JP2015025130A - Polymerizable compounds and use thereof in liquid crystal displays - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide polymerizable compounds and use thereof in liquid crystal displays.SOLUTION: The present invention relates to polymerizable compounds, to processes and intermediates for the preparation thereof, and to the use thereof for optical, electro-optical and electronic purposes, in particular in liquid-crystal (LC) media and LC displays, especially in LC displays of the PS (polymer sustained) or PSA (polymer sustained alignment) type.

Description

  The present invention is for optical, electro-optical and electronic purposes, in particular in liquid-crystal (LC) media and LC displays, in particular PS (polymer-stained) or PSA (polymer-stained). The present invention relates to polymerizable compounds, methods and intermediates for their preparation, and their use in LC displays of the type alignment.

  Currently used liquid crystal displays (LC displays) are usually of the TN (“twisted nematic”) type. However, these have the disadvantage that the viewing angle dependence of contrast is strong. In addition, so-called VA ("vertical alignment") displays with a wider viewing angle are known. The LC cell of a VA display contains an LC media layer between two transparent electrodes, where typically the LC media has a negative value of dielectric (DC) anisotropy. With the switch off, the LC layer molecules are oriented perpendicular to the electrode surface (homeotropic) or have a tilted homeotropic orientation. When a voltage is applied to the two electrodes, reorientation of LC molecules parallel to the electrode surface occurs.

  Furthermore, an OCB (Optically Compensated Bend) display is known, which is based on the birefringence effect and has a so-called “bend” orientation and usually a positive (DC) anisotropic LC layer. It has been. When a voltage is applied, LC molecules reorientate perpendicular to the electrode surface. In addition, OCB displays typically contain one or more birefringent optical retardation films to prevent undesirable transparency of the bend cell to light in the dark state. OCB displays have a wider viewing angle and shorter response times compared to TN displays.

  Also, an LC layer is contained between two substrates, two electrodes are disposed on only one of the two substrates, and the two electrodes are preferably an intermesh type so-called IPS having a comb structure. ("In-plane switching": in-plane switching) displays are also known. When a voltage is applied to the electrodes, it creates an electric field between the electrodes that has a significant component parallel to the LC layer. For this reason, reorientation of LC molecules occurs in the layer plane.

  Furthermore, so-called FFS (“fringe-field switching”) displays have been proposed (in particular SH Jun et al., Jpn. J. Appl. Phys., 43, 3, 2004, See page 1028; Non-Patent Document 1), the display also contains two electrodes on the same substrate, but in contrast to an IPS display, only one of these has been structured in a comb-like fashion. The shape of the electrode, the other electrode is not structured. Thereby, a strong so-called “fringe field” is generated, ie a strong electric field in the vicinity of the electrode ends and an electric field having both strong vertical and strong horizontal components throughout the cell. Both IPS displays and FFS displays have a low viewing angle dependence with low contrast.

  In more recent types of VA displays, the uniform orientation of LC molecules is limited to multiple relatively small domains within the LC cell. There may be disclination between these domains, also known as tilt domains. Compared to conventional VA displays, VA displays with tilt domains have greater contrast and half-tone viewing angle independence. In addition, the manufacture of this type of display is simpler since no additional treatment of the electrode surface for uniform alignment of the molecules in the switched-on state, for example rubbing, is necessary anymore. Instead, the preferential direction of the tilt or pretilt angle is controlled by the special design of the electrode.

  In so-called MVA (“multidomain vertical alignment”) displays, this is usually achieved by an electrode with protrusions, resulting in a local pretilt. As a result, upon application of a voltage, LC molecules are oriented in different directions parallel to the electrode surface and in differently defined regions in the cell. Thereby, “controlled” switching is achieved and the formation of interfering disclination lines is prevented. This orientation improves the viewing angle of the display, however, it results in reduced transparency to light.

  For further development of MVA, protrusions on only one electrode side are used, while the opposite electrode has a slit, improving the transparency to light. When a voltage is applied, the slotted electrode creates an inhomogeneous electric field in the LC cell, meaning that controlled switching is further achieved. In order to further improve the transparency to light, the distance between the slit and the protrusion can be increased, but this results in a longer response time.

  In so-called PVA (patterned VA), protrusions are completely unnecessary, and both electrodes are structured by slits on opposite sides, resulting in increased contrast and improved transparency to light. However, it is technically difficult and the display becomes more sensitive to mechanical influences (tapping etc.). However, in many applications, such as monitors and especially television screens, there is a need to reduce display response time and improve contrast and brightness (transparency).

  Further developments are so-called PS (polymer sustained) or PSA (polymer sustained alignment) displays, for which often the term “polymer stabilization” is also used. In these displays, a small amount (eg, 0.3% by weight, typically less than 1% by weight) of one or more polymerizable compounds (one or many) is added to the LC medium and placed in the LC cell. After the introduction, it is polymerized or crosslinked in situ, usually by UV photopolymerization, with or without voltage applied between the electrodes. The addition of polymerizable mesogens or liquid crystal compounds, also known as reactive mesogens or “RM” (reactive mesogens), to LC mixtures has proven particularly suitable.

  Unless otherwise indicated, the term “PSA” is used below to represent PS displays and PSA displays.

  For the time being, the principle of PS (A) is used in various classic LC displays. Thus, for example, PSA-VA, PSA-OCB, PSA-IPS, PSA-FFS and PSA-TN displays are known. Preferably, in the case of PSA-VA and PSA-OCB displays, a voltage is applied, and in the case of a PSA-IPS display, a polymerizable compound (one type or multiple types) is polymerized with or without application of a voltage. . As shown in the test cell, the PS (A) method results in a pretilt in the cell. In the case of PSA-OCB displays, it is possible to stabilize the bend structure, for example, so that the offset voltage is unnecessary or can be reduced. For PSA-VA displays, pretilt has a positive effect on response time. For PSA-VA displays, standard MVA or PVA pixel and electrode layouts can be used. In addition, however, it is possible, for example, to operate with only one side of the electrode structured and without protrusions, which greatly simplifies the manufacture and at the same time results in a very good contrast and at the same time transparent to light. The properties are very good.

  In addition, so-called positive VA displays have proven to be a particularly preferred embodiment. In this case, the initial alignment of the liquid crystal in the initial state with no voltage applied is homeotropic, ie essentially perpendicular to the substrate, just as in the case of a classic VA display. However, in contrast to classic VA displays, positive VA displays use dielectrically positive LC media. By applying a voltage to the comb electrodes that generate an electric field essentially parallel to the layer of LC media, the LC molecules are converted to an orientation essentially parallel to the substrate. This type of comb-like electrode is also usually used in an IPS display. Corresponding polymer stabilization (PSA) has also proven to be advantageous for positive VA displays, and a significant reduction in response time can be achieved.

  PSA-VA displays are disclosed in, for example, Japanese Patent Application Laid-Open No. 10-036847 (Patent Document 1), European Patent Application Publication No. 1 170 626 (Patent Document 2), US Pat. No. 6,861,107 (Patent Document 1). Document 3), US Patent No. 7,169,449 (Patent Document 4), US Patent Application Publication No. 2004/0191428 (Patent Document 5), US Patent Application Publication No. 2006/0066793 (Patent Document) 6) and US Patent Application Publication No. 2006/0103804 (Patent Document 7). The PSA-OCB display is, for example, T.I. -J-Chen et al., Jpn. J. et al. Appl. Phys. 45, 2006, pages 2702-2704 (Non-Patent Document 2) and S.A. H. Kim, L.M. -C-Chien, Jpn. J. et al. Appl. Phys. 43, 2004, pages 7463-7647 (Non-patent Document 3). PSA-IPS displays are described in, for example, US Pat. No. 6,177,972 (Patent Document 8) and Appl. Phys. Lett. 1999, 75 (21), 3264 (Non-patent Document 4). The PSA-TN display is described in, for example, Optics Express 2004, Vol. 12 (7), page 1221 (Non-patent Document 5).

  Similar to the conventional LC display described above, the PSA display can operate as an active matrix or passive matrix display. In the case of active matrix displays, individual pixels are typically addressed by integrated nonlinear active elements such as transistors (eg, thin-film transistors (“TFTs”)), while in the case of passive matrix displays The pixels are usually addressed by the multiplex method, although both methods are known from the prior art.

  There is also a continuing need to optimize not only the response time of LC displays, but also the contrast and brightness (and therefore transparency), especially for monitors and especially for television applications. Here, the PSA method can provide significant advantages. Especially for PSA-VA, PSA-IPS, PSA-FFS and PSA-positive VA displays, the response time is reduced in relation to the pretilt measurable in the test cell without significantly affecting other parameters. Can be achieved.

  In the prior art, for example, polymerizable compounds of the following formula are used.

式中、例えば、米国特許第７，１６９，４４９号明細書（特許文献９）に記載される通り、Ｐは重合性基、通常、アクリレートまたはメタクリレート基を表す。

In the formula, for example, as described in US Pat. No. 7,169,449 (Patent Document 9), P represents a polymerizable group, usually an acrylate or methacrylate group.

  However, for example, an inappropriate tilt is formed, or no tilt is formed, or, for example, a so-called “voltage holding ratio” (VHR or HR) is inappropriate for TFT display applications. This raises the problem that not all combinations of LC mixture (also referred to below as “LC host mixture”) + polymerizable component (typically RM) are suitable for PSA displays. In addition, it has been found that LC mixtures and RMs known from the prior art still have several disadvantages when used in PSA displays. Thus, not all known RMs that are soluble in the LC mixture are suitable for use in PSA displays. In addition, in addition to direct measurement of pretilt in PSA displays, it is often difficult to find an appropriate selection requirement for RM. If it is desirable to polymerize with UV light without the addition of a photoinitiator (this may be advantageous for certain applications), the scope for selection of an appropriate RM is even narrower.

  In addition, the selected combination of LC host mixture / RM must have the lowest possible rotational viscosity and the best possible electrical properties. In particular, the selected combination must have the highest possible VHR. In PSA displays, UV exposure is an integral part of the display manufacturing process, but it also occurs as a normal exposure during the operation of the display after the end of production, so it is high after UV light irradiation. VHR is particularly necessary.

  For PSA displays that produce particularly small pretilt angles, it would be particularly desirable to have new materials available. Preferred materials here produce a lower pretilt angle than the known materials to date and / or can be achieved with known materials upon polymerization at the same exposure time A (higher) pretilt angle can already be achieved after a shorter exposure time. Therefore, the manufacturing time (tact time) of the display can be shortened, and the cost of the manufacturing process can be reduced.

  A further problem in the manufacture of PSA displays is the presence or removal of residual amounts of unpolymerized RM, especially after the polymerization step to create a pretilt angle in the display. For example, this type of unreacted RM can adversely affect display characteristics, for example, by polymerizing in an uncontrolled manner during post-production operation of the display.

  Thus, PSA displays known from the prior art often exhibit the undesired effect of so-called "image sticking" or "image focus", i.e. generated in the LC display by the temporary address of the individual pixels. The image still remains visible even after the electric field in these pixels is switched off or even after other pixels are addressed.

  On the other hand, this “image sticking” can occur when using LC host mixtures with low VHR. Daylight or the UV component of the backlight can cause undesirable decomposition reactions of LC molecules in situ, thus initiating the generation of ionic or free radical impurities. These may in particular accumulate in the electrode or the alignment layer, where the effective applied voltage is reduced by the impurities. This effect can also be observed in conventional LC displays that do not have a polymer component.

  In addition, the effect of additional “image sticking” caused by the presence of unpolymerized RM is often observed in PSA displays. Here, uncontrolled polymerization of the remaining RM is initiated by UV light or backlight from the environment. For this reason, in the display area where the switch is turned on, the tilt angle changes after a number of address cycles. As a result, a change in transmittance may occur in the area where the switch is turned on, while the transmittance remains unchanged in the area where the switch is not turned on.

  Therefore, it is desirable when producing PSA displays that the polymerization of RM proceeds as completely as possible and that the presence of unpolymerized RM in the display is eliminated as much as possible and reduced to a minimum. For this purpose, a material capable of complete polymerization with high efficiency is required. In addition, residual amounts of these controlled reactions may be desired. This would be more convenient if the RM polymerizes faster and more efficiently than known materials to date.

  Thus, VA and OCB type PSA displays, which exhibit the above disadvantages or only to a minor extent and have improved properties, and LC media and polymerizable compounds for use in such displays, There is still a great demand for. In addition, it has advantageous properties, in particular a high resistivity and a short response time even at low temperatures in a wide operating temperature range, and a low threshold voltage, a low pretilt angle, a large number of halftones, a high contrast and a wide field of view. Enables corners, high values of “voltage holding ratio” (VHR) and low temperature stability (also known as “LTS”), ie individual components are spontaneous after UV exposure There is a tremendous demand for PSA displays that have the stability of LC mixtures against crystallization and precipitation and materials for use in PSA displays.

  The present invention does not have the disadvantages indicated above, or only to a reduced extent, and allows for the rapid and complete polymerization as possible and the establishment of a low pretilt angle as soon as possible. Reducing or preventing the occurrence of “image sticking” in the display, preferably at the same time enabling a very high resistivity value, a low threshold voltage and a short response time and suitable for use in PSA displays, in particular Based on the objective of providing RMs and LC media containing them.

  It is a further object of the present invention to provide novel RMs and methods and intermediates suitable for their preparation, especially for optical, electro-optical and electronic applications.

  In particular, the present invention provides a polymerizable compound that produces a greater maximum pretilt after photopolymerization and, as a result, achieves the desired pretilt more quickly, thus significantly reducing the time in the manufacture of LC displays. Based on

  This object has been achieved according to the present invention by providing materials, methods and LC displays as described in this application. In particular, surprisingly, a PSA display containing one or more polymerized compounds according to the invention is provided, or one or more polymerizable compounds according to the invention are used to produce this type of PSA display. It has been found that some or all of the above objectives can be achieved by using an LC medium containing.

  The use of this type of polymerizable compound in LC media and PSA displays according to the present invention results in a particularly rapid achievement of the desired pretilt and a significant reduction in display manufacturing time. This was shown for LC media by measuring the exposure time dependence of pretilt in a VA tilt measurement cell. In particular, it was possible to achieve pretilt without adding a photoinitiator.

  In addition, in the PSA display, the polymerizable compound according to the present invention exhibits a significantly higher polymerization rate, so that a smaller amount of unreacted material remains in the cell, and the electro-optical characteristics of the cell are improved. The amount of these controlled reactions is more convenient.

  Japanese Patent Application Laid-Open No. 2000-281629 (Patent Document 10) describes a rod-shaped polymerizable compound of the following formula and a cholesteric polymer film produced therefrom and used as a reflective polarizer.

国際特許出願公開第２００８／１２１５８５号パンフレット（特許文献１１）には、コンペンセーションフィルムにおいて使用するためのモノマーとして以下の式の１−ビニルピレンが記載されている。

International Patent Application Publication No. 2008/121585 (Patent Document 11) describes 1-vinylpyrene having the following formula as a monomer for use in a compensation film.

しかしながら、ＰＳＡディスプレイにおいてプレチルト角を生成するために、そのような化合物を使用することは、特開２０００−２８１６２９号公報（特許文献１０）または国際特許出願公開第２００８／１２１５８５号パンフレット（特許文献１１）に記載されておらず、自明でもない。

However, the use of such a compound to generate a pretilt angle in a PSA display is disclosed in JP 2000-281629 (Patent Document 10) or International Patent Application Publication No. 2008/121585 (Patent Document 11). ) And not self-explanatory.

Japanese Patent Laid-Open No. 10-036847 European Patent Application Publication No. 1 170 626 US Pat. No. 6,861,107 US Pat. No. 7,169,449 US Patent Application Publication No. 2004/0191428 US Patent Application Publication No. 2006/0066793 US Patent Application Publication No. 2006/0103804 US Pat. No. 6,177,972 US Pat. No. 7,169,449 JP 2000-281629 A International Patent Application Publication No. 2008/121585 Pamphlet

S. H. Jung et al., Jpn. J. et al. Appl. Phys. 43, No. 3, 2004, page 1028 T. T. et al. -J-Chen et al., Jpn. J. et al. Appl. Phys. 45, 2006, 2702-2704 S. H. Kim, L.M. -C-Chien, Jpn. J. et al. Appl. Phys. 43, 2004, p. 7643-7647. Appl. Phys. Lett. 1999, 75 (21), 3264 Optics Express 2004, 12 (7), 1221

  Also, the use of the polymerizable compounds according to the present invention in PSA displays to polymerize in situ in an electric field and quickly establish a tilt angle is not described in the prior art and is not obvious.

  In addition, quite surprisingly, the polymerizable compounds according to the present invention, when used in PSA displays, produce significantly faster tilt angles and faster and more complete polymerization than polymerizable compounds known from the prior art. It was found to show. This was confirmed by direct comparison experiments. This result is not described in the prior art and is not obvious.

  Thus, the present invention relates to compounds of formula I (also below “polymerization according to the invention”) in liquid crystal (LC) media and LC displays of the PS or PSA (polymer-sustained alignment) type. Also referred to as a “chemical compound”).

式中、個々の基は以下の意味を有する：
Ｗ^１、Ｗ^２は、それぞれ互いに独立に、−ＣＹ_２ＣＹ_２−、−ＣＹ＝ＣＹ−、−ＣＹ_２−Ｏ−、−Ｏ−ＣＹ_２−、−Ｃ（Ｏ）−Ｏ−、−Ｏ−Ｃ（Ｏ）−、−Ｃ（Ｒ^ｃＲ^ｄ）−、−Ｏ−、−Ｓ−、−ＮＲ^ｅ−を表し、
Ｙは、それぞれの出現において同一または異なって、ＨまたはＦを表し、
Ｒ^ａ、Ｒ^ｂは、それぞれ互いに独立に、Ｐ−Ｓｐ−、Ｈ、Ｆ、Ｃｌ、Ｂｒ、Ｉ、−ＣＮ、−ＮＯ_２、−ＮＣＯ、−ＮＣＳ、−ＯＣＮ、−ＳＣＮ、ＳＦ_５、直鎖状または分岐状で１〜２５個のＣ原子を有するアルキル（ただし加えて、１個以上の隣接していないＣＨ_２基は、それぞれ互いに独立に、Ｏおよび／またはＳ原子が互いに直接連結しないようにして、アリーレン、−Ｃ（Ｒ^０）＝Ｃ（Ｒ^００）−、−Ｃ≡Ｃ−、−Ｎ（Ｒ^０）−、−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯ−Ｏ−、−Ｏ−ＣＯ−、−Ｏ−ＣＯ−Ｏ−で置き換えられていてもよく、ただし加えて、１個以上のＨ原子は、Ｆ、Ｃｌ、Ｂｒ、Ｉ、ＣＮまたはＰ−Ｓｐ−で置き換えられていてもよい。）、または、好ましくは、２〜２５個のＣ原子を有するアリールまたはヘテロアリール（該基は、また、２個以上の縮合環を含有していてもよく、該基は、Ｌで一置換または多置換されていてもよい。）を表し、
ただし、基Ｒ^ａおよびＲ^ｂの少なくとも一方は、基Ｐ−Ｓｐ−を表すか含有し、
Ｒ^ｃ、Ｒ^ｄ、Ｒ^ｅは、それぞれ互いに独立に、Ｈ、または、直鎖状または分岐状で１〜１２個のＣ原子を有するアルキルを表し、
Ｐは、それぞれの出現において同一または異なって、重合性基を表し、
Ｓｐは、それぞれの出現において同一または異なって、スペーサー基または単結合を表し、
Ａ^１、Ａ^２は、それぞれ互いに独立に、好ましくは、４〜２５個のＣ原子を有する芳香族、ヘテロ芳香族、脂環式またはヘテロ環式基を表し、該基は、また、縮合環を含有していてもよく、該基は、Ｌで一置換または多置換されていてもよく、
Ｌは、それぞれの出現において同一または異なって、Ｐ−Ｓｐ−、ＯＨ、ＣＨ_２ＯＨ、ハロゲン、−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、置換されていてもよいシリル、または、置換されていてもよい炭素基または炭化水素基を表し、
Ｒ^ｘは、Ｐ−Ｓｐ、Ｈ、ハロゲン、直鎖状、分岐状または環状で、１〜２５個、好ましくは、１〜１２個のＣ原子を有するアルキルを表し、ただし加えて、１個以上の隣接していないＣＨ_２基は、Ｏおよび／またはＳ原子が互いに直接連結しないようにして、−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯ−Ｏ−、−Ｏ−ＣＯ−、−Ｏ−ＣＯ−Ｏ−で置き換えられていてもよく、ただし加えて、１個以上のＨ原子は、Ｆ、ＣｌまたはＰ−Ｓｐ−で置き換えられていてもよく、
Ｙ^１は、ハロゲンを表し、
Ｚ^１、Ｚ^２は、それぞれ互いに独立に、−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−、−ＣＨ＝ＣＦ−、−ＣＦ＝ＣＨ−、−Ｃ≡Ｃ−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−ＣＨ_２−ＣＨ_２−ＣＯＯ−、−ＯＣＯ−ＣＨ_２−ＣＨ_２−、−Ｃ（Ｒ^０Ｒ^００）−、−Ｃ（Ｒ^ｙＲ^ｚ）−または単結合を表し、
Ｒ^０、Ｒ^００は、それぞれ互いに独立に、それぞれの出現において同一または異なって、Ｈ、または、１〜１２個のＣ原子を有するアルキルを表し、
Ｒ^ｙ、Ｒ^ｚは、それぞれ互いに独立に、Ｈ、Ｆ、ＣＨ_３またはＣＦ_３を表し、
ｎは、それぞれの出現において同一または異なって、１、２、３または４を表し、
ｐ、ｑは、それぞれ互いに独立に、０、１または２を表し、
ｒは、それぞれの出現において同一または異なって、０、１または２を表す。

In the formula, the individual groups have the following meanings:
W ¹ and W ² are each independently of each other, —CY ₂ CY ₂ —, —CY═CY—, —CY ₂ —O—, —O—CY ₂ —, —C (O) —O—, —O. ^{-C (O) -, - C} (R c R d) -, - O -, - S -, - NR e - represent,
Y is the same or different at each occurrence and represents H or F;
R ^a and R ^b are independently of each other P-Sp-, H, F, Cl, Br, I, -CN, -NO ₂ , -NCO, -NCS, -OCN, -SCN, SF ₅ , direct Chain or branched alkyl having 1 to 25 C atoms (in addition, one or more non-adjacent CH ₂ groups are each independently of each other, O and / or S atoms are not directly linked to each other) Thus, arylene, —C (R ⁰ ) = C (R ⁰⁰ ) —, —C≡C—, —N (R ⁰ ) —, —O—, —S—, —CO—, —CO—O -, -O-CO-, -O-CO-O- may be substituted, but in addition one or more H atoms may be F, Cl, Br, I, CN or P-Sp-. Optionally substituted aryl) having 2 to 25 C atoms or Heteroaryl (said group, also may contain two or more fused rings, said group may be mono- or polysubstituted by L.) Represent,
Provided that at least one of the groups R ^a and R ^b represents or contains the group P-Sp-
R ^c , R ^d and R ^e each independently represent H or a linear or branched alkyl having 1 to 12 C atoms,
P is the same or different at each occurrence and represents a polymerizable group;
Sp is the same or different at each occurrence and represents a spacer group or a single bond,
A ¹ and A ² each independently represent an aromatic, heteroaromatic, alicyclic or heterocyclic group having preferably 4 to 25 C atoms, which group is also a fused ring The group may be mono- or polysubstituted with L,
L is the same or different at each occurrence, and P—Sp—, OH, CH ₂ OH, halogen, —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, or optionally substituted carbon group Or a hydrocarbon group,
R ^x represents P-Sp, H, halogen, linear, branched or cyclic and represents an alkyl having 1 to 25, preferably 1 to 12, C atoms, in addition, one or more Non-adjacent CH ₂ groups can be defined as —O—, —S—, —CO—, —CO—O—, —O—CO—, —, such that the O and / or S atoms are not directly linked to each other. May be replaced by O-CO-O-, but in addition, one or more H atoms may be replaced by F, Cl or P-Sp-
Y ¹ represents halogen,
Z ¹ and Z ² are each independently of each other —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—, —CH═CF—, —CF═CH—, —C≡C—, —CH═CH _{-COO -, - OCO-CH =} CH -, - CH 2 -CH 2 -COO -, - OCO-CH 2 -CH 2 -, - C (R 0 R 00) -, - C (R y R z) -Or a single bond,
R ⁰ and R ⁰⁰ are each independently of each other, the same or different at each occurrence, H or alkyl having 1 to 12 C atoms,
R ^y and R ^z each independently represent H, F, CH ₃ or CF ₃ ;
n is the same or different at each occurrence and represents 1, 2, 3 or 4;
p and q each independently represent 0, 1 or 2,
r is the same or different at each occurrence and represents 0, 1 or 2.

