viscosity and a low threshold voltage is required. At present, no single compound satisfies all the above-mentioned conditions, and the present situation is that several to several tens of liquid crystal compounds are mixed to meet the required characteristics. Furthermore, further improvement in response speed is required for recent high-definition TV, 3D compatible display, and the like.

  Many proposals have been made for nematic liquid crystal compositions using cyclohexane compounds and excellent in responsiveness. For example, a nematic that has a large pretilt angle that can be formed, a significantly low stripe-domain generation rate, is chemically stable, can be driven at low voltage, and has high-speed response that can respond to high-time-division driving. Liquid crystal composition (Patent Document 1) A nematic liquid crystal composition having a wide drivable temperature range, excellent response, and good contrast with respect to a desired birefringence size is provided. It is a novel cyclohexane compound that provides liquid crystal display devices such as TN-LCD, STN-LCD, TFT-LCD with improved optical characteristics, and the response speed from the antiferroelectric state to the ferroelectric state is improved. In addition, there is an antiferroelectric liquid crystal composition (Patent Document 2). In addition, there is a material for a liquid crystal display cell that has a cyclohexane ring and can effectively reduce the threshold voltage without increasing the viscosity when mixed with a liquid crystal composition that is currently widely used (Patent Literature). 3). However, each of the proposals so far has not been satisfactory with respect to the response speed.

JP-A-6-56717 JP-A-7-126205 JP2012-180284

  The problem to be solved by the present invention is to improve the response speed of a nematic liquid crystal compound having a positive dielectric anisotropy and a negative dielectric anisotropy.

（式（１）中、Ｒ_１，Ｒ_２は、それぞれ同一または異なって、Ｒ，ＲＯＣＯ，ＲＣＯＯを表わし、Ｒはアルキル基、アルケニル基またはアルキニル基を示す。該アルキル基、アルケニル基またはアルキニル基はハロゲン原子又はシアノ基により置換されていてもよく、該アルキル基、アルケニル基またはアルキニル基中のＣＨ_２基の一部は、−Ｏ−、−ＣＯ−又は−ＣＯＯ−で置き換えられていてもよい。Ｘ、Ｙは各々独立にハロゲン原子又は水素原子を表わし、同時に水素原子を表わすことはない。または、Ｘは酸素原子を表わし、Ｙは該酸素原子への直接結合を表わす。）
で表わされるシクロヘキサン化合物群の少なくとも１種類の化合物を含有し、
第二成分として、下記式（２）：

（式（２）中、ＡおよびＢは、同一または異なって、Ｐ−Ｑ−、Ｈ、ハロゲン、ＳＦ_５、ＮＯ_２、炭素基または炭化水素基を表し、ただし、ＡおよびＢの少なくとも一方はＰ−Ｑ−を表し、
Ｐは重合性基を表し、
Ｑはスペーサー基または単結合を表し、
ｉ個のＬおよびｋ個のＮは、それぞれ同一または異なって、１，３−フェニレン、１，４−フェニレン、ナフタレン−１，３−ジイル、ナフタレン−１，６−ジイル、ナフタレン−２，５−ジイルまたはナフタレン−２，７−ジイル（ただし、これらの基における１個以上のＣＨ基は窒素原子で置き換えられていてもよい）、シクロヘキサン−１，３−ジイル（ただし、１個以上の隣接していないＣＨ_２基は酸素原子および／または硫黄原子で置き換えられていてもよい）、１，３−シクロヘキセニレン、ピペリジン−２，４−ジイル、ピペリジン−２，６−ジイル、デカヒドロナフタレン−２，７−ジイル、１，２，３，４−テトラヒドロナフタレン−２，７−ジイルまたはインダン−２，４−ジイルを表し、ただし、これら全ての基は無置換であっても、Ｔにより単置換または多置換されていてもよく、ただし、ｉ＝ｋ＝１の場合、基ＬおよびＮの一方はＭに示される意味の１つも有してよく、
ｊ個のＭは、それぞれ同一または異なって、１，３−フェニレン、１，４−フェニレン、ナフタレン−１，４−ジイルまたはナフタレン−２，６−ジイル（ただし、これらの基における１個以上のＣＨ基は窒素原子で置き換えられていてもよい）、シクロヘキサン−１，４−ジイル（ただし、１個以上の隣接していないＣＨ_２基は酸素原子および／または硫黄原子で置き換えられていてもよい）、１，４−シクロヘキセニレン、ビシクロ［１．１．１］ペンタン−１，３−ジイル、ビシクロ［２．２．２］オクタン−１，４−ジイル、スピロ［３．３］ヘプタン−２，６−ジイル、ピペリジン−２，５−ジイル、デカヒドロナフタレン−２，６−ジイル、１，２，３，４−テトラヒドロナフタレン−２，６−ジイル、インダン−２，５−ジイル、チオフェン−２，５−ジイル、フルオレン−２，７−ジイルまたはオクタヒドロ−４，７−メタノインダン−２，５−ジイルを表し、ただし、これら全ての基は無置換であっても、Ｔにより単置換または多置換されていてもよく、また、Ｌに示される意味の１つを有してもよく、
Ｔは、Ｐ−Ｑ−、Ｈ、ＯＨ、ハロゲン、ＳＦ_５、ＮＯ_２、炭素基または炭化水素基を表し、
ｉ個のＷおよびｊ個のＺは、それぞれ同一または異なって、−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯ−Ｏ−、−ＯＣＯ−、−Ｏ−ＣＯ−Ｏ−、−ＯＣＨ_２−、−ＣＨ_２Ｏ−、−ＳＣＨ_２−、−ＣＨ_２Ｓ−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、−ＣＦ_２Ｓ−、−ＳＣＦ_２−、−（ＣＨ_２）_ｎ−、−ＣＦ_２ＣＨ_２−、−ＣＨ_２ＣＦ_２−、−（ＣＦ_２）_ｎ−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−、−Ｃ≡Ｃ−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−ＣＵＶまたは単結合を表し、
ＵおよびＶは、それぞれ互いに独立に、Ｈまたは１〜１２個の炭素原子を有するアルキルを表し、
ｉおよびｋは、それぞれ互いに独立に、０または１を表し、ただし、ｉ＋ｋ＞０であり、
ｊは、０、１、２または３を表し、
ｎは、１、２、３または４を表す。）
を含有する液晶組成物である。 The present invention includes the following. That is, as the first component, the following formula (1)

(In Formula (1), R ₁ and R ₂ are the same or different and each represents R, ROCO, or RCOO, and R represents an alkyl group, an alkenyl group, or an alkynyl group. The alkyl group, alkenyl group, or alkynyl group. May be substituted by a halogen atom or a cyano group, and a part of the CH ₂ group in the alkyl group, alkenyl group or alkynyl group may be substituted by —O—, —CO— or —COO—. X and Y each independently represent a halogen atom or a hydrogen atom, and at the same time do not represent a hydrogen atom, or X represents an oxygen atom, and Y represents a direct bond to the oxygen atom.
Containing at least one compound of the cyclohexane compound group represented by:
As the second component, the following formula (2):

(In the formula (2), A and B are the same or different, P-Q-, H, _halogen, SF 5, NO _2, represents a carbon group or hydrocarbon group, provided that at least one of A and B P-Q-
P represents a polymerizable group,
Q represents a spacer group or a single bond,
i L and k N are the same or different and are 1,3-phenylene, 1,4-phenylene, naphthalene-1,3-diyl, naphthalene-1,6-diyl, naphthalene-2,5. -Diyl or naphthalene-2,7-diyl (where one or more CH groups in these groups may be replaced by nitrogen atoms), cyclohexane-1,3-diyl (but one or more adjacent groups) The non-CH ₂ group may be replaced by an oxygen atom and / or a sulfur atom), 1,3-cyclohexenylene, piperidine-2,4-diyl, piperidine-2,6-diyl, decahydronaphthalene -2,7-diyl, 1,2,3,4-tetrahydronaphthalene-2,7-diyl or indan-2,4-diyl, all of which are May be substituted or monosubstituted or polysubstituted by T, provided that when i = k = 1, one of the groups L and N may also have one of the meanings indicated for M;
j Ms are the same or different and are each 1,3-phenylene, 1,4-phenylene, naphthalene-1,4-diyl or naphthalene-2,6-diyl (provided that one or more of these groups are CH group may be replaced by a nitrogen atom), cyclohexane-1,4-diyl (provided that one or more non-adjacent CH ₂ groups may be replaced by an oxygen atom and / or a sulfur atom) ), 1,4-cyclohexenylene, bicyclo [1.1.1] pentane-1,3-diyl, bicyclo [2.2.2] octane-1,4-diyl, spiro [3.3] heptane- 2,6-diyl, piperidine-2,5-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, indane-2,5-dii Represents thiophene-2,5-diyl, fluorene-2,7-diyl or octahydro-4,7-methanoindan-2,5-diyl, although all these groups are unsubstituted, May be mono- or poly-substituted and may have one of the meanings indicated for L;
T represents PQ-, H, OH, halogen, SF ₅ , NO ₂ , a carbon group or a hydrocarbon group,
i W and j Z are the same or different and are each -O-, -S-, -CO-, -CO-O-, -OCO-, -O-CO-O-, -OCH _{2 -, - CH 2 O -,} - SCH 2 -, - CH 2 S -, - CF 2 O -, - OCF 2 -, - CF 2 S -, - SCF 2 -, - (CH 2) n -, - CF ₂ CH ₂ —, —CH ₂ CF ₂ —, — (CF ₂ ) _n —, —CH═CH—, —CF═CF—, —C≡C—, —CH═CH—COO—, —OCO—. Represents CH═CH—, —CUV or a single bond,
U and V each independently of one another represent H or alkyl having 1 to 12 carbon atoms;
i and k each independently represent 0 or 1, provided that i + k>0;
j represents 0, 1, 2 or 3;
n represents 1, 2, 3 or 4. )
Is a liquid crystal composition containing

  The inventors of the present invention who have studied the liquid crystal composition have found that the response speed of the liquid crystal composition obtained by adding a specific low molecular weight compound to the mother liquid crystal is improved, and have completed the present invention. .

  Terms used in this specification are as follows. The liquid crystal composition is one or a mixture of two or more compounds having a liquid crystal phase such as a nematic phase or a smectic phase, and one or more compounds having a liquid crystal phase and one or two or more liquid crystals. It means a mixture of compounds having no phase. The liquid crystal display element means a liquid crystal display panel or a liquid display module.

1. First component 1.1. Cyclohexane Compound The first component constituting the liquid crystal composition according to the present invention includes a cyclohexane compound represented by the following general formula (1). The compound of the formula (1) means one or more compounds represented by the formula (1), and the two or more compounds may be a compound group. The same applies to the following formula (2). Moreover, in the compound group contained in Formula (1), although it describes as Formula (1-1), Formula (1-2), etc., these classify | categorize the compound group which belongs to Formula (1) according to a functional group etc. When the compound group of formula (1-1) is further classified, it is described as formula (1-1-1), formula (1-1-2) or the like. The formula (1), the formula (1-1), etc. are not described, and the formula may be omitted and only (1), (1-1) may be described. The same applies to the following formula (2).

In formula (1), R ₁ and R ₂ are the same or different and each represents R, ROCO, or RCOO, and R represents an alkyl group, an alkenyl group, or an alkynyl group. The alkyl group, alkenyl group or alkynyl group may be substituted with a halogen atom or a cyano group, and a part of the CH ₂ group in the alkyl group, alkenyl group or alkynyl group may be —O—, —CO— or -COO- may be substituted. X and Y each independently represent a halogen atom or a hydrogen atom, and do not represent a hydrogen atom at the same time. Alternatively, X represents an oxygen atom, and Y represents a direct bond to the oxygen atom.

Examples of the group represented by R include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, vinyl, allyl, butenyl, ethynyl, propynyl, butynyl, methoxymethyl, ethoxymethyl, propoxymethyl. , Butoxymethyl, methoxyethyl, ethoxyethyl, perfluoromethyl, perfluoroethyl, perfluoropropyl, monofluoromethyl, difluoromethyl, trifluoromethyl, perfluorovinyl, perfluoroallyl, isopropyl, 1-methylpropyl, 2- Examples include methylpropyl, 2-butylmethyl, 3-methylbutyl, 2-methylpentyl, 3-methylpentyl, 2-ethylhexyl, 2-propylpentyl, 1-methylpentyl and the like. R ₁ and R ₂ are preferably an unsubstituted alkyl group or an unsubstituted alkenyl group.

  When the compound of the present invention represented by the general formula (1) may exist as a mixture of a plurality of stereoisomers and can be in the form of a cis / trans isomer, the trans isomer is generally used. Is preferred.

Typical specific examples of the cyclohexane compound group represented by the general formula (1) include formulas (1-1) to (1-5). However, it is not limited to these compound groups. Incidentally, R ₁ and R ₂ in the formulas (1-1) to (1-5) which are the compound group of the formula (1) are the same as those in the general formula (1).

  Although the method of manufacturing the cyclohexane compound of Formula (1) is not specifically limited, For example, it can manufacture by the manufacturing method represented by the scheme shown below.

1.2. Mother liquid crystal The above cyclohexane compound constitutes the first component (mother liquid crystal) of the liquid crystal composition of the present invention by blending it with other liquid crystal compound or liquid crystal analog or a mixture thereof in an arbitrary ratio.

  As another compound to mix | blend, at least 1 type of compound of each compound group represented by following formula (2), (3) and (4) can be illustrated.

  In the formulas (2), (3) and (4), R represents an alkyl group, and X represents H or F.

  Examples of the other compound include at least one compound of the compound group represented by the formula (5).

In the formula (5), Y represents an F atom or OCF ₃ , and R represents an alkyl group.

  Examples of the other compounds include at least one compound of each compound group represented by formulas (6), (7), and (8).

  The compound group of Formula (6) is shown below.

In Formula (6), R ₃ and R ₄ are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, alkenyloxy having 2 to 11 carbons, or any In the formula (7) and (8) below, and the ring A and the ring B are independently a cyclohexyl group or a phenyl group. And ring B may be absent, X ₁ and X ₂ are independently fluorine or chlorine, and Z ₁ is independently methyleneoxy, carbonyloxy, ethylene or a single bond.

  The compound group of Formula (7) is shown below.

In Formula (7), Z ₂ is a single bond or ethylene.

  The compound group of Formula (8) is shown below.

In formula (8), ring C and ring D are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 3-fluoro-1,4-phenylene. And when p is 1, ring D is 1,4-phenylene and Z ₁ is independently a single bond, ethylene, methyleneoxy, or carbonyloxy. p is a numerical value of 1, 2 or 3.

（式（２）中、ＡおよびＢは、同一または異なって、Ｐ−Ｑ−、Ｈ、ハロゲン、ＳＦ_５、ＮＯ_２、炭素基または炭化水素基を表し、ただし、ＡおよびＢの少なくとも一方はＰ−Ｑ−を表し、
Ｐは重合性基を表し、
Ｑはスペーサー基または単結合を表し、
ｉ個のＬおよびｋ個のＮは、それぞれ同一または異なって、１，３−フェニレン、１，４−フェニレン、ナフタレン−１，３−ジイル、ナフタレン−１，６−ジイル、ナフタレン−２，５−ジイルまたはナフタレン−２，７−ジイル（ただし、これらの基における１個以上のＣＨ基は窒素原子で置き換えられていてもよい）、シクロヘキサン−１，３−ジイル（ただし、１個以上の隣接していないＣＨ_２基は酸素原子および／または硫黄原子で置き換えられていてもよい）、１，３−シクロヘキセニレン、ピペリジン−２，４−ジイル、ピペリジン−２，６−ジイル、デカヒドロナフタレン−２，７−ジイル、１，２，３，４−テトラヒドロナフタレン−２，７−ジイルまたはインダン−２，４−ジイルを表し、ただし、これら全ての基は無置換であっても、Ｔにより単置換または多置換されていてもよく、ただし、ｉ＝ｋ＝１の場合、基ＬおよびＮの一方はＭに示される意味の１つも有してよく、
ｊ個のＭは、それぞれ同一または異なって、１，３−フェニレン、１，４−フェニレン、ナフタレン−１，４−ジイルまたはナフタレン−２，６−ジイル（ただし、これらの基における１個以上のＣＨ基は窒素原子で置き換えられていてもよい）、シクロヘキサン−１，４−ジイル（ただし、１個以上の隣接していないＣＨ_２基は酸素原子および／または硫黄原子で置き換えられていてもよい）、１，４−シクロヘキセニレン、ビシクロ［１．１．１］ペンタン−１，３−ジイル、ビシクロ［２．２．２］オクタン−１，４−ジイル、スピロ［３．３］ヘプタン−２，６−ジイル、ピペリジン−２，５−ジイル、デカヒドロナフタレン−２，６−ジイル、１，２，３，４−テトラヒドロナフタレン−２，６−ジイル、インダン−２，５−ジイル、チオフェン−２，５−ジイル、フルオレン−２，７−ジイルまたはオクタヒドロ−４，７−メタノインダン−２，５−ジイルを表し、ただし、これら全ての基は無置換であっても、Ｔにより単置換または多置換されていてもよく、また、Ｌに示される意味の１つを有してもよく、
Ｔは、Ｐ−Ｑ−、Ｈ、ＯＨ、ハロゲン、ＳＦ_５、ＮＯ_２、炭素基または炭化水素基を表し、
ｉ個のＷおよびｊ個のＺは、それぞれ同一または異なって、−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯ−Ｏ−、−ＯＣＯ−、−Ｏ−ＣＯ−Ｏ−、−ＯＣＨ_２−、−ＣＨ_２Ｏ−、−ＳＣＨ_２−、−ＣＨ_２Ｓ−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、−ＣＦ_２Ｓ−、−ＳＣＦ_２−、−（ＣＨ_２）_ｎ−、−ＣＦ_２ＣＨ_２−、−ＣＨ_２ＣＦ_２−、−（ＣＦ_２）_ｎ−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−、−Ｃ≡Ｃ−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−ＣＵＶまたは単結合を表し、
ＵおよびＶは、それぞれ互いに独立に、Ｈまたは１〜１２個の炭素原子を有するアルキルを表し、
ｉおよびｋは、それぞれ互いに独立に、０または１を表し、ただし、ｉ＋ｋ＞０であり、
ｊは、０、１、２または３を表し、
ｎは、１、２、３または４を表す。）
である。 2. Second Component The second component constituting the liquid crystal composition according to the present invention is represented by the following formula (2):

(In the formula (2), A and B are the same or different, P-Q-, H, _halogen, SF 5, NO _2, represents a carbon group or hydrocarbon group, provided that at least one of A and B P-Q-
P represents a polymerizable group,
Q represents a spacer group or a single bond,
i L and k N are the same or different and are 1,3-phenylene, 1,4-phenylene, naphthalene-1,3-diyl, naphthalene-1,6-diyl, naphthalene-2,5. -Diyl or naphthalene-2,7-diyl (where one or more CH groups in these groups may be replaced by nitrogen atoms), cyclohexane-1,3-diyl (but one or more adjacent groups) The non-CH ₂ group may be replaced by an oxygen atom and / or a sulfur atom), 1,3-cyclohexenylene, piperidine-2,4-diyl, piperidine-2,6-diyl, decahydronaphthalene -2,7-diyl, 1,2,3,4-tetrahydronaphthalene-2,7-diyl or indan-2,4-diyl, all of which are May be substituted or monosubstituted or polysubstituted by T, provided that when i = k = 1, one of the groups L and N may also have one of the meanings indicated for M;
j Ms are the same or different and are each 1,3-phenylene, 1,4-phenylene, naphthalene-1,4-diyl or naphthalene-2,6-diyl (provided that one or more of these groups are CH group may be replaced by a nitrogen atom), cyclohexane-1,4-diyl (provided that one or more non-adjacent CH ₂ groups may be replaced by an oxygen atom and / or a sulfur atom) ), 1,4-cyclohexenylene, bicyclo [1.1.1] pentane-1,3-diyl, bicyclo [2.2.2] octane-1,4-diyl, spiro [3.3] heptane- 2,6-diyl, piperidine-2,5-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, indane-2,5-dii Represents thiophene-2,5-diyl, fluorene-2,7-diyl or octahydro-4,7-methanoindan-2,5-diyl, although all these groups are unsubstituted, May be mono- or poly-substituted and may have one of the meanings indicated for L;
T represents PQ-, H, OH, halogen, SF ₅ , NO ₂ , a carbon group or a hydrocarbon group,
i W and j Z are the same or different and are each -O-, -S-, -CO-, -CO-O-, -OCO-, -O-CO-O-, -OCH _{2 -, - CH 2 O -,} - SCH 2 -, - CH 2 S -, - CF 2 O -, - OCF 2 -, - CF 2 S -, - SCF 2 -, - (CH 2) n -, - CF ₂ CH ₂ —, —CH ₂ CF ₂ —, — (CF ₂ ) _n —, —CH═CH—, —CF═CF—, —C≡C—, —CH═CH—COO—, —OCO—. Represents CH═CH—, —CUV or a single bond,
U and V each independently of one another represent H or alkyl having 1 to 12 carbon atoms;
i and k each independently represent 0 or 1, provided that i + k>0;
j represents 0, 1, 2 or 3;
n represents 1, 2, 3 or 4. )
It is.

  The compound of the formula (2) of the present invention is particularly improved in response speed by mixing with the first component (mother liquid crystal) of the liquid crystal composition of the present invention.

Particularly preferred compounds of formula (2) are
L, M, N, W, Z, P, Q, i, j, k and n have the above meanings,
T _{is, P-Q-, OH, CH} 2 OH, F, Cl, Br, I, -CN, -NO 2, -NCO, -NCS, -OCN, -SCN, -C (= O) N (R ^{_{x) 2, -C (= O}} ) Y 1, -C (= O) R x, -N (R x) 2, optionally substituted silyl also be, optionally substituted 6-20 carbons Represents an aryl having atoms, or a linear or branched alkyl having 1 to 25 carbon atoms, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy, provided that one or more hydrogen atoms May be replaced by F, Cl or PQ-
Y ¹ represents halogen,
R ^x is PQ-, H, halogen, linear, branched or cyclic alkyl having 1 to 25 carbon atoms, provided that one or more non-adjacent CH ₂ groups are oxygen atoms And / or is replaced by —O—, —S—, —CO—, —CO—O—, —O—CO—, —O—CO—O—, so that the sulfur atoms are not directly linked to each other. And one or more hydrogen atoms may be replaced by F, Cl or PQ-), an optionally substituted aryl or aryloxy group having 6 to 40 carbon atoms, Or represents a heteroaryl or heteroaryloxy group having 2 to 40 carbon atoms which may be substituted,
A and B represent PQ-, H, T as defined above, linear or branched alkyl having 1 to 25 carbon atoms, provided that one or more are not adjacent The CH ₂ groups are independently of each other such that oxygen atoms and / or sulfur atoms are not directly linked to each other, and —C (R ^x ) ═C (R ^x ) —, —C≡C—, —N (R ^x ) —, —O—, —S—, —CO—, —CO—O—, —O—CO—, —O—CO—O—, and one or more hydrogens. The atoms may be replaced with F, Cl, Br, I, CN or PQ-, provided that at least one of the groups A and B is PQ-.

Preferably A and B are the same or different and represent the group PQ-.
Preferably, A and B are the same or different and represent the group PQ-, provided that one of the groups Q represents a single bond.
Preferably one of A and B represents PQ- and the other represents T, as defined above, linear or branched alkyl having 1 to 25 carbon atoms, provided that one The above non-adjacent CH ₂ groups are independently of each other such that oxygen atoms and / or sulfur atoms are not directly connected to each other, so that —C (R ^x ) ═C (R ^x ) —, —C≡C -, -N (R ^x )-, -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O- may be substituted, One or more hydrogen atoms may be replaced by F, Cl, Br, I, CN or PQ-.
Preferably, Q represents a single bond.
Preferably, W and Z represent a single bond.
Preferably, M is 1,3-phenylene, 1,4-phenylene, naphthalene-1,4-diyl or naphthalene-2,6-diyl (provided that one or more CH groups in these groups are nitrogen atoms) May be substituted), cyclohexane-1,4-diyl (where one or more non-adjacent CH ₂ groups may be replaced by oxygen and / or sulfur atoms), 1,4- Cyclohexenylene, bicyclo [1.1.1] pentane-1,3-diyl, bicyclo [2.2.2] octane-1,4-diyl, spiro [3.3] heptane-2,6-diyl, Piperidine-2,5-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, indan-2,5-diyl, thiophene-2,5-di Selected from yl, fluorene-2,7-diyl or octahydro-4,7-methanoindan-2,5-diyl, provided that all these groups are unsubstituted or monosubstituted or polysubstituted by T. May be.
Preferably, M is 1,3-phenylene, 1,4-phenylene, naphthalene-1,4-diyl or naphthalene-2,6-diyl (provided that one or more CH groups in these groups are nitrogen atoms) However, all these groups may be unsubstituted or mono- or polysubstituted by T.
L and N are 1,3-phenylene, 1,4-phenylene, naphthalene-1,3-diyl, naphthalene-1,6-diyl, naphthalene-2,5-diyl and naphthalene-2,7-diyl (provided that Wherein one or more CH groups in these groups may be replaced by nitrogen atoms), provided that all these groups are unsubstituted or monosubstituted or polysubstituted by T. Also good.
Preferably, the groups L and / or N linked to the adjacent ring groups L, M, N or the corresponding bridging groups W, Z in the meta or para position are one or more substitutions representing PQ- It has the group T.
Preferably, i = k = 1 and j = 0, 1 or 2.
Preferably, i = j = 0 and k = 1.

  “Halogen” represents F, Cl, Br or I.

  The polymerizable group P is a group suitable for a polymerization reaction such as free radical or ionic chain polymerization, polyaddition or polycondensation, or a polymer-analogous reaction such as addition or condensation onto a polymer main chain, for example. is there. Particularly preferred are groups for chain polymerization, in particular those containing C═C double bonds or C≡C triple bonds, and groups suitable for ring-opening polymerization such as, for example, oxetane or epoxy groups.

The group P is preferably CH ₂ ═CW ¹ —COO—, CH ₂ ═CW ¹ —CO—,

ＣＨ_２＝ＣＷ^２−（Ｏ）_ｋ３−、ＣＷ^１＝ＣＨ−ＣＯ−（Ｏ）_ｋ３−、ＣＷ^１＝ＣＨ−ＣＯ−ＮＨ−、ＣＨ_２＝ＣＷ^１−ＣＯ−ＮＨ−、ＣＨ_３−ＣＨ＝ＣＨ−Ｏ−、（ＣＨ_２＝ＣＨ）_２ＣＨ−ＯＣＯ−、（ＣＨ_２＝ＣＨ−ＣＨ_２）_２ＣＨ−ＯＣＯ−、（ＣＨ_２＝ＣＨ）_２ＣＨ−Ｏ−、（ＣＨ_２＝ＣＨ−ＣＨ_２）_２Ｎ−、（ＣＨ_２＝ＣＨ−ＣＨ_２）_２Ｎ−ＣＯ−、ＨＯ−ＣＷ^２Ｗ^３−、ＨＳ−ＣＷ^２Ｗ^３−、ＨＷ^２Ｎ−、ＨＯ−ＣＷ^２Ｗ^３−ＮＨ−、ＣＨ_２＝ＣＷ^１−ＣＯ−ＮＨ−、ＣＨ_２＝ＣＨ−（ＣＯＯ）_ｋ１−Ｐｈｅ−（Ｏ）_ｋ２−、ＣＨ_２＝ＣＨ−（ＣＯ）_ｋ１−Ｐｈｅ−（Ｏ）_ｋ２−、Ｐｈｅ−ＣＨ＝ＣＨ−、ＨＯＯＣ−、ＯＣＮ−およびＷ^４Ｗ^５Ｗ^６Ｓｉ−より選択され、式中、Ｗ^１は、Ｈ、Ｆ、Ｃｌ、ＣＮ、ＣＦ_３、フェニルまたは１〜５個の炭素原子を有するアルキルを表し、特に、Ｈ、Ｆ、ＣｌまたはＣＨ_３であり、Ｗ^２およびＷ^３は、それぞれ互いに独立に、Ｈまたは１〜５個の炭素原子を有するアルキルを表し、特に、Ｈ、メチル、エチルまたはｎ−プロピルであり、Ｗ^４、Ｗ^５およびＷ^６は、それぞれ互いに独立に、Ｃｌ、１〜５個の炭素原子を有するオキサアルキルまたはオキサカルボニルアルキルを表し、Ｗ^７およびＷ^８は、それぞれ互いに独立に、Ｈ、Ｃｌまたは１〜５個の炭素原子を有するアルキルを表し、Ｐｈｅは、上に定義したとおりの基Ｔの１個以上で置換されていてもよい１，３−フェニレンまたは１，４−フェニレンを表し、ｋ_１、ｋ_２およびｋ_３は、それぞれ互いに独立に、０または１を表し、ｋ_３は、好ましくは、１を表す。

_{^{CH 2 = CW 2 - (O}} ) k3 -, CW 1 = CH-CO- (O) k3 -, CW 1 = CH-CO-NH-, CH 2 = CW 1 -CO-NH-, CH 3 -CH _{= CH-O -, (CH} 2 = CH) 2 CH-OCO -, (CH 2 = CH-CH 2) 2 CH-OCO -, (CH 2 = CH) 2 CH-O -, (CH 2 = CH _{-CH 2) 2 N -, (} CH 2 = CH-CH 2) 2 N-CO-, HO-CW 2 W 3 -, HS-CW 2 W 3 -, HW 2 N-, HO-CW 2 W 3 _{^{-NH-, CH 2 = CW 1 -CO}} -NH-, CH 2 = CH- (COO) k1 -Phe- (O) k2 -, CH 2 = CH- (CO) k1 -Phe- (O) k2 - , Phe-CH = CH-, HOOC- , selected OCN- and ^W 4 ^W 5 ^W 6 Si- than Wherein, ^{W 1} represents H, F, Cl, CN, CF _3, a phenyl or alkyl with 1-5 carbon atoms, in particular, H, F, Cl or CH _3, ^{W 2} and W ³ independently of each other represents H or alkyl having 1 to 5 carbon atoms, in particular H, methyl, ethyl or n-propyl, and W ⁴ , W ⁵ and W ⁶ are each independently of each other. And Cl represents oxaalkyl or oxacarbonylalkyl having 1 to 5 carbon atoms, and W ⁷ and W ⁸ each independently represent H, Cl or alkyl having 1 to 5 carbon atoms. , Phe represents that may be mentioned are 1,3-phenylene or 1,4-phenylene substituted with one or more groups T as defined _above, k 1, _{k 2} and _{k 3} are each other respectively Independently represents 0 or 1, _{k 3} preferably represents 1.

Especially preferred groups P _{are, CH 2 = CH-COO-,} CH 2 = C (CH 3) -COO-, CH 2 = CH-, CH 2 = CH-O -, (CH 2 = CH) 2 CH-OCO _{-, (CH 2 = CH)} 2 CH-O-,

であり、特に、ビニルオキシ、アクリレート、メタクリレート、フルオロアクリレート、
クロロアクリレート、オキセタンおよびエポキシドである。

In particular, vinyloxy, acrylate, methacrylate, fluoroacrylate,
Chloroacrylate, oxetane and epoxide.

  Spacer groups in Q are known to those skilled in the art and are described, for example, in Pure Appl. Chem. 73 (No. 5), 888 (2001) and C.I. Tschierske, G.M. Pelzl, S.M. Diele, Angew. Chem. 2004, 116, 6340-6368. Unless otherwise specified, a spacer group represents a flexible group that connects a mesogenic group and a polymerizable group (one or more) to each other in a reactive mesogenic compound (hereinafter sometimes referred to as “RM”). .

  Mesogenic groups are known to those skilled in the art and are described in the literature and contribute essentially to the generation of liquid crystal (LC) phases in low molecular weight or high molecular weight materials due to the anisotropy of attractive and repulsive interactions. Represents a group. A compound containing a mesogenic group (mesogenic compound) itself does not necessarily have a liquid crystal phase. It is also possible for the mesogenic compound to exhibit a liquid crystal phase behavior only after mixing with other compounds and / or after polymerization. A typical mesogenic group is, for example, a rigid rod-like or disc-like unit. A review of terms and definitions used with respect to mesogenic or liquid crystal compounds can be found in Pure Appl. Chem. 73 (No. 5), 888 (2001) and C.I. Tschierske, G.M. Pelzl, S.M. Diele, Angew. Chem. 2004, 116, 6340-6368.

  Reactive mesogen (RM) represents a compound containing a mesogenic group and one or more functional groups suitable for polymerization (polymerizable group or P).

The spacer group is preferably selected from the formula Q′-X ′ such that the group “PQ—” matches the formula “PQ′-X′—”
Where Q ′ represents an alkylene having 1 to 20, preferably 1 to 12, carbon atoms, provided that it may be mono- or polysubstituted with F, Cl, Br, I or CN, and One or more non-adjacent CH ₂ groups are each independently of the other —O—, —S—, —NH—, —NR ⁰ , so that the oxygen and / or sulfur atoms are not directly linked to each other. —, —SiR ⁰ R ⁰⁰ —, —CO—, —COO—, —OCO—, —OCO—O—, —S—CO—, —CO—S—, —NR ⁰ —CO—O—, —O. -CO-NR ^0- , -NR ⁰ -CO-NR ^0- , -CH = CH- or -C≡C- may be substituted,
X ′ represents —O—, —S—, —CO—, —COO—, —OCO—, —O—COO—, —CO—NR ⁰ —, —NR ⁰ —CO—, —NR ⁰ —CO—. NR ⁰ −, —OCH ₂ —, —CH ₂ O—, —SCH ₂ —, —CH ₂ S—, —CF ₂ O—, —OCF ₂ —, —CF ₂ S—, —SCF ₂ —, —CF ₂ CH ₂ —, —CH ₂ CF ₂ —, —CF ₂ CF ₂ —, —CH═N—, —N═CH—, —N═N—, —CH═CR ⁰ —, —CY ² = CY ³ -, -C≡C-, -CH = CH-COO-, -OCO-CH = CH- or a single bond,
R ⁰ and R ⁰⁰ each independently represent H or alkyl having 1 to 12 carbon atoms, and Y ² and Y ³ each independently represent H, F, Cl or CN.

X ′ is preferably —O—, —S—, —CO—, —COO—, —OCO—, —O—COO—, —CO—NR ⁰ —, —NR ⁰ —CO—, —NR ^0. -CO-NR < ⁰ >-or a single bond.

Typical Q ′ is, for example, — (CH ₂ ) _p1 —, — (CH ₂ CH ₂ O) _{q 1} —CH ₂ CH ₂ —, —CH ₂ CH ₂ —S—CH ₂ CH ₂ —, —CH _2. CH ₂ —NH—CH ₂ CH ₂ — or — (SiR ⁰ R ⁰⁰ —O) _p1 —, where p1 is an integer from 1 to 12, q1 is an integer from 1 to 3, and R ⁰ and R ⁰⁰ Has the above meaning.

Particularly preferred groups -X'-Q'- _{is, - (CH 2) p1 -} , - O- (CH 2) p1 -, - OCO- (CH 2) p1 -, - OCOO- (CH 2) p1 - in is there.

  Particularly preferred groups Q ′ are, for example, in each case linear ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, octadecylene, ethyleneoxyethylene, methyleneoxybutylene, ethylene. Thioethylene, ethylene-N-methyliminoethylene, 1-methylalkylene, ethenylene, propenylene and butenylene.

  The “carbon group” is a monovalent or polyvalent organic group containing at least one carbon atom, and further contains no atoms (for example, —C≡C— etc.), or any Optionally, it further includes one or more atoms such as N, O, S, P, Si, Se, As, Te or Ge (eg, carbonyl, etc.). A “hydrocarbon group” is a carbon group that further contains one or more hydrogen atoms and optionally, for example, N, O, S, P, Si, Se, As, Te, Ge or the like. The term may contain one or more heteroatoms.

  The carbon group or hydrocarbon group may be a saturated group or an unsaturated group. Unsaturated groups are, for example, aryl, alkenyl or alkynyl groups. The carbon group or hydrocarbon group having more than 3 carbon atoms may be linear, branched and / or cyclic, and may have a spiro bond or a condensed ring.

  Preferred carbon and hydrocarbon groups are optionally substituted alkyl, alkenyl, alkynyl, alkoxy, alkylcarbonyl having 1 to 40, preferably 1 to 25, particularly preferably 1 to 18 carbon atoms, Alkoxycarbonyl, alkylcarbonyloxy and alkoxycarbonyloxy, optionally substituted aryl or aryloxy having 6 to 40, preferably 6 to 25 carbon atoms, or optionally substituted 6 to 40, Alkylaryl, arylalkyl, alkylaryloxy, arylalkyloxy, arylcarbonyl, aryloxycarbonyl, arylcarbonyloxy and aryloxycarbonyloxy having 6 to 25 carbon atoms are preferred.

Further preferred carbon and hydrocarbon _groups, C 1 _{-C 40 alkyl,} C 2 _{-C 40 alkenyl,} C 2 _{-C 40 alkynyl,} C 3 _{-C 40 allyl,} C 4 _{-C 40 alkadienyl, C} 4 ~ C _{40 polyenyl,} C 6 _{-C 40 aryl,} C 6 _{-C 40 alkylaryl,} C 6 _{-C 40 arylalkyl,} C 6 _{-C 40} alkyl _aryloxy, C 6 _{-C 40 arylalkyloxy,} C 2 _{-C 40 heteroaryl,} C 4 _{-C 40 cycloalkyl,} or the like C 4 _{-C 40} cycloalkenyl. Particularly _preferably, C 1 _{-C 22 alkyl,} C 2 _{-C 22 alkenyl,} C 2 _{-C 22 alkynyl,} C 3 _{-C 22 allyl,} C 4 _{-C 22 alkadienyl,} C 6 _{-C 12} aryl, _{C 6} -C ₂₀ arylalkyl and _C 2 _{-C 20} heteroaryl.

Further preferred carbon groups and hydrocarbon groups are linear, branched or cyclic alkyl groups having 1 to 40, preferably 1 to 25 carbon atoms, which are unsubstituted or F, Mono- or polysubstituted with Cl, Br, I or CN, provided that one or more non-adjacent CH ₂ groups are each in contact with each other such that the oxygen and / or sulfur atoms are not directly linked to each other. Independently, -C ( ^Rx ) = C ( ^Rx )-, -C≡C-, -N ( ^Rx )-, -O-, -S-, -CO-, -CO-O-,- O-CO- and -O-CO-O- may be substituted.

R ^x is preferably H, halogen, a linear, branched or cyclic alkyl chain having 1 to 25 carbon atoms, provided that one or more non-adjacent carbon atoms are —O—, — S—, —CO—, —CO—O—, —O—CO—, —O—CO—O— may be substituted, and one or more hydrogen atoms may be substituted with fluorine) Represents an optionally substituted aryl or aryloxy group having 6 to 40 carbon atoms, or an optionally substituted heteroaryl or heteroaryloxy group having 5 to 40 carbon atoms.

  “Alkyl”, “aryl”, “heteroaryl” and the like are intended to encompass polyvalent groups such as alkylene, arylene, heteroarylene, and the like.

  “Aryl” refers to an aromatic carbon group or a group derived therefrom. “Heteroaryl” refers to “aryl” as defined above containing one or more heteroatoms.

  Preferred alkyl groups are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, 2-methylbutyl, n-pentyl, s-pentyl, cyclopentyl, n-hexyl, cyclohexyl. 2-ethylhexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, dodecanyl, trifluoromethyl, perfluoro-n-butyl, 2, 2,2-trifluoroethyl, perfluorooctyl, perfluorohexyl and the like.

  Preferred alkenyl groups are, for example, ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl and the like.

  Preferred alkynyl groups are, for example, ethynyl, propynyl, butynyl, pentynyl, hexynyl, octynyl and the like.

  Preferred alkoxy groups are, for example, methoxy, ethoxy, 2-methoxyethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, 2-methylbutoxy, n-pentoxy, n -Hexoxy, n-heptyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, n-undecyloxy, n-dodecyloxy and the like.

  Aryl and heteroaryl groups can be monocyclic or polycyclic, that is, they can have one ring (eg, phenyl, etc.) or two or more rings. And two or more rings may be fused (for example, naphthyl), may be linked by a covalent bond (for example, biphenyl), or a fused ring And a combination of linking rings. A heteroaryl group contains one or more heteroatoms, preferably a heteroatom selected from O, N, S and Se.

  Monocyclic, bicyclic or tricyclic aryl groups having 6 to 25 carbon atoms and monocyclic, bicyclic or tricyclic heteroaryl groups having 2 to 25 carbon atoms are particularly preferred, these being fused rings May be contained and may be substituted. Further, 5-membered, 6-membered or 7-membered aryl and heteroaryl groups are preferred, provided that one or more CH groups are nitrogen atoms, sulfur atoms so that oxygen atoms and / or sulfur atoms are not directly linked to each other. Alternatively, it may be replaced with an oxygen atom.

  Preferred aryl groups are, for example, phenyl, biphenyl, terphenyl, [1,1 ′: 3 ′, 1 ″] terphenyl-2′-yl, naphthyl, anthracene, binaphthyl, phenanthrene, pyrene, dihydropyrene, chrysene, perylene. Tetracene, pentacene, benzopyrene, fluorene, indene, indenofluorene, spirobifluorene and the like.

  Preferred heteroaryl groups are, for example, pyrrole, pyrazole, imidazole, 1,2,3-triazole, 1,2,4-triazole, tetrazole, furan, thiophene, selenophene, oxazole, isoxazole, 1,2-thiazole, 1, , 3-thiazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3 5-membered rings such as thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole; pyridine, pyridazine, pyrimidine, pyrazine, 1,3,5-triazine, 1, 2,4-triazine, 1,2,3-triazine, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2, 6-membered rings such as 3,5-tetrazine; or indole, isoindole, indolizine, indazole, benzimidazole, benzotriazole, purine, naphthaimidazole, phenanthrimidazole, pyridaimidazole, pyrazineimidazole, quinoxaline imidazole, benzoxa Sol, naphthoxazole, anthroxazole, phenanthroxazole, isoxazole, benzothiazole, benzofuran, isobenzofuran, dibenzofuran, quinoline, isoquinoline, pteridine, benzo-5,6-quinoline, benzo-6,7-quinoline, Benzo-7,8-quinoline, benzoisoquinoline, acridine, phenothiazine, phenoxazine, benzopyridazine, benzopyrimidine, quinoxaline, phenazine, naphth Condensed groups such as lysine, azacarbazole, benzocarboline, phenanthridine, phenanthroline, thieno [2,3b] thiophene, thieno [3,2b] thiophene, dithienothiophene, isobenzothiophene, dibenzothiophene, benzothiadiazothiophene; Or a combination of these groups. The heteroaryl group may also be substituted with an alkyl, alkoxy, thioalkyl, fluorine, fluoroalkyl, or additional aryl or heteroaryl group.

The aryl, heteroaryl, carbon group and hydrocarbon group may have one or more substituents, which are preferably silyl, sulfo, sulfonyl, formyl, amine, imine, nitrile, mercapto, Selected from the group comprising nitro, halogen, C _1-12 alkyl, C _6-12 aryl, C _1-12 alkoxy, hydroxyl, or combinations of these groups.

  Preferred substituents are, for example, solubility-promoting groups such as alkyl or alkoxy, electron-withdrawing groups such as fluorine, nitro or nitrile, or groups which increase the glass transition temperature (Tg) of the polymer, in particular t- Bulky groups such as butyl or optionally substituted aryl groups.

More preferred substituents are, for example, F, Cl, Br, I, —CN, —NO ₂ , —NCO, —NCS, —OCN, —SCN, —C (═O) N (R ^x ) ₂ , —C. (═O) Y ¹ , —C (═O) R ^x , —N (R ^x ) ₂ , wherein R ^x has the above-mentioned meaning, Y ¹ is halogen, 6 to 40, preferably Is optionally substituted silyl or aryl having 6 to 20 carbon atoms, and linear or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy having 1 to 25 carbon atoms Or represents alkoxycarbonyloxy, wherein one or more hydrogen atoms may be replaced by F or Cl.

Substituted silyl or aryl is preferably halogen, —CN, R ⁰ , —OR ⁰ , —CO—R ⁰ , —CO—O—R ⁰ , —O—CO—R ⁰ or —O—CO—. It may be substituted with O—R ^0, where R ⁰ is as defined above.

Further preferred substituents are, for _{example, F, Cl, CN, NO} 2, CH 3, C 2 H 5, OCH 3, OC 2 H 5, COCH 3, COC 2 H 5, COOCH 3, COOC 2 H 5, CF ₃ , OCF ₃ , OCHF ₂ , OC ₂ F ₅ , phenyl.

Preferred compounds of formula (2) contain one or more branched groups R ^a and / or R ^b and / or polyfunctional polymerizable groups containing two or more polymerizable groups P. Suitable groups of this type and polymerizable compounds containing them are described, for example, in US Pat. No. 7,060,200 or US Patent Application Publication No. 2006/0172090. Polyfunctional polymerizable groups selected from the following formulas are particularly preferred.

式中、
ａｌｋｙｌは、単結合または１〜１２個の炭素原子を有する直鎖状または分岐状のアルキレンを表し、但し、１個以上の隣接していないＣＨ_２基は、酸素原子および／または硫黄原子が互いに直接連結しないようにして、それぞれ互いに独立に、−Ｃ（Ｒ^ｘ）＝Ｃ（Ｒ^ｘ）−、−Ｃ≡Ｃ−、−Ｎ（Ｒ^ｘ）−、−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯ−Ｏ−、−Ｏ−ＣＯ−、−Ｏ−ＣＯ−Ｏ−で置き換えられていてもよく、１個以上の水素原子はＦ、ＣｌまたはＣＮで置き換えられていてもよく、ここで、Ｒ^ｘは上に定義したとおりであり、好ましくは、上に定義したとおりのＲ^０を表し、
ａａおよびｂｂは、それぞれ互いに独立に、０、１、２、３、４、５または６を表し、
Ｘは、Ｘ’に示される意味の１つを有し、
Ｐ^１〜５は、それぞれ互いに独立に、上でＰに示される意味の１つを有する。

Where
alkyl represents a single bond or a linear or branched alkylene having 1 to 12 carbon atoms, provided that one or more non-adjacent CH ₂ groups have an oxygen atom and / or a sulfur atom attached to each other. -C (R ^x ) = C (R ^x )-, -C≡C-, -N (R ^x )-, -O-, -S-, -CO, without being directly connected to each other. -, -CO-O-, -O-CO-, -O-CO-O-, and one or more hydrogen atoms may be replaced by F, Cl or CN, where Wherein R ^x is as defined above, preferably represents R ⁰ as defined above,
aa and bb each independently represent 0, 1, 2, 3, 4, 5 or 6;
X has one of the meanings indicated for X ′;
P ^1-5 each independently of one another have one of the meanings indicated above for P.

  Polymerizable compounds are known to those skilled in the art and are described, for example, in the organic chemistry of the City of Stuttgart, such as the Hobben-Weyl ed. It is prepared according to the method. Synthesis of polymerizable acrylates and methacrylates of formula I can be carried out according to the methods described in US Pat. No. 5,723,066. Specific examples are described in the examples.

In the simplest case, it is represented by the general formula HO-LW- (M-Z) _i -N-OH, where L, M, N, W, Z and i are as defined above. Commercially available diols such as 1- (3-hydroxyphenyl) phenyl-3-ol and the like, corresponding acid, acid derivatives, or halogenated compounds containing the group P, such as (meth) acryloyl chloride or (meth) ) Synthesis is performed by esterification or etherification using acrylic acid or the like in the presence of a dehydrating agent such as DCC (dicyclohexylcarbodiimide).

  One more specific example of the second component compound is divinylbenzene.

で表されるが、本発明においてはいずれか一方又は両方の混合物を用いることができる。 Divinylbenzene is represented by the following formula (3):

In the present invention, either one or a mixture of both can be used.

で表されるアクリル酸誘導体である。 Another specific example of the more preferable second component compound is the following formula (4):

It is an acrylic acid derivative represented by.

（式（１）中、Ｒ_１，Ｒ_２、Ｘ、Ｙは上に定義したとおりである。）
で表わされるシクロヘキサン化合物群の少なくとも１種類の化合物を含有し、
第二成分として、下記式（２）：

（式（２）中、Ａ、Ｂ、Ｌ、Ｍ、Ｎ、Ｗ、Ｚ、ｉ、ｊ、ｋは上に定義したとおりである。）
を含有する液晶組成物である。 3. Application Example As described above, the present invention has the following formula (1) as the first component.

(In formula (1), R ₁ , R ₂ , X and Y are as defined above.)
Containing at least one compound of the cyclohexane compound group represented by:
As the second component, the following formula (2):

(In formula (2), A, B, L, M, N, W, Z, i, j, and k are as defined above.)
Is a liquid crystal composition containing

  The liquid crystal composition according to the present invention preferably comprises less than 5%, more preferably less than 3%, particularly preferably less than 2% of the second component compound.

  The liquid crystal composition according to the present invention is suitable for electro-optical applications. In particular, it is suitable for use in PSA (polymer sustained alignment) type liquid crystal (LC) displays. The liquid crystal composition according to the present invention can be sealed in a liquid crystal cell to form an electro-optic display element.

Hereinafter, the present invention will be described in more detail with reference to examples and the like, but the present invention is not limited by the following examples and the like.
The percentage is weight percent. All temperatures are given in degrees Celsius. The NI temperature represents a nematic phase isotropic phase transition temperature, and Δn represents optical anisotropy (589 nm, 25 ° C.). Δn was determined by extrapolation after measurement using a liquid crystal composition obtained by adding 10% of the compound of the present invention to the mother liquid crystal D shown below.

Synthesis example 1
Of the compound group represented by the formula (1-4), the method for synthesizing the compound (1-4-1) shown below is as follows.
2-chloro-5-ethylhexanone and 4-npropylcyclohexylmagnesium chloride are reacted in diethyl ether or THF solvent in the presence of zinc chloride and copper (II) acetylacetonate, and subjected to ordinary treatment to give compound 1- 4-1.
Δn = 0.059 m / z = 250

  The compounds of formulas (1-4-2) to (1-4-4) shown below are synthesized in the same manner as the compounds of formula (1-4-1).

Synthesis example 2
The method for synthesizing the compound of formula (1-1-1) shown below is as follows.
2.12 g of the compound of formula (1-4-1) and 0.8 g of NaBH ₄ were added to 12 ml of isopropanol, and heated under reflux for 32 hours. Then, toluene extraction was carried out, and a compound of the formula (1-5-1) shown below was obtained by silica gel column treatment (heptane / ethyl acetate = 5/1).
0.82 g of the compound of the formula (1-5-1) was dissolved in 8 ml of dichloromethane, 0.56 g of DAST was added at 4 ° C., and then stirred at room temperature for 28 hours. The reaction mixture was poured into ice water and extracted with dichloromethane. Silica gel column treatment (heptane 100%) and Kugelrohr distillation were performed to obtain 0.3 g of the target compound of the formula (1-1-1).
Δn = 0.067 m / z = 254

  The compounds of the following formulas (1-5-2) to (1-5-3) are synthesized in the same manner as the compound of the following formula (1-5-1).

  The compounds of formulas (1-1-2) to (1-1-10) are also synthesized in the same manner as the compound of (1-1-1).

Synthesis example 3
A method for synthesizing the compound of the formula (1-2-1) represented by the following formula is as follows.
In 8 ml of dichloromethane, 0.5 g of the compound of the formula (1-4-1) was dissolved, and 0.5 g of DAST was added at 4 ° C. Thereafter, the mixture was stirred at room temperature for 38 hours. Thereafter, the same treatment as in Synthesis Example 2 was performed to obtain 0.2 g of the compound of formula (1-2-1).
Δn = 0.062 m / z = 272

  Compounds of formula (1-2-2) to (1-2-9) are synthesized in the same manner as the compound of formula (1-2-1).

Synthesis example 4
A method for synthesizing the compound of the formula (1-3-1) shown below is as follows.
The compound of the formula (1-3-1) is synthesized by the following known synthesis method.

In 10 ml of carbon tetrachloride (CCl ₄ ), 0.8 g of the compound of the formula (1-5-2) and 2.0 g of TPP (triphenylphosphine) were dissolved and heated under reflux for 25 hours. The generated triphenylphosphine oxide is filtered and washed with heptane, and then subjected to normal treatment, followed by silica gel column treatment (heptane 100%) to obtain 0.2 g of the compound of formula (1-3-1). It was.
m / z = 312

  Compounds of formula (1-3-2) to (1-3-4) are also synthesized in the same manner as the compound of formula (1-3-1).

で表される化合物を調製した。
下記式（５）で表される化合物２５％と、式（６）の化合物群である下記式：

（式中、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５、Ｒ^１６およびＲ^１７は、それぞれ独立に炭素原子数２〜５個の飽和アルキル基である。）で表される化合物群の等重量混合物７５％とを混合して、第一成分（母液晶）を調製した。 Example 1
According to the method described in Synthesis Example 3, the following formula (5):

The compound represented by these was prepared.
25% of the compound represented by the following formula (5) and the following formula which is a compound group of the formula (6)

(Wherein R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are each independently a saturated alkyl group having 2 to 5 carbon atoms). The first component (mother liquid crystal) was prepared by mixing 75% of the same weight mixture.

で表されるアクリル酸誘導体（以下、ＲＭ−００５という）を用意した。 Divinylbenzene as the second component A, and the following formula (4) as the second component B:

An acrylic acid derivative represented by (hereinafter referred to as RM-005) was prepared.

  Divinyl benzene manufactured by Aldrich was used.

  RM-005 manufactured by LCC was used as the compound of the formula (4).

  A liquid crystal composition 2 containing 98% of the mother liquid crystal and 2% divinylbenzene and a liquid crystal composition 3 containing 98% of the mother liquid crystal and 2% RM-005 were prepared. A rectangular wave was applied at a voltage of 10 V, and the time for changing to a 50% transmitted light amount when the voltage was off was measured as a response speed. The results are shown in Table 1. As a control, the same measurement was performed for the liquid crystal composition 1 containing only the first component (mother liquid crystal), and the results are also shown in Table 1.

注：
第二成分Ａ： ジビニルベンゼン
第二成分Ｂ：

ＲＭ−００５
第一成分（母液晶）：

３ＨＦＦＨ３ ２５％
その他 ７５％
の混合物（ＮＩ： ８７ ℃ Δｎ： ０．０８ Δε：−５．５０）

note:
Second component A: Divinylbenzene second component B:

RM-005
First component (mother liquid crystal):

3HFFH3 25%
Other 75%
(NI: 87 ° C. Δn: 0.08 Δε: −5.50)

  As shown in Table 1, according to the present invention, a liquid crystal composition having improved response speed can be obtained.

  There is a demand for further improvement in response speed such as high-definition TV and 3D display in recent years, but the present invention is a liquid crystal composition that can meet such a demand, and future demand is expected.

Claims (1)

As the first component, the following formula (1)

(In Formula (1), R ₁ and R ₂ are the same or different and each represents R, ROCO, or RCOO, and R represents an alkyl group, an alkenyl group, or an alkynyl group. The alkyl group, alkenyl group, or alkynyl group. May be substituted by a halogen atom or a cyano group, and a part of the CH ₂ group in the alkyl group, alkenyl group or alkynyl group may be substituted by —O—, —CO— or —COO—. X and Y each independently represent a halogen atom or a hydrogen atom, and at the same time do not represent a hydrogen atom, or X represents an oxygen atom, and Y represents a direct bond to the oxygen atom.
Containing at least one compound of the cyclohexane compound group represented by:
As the second component, the following formula (2):

(In the formula (2), A and B are the same or different, P-Q-, H, _halogen, SF 5, NO _2, represents a carbon group or hydrocarbon group, provided that at least one of A and B P-Q-
P represents a polymerizable group,
Q represents a spacer group or a single bond,
i L and k N are the same or different and are 1,3-phenylene, 1,4-phenylene, naphthalene-1,3-diyl, naphthalene-1,6-diyl, naphthalene-2,5. -Diyl or naphthalene-2,7-diyl (where one or more CH groups in these groups may be replaced by nitrogen atoms), cyclohexane-1,3-diyl (but one or more adjacent groups) The non-CH ₂ group may be replaced by an oxygen atom and / or a sulfur atom), 1,3-cyclohexenylene, piperidine-2,4-diyl, piperidine-2,6-diyl, decahydronaphthalene -2,7-diyl, 1,2,3,4-tetrahydronaphthalene-2,7-diyl or indan-2,4-diyl, all of which are May be substituted or monosubstituted or polysubstituted by T, provided that when i = k = 1, one of the groups L and N may also have one of the meanings indicated for M;
j Ms are the same or different and are each 1,3-phenylene, 1,4-phenylene, naphthalene-1,4-diyl or naphthalene-2,6-diyl (provided that one or more of these groups are CH group may be replaced by a nitrogen atom), cyclohexane-1,4-diyl (provided that one or more non-adjacent CH ₂ groups may be replaced by an oxygen atom and / or a sulfur atom) ), 1,4-cyclohexenylene, bicyclo [1.1.1] pentane-1,3-diyl, bicyclo [2.2.2] octane-1,4-diyl, spiro [3.3] heptane- 2,6-diyl, piperidine-2,5-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, indane-2,5-dii Represents thiophene-2,5-diyl, fluorene-2,7-diyl or octahydro-4,7-methanoindan-2,5-diyl, although all these groups are unsubstituted, May be mono- or poly-substituted and may have one of the meanings indicated for L;
T represents PQ-, H, OH, halogen, SF ₅ , NO ₂ , a carbon group or a hydrocarbon group,
i W and j Z are the same or different and are each -O-, -S-, -CO-, -CO-O-, -OCO-, -O-CO-O-, -OCH _{2 -, - CH 2 O -,} - SCH 2 -, - CH 2 S -, - CF 2 O -, - OCF 2 -, - CF 2 S -, - SCF 2 -, - (CH 2) n -, - CF ₂ CH ₂ —, —CH ₂ CF ₂ —, — (CF ₂ ) _n —, —CH═CH—, —CF═CF—, —C≡C—, —CH═CH—COO—, —OCO—. Represents CH═CH—, —CUV or a single bond,
U and V each independently of one another represent H or alkyl having 1 to 12 carbon atoms;
i and k each independently represent 0 or 1, provided that i + k>0;
j represents 0, 1, 2 or 3;
n represents 1, 2, 3 or 4. )
A liquid crystal composition comprising: