JP2005179680A - Liquid crystal medium and liquid crystal display - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid crystal medium having an appropriately high Δε, a wide nematic phase range, suitable Δn and resistivity, and having a high viscosity and exhibiting a stability to irradiation. <P>SOLUTION: The liquid crystal medium comprises a first positive dielectric anisotropy component comprising one or more positive dielectric anisotropy compound of formula I and a second positive dielectric anisotropy component comprising one or more compound of formula II. A liquid crystal system comprising the liquid crystal medium and a polymer material, and an electro-optical display, are provided. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to liquid crystal media, liquid crystal systems comprising these media and polymers, in particular PDLC type, in particular reverse type PDLC, and liquid crystal displays, preferably active matrix driven displays.

  Liquid crystal displays (LCDs) are widely used for displaying information. The electro-optic modes used include, for example, twisted nematic (TN) mode, super twisted nematic (STN) mode and electrically controlled birefringence (ECB) mode and various variations thereof, and other modes. is there. All these modes use an electric field, which is substantially perpendicular to the substrate, ie to each liquid crystal layer, but in addition to these modes, for example, in-plane switching (IPS) mode (eg Germany) There are also electro-optic modes that use a substantially parallel electric field on the substrate, i.e. each of the liquid crystal layers, such as patent 4000451 and EP 0588568).

  In addition to a variety of different modes in which a liquid crystal medium that has been pretreated so that a uniform alignment of the liquid crystal material is usually obtained is aligned on the surface, a composite that uses a combination of a low molecular weight liquid crystal material and a polymer material. There are uses utilizing the system, and examples thereof include, for example, a polymer dispersed liquid crystal (PDLC) system, nematic curvilinearily aligned phase (NCAP) disclosed in WO91 / 05029. System, polymer network (PN) system, or axially symmetric micro-domain (ASM) system. These composite systems typically use an electric field that is substantially perpendicular to the composite layer.

  LCDs are used for direct view displays as well as projection displays. In addition to these applications, LCDs, particularly complex systems such as PDLC, specifically LCDs including so-called reverse type PDLC or reverse mode PDLC are well known to those skilled in the art. It is used for practical purposes. These reverse PDLCs produce the opposite contrast, ie, contrary to normal PDLC, they are transparent when no voltage is applied and scatter when the voltage is applied. This is generally and preferably achieved by using a mesomorphic or liquid crystalline polymer as the polymer material. This liquid crystalline polymer can be aligned before and during polymerization, and is preferably aligned. Therefore, the orientation is maintained in the liquid crystal system.

  In composite systems, a liquid crystal medium with a relatively high birefringence (Δn) is required to achieve an efficient scattering state and achieve excellent contrast. In reverse PDLC, Δn must match the Δn of the liquid crystalline polymer and the effective Δn of the liquid crystalline polymer in the cured liquid crystal system, respectively.

  Good compatibility with composite polymer precursors and easy layer separation during composite formation are obvious requirements for liquid crystals for such applications.

  Some systems cause solvent induced phase separation (SIPS), but in most systems phase separation does not start spontaneously. More importantly, phase separation is not complete in this way in most systems. Phase separation is initiated by initiating polymerization using an initiator. The initiator may be a heat activated initiator or a photoinitiator. In systems where phase separation is initiated by exposure to heat or radiation or light irradiation, especially for curing with actinic radiation, the liquid crystal medium must be stable under the exposure conditions. This is particularly true for UV curing, which is otherwise preferred. In UV curing, it is necessary to use a liquid crystal medium that is particularly stable for exposure to UV. This is a difficult requirement since at the same time the birefringence of this medium must be high.

  The clearing point is not high enough, the range of the nematic phase is undesirably narrow, the minimum temperature of stability of the nematic phase is quite high, the dielectric anisotropy is too low, and therefore the operating voltage is too high, Inadequate elastic constants, too high a viscosity, and finally too low stability to exposure to UV radiation, or a combination of these are the most typical undesirable tradeoffs.

  Another promising electro-optic mode used in LCDs is the optically compensated bent (OCB) mode. This mode is described in, for example, Yamaguchi et al., “Wide-Viewing-Angle Display Mode for the Active-Matrix LCD Using Bend-Alignment Liquid-Crystal Cell”, SID 93, Digest, page 277 (1993).

  This mode is very promising. Since it is characterized by a satisfactory viewing angle dependency, it is particularly suitable for direct viewing applications. Response time is also extremely short. However, for video speed response to changing gradation display, the response time still needs improvement. Compared to the conventional TN display, the OCB display has a much smaller deformation amount of the orientation vector (director). In a TN display, the orientation vector is oriented substantially parallel to the substrate when no voltage is applied, and its direction changes substantially perpendicular to the substrate when a drive voltage is applied. On the other hand, in an OCB display, the orientation vector direction will eventually change to the same orientation, but will start from a start-up arrangement that is already almost homeotropically vented. That is, the liquid crystal medium to be used needs to have higher birefringence.

Liquid crystal compositions having a high birefringence value suitable for LCD displays, particularly AMD displays, are disclosed in, for example, US Pat. No. 5,328,644 and JP-A-06-264059.
German Patent No. 4000451 European Patent No. 0588568 US Pat. No. 5,328,644 Japanese Patent Laid-Open No. 06-264059 Yamaguchi et al., “Wide-Viewing-Angle Display Mode for the Active-Matrix LCD Using Bend-Alignment Liquid-Crystal Cell”, SID93, Digest, 277 (1993)

  Therefore, the nematic phase range is wide, the viscosity is low, the optical anisotropy Δn is appropriate according to the display mode used, and Δn is appropriately high especially for composite systems such as OCB and PDCL. , And especially for the latter, the compatibility with the polymer precursor of the composite system is adequately good, and the polymer precursor has sufficient stability under curing conditions, in particular curing with actinic radiation, etc. There is a great need for liquid crystals with properties suitable for typical applications.

  Liquid crystal displays (LCDs) are widely used for displaying information. The electro-optic modes used include, for example, twisted nematic (TN) mode, super twisted nematic (STN) mode, optical compensation bent (OCB) mode, and electric field controlled birefringence (ECB) mode and various variations thereof. There are other modes as well. All of these modes use an electric field, which is substantially perpendicular to the substrate and the liquid crystal layer, respectively, but in addition to these modes, for example, in-plane switching modes (eg German Patent 4000451 and European There is also an electro-optical mode using an electric field substantially parallel to the substrate and the liquid crystal layer, as disclosed in Japanese Patent No. 0588568. In particular, this electro-optic mode is used in the latest LCD for desktop monitors.

  The liquid crystal medium of the present invention is suitably used for PDLC displays, particularly reverse type PDLC displays.

  The display of the present invention is preferably driven by an active matrix system (addressing) (active matrix LCD, AMD for short), preferably driven by a matrix of thin film transistors (TFTs). However, the liquid crystal of the present invention can be advantageously used in a display having other driving means.

  These displays require new liquid crystal media with improved properties. In particular, the birefringence (Δn) must be sufficiently high. Furthermore, the dielectric anisotropy (Δε) must be sufficiently high so that the operating voltage can be lowered reasonably. Δε is preferably higher than 6, more preferably higher than 7, or higher than 8, but is preferably 15 or lower, particularly preferably 10 or lower. Otherwise, for most AMD, the resistivity of the mixture tends to be unacceptably low. In addition to this parameter, the liquid crystal medium needs to have a suitably wide nematic phase range, a low rotational viscosity and, as mentioned above, a specific resistance that is at least moderately high.

  Liquid crystal compositions having a high birefringence value suitable for LCD displays, particularly AMD displays, are disclosed in, for example, US Pat. No. 5,328,644 and JP-A-06-264059. However, these compositions have significant drawbacks. Among the defects, most of these compositions have birefringence values that are too low and / or the required operating voltage is too high. Many of these compositions are also too low in resistivity and / or unsuitable due to too long response times and / or incompatible with polymer precursors and / or sufficient for radiation Not stable.

  Therefore, a wide range of nematic phases, a high Δε, a suitably high optical anisotropy Δn depending on the display mode used, a sufficiently high resistance, and in particular a low viscosity, and There is a great need for liquid crystals having properties suitable for practical use, such as excellent stability against radiation, particularly ultraviolet rays.

  The liquid crystal medium of the present invention contains at least one positive dielectric anisotropic compound (component A) having a specific structure and at least one positive dielectric anisotropic compound (component B) having a specific structure. The liquid crystal system (liquid crystal system) of the present invention includes at least the liquid crystal medium and a polymer. Also, in this liquid crystal system, the liquid crystal medium can be encapsulated with a polymer in the form of droplets or can exist continuously. An anisotropic polymer can be used as this polymer. The invention further relates to the use of this liquid crystal medium in a liquid crystal system. Furthermore, the liquid crystal display of the present invention is characterized by including this liquid crystal medium. This liquid crystal display is preferably driven by an active matrix system. The invention further relates to the use of such a liquid crystal medium in a liquid crystal display.

  It has been surprisingly found by the present invention that a liquid crystal medium with a reasonably high Δε and a suitable phase range, Δn and resistivity can be realized. This liquid-crystalline medium does not show the disadvantages of the prior art materials, in particular the high viscosity and the low stability to irradiation, or at least these disadvantages are significantly improved.

These improved liquid crystal media according to the present application comprise at least the following components:
One or more positive dielectric anisotropy compounds of the formula I

(Where
R ¹ is alkyl having 1 to 7 carbons, alkoxy, fluorinated alkyl or fluorinated alkoxy, alkenyl having 2 to 7 carbons, alkenyloxy, alkoxyalkyl or alkenyl fluoride, preferably alkyl or alkenyl. Yes, preferably n-alkyl or 1-E-alkenyl, particularly preferably n-alkyl,

And if present

Are independent of each other

And preferably

And
One of Z ¹¹ and Z ¹² is —CF ₂ —O— or —O—CF ₂ —, preferably —CF ₂ —O—, while the other, if present, is a single bond, — _{CH 2 -CH 2 -, - CF} 2 -CF 2 -, - CH 2 -O -, - O-CH 2 -, - CF 2 -O -, - O-CF 2 -, - CH = CH -, - CF═CF—, —CF═CH—, —CH═CF— or —CO—O—, preferably a single bond or —CH ₂ —CH ₂ —, particularly preferably a single bond,
X ¹ is halogen, fluorinated alkyl or fluorinated alkoxy having 1 to 4 carbon atoms, respectively, or fluorinated alkenyl having 2 to 4 carbon atoms, preferably F, Cl, —OCF ₂ H, —OCF ₃ or —CF ₃ , particularly preferably F or —OCF ₃ ,
Y ¹¹ and Y ¹² are independently of each other H or F, preferably at least one is F, and preferably both are F when X ¹ is halogen,
n is 0, 1 or 2, preferably 0 or 1, particularly preferably 1.
A component A which is a first positive dielectric anisotropy component comprising:
One or more positive dielectric anisotropic compounds of the formula II

(Where
R ² is alkyl having 1 to 9 carbons, preferably 1 to 7 carbons, alkoxy, fluorinated alkyl or fluorinated alkoxy, alkenyl having 2 to 7 carbons, alkenyloxy, alkoxyalkyl or fluorinated alkenyl. And is preferably alkyl or alkenyl, preferably n-alkyl or 1-E-alkenyl, particularly preferably n-alkyl,

And if present

Are independent of each other

And preferably

And
Z ²¹ and, if present, Z ^22, independently of one another, a single _{bond, -CH 2 -CH 2 -, -} CF 2 -CF 2 -, - CH 2 -O -, - O-CH 2 -, - CH═CH—, —CF═CF—, —CF═CH—, —CH═CF— or —CO—O—, preferably a single bond or —CH ₂ —CH ₂ —, particularly preferably a single bond. Is a bond,
X ² is halogen, fluorinated alkyl or fluorinated alkoxy each having 1 to 4 carbon atoms, or alkenyl fluoride having 2 to 4 carbon atoms, preferably F, Cl, —OCF ₂ H, —OCF ₃ Or -CF ₃ , particularly preferably F, Cl or -OCF ₃ ,
Y ²¹ and Y ²² are independently of each other H or F, preferably at least one is F, and preferably both are F when X ¹ is halogen,
m is 0, 1 or 2, preferably 1 or 2, particularly preferably 1.
A component B which is a second positive dielectric anisotropy component consisting of:
Optionally one or more neutral dielectric anisotropic compounds of formula III

(Where
R ³¹ and R ³² are each independently alkyl having 1 to 7 carbons, alkoxy, fluorinated alkyl or fluorinated alkoxy, alkenyl having 2 to 7 carbons, alkenyloxy, alkoxyalkyl or fluorinated alkenyl. , Preferably alkyl, alkoxy or alkenyl, particularly preferably n-alkyl or n-alkoxy, particularly preferably at least one of R ³¹ and R ³² is alkyl,

Are independent of each other, as well as

Are present independently of each other,

And preferably

At least one, or two of them, at least one of them, preferably both

And preferably

At least one, preferably at least

Is

And preferably

At least one, preferably at least

Is

And
Z ³¹ and Z ³² are independently of each other, and when two Z ³¹ are present, they are also independently of each other —CH ₂ —CH ₂ —, —CO—O—, trans—CH═CH—, trans— CF═CF—, —CH ₂ —O—, —CF ₂ —O— or a single bond, preferably at least one of them is a single bond, particularly preferably all are single bonds,
k is 0, 1 or 2, preferably 0 or 2)
A component C which is a first neutral dielectric anisotropy component comprising:
-Optionally, a component D which is a third positive dielectric anisotropy component consisting of one or more positive dielectric anisotropy compounds other than formula I and formula II;
-Optionally, a component E which is a second neutral dielectric anisotropy component consisting of one or more neutral dielectric anisotropy compounds;
-Further optionally, component F which is a negative dielectric anisotropy component comprising a negative dielectric anisotropy compound
Can be used.

  The invention also relates to the use of the liquid-crystal media of the invention in composite systems comprising liquid-crystal media and polymeric materials, and to these systems, their use in electro-optic displays, and the respective electro-optic displays.

  The liquid crystal mixture according to the present invention preferably contains component C which is the neutral dielectric anisotropy component. This component has a dielectric anisotropy in the range of -1.5 to +3. This component basically consists in particular preferably of all positive dielectric anisotropy compounds. This component preferably comprises one or more neutral dielectric anisotropic compounds of formula III.

  Optionally, the liquid crystal mixture according to the invention comprises a component F having negative dielectric anisotropy. This component has a dielectric anisotropy less than -1.5, consists of a negative dielectric anisotropy compound, and includes a compound of formula IV.

(Where
R ⁴¹ and R ⁴² , independently of one another, have the meaning given for R ³¹ in formula III above,

Is

And preferably

And

Is

And
Z ⁴¹ and Z ^42, independently of one _{another, -CH 2 -CH 2 -, -} COO-, trans -CH = CH-, trans _{-CF = CF -, - CH 2} O -, - CF 2 O- or a single Preferably at least one of them is a single bond, particularly preferably both are single bonds,
L ⁴¹ and L ⁴² , independently of one another, are ═C (—F) — or ═N—, preferably at least one of them is ═C (—F) —, particularly preferably both are ═ C (-F)-,
i is 0 or 1)
The compounds of formula I are a group of compounds of formulas I-1 to I-3, preferably I-2

(Where each parameter has its respective meaning given in Formula I above)
It is preferable to select from.

  Compounds of formula I-2 are of the group of formulas I-2a to I-2i, preferably I-2b, I-2c, I-2h and I-2i, especially I-2b and I-2i

(Wherein each parameter has its respective meaning given in formula I-2 above).

  The liquid-crystalline medium according to the invention comprises compounds selected from the group of formulas I-1 to I-3, preferably I-2a to I-2i, preferably consisting mostly of these, particularly preferably all of these It is preferable to contain the component A which consists of.

  In this application, with respect to a composition, “comprising” means that the entity referred to, eg, the medium or component, contains one or more of such components, or one or more of such compounds, preferably at a total concentration of 10% or more. Particularly preferably, it means to contain 20% or more.

  In this context, “mostly consists of” means that the entity referred to contains 80% or more, preferably 90% or more, particularly preferably one or more of the components, or one or more of the compounds. It means to contain 95% or more.

  In this regard, “consisting entirely of” means that the entity referred to is one or more of the components or one or more of the compounds of 98% or more, preferably 99% or more, particularly preferably It means to contain 100.0%.

  The compound of formula II is a group of compounds of formula II-1 to II-6, preferably II-2, II-3, II-4 and II-5

(Wherein each parameter has its respective meaning given in Formula II above. Also, the phenyl ring can optionally be further substituted with F. Preferably, Formulas II-3 and II- The central phenyl ring of 4 as well as the left phenyl ring of formula II-4 may optionally be substituted with F)
It is preferable to select from.

  Compounds of formula II-1 are of the group of formulas II-1a to II-1d, preferably II-1a to II-1c, particularly preferably II-1a and II-1c

(In the formula, each parameter has the meaning given in Formula II-1 above. In addition, R ² is alkyl having 5 to 9 carbon atoms, preferably 5 to 7 carbon atoms. preferable)
It is preferable to select from.

  Compounds of formula II-2 are of the group of formulas II-2a to II-2d, preferably II-2b and II-2c

(Where each parameter has its respective meaning given in Formula II-2 above)
It is preferable to select from.

  The compound of formula II-3 is of the group of formula II-3a to II-3d, preferably II-3a and II-3c

(Wherein each parameter has its respective meaning given in Formula II-3 above)
It is preferable to select from.

  Compounds of formula II-4 are of the group of formulas II-4a to II-4h, preferably II-4d and II-4h

(Wherein each parameter has its respective meaning given in Formula II-4 above)
It is preferable to select from.

  The compound of formula II-5 is of the group of formula II-5a to II-5d, preferably II-5b and II-5d, preferably II-5d

(Wherein each parameter has its respective meaning given in Formula II-5 above)
It is preferable to select from.

  Compounds of formula II-6 are of the group of formulas II-6a to II-6g, preferably II-6d and II-6f

(Wherein each parameter has its respective meaning given in Formula II-6 above)
It is preferable to select from.

Component A is one or more compounds of formula I, preferably a compound of formula I-2, preferably a compound selected from the group of formulas I-2d and I-2i, wherein X ¹ is F It is preferable to contain.

Component B is one or more compounds of formula II, preferably from compounds of formula II where X ² is F or Cl, preferably from the group of formulas II-2, II-3 and II-5 It is preferred to include selected compounds, more preferably compounds selected from the group of formulas II-2b, II-3a, II-4d, II-4h and II-5d.

  In another preferred embodiment, the liquid crystal medium contains a liquid crystal component C consisting of one or more compounds of formula III.

  The compound of formula III is a group of formula III-1 to III-3, preferably III-1 and / or III-3

(Wherein the parameters have their respective meanings given in formula III above and k is 2)
Is preferably selected from.

  The compound of formula III-1 is a group of formula III-1a to III-1d, preferably III-1a and / or III-1c

(Wherein the parameters have their respective meanings given in formula III-1 above)
Is preferably selected from.

  The compound of formula III-2 is a group of formula III-2a to III-2f, preferably a group of III-2a and III-2d

(Wherein the parameters have their respective meanings given in formula III-2 above)
Is preferably selected from.

  The compound of formula III-3 is a group of formula III-3a to III-3c, preferably III-3a and / or III-3c

(Wherein the parameters have their respective meanings given in formula III-3 above)
Is preferably selected from.

  Other liquid crystalline compounds as well as non-liquid crystalline compounds have not been explicitly described so far, but can be used optionally and advantageously in the medium according to the invention. Such compounds are known to those skilled in the art.

  In order to adjust the physical properties, the medium of the present invention can optionally contain another liquid crystal compound. Such compounds are known to those skilled in the art. These concentrations in the medium according to the invention are preferably from 0% to 30%, more preferably from 0% to 20%, particularly preferably from 0.5% to 15%.

  Preferably, components D and E of the liquid crystal medium according to the invention are used up to a total concentration of 50%.

  The liquid crystal medium preferably contains 50% to 100% of components A, B and C, more preferably 70% to 100%, particularly preferably 80% to 100%, particularly 90% to 100%. To do. The liquid crystal medium comprises one or more compounds of the formulas I to III, respectively, preferably consisting mostly of these, particularly preferably consisting entirely of these.

  In a preferred embodiment of the invention, the liquid-crystalline medium according to the invention comprises components A, B and C, preferably consisting mostly of these, particularly preferably consisting entirely of these.

  Component A is preferably used at a concentration of 3% to 80% of the total mixture, preferably 4% to 60%, more preferably 9% to 50%, particularly preferably 11% to 45%. Is done.

  Component B is preferably used at a concentration of 0% to 80% of the total mixture, preferably 5% to 70%, more preferably 10% to 65%, particularly preferably 20% to 63%. Is done.

  Component C is preferably used at a concentration of 0% to 60% of the total mixture, preferably 10% to 55%, more preferably 25% to 50%, particularly preferably 30% to 45%. Is done.

  The liquid crystal medium according to the present invention is characterized in that the clearing point is 85 ° C. or higher, more preferably 90 ° C. or higher, particularly 95 ° C. or higher. The clearing point is preferably 110 ° C. or lower, more preferably 100 ° C. or lower.

  The Δn of the liquid crystal medium according to the present invention depends on the intended application. Δn of the liquid crystal medium is preferably in the range of 0.090 to 0.280, more preferably in the range of 0.100 to 0.250, and particularly preferably in the range of 0.120 to 0.200. In a first preferred embodiment, the Δn of the liquid crystal medium is in the range of 0.090 to 0.150, more preferably in the range of 0.100 to 0.140, particularly preferably in the range of 0.110 to 0.130. is there. In a second preferred embodiment, the Δn of the liquid crystal medium is in the range of 0.130 to 0.190, more preferably in the range of 0.140 to 0.180, particularly preferably in the range of 0.150 to 0.170. is there.

  The Δε of the liquid crystal medium according to the present invention at 1 kHz and 20 ° C. is preferably 6.0 or more, more preferably 7.5 or more, particularly preferably 8.0 or more, particularly 8.5 or more. However, this Δε is preferably 15.0 or less, more preferably 10.0 or less, and particularly preferably 9.0 or less.

  The nematic phase of the medium according to the invention is preferably at least 0 ° C. to 90 ° C., more preferably at least −20 ° C. to 90 ° C., particularly preferably at least −30 ° C. to 90 ° C., in particular at least −30 ° C. to 90 ° C. Extends to a temperature range of ° C. Here, extending to at least the low temperature to high temperature range means that the nematic phase of the medium of the present invention extends at least to this low temperature limit, preferably to a temperature below this low temperature limit, as well as at least this It means extending to the high temperature limit, preferably to higher temperatures.

  In this application, the term “positive dielectric anisotropic compound” describes a compound with Δε> 3.0, and “neutral dielectric anisotropic compound” with −1.5 ≦ Δε ≦ 3. 0.0 and a “negative dielectric anisotropy compound” is a compound with Δε <−1.5. The same applies for “components”. Δε is measured at 1 kHz and 20 ° C. Depending on the dielectric anisotropy of the compound and the situation, the dielectric anisotropy of the component of interest is determined from the results of a solution in which 10% of each compound is added to the nematic host mixture. The volumes of these test mixtures are measured in both homeotropic and homogeneous array cells. The cell gap for both types of cells is about 10 μm. The voltage to be applied is a rectangular wave having a frequency of 1 kHz and an effective value (average double root value) of usually 0.5 V to 1.0 V. However, this voltage is always chosen to be below the volume threshold of the respective test mixture.

  As the host mixture, the mixture ZLI-4792 is used for the positive dielectric anisotropic compound, and the mixture ZLI-3086 is used for the neutral dielectric dielectric compound and the negative dielectric anisotropic compound (both from Merck KGaA, Germany). Manufactured) are used respectively. The dielectric constant of the compound is measured from the change in the value of the host mixture when the compound of interest is added, and extrapolated to the concentration of the compound of interest of 100%. Components having a nematic phase at a measurement temperature of 20 ° C. are measured in the same manner, and all other components are treated in the same way as compounds.

  For liquid crystal mixtures and liquid crystal components, unlike the testing of single compounds and components that do not have their own nematic phase at 20 ° C., a test cell with a cell gap of 22 μm is used to measure Δε, and the applied voltage Is 0.3V.

The term “threshold voltage” refers to the optical threshold in this application and is used for a relative contrast of 10% (V ₁₀ ) unless explicitly stated. The term “saturation voltage” refers to optical saturation, and is used when the relative contrast is 90% (V ₉₀ ) unless otherwise clearly indicated. The capacitive threshold voltage (V ₀ , also called Fredericks transition threshold V _Fr ) is used only when explicitly presented.

  All parameter ranges presented in this application include limit values unless expressly stated otherwise.

Throughout this application, unless stated otherwise, all concentrations are in weight percent, which are for each complete mixture, and all temperatures are in degrees Celsius (Celsius). Celsius temperature is also used for all temperature differences. All physical properties are measured at a temperature of 20 ° C. according to “Merck Liquid Crystals, Physical Properties of Liquid Crystals”, November 1997, Merck KGaA, Germany, unless explicitly stated otherwise. Optical anisotropy (Δn) is measured at a wavelength of 589.3 nm. The dielectric anisotropy (Δε) is measured at a frequency of 1 kHz. The threshold voltage and all other electro-optic properties were measured using a test cell made of Merck KGaA (Germany). The test cell for measuring Δε had a cell gap of 22 μm. The electrode was a circular electrode having an area of 1.13 cm ² and having a guard ring. Alignment layer is homeotropic alignment

For SE-1211 from Nissan Chemical (Japan), homogeneous orientation

Was polyimide AL-1054 made by Nippon Synthetic Rubber (Japan). The capacity was measured with a frequency response analyzer HP4274A manufactured by Hewlett Packard (USA) using a sine wave having a voltage of 0.3 Vrms. The light used in the electro-optic measurement was white light. The apparatus used was a commercially available apparatus manufactured by Otsuka (Japan). The characteristic voltage was obtained by vertical observation. The threshold (V ₁₀ ) -mid gray (V ₅₀ )-and saturation (V ₉₀ ) voltages were measured at 10%, 50% and 90% relative contrast, respectively.

  The liquid crystal medium according to the present invention can contain other additives and chiral dopants in conventional concentrations. The total concentration of these other components is in the range of 0% to 10%, preferably 0.1% to 6%, based on the entire mixture. The concentration of the individual compounds used is preferably in the range of 0.1% to 3%. These concentrations and the concentrations of similar additives are not added to the concentration values and concentration ranges of the liquid crystal component and liquid crystal compound of the liquid crystal medium in the present application.

  The liquid crystal medium of the present invention comprises several types of compounds, preferably 3 to 30 types, more preferably 8 to 20 types, and particularly preferably 10 to 16 types.

  These compounds are mixed by a usual method. Generally, the required amount of a compound with a small amount used is dissolved in a compound with a large amount used. If the temperature at that time is higher than the clearing point of the compound used at a high concentration, the completion of the dissolution process can be observed particularly easily. However, it is also possible to prepare the medium by other conventional methods. For example, it is possible to use a so-called premix, such as a homologous or eutectic mixture of compounds, or a so-called multi-bottle system in which the components are mixtures that can be used as such.

  By adding appropriate additives, the liquid crystal medium of the present invention can be improved so that the liquid crystal medium can be used in all known liquid crystal displays. This liquid crystal medium can be used as it is for TN-, TN-AMD, ECB-AMD, VAN-AMD, IPS, OCB LCD and the like. For example, a liquid crystal display having a configuration in which a layer of the liquid crystal mixture of the present invention is disposed between two electrodes can be obtained. Furthermore, it is used in particular in ASM-PA LCD, and in particular in complex systems such as PDLC, NCAP and PN LCD. In PDLC, for example, a sheet-like layer having a structure in which a liquid crystal mixture forms micro droplets (encapsulated micro droplets) in an optically isotropic transparent polymer matrix is provided between electrodes. The thing which has the structure arrange | positioned can be mentioned, A well-known polymer can be utilized as a polymer.

  The melting point T (C, N), the transition T (S, N) from the smectic (S) phase to the nematic (N) phase and the clearing point T (N, I) of the liquid crystal include all the temperatures of the present invention. Similarly, Celsius (Celsius) is used. Temperature (Celsius) is used for the temperature difference.

In the present application, particularly in the following examples, the structure of the liquid crystal compound is represented by an abbreviation also called an acronym. The conversion of abbreviations to the corresponding structure is straightforward according to the following Tables A-1 to A-2 and B-1 to B-3. All C _n H _{2n + 1} and C _m H _{2m + 1} groups are straight chain alkyl groups having n and m C atoms, respectively. The interpretation of Table B is self-explanatory. Table A shows only the core abbreviations of the structure. Individual compounds are represented by core abbreviations, followed by a hyphen, followed by a code identifying the substituents R ¹ , R ² , L ¹ and L ² .

The liquid crystal medium according to the invention is preferably
-Selected from a group of compounds of the formulas of Tables A and B, preferably selected from a group of compounds of the formulas of Table A, preferably 7 or more, preferably 8 or more, of different formulas, preferably Is selected from the group of compounds of the different formulas, one, two or more, preferably three or more, and / or the compounds of the formulas in Table B, preferably two, three, four As mentioned above, Preferably 5 or more types of compounds are included.

  The following examples illustrate the present invention without limiting it in any way.

However, the examples illustrate representative preferred embodiments. The examples illustrate the use of representative and preferred ingredients and illustrate their concentrations. In addition, the examples illustrate possible variations in the physical properties of the composition and illustrate to a person skilled in the art what properties can be obtained and to what extent they can be changed. . In particular, the various combinations of properties that it is desirable to be able to achieve are thus clearly indicated to those skilled in the art.
(Example 1)
A liquid crystal mixture having the composition and characteristics shown in the following table was obtained.

Note: nd: unidentified This mixture has a advantageously low Δn value, a reasonably high Δε value and a particularly low rotational viscosity. Furthermore, this mixture is excellent in stability against ultraviolet rays. This mixture is suitable for PDLC displays, especially reverse PDLC.
(Example 2)
A liquid crystal mixture having the composition and characteristics shown in the following table was obtained.

Note: nd: unidentified This mixture has a advantageously high Δn value, a suitably high Δε value and a particularly low rotational viscosity. Furthermore, this mixture is excellent in stability against ultraviolet rays. This mixture is suitable for PDLC displays, especially reverse PDLC.

(Comparative example)
A liquid crystal mixture having the composition and characteristics shown in the following table was obtained.

The birefringence of this mixture is equivalent to Example 2. However, it is not preferable because the rotational viscosity is high.
(Example 3)
A liquid crystal mixture having the composition and characteristics shown in the following table was obtained.

Note: nd: unidentified This mixture has a favorable [Delta] n and is very suitable for PDLC displays, especially reverse