  The invention further relates to an LC medium comprising one or more compounds of formula I and one or more additional compounds which may be mesogenic, liquid crystalline and / or polymerizable.

  The invention further relates to an LC medium comprising a polymer obtainable by polymerizing one or more compounds of the formula I with mesogens, liquid crystals and / or one or more additional compounds which may be polymerizable.

The present invention further provides:
A polymerizable component A) comprising one or more compounds of formula I, and one or more, preferably two or more low molecular weight (monomeric and non-polymerizable) compounds as described above and below And a liquid crystal component B) which is also referred to below as “LC host mixture”.

  The present invention further provides a method of preparing an LC medium as described above and below, wherein one or more low molecular weight liquid crystal compounds or LC host mixtures as described above and below are represented by the formula I To one or more compounds and a further liquid crystal compound and / or additive as an optional component.

  The present invention is further preferably for generating a tilt angle in an LC medium by in situ polymerization of a compound of formula I (one or more) in a PSA display while applying an electric or magnetic field. It relates to the use of compounds of formula I according to the invention and LC media in PS, PSA displays, in particular in PS and PSA displays containing LC media.

  The invention further comprises LC displays, in particular PS or PSA displays, in particular PSA-VA, PSA-OCB, PSA-IPS, PSA containing one or more compounds of formula I according to the invention or LC media. -For FFS, PSA-VA or PSA-positive TN displays.

  The present invention further includes two substrates and two electrodes (provided that at least one substrate is transparent to light and at least one substrate has one or two electrodes), and a substrate. LC medium layer comprising a polymerized component and a low molecular weight component disposed in between (wherein the polymerized component comprises one or more polymerizable compounds, preferably in the LC medium between the substrates of the LC cell, For at least one polymerizable compound, wherein the at least one polymerizable compound is a compound of formula I). .

  The invention further relates to a method of manufacturing an LC display as described above and below, comprising one or more low molecular weight liquid crystal compounds or LC host mixtures as described above and below, and a compound of formula I An LC medium comprising one or more compounds is introduced into an LC cell having two substrates and two electrodes as described above and below, preferably polymerizing while applying a voltage to the electrodes The present invention relates to a method for polymerizing a functional compound.

  The PS and PSA displays according to the present invention are provided on one or both of the substrates forming the LC cell and preferably have two electrodes in the form of a transparent layer. In each case, one electrode is provided on each of the two substrates, for example according to the invention, as in the PSA-VA, PSA-OCB or PSA-TN display according to the invention. As in PSA-positive VA, PSA-IPS or PSA-FFS displays, two electrodes are either provided on only one of the two substrates and the other substrate has no electrodes.

  The present invention further relates to novel compounds of formula I, methods for preparing them, and novel intermediates used or obtained in these methods.

  The following meanings apply above and below:

  The terms “tilt” and “tilt angle” relate to an orientation tilted with respect to the cell surface of the LC molecules of the LC medium in an LC display (here, preferably a PS or PSA display). In the present specification, the tilt angle represents an average angle (less than 90 °) between the molecular long axis (LC director) of the LC molecule and the surface of the flat parallel outer plate forming the LC cell. A low value of the tilt angle (i.e., far from the 90 ° angle) corresponds to a large tilt. A suitable method for measuring the tilt angle is given in the examples. Unless otherwise indicated, the angle values disclosed above and below relate to this measurement method.

  The term “mesogenic group” is known to the person skilled in the art and is described in the literature, due to its attractive and repulsive anisotropy of liquid crystals (LC) in low molecular weight or high molecular weight materials. Represents a group that essentially contributes to the generation of a phase. A compound containing a mesogenic group (mesogenic compound) itself does not necessarily have an LC phase. It is also possible for mesogenic compounds to exhibit LC 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 LC 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.

  The term “spacer group”, also referred to as “Sp” above and below, is known to the person skilled in the art and described in the literature, see, for example, 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 indicated, the term “spacer group” or “spacer” refers to a flexible group that links a mesogenic group and a polymerizable group (one or several) to each other in a polymerizable mesogenic compound above and below. Represents.

  The term “reactive mesogen” or “RM” refers to a compound containing a mesogenic group and one or more functional groups suitable for polymerization (also referred to as polymerizable group or group P).

  The terms “low molecular weight compound” and “non-polymerizable compound” are usually monomeric and functional groups suitable for polymerization under the usual conditions known to those skilled in the art, in particular the conditions used for the polymerization of RMs. Represents a compound not containing.

  The term “organic group” represents a carbon or hydrocarbon group.

  The term “carbon group” denotes a monovalent or polyvalent organic group containing at least one carbon atom, preferably 1 to 40 C atoms, provided that it contains no further atoms (eg , -C≡C-, etc.) or may contain one or more additional atoms such as N, O, S, P, Si, Se, As, Te or Ge (eg carbonyl Etc.) The term “hydrocarbon group” additionally includes one or more H atoms and, optionally, one or more heteroatoms such as N, O, S, P, Si, Se, As, Te or Ge. And a carbon group containing

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

  The carbon group or hydrocarbon group may be a saturated or unsaturated group. Unsaturated groups are, for example, aryl, alkenyl or alkynyl groups. A carbon or hydrocarbon group having more than 3 C atoms may be linear, branched and / or cyclic and may contain spiro bonds or fused rings.

  The terms “alkyl”, “aryl”, “heteroaryl” and the like also include polyvalent groups such as alkylene, arylene, heteroarylene and the like.

  The term “aryl” refers to an aromatic carbon group or a group derived therefrom. The term “heteroaryl” represents “aryl” as defined above containing one or more heteroatoms.

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

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} hetero _aryl, C 4 _{-C 40 cycloalkyl,} or the like C 4 _{-C 40} cycloalkenyl. 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} aryl alkyl and _C 2 _{-C 20} heteroaryl being particularly preferred.

More preferred carbon and hydrocarbon groups are linear, branched or cyclic alkyl groups having 1 to 40, preferably 1 to 25 C atoms, which groups are unsubstituted or F, Cl , Br, I or CN mono- or poly-substituted, provided that one or more non-adjacent CH ₂ groups are independently of each other such that the O and / or S atoms are not directly linked to each other. , -C (R ^x ) = C (R ^x )-, -C≡C-, -N (R ^x )-, -O-, -S-, -CO-, -CO-O-, -O- CO- and -O-CO-O- may be substituted.

R ^x is preferably an H, halogen, linear, branched or cyclic alkyl chain having 1 to 25 C atoms (in addition, one or more non-adjacent C atoms are —O -, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O- may be substituted, provided that one or more H atoms are fluorine. Optionally substituted aryl) or an aryloxy group having 6 to 40 C atoms, or heteroaryl having 2 to 40 C atoms which may be substituted or Represents a heteroaryloxy group;

  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-heptoxy, n-octoxy, n-nonoxy, n-decoxy, n-undecoxy, n-dedecoxy and the like.

  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-heptoxy, n-octoxy, n-nonoxy, n-decoxy, n-undecoxy, n-dedecoxy and the like.

  Preferred amino groups are, for example, dimethylamino, methylamino, methylphenylamino, phenylamino and the like.

  Aryl and heteroaryl groups can be either monocyclic or polycyclic, that is, they can contain one ring (eg, phenyl, etc.) or two or more rings, and the groups are fused (Eg, naphthyl, etc.), may be covalently bonded (eg, biphenyl, etc.), or may contain a combination of fused and linked rings. A heteroaryl group preferably contains one or more heteroatoms selected from O, N, S and Se.

  Particularly preferred are monocyclic, bicyclic or tricyclic aryl groups having 6 to 25 C atoms and monocyclic, bicyclic or tricyclic heteroaryl groups having 2 to 25 C atoms, which groups are fused It may contain a ring and may be substituted. In addition, 5-, 6- or 7-membered aryl and heteroaryl groups are preferred, but in addition, one or more CH groups may be substituted with N, S, such that the O and / or S atoms are not directly linked to one another. Or it may be replaced by O.

  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, , 5-tetrazine and the like; 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, naphthy Condensed groups such as gin, 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 further aryl or heteroaryl group.

  (Non-aromatic) alicyclic and heterocyclic groups may also contain saturated rings, i.e. containing exclusively single bonds, and also partially unsaturated rings, i.e. multiple bonds. Includes both things. The heterocyclic ring preferably contains one or more heteroatoms selected from Si, O, N, S and Se.

(Non-aromatic) alicyclic and heterocyclic groups are monocyclic, i.e. contain only one ring (e.g. cyclohexane, etc.) or are polycyclic, i.e. contain multiple rings (Eg, decahydronaphthalene or bicyclooctane). Saturated groups are particularly preferred. Furthermore, monocyclic, bicyclic or tricyclic groups having 3 to 25 C atoms are preferred, which groups may contain fused rings and may be substituted. Furthermore, 5-membered, 6-membered, 7-membered or 8-membered carbocyclic groups are preferred, but in addition, one or more C atoms may be replaced by Si and / or one or more CH groups. May be replaced by N and / or one or more non-adjacent CH ₂ groups may be replaced by —O— and / or —S—.

  Preferred alicyclic and heterocyclic groups are, for example, 5-membered groups such as cyclopentane, tetrahydrofuran, tetrahydrothiofuran, pyrrolidine, cyclohexane, silinane, cyclohexene, tetrahydropyran, tetrahydrothiopyran, 1,3-dioxane, 1, 6-membered groups such as 3-dithiane and piperidine, 7-membered groups such as cycloheptane, tetrahydronaphthalene, decahydronaphthalene, indane, bicyclo [1.1.1] pentane-1,3-diyl, bicyclo [2.2. 2] Condensed groups such as octane-1,4-diyl, spiro [3.3] heptane-2,6-diyl, octahydro-4,7-methanoindane-2,5-diyl.

  Preferred substituents are, for example, solubility-promoting groups such as alkyl or alkoxy, electron withdrawing groups such as fluorine, nitro or nitrile, or groups for increasing the glass transition temperature (Tg) in the polymer, especially for example t-butyl. Alternatively, it is a bulky group such as an optionally substituted aryl group.

Preferred substituents, also referred to as “L” above and below, are, for example, F, Cl, Br, I, OH, —CN, —NO ₂ , —NCO, —NCS, —OCN, —SCN, —C (═O ) N (R ^x ) ₂ , —C (═O) Y ¹ , —C (═O) R ^x , —C (═O) OR ^x , —N (R ^x ) ₂ , wherein R ^x Has the meaning indicated above and Y ¹ is halogen, optionally substituted silyl, optionally substituted 4-40, preferably 4-20, ring or aryl or heteroaryl And represents a linear or branched alkyl, alkenyl, alkynyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 25 C atoms, provided that one or more H atom It 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. Means substituted by —CO—O—R ⁰ , where R ⁰ has the meaning indicated above.

Particularly preferred substituents L 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 , and phenyl.

であり、式中、Ｌは上で示される意味の１つを有する。

Where L has one of the meanings indicated above.

  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 on the main chain. Groups for chain polymerization, particularly those containing C═C double bonds or —C≡C-triple bonds, and groups suitable for ring-opening polymerization such as, for example, oxetane or epoxide groups are particularly preferred.

Preferred groups P ^{_{are, CH 2 = CW 1 -CO-}} O-, 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−から成る群より選択され、式中、Ｗ^１は、Ｈ、Ｆ、Ｃｌ、ＣＮ、ＣＦ_３、フェニルまたは１〜５個のＣ原子を有するアルキル、特に、Ｈ、Ｆ、ＣｌまたはＣＨ_３を表し、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Ｃ原子を有するアルキル、特に、Ｈ、メチル、エチルまたはｎ−プロピルを表し、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Ｃ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、１〜５個のＣ原子を有するアルキルを表し、Ｐｈｅは、上に定義される通りでＰ−Ｓｐ−とは異なる１個以上の基Ｌで置換されていてもよい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を表し、ｋ_４は１〜１０の整数を表す。

_{^{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- , OCN- and ^W 4 ^W 5 ^W 6 group consisting of Si- Is selected, wherein, ^{W 1} is an alkyl having H, F, Cl, CN, CF _3, phenyl or 1-5 C atoms, in particular, represent H, F, Cl or CH _3, ^{W 2} and W ³ each independently represents H or alkyl having 1 to 5 C atoms, in particular H, methyl, ethyl or n-propyl, and W ⁴ , W ⁵ and W ⁶ each independently , Cl, oxaalkyl or oxacarbonylalkyl having 1 to 5 C atoms, W ⁷ and W ⁸ each independently of one another represent H, Cl, alkyl having 1 to 5 C atoms, Phe represents 1,4-phenylene, as defined above, optionally substituted by one or more groups L different from P-Sp-, wherein k ₁ , k ₂ and k ₃ are each Independently, 0 or The stands, _{k 3} preferably represents 1, _{k 4} is an integer of 1 to 10.

Particularly preferred groups P are CH ₂ ═CW ¹ —CO—O—, CH ₂ ═CW ¹ —CO—,

ＣＨ_２＝ＣＷ^２−Ｏ−、ＣＷ^１＝ＣＨ−ＣＯ−（Ｏ）_ｋ３−、ＣＷ^１＝ＣＨ−ＣＯ−ＮＨ−、ＣＨ_２＝ＣＷ^１−ＣＯ−ＮＨ−、（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−、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−およびＷ^４Ｗ^５Ｗ^６Ｓｉ−から成る群より選択され、式中、Ｗ^１は、Ｈ、Ｆ、Ｃｌ、ＣＮ、ＣＦ_３、フェニルまたは１〜５個のＣ原子を有するアルキル、特に、Ｈ、Ｆ、ＣｌまたはＣＨ_３を表し、Ｗ^２およびＷ^３は、それぞれ互いに独立に、Ｈまたは１個、２個、３個、４個または５個のＣ原子を有するアルキル、特に、Ｈ、メチル、エチルまたはｎ−プロピルを表し、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Ｃ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、１〜５個のＣ原子を有するアルキルを表し、Ｐｈｅ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を表し、ｋ_４は１〜１０の整数を表す。

^{_{CH 2 = CW 2 -O-, CW}} 1 = CH-CO- (O) k3 -, CW 1 = CH-CO-NH-, CH 2 = CW 1 -CO-NH -, (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-,}} 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- and ^W 4 ^W 5 ^W 6 is selected from the group consisting of Si-, wherein, ^{W 1} is, H, F, Cl, CN , CF 3, phenyl or 1 Represents an alkyl having ˜5 C atoms, in particular H, F, Cl or CH ₃ , W ² And W ³ each independently of one another represents H or an alkyl having 1, 2, 3, 4 or 5 C atoms, in particular H, methyl, ethyl or n-propyl, and W ⁴ , W ⁵ and W ⁶ each independently represent Cl, oxaalkyl or oxacarbonylalkyl having 1 to 5 C atoms, and W ⁷ and W ⁸ each independently represent H, Cl, 1 to 5 Represents alkyl having 5 C atoms, Phe represents 1,4-phenylene, k ₁ , k ₂ and k ₃ each independently represent 0 or 1; k ₃ is preferably 1 And k ₄ represents an integer of 1 to 10.

Very particularly preferred groups P are CH ₂ ═CW ¹ —CO—O—, in particular CH ₂ ═CH—CO—O—, CH ₂ ═C (CH ₃ ) —CO—O— and CH ₂ ═CF. -CO-O-, _{furthermore, CH 2 = CH-O -} , (CH 2 = CH) 2 CH-O-CO -, (CH 2 = CH) 2 CH-O-,

から成る群より選択される。

Selected from the group consisting of

Further very particularly preferred groups Pa ^{, b} are vinyloxy, acrylate, methacrylate, fluoroacrylate, chloroacrylate, oxetane, 3-ethyloxetane and epoxy groups, particularly preferably acrylate or methacrylate groups.

Preferred spacer groups Sp are selected from the formula Sp ″ -X ″ such that the group “P-Sp-” corresponds to the formula “P-Sp ″ -X ″-”, provided that
Sp ″ represents an alkylene having 1 to 20, preferably 1 to 12, C atoms, which group may be mono- or polysubstituted with F, Cl, Br, I or CN, provided that In addition, one or more non-adjacent CH ₂ groups are each independently of each other such that the O and / or S atoms are not directly linked to each other, so that —O—, —S—, —NH—, —N ^{(R 0) -, - Si} (R 00 R 000) -, - CO -, - CO-O -, - O-CO -, - O-CO-O -, - S-CO -, - CO-S ^{-, - N (R 00)} -CO-O -, - O-CO-N (R 00) -, - N (R 00) -CO-N (R 00) -, - CH = CH- or -C May be replaced by ≡C-
X ″ represents —O—, —S—, —CO—, —CO—O—, —O—CO—, —O—CO—O—, —CO—N (R ⁰⁰ ) —, —N (R ^{00) -CO -, - N (} R 00) -CO-N (R 00) -, - 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—CO—O—, —O—CO—CH═CH— or a single bond. ,
R ⁰⁰ and R ⁰⁰⁰ each independently represent H or alkyl having 1 to 12 C 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 spacer groups Sp ″ are, 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 ⁰⁰ R ⁰⁰⁰ —O) _p1 —, wherein p1 is an integer of 1 to 12, q1 is an integer of 1 to 3, and R ⁰⁰ And R ⁰⁰⁰ have the meanings indicated above.

Particularly preferred groups -Sp "-X" - _{is, - (CH 2) p1 -} , - (CH 2) p1 -O -, - (CH 2) p1 -O-CO -, - (CH 2) p1 -O -CO-O-, where p1 and q1 have the meanings indicated above.

  Particularly preferred groups Sp ″ 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.

  In a further preferred embodiment of the present invention, P in the formula I represents a group containing two or more polymerizable groups (polyfunctional polymerizable group). Suitable groups of this type, polymerizable compounds containing them and their preparation 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、直鎖状または分岐状で１〜１２個のＣ原子を有するアルキレンを表し、ただし、１個以上の隣接していないＣＨ_２基は、それぞれ互いに独立に、Ｏおよび／またはＳ原子が互いに直接連結しないようにして、−Ｃ（Ｒ^００）＝Ｃ（Ｒ^０００）−、−Ｃ≡Ｃ−、−Ｎ（Ｒ^００）−、−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯ−Ｏ−、−Ｏ−ＣＯ−、−Ｏ−ＣＯ−Ｏ−で置き換えられていてもよく、ただし加えて、１個以上のＨ原子は、Ｆ、ＣｌまたはＣＮで置き換えられていてもよく、ただし、Ｒ^００およびＲ^０００は上で示される意味を有し、
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、および
Ｐ^１〜５は、それぞれ互いに独立に、Ｐ^ａ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 C atoms, provided that one or more non-adjacent CH ₂ groups are independently of each other O and And / or S atoms are not directly linked to each other so that —C (R ⁰⁰ ) ═C (R ⁰⁰⁰ ) —, —C≡C—, —N (R ⁰⁰ ) —, —O—, —S—, — May be replaced by CO-, -CO-O-, -O-CO-, -O-CO-O-, in addition, one or more H atoms may be replaced by F, Cl or CN. Provided that R ⁰⁰ and R ⁰⁰⁰ have the meanings indicated above;
aa and bb each independently represent 0, 1, 2, 3, 4, 5 or 6;
X has one of the meanings indicated for X ', and P ^{1 to 5} are each, independently of one another, have one of the meanings indicated for P ^a.

  Particularly preferred compounds of formula I are those of sub-formula IA.

式中、Ｒ^ａ、Ｒ^ｂ、Ｗ^１、Ｗ^２、Ａ^１、Ａ^２、Ｚ^１、Ｚ^２、Ｌ、ｐ、ｑおよびｒは、式Ｉにおいて示される意味、または、上および下で示される意味の１つを有する。

Wherein R ^a , R ^b , W ¹ , W ² , A ¹ , A ² , Z ¹ , Z ² , L, p, q and r are as indicated in formula I, or above and below One of the meanings.

  The following compounds of formula I and IA are particularly preferred:

A ¹ and A ² are each independently 1,4-phenylene, naphthalene-1,4-diyl or naphthalene-2,6-diyl (in addition, one or more CH groups in these groups are N may be replaced with N), cyclohexane-1,4-diyl (but one or more non-adjacent CH ₂ groups may be replaced with O and / or S). 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-1,4-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, indan-2,5-diyl, octahydro- 4 , 7-methanoindan-2,5-diyl, phenanthrene-2,7-diyl, anthracene-2,7-diyl, phenanthrene-2,7-diyl, 9,10-dihydrophenanthrene-2,7-diyl, 6H- Benzo [c] chromene-3,8-diyl, 9H-fluorene-2,7-diyl, 9,9-dimethyl-9H-fluorene-2,7-diyl, dibenzofuran-3,7-diyl, 2-oxo- 2H-chromen-7-yl, 4-phenyl-2-oxo-2H-chromen-7-yl, 4-oxo-4H-chromen-6-yl, 4-phenyl-4-oxo-4H-chromene-6 Provided that all these groups may be unsubstituted or mono- or polysubstituted with L, provided that among these all groups cyclohexane and Aromatic groups very particularly preferred.

L _{is, P-Sp-, 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, silyl optionally substituted, an optionally substituted well 6-20 of C Aryl having atoms, linear or branched 1 to 25, preferably alkyl or alkoxy having 1 to 12 C atoms, or linear or branched 2 to 25, preferably Represents alkenyl, alkynyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 2 to 12 C atoms, but in addition, one or more H atoms in all these groups is F, Cl , P or It may be replaced with P-Sp-.

Y ¹ represents halogen.

R ^x represents P-Sp-, H, halogen, linear, branched or cyclic and represents an alkyl having 1 to 25, preferably 1 to 12 C atoms, but in addition, one or more Non-adjacent CH ₂ groups can be defined as —O—, —S—, —CO—, —CO—O—, —O—CO—, —, such that the O and / or S atoms are not directly linked to each other. O-CO-O- may be substituted, but in addition one or more H atoms may be replaced by F, Cl or P-Sp-.

  Further preferred compounds of formulas I and IA and their subformulas shown above and below are selected from one or more of the following preferred embodiments, and the embodiments can be combined with one another as desired.

W ¹ and W ² are each independently of each other —CH ₂ CH ₂ —, —CH═CH—, —CH ₂ —O—, —O—CH ₂ —, —C (R ^c R ^d ) — or -O- is represented.

· ^{W 1} and ^{W 2,} is both at the same time not represent -CH = CH-, preferably (in the formula, Y is H or F.) Is both simultaneously -CY = CY- represent Absent.

R ^c and R ^d each independently of one another represent H or alkyl having 1 to 6 C atoms, preferably H, methyl or ethyl.

One or both of the radicals W ¹ and W ² represents —N (R ^e ), where R ^e represents H or alkyl having 1 to 6 C atoms, preferably H, methyl or ethyl.

One of the groups W ¹ and W ² represents —CH ₂ CH ₂ — or —CH═CH— and the other represents —CH ₂ CH ₂ —, —CH ₂ O—, —OCH ₂ — or —C (CR ^{cR d} ) ₂ — (wherein R ^c and R ^d preferably represent methyl).

One of the groups W ¹ and W ² represents —CH ₂ CH ₂ — and the other represents —CH ₂ O— or —OCH ₂ —.

One of the groups W ¹ and W ² represents —CH═CH— and the other represents —CH ₂ O— or —OCH ₂ —.

One of the radicals W ¹ and W ² represents —CH ₂ CH ₂ — and the other represents —C (CH ₃ ) ₂ —.

One of the radicals W ¹ and W ² represents —CH═CH— and the other represents —C (CH ₃ ) ₂ —.

· ^{W 1} is represents _-CH 2 CH ₂ -, ^{W 2} represents a _-CH 2 O-.

· ^{W 1} represents -CH = CH-, ^{W 2} represents a _-CH 2 O-.

· ^{W 1} and ^{W 2,} _{-CH 2} CH 2 - represents a.

· ^{W 1} and ^{W 2} represents the -CH = CH-.

  Y represents H.

One of the radicals R ^a and R ^b represents P-Sp- and the other is different from P-Sp-.

R ^a and R ^b represent the same or different group P-Sp-.

· ^{R a} and ^{R b} represents a P-Sp-, however, Sp the definitive one of the radicals ^{R a} and ^{R b} represents a single bond, Sp of the other radicals ^{R a} and ^{R b} are different from a single bond, preferably Represents a group of the formula Sp ″ -X ″ such that this group P-Sp- corresponds to the formula P-Sp ″ -X ″-.

R ^a and R ^b represent the same or different group P-Sp- (wherein both groups Sp represent a single bond).

One of the groups R ^a and R ^b represents or contains the group P-Sp-, the other is preferably linear or branched and non-polymerized selected from alkyl having 1 to 25 C atoms Represents, in addition, one or more non-adjacent CH ₂ groups, independently of one another, in such a way that the O and / or S atoms are not directly linked to one another, —C (R ⁰⁰ ) ═C ^{(R 000) -, - C≡C} -, - N (R 00) -, - O -, - S -, - CO -, - CO-O -, - O-CO -, - O-CO-O May be replaced with-, but in addition, one or more H atoms may be replaced with F, Cl, Br, I or CN.

R ^a and R ^b are different from H.

One of the radicals R ^a and R ^b represents P-Sp— and the other is different from H.

The group R ^a or R ^b different from P-Sp- is alkyl having 1 to 12, preferably 5 to 12 C atoms, alkoxy having 1 to 12 C atoms, or 2 to 11 Represents an alkenyl having C atoms, but in addition one or more H atoms in all these groups may be replaced by F.

R ^a and / or R ^b represents a linear or branched alkyl having 1 to 25, preferably 1 to 12 C atoms, but in addition, one or more are not adjacent The CH ₂ groups are independently of each other such that the O and / or S atoms are not directly connected to each other so that —C (R ⁰⁰ ) ═C (R ⁰⁰⁰ ) —, —C≡C—, —N (R ⁰⁰ )-, -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, but in addition one or more The H atom may be replaced with F, Cl, Br, I or CN.

  -Sp represents a single bond.

Sp is — (CH ₂ ) _p1 —, — (CH ₂ ) _p1 —O—, — (CH ₂ ) _p1 —O—CO—, — (CH ₂ ) _p1 —O—CO—O—, preferably , — (CH ₂ ) _p1 — or — (CH ₂ ) _p1 —O— (wherein _p1 represents an integer of 1 to 12, preferably 1 to 5, particularly preferably 1 to 3). Represent.

  Sp and / or Sp ″ represents an alkylene group having 1 to 5, preferably 1 to 3 C atoms.

A ¹ and A ² are each independently the same or different at each occurrence, and are phenylene-1,4-diyl, naphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2 , 6-diyl, decahydronaphthalene-2,6-diyl, trans-cyclohexylene-1,4-diyl, dibenzofuran-3,7-diyl, but unsaturated or aromatic In the above-mentioned groups containing a group ring, one or two CH groups in these rings may be replaced by N, provided that in all the above-mentioned groups the individual rings are as defined above. L may be monosubstituted or polysubstituted.

A ¹ and A ² represent phenylene-1,4-diyl, which may be mono- or polysubstituted with L as described above and below.

  -L does not represent a polymerizable group and does not contain it.

L is preferably non-polymerizable selected from F, Cl, -CN and alkyl which is linear or branched and has 1 to 25, particularly preferably 1 to 10 C atoms And in addition, one or more non-adjacent CH ₂ groups are each independently of each other such that the O and / or S atoms are not directly linked to each other, so that —C (R ⁰⁰ ) ═C ( ^{R 000) -, - C≡C -} , - N (R 00) -, - O -, - S -, - CO -, - CO-O -, - O-CO -, - O-CO-O- But in addition one or more H atoms may be replaced by F, Cl, Br, I or CN.

· L _{is, F, Cl, Br, I} , -CN, -NO 2, -NCO, -NCS, -OCN or -SCN, preferably represents F.

-One or both groups (L) In _r , r represents 1.

-One or both groups (L) In _r , r represents 1 and L represents F.

  L is linear or branched alkyl or alkoxy having 1 to 12 C atoms, or linear or branched alkenyl, alkynyl, alkylcarbonyl, alkoxy having 2 to 12 C atoms Represents carbonyl, alkylcarbonyloxy or alkoxycarbonyloxy, but in addition one or more H atoms in all these groups may be replaced by F, Cl or P-Sp-.

  * L represents P-Sp-.

Z ¹ and Z ² are each independently the same or different at each occurrence, and are —O—, —CO—O—, —OCO—, —OCH ₂ —, —CH ₂ O—, —CF _2. O—, —OCF ₂ —, —CH ₂ CH ₂ —, —CH═CH—, —CF═CF—, —CH═CF—, —CF═CH—, —C≡C—, a group consisting of a single bond More selected.

· ^{Z 1} and ^{Z 2} represents a single bond.

Z ¹ and Z ² are different from —C≡C—.

  P is 0 and q is 0.

  P is 1 and q is 1.

  P is 0 and q is 1, or p is 1 and q is 0.

When W ¹ and W ² represent —CH═CH—, Z ¹ does not represent —C≡C— and / or A ¹ does not represent 1,4-phenylene, particularly preferably Does not represent an aromatic group.

When W ¹ and W ² represent —CH═CH—, Z ² does not represent —C≡C— and / or A ² does not represent 1,4-phenylene, particularly preferably Does not represent an aromatic group.

^{· R a - (A 1 -Z} 1) p - and _{^{- (Z 2 -A 2) q}} -R b does not represent a halogen.

  Particularly preferred compounds of formula I and IA are selected from the group consisting of:

式中、Ｓｐ、Ｌおよびｒは、上および下で示される意味の１つを有し、Ｐ^ａおよびＰ^ｂは、それぞれ互いに独立に、Ｐに示される意味の１つを有し、Ｒ’およびＲ”は、それぞれ互いに独立に、Ｈまたは１〜１２個のＣ原子を有するアルキルを表し、ｓ１は０または１である。Ｒ’およびＲ”は、好ましくは、メチルまたはエチルを表す。

Wherein Sp, L and r have one of the meanings indicated above and below, and P ^a and P ^b each independently of one another have one of the meanings indicated for P, R ′ And R ″, independently of one another, represent H or alkyl having 1 to 12 C atoms, and s1 is 0 or 1. R ′ and R ″ preferably represent methyl or ethyl.

P, P ^a and P ^b in the compounds of the formulas I and IA and sub-formulas I1 to I28 preferably represent acrylates or methacrylates, furthermore fluoroacrylates.

Sp in the compounds of formulas I and IA and sub-formulas I1 to I28 is preferably — (CH ₂ ) _p1 —, — (CH ₂ ) _p1 —O—, — (CH ₂ ) _p1 —O—CO— or — (CH ₂ ) _p1 —O—CO—O— or a mirror image thereof, wherein p1 represents an integer of 1 to 12, preferably 1 to 6, particularly preferably 1, 2, 3 or 4. However, the connection to the adjacent benzene ring is through the O atom.

The invention further relates to novel compounds of the formulas I and IA and their subformulas as defined above and below, provided that
When W ¹ and W ² represent —CH═CH—,
Z ¹ does not represent —C≡C— and / or A ¹ does not represent 1,4-phenylene, particularly preferably does not represent an aromatic group, and
Z ² does not represent —C≡C— and / or A ² does not represent 1,4-phenylene, particularly preferably does not represent an aromatic group, and
1-vinylpyrene is excluded.
Absent. )

  The invention further relates to novel intermediates for preparing compounds of formula I selected from formula II, preferably selected from formula IIA.

式中、Ｗ^１、Ｗ^２、Ｓｐ、Ｌ、Ａ^１、Ａ^２、Ｚ^１、Ｚ^２、ｐ、ｑおよびｒは、式Ｉまたは上および下で示される意味を有し、ＧおよびＧ’は、それぞれ互いに独立に、Ｈ原子または保護基を表す。

In which W ¹ , W ² , Sp, L, A ¹ , A ² , Z ¹ , Z ² , p, q and r have the meanings given in Formula I or above and below, and G and G ′ Each independently represents a H atom or a protecting group.

  Suitable protecting groups G are known to those skilled in the art. Preferred protecting groups are alkyl, acyl and alkylsilyl or arylsilyl groups, 2-tetrahydropyranyl or methoxymethyl.

Particularly preferred intermediates of the formulas II and IIA are the above-mentioned sub-formulas I1 to I28 in which P ^a in each case represents G—O— and P ^b in each case represents —O—G ′. (Wherein G and G ′ preferably represent H).

  Particularly suitable and preferred methods of preparing compounds and intermediates of formulas I and II and their subformulas are illustrated by way of example in the following schemes and preferably comprise one or more of the following steps:

  Compounds and intermediates of Formulas I and II and their subformulas are known to those skilled in the art and are described, for example, by Houben-Weyl, Methoden der organicis Chemie [Methods of Organic Chemistry], Thime-Verlag, St. It can be prepared analogously to the method described in the standard chemistry book.

For example, compounds of formula I are synthesized by esterifying or etherifying an intermediate of formula II using the corresponding acid, acid derivative or halogenated compound containing the group P. As illustrated by way of example in Scheme 1, in the presence of a base and optionally 4- (N, N-dimethylamino) pyridine (DMAP: 4- (N, N-dimethylamino) pyridine) ) Using an acid derivative such as acryloyl or anhydrous (meth) acrylic acid, wherein R ^a and R ^b represent P-Sp— and P is, for example, an acrylate or methacrylate group, It can be obtained by esterifying the corresponding alcohol of formula II where 'is H. Furthermore, the alcohol can also be esterified using (meth) acrylic acid in the presence of a dehydrating agent, for example by the Steglitch method using dicyclohexylcarbodiimide (DCC).

  Thus, the present invention further provides a process for preparing a compound of formula I using the corresponding acid, acid derivative or halogenated compound containing group P in the presence of a dehydrating agent To a method of esterifying or etherifying the compound of

ピレンを水素化（Ｐ．Ｓｏｕｓｔｅｋら、Ｄｙｅｓ ａｎｄ Ｐｉｇｍｅｎｔｓ ７８巻（２００８年）１３９〜１４７頁）することで親構造４，５，９，１０−テトラヒドロピレン（１、ＷおよびＷ’はＣＨ_２ＣＨ_２）を入手し、ハロゲン化することで選択的に官能化できる（スキーム２）。Ａ．Ｄ．Ａｂｅｌｌら、Ｊ．Ｃｈｅｍ．Ｓｏｃ．、Ｐｅｒｋｉｎ Ｔｒａｎｓ．１巻、１９９７年、１６６３〜１６６８頁に従って、４，５，９，１０−テトラヒドロヒドロピレン（４）より、２，７−ジブロモ−４，５，９，１０−テトラヒドロピレン（５、ＨａｌはＢｒ）を与える。Ｈ．Ｓｕｚｕｋｉ、Ｏｒｇａｎｉｃ Ｓｙｎｔｈｅｓｅｓ、Ｃｏｌｌ．６巻、７００頁（１９８８年）に従って、ヨウ素化により、対応する２，７−ジヨード−４，５，９，１０−テトラヒドロピレン（５、ＨａｌはＩ）を与える。

Hydrogenation of pyrene (P. Soustek et al., Dies and Pigments 78 (2008) pp. 139-147) allows the parent structure 4,5,9,10-tetrahydropyrene (1, W and W ′ are CH ₂ CH ₂ ) can be obtained and selectively functionalized by halogenation (Scheme 2). A. D. Abell et al. Chem. Soc. Perkin Trans. 1, 1997, pages 1663 to 1668, from 4,5,9,10-tetrahydrohydropyrene (4) to 2,7-dibromo-4,5,9,10-tetrahydropyrene (5, Hal is Br )give. H. Suzuki, Organic Synthesis, Coll. 6, 700 (1988), iodination gives the corresponding 2,7-diiodo-4,5,9,10-tetrahydropyrene (5, Hal is I).

例えば、ブチルリチウムを使用する金属化およびホウ酸エステルとの反応によって、ジハロゲン化合物５よりボロン酸を調製でき、酸化することでフェノール６を与える（スキーム３）。代替法は、Ｓ．Ｌ．Ｂｕｃｈｗａｌｄら、Ｊ．Ａｍ．Ｃｈｅｍ．Ｓｏｃ．２００６年、１２８巻、１０６９４〜１０６９５頁に従って、パラジウム触媒の存在下におけるＫＯＨでの処理である。アクリル酸を使用するエステル化によって（メタ）アクリレート７が与えられる。

For example, boronic acid can be prepared from dihalogen compound 5 by metallization using butyllithium and reaction with a borate ester, which gives phenol 6 by oxidation (Scheme 3). An alternative is S. L. Buchwald et al. Am. Chem. Soc. Treatment with KOH in the presence of a palladium catalyst according to 2006, 128, 10694-10695. Esterification using acrylic acid gives (meth) acrylate 7.

トリイソプロピルボレートの存在下における一金属化によってジイソプロピルボロネートを与え、これを加水分解および酸化することで一ヒドロキシ化合物（８、スキーム４）を与え、第２の工程において、これを更に転化できる。よって、末端アルキノールに対する薗頭カップリングによりアルキン９を与え、それより、水素化およびエステル化によって、スペーサー基を含有する化合物１０が入手可能である。

Monometallation in the presence of triisopropylborate gives diisopropylboronate, which is hydrolyzed and oxidized to give the monohydroxy compound (8, Scheme 4), which can be further converted in the second step. Thus, Sonogashira coupling to terminal alkynol provides alkyne 9, from which compound 10 containing a spacer group is available by hydrogenation and esterification.

対応して、Ｓ．Ｓｏｎｇら、Ｔｅｔｒａｈｅｄｒｏｎ Ｌｅｔｔｅｒｓ ２００８年、４９巻、３５８２〜３５８７頁に記載される通り、商業的に入手可能な４Ｈ−シクロペンタ［ｄｅｆ］フェナントレン１１より誘導体１２が入手でき（スキーム５）、スキーム３および４に従って、化合物１３および１４を与えることができる。

Correspondingly, S.M. Song 12 is available from commercially available 4H-cyclopenta [def] phenanthrene 11 (Scheme 5), Schemes 3 and 4 as described in Song et al., Tetrahedron Letters 2008, 49, 3582-3587. To give compounds 13 and 14.

適切な中間体、例えば、化合物５、８または１２を芳香族化することで、対応する不飽和化合物１５〜１８を与える。芳香族化のための適切な反応条件は、例えば、不活性溶媒中においてジクロロジシアノベンゾキノン（ＤＤＱ：ｄｉｃｈｌｏｒｏｄｉｃｙａｎｏｂｅｎｚｏｑｕｉｎｏｎｅ）で処理（Ｖ．Ｖ．Ｆｉｌｉｃｈｅｖら、Ｃｈｅｍｉｓｔｒｙ−Ａ Ｅｕｒｏｐｅａｎ Ｊｏｕｒｎａｌ ２００８年、１４巻（３２号）、９９６８〜９９８０）する、または、ハロゲン化水素の脱離によるハロゲン化（Ｐ．Ｓｏｕｓｔｅｋら、Ｄｙｅｓ ａｎｄ Ｐｉｇｍｅｎｔｓ ７８巻（２００８年）１３９〜１４７頁；Ｓ．Ｓｏｎｇら、Ｔｅｔｒａｈｅｄｒｏｎ Ｌｅｔｔｅｒｓ ４９巻（２００８年）３５８２〜３５８７頁）である。

Aromatization of a suitable intermediate, for example compound 5, 8 or 12, gives the corresponding unsaturated compounds 15-18. Suitable reaction conditions for aromatization are for example treated with dichlorodicyanobenzoquinone (DDQ) in an inert solvent (VV Filichev et al., Chemistry-A European Journal 2008, 14 (32). ), 9968-9980), or halogenation by elimination of hydrogen halides (P. Soustek et al., Dies and Pigments 78 (2008) 139-147; S. Song et al., Tetrahedron Letters 49 (2008). Year) 3582-3585).

フラビジン（１９）は天然物で、ランより単離される（例えば、Ｇ．Ｋ．Ｊａｙａｐｒａｋａｓｈａら、Ｂｉｏｏｒｇａｎｉｃ ＆ Ｍｅｄｉｃｉｎａｌ Ｃｈｅｍｉｓｔｒｙ ２００４年、１２巻、５１４１〜５１４６頁参照）。

Flavidin (19) is a natural product and is isolated from orchids (see, for example, GK Jayaprakasha et al., Bioorganic & Medicinal Chemistry 2004, 12, 5141-5146).

上記の通り、本発明による誘導体２０が１９より得られ、上記の通り芳香族化して２１を与える。

As described above, derivative 20 according to the present invention is obtained from 19 and is aromatized to give 21 as described above.

A number of standard reactions can convert the intermediate compounds shown in the schemes to the compounds according to the invention (Scheme 6). For example, aryl derivatives 23 can be obtained from aryl metal compounds by coupling reactions catalyzed by transition metals such as Suzuki coupling (22, M is —B (OH) ₂ . To the desired compound 25.

本発明は、更に、式ＩおよびＩＩの化合物を調製するためで、特には、式ＩＩの化合物から式Ｉの化合物を調製するための、上および下に記載される方法に関する。

The present invention further relates to the processes described above and below for preparing compounds of formula I and II, in particular for preparing compounds of formula I from compounds of formula II.

  In order to manufacture a PSA display, a polymerizable compound is polymerized by in-situ polymerization in an LC medium between LC display substrates while applying a voltage, or (one compound contains two or more polymerizable groups). Crosslink (if included). The polymerization can be performed in one step. In order to generate a pretilt angle, polymerization is first performed in the first step while applying a voltage, and then, in order to polymerize or crosslink (final cure) the compound that did not react in the first step, It is also possible to carry out the polymerization without applying a voltage in the polymerization step.

  Suitable and preferred polymerization methods are, for example, thermal or photopolymerization, preferably photopolymerization, in particular UV photopolymerization. Moreover, in this specification, 1 or more types of initiators can also be added as an arbitrary component. Appropriate conditions for polymerization and the appropriate type and amount of initiator are known to those skilled in the art and are described in the literature. For example, the commercially available photoinitiators Irgacure 651 (registered trademark), Irgacure 184 (registered trademark), Irgacure 907 (registered trademark), Irgacure 369 (registered trademark) or Darocur 1173 (registered trademark) (Ciba) can be used for free radical polymerization. Suitable. If an initiator is used, its proportion is preferably 0.001 to 5% by weight, particularly preferably 0.001 to 1% by weight.

  The polymerizable compounds according to the invention are also suitable for polymerization without initiators, for example, lower material costs and particularly less impurities in the LC medium due to the amount of initiator or its degradation products remaining. It is accompanied by remarkable advantages such as. Therefore, the polymerization can also be performed without adding an initiator. Thus, in a preferred embodiment, the LC medium does not contain a polymerization initiator.

  Also, for example, the polymerizable component A) or the LC medium can contain one or more stabilizers in order to prevent undesired spontaneous polymerization of the RM during storage or transport. Appropriate types and amounts of stabilizers are known to those skilled in the art and are described in the literature. For example, commercially available stabilizers of the Irganox® series (Ciba), such as Irganox® 1076, are particularly suitable. If stabilizers are used, the proportion of stabilizers based on the total amount of RM or polymerizable component A) is preferably 10 to 10,000 ppm, very preferably 50 to 500 ppm.

  The LC media according to the invention for use in PSA displays are preferably less than 5% by weight, particularly preferably less than 1% by weight, very particularly preferably less than 0.5% by weight of polymerizable compounds, in particular those of the formula I mentioned above. And polymerizable compounds of the sub-formula thereof.

  LC media comprising one, two or three kinds of polymerizable compounds according to the invention are particularly preferred.

  Furthermore, LC media in which the polymerizable component (component A) exclusively contains the polymerizable compound according to the invention are preferred.

  Furthermore, LC media in which component B) is an LC compound or LC mixture having a nematic liquid crystal phase are preferred.

  Furthermore, LC media in which the achiral polymerizable compounds according to the invention and the compounds of components A) and / or B) are exclusively selected from the group consisting of achiral compounds are preferred.

  Furthermore, the polymerizable component or component A) contains one (one reactive) one or more polymerizable compounds according to the invention and one or more, preferably two polymerizable groups, containing one polymerizable group. Preferred is an LC medium containing one or more (bireactive or multireactive) one or more polymerizable compounds according to the invention.

  Furthermore, PSA displays and LC media in which the polymerizable component or component A) exclusively comprises a (bireactive) polymerizable compound according to the invention containing two polymerizable groups is preferred.

  The proportion of polymerizable component or component A) in the LC medium according to the invention is preferably less than 5%, particularly preferably less than 1%, very particularly preferably less than 0.5%.

  The proportion of liquid crystal component or component B) in the LC medium according to the invention is preferably more than 95%, particularly preferably more than 99%.

  The polymerizable compounds according to the invention can also be polymerized separately, but also a mixture comprising two or more polymerizable compounds according to the invention, or one or more polymerizable compounds according to the invention and preferably a mesogen or It is also possible to polymerize a mixture comprising one or more further polymerizable compounds (comonomer) which are liquid crystals. When polymerizing such a mixture, a copolymer is formed. The invention further relates to the polymerizable mixture described above and below. The polymerizable compound and comonomer are mesogens or non-mesogens, preferably mesogens or liquid crystals.

  In particular, suitable and preferred mesogenic comonomers for use in PSA displays are selected, for example, from the following formula:

式中、個々の基は以下の意味を有する：
Ｐ^１およびＰ^２は、それぞれ互いに独立に、好ましくは、上および下でＰに示される意味の１つを有する重合性基、特に好ましくは、アクリレート、メタクリレート、フルオロアクリレート、オキセタン、ビニルオキシまたはエポキシド基を表し、
Ｓｐ^１およびＳｐ^２は、それぞれ互いに独立に、単結合、または、好ましくは、上および下でＳｐに示される意味の１つを有するスペーサー基を表し、特に好ましくは、−（ＣＨ_２）_ｐ１−、−（ＣＨ_２）_ｐ１−Ｏ−、−（ＣＨ_２）_ｐ１−ＣＯ−Ｏ−または−（ＣＨ_２）_ｐ１−Ｏ−ＣＯ−Ｏ−（式中、ｐ１は、１〜１２の整数である。）を表し、ただし、最後に述べた基において隣接する環への連結はＯ原子を介しており、
ただし加えて、存在する基Ｐ^１−Ｓｐ^１−およびＰ^２−Ｓｐ^２−の少なくとも一方がＲ^ａａを表さないことを条件として、１つ以上の基Ｐ^１−Ｓｐ^１−およびＰ^２−Ｓｐ^２−はＲ^ａａを表してもよく、
Ｒ^ａａは、Ｈ、Ｆ、Ｃｌ、ＣＮ、または、直鎖状または分岐状で１〜２５個のＣ原子を有するアルキル（ただし加えて、１個以上の隣接していないＣＨ_２基は、それぞれ互いに独立に、Ｏおよび／またはＳ原子が互いに直接連結しないようにして、Ｃ（Ｒ^０）＝Ｃ（Ｒ^００）−、−Ｃ≡Ｃ−、−Ｎ（Ｒ^０）−、−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯ−Ｏ−、−Ｏ−ＣＯ−、−Ｏ−ＣＯ−Ｏ−で置き換えられていてもよく、ただし加えて、１個以上のＨ原子は、Ｆ、Ｃｌ、ＣＮまたはＰ^１−Ｓｐ^１−で置き換えられていてもよい。）、特に好ましくは、直鎖状または分岐状で、一フッ素化または多フッ素化されていてもよく、１〜１２個のＣ原子を有するアルキル、アルコキシ、アルケニル、アルキニル、アルキルカルボニル、アルコキシカルボニル、アルキルカルボニルオキシまたはアルコキシカルボニルオキシ（ただし、アルケニルおよびアルキニル基は少なくとも２個のＣ原子を有し、分岐状の基は少なくとも３個のＣ原子を有する。）を表し、
Ｒ^０、Ｒ^００は、それぞれ互いに独立に、それぞれの出現において同一または異なって、Ｈ、または、１〜１２個のＣ原子を有するアルキルを表し、
Ｒ^ｙおよびＲ^ｚは、それぞれ互いに独立に、Ｈ、Ｆ、ＣＨ_３またはＣＦ_３を表し、
Ｚ^１は、−Ｏ−、−ＣＯ−、−Ｃ（Ｒ^ｙＲ^ｚ）−または−ＣＦ_２ＣＦ_２−を表し、
Ｚ^２およびＺ^３は、それぞれ互いに独立に、−ＣＯ−Ｏ−、−Ｏ−ＣＯ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−または−（ＣＨ_２）_ｎ−を表し、ただし、ｎは、２、３または４であり、
Ｌは、それぞれの出現において同一または異なって、Ｆ、Ｃｌ、ＣＮ、または、直鎖状または分岐状で、一フッ素化または多フッ素化されていてもよく、１〜１２個のＣ原子を有するアルキル、アルコキシ、アルケニル、アルキニル、アルキルカルボニル、アルコキシカルボニル、アルキルカルボニルオキシまたはアルコキシカルボニルオキシ、好ましくは、Ｆを表し、
Ｌ’およびＬ”は、それぞれ互いに独立に、Ｈ、ＦまたはＣｌを表し、
ｒは、０、１、２、３または４を表し、
ｓは、０、１、２または３を表し、
ｔは、０、１または２を表し、
ｘは、０または１を表す。

In the formula, the individual groups have the following meanings:
P ¹ and P ² are each independently of each other preferably a polymerizable group having one of the meanings indicated for P above and below, particularly preferably an acrylate, methacrylate, fluoroacrylate, oxetane, vinyloxy or epoxide group Represents
Sp ¹ and Sp ² each independently represent a single bond or, preferably, a spacer group having one of the meanings shown above and below, particularly preferably — (CH ₂ ) _p1 — , — (CH ₂ ) _p1 —O—, — (CH ₂ ) _p1 —CO—O— or — (CH ₂ ) _p1 —O—CO—O— (wherein p1 is an integer of 1 to 12) Wherein the linkage to the adjacent ring in the last mentioned group is through the O atom,
However, in addition, present group ^P 1 -Sp ¹ - and ^P 2 -Sp ² - the condition that at least one does not represent ^{R aa,} 1 one or more groups ^P 1 -Sp ¹ - and ^{P 2} - Sp ² − may represent R ^aa ,
R ^aa is H, F, Cl, CN or linear or branched alkyl having 1 to 25 C atoms (in addition, one or more non-adjacent CH ₂ groups are each Independently of one another, C (R ⁰ ) ═C (R ⁰⁰ ) —, —C≡C—, —N (R ⁰ ) —, —O—, such that O and / or S atoms are not directly linked to one another. -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O- may be substituted, but in addition, one or more H atoms may be F, Cl , CN or P ¹ -Sp ^1- may be substituted.), Particularly preferably linear or branched, may be monofluorinated or polyfluorinated, 1 to 12 C Atom-containing alkyl, alkoxy, alkenyl, alkynyl, alkylcarbonyl, alkoxy Carbonyl, alkylcarbonyloxy or alkoxycarbonyloxy (where the alkenyl and alkynyl groups having at least 2 C atoms, branched groups have. At least 3 C atoms) represent,
R ⁰ and R ⁰⁰ are each independently of each other, the same or different at each occurrence, H or alkyl having 1 to 12 C atoms,
R ^y and R ^z each independently represent H, F, CH ₃ or CF ₃ ,
Z ¹ represents —O—, —CO—, —C (R ^y R ^z ) — or —CF ₂ CF ₂ —,
Z ² and Z ³ are each independently of each other —CO—O—, —O—CO—, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, —OCF ₂ — or — (CH _{2 N} represents-, wherein n is 2, 3 or 4;
L is the same or different at each occurrence, F, Cl, CN, or linear or branched, may be monofluorinated or polyfluorinated, and has 1 to 12 C atoms Alkyl, alkoxy, alkenyl, alkynyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy, preferably F,
L ′ and L ″ each independently represent H, F or Cl,
r represents 0, 1, 2, 3 or 4;
s represents 0, 1, 2 or 3,
t represents 0, 1 or 2;
x represents 0 or 1;

  In addition to the polymerizable compounds described above, the LC medium for use in the LC display according to the present invention is an LC comprising one or more, preferably two or more low molecular weight (ie monomeric or unpolymerized) compounds. Including mixtures ("host mixtures"). Unpolymerized compounds are stable or non-reactive with respect to polymerization reactions under the conditions used for the polymerization of polymerizable compounds. In principle, any LC mixture suitable for use in conventional VA and OCB displays is suitable as a host mixture. Suitable LC mixtures are known to those skilled in the art, for example mixtures in VA displays in EP 1 378 557 and EP 1 306 418 and DE 102 24 046. It is a mixture for OCB display in Japanese Patent Publication No. Gazette and is described in the literature.

  In a first preferred embodiment of the invention, the LC medium comprises an LC host mixture based on a compound having negative dielectric anisotropy. Such LC media are particularly suitable for use in PSA-VA displays. Particularly preferred embodiments of this type of LC medium are described in items a) to x) below.

  a) LC medium comprising one or more compounds selected from the group consisting of the formulas CY and / or PY:

式中、個々の基は、以下の意味を有する：
ａは、１または２を表し、
ｂは、０または１を表し、

In the formula, the individual groups have the following meanings:
a represents 1 or 2,
b represents 0 or 1,

Ｒ^１およびＲ^２は、それぞれ互いに独立に、１〜１２個のＣ原子を有するアルキル（ただし加えて、１個または２個の隣接していないＣＨ_２基は、Ｏ原子が互いに直接連結しないようにして、−Ｏ−、−ＣＨ＝ＣＨ−、−ＣＯ−、−ＯＣＯ−または−ＣＯＯ−で置き換えられていてもよい。）、好ましくは、１〜６個のＣ原子を有するアルキルまたはアルコキシを表し、
Ｚ^ｘおよびＺ^ｙは、それぞれ互いに独立に、−ＣＨ_２ＣＨ_２−、−ＣＨ＝ＣＨ−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＯ−Ｏ−、−Ｏ−ＣＯ−、−Ｃ_２Ｆ_４−、−ＣＦ＝ＣＦ−、−ＣＨ＝ＣＨ−ＣＨ_２Ｏ−または単結合、好ましくは、単結合を表し、
Ｌ^１〜４は、それぞれ互いに独立に、Ｆ、Ｃｌ、ＯＣＦ_３、ＣＦ_３、ＣＨ_３、ＣＨ_２Ｆ、ＣＨＦ_２を表す。

R ¹ and R ² are each independently an alkyl having 1 to 12 C atoms (but one or two non-adjacent CH ₂ groups are such that the O atoms are not directly linked to each other). And may be replaced by -O-, -CH = CH-, -CO-, -OCO- or -COO-), preferably an alkyl or alkoxy having 1 to 6 C atoms. Represent,
Z ^x and Z ^y are each independently of each other —CH ₂ CH ₂ —, —CH═CH—, —CF ₂ O—, —OCF ₂ —, —CH ₂ O—, —OCH ₂ —, —CO—. O—, —O—CO—, —C ₂ F ₄ —, —CF═CF—, —CH═CH—CH ₂ O— or a single bond, preferably a single bond,
L ^1-4 each independently represents F, Cl, OCF ₃ , CF ₃ , CH ₃ , CH ₂ F, or CHF ₂ .

Preferably, both groups L ¹ and L ² represent F, or one of groups L ¹ and L ² represents F and the other represents Cl, or both groups L ³ and L ⁴ are Represents one or one of the groups L ³ and L ⁴ represents F and the other represents Cl.

  The compound of formula CY is preferably selected from the group consisting of the following sub-formulas:

式中、ａは１または２を表し、ａｌｋｙｌおよびａｌｋｙｌ^＊は、それぞれ互いに独立に、１〜６個のＣ原子を有する直鎖状のアルキル基を表し、ａｌｋｅｎｙｌは、２〜６個のＣ原子を有する直鎖状のアルケニル基を表し、（Ｏ）は酸素原子または単結合を表す。ａｌｋｅｎｙｌは、好ましくは、ＣＨ_２＝ＣＨ−、ＣＨ_２＝ＣＨＣＨ_２ＣＨ_２−、ＣＨ_３−ＣＨ＝ＣＨ−、ＣＨ_３−ＣＨ_２−ＣＨ＝ＣＨ−、ＣＨ_３−（ＣＨ_２）_２−ＣＨ＝ＣＨ−、ＣＨ_３−（ＣＨ_２）_３−ＣＨ＝ＣＨ−またはＣＨ_３−ＣＨ＝ＣＨ−（ＣＨ_２）_２−を表す。

In the formula, a represents 1 or 2, alkyl and alkyl ^* each independently represent a linear alkyl group having 1 to 6 C atoms, and alkenyl represents 2 to 6 C atoms. Represents a linear alkenyl group having a hydrogen atom, and (O) represents an oxygen atom or a single bond. alkenyl is preferably CH ₂ ═CH—, CH ₂ ═CHCH ₂ CH ₂ —, CH ₃ —CH═CH—, CH ₃ —CH ₂ —CH═CH—, CH ₃ — (CH ₂ ) ₂ —CH. _{= CH-, CH 3 - (CH} 2) 3 -CH = CH- or _{CH 3 -CH = CH- (CH 2} ) 2 - represents a.

  The compound of formula PY is preferably selected from the group consisting of:

式中、ａｌｋｙｌおよびａｌｋｙｌ^＊は、それぞれ互いに独立に、１〜６個のＣ原子を有する直鎖状のアルキル基を表し、ａｌｋｅｎｙｌは、２〜６個のＣ原子を有する直鎖状のアルケニル基を表し、（Ｏ）は酸素原子または単結合を表す。ａｌｋｅｎｙｌは、好ましくは、ＣＨ_２＝ＣＨ−、ＣＨ_２＝ＣＨＣＨ_２ＣＨ_２−、ＣＨ_３−ＣＨ＝ＣＨ−、ＣＨ_３−ＣＨ_２−ＣＨ＝ＣＨ−、ＣＨ_３−（ＣＨ_２）_２−ＣＨ＝ＣＨ−、ＣＨ_３−（ＣＨ_２）_３−ＣＨ＝ＣＨ−またはＣＨ_３−ＣＨ＝ＣＨ−（ＣＨ_２）_２−を表す。

In the formula, alkyl and alkyl ^* each independently represent a linear alkyl group having 1 to 6 C atoms, and alkenyl represents a linear alkenyl group having 2 to 6 C atoms. (O) represents an oxygen atom or a single bond. alkenyl is preferably CH ₂ ═CH—, CH ₂ ═CHCH ₂ CH ₂ —, CH ₃ —CH═CH—, CH ₃ —CH ₂ —CH═CH—, CH ₃ — (CH ₂ ) ₂ —CH. _{= CH-, CH 3 - (CH} 2) 3 -CH = CH- or _{CH 3 -CH = CH- (CH 2} ) 2 - represents a.

  b) LC medium additionally comprising one or more compounds of the following formula:

式中、個々の基は、以下の意味を有する：

In the formula, the individual groups have the following meanings:

Ｒ^３およびＲ^４は、それぞれ互いに独立に、１〜１２個のＣ原子を有するアルキルを表し、ただし加えて、１個または２個の隣接していないＣＨ_２基は、Ｏ原子が互いに直接連結しないようにして、−Ｏ−、−ＣＨ＝ＣＨ−、−ＣＯ−、−Ｏ−ＣＯ−または−ＣＯ−Ｏ−で置き換えられていてもよく、
Ｚ^ｙは、−ＣＨ_２ＣＨ_２−、−ＣＨ＝ＣＨ−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＯ−Ｏ−、−Ｏ−ＣＯ−、−Ｃ_２Ｆ_４−、−ＣＦ＝ＣＦ−、−ＣＨ＝ＣＨＣＨ_２Ｏ−または単結合、好ましくは、単結合を表す。

R ³ and R ⁴ each independently represent an alkyl having 1 to 12 C atoms, provided that one or two non-adjacent CH ₂ groups are linked directly to each other by O atoms. May be replaced by —O—, —CH═CH—, —CO—, —O—CO— or —CO—O—,
Z ^y _{is, -CH 2 CH 2 -, -} CH = CH -, - CF 2 O -, - OCF 2 -, - CH 2 O -, - OCH 2 -, - CO-O -, - O-CO- , —C ₂ F ₄ —, —CF═CF—, —CH═CHCH ₂ O—, or a single bond, preferably a single bond.

  The compound of formula ZK is preferably selected from the group consisting of:

式中、ａｌｋｙｌおよびａｌｋｙｌ^＊は、それぞれ互いに独立に、１〜６個のＣ原子を有する直鎖状のアルキル基を表し、ａｌｋｅｎｙｌは、２〜６個のＣ原子を有する直鎖状のアルケニル基を表す。ａｌｋｅｎｙｌは、好ましくは、ＣＨ_２＝ＣＨ−、ＣＨ_２＝ＣＨＣＨ_２ＣＨ_２−、ＣＨ_３−ＣＨ＝ＣＨ−、ＣＨ_３−ＣＨ_２−ＣＨ＝ＣＨ−、ＣＨ_３−（ＣＨ_２）_２−ＣＨ＝ＣＨ−、ＣＨ_３−（ＣＨ_２）_３−ＣＨ＝ＣＨ−またはＣＨ_３−ＣＨ＝ＣＨ−（ＣＨ_２）_２−を表す。

In the formula, alkyl and alkyl ^* each independently represent a linear alkyl group having 1 to 6 C atoms, and alkenyl represents a linear alkenyl group having 2 to 6 C atoms. Represents. alkenyl is preferably CH ₂ ═CH—, CH ₂ ═CHCH ₂ CH ₂ —, CH ₃ —CH═CH—, CH ₃ —CH ₂ —CH═CH—, CH ₃ — (CH ₂ ) ₂ —CH. _{= CH-, CH 3 - (CH} 2) 3 -CH = CH- or _{CH 3 -CH = CH- (CH 2} ) 2 - represents a.

  c) LC medium additionally comprising one or more compounds of the following formula:

式中、個々の基は、それぞれの出現において同一または異なって、以下の意味を有する：
Ｒ^５およびＲ^６は、それぞれ互いに独立に、上でＲ^１に示される意味の１つを有し、

In the formula, the individual groups are the same or different at each occurrence and have the following meanings:
R ⁵ and R ⁶ each independently of one another have one of the meanings indicated above for R ¹ ,

ｅは、１または２を表す。

e represents 1 or 2.

  The compound of formula DK is preferably selected from the group consisting of:

式中、ａｌｋｙｌおよびａｌｋｙｌ^＊は、それぞれ互いに独立に、１〜６個のＣ原子を有する直鎖状のアルキル基を表し、ａｌｋｅｎｙｌおよびａｌｋｅｎｙｌ^＊は、それぞれ互いに独立に、２〜６個のＣ原子を有する直鎖状のアルケニル基を表す。ａｌｋｅｎｙｌおよびａｌｋｅｎｙｌ^＊は、好ましくは、ＣＨ_２＝ＣＨ−、ＣＨ_２＝ＣＨＣＨ_２ＣＨ_２−、ＣＨ_３−ＣＨ＝ＣＨ−、ＣＨ_３−ＣＨ_２−ＣＨ＝ＣＨ−、ＣＨ_３−（ＣＨ_２）_２−ＣＨ＝ＣＨ−、ＣＨ_３−（ＣＨ_２）_３−ＣＨ＝ＣＨ−またはＣＨ_３−ＣＨ＝ＣＨ−（ＣＨ_２）_２−を表す。

In the formula, alkyl and alkyl ^* each independently represent a linear alkyl group having 1 to 6 C atoms, and alkenyl and alkenyl ^* are each independently 2 to 6 C atoms. Represents a straight-chain alkenyl group having alkenyl and alkenyl ^* are preferably CH ₂ ═CH—, CH ₂ ═CHCH ₂ CH ₂ —, CH ₃ —CH═CH—, CH ₃ —CH ₂ —CH═CH—, CH ₃ — (CH ₂ ). _{2 -CH = CH-, CH 3 -} (CH 2) 3 -CH = CH- or _{CH 3 -CH = CH- (CH 2} ) 2 - represents a.

  d) LC medium additionally comprising one or more compounds of the following formula:

式中、個々の基は以下の意味を有する：

In the formula, the individual groups have the following meanings:

ｆは、０または１を表し、
Ｒ^１およびＲ^２は、それぞれ互いに独立に、１〜１２個のＣ原子を有するアルキルを表し、ただし加えて、１個または２個の隣接していないＣＨ_２基は、Ｏ原子が互いに直接連結しないようにして、−Ｏ−、−ＣＨ＝ＣＨ−、−ＣＯ−、−ＯＣＯ−または−ＣＯＯ−で置き換えられていてもよく、
Ｚ^ｘおよびＺ^ｙは、それぞれ互いに独立に、−ＣＨ_２ＣＨ_２−、−ＣＨ＝ＣＨ−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＯ−Ｏ−、−Ｏ−ＣＯ−、−Ｃ_２Ｆ_４−、−ＣＦ＝ＣＦ−、−ＣＨ＝ＣＨＣＨ_２Ｏ−または単結合、好ましくは単結合を表し、
Ｌ^１およびＬ^２は、それぞれ互いに独立に、Ｆ、Ｃｌ、ＯＣＦ_３、ＣＦ_３、ＣＨ_３、ＣＨ_２Ｆ、ＣＨＦ_２を表す。

f represents 0 or 1,
R ¹ and R ² each independently represent an alkyl having 1 to 12 C atoms, provided that one or two non-adjacent CH ₂ groups are linked directly to each other by O atoms May be replaced by -O-, -CH = CH-, -CO-, -OCO- or -COO-
Z ^x and Z ^y are each independently of each other —CH ₂ CH ₂ —, —CH═CH—, —CF ₂ O—, —OCF ₂ —, —CH ₂ O—, —OCH ₂ —, —CO—. O—, —O—CO—, —C ₂ F ₄ —, —CF═CF—, —CH═CHCH ₂ O— or a single bond, preferably a single bond,
L ¹ and L ² each independently represent F, Cl, OCF ₃ , CF ₃ , CH ₃ , CH ₂ F, or CHF ₂ .

Preferably, both groups L ¹ and L ² represent F, or one of the groups L ¹ and L ² represents F and the other represents Cl.

  The compound of formula LY is preferably selected from the group consisting of the following sub-formulas:

式中、Ｒ^１は上で示される意味を有し、ａｌｋｙｌは１〜６個のＣ原子を有する直鎖状のアルキル基を表し、（Ｏ）は酸素原子または単結合を表し、ｖは１〜６の整数を表す。Ｒ^１は、好ましくは、１〜６個のＣ原子を有する直鎖状のアルキルまたは２〜６個のＣ原子を有する直鎖状のアルケニル、特に、ＣＨ_３、Ｃ_２Ｈ_５、ｎ−Ｃ_３Ｈ_７、ｎ−Ｃ_４Ｈ_９、ｎ−Ｃ_５Ｈ_１１、ＣＨ_２＝ＣＨ−、ＣＨ_２＝ＣＨＣＨ_２ＣＨ_２−、ＣＨ_３−ＣＨ＝ＣＨ−、ＣＨ_３−ＣＨ_２−ＣＨ＝ＣＨ−、ＣＨ_３−（ＣＨ_２）_２−ＣＨ＝ＣＨ−、ＣＨ_３−（ＣＨ_２）_３−ＣＨ＝ＣＨ−またはＣＨ_３−ＣＨ＝ＣＨ−（ＣＨ_２）_２−を表す。

In which R ¹ has the meaning indicated above, alkyl represents a linear alkyl group having 1 to 6 C atoms, (O) represents an oxygen atom or a single bond, and v represents 1 Represents an integer of ~ 6. R ¹ is preferably straight-chain alkyl having 1 to 6 C atoms or straight-chain alkenyl having 2 to 6 C atoms, in particular CH ₃ , C ₂ H ₅ , n—C _{3 H 7, n-C 4} H 9, n-C 5 H 11, CH 2 = CH-, CH 2 = CHCH 2 CH 2 -, CH 3 -CH = CH-, CH 3 -CH 2 -CH = CH _{-, CH 3 - (CH 2} ) 2 -CH = CH-, CH 3 - (CH 2) 3 -CH = CH- or _{CH 3 -CH = CH- (CH 2} ) 2 - represents a.

  e) LC medium additionally comprising one or more compounds selected from the group consisting of:

式中、ａｌｋｙｌはＣ_１〜６アルキルを表し、Ｌ^ｘはＨまたはＦを表し、Ｘは、Ｆ、Ｃｌ、ＯＣＦ_３、ＯＣＨＦ_２またはＯＣＨ＝ＣＦ_２を表す。ＸがＦを表す式Ｇ１の化合物が特に好ましい。

Wherein, alkyl represents _{C 1 to 6} alkyl, ^{L x} represents H or F, X represents F, _Cl, and OCF 3, OCHF ₂ or OCH = CF _2. Particular preference is given to compounds of the formula G1 in which X represents F.

  f) LC medium additionally comprising one or more compounds selected from the group consisting of:

式中、Ｒ^５はＲ^１に上で示される意味の１つを有し、ａｌｋｙｌはＣ_１〜６アルキルを表し、ｄは０または１を表し、ｚおよびｍは、それぞれ互いに独立に、１〜６の整数を表す。これらの化合物においてＲ^５は、特に好ましくは、Ｃ_１〜６−アルキルまたは−アルコキシまたはＣ_２〜６−アルケニルであり、ｄは、好ましくは、１である。本発明によるＬＣ媒体は、好ましくは、上述の式の１種類以上の化合物を５重量％以上の量で含む。

In which R ⁵ has ^one of the meanings indicated above for R ¹ , alkyl represents C _1-6 alkyl, d represents 0 or 1, z and m are each independently of each other 1 Represents an integer of ~ 6. In these compounds, R ⁵ is particularly preferably C _1-6 -alkyl or -alkoxy or C _2-6 -alkenyl, and d is preferably 1. The LC medium according to the invention preferably comprises one or more compounds of the above formula in an amount of 5% by weight or more.

  g) LC medium additionally comprising one or more biphenyl compounds selected from the group consisting of:

式中、ａｌｋｙｌおよびａｌｋｙｌ^＊は、それぞれ互いに独立に、１〜６個のＣ原子を有する直鎖状のアルキル基を表し、ａｌｋｅｎｙｌおよびａｌｋｅｎｙｌ^＊は、それぞれ互いに独立に、２〜６個のＣ原子を有する直鎖状のアルケニル基を表す。ａｌｋｅｎｙｌおよびａｌｋｅｎｙｌ^＊は、好ましくは、ＣＨ_２＝ＣＨ−、ＣＨ_２＝ＣＨＣＨ_２ＣＨ_２−、ＣＨ_３−ＣＨ＝ＣＨ−、ＣＨ_３−ＣＨ_２−ＣＨ＝ＣＨ−、ＣＨ_３−（ＣＨ_２）_２−ＣＨ＝ＣＨ−、ＣＨ_３−（ＣＨ_２）_３−ＣＨ＝ＣＨ−またはＣＨ_３−ＣＨ＝ＣＨ−（ＣＨ_２）_２−を表す。

In the formula, alkyl and alkyl ^* each independently represent a linear alkyl group having 1 to 6 C atoms, and alkenyl and alkenyl ^* are each independently 2 to 6 C atoms. Represents a straight-chain alkenyl group having alkenyl and alkenyl ^* are preferably CH ₂ ═CH—, CH ₂ ═CHCH ₂ CH ₂ —, CH ₃ —CH═CH—, CH ₃ —CH ₂ —CH═CH—, CH ₃ — (CH ₂ ). _{2 -CH = CH-, CH 3 -} (CH 2) 3 -CH = CH- or _{CH 3 -CH = CH- (CH 2} ) 2 - represents a.

  The proportion of the biphenyls of the formulas B1 to B3 in the LC mixture is preferably at least 3% by weight, in particular 5% by weight or more.

  Particular preference is given to compounds of the formula B2.

  The compounds of formula B1-B3 are preferably selected from the group consisting of the following sub-formulas:

式中、ａｌｋｙｌ^＊は、１〜６個のＣ原子を有するアルキル基を表す。本発明による媒体は、特に好ましくは、式Ｂ１ａおよび／またはＢ２ｃの１種類以上の化合物を含む。

In the formula, alkyl ^* represents an alkyl group having 1 to 6 C atoms. The medium according to the invention particularly preferably comprises one or more compounds of the formulas B1a and / or B2c.

  h) LC medium additionally comprising one or more terphenyl compounds of the following formula:

式中、Ｒ^５およびＲ^６は、それぞれ互いに独立に、上でＲ^１に示される意味の１つを有し、

In which R ⁵ and R ⁶ each independently of one another have one of the meanings indicated above for R ¹ ,

式中、Ｌ^５はＦまたはＣｌ、好ましくは、Ｆを表し、Ｌ^６はＦ、Ｃｌ、ＯＣＦ_３、ＣＦ_３、ＣＨ_３、ＣＨ_２ＦまたはＣＨＦ_２、好ましくはＦを表す。

In the formula, L ⁵ represents F or Cl, preferably F, and L ⁶ represents F, Cl, OCF ₃ , CF ₃ , CH ₃ , CH ₂ F or CHF ₂ , preferably F.

  The compound of formula T is preferably selected from the group consisting of:

式中、Ｒは１〜７個のＣ原子を有する直鎖状のアルキルまたはアルコキシ基を表し、Ｒ^＊は２〜７個のＣ原子を有する直鎖状のアルケニル基を表し、（Ｏ）は酸素原子または単結合を表し、ｍは１〜６の整数を表す。Ｒ^＊は、好ましくは、ＣＨ_２＝ＣＨ−、ＣＨ_２＝ＣＨＣＨ_２ＣＨ_２−、ＣＨ_３−ＣＨ＝ＣＨ−、ＣＨ_３−ＣＨ_２−ＣＨ＝ＣＨ−、ＣＨ_３−（ＣＨ_２）_２−ＣＨ＝ＣＨ−、ＣＨ_３−（ＣＨ_２）_３−ＣＨ＝ＣＨ−またはＣＨ_３−ＣＨ＝ＣＨ−（ＣＨ_２）_２−を表す。

In the formula, R represents a linear alkyl or alkoxy group having 1 to 7 C atoms, R ^* represents a linear alkenyl group having 2 to 7 C atoms, and (O) is An oxygen atom or a single bond is represented, and m represents an integer of 1 to 6. R ^* is _{preferably, CH 2 = CH-, CH 2} = CHCH 2 CH 2 -, CH 3 -CH = CH-, CH 3 -CH 2 -CH = CH-, CH 3 - (CH 2) 2 - _{CH = CH-, CH 3 - (} CH 2) 3 -CH = CH- or _{CH 3 -CH = CH- (CH 2} ) 2 - represents a.

  R preferably represents methyl, ethyl, propyl, butyl, pentyl, hexyl, methoxy, ethoxy, propoxy, butoxy or pentoxy.

  The LC medium according to the invention preferably comprises terphenyls of the formula T and its preferred subformations in an amount of 0.5 to 30% by weight, in particular 1 to 20% by weight.

  Particular preference is given to compounds of the formulas T1, T2, T3 and T21. In these compounds, R preferably represents alkyl each having 1 to 5 C atoms, and further alkoxy.

  When the Δn value of the mixture is 0.1 or more, terphenyls are preferably used in the mixture according to the invention. Preferred mixtures comprise 2 to 20% by weight of one or more terphenyl compounds of the formula T (preferably selected from the group of compounds T1 to T22).

  i) LC medium additionally comprising one or more compounds selected from the group consisting of:

式中、Ｒ^１およびＲ^２は上で示される意味を有し、好ましくは、それぞれ互いに独立に、１〜６個のＣ原子を有する直鎖状のアルキルまたは２〜６個のＣ原子を有する直鎖状のアルケニルを表す。

In which R ¹ and R ² have the meanings indicated above, preferably each independently of one another of a straight-chain alkyl having 1 to 6 C atoms or 2 to 6 C atoms. Represents linear alkenyl.

  Preferred media include one or more compounds selected from the formulas O1, O3 and O4.

  k) LC medium additionally comprising one or more compounds of the following formula, preferably in an amount of more than 3% by weight, in particular 5% by weight or more, very particularly preferably 5-30% by weight:

式中、

Where

Ｒ^９は、Ｈ、ＣＨ_３、Ｃ_２Ｈ_５またはｎ−Ｃ_３Ｈ_７を表し、（Ｆ）は任意のフッ素置換を表し、ｑは１、２または３を表し、Ｒ^７はＲ^１に示される意味の１つを有する。

R ⁹ represents H, CH ₃ , C ₂ H ₅ or n-C ₃ H ₇ , (F) represents optional fluorine substitution, q represents 1, 2 or 3, and R ⁷ represents R ¹ Has one of the meanings indicated.

  Particularly preferred compounds of formula FI are selected from the group consisting of:

式中、Ｒ^７は、好ましくは、直鎖状のアルキルを表し、Ｒ^９は、ＣＨ_３、Ｃ_２Ｈ_５またはｎ−Ｃ_３Ｈ_７を表す。式ＦＩ１、ＦＩ２およびＦＩ３の化合物が特に好ましい。

In the formula, R ⁷ preferably represents linear alkyl, and R ⁹ represents CH ₃ , C ₂ H ₅ or n-C ₃ H ₇ . Particular preference is given to compounds of the formulas FI1, FI2 and FI3.

  m) LC medium additionally comprising one or more compounds selected from the group consisting of:

式中、Ｒ^８はＲ^１に示される意味を有し、ａｌｋｙｌは１〜６個のＣ原子を有する直鎖状のアルキル基を表す。

In the formula, R ⁸ has the meaning shown in R ¹ and alkyl represents a linear alkyl group having 1 to 6 C atoms.

  n) LC medium additionally comprising one or more compounds containing tetrahydronaphthyl or naphthyl units, for example compounds selected from the group consisting of:

式中、Ｒ^１０およびＲ^１１は、それぞれ互いに独立に、Ｒ^１に示される意味の１つを有し、好ましくは、１〜６個のＣ原子を有する直鎖状のアルキルまたはアルコキシまたは２〜６個のＣ原子を有する直鎖状のアルケニルを表し、Ｚ^１およびＺ^２は、それぞれ互いに独立に、−Ｃ_２Ｈ_４−、−ＣＨ＝ＣＨ−、−（ＣＨ_２）_４−、−（ＣＨ_２）_３Ｏ−、−Ｏ（ＣＨ_２）_３−、−ＣＨ＝ＣＨＣＨ_２ＣＨ_２−、−ＣＨ_２ＣＨ_２ＣＨ＝ＣＨ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＯ−Ｏ−、−Ｏ−ＣＯ−、−Ｃ_２Ｆ_４−、−ＣＦ＝ＣＦ−、−ＣＦ＝ＣＨ−、−ＣＨ＝ＣＦ−、−ＣＨ_２−または単結合を表す。

In which R ¹⁰ and R ¹¹ each independently of one another have one of the meanings indicated for R ¹ and are preferably straight-chain alkyl or alkoxy having 1 to 6 C atoms or 2- Represents straight-chain alkenyl having 6 C atoms, and Z ¹ and Z ² are each independently of each other —C ₂ H ₄ —, —CH═CH—, — (CH ₂ ) ₄ —, — ( _{CH 2) 3 O -, -} O (CH 2) 3 -, - CH = CHCH 2 CH 2 -, - CH 2 CH 2 CH = CH -, - CH 2 O -, - OCH 2 -, - CO-O _{-, - O-CO -,} - C 2 F 4 -, - CF = CF -, - CF = CH -, - CH = CF -, - represents a single bond or - CH _2.

  o) LC medium additionally comprising one or more difluorodibenzochromans and / or chromans of the following formula, preferably in an amount of 3-20% by weight, in particular 3-15% by weight:

式中、Ｒ^１１およびＲ^１２は、それぞれ互いに独立に、上で示される意味を有し、環Ｍは、トランス−１，４−シクロヘキシレンまたは１，４−フェニレンを表し、Ｚ^ｍは、−Ｃ_２Ｈ_４−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＯ−Ｏ−または−Ｏ−ＣＯ−を表し、ｃは、０または１を表す。

In which R ¹¹ and R ¹² each independently of one another have the meaning indicated above, ring M represents trans-1,4-cyclohexylene or 1,4-phenylene, and Z ^m represents — C ₂ H ₄ —, —CH ₂ O—, —OCH ₂ —, —CO—O— or —O—CO— is represented, and c represents 0 or 1.

  Particularly preferred compounds of formula BC and CR are selected from the group consisting of:

式中、ａｌｋｙｌおよびａｌｋｙｌ^＊は、それぞれ互いに独立に、１〜６個のＣ原子を有する直鎖状のアルキル基を表し、（Ｏ）は、酸素原子または単結合を表し、ａｌｋｅｎｙｌおよびａｌｋｅｎｙｌ^＊は、それぞれ互いに独立に、２〜６個のＣ原子を有する直鎖状のアルケニル基を表す。ａｌｋｅｎｙｌおよびａｌｋｅｎｙｌ^＊は、好ましくは、ＣＨ_２＝ＣＨ−、ＣＨ_２＝ＣＨＣＨ_２ＣＨ_２−、ＣＨ_３−ＣＨ＝ＣＨ−、ＣＨ_３−ＣＨ_２−ＣＨ＝ＣＨ−、ＣＨ_３−（ＣＨ_２）_２−ＣＨ＝ＣＨ−、ＣＨ_３−（ＣＨ_２）_３−ＣＨ＝ＣＨ−またはＣＨ_３−ＣＨ＝ＣＨ−（ＣＨ_２）_２−を表す。

In the formula, alkyl and alkyl ^* each independently represent a linear alkyl group having 1 to 6 C atoms, (O) represents an oxygen atom or a single bond, and alkenyl and alkenyl ^* are Each independently represents a linear alkenyl group having 2 to 6 C atoms. alkenyl and alkenyl ^* are preferably CH ₂ ═CH—, CH ₂ ═CHCH ₂ CH ₂ —, CH ₃ —CH═CH—, CH ₃ —CH ₂ —CH═CH—, CH ₃ — (CH ₂ ). _{2 -CH = CH-, CH 3 -} (CH 2) 3 -CH = CH- or _{CH 3 -CH = CH- (CH 2} ) 2 - represents a.

  Very particular preference is given to mixtures comprising one, two or three compounds of the formula BC-2.

  p) LC media additionally comprising one or more fluorinated phenanthrenes and / or dibenzofurans of the following formula:

式中、Ｒ^１１およびＲ^１２は、それぞれ互いに独立に、上で示される意味を有し、ｂは０または１を表し、ＬはＦを表し、ｒは１、２または３を表す。

In the formula, R ¹¹ and R ¹² each independently have the meaning shown above, b represents 0 or 1, L represents F, and r represents 1, 2 or 3.

  Particularly preferred compounds of formula PH and BF are selected from the group consisting of the following sub-formulas:

式中、ＲおよびＲ’は、それぞれ互いに独立に、１〜７個のＣ原子を有する直鎖状のアルキルまたはアルコキシ基を表す。

In the formula, R and R ′ each independently represent a linear alkyl or alkoxy group having 1 to 7 C atoms.

q) LC medium free of polymerizable compounds according to the invention, in particular compounds containing a terminal vinyloxy group (—O—CH═CH ₂ ) apart from formula I or sub-formulas and comonomers thereof.

  r) LC medium preferably selected from the polymerizable compounds according to the invention, in particular 1 to 5, preferably 1, 2 or 3 types of polymerizable compounds of the formula I or sub-formula thereof .

  s) LC media in which the proportion in the mixture of polymerizable compounds of the formula I or sub-formula thereof is in particular 0.05 to 5%, preferably 0.1 to 1%.

  t) LC medium comprising 1-8, preferably 1-5, compounds of formula CY1, CY2, PY1 and / or PY2. The total proportion of these compounds in the mixture is preferably 5 to 60%, particularly preferably 10 to 35%. The content of these individual compounds is preferably 2 to 20% in each case.

  u) LC medium comprising 1-8, preferably 1-5, compounds of formula CY9, CY10, PY9 and / or PY10. The total proportion of these compounds in the mixture is preferably 5 to 60%, particularly preferably 10 to 35%. The content of these individual compounds is preferably 2 to 20% in each case.

  v) LC medium comprising 1-10, preferably 1-8, compounds of the formula ZK, in particular compounds of the formulas ZK1, ZK2 and / or ZK6. The total proportion of these compounds in the mixture is preferably 3 to 25%, particularly preferably 5 to 45%. The content of these individual compounds is preferably 2 to 20% in each case.

  w) LC medium in which the proportion of compounds of the formulas CY, PY and ZK in the mixture is more than 70%, preferably more than 80%.

  x) A PSA-VA display having a pretilt angle of preferably 85 ° or less, particularly preferably 80 ° or less.

  In a second preferred embodiment of the invention, the LC medium comprises an LC host mixture based on a compound having positive dielectric anisotropy. This type of LC media is particularly suitable for use in PSA-OCB, PSA-TN, PSA-positive VA, PSA-IPS and PSA-FFS displays. A particularly preferred embodiment of such a display is given below.

  An LC medium comprising one or more compounds selected from the group consisting of compounds of the following formula:

式ＡＡおよび／またはＢＢの化合物に加えて、以下の式の１種類以上の化合物を含むＬＣ媒体。

LC medium comprising, in addition to a compound of formula AA and / or BB, one or more compounds of the following formula:

式ＡＡ、ＢＢおよびＣＣにおいて、個々の基は以下の意味を有する：

In the formulas AA, BB and CC, the individual groups have the following meanings:

Ｒ^２１、Ｒ^３１、Ｒ^４１、Ｒ^４２は、それぞれ互いに独立に、１〜９個のＣ原子を有するアルキル、アルコキシ、オキサアルキルまたはフルオロアルキル、または、２〜９個のＣ原子を有するアルケニルを表し、
Ｘ^０は、Ｆ、Ｃｌ、１〜６個のＣ原子を有するハロゲン化されたアルキルまたはアルコキシ、または、２〜６個のＣ原子を有するハロゲン化されたアルケニルまたはアルケニルオキシを表し、
Ｚ^３１は、−ＣＨ_２ＣＨ_２−、−ＣＦ_２ＣＦ_２−、−ＣＯＯ−、トランス−ＣＨ＝ＣＨ−、トランス−ＣＦ＝ＣＦ−、−ＣＨ_２Ｏ−または単結合、好ましくは、−ＣＨ_２ＣＨ_２−、−ＣＯＯ−、トランス−ＣＨ＝ＣＨ−または単結合、特に好ましくは、−ＣＯＯ−、トランス−ＣＨ＝ＣＨ−または単結合を表し、
Ｚ^４１、Ｚ^４２は、−ＣＨ_２ＣＨ_２−、−ＣＯＯ−、トランス−ＣＨ＝ＣＨ−、トランス−ＣＦ＝ＣＦ−、−ＣＨ_２Ｏ−、−ＣＦ_２Ｏ−、−Ｃ≡Ｃ−または単結合、好ましくは、単結合を表し、
Ｌ^２１、Ｌ^２２、Ｌ^３１、Ｌ^３２は、ＨまたはＦを表し、
ｇは、１、２または３を表し、
ｈは、０、１、２または３を表す。

R ²¹ , R ³¹ , R ⁴¹ , R ⁴² are each independently an alkyl having 1 to 9 C atoms, alkoxy, oxaalkyl or fluoroalkyl, or alkenyl having 2 to 9 C atoms. Represent,
X ⁰ represents F, Cl, halogenated alkyl or alkoxy having 1 to 6 C atoms, or halogenated alkenyl or alkenyloxy having 2 to 6 C atoms,
Z ³¹ is —CH ₂ CH ₂ —, —CF ₂ CF ₂ —, —COO—, trans—CH═CH—, trans—CF═CF—, —CH ₂ O— or a single bond, preferably —CH ₂ CH ₂ —, —COO—, trans—CH═CH— or a single bond, particularly preferably —COO—, trans—CH═CH— or a single bond,
Z ⁴¹ and Z ⁴² are —CH ₂ CH ₂ —, —COO—, trans—CH═CH—, trans—CF═CF—, —CH ₂ O—, —CF ₂ O—, —C≡C— or Represents a single bond, preferably a single bond,
L ²¹ , L ²² , L ³¹ and L ³² represent H or F,
g represents 1, 2 or 3;
h represents 0, 1, 2 or 3.

X ⁰ is preferably F, Cl, CF ₃ , CHF ₂ , OCF ₃ , OCHF ₂ , OCHFHCF ₃ , OCHFHCHF ₂ , OCHFHCHF ₂ , OCF ₂ CH ₃ , OCF ₂ CHF ₂ , OCF ₂ CHF ₂ , OCF ₂ CF _{2 CHF 2, OCF 2 CF 2} CHF 2, OCFHCF 2 CF 3, OCFHCF 2 CHF 2, OCF 2 CF 2 CF 3, OCF 2 CF 2 CClF 2, OCClFCF 2 CF 3 or CH = CF _2, particularly preferably, F or an OCF _3.

  The compound of formula AA is preferably selected from the group consisting of:

式中、Ａ^２１、Ｒ^２１、Ｘ^０、Ｌ^２１およびＬ^２２は、式ＡＡで示される意味を有し、Ｌ^２３およびＬ^２４は、それぞれ互いに独立に、ＨまたはＦを表し、Ｘ^０は、好ましくは、Ｆを表す。式ＡＡ１およびＡＡ２の化合物が特に好ましい。

In the formula, A ²¹ , R ²¹ , X ⁰ , L ²¹ and L ²² have the meanings indicated by formula AA, L ²³ and L ²⁴ each independently represent H or F, and X ⁰ is , Preferably represents F. Particularly preferred are compounds of formula AA1 and AA2.

  Particularly preferred compounds of formula AA1 are selected from the group consisting of:

式中、Ｒ^０は、式ＡＡ１においてＲ^２１に示される意味の１つを有し、Ｘ^０、Ｌ^２１およびＬ^２２は、式ＡＡ１において示される意味を有し、Ｌ^２３、Ｌ^２４、Ｌ^２５およびＬ^２６は、それぞれ互いに独立に、ＨまたはＦを表し、Ｘ^０は、好ましくは、Ｆを表す。

In which R ⁰ has one of the meanings indicated for R ²¹ in formula AA1, and X ⁰ , L ²¹ and L ²² have the meanings indicated for formula AA1, L ²³ , L ²⁴ , L ²⁵ and L ²⁶ each independently represent H or F, and X ⁰ preferably represents F.

  Very particularly preferred compounds of the formula AA1 are selected from the group consisting of:

式中、Ｒ^０は、式ＡＡ１においてＲ^２１に示される意味を有する。

In which R ⁰ has the meaning indicated for R ²¹ in formula AA1.

  Particularly preferred compounds of formula AA2 are selected from the group consisting of:

式中、Ｒ^０は、式ＡＡ１においてＲ^２１に示される意味を有し、Ｘ^０、Ｌ^２１およびＬ^２２は、式ＡＡにおいて示される意味を有し、Ｌ^２３、Ｌ^２４、Ｌ^２５およびＬ^２６は、それぞれ互いに独立に、ＨまたはＦを表し、Ｘ^０は、好ましくは、Ｆを表す。

In which R ⁰ has the meaning shown in R ²¹ in formula AA1, X ⁰ , L ²¹ and L ²² have the meaning shown in formula AA, and L ²³ , L ²⁴ , L ²⁵ and L ²⁶ each independently represent H or F, and X ⁰ preferably represents F.

  Very particularly preferred compounds of formula AA2 are selected from the group consisting of:

式中、Ｒ^０は、式ＡＡ１においてＲ^２１に示される意味を有する。

In which R ⁰ has the meaning indicated for R ²¹ in formula AA1.

  Particularly preferred compounds of formula AA3 are selected from the group consisting of:

式中、Ｒ^０は、式ＡＡ１においてＲ^２１に示される意味を有し、Ｘ^０、Ｌ^２１およびＬ^２２は、式ＡＡ３において示される意味を有し、Ｘ^０は、好ましくは、Ｆを表す。

In which R ⁰ has the meaning indicated by R ²¹ in formula AA1, X ⁰ , L ²¹ and L ²² have the meaning indicated in formula AA3, and X ⁰ preferably represents F. .

  Particularly preferred compounds of formula AA4 are selected from the group consisting of:

式中、Ｒ^０は、式ＡＡ１においてＲ^２１に示される意味を有する。

In which R ⁰ has the meaning indicated for R ²¹ in formula AA1.

  The compound of formula BB is preferably selected from the group consisting of:

式中、Ａ^３１、Ａ^３２、Ｒ^３１、Ｘ^０、Ｌ^３１およびＬ^３２は、式ＢＢで示される意味を有し、Ｘ^０は、好ましくは、Ｆを表す。式ＢＢ１およびＢＢ２の化合物が特に好ましい。

In the formula, A ³¹ , A ³² , R ³¹ , X ⁰ , L ³¹ and L ³² have the meanings indicated by formula BB, and X ⁰ preferably represents F. Particularly preferred are compounds of formula BB1 and BB2.

  Particularly preferred compounds of formula BB1 are selected from the group consisting of:

式中、Ｒ^３は、式ＢＢ１においてＲ^３１に示される意味を有し、Ｘ^０、Ｌ^３１およびＬ^３２は、式ＢＢ１において示される意味を有し、Ｘ^０は、好ましくは、Ｆを表す。

In which R ³ has the meaning indicated by R ³¹ in formula BB1, X ⁰ , L ³¹ and L ³² have the meaning indicated in formula BB1, and X ⁰ preferably represents F. .

  Very particularly preferred compounds of the formula BB1a are selected from the group consisting of:

式中、Ｒ^３は、式ＢＢ１においてＲ^３１に示される意味を有する。

In which R ³ has the meaning indicated for R ³¹ in formula BB1.

  Very particularly preferred compounds of the formula BB1b are selected from the group consisting of:

式中、Ｒ^３は、式ＢＢ１においてＲ^３１に示される意味を有する。

In which R ³ has the meaning indicated for R ³¹ in formula BB1.

  Particularly preferred compounds of formula BB2 are selected from the group consisting of:

式中、Ｒ^０は、式ＢＢ２においてＲ^２１に示される意味の１つを有し、Ｘ^０、Ｌ^３１およびＬ^３２は、式ＢＢ２において示される意味を有し、Ｌ^３３、Ｌ^３４、Ｌ^３５およびＬ^３６は、それぞれ互いに独立に、ＨまたはＦを表し、Ｘ^０は、好ましくは、Ｆを表す。

In which R ⁰ has one of the meanings indicated for R ²¹ in formula BB2, and X ⁰ , L ³¹ and L ³² have the meanings indicated for formula BB2, L ³³ , L ³⁴ , L ³⁵ and L ³⁶ each independently represent H or F, and X ⁰ preferably represents F.

  Very particularly preferred compounds of the formula BB2a are selected from the group consisting of:

式中、Ｒ^３は、式ＢＢ２においてＲ^３１に示される意味を有する。

In which R ³ has the meaning indicated for R ³¹ in formula BB2.

  Very particularly preferred compounds of the formula BB2b are selected from the group consisting of:

式中、Ｒ^３は、式ＢＢ２においてＲ^３１に示される意味を有する。

In which R ³ has the meaning indicated for R ³¹ in formula BB2.

  Very particularly preferred compounds of the formula BB2c are selected from the group consisting of:

式中、Ｒ^３は、式ＢＢ２においてＲ^３１に示される意味を有する。

In which R ³ has the meaning indicated for R ³¹ in formula BB2.

  Very particularly preferred compounds of the formulas BB2d and BB2e are selected from the group consisting of:

式中、Ｒ^３は、式ＢＢ２においてＲ^３１に示される意味を有する。

In which R ³ has the meaning indicated for R ³¹ in formula BB2.

  Very particularly preferred compounds of the formula BB2f are selected from the group consisting of:

式中、Ｒ^３は、式ＢＢ２においてＲ^３１に示される意味を有する。

In which R ³ has the meaning indicated for R ³¹ in formula BB2.

  Very particularly preferred compounds of the formula BB2g are selected from the group consisting of:

式中、Ｒ^３は、式ＢＢ２においてＲ^３１に示される意味を有する。

In which R ³ has the meaning indicated for R ³¹ in formula BB2.

  Very particularly preferred compounds of the formula BB2h are selected from the group consisting of:

式中、Ｒ^３は、式ＢＢ２においてＲ^３１に示される意味を有する。

In which R ³ has the meaning indicated for R ³¹ in formula BB2.

  Very particularly preferred compounds of the formula BB2i are selected from the group consisting of:

式中、Ｒ^３は、式ＢＢ２においてＲ^３１に示される意味を有する。

In which R ³ has the meaning indicated for R ³¹ in formula BB2.

  Very particularly preferred compounds of the formula BB2k are selected from the group consisting of:

式中、Ｒ^３は、式ＢＢ２においてＲ^３１に示される意味を有する。

In which R ³ has the meaning indicated for R ³¹ in formula BB2.

  Instead of or in addition to compounds of formula BB1 and / or BB2, the LC medium may also contain one or more compounds of formula BB3 as defined above.

  Particularly preferred compounds of formula BB3 are selected from the group consisting of:

式中、Ｒ^３は、式ＢＢ３においてＲ^３１に示される意味を有する。

In which R ³ has the meaning indicated for R ³¹ in formula BB3.

  In addition to the compounds of formula AA and / or BB, the LC medium according to the second preferred embodiment is preferably a dielectrically neutral compound having a dielectric anisotropy of −1.5 to +3 (the compound is , Selected from the group consisting of compounds of formula CC as defined above).

  Particularly preferred compounds of formula CC are selected from the group consisting of:

式中、Ｒ^４１およびＲ^４２は式ＣＣにおいて示される意味を有し、好ましくは、それぞれ互いに独立に、１〜７個のＣ原子を有するアルキル、アルコキシ、フッ素化アルキルまたはフッ素化アルコキシ、または、２〜７個のＣ原子を有するアルケニル、アルケニルオキシ、アルコキシアルキルまたはフッ素化アルケニルを表し、Ｌ^４は、ＨまたはＦを表す。

In which R ⁴¹ and R ⁴² have the meanings indicated in formula CC, preferably, independently of one another, alkyl having 1 to 7 C atoms, alkoxy, fluorinated alkyl or fluorinated alkoxy, or Represents alkenyl, alkenyloxy, alkoxyalkyl or fluorinated alkenyl having 2 to 7 C atoms, L ⁴ represents H or F;

  Instead of adding to the compound of formula CC, the LC medium according to the second preferred embodiment is preferably a dielectrically neutral compound having a dielectric anisotropy of -1.5 to +3 (the compound is of formula Selected from the group consisting of compounds of DD).

式中、Ａ^４１、Ａ^４２、Ｚ^４１、Ｚ^４２、Ｒ^４１、Ｒ^４２およびｈは、式ＣＣにおいて示される意味を有する。

In which A ⁴¹ , A ⁴² , Z ⁴¹ , Z ⁴² , R ⁴¹ , R ⁴² and h have the meanings indicated in formula CC.

  Particularly preferred compounds of formula DD are selected from the group consisting of:

式中、Ｒ^４１およびＲ^４２は、式ＤＤにおいて示される意味を有し、Ｒ^４１は、好ましくは、アルキルを表し、式ＤＤ１において、Ｒ^４２は、好ましくは、アルケニル、特に好ましくは、−（ＣＨ_２）_２−ＣＨ＝ＣＨ−ＣＨ_３を表し、式ＤＤ２において、Ｒ^４２は、好ましくは、アルキル、−（ＣＨ_２）_２−ＣＨ＝ＣＨ_２または−（ＣＨ_２）_２−ＣＨ＝ＣＨ−ＣＨ_３を表す。

In which R ⁴¹ and R ⁴² have the meanings indicated in formula DD, R ⁴¹ preferably represents alkyl, and in formula DD1, R ⁴² is preferably alkenyl, particularly preferably — ( CH ₂₎ represents ₂ -CH = CH-CH _3, in formula ^{DD2, R 42} is preferably _{alkyl, - (CH 2) 2 -CH} = CH 2 or _{- (CH 2) 2 -CH =} CH- It represents a CH _3.

  The concentration of the compounds of the formulas AA and BB in the LC medium according to the invention is preferably 2% to 60%, particularly preferably 3% to 35%, very particularly preferably 4% to 30% of the total mixture. %.

  The concentration of the compounds of the formulas CC and DD in the LC medium according to the invention is preferably from 2% to 70%, in particular from 5% to 65%, particularly preferably from 10% to 60%, of the whole mixture Particularly preferably, it is 10% (preferably 15%) to 50%.

  By combining a low molecular weight compound as a component of the LC host mixture according to the preferred embodiment described above with the polymerized compound described above, in the LC medium according to the invention, low threshold voltage, low rotational viscosity and very good low temperature stability. Always occur simultaneously with a high clearing point and a high HR value, and a particularly low pretilt angle can be quickly established in PSA displays. In particular, in PSA displays, LC media also exhibit significantly shortened response times, and in particular, half-tone response times, compared to media from the prior art.

  The liquid crystal mixture preferably has a nematic phase range of at least 80 K, particularly preferably of at least 100 K, and a rotational viscosity at 20 ° C. of 250 mPa · s or less, preferably 200 mPa · s or less.

  In a VA type display according to the invention, in the switched-off state, the molecules in the LC medium layer are oriented perpendicular to the electrode surface (homeotropic orientation) or have a tilt homeotropic orientation. When a voltage is applied to the electrode, realignment of LC molecules whose molecular long axis is parallel to the electrode surface occurs.

  The LC medium according to the invention of the first preferred embodiment, in particular for use in a PSA-VA type display, preferably at about −0.5 to −10, in particular about 20 ° C. and 1 kHz. It has a negative dielectric anisotropy Δε of −2.5 to −7.5.

  In the LC medium according to the invention of the first preferred embodiment, in particular for use in a PSA-VA type display, the birefringence Δn is preferably less than 0.16, particularly preferably 0.06 and 0. Between 14, in particular between 0.07 and 0.12.

  In the OCB type display according to the invention, the molecules in the LC media layer have a “bend” orientation. When a voltage is applied, LC molecules reorientate with the molecular long axis perpendicular to the electrode surface.

  The LC medium according to the invention for use in a PSA-OCB type display is preferably one having a positive dielectric anisotropy Δε according to the second preferred embodiment, preferably at 20 ° C. and 1 kHz, It has a dielectric anisotropy Δε of about +4 to +17.

  In the LC medium according to the invention of the second preferred embodiment for use in OCB type displays, the birefringence Δn is preferably between 0.14 and 0.22, in particular between 0.16 and 0.22. Between.

  The LC medium according to the invention of the second preferred embodiment is in particular for use in PSA-TN, PSA-positive VA, PSA-IPS and PSA-FFS type displays, preferably 20 At + ° C. and 1 kHz, it has a positive dielectric anisotropy Δε of +2 to +30, particularly preferably +2 to +17, very particularly preferably +3 to +15.

  In a second preferred embodiment of the LC medium according to the invention, in particular for use in PSA-TN, PSA-IPS and PSA-FFS type displays, the birefringence Δn is preferably 0.07 and 0 .15, in particular between 0.08 and 0.13.

  The LC medium according to the invention may also contain further additives known to the person skilled in the art and described in the literature, such as, for example, polymerization initiators, inhibitors, stabilizers, surface-activating substances or chiral dopants. . These may be polymerizable or non-polymerizable. Accordingly, the polymerizable additive belongs to the polymerizable component or component A). Thus, the non-polymerizable additive is considered to belong to the non-polymerizable component or component B).

  The LC medium may include, for example, one or more chiral dopants, preferably those selected from the group consisting of compounds from Table B below.

  Further, for example, 0 to 15% by weight of a pleochroic dye, further nanoparticles, a conductive salt for improving conductivity, preferably ethyldimethyldodecylammonium 4-hexoxybenzoate, tetrabutylammonium tetraphenylborate Or complex salts of crown ethers (see, for example, Haller et al., Mol. Cryst. Liq. Cryst. 24, 249-258 (1973)), or dielectric anisotropy, viscosity and / or nematic phase orientation. Substances for modification can be added to the LC medium. Substances of this type are, for example, German Patent Application Publication No. 22 09 127, German Patent Application Publication No. 22 40 864, German Patent Application Publication No. 23 21 632, German Patent Application Publication No. No. 23 38 281, German Patent Application Publication No. 24 50 088, German Patent Application Publication No. 26 37 430 and German Patent Application Publication No. 28 53 728.

  Since the individual components of preferred embodiments a) to z) of the LC medium according to the invention are known or their preparation is based on standard methods described in the literature, the preparation methods are Can be guided more easily than the prior art. Corresponding compounds of the formula CY are described, for example, in EP-A-0 364 538. Corresponding compounds of the formula ZK are described, for example, in German Offenlegungsschrift 26 36 684 and German Offenlegungsschrift 33 21 373.

  The LC medium that can be used according to the invention is, for example, one or more of the above-mentioned compounds, one or more polymerizable compounds as defined above, and optionally further liquid crystal compounds and / or additives. By itself in a conventional manner. In general, the desired amount of the components used in smaller amounts is dissolved in the components making up the major constituents, preferably at elevated temperatures. It is also possible to mix a solution of components in an organic solvent, for example acetone, chloroform or methanol, and after complete mixing, the solvent can be removed again, for example by distillation. The invention further relates to a method for preparing the LC medium according to the invention.

  It goes without saying to those skilled in the art that the LC medium according to the present invention may also contain compounds in which, for example, H, N, O, Cl, F are replaced by the corresponding isotopes.

  The structure of the LC display according to the invention corresponds to the usual construction for a PSA display as described in the prior art cited at the beginning. A structure without protrusions is preferable. In particular, it is preferable that the electrode on the color filter side is not structured, and only the electrode on the TFT side has a slot. A particularly suitable and preferred electrode structure for PSA-VA displays is described, for example, in US 2006/0066793.

  The following examples illustrate the present invention without limiting it. However, they show the person skilled in the art the preferred mixing concept of the compounds used preferably, their respective concentrations and their combinations with one another. In addition, the examples illustrate what properties and combinations of properties are available.

Use the following abbreviations:
(N, m, z: in each case, independently of each other 1, 2, 3, 4, 5 or 6)

本発明の好ましい実施形態において、本発明によるＬＣ媒体は、表Ａからの化合物から成る群より選択される１種類以上の化合物を含む。

In a preferred embodiment of the invention, the LC medium according to the invention comprises one or more compounds selected from the group consisting of compounds from Table A.

  Table B shows the available chiral dopants that can be added to the LC medium according to the invention.

ＬＣ媒体は、好ましくは０〜１０重量％、特には０．０１〜５重量％、特に好ましくは０．１〜３重量％のドーパントを含む。ＬＣ媒体は、好ましくは、表Ｂからの化合物から成る群より選択される１種類以上のドーパントを含む。

The LC medium preferably contains 0 to 10% by weight, in particular 0.01 to 5% by weight, particularly preferably 0.1 to 3% by weight of dopant. The LC medium preferably comprises one or more dopants selected from the group consisting of compounds from Table B.

  Table C shows the available stabilizers that can be added to the LC medium according to the invention, where n is an integer from 1 to 12, preferably 1, 2, 3, 4, 5, 6, 7 or 8 And the terminal methyl group is not shown).

ＬＣ媒体は、好ましくは０〜１０重量％、特には１ｐｐｍ〜５重量％、特に好ましくは１ｐｐｍ〜１重量％の安定剤を含む。ＬＣ媒体は、好ましくは、表Ｃからの化合物から成る群より選択される１種類以上の安定剤を含む。

The LC medium preferably contains 0 to 10% by weight of stabilizer, in particular 1 ppm to 5% by weight, particularly preferably 1 ppm to 1% by weight. The LC medium preferably comprises one or more stabilizers selected from the group consisting of compounds from Table C.

  Table D shows exemplary compounds that can be used in the LC medium according to the invention, preferably as reactive mesogenic compounds.

本発明の好ましい実施形態において、メソゲン媒体は、表Ｄからの化合物から成る群より選択される１種類以上の化合物を含む。

In a preferred embodiment of the present invention, the mesogenic medium comprises one or more compounds selected from the group consisting of compounds from Table D.

In addition, the following abbreviations and symbols are used:
V ₀ is the capacity threshold voltage (V) at 20 ° C.
n _e is the extraordinary refractive index at 20 ° C. and 589 nm,
n ₀ is the ordinary refractive index at 20 ° C. and 589 nm,
Δn is the optical anisotropy at 20 ° C. and 589 nm,
ε _⊥ is the dielectric constant perpendicular to the director at 20 ° C. and 1 kHz,
ε _‖ is the dielectric constant parallel to the director at 20 ° C. and 1 kHz,
Δε is the dielectric anisotropy at 20 ° C. and 1 kHz,
cl. p. , T (N, I) is the clearing point (° C.)
γ ₁ is the rotational viscosity (mPa · s) at 20 ° C.
K ₁ is the elastic constant (pN) for “spray” deformation at 20 ° C.
K ₂ is the elastic constant (pN) for “twist” deformation at 20 ° C.
K ₃ is the elastic constant (pN) for “bend” deformation at 20 ° C.

  Unless otherwise stated, all concentrations in this application are given in weight percent and relate to LC media containing the entire corresponding mixture, ie, all solids or liquid crystal components, and no solvent.

  Unless otherwise stated, such as melting point T (C, N), smectic (S) to nematic (N) phase transition T (S, N) and clearing point T (N, I) All temperature values are given in degrees Celsius (° C). m. p. Represents the melting point, cl. p. Is the clearing point. Furthermore, C is a crystalline state, N is a nematic phase, S is a smectic phase, and I is an isotropic phase. Data between these symbols represents the transition temperature.

  All physical properties are determined or determined according to “Melk liquid crystal, liquid crystal physical properties” November 1997, according to Merck GmbH, Germany, unless otherwise indicated in each case temperature 20 ° C. is applied, Δn is determined at 589 nm, and Δε is determined at 1 kHz.

For the purposes of the present invention, the term “threshold voltage” relates to the capacity threshold (V ₀ ), also known as the Fredericks threshold, unless explicitly indicated otherwise. In the examples, the optical threshold for 10% relative contrast (C1 ₀ ), which is generally normal, may also be shown.

  The display used for measuring the capacitance threshold voltage consists of two flat parallel glass skins separated by a distance of 20 μm, each skin is not rubbed on the inner electrode layer and on the outermost surface. It has a polyimide alignment layer, and the alignment layer is effective for homeotropic edge alignment of liquid crystal molecules.

  The display or test cell used for measuring the tilt angle consists of two flat parallel glass skins separated by a distance of 4 μm, each skin with an electrode layer on the inside and a polyimide on the outermost surface. However, the two polyimide alignment layers are rubbed antiparallel to each other, which is effective for homeotropic edge alignment of liquid crystal molecules.

While a voltage is applied to the display (usually 10 to 30 V alternating current, 1 kHz), UVA light of a predetermined intensity (usually 365 nm) is irradiated at a given time to polymerize in the display or test cell. Polymerize the compound. Unless otherwise indicated in the examples, a 28 mW / cm ² mercury vapor lamp is used and the intensity is measured using a standard UV meter (model Ushio UNI meter) fitted with a 365 nm bandpass filter.

  The tilt angle is determined by a rotating crystal experiment (Autronic-Melchers TBA-105). In the present specification, a low value (i.e., far from the angle of 90 °) corresponds to a large tilt.

  The VHR value is measured as follows: 0.3% polymerizable monomer compound is added to the LC host mixture and the resulting mixture is rubbed at TN-VHR test cell (rubbed at 90 °, TN polyimide alignment layer, layer thickness d is About 6 μm). Before and after 2 hours of UV exposure (sunshine test), the HR value is determined with a pulse of 1 V, 60 Hz and 64 μs after 5 minutes at 100 ° C. (measuring device: Autronic-Melchers VHRM-105).

  To examine the stability of the LC mixture against low temperature stability (also referred to as “LTS” (low-temperature stability)), ie, the individual components spontaneously crystallize and precipitate at low temperatures. A bottle containing the / RM mixture is placed in a storage at -10 ° C and periodically checked to see if the mixture has crystallized or precipitated.

<Example 1>
2-methylacrylic acid 7- (2-methylacryloyloxy) -4,5,9,10-tetrahydropyren-2-yl <1.1 2,7-diiodo-4,5,9,10-tetrahydropyrene>

７．７０ｇ（３６．２ｍｍｏｌ）の４，５，９，１０−テトラヒドロピレン、３．３０ｇ（１４．５ｍｍｏｌ）の過ヨウ素酸および９．００ｇ（３５．５ｍｍｏｌ）のヨウ素を、７０ｍｌの氷酢酸中における２．２ｍｌの濃硫酸および１５ｍｌの水の溶液中において、７０℃で１時間加熱する。引き続いて、溶液を氷水に加え、酢酸エチルで３回抽出する。合わされた有機相を希亜硫酸水素ナトリウム溶液および飽和炭酸水素ナトリウム溶液で洗浄し、硫酸ナトリウム上で乾燥する。溶媒を真空中で除去し、残渣をトルエン／ヘプタン（２：１）でシリカゲル上においてクロマトグラフする。粗生成物をヘプタン／トルエン（１：１）より結晶化し、無色の固体として、２，７−ジヨード−４，５，９，１０−テトラヒドロピレンを与える。

7.70 g (36.2 mmol) 4,5,9,10-tetrahydropyrene, 3.30 g (14.5 mmol) periodic acid and 9.00 g (35.5 mmol) iodine in 70 ml glacial acetic acid. In a solution of 2.2 ml of concentrated sulfuric acid and 15 ml of water at 70 ° C. for 1 hour. Subsequently, the solution is added to ice water and extracted three times with ethyl acetate. The combined organic phases are washed with dilute sodium hydrogen sulfite solution and saturated sodium hydrogen carbonate solution and dried over sodium sulfate. The solvent is removed in vacuo and the residue is chromatographed on silica gel with toluene / heptane (2: 1). The crude product is crystallized from heptane / toluene (1: 1) to give 2,7-diiodo-4,5,9,10-tetrahydropyrene as a colorless solid.

＜１．２ ４，５，９，１０−テトラヒドロピレン−２，７−ジオール＞

<1.2 4,5,9,10-tetrahydropyrene-2,7-diol>

最初に、３．２０ｇ（６．８０ｍｍｏｌ）の２，７−ジヨード−４，５，９，１０−テトラヒドロピレンを４０ｍｌのジオキサン中に導入し、２０ｍｌの水中の１．５０ｇ（２６．７ｍｍｏｌ）の水酸化カリウム、３００ｍｇ（０．５２２ｍｍｏｌ）のビス（ジベンジリデンアセトン）パラジウムおよび４５０ｍｇの２−ジ−ｔｅｒｔ−ブチルホスフィノ−２’，４’，６’−トリイソプロピルビフェニルの溶液を加え、バッチを８０℃で３時間加熱する。引き続いて、溶液を１００ｍｌのトルエンで希釈し、水で抽出する。合わされた有機相を希塩酸を使用して酸性とし、酢酸エチルで３回抽出する。合わされた有機相を水洗し、硫酸ナトリウム上で乾燥する。溶媒を真空中で除去し、残渣をトルエン／酢酸エチル（７：３）でシリカゲル上においてクロマトグラフし、粗生成物をトルエン／ヘプタン（１：１）より結晶化し、無色の結晶として、４，５，９，１０−テトラヒドロピレン−２，７−ジオールを与える。

First, 3.20 g (6.80 mmol) of 2,7-diiodo-4,5,9,10-tetrahydropyrene was introduced into 40 ml of dioxane and 1.50 g (26.7 mmol) of 20 ml of water. A solution of potassium hydroxide, 300 mg (0.522 mmol) bis (dibenzylideneacetone) palladium and 450 mg 2-di-tert-butylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl was added and the batch was Heat at 80 ° C. for 3 hours. Subsequently, the solution is diluted with 100 ml of toluene and extracted with water. The combined organic phases are acidified using dilute hydrochloric acid and extracted three times with ethyl acetate. The combined organic phases are washed with water and dried over sodium sulfate. The solvent is removed in vacuo, the residue is chromatographed on silica gel with toluene / ethyl acetate (7: 3), and the crude product is crystallized from toluene / heptane (1: 1) to give 4,4 as colorless crystals. 5,9,10-tetrahydropyrene-2,7-diol is obtained.

＜１．３ ２−メチルアクリル酸７−（２−メチルアクリロイルオキシ）−４，５，９，１０−テトラヒドロピレン−２−イル＞

<1.3 2-Methylacrylic acid 7- (2-methylacryloyloxy) -4,5,9,10-tetrahydropyren-2-yl>

９００ｍｇ（３．５５ｍｍｏｌ）の４，５，９，１０−テトラヒドロピレン−２，７−ジオールを１５ｍｌのジクロロメタン中に懸濁し、１．３ｍｌのピリジンおよび５０ｍｇのＤＭＡＰを加え、引き続いて、２５ｍｌのジクロロメタン中の１．５ｇ（９ｍｍｏｌ）のアクリル酸無水物の溶液を、氷冷しながら滴下で加える。３０分後に冷却を取り外し、バッチを放置して室温で一晩攪拌する。引き続いて、溶液をシリカゲルに通して濾過し、濾液をエバポレートし、粗生成物をヘプタン／トルエンより再結晶し、融点１４６℃の無色の結晶として２−メチルアクリル酸７−（２−メチルアクリロイルオキシ）−４，５，９，１０−テトラヒドロピレン−２−イルを与える。

900 mg (3.55 mmol) 4,5,9,10-tetrahydropyrene-2,7-diol are suspended in 15 ml dichloromethane, 1.3 ml pyridine and 50 mg DMAP are added, followed by 25 ml dichloromethane. A solution of 1.5 g (9 mmol) of acrylic anhydride in is added dropwise with ice cooling. Remove cooling after 30 minutes and leave the batch to stir overnight at room temperature. Subsequently, the solution is filtered through silica gel, the filtrate is evaporated, the crude product is recrystallized from heptane / toluene and 2-methylacrylic acid 7- (2-methylacryloyloxy) as colorless crystals with a melting point of 146 ° C. ) -4,5,9,10-tetrahydropyren-2-yl.

<Example 2>
2-methylacrylic acid 7- [4- (2-methylacryloyloxy) but-1-ynyl] -4,5,9,10-tetrahydropyren-2-yl <2.1 2,7-dibromo-4, 5,9,10-Tetrahydropyrene>

最初に、２０．６ｇ（９４．６ｍｍｏｌ）の４，５，９，１０−テトラヒドロピレンを１６０ｍｌのリン酸トリメチル中に導入し、４０ｍｌのリン酸トリメチル中の１７ｍｌ（３３２ｍｍｏｌ）の臭素の溶液を、温度が２５℃を超えない速度で、穏やかに冷却しながら加える。バッチを放置して更に３時間攪拌し、８００ｍｌの氷水に加え、重亜硫酸ナトリウム溶液を加えて過剰の臭素を分解する。１５分後、沈殿してくる生成物を吸引で濾別し、温めながらトルエン中に溶解し、シリカゲルに通して濾過し、トルエン／ヘプタンより再結晶し、無色の結晶として２，７−ジブロモ−４，５，９，１０−テトラヒドロピレンを与える。

First, 20.6 g (94.6 mmol) of 4,5,9,10-tetrahydropyrene was introduced into 160 ml of trimethyl phosphate and a solution of 17 ml (332 mmol) of bromine in 40 ml of trimethyl phosphate was added. The temperature is added at a rate not exceeding 25 ° C. with gentle cooling. The batch is left to stir for an additional 3 hours, added to 800 ml of ice water, and sodium bisulfite solution is added to decompose excess bromine. After 15 minutes, the precipitated product is filtered off with suction, dissolved in toluene while warming, filtered through silica gel, recrystallized from toluene / heptane, and 2,7-dibromo- 4,5,9,10-tetrahydropyrene is obtained.

    <2.2 7-Bromo-4,5,9,10-tetrahydropyren-2-ol>

最初に、６．４０ｇ（１６．９ｍｍｏｌ）の２，７−ジブロモ−４，５，９，１０−テトラヒドロピレンおよび７ｍｌ（３０ｍｍｏｌ）のホウ酸トリイソプロピルを２００ｍｌのＴＨＦ中に導入し、１５ｍｌ（２４ｍｍｏｌ）のヘキサン中のｎ−ブチルリチウム１５パーセント溶液を、−７０℃において加える。添加が完了した時点で、混合物を更に１時間攪拌し、２Ｍ塩酸を使用して加水分解し、放置して解凍し、ＭＴＢエーテルで２回抽出する。合わされた有機相をエバポレートし、残渣を１００ｍｌのトルエン、２０ｍｌの２Ｍ水酸化ナトリウム溶液および２０ｍｌの水の混合物中に、激しく攪拌しながら懸濁し、１０ｍｌの３０パーセント過酸化水素を、４０℃において、ゆっくり加える。添加が完了した時点で、バッチを放置して更に１時間攪拌し、１００ｍｌの水に加え、２Ｍの塩酸を使用して酸性とする。水相を分離・除去し、酢酸エチルで３回抽出する。合わされた有機相を硫酸アンモニウム鉄（ＩＩ）溶液および飽和塩化ナトリウム溶液で洗浄し、硫酸ナトリウム上で乾燥する。真空中で溶媒を除去し、残渣をジクロロメタンでシリカゲル上においてクロマトグラフし、粗生成物をトルエンより再結晶化し、無色の結晶として、７−ブロモ−４，５，９，１０−テトラヒドロピレン−２−オールを与える。

First, 6.40 g (16.9 mmol) 2,7-dibromo-4,5,9,10-tetrahydropyrene and 7 ml (30 mmol) triisopropyl borate were introduced into 200 ml THF and 15 ml (24 mmol ) Is added at -70 ° C. When the addition is complete, the mixture is stirred for an additional hour, hydrolyzed using 2M hydrochloric acid, allowed to thaw and extracted twice with MTB ether. The combined organic phases are evaporated, the residue is suspended in a mixture of 100 ml toluene, 20 ml 2M sodium hydroxide solution and 20 ml water with vigorous stirring and 10 ml 30 percent hydrogen peroxide at 40 ° C. Add slowly. When the addition is complete, the batch is left to stir for an additional hour, added to 100 ml of water and acidified using 2M hydrochloric acid. The aqueous phase is separated and removed and extracted three times with ethyl acetate. The combined organic phases are washed with ammonium iron (II) sulfate solution and saturated sodium chloride solution and dried over sodium sulfate. The solvent is removed in vacuo, the residue is chromatographed on silica gel with dichloromethane and the crude product is recrystallized from toluene to give 7-bromo-4,5,9,10-tetrahydropyrene-2 as colorless crystals. -Give oars.

    <2.3 7- (4-Hydroxybut-1-ynyl) -4,5,9,10-tetrahydropyren-2-ol>

最初に、８．８０ｇ（２８．３ｍｍｏｌ）の７−ブロモ−４，５，９，１０−テトラヒドロピレン−２−オールを１００ｍｌのＴＨＦ中に導入し、１．７ｇ（２．４２ｍｍｏｌ）の塩化ビス（トリフェニルホスフィン）パラジウム（ＩＩ）、０．４ｇ（２．１０ｍｍｏｌ）のヨウ化銅（Ｉ）および１１ｍｌのジイソプロピルアミンを加え、引き続き、２０ｍｌのＴＨＦ中の５．０ｇ（７８．３ｍｍｏｌ）の１−ブチンの溶液を、６５℃で１時間かけて滴下で加える。添加が完了した時点で、バッチを放置して更に２時間攪拌し、水に加え、２Ｎの塩酸を使用して酸性とする。水相を分離・除去し、酢酸エチルで３回抽出する。合わされた有機相を水洗し、硫酸ナトリウム上で乾燥し、真空中で溶媒を除去する。粗生成物をジクロロメタン／酢酸エチル（４：１）でシリカゲルに通して濾過し、トルエンより再結晶して、無色の固体として７−ヨード−９，１０−ジヒドロフェナントレン−２−オールを与える。

First, 8.80 g (28.3 mmol) of 7-bromo-4,5,9,10-tetrahydropyren-2-ol was introduced into 100 ml of THF and 1.7 g (2.42 mmol) of bis chloride was introduced. (Triphenylphosphine) palladium (II), 0.4 g (2.10 mmol) of copper (I) iodide and 11 ml of diisopropylamine were added followed by 5.0 g (78.3 mmol) of 1 in 20 ml of THF. -A solution of butyne is added dropwise at 65 ° C over 1 hour. When the addition is complete, the batch is left to stir for an additional 2 hours, added to water and acidified using 2N hydrochloric acid. The aqueous phase is separated and removed and extracted three times with ethyl acetate. The combined organic phases are washed with water, dried over sodium sulfate and the solvent is removed in vacuo. The crude product is filtered through silica gel with dichloromethane / ethyl acetate (4: 1) and recrystallized from toluene to give 7-iodo-9,10-dihydrophenanthren-2-ol as a colorless solid.

    <2.4 2-methylacrylic acid 7- [4- (2-methylacryloyloxy) but-1-ynyl] -4,5,9,10-tetrahydropyren-2-yl>

例１に類似して、７−（４−ヒドロキシブタ−１−イニル）−４，５，９，１０−テトラヒドロピレン−２−オールより、２−メチルアクリル酸７−［４−（２−メチルアクリロイルオキシ）ブタ−１−イニル］−４，５，９，１０−テトラヒドロピレン−２−イルを、融点１２１℃の無色の結晶として与える。

Analogously to Example 1, from 7- (4-hydroxybut-1-ynyl) -4,5,9,10-tetrahydropyren-2-ol, 2-methylacrylic acid 7- [4- (2-methyl Acryloyloxy) but-1-ynyl] -4,5,9,10-tetrahydropyren-2-yl is obtained as colorless crystals having a melting point of 121 ° C.

<Example 3>
2- [7- (2-Methylacryloyloxy) -4,5,9,10-tetrahydropyren-2-yl] butyl <3.1 7- (4-hydroxybutyl) -4,5 , 9,10-Tetrahydropyren-2-ol>

７−（４−ヒドロキシブタ−１−イニル）−４，５，９，１０−テトラヒドロピレン−２−オールを、ＴＨＦ中で、パラジウム／活性炭触媒上において水素化する。触媒を濾過・除去し、真空中で溶媒を除去し、残渣をトルエンより再結晶して、無色の固体として、７−（４−ヒドロキシブチル）−４，５，９，１０−テトラヒドロピレン−２−オールを与える。

7- (4-Hydroxybut-1-ynyl) -4,5,9,10-tetrahydropyren-2-ol is hydrogenated over a palladium / activated carbon catalyst in THF. The catalyst is filtered and removed, the solvent is removed in vacuo, and the residue is recrystallized from toluene to give 7- (4-hydroxybutyl) -4,5,9,10-tetrahydropyrene-2 as a colorless solid. -Give oars.

    <3.2 2-Methylacrylic acid 4- [7- (2-methylacryloyloxy) -4,5,9,10-tetrahydropyren-2-yl] butyl>

例１に類似して、７−（４−ヒドロキシブチル）−４，５，９，１０−テトラヒドロピレン−２−オールより、２−メチルアクリル酸４−［７−（２−メチルアクリロイルオキシ）−４，５，９，１０−テトラヒドロピレン−２−イル］ブチルを、融点１１０℃の無色の結晶として与える。

In analogy to Example 1, from 7- (4-hydroxybutyl) -4,5,9,10-tetrahydropyren-2-ol, 2-methylacrylic acid 4- [7- (2-methylacryloyloxy)- 4,5,9,10-Tetrahydropyren-2-yl] butyl is obtained as colorless crystals with a melting point of 110 ° C.

<Example 4>
2,4-Dimethyl-6- (2-methylacryloyloxy) -8,9-dihydro-4H-cyclopenta [def] phenanthren-2-yl 2-methyl acrylate <4.1 2,6-dibromo-4, 4-Dimethyl-8,9-dihydro-4H-cyclopenta [def] phenanthrene>

最初に、３．５０ｇ（１９．９ｍｍｏｌ）の４，４−ジメチル−８，９−ジヒドロ−４Ｈ−シクロペンタ［ｄｅｆ］フェナントレン（ＣＡＳ番号１０３５３０４−３１−４）をリン酸トリメチル中に導入し、１０ｍｌのリン酸トリメチル中の３．５ｍｌ（６８ｍｍｏｌ）の臭素の溶液を、２５℃において、穏やかに冷却しながら滴下で加える。バッチを放置して室温で４時間攪拌し、１５０ｍｌの氷水および１００ｍｌのトルエンに加え、重亜硫酸ナトリウム溶液を使用して過剰の臭素をつぶす。水相を分離・除去し、トルエンで１回抽出する。合わされた有機相を水洗し、硫酸ナトリウム上で乾燥し、真空中で溶媒を除去する。粗生成物をトルエン／ヘプタン（１：１）でシリカゲルに通して濾過し、トルエン／ヘプタン（１：１）より再結晶して、無色の結晶として、２，６−ジブロモ−４，４−ジメチル−８，９−ジヒドロ−４Ｈ−シクロペンタ［ｄｅｆ］フェナントレンを与える。

First, 3.50 g (19.9 mmol) of 4,4-dimethyl-8,9-dihydro-4H-cyclopenta [def] phenanthrene (CAS number 1035304-31-4) was introduced into trimethyl phosphate and 10 ml A solution of 3.5 ml (68 mmol) of bromine in 1 ml of trimethyl phosphate is added dropwise at 25 ° C. with gentle cooling. The batch is left to stir at room temperature for 4 hours, added to 150 ml ice water and 100 ml toluene, and excess bromine is crushed using sodium bisulfite solution. The aqueous phase is separated and removed and extracted once with toluene. The combined organic phases are washed with water, dried over sodium sulfate and the solvent is removed in vacuo. The crude product was filtered through silica gel with toluene / heptane (1: 1) and recrystallized from toluene / heptane (1: 1) to give 2,6-dibromo-4,4-dimethyl as colorless crystals. This gives -8,9-dihydro-4H-cyclopenta [def] phenanthrene.

＜４．２ ４，４−ジメチル−８，９−ジヒドロ−４Ｈ−シクロペンタ［ｄｅｆ］フェナントレン−２，６−ジオール＞

<4.2 4,4-Dimethyl-8,9-dihydro-4H-cyclopenta [def] phenanthrene-2,6-diol>

例１．２で記載される合成に類似して、２，６−ジブロモ−４，４−ジメチル−８，９−ジヒドロ−４Ｈ−シクロペンタ［ｄｅｆ］フェナントレンより、無色の結晶として、４，４−ジメチル−８，９−ジヒドロ−４Ｈ−シクロペンタ［ｄｅｆ］フェナントレン−２，６−ジオールを与える。

Analogous to the synthesis described in Example 1.2, 2,4-dibromo-4,4-dimethyl-8,9-dihydro-4H-cyclopenta [def] phenanthrene gives 4,4- Dimethyl-8,9-dihydro-4H-cyclopenta [def] phenanthrene-2,6-diol is obtained.

＜４．３ ２−メチルアクリル酸４，４−ジメチル−６−（２−メチルアクリロイルオキシ）−８，９−ジヒドロ−４Ｈ−シクロペンタ［ｄｅｆ］フェナントレン−２−イル＞

<4.3 2,4-Dimethyl-6- (2-methylacryloyloxy) -8,9-dihydro-4H-cyclopenta [def] phenanthren-2-yl 2-methylacrylate>

例１に類似して、４，４−ジメチル−８，９−ジヒドロ−４Ｈ−シクロペンタ［ｄｅｆ］フェナントレン−２，６−ジオールより、融点７７℃の無色の結晶として、２−メチルアクリル酸４，４−ジメチル−６−（２−メチルアクリロイルオキシ）−８，９−ジヒドロ−４Ｈ−シクロペンタ［ｄｅｆ］フェナントレン−２−イルを与える。

Similar to Example 1, from 4,4-dimethyl-8,9-dihydro-4H-cyclopenta [def] phenanthrene-2,6-diol as colorless crystals having a melting point of 77 ° C., 4-methylacrylic acid 4, 4-Dimethyl-6- (2-methylacryloyloxy) -8,9-dihydro-4H-cyclopenta [def] phenanthren-2-yl is obtained.

<Example 5>
2-methylacrylic acid 4,4-dimethyl-6- (2-methylacryloyloxy) -4H-cyclopenta [def] phenanthren-2-yl <5.1 2,6-dibromo-4,4-dimethyl-4H- Cyclopenta [def] phenanthrene>

最初に、２．２０ｇ（５．８２ｍｍｏｌ）の２，６−ジブロモ−４，４−ジメチル−８，９−ジヒドロ−４Ｈ−シクロペンタ［ｄｅｆ］フェナントレン、１．１０ｇ（６．１８ｍｍｏｌ）のＮ−ブロモコハク酸イミドおよび５０ｍｇのアゾビス（イソブチロニトリル）を、３０ｍｌの四塩化炭素に導入し、沸騰するまで、ゆっくりと加熱する。３時間後、バッチを６０℃まで冷却し、２０ｍｌの氷酢酸中１．５ｇの酢酸ナトリウムの溶液を加え、引き続いて、混合物を放置し、７０℃において４時間攪拌する。引き続いて、溶液をジクロロメタンに加え、２回水洗し、硫酸ナトリウム上で乾燥し、真空中で蒸発させる。残渣をトルエンでシリカゲルに通して濾過し、ヘプタンより再結晶して、無色の結晶として、２，６−ジブロモ−４，４−ジメチル−４Ｈ−シクロペンタ［ｄｅｆ］フェナントレンを与える。

First, 2.20 g (5.82 mmol) of 2,6-dibromo-4,4-dimethyl-8,9-dihydro-4H-cyclopenta [def] phenanthrene, 1.10 g (6.18 mmol) of N-bromosuccinate. Acid imide and 50 mg of azobis (isobutyronitrile) are introduced into 30 ml of carbon tetrachloride and heated slowly until boiling. After 3 hours, the batch is cooled to 60 ° C., a solution of 1.5 g sodium acetate in 20 ml glacial acetic acid is added and the mixture is subsequently left to stir at 70 ° C. for 4 hours. Subsequently, the solution is added to dichloromethane, washed twice with water, dried over sodium sulfate and evaporated in vacuo. The residue is filtered through silica gel with toluene and recrystallized from heptane to give 2,6-dibromo-4,4-dimethyl-4H-cyclopenta [def] phenanthrene as colorless crystals.

＜５．２ ４，４−ジメチル−４Ｈ−シクロペンタ［ｄｅｆ］フェナントレン−２，６−ジオール＞

<5.2 4,4-Dimethyl-4H-cyclopenta [def] phenanthrene-2,6-diol>

例１．２で記載される合成に類似して、２，６−ジブロモ−４，４−ジメチル−８，９−ジヒドロ−４Ｈ−シクロペンタ［ｄｅｆ］フェナントレンより、無色の結晶として、４，４−ジメチル−４Ｈ−シクロペンタ［ｄｅｆ］フェナントレン−２，６−ジオールを与える。

Analogous to the synthesis described in Example 1.2, 2,4-dibromo-4,4-dimethyl-8,9-dihydro-4H-cyclopenta [def] phenanthrene gives 4,4- Dimethyl-4H-cyclopenta [def] phenanthrene-2,6-diol is obtained.

    <5.3 2,4-Dimethyl-6- (2-methylacryloyloxy) -4H-cyclopenta [def] phenanthren-2-yl 2-methylacrylate>

例１に類似して、４，４−ジメチル−４Ｈ−シクロペンタ［ｄｅｆ］フェナントレン−２，６−ジオールより、融点１７０℃の無色の結晶として、２−メチルアクリル酸４，４−ジメチル−６−（２−メチルアクリロイルオキシ）−４Ｈ−シクロペンタ［ｄｅｆ］フェナントレン−２−イルを与える。

Similar to Example 1, from 4,4-dimethyl-4H-cyclopenta [def] phenanthrene-2,6-diol as colorless crystals having a melting point of 170 ° C., 4-methylacrylic acid 4,4-dimethyl-6- (2-Methylacryloyloxy) -4H-cyclopenta [def] phenanthren-2-yl is obtained.

<Use Example 1>
The nematic LC mixture N1 is formulated as follows.

下に示す例からの０．３％の重合性モノマー化合物をＬＣ混合物Ｎ１に加え、結果として生じる混合物をＶＡ ｅ／ｏ試験用セル（逆平行にラビングされたＶＡ−ポリイミド配向層、層厚ｄは約４μｍ）中に導入する。２４Ｖの電圧（交流）を印加しながら示される時間で５０ｍＷ／ｃｍ^２の強度を有するＵＶ光をセルに照射し、モノマー化合物の重合を起こす。ＵＶ照射の前後において、回転結晶実験（Ａｕｔｒｏｎｉｃ−Ｍｅｌｃｈｅｒｓ ＴＢＡ−１０５）によりチルト角を決定する。

0.3% of the polymerizable monomer compound from the example shown below is added to the LC mixture N1, and the resulting mixture is added to the VA e / o test cell (anti-parallel rubbed VA-polyimide alignment layer, layer thickness d Is introduced in about 4 μm). The cell is irradiated with UV light having an intensity of 50 mW / cm ² for the time indicated while applying a voltage (alternating current) of 24 V to cause polymerization of the monomer compound. Before and after UV irradiation, the tilt angle is determined by a rotating crystal experiment (Autronic-Melchers TBA-105).

  To determine the polymerization rate, the HPLC method is used to measure the residual content (% by weight) of unpolymerized RM in the test cell after various exposure times. For this, the respective mixtures are polymerized in the test cell under the conditions indicated. The mixture is then washed from the test cell using methyl ethyl ketone and measured.

  For comparison purposes, the above experiments are carried out with the polymerizable compounds C1 to C3 known from the prior art.

チルト角の結果を、表１にまとめる。種々の曝露時間後のＲＭ濃度を、表２にまとめる。

The tilt angle results are summarized in Table 1. RM concentrations after various exposure times are summarized in Table 2.

表１より見て取れる通り、重合後において、先行技術からのモノマーＣ１〜Ｃ３よりも、例１〜５からの本発明によるモノマーによって、より迅速に小さいチルト角を達成できる。加えて、表２より見て取れる通り、モノマーＣ１〜Ｃ３よりも、例１〜３からの本発明によるモノマーによって、著しく更に速い重合速度が達成される。

As can be seen from Table 1, after polymerization, a smaller tilt angle can be achieved more rapidly with the monomers according to the invention from Examples 1-5 than with the monomers C1-C3 from the prior art. In addition, as can be seen from Table 2, significantly faster polymerization rates are achieved with the monomers according to the invention from Examples 1 to 3 than with monomers C1 to C3.

Claims (15)

Use of compounds of formula I in PS or PSA type LC media and LC displays.

In which the individual groups have the following meanings:
W ¹ and W ² are each independently of each other, —CY ₂ CY ₂ —, —CY═CY—, —CY ₂ —O—, —O—CY ₂ —, —C (O) —O—, —O. ^{-C (O) -, - C} (R c R d) -, - O -, - S -, - NR e - represent,
Y is the same or different at each occurrence and represents H or F;
R ^a and R ^b are independently of each other P-Sp-, H, F, Cl, Br, I, -CN, -NO ₂ , -NCO, -NCS, -OCN, -SCN, SF ₅ , direct Chain or branched alkyl having 1 to 25 C atoms (in addition, one or more non-adjacent CH ₂ groups are each independently of each other, O and / or S atoms are not directly linked to each other) Thus, arylene, —C (R ⁰ ) = C (R ⁰⁰ ) —, —C≡C—, —N (R ⁰ ) —, —O—, —S—, —CO—, —CO—O -, -O-CO-, -O-CO-O- may be substituted, but in addition one or more H atoms may be F, Cl, Br, I, CN or P-Sp-. Optionally substituted aryl) having 2 to 25 C atoms or Heteroaryl (said group, also may contain two or more fused rings, said group may be mono- or polysubstituted by L.) Represents the proviso that ^the radicals R ^a and R at least one of ^b represents or contains the group P-Sp-
R ^c , R ^d and R ^e each independently represent H or a linear or branched alkyl having 1 to 12 C atoms,
P is the same or different at each occurrence and represents a polymerizable group;
Sp is the same or different at each occurrence and represents a spacer group or a single bond,
A ¹ and A ² each independently represent an aromatic, heteroaromatic, alicyclic or heterocyclic group having preferably 4 to 25 C atoms, which group is also a fused ring The group may be mono- or polysubstituted with L,
L is the same or different at each occurrence, and P—Sp—, OH, CH ₂ OH, halogen, —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, or optionally substituted carbon group Or a hydrocarbon group,
R ^x represents P-Sp, H, halogen, linear, branched or cyclic and represents an alkyl having 1 to 25, preferably 1 to 12, C atoms, in addition, one or more Non-adjacent CH ₂ groups can be defined as —O—, —S—, —CO—, —CO—O—, —O—CO—, —, such that the O and / or S atoms are not directly linked to each other. May be replaced by O-CO-O-, but in addition, one or more H atoms may be replaced by F, Cl or P-Sp-
Y ¹ represents halogen,
Z ¹ and Z ² are each independently of each other —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—, —CH═CF—, —CF═CH—, —C≡C—, —CH═CH _{-COO -, - OCO-CH =} CH -, - CH 2 -CH 2 -COO -, - OCO-CH 2 -CH 2 -, - C (R 0 R 00) -, - C (R y R z) -Or a single bond,
R ⁰ and R ⁰⁰ are each independently of each other, the same or different at each occurrence, H or alkyl having 1 to 12 C atoms,
R ^y and R ^z each independently represent H, F, CH ₃ or CF ₃ ;
n is the same or different at each occurrence and represents 1, 2, 3 or 4;
p and q each independently represent 0, 1 or 2,
r is the same or different at each occurrence and represents 0, 1 or 2. ) Use according to claim 1, characterized in that the compound of formula I is selected from formula IA.

(Wherein R ^a , R ^b , W ¹ , W ² , A ¹ , A ² , Z ¹ , Z ² , L, p, q and r have the meanings indicated in claim 1). In compounds of formula I and IA:
A ¹ and A ² are each independently 1,4-phenylene, naphthalene-1,4-diyl or naphthalene-2,6-diyl (in addition, one or more CH groups in these groups are N may be replaced with N), cyclohexane-1,4-diyl (but one or more non-adjacent CH ₂ groups may be replaced with O and / or S). 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-1,4-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, indan-2,5-diyl, octahydro- 4 , 7-methanoindan-2,5-diyl, phenanthrene-2,7-diyl, anthracene-2,7-diyl, phenanthrene-2,7-diyl, 9,10-dihydrophenanthrene-2,7-diyl, 6H- Benzo [c] chromene-3,8-diyl, 9H-fluorene-2,7-diyl, 9,9-dimethyl-9H-fluorene-2,7-diyl, dibenzofuran-3,7-diyl, 2-oxo- 2H-chromen-7-yl, 4-phenyl-2-oxo-2H-chromen-7-yl, 4-oxo-4H-chromen-6-yl, 4-phenyl-4-oxo-4H-chromene-6 Provided that all these groups may be unsubstituted or mono- or polysubstituted with L, provided that among these all groups cyclohexane and Very particularly preferably an aromatic group, and _{L, P-Sp-, 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, substituted Aryl having 6 to 20 C atoms, linear or branched, 1 to 25, preferably alkyl or alkoxy having 1 to 12 C atoms, or linear or branched Represents alkenyl, alkynyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 2 to 25, preferably 2 to 12, C atoms in the form of all but in all these groups One or more H atoms may be replaced by F, Cl, P or P-Sp-;
However, the use according to claim 1 or 2, characterized in that R ^x and Y ¹ have the meaning indicated in claim 1.   Two substrates and two electrodes (provided that at least one substrate is transparent to light and at least one substrate has one or two electrodes) and a substrate and is polymerized LC medium layer containing a component having a low molecular weight and a low molecular weight component (however, the polymerized component is formed by applying one or more polymerizable compounds in the LC medium between the LC cell substrates, preferably applying a voltage to the electrodes. Wherein at least one polymerizable compound is a polymerizable compound according to any one of claims 1 to 3). Or use of a compound according to any one of claims 1 to 3 in a PSA type LC display. 5. Use according to any one of claims 1 to 4, characterized in that the LC medium comprises one or more compounds of the formula CY and / or PY.

In which the individual groups have the following meanings:
a represents 1 or 2,
b represents 0 or 1,

R ¹ and R ² each independently represent an alkyl having 1 to 12 C atoms, provided that one or two non-adjacent CH ₂ groups are linked directly to each other by O atoms May be replaced by —O—, —CH═CH—, —CO—, —O—CO— or —CO—O—,
Z ^x represents —CH═CH—, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, —OCF ₂ —, —O—, —CH ₂ —, —CH ₂ CH ₂ — or a single bond. Preferably represents a single bond,
L ^1-4 each independently represents F, Cl, OCF ₃ , CF ₃ , CH ₃ , CH ₂ F, or CHF ₂ . ) 6. Use according to any one of the preceding claims, wherein the LC medium comprises one or more compounds of the following formula:

In which the individual groups have the following meanings:

Represents

Represents
R ³ and R ⁴ each independently represent an alkyl having 1 to 12 C atoms, provided that one or two non-adjacent CH ₂ groups are linked directly to each other by O atoms. May be replaced by —O—, —CH═CH—, —CO—, —O—CO— or —CO—O—,
Z ^y _{is, -CH 2 CH 2 -, -} CH = CH -, - CF 2 O -, - OCF 2 -, - CH 2 O -, - OCH 2 -, - COO -, - OCO -, - C 2 F ₄ —, —CF═CF— or a single bond is represented. )   The LC display according to any one of claims 1 to 6.   8. The LC display according to claim 7, which is a PSA-VA, PSA-OCB, PSA-IPS, PSA-FFS, PSA-positive VA or PSA-TN display.   LC medium containing the 1 or more types of polymeric compound as described in any one of Claims 1-3. The LC medium according to claim 9, wherein
A polymerizable component A) containing one or more polymerizable compounds, and a liquid crystal component B) containing one or more low molecular weight compounds,
LC medium, characterized in that component A) contains one or more polymerizable compounds according to any one of claims 1-3.   11. LC medium according to claim 9 or 10, wherein component B) comprises one or more compounds selected from the formulas CY, PY and ZK according to claim 5 or 6. A compound of formula I or IA as defined in any one of claims 1 to 3, comprising
When W ¹ and W ² represent CH═CH,
Z ¹ does not represent —C≡C— and / or A ¹ does not represent 1,4-phenylene, and
Z ² does not represent —C≡C— and / or A ² does not represent 1,4-phenylene, and
1-vinylpyrene is an excluded compound. A compound of formula II or IIA.

Wherein W ¹ , W ² , Sp, A ¹ , A ² , Z ¹ , Z ² , L, p, q and r have the meanings given in any one of claims 1-3. , G and G ′ each independently represent a H atom or a protecting group.)   A method for preparing a compound according to any one of claims 1 to 3, using a corresponding acid, acid derivative or halogenated compound containing a group P in the presence of a dehydrating reagent, A method for esterifying or etherifying the compound of claim 13.   A method of manufacturing an LC display of PS or PSA type, wherein the LC medium according to any one of claims 9 to 11 comprises an LC cell having two substrates and two electrodes, provided that at least one The substrate is transparent to light, and at least one substrate has one or two electrodes.) Preferably, the polymerizable compound is polymerized while applying a voltage to the electrodes.