JP2011529129A - LCD display - Google Patents

Abstract

A liquid crystal display is provided.
The present invention relates to a liquid-crystal (LC) medium for use in an LC display of PS (polymer stabilized) or PSA (polymer sustained alignment) type.
[Selection figure] None

Description

  The present invention relates to liquid-crystal (LC) media for use in PS (polymer stabilized) or PSA (polymer sustained alignment) type LC displays.

  Most liquid crystal displays (LC displays) currently used are 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 having a wider viewing angle are known. The LC cell of a VA display contains a layer of LC medium between two transparent electrodes, where the LC medium usually 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 electrode, 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 known is an IPS (in-plane switching) display that contains an LC layer between two substrates, but usually has two interdigital interdigital electrodes located on only one substrate. It has been. When a voltage is applied to the electrodes, it generates an electric field with a significant component parallel to the LC layer. Thereby, reorientation of LC molecules occurs in the layer plane. In addition, so-called FFS (fringe field switching) displays have been proposed (in particular SH Jun et al., Jpn. J. Appl. Phys., Vol. 43, No. 3, 2004, 1028). See Non-Patent Document 1), which also contains two electrodes on the same substrate, but in contrast to an IPS display, only one of these is a structured (comb-shaped) electrode shape. 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 the IPS display and the FFS display have a low viewing angle dependency of 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 a 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 tilt or pretilt angle is controlled by specially designing the electrodes. In so-called MVA (multidomain vertical alignment) displays, this is usually achieved by electrodes having protrusions that produce local pretilts. 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 interferometric 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, only one electrode side protrusion is used, while the opposite electrode has a slit to improve transparency to light. When a voltage is applied, the slit electrode creates an inhomogeneous electric field in the LC cell, meaning that controlled switching is further achieved. To further improve the transparency to light, the gap between the slit and the protrusion can be increased, but this in turn results in a longer response time. In so-called PVA (patterned VA), the projections are completely unnecessary in that both electrodes are structured by opposing slits, thereby increasing contrast and providing transparency to light. The result is improved but technically difficult and the display is more sensitive to mechanical effects (such as finger strikes). However, in many applications, such as monitors and especially TV screens, it is desirable to shorten the response time of the display and improve contrast and brightness (transparency).

  A further development is the so-called PS (polymer stabilized) or PSA (polymer sustained alignment) display. In these, a small amount (for example, 0.3% by weight, typically less than 1% by weight) of a polymerizable compound is added to the LC medium, introduced into the LC cell, and then a voltage is applied between the electrodes. Polymerize or crosslink in situ by UV photopolymerization. The addition of polymerizable mesogens or liquid crystal compounds, also known as “reactive mesogens” (RM), to the LC mixture has proven particularly suitable.

  For the time being, the principle of PS or PSA is used in various classic LC displays. Thus, for example, PSA-VA, PSA-OCB, PS-IPS and PS-TN displays are known. As shown in the test cell, the PSA method results in a pretilt in the cell. Therefore, in the case of a PSA-OCB display, it is possible to stabilize the bend structure so that the offset voltage is unnecessary or can be reduced. For PSA-VA displays, this 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.

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

  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, 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). PS-IPS displays are disclosed in, for example, US Pat. No. 6,177,972 (Patent Document 8) and Appl. Phys. Lett. 1999, Vol. 75 (No. 21), page 3264 (Non-Patent Document 4). The PS-TN display is described in, for example, Optics Express 2004, Vol. 12 (No. 7), page 1221 (Non-patent Document 5).

  There is a continuing need for optimizing contrast and brightness (and hence transparency) as well as response time of LC displays, especially for monitors, especially television applications. Again, the PSA method still appears to provide significant advantages. In particular, in the case of PSA-VA, the response time can be shortened in correlation with the pretilt that can be measured in the test cell without significantly adversely affecting other parameters.

  However, it has been found that LC mixtures and RMs known from the prior art still have some disadvantages when used in PSA displays. Thus, it is far from saying that all desirable soluble RMs are suitable for PSA displays, and it often appears difficult to find a more appropriate selection requirement than just a direct PSA experiment that measures pretilt. Where it is desirable to polymerize using UV light without the addition of a photoinitiator, it may be advantageous for certain applications, but the choice is further narrowed.

  In addition, the selected “material system”, which is the LC mixture (also referred to below as the “LC host mixture”) + polymerizable component, provides the best possible electrical properties, in particular the “voltage holding ratio” (HR or VHR). With regard to PSA-VA, (UV) light irradiation is an indispensable part of processing. However, since it naturally occurs as “normal” stress even in a display after production is finished, in particular, after (UV) light irradiation. A high HR is centrally important.

  However, all LC mixture + polymerizable component combinations are “functional” because, for example, inappropriate tilt occurs or not at all, or because HR is inappropriate for TFT display applications, for example. Unlimited problems arise.

  Thus, in particular the VA type PSA display having the above disadvantages or only to a minor extent and having improved properties, and LC media for use in such a display and There continues to be a great demand for polymerizable compounds. In particular, it has a short response time even at low temperatures over a wide operating temperature range at the same time as a high resistivity, and a low threshold voltage that allows multiple halftones, high contrast and a wide viewing angle, after UV exposure There is a great demand for PSA displays or materials with a high value of voltage holding ratio (HR). In PSA displays for portable applications, it is particularly desirable to have available LC media that exhibit low threshold voltages and high birefringence.

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

S. H. Jung et al., Jpn. J. et al. Appl. Phys. 43, No. 3, 2004, page 1028 T.A. -J-Chen et al., Jpn. J. et al. Appl. Phys. Volume 45, 2006, 2702-2704 S. H. Kim, L.M. -C-Chien, Jpn. J. et al. Appl. Phys. Volume 43, 2004, pages 7463-7647 Appl. Phys. Lett. 1999, Volume 75 (No. 21), p. 3264 Optics Express 2004, Volume 12 (No. 7), page 1221

  The present invention does not have the disadvantages indicated above or has only been reduced to a pre-tilt angle setting and preferably at the same time very high resistivity, low threshold voltage and short The objective was to provide a PSA display that allows response time.

  Surprisingly, it has been found that this object can be achieved by using a PSA display according to the invention containing LC media as described hereinafter. Particularly surprisingly, mesogens or liquid crystal compounds in which the non-polymerizable component (host component) has one or more phenylene groups which are disubstituted in the 2 and 3 positions by F and / or Cl, preferably F. Achieving significantly lower threshold voltages and higher birefringence when using LC mixtures, which are nematic mixtures consisting essentially of LC media and LC host components as disclosed in the prior art Has been found to be possible. In addition, the LC media of the present invention has a high resistivity value and good low temperature stability (LTS) against unwanted spontaneous crystallization, and when used in PSA displays, even with photoinitiators. Even if it is not used, it shows an appropriate tilt angle.

Thus, the present invention
A polymerizable component comprising one or more polymerizable compounds;
Including nematic ingredients,
The nematic component is preferably one or more compounds selected from mesogenic or liquid crystal compounds containing one or more 1,4-phenylene groups that are disubstituted at the 2- and 3-positions by F and / or Cl. The present invention relates to a liquid-crystal (LC) medium comprising 90 to 100% by weight, preferably more than 90% by weight and up to 100% by weight.

  The present invention is further described above and below wherein the nematic component contains 90-100% by weight of a compound selected from the group consisting of the following formulas, preferably greater than 90% and up to 100% by weight. The LC medium as described above.

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 which 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またはアルケニルを表し、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、
Ｒ^５およびＲ^６は、それぞれ互いに独立に、Ｒ^１について上に示される意味の１つを有し、
Ｚ^ｘは、−ＣＨ＝ＣＨ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、−Ｏ−、−ＣＨ_２−、−ＣＨ_２ＣＨ_２−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またはＣｌを表し、
Ｌ^５およびＬ^６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 each independently represents an alkyl or alkenyl having 1 to 12 C atoms, provided that one or two non-adjacent CH ₂ groups are May not be directly linked and may be replaced by —O—, —CH═CH—, —CO—, —OCO— or —COO—,
R ⁵ and R ⁶ each independently of one another have one of the meanings indicated above for R ¹ ;
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 or Cl,
L ⁵ and L ⁶ each independently represent F, Cl, OCF ₃ , CF ₃ , CH ₃ , CH ₂ F, or CHF ₂ .

  The present invention further provides the use of LC media as described above and below in LC displays, preferably in PS (polymer stabilized) or PSA (polymer sustained alignment) type displays. About.

  The present invention further relates to an LC display, preferably in a PS (polymer stabilized) or PSA (polymer sustained alignment) type display in which the polymerizable component is polymerized above and below. To the use of LC media as described in.

  The invention further relates to an LC display, preferably a PS or PSA type display, very preferably a PSA-VA or PSA-IPS display, comprising an LC medium as described above and below.

  The invention is further preferably a PS or PSA type display, very preferably a PSA-VA or PSA-IPS display provided that the polymerizable component is polymerized above and below. The present invention relates to an LC display comprising street LC media.

  Preferably, the PSA display has two substrates and two electrodes, provided that at least one of the substrates is transparent to light and at least one of the substrates is provided thereon. And an LC medium layer disposed between the substrates and including a polymerized component and a low molecular weight component (wherein the polymerized component contains one or more polymerizable compounds and the display). It can be obtained by polymerizing between the substrates of the cell in the LC medium while applying a voltage to the electrodes, provided that the low molecular weight component is a nematic component as described above and below.) A display cell comprising:

  The present invention further comprises an LC medium comprising one or more polymerizable compounds and a nematic component as described above and below, with two substrates and two electrodes (provided that at least one of the substrates is not exposed to light). And at least one of the substrates has one or two electrodes provided thereon) and is provided with one or more types of electrodes while applying a voltage to the electrodes. To a method for producing a display as described above and below by polymerizing said polymerizable compound.

  The PS display and PSA display of the present invention preferably have two electrodes as a transparent layer (provided that these two electrodes are provided on one or both of the two substrates forming the display cell). Containing. Thus, for example, in the VA type display of the present invention, either one of the electrodes is provided on each of the two substrates, or in the case of the IPS or FFS type display of the present invention, two electrodes are provided. Both electrodes are provided on one substrate and no electrode is provided on the other substrate.

  The LC medium for use in the LC display according to the present invention comprises one or more polymerizable compounds and one or more, preferably two or more low molecular weight (ie monomeric or unpolymerized) compounds (which are usually , Selected from mesogens or liquid crystal compounds) (“host mixtures”). The latter is stable or non-reactive to polymerization reactions under the conditions used for the polymerization of polymerizable compounds.

  Preferably, the LC medium according to the invention consists essentially of one or more polymerizable compounds and a nematic component (or host LC mixture) as described above and below. However, the LC medium may additionally contain one or more additional components or additives selected from, for example, chiral dopants, polymerization initiators, inhibitors, stabilizers, surfactants, nanoparticles, etc. Good.

  The nematic component or LC host mixture is preferably a nematic LC mixture. The terms “nematic component” and “nematic LC mixture” as used herein have a nematic LC phase, but in addition, an LC mixture that may have other LC phases (eg, smectic phase, etc.), however Very preferably means an LC mixture with only a nematic LC phase and no other LC phases.

  The LC host mixtures and LC media according to the present invention are advantageous because they exhibit significantly lower threshold voltages and higher birefringence compared to PSA displays containing LC host components as disclosed in the prior art. is there. It is therefore particularly suitable for use in PSA displays for portable applications.

  The present invention further relates to a novel nematic component and LC host mixture as described above and below (ie, it contains no polymerizable compounds but consists essentially of non-polymerizable or low molecular weight compounds). These LC mixtures can be used in VA type conventional displays such as VA displays and MVA displays. The invention further relates to LC displays, preferably VA and MVA displays containing such LC mixtures.

For the nematic component, compounds containing one or more 1,4-phenylene groups in which the 2-position and the 3-position are disubstituted by F are particularly preferred. Even more preferred are compounds of formula CY, PY and TY where L ¹ , L ² , L ³ and L ⁴ represent F.

In the formulas CY, PY and TY, preferably both groups L ¹ and L ² represent F, or one of the groups L ¹ and L ² represents F, the other represents Cl, and preferably Both groups L ³ and L ⁴ represent F, or one of the groups L ³ and L ⁴ represents F and the other represents Cl.

  Particular preference is given to LC mixtures containing at least one compound of the formula CY. Even more preferred are LC mixtures containing at least one compound of formula CY and at least one compound of formula PY. Even more preferred are LC mixtures containing at least one compound of each of the formulas CY, PY and TY.

  Further preferred LC media and LC host mixtures are shown below.

  a) LC host mixture comprising one or more compounds selected from 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Ｏ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, and alkyl and alkyl ^* each independently represent a linear alkyl group having 1 to 6 C atoms, and alkenyl represents 2 to 6 C atoms. And (O) represents an O 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 host mixture comprising one or more compounds selected from the following sub-formulas:

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Ｏ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 O 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.

  c) LC host mixture comprising one or more compounds selected from the following sub-formulas:

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Ｏ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 O atom or a single bond is represented, m represents the integer of 1-6. 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.

  d) LC host mixture 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 which 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−、−ＣＯＯ−、−ＯＣＯ−、−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^５およびＬ^６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 —, —COO—. _{, -OCO -, - C 2 F} 4 -, - CF = CF -, - CH = CHCH 2 O- or a single bond, preferably a single bond,
L ⁵ and L ⁶ each independently represent F, Cl, OCF ₃ , CF ₃ , CH ₃ , CH ₂ F, or CHF ₂ .

Preferably both groups L ⁵ and L ⁶ represent F or one of the groups L ⁵ and L ⁶ represents F and the other represents Cl.

  The compound of formula LY is preferably selected from the following subformulae:

式中、Ｒ^１は上述の意味を有し、（Ｏ）はＯ原子または単結合を表し、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、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。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０重量％より多く１０重量％以下の量で含む。

In the formula, R ¹ has the above-mentioned meaning, (O) represents an O atom or a single bond, alkyl represents a linear alkyl group having 1 to 6 C atoms, and v represents 1 to 6 Represents an integer. R ¹ is preferably linear alkyl having 1 to 6 C atoms or linear 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. The LC medium according to the present invention preferably comprises one or more compounds of the above formula in an amount greater than 0% and not more than 10% by weight.

  e) LC host mixture additionally comprising one or more compounds selected from the following formula:

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ける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０重量％より多く１０重量％以下の量で含む。

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 one another, The integer of 1-6 is represented. R ⁵ in these compounds 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 present invention preferably comprises one or more compounds of the above formula in an amount greater than 0% and not more than 10% by weight.

  f) LC host mixture 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基を表し、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 any fluorine substituent, q represents 1, 2 or 3, R ⁷ represents R ¹ has ^one of the meanings indicated.

  Particularly preferred compounds of formula FI are selected from the following subformulae:

式中、Ｒ^７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 a straight-chain alkyl having 1 to 6 C atoms, 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.

  g) LC host mixture additionally comprising one or more compounds of the following formula:

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.

  h) LC host mixture additionally comprising one or more compounds containing tetrahydronaphthyl or naphthyl units, for example compounds selected from the following formulae:

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直鎖状のアルコキシまたは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−、−ＣＯＯ−、−ＯＣＯ−、−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 , preferably linear alkyl having 1 to 6 C atoms or linear Represents alkoxy or straight-chain alkenyl having 2 to 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 -, —COO—, —OCO—, —C ₂ F ₄ —, —CF═CF—, —CF═CH—, —CH═CF—, —CH ₂ — or a single bond are represented.

  i) LC host mixtures 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、上述の意味を有し、ｃは０または１を表す。

In the formula, R ¹¹ and R ¹² each independently have the above-mentioned meaning, and c represents 0 or 1.

  Particularly preferred compounds of formula BC and CR are selected from the following subformulae:

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.

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

  k) LC host mixtures additionally comprising one or more fluorinated phenanthrenes 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、上述の意味を有し、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 above-mentioned meaning, b represents 0 or 1, L represents F, and r represents 1, 2 or 3.

  Particularly preferred compounds of the formulas PH and BF are selected from the following subformulae:

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.

  l) The proportion of the compound containing one or more 1,4-phenylene groups substituted in the 2 and 3 positions by F and / or Cl with respect to the total host mixture (or nematic component) is greater than 90% by weight, Preferably more than 95% by weight, very preferably more than 98% by weight and most preferably 100% by weight.

  m) LC host mixture or nematic component comprising one or more, preferably 3-20, compounds of formula CY, PY and / or TY. The proportion of these compounds in the total host mixture is preferably more than 90% up to 100% by weight, very preferably more than 95% by weight and most preferably 100% by weight. The content of these individual compounds is preferably 2 to 30% by weight in each case.

  n) Compounds of formula CY, PY and TY are very preferably from the group consisting of formulas CY1, CY2, CY9, CY10, PY1, PY2, PY9, PY10, TY1 and TY2, LC host mixture or nematic component selected from the group consisting of PY9, PY10 and TY1.

o) LC medium free of compounds containing terminal vinyl or vinyloxy groups (—CH═CH ₂ , —O—CH═CH ₂ ) apart from polymerizable compounds as described above and below.

  p) LC medium comprising 1 to 5, preferably 1, 2 or 3 polymerizable compounds.

  q) The LC medium in which the ratio of the polymerizable compound in the whole medium is 0.05 to 5%, preferably 0.1 to 1%.

  r) LC medium additionally comprising one or more, very preferably selected from Table B, preferably containing low molecular weight and / or non-polymerizable chiral dopant, preferably in the concentration range given in Table B.

  The LC host mixture may also contain more than 0% and less than 10% of compounds without a phenylene ring substituted in the 2 and 3 positions by F and / or Cl. Such compounds, if present, are preferably selected from the following embodiments.

  1) LC host mixture 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−、−ＯＣＯ−または−ＣＯＯ−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−、−ＣＯＯ−、−ＯＣＯ−、−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-, -OCO- or -COO-
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—, —CH═CHCH ₂ O— or a single bond, preferably a single bond.

  The compound of formula ZK is preferably selected from the following subformulae:

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.

  2) LC host mixture 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 following subformulae:

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.

  3) LC host mixture additionally comprising one or more compounds selected from the following formula:

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 is _{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.

  4) LC host mixture additionally comprising one or more biphenyl compounds of the following formula:

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 formulas B1-B3 are preferably selected from the following subformulae:

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.

  5) LC host mixture 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 following subformulae:

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.

  6) LC host mixture additionally comprising one or more compounds of the following formula:

式中、Ｒ^１およびＲ^２は上述の意味を有し、好ましくは、それぞれ互いに独立に、直鎖状のアルキルまたはアルケニルを表す。

In the formula, R ¹ and R ² have the above-mentioned meanings, and preferably each independently represents a linear alkyl or alkenyl.

  Preferred mixtures comprise one or more compounds selected from the formulas O1, O3 and O4.

  By combining the polymerized compounds described above and below with the compounds of the preferred embodiments described above, a low threshold voltage and very good while maintaining a high clearing point and a high HR value in the LC media according to the present invention. It is effective for low temperature stability and can set a pretilt angle in a PSA display. In particular, in the PSA display, the LC medium exhibits a significantly shortened response time, and in particular, a shortened halftone response time, compared to media from the prior art.

  The LC host mixture preferably has a nematic phase range of at least 80 K, particularly preferably at least 100 K, and a rotational viscosity at 20 ° C. of 450 mPa · s or less, preferably 350 mPa · s or less.

  The LC host mixture preferably has a negative dielectric anisotropy, preferably a Δε of about −0.5 to −7.5, in particular about −2.5 to −6.0 at 20 ° C. and 1 kHz. Have

  The LC host mixture preferably has a birefringence Δn higher than 0.06, very preferably higher than 0.09, most preferably higher than 0.12, preferably lower than 0.20, very preferable Has a birefringence Δn lower than 0.18, most preferably lower than 0.16.

  The LC medium may also contain further additives known to those skilled in the art and described in the literature, such as, for example, polymerization initiators, inhibitors, stabilizers, surface activators or chiral dopants. These additives may be polymerizable or non-polymerizable. Therefore, the polymerizable additive belongs to the polymerizable component, and the non-polymerizable additive belongs to the nematic component of the LC medium.

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

  For example, 0-15% by weight of pleochroic dyes can be added, and in order to improve conductivity, nanoparticles, conductive salts, preferably ethyl dimethyl dodecyl ammonium 4-hexoxybenzoate, tetrabutyl A complex salt of ammonium tetraphenylborate or crown ether can be added (see, for example, Haller et al., Mol. Cryst. Liq. Cryst. 24, 249-258, 1973) or a dielectric difference in the nematic phase. Substances for modifying the isotropic, viscosity and / or orientation can be added. 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 of the LC media according to the invention are known or the procedures for preparing them are based on standard methods described in the literature, the procedures for preparing them are determined by those skilled in the art. It can either 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.

  More preferred are LC media comprising one, two or three polymerizable compounds as described above and below.

  Even more preferred are LC media comprising or preferably consisting exclusively of achiral polymerizable compounds and achiral compounds.

  The polymerizable component contains one or more polymerizable compounds containing one polymerizable group (monoreactive) and two or more, preferably two polymerizable groups (bireactive or multireactive) More preferred are PSA displays and LC media comprising one or more polymerizable compounds.

  Further preferred are PSA displays and LC media in which the polymerizable component consists exclusively of polymerizable compounds containing two polymerizable groups (bireactive).

  The polymerizable compounds can be added individually to the LC medium, but it is also possible to use a mixture comprising two or more polymerizable compounds according to the invention. When such a mixture is polymerized, a copolymer is formed. The invention further relates to the polymerizable mixture described above and below. The polymerizable compound is a mesogen or non-mesogen, preferably a mesogen or a liquid crystal.

  The proportion of polymerizable components in the LC medium is preferably less than 5%, in particular less than 1%, very preferably less than 0.5%.

  The proportion of nematic component in the LC medium is preferably more than 95%, very preferably more than 99%.

  In a preferred embodiment of the invention, the polymerizable compound is selected from Formula I.

式中、個々の基は、以下の意味を有する：
Ｒ^ａおよびＲ^ｂは、それぞれ互いに独立に、Ｐ−Ｓｐ−、Ｈ、ハロゲン、ＳＦ_５、ＮＯ_２、炭素基または炭化水素基を表し、
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およびＡ^２は、それぞれ互いに独立に、好ましくは４〜２５個の環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、また、該基は縮合環を含有してもよく、該基はＬにより一置換または多置換されていてもよく、
Ｚ^１は、それぞれの出現において同一または異なって、−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯ−Ｏ−、−ＯＣＯ−、−Ｏ−ＣＯ−Ｏ−、−ＯＣＨ_２−、−ＣＨ_２Ｏ−、−ＳＣＨ_２−、−ＣＨ_２Ｓ−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、−ＣＦ_２Ｓ−、−ＳＣＦ_２−、−（ＣＨ_２）_ｎ１−、−ＣＦ_２ＣＨ_２−、−ＣＨ_２ＣＦ_２−、−（ＣＦ_２）_ｎ１−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−、−Ｃ≡Ｃ−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＯＣＯ−ＣＨ＝ＣＨ−、ＣＲ^０Ｒ^００または単結合を表し、
Ｌは、Ｐ−Ｓｐ−、Ｈ、ＯＨ、ＣＨ_２ＯＨ、ハロゲン、ＳＦ_５、ＮＯ_２、炭素基または炭化水素基を表し、
Ｒ^０およびＲ^００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、
ｍ１は、０、１、２、３または４を表し、
ｎ１は、１、２、３または４を表し、
ただし、基Ｒ^ａ、Ｒ^ｂおよびＬの少なくとも１つはＰ−Ｓｐ−を表す。

In the formula, the individual groups have the following meanings:
R ^a and R ^b each independently represent P-Sp-, H, halogen, SF ₅ , NO ₂ , a carbon group or a hydrocarbon group,
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 ring atoms, and the group contains a fused ring The group may be mono- or polysubstituted by L;
Z ¹ is the same or different at each occurrence, and represents —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 ) _n1 —, —CF ₂ CH _{2 -, - CH 2 CF 2 -} , - (CF 2) n1 -, - CH = CH -, - CF = CF -, - C≡C -, - CH = CH-COO -, - OCO-CH = CH- , CR ⁰ R ⁰⁰ or a single bond,
L represents P-Sp-, H, OH, CH 2 OH, _halogen, SF 5, NO _2, carbon group or a hydrocarbon group,
R ⁰ and R ⁰⁰ each independently of one another represent H or alkyl having 1 to 12 C atoms;
m1 represents 0, 1, 2, 3 or 4;
n1 represents 1, 2, 3 or 4;
However, at least one of the groups R ^a , R ^b and L represents P-Sp-.

Particularly preferred compounds of formula I are
A ¹ and A ² are each independently of each other 1,4-phenylene, naphthalene-1,4-diyl or naphthalene-2,6-diyl (in which one or more CH groups in these groups are N Cyclohexane-1,4-diyl (but one or more non-adjacent CH ₂ groups may be replaced by 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-methanoindane-2,5-diyl or represents a phenanthrene-2,7-diyl, with the proviso that even these all groups unsubstituted may be mono- or polysubstituted by L,
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 alkyl or alkoxy having 1 to 25 C atoms, linear or branched alkenyl, alkynyl, alkylcarbonyl, alkoxycarbonyl having 2 to 25 C atoms Represents alkylcarbonyloxy or alkoxycarbonyloxy, but in addition, in all these groups one or more H atoms may be replaced by F, Cl or P-Sp-
Y ¹ represents halogen,
R ^x is P-Sp-, H, halogen, linear, branched or cyclic alkyl having 1 to 25 C atoms (in addition, one or more non-adjacent CH ₂ groups are O and / or S atoms are not directly bonded to each other and are replaced by -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O- Or in addition, however, one or more H atoms may be replaced by F, Cl or P-Sp-)), an aryl having 6-40 C atoms which may be substituted or Represents an aryloxy group or a heteroaryl or heteroaryloxy group having 2 to 40 C atoms which may be substituted;
R ^a and R ^b each independently of one another represent P-Sp-, H, L as defined above or linear or branched alkyl having 1 to 25 C atoms, In addition, however, 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, so that —C (R ^x ) ═C (R ^x ) — , —C≡C—, —N (R ^x ) —, —O—, —S—, —CO—, —CO—O—, —O—CO—, —O—CO—O—. In addition, however, one or more H atoms may be replaced by F, Cl, Br, I, CN or P-Sp-
However, at least one of the groups R ^a , R ^b and L represents P-Sp-.

Particular preference is given to compounds of the formula I in which one or both of the radicals R ^a and R ^b represent P-Sp-.

  Particularly preferred compounds of formula I are selected from the following subformulae:

式中、Ｐ、Ｓｐ、ＬおよびＺ^１は、それぞれの出現において同一または異なって、上述の意味の１つを有し、
Ｒは、Ｒ^ｘに示される意味の１つを有し、好ましくは、Ｐ−Ｓｐ−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またはアルコキシを表し、
Ｌは、上に定義される通りであり、好ましくは、ＦまたはＣＨ_３を表し、
Ｚ^１は、好ましくは、−ＣＯＯ−、−ＯＣＯ−または単結合を表し、
Ｚ^ｘは、−Ｏ−、−ＣＯ−またはＣＲ^ｙＲ^ｚを表し、
Ｒ^ｙおよびＲ^ｚは、互いに独立に、Ｈ、Ｆ、ＣＨ_３またはＣＦ_３を表し、
ｍ２およびｍ３は、それぞれ互いに独立に、１〜８の整数を表し、
ｏは、０または１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。

Wherein P, Sp, L and Z ¹ are the same or different at each occurrence and have one of the above meanings;
R has one of the meanings indicated for R ^x and preferably represents P-Sp- or linear or branched alkyl or alkoxy having 1 to 12 C atoms,
L is as defined above and preferably represents F or CH ₃
Z ¹ preferably represents -COO-, -OCO- or a single bond,
Z ^x represents —O—, —CO— or CR ^y R ^z ,
R ^y and R ^z independently of one another represent H, F, CH ₃ or CF ₃ ;
m2 and m3 each independently represent an integer of 1 to 8,
o represents 0 or 1,
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 a further preferred embodiment of the invention, the polymerizable compound is a chiral compound selected from formula II:

式中、Ａ^１、Ｚ^１およびｍ１は、それぞれの出現において同一または異なって、式Ｉにおいて示される意味の１つを有し、
Ｒ^＊は、それぞれの出現において同一または異なって、式ＩにおけるＲ^ａに示される意味の１つを有し、
Ｑは、Ｌにより一置換または多置換されていてもよいｋ価のキラル基を表し、
ｋは、１、２、３、４、５または６であり、
ただし、化合物は、上に定義される通りの基Ｐ−Ｓｐ−を表すか含有する基Ｒ^＊またはＬの少なくとも一方を含有する。

In which A ¹ , Z ¹ and m1 are the same or different at each occurrence and have one of the meanings indicated in formula I;
R ^* is the same or different at each occurrence and has one of the meanings indicated for R ^a in formula I;
Q represents a k-valent chiral group which may be mono- or polysubstituted by L,
k is 1, 2, 3, 4, 5 or 6;
However, the compound contains at least one of the groups R ^* or L which represents or contains the group P-Sp- as defined above.

  Particularly preferred compounds of the formula II contain the monovalent group Q of the formula III.

式中、Ｌおよびｒは、それぞれの出現において同一または異なって、上で示される意味を有し、
Ａ^＊およびＢ^＊は、それぞれ互いに独立に、縮合されたベンゼン、シクロヘキサンまたはシクロヘキセンを表し、
ｔ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を表し、および
ｕ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 which L and r are the same or different at each occurrence and have the meanings indicated above;
A ^* and B ^* each independently represent a fused benzene, cyclohexane or cyclohexene;
t is the same or different at each occurrence and represents 0, 1 or 2, and u is the same or different at each occurrence and represents 0, 1 or 2.

  Particular preference is given to groups of the formula III in which x represents 1 or 2.

Further preferred compounds of formula II contain a monovalent group Q of formula IV or one or more groups R ^* .

式中、
Ｑ^１は、１〜９個のＣ原子を有するアルキレンまたはアルキレンオキシまたは単結合を表し、
Ｑ^２は、１〜１０個のＣ原子を有するフッ素化されていてもよいアルキルまたはアルコキシを表し、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および／またはＳ原子が互いに直接連結しないように、−Ｏ−、−Ｓ−、−ＣＨ＝ＣＨ−、−ＣＯ−、−ＯＣＯ−、−ＣＯＯ−、−Ｏ−ＣＯＯ−、−Ｓ−ＣＯ−、−ＣＯ−Ｓ−または−Ｃ≡Ｃ−で置き換えられていてもよく、
Ｑ^３は、Ｆ、Ｃｌ、ＣＮまたはＱ^２で定義される通りであるがＱ^２とは異なるアルキルまたはアルコキシを表す。

Where
Q ¹ represents alkylene or alkyleneoxy or a single bond having 1 to 9 C atoms,
Q ² represents an optionally fluorinated alkyl or alkoxy having 1 to 10 C atoms, but in addition 1 or 2 non-adjacent CH ₂ groups are O and / or S -O-, -S-, -CH = CH-, -CO-, -OCO-, -COO-, -O-COO-, -S-CO-, -CO- so that the atoms are not directly connected to each other. May be replaced by S- or -C≡C-
Q ³ represents alkyl or alkoxy as defined by F, Cl, CN or Q ² but different from Q ² .

  Preferred groups of formula IV are, for example, 2-butyl (ie 1-methylpropyl), 2-methylbutyl, 2-methylpentyl, 3-methylpentyl, 2-ethylhexyl, 2-propylpentyl, especially 2-methylbutyl, 2-methylbutoxy, 2-methylpentoxy, 3-methylpentoxy, 2-ethylhexoxy, 1-methylhexoxy, 2-octyloxy, 2-oxa-3-methylbutyl, 3-oxa-4-methylpentyl, 4-methyl Hexyl, 2-hexyl, 2-octyl, 2-nonyl, 2-decyl, 2-dodecyl, 6-methoxyoctoxy, 6-methyloctoxy, 6-methyloctanoyloxy, 5-methylheptyloxycarbonyl, 2- Methylbutyryloxy, 3-methylvaleroyloxy, 4-methylhexanoyloxy, -Chloropropionyloxy, 2-chloro-3-methylbutyryloxy, 2-chloro-4-methylvaleryloxy, 2-chloro-3-methylvaleryloxy, 2-methyl-3-oxapentyl, 2-methyl -3-oxahexyl, 1-methoxypropyl-2-oxy, 1-ethoxypropyl-2-oxy, 1-propoxypropyl-2-oxy, 1-butoxypropyl-2-oxy, 2-fluorooctyloxy, 2- Fluorodecyloxy, 1,1,1-trifluoro-2-octyloxy, 1,1,1-trifluoro-2-octyl, 2-fluoromethyloctyloxy.

  Further preferred compounds of formula II contain the divalent group Q of formula V.

式中、Ｌ、ｒ、ｔ、Ａ^＊およびＢ^＊は、上に示される意味を有する。

In which L, r, t, A ^* and B ^* have the meanings indicated above.

  Further preferred compounds of formula II contain a divalent group Q selected from the following formula:

式中、Ｐｈｅは、Ｌにより一置換または多置換されていてもよいフェニルを表し、および、Ｒ^ｘは、Ｆまたは１〜４個のＣ原子を有するフッ素化されていてもよいアルキルを表す。

In the formula, Phe represents phenyl which may be mono-substituted or poly-substituted by L, and R ^x represents F or optionally fluorinated alkyl having 1 to 4 C atoms.

  Particularly preferred compounds of formula II are selected from the following subformulae:

式中、Ｌ、Ｐ、Ｓｐ、ｍ１、ｒおよびｔは、上に示される意味を有し、ＺおよびＡは、それぞれの出現において同一または異なって、それぞれＺ^１およびＡ^１に示される意味の１つを有し、ｔ１は、それぞれの出現において同一または異なって、０または１を表す。

In which L, P, Sp, m1, r and t have the meanings indicated above, Z and A are the same or different at each occurrence and have the meanings indicated for Z ¹ and A ¹ respectively. And t1 is the same or different at each occurrence and represents 0 or 1.

  The chiral compounds of formula II can be used in optically active form, ie as pure enantiomers, or as any desired mixture of two enantiomers, or in any of their racemates. The use of racemates is preferred. For example, the use of racemates has several advantages over the use of pure enantiomers, such as significantly simpler synthesis and lower material costs.

  Above and below, the following meanings apply:

  The term “mesogenic group” is known to the person skilled in the art and is described in the literature, and due to its anisotropy of attractive and repulsive interactions, it leads to the generation of liquid crystal (LC) phases in low molecular weight or polymeric substances. Represents an essentially contributing group. 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 above and below as “Sp”, is known to the person skilled in the art and is 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” is used above and below to link a mesogenic group and polymerizable group (s) together in a polymerizable mesogenic compound (“RM”). Represents a flexible group.

  The term “reactive mesogen” or “RM” refers to a compound containing a mesogenic group and one or more functional groups suitable for polymerization (also known 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 containing no

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

  The term “carbon group” refers to a monovalent or polyvalent organic group containing at least one carbon atom, the group containing no further atoms (eg, —C≡C—, etc.), For example, it 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” includes one or more H atoms in addition and optionally one or more heteroatoms such as N, O, S, P, Si, Se, As, Te or Ge. Represents a carbon group contained as

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

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

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

  The term “aryl” represents an aromatic carbon group or a group derived therefrom. The term “heteroaryl” refers to “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, or 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, wherein 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 H, halogen, a 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-, provided that one or more H atoms are replaced by fluorine An optionally substituted aryl or aryloxy group having 6 to 40 C atoms, or an optionally substituted heteroaryl or heteroaryloxy group having 2 to 40 C atoms. Represents.

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

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

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

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

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

  Aryl and heteroaryl groups can be monocyclic or polycyclic, that is, they can contain one ring (eg, phenyl, etc.) or more than one ring, and the The groups may be fused (eg, naphthyl, etc.) or covalently linked (eg, biphenyl), 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.

  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 are particularly preferred, The group may contain a condensed ring and may be substituted. Furthermore, 5-membered, 6-membered or 7-membered aryl and heteroaryl groups are preferred, but in addition, one or more CH groups are N, S, such that the O and / or S atoms are not directly linked to each other. 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, benzoxazole , 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, naphthyl , 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 may be monocyclic, i.e. contain only one ring (e.g. cyclohexane, etc.) or polycyclic, i.e. multiple rings (For example, 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, and 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.

Aryl, heteroaryl, carbon and hydrocarbon groups are preferably silyl, sulfo, sulfonyl, formyl, amine, imine, nitrile, mercapto, nitro, halogen, C _1-12 alkyl, C _6-12 aryl, C ₁ It may have one or more substituents selected from the group consisting of ₁₂ alkoxy, hydroxyl, or a combination of these groups.

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

Preferred substituents, also referred to as “L” below, are, for example, F, Cl, Br, I, —CN, —NO ₂ , —NCO, —NCS, —OCN, —SCN, —C (═O) N ( R ^x ) ₂ , —C (═O) Y ¹ , —C (═O) R ^x , —N (R ^x ) ₂ (where R ^x has the above-mentioned meaning and Y ¹ represents halogen. ), Optionally substituted silyl or aryl having 6 to 40, preferably 6 to 20 C atoms, and linear or branched alkyl, alkoxy having 1 to 25 C atoms, Alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy, wherein one or more H atoms may be replaced by F or Cl.

“Substituted silyl or aryl” is preferably halogen, —CN, R ⁰ , —OR ⁰ , —CO—R ⁰ , —CO—O—R ⁰ , —O—CO—R ⁰ or —O—. Means substitution by CO—O—R ⁰ , where R ⁰ has the above-mentioned meaning.

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.

式中、Ｌは上述の意味の１つを有する。

In which L has one of the above-mentioned meanings.

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

Preferred polymerizable group P ^{_{is, CH 2 = CW 1 -COO-,}} CH 2 = CW 1 -CO-,

ＣＨ_２＝ＣＷ^２−（Ｏ）_ｋ３−、ＣＷ^１＝ＣＨ−ＣＯ−（Ｏ）_ｋ３−、ＣＷ^１＝ＣＨ−ＣＯ−ＮＨ−、ＣＨ_２＝ＣＷ^１−ＣＯ−ＮＨ−、ＣＨ_３−ＣＨ＝ＣＨ−Ｏ−、（ＣＨ_２＝ＣＨ）_２ＣＨ−ＯＣＯ−、（ＣＨ_２＝ＣＨ−ＣＨ_２）_２ＣＨ−ＯＣＯ−、（ＣＨ_２＝ＣＨ）_２ＣＨ−Ｏ−、（ＣＨ_２＝ＣＨ−ＣＨ_２）_２Ｎ−、（ＣＨ_２＝ＣＨ−ＣＨ_２）_２Ｎ−ＣＯ−、ＨＯ−ＣＷ^２Ｗ^３−、ＨＳ−ＣＷ^２Ｗ^３−、ＨＷ^２Ｎ−、ＨＯ−ＣＷ^２Ｗ^３−ＮＨ−、ＣＨ_２＝ＣＷ^１−ＣＯ−ＮＨ−、ＣＨ_２＝ＣＨ−（ＣＯＯ）_ｋ１−Ｐｈｅ−（Ｏ）_ｋ２−、ＣＨ_２＝ＣＨ−（ＣＯ）_ｋ１−Ｐｈｅ−（Ｏ）_ｋ２−、Ｐｈｅ−ＣＨ＝ＣＨ−、ＨＯＯＣ−、ＯＣＮ−およびＷ^４Ｗ^５Ｗ^６Ｓｉ−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または１〜５個のＣ原子を有するアルキルを表し、Ｐｈｅは、上で定義される通りで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の整数である。

_{^{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 or alkyl having 1 to 5 C atoms, Phe represents 1,4-phenylene, as defined above, optionally substituted with one or more groups L different from P-Sp, and k ₁ , k ₂ and k ₃ are each independently of each other In addition, 0 or It represents 1, _{k 3} preferably denotes 1, _{k 4} is an integer of from 1 to 10.

Particularly preferred groups P are CH ₂ ═CH—COO—, CH ₂ ═C (CH ₃ ) —COO—, CH ₂ ═CF—COO—, CH ₂ ═CH—, CH ₂ ═CH—O—, (CH _{2 = CH) 2 CH-OCO} -, (CH 2 = CH) 2 CH-O-,

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

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

  In a further preferred embodiment of the invention, the polymerizable compounds of formulas I and II and their subformulae are one containing two or more polymerizable groups P instead of one or more groups P-Sp-. It contains the above branched group (polyfunctional polymerizable group). Suitable groups of this type, polymerizable compounds containing them, are described, for example, in US Pat. No. 7,060,200 or US Publication No. 2006/0172090. Polyfunctional polymerizable groups selected from the following formulas are particularly preferred.

式中、
ａｌｋｙｌは、単結合または１〜１２個のＣ原子を有する直鎖状または分岐状のアルキレンを表し、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^ｘ）＝Ｃ（Ｒ^ｘ）−、−Ｃ≡Ｃ−、−Ｎ（Ｒ^ｘ）−、−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯ−Ｏ−、−Ｏ−ＣＯ−、−Ｏ−ＣＯ−Ｏ−で置き換えられていてもよく、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^ｘは上述の意味を有し、好ましくは、上で定義される通りのＲ^０を表し、
ａａおよびｂｂは、それぞれ互いに独立に、０、１、２、３、４、５または６を表し、
Ｘは、Ｘ’に示される意味の１つを有し、および
Ｐ^１〜５は、それぞれ互いに独立に、上でＰに示される意味の１つを有する。

Where
alkyl represents a single bond or a linear or branched alkylene having 1 to 12 C atoms, provided that one or more non-adjacent CH ₂ groups are each independently of one another O and / or S atoms are not directly connected to each other so that —C (R ^x ) ═C (R ^x ) —, —C≡C—, —N (R ^x ) —, —O—, —S—, —CO— , -CO-O-, -O-CO-, -O-CO-O-, but in addition, one or more H atoms are replaced by F, Cl or CN Provided that R ^x has the above-mentioned meaning and preferably represents R ⁰ as defined above;
aa and bb each independently represent 0, 1, 2, 3, 4, 5 or 6;
X has one of the meanings indicated for X ′, and P ^1-5 each independently of one another have one of the meanings indicated for P above.

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 may be independently of each other —O—, —S—, —NH—, —NR, such that the O and / or S atoms are not directly linked to each other. ^{0 -, - SiR 0 R 00} -, - CO -, - COO -, - OCO -, - OCO-O -, - S-CO -, - CO-S -, - NR 0 -CO-O -, - O—CO—NR ⁰ —, —NR ⁰ —CO—NR ⁰ —, —CH═CH— or —C≡C— may be substituted,
X ′ represents —O—, —S—, —CO—, —COO—, —OCO—, —O—COO—, —CO—NR ⁰ —, —NR ⁰ —CO—, —NR ⁰ —CO—. NR ⁰ −, —OCH ₂ —, —CH ₂ O—, —SCH ₂ —, —CH ₂ S—, —CF ₂ O—, —OCF ₂ —, —CF ₂ S—, —SCF ₂ —, —CF ₂ CH ₂ —, —CH ₂ CF ₂ —, —CF ₂ CF ₂ —, —CH═N—, —N═CH—, —N═N—, —CH═CR ⁰ —, —CY ² = CY ³ -, -C≡C-, -CH = CH-COO-, -OCO-CH = CH- or a single bond,
R ⁰ and R ⁰⁰ each independently represent H or alkyl having 1 to 12 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 ⁰ R ⁰⁰ —O) _p1 —, wherein p1 is an integer from 1 to 12, q1 is an integer from 1 to 3, and R ⁰ and R ⁰⁰ has the above-mentioned meaning.

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

  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.

  Polymerizable compounds are known to those skilled in the art and are described, for example, in standard organic chemistry such as the Hohen-Weyl ed., Methoden der organischen Chemie [Methods of Organic Chemistry], Thiem-Verlag, Stuttgart, and the like. Prepared analogously to the method. The synthesis of polymerizable acrylates and methacrylates of formula I can be performed analogously to the method described in US Pat. No. 5,723,066. Furthermore, particularly preferred methods are given in the examples.

In the simplest case, for example, the general formula HO-A ^1- (Z ¹ -A) such as 2,6-dihydroxynaphthalene (naphthalene-2,6-diol) or 1- (4-hydroxyphenyl) phenyl-4-ol ²⁾ _m1 -OH ^(wherein, a ^1, a 2, ^{Z 1} and m are the commercially available diols having) the abovementioned meaning, for example, containing a group P, such as methacryloyl chloride or methacrylic acid The corresponding acid, acid derivative or halogenated compound is used for synthesis by esterification or etherification in the presence of a dehydrating agent such as DCC (dicyclohexylcarbodiimide).

  The polymerizable compound is polymerized or crosslinked by in situ polymerization in the LC medium between the substrates of the LC display by applying a voltage (when the compound contains two or more polymerizable groups). Suitable and preferred polymerization methods are, for example, thermal or photopolymerization, preferably photopolymerization, in particular UV photopolymerization. If necessary, one or more initiators can be added here. 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, commercially available photopolymerization initiators 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. When using an initiator, the ratio of the initiator in the whole mixture is preferably 0.001 to 5% by weight, particularly preferably 0.001 to 1% by weight. However, the polymerization can also be carried out without adding an initiator. In a further preferred embodiment, the LC medium does not contain a polymerization initiator.

  Also, for example, the polymerizable component or LC medium may contain one or more stabilizers to prevent undesired spontaneous polymerization of RMs 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) are particularly suitable. If a stabilizer is used, the proportion of stabilizer based on the total amount of RM or polymerizable component A) is preferably 10 to 5000 ppm, very preferably 50 to 500 ppm.

  The polymerizable compounds according to the invention are also suitable for polymerization without initiators, which means that, for example, the material costs are lower and the impurities in the LC medium due to the amount of initiator or its degradation products remaining. It is accompanied by notable advantages such as a particularly small amount.

  The LC medium according to the invention preferably comprises less than 5%, particularly preferably less than 1%, very particularly preferably less than 0.5% of polymerizable compounds, in particular polymerizable compounds of the above-mentioned formula.

  The polymerizable compounds according to the invention can be added individually to the LC medium, but it is also possible to use a mixture comprising two or more polymerizable compounds. Polymerization of this type of mixture forms a copolymer. The invention further relates to the polymerizable mixture described above and below.

  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 the component solutions in an organic solvent such as 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 configuration of the LC display according to the invention corresponds to the usual structure for a PSA display as described in the prior art cited at the outset. A structure without protrusions, in particular, an electrode on the color filter side is not structured and only the TFT side electrode has a slit is preferable. A particularly suitable and preferred electrode structure for PSA-VA displays is described, for example, in US 2006/0066793.

  Unless the context clearly indicates otherwise, terms used herein as plural are to be interpreted herein as including the singular and vice versa.

  Throughout the description and claims herein, the words “comprise” and “contain” and use of the word, eg, “comprising” and “comprises” mean “including but not limited to”. , Not intended to exclude other components (not excluded).

  It will be appreciated that modifications can be made to the above-described embodiments of the invention while remaining within the scope of the invention. Each aspect disclosed herein may be replaced by an alternative aspect serving the same, equivalent, or similar purpose, unless explicitly stated otherwise. Thus, unless expressly stated otherwise, each aspect disclosed is one example only of a generic series of equivalent or similar aspects.

  All aspects disclosed herein may be combined in any combination, except for combinations in which at least some such aspects and / or steps are mutually exclusive. In particular, the preferred embodiments of the present invention can be applied to all forms of the present invention and may be used in any combination. Similarly, aspects described in non-essential combinations may be used separately (not in combination).

  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.

The following abbreviations are used in the table below:
(N, m, z: each independently 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 possible 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 possible stabilizers that can be added to the LC medium according to the invention (n represents here an integer from 1 to 12).

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０．１〜１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 0.01 to 5% by weight, particularly preferably 0.1 to 1% by weight. The LC medium preferably comprises one or more stabilizers selected from the group consisting of compounds from Table C.

In addition, the following abbreviations and symbols are used:
V ₀ represents a capacity threshold voltage [V] at 20 ° C.
n _e represents an extraordinary refractive index at 20 ° C. and 589 nm,
n ₀ represents the ordinary refractive index at 20 ° C. and 589 nm,
Δn represents the optical anisotropy at 20 ° C. and 589 nm,
_ε⊥ represents the dielectric constant perpendicular to the director at 20 ° C. and 1 kHz,
_ε‖ represents the dielectric constant parallel to the director at 20 ° C. and 1 kHz,
Δε represents the dielectric anisotropy at 20 ° C. and 1 kHz,
cl. p. , T (N, I) represents the clearing point [° C.]
γ ₁ represents the rotational viscosity [mPa · s] at 20 ° C.
K ₁ represents the elastic constant [pN] for the “spray” deformation at 20 ° C.
K ₂ represents the elastic constant [pN] for the “twist” deformation at 20 ° C.
K ₃ represents the elastic constant [pN] for the “bend” deformation at 20 ° C.
LTS represents the low temperature stability (phase) determined in the test cell,
HR ₂₀ represents a voltage holding ratio [%] at 20 ° C., and HR ₁₀₀ represents a voltage holding ratio [%] at 100 ° C.

  Unless otherwise stated, all concentrations in this application are given in weight percent and relate to the corresponding mixture or mixture component unless otherwise stated.

  Unless indicated otherwise, it is shown in this application 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).

  All physical properties are determined or determined in accordance with “Melk liquid crystal, liquid crystal physical properties” November 1997, according to Merck, Germany, and in each case, unless otherwise specified Temperature is applied, Δn is determined at 589 nm, and Δε is determined at 1 kHz.

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

  The display used for measuring the capacitance threshold voltage has two flat parallel outer plates separated by a distance of 4 μm and an electrode layer covering a polyimide alignment layer rubbed inside the outer plate. The alignment layer causes homeotropic edge alignment of the liquid crystal molecules.

The polymerizable compound is polymerized in the display by simultaneously applying a voltage to the display by UV irradiation for a predetermined time (usually 10 to 30 V AC, 1 kHz). In the examples, the intensity was measured using a standard UV meter (Ushio UNI meter model) fitted with a 365 nm bandpass filter using a 28 mW / cm ² mercury vapor lamp unless otherwise indicated.

  The tilt angle is determined by a rotating crystal experiment (Autronic-Melchers TBA-105). Here, a low value (that is, a large deviation from the angle of 90 °) corresponds to a large tilt.

<Example 1>
LC media consisting of the following components a) to c) are suitable for use in PS-VA displays.

  a) Nematic LC host mixture N1 having the composition shown below 99.00%.

ｂ）０．２５％の下に示す重合性モノマー化合物Ａ。

b) Polymerizable monomer compound A shown below 0.25%.

ｃ）０．７５％のキラルドーパントＳ−４０１１。

c) 0.75% chiral dopant S-4011.

<Example 2>
LC media consisting of 99.50% nematic LC host mixture N1 (see Example 1) and 0.50% polymerizable monomer compound A (see Example 1) is suitable for use in PS-VA displays.

<Example 2>
An LC medium consisting of 99.50% nematic LC host mixture N1 (see Example 1), 0.25% polymerizable monomer compound A (see Example 1) and 0.25% chiral dopant S-5011 is PS- Suitable for use in VA displays.

<Example 3>
LC media consisting of 99.00% nematic LC host mixture N1 (see Example 1), polymerizable monomer compound B shown below 0.25% and 0.75% chiral dopant S-4011 is a PS-VA display Suitable for use in.

＜例４＞
９９．５０％のネマチックＬＣホスト混合物Ｎ１（例１参照）および０．５０％の下に示す重合性モノマー化合物Ｃから成るＬＣ媒体は、ＰＳ−ＶＡディスプレイにおける使用に適する。

<Example 4>
LC media consisting of 99.50% nematic LC host mixture N1 (see Example 1) and polymerizable monomer compound C shown below 0.50% are suitable for use in PS-VA displays.

＜例５＞
９９．００％のネマチックＬＣホスト混合物Ｎ１（例１参照）、０．２５％の下に示す重合性モノマー化合物Ｄおよび０．７５％のキラルドーパントＳ−２０１１から成るＬＣ媒体は、ＰＳ−ＶＡディスプレイにおける使用に適する。

<Example 5>
LC media consisting of 99.00% nematic LC host mixture N1 (see Example 1), polymerizable monomer compound D shown below 0.25% and 0.75% chiral dopant S-2011 is a PS-VA display. Suitable for use in.

Claims (10)

A polymerizable component comprising one or more polymerizable compounds;
Including nematic ingredients,
The nematic component contains 90 to 100% by weight of one or more compounds containing one or more 1,4-phenylene groups substituted at the 2-position and 3-position with F and / or Cl. A liquid-crystal (LC) medium. The LC medium according to claim 1, wherein the nematic component contains 90 to 100% by weight of a compound selected from the group consisting of the following formulae.

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 represents an alkyl or alkenyl having 1 to 12 C atoms, provided that one or two non-adjacent CH ₂ groups are May not be directly linked and may be replaced by —O—, —CH═CH—, —CO—, —OCO— or —COO—,
R ⁵ and R ⁶ each independently of one another have one of the meanings indicated above for R ¹ ;
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 or Cl,
L ⁵ and L ⁶ each independently represent F, Cl, OCF ₃ , CF ₃ , CH ₃ , CH ₂ F, or CHF ₂ . ) The LC medium according to claim 1, comprising at least one compound selected from the following formulae.

(Wherein 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. (O represents an O atom or a single bond.) The LC medium according to any one of claims 1 to 3, comprising at least one compound selected from the following formulae.

(In the formula, alkyl and alkyl ^* each independently represent a linear alkyl group having 1 to 6 C atoms, and alkenyl is a linear alkenyl group having 2 to 6 C atoms. (O) represents an O atom or a single bond.) The LC medium according to any one of claims 1 to 4, comprising one or more compounds selected from the following formulae.

Wherein 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) Represents an O atom or a single bond, and m represents an integer of 1 to 6.) LC medium according to any one of claims 1 to 5, characterized in that the polymerizable compound is selected from formula I or II.

In which the individual groups have the following meanings:
R ^a and R ^b each independently represent P—Sp—, H, halogen, SF ₅ , NO ₂ , a carbon group or a hydrocarbon group, provided that at least one of the groups R ^a and R ^b is P— Sp-
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, preferably having 4 to 25 C atoms, and the group contains a fused ring The group may be mono- or polysubstituted by L;
Z ¹ is the same or different at each occurrence, and represents —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 ) _n1 —, —CF ₂ CH _{2 -, - CH 2 CF 2 -} , - (CF 2) n1 -, - CH = CH -, - CF = CF -, - C≡C -, - CH = CH-COO -, - OCO-CH = CH- , CR ⁰ R ⁰⁰ or a single bond,
L represents P-Sp-, H, OH, CH 2 OH, _halogen, SF 5, NO _2, carbon group or a hydrocarbon group,
R ⁰ and R ⁰⁰ each independently of one another represent H or alkyl having 1 to 12 C atoms;
m1 represents 0, 1, 2, 3 or 4;
n1 represents 1, 2, 3 or 4;
R ^* is the same or different at each occurrence and has one of the meanings indicated for R ^a in formula I;
Q represents a k-valent chiral group which may be mono- or polysubstituted by L,
k represents 1, 2, 3, 4, 5 or 6. )   LC medium which is a nematic component as defined in any one of claims 1-5.   Use of an LC medium according to any one of claims 1 to 7 in an LC display.   An LC display comprising the LC medium according to any one of claims 1 to 7, preferably a VA, MVA, PS, PSA, PS-VA or PS-IPS mode display.   Two substrates and two electrodes (provided that at least one of the substrates is transparent to light and at least one of the substrates has one or two electrodes provided thereon). And an LC medium layer disposed between the substrates and comprising a polymerized component and a low molecular weight component (wherein the polymerized component comprises one or more polymerizable compounds between the substrates of the display cell). The low molecular weight component is a nematic component according to any one of claims 1 to 5, wherein the low molecular weight component is polymerized while applying a voltage to the electrode in an LC medium. 10. The LC display according to claim 9, comprising a display cell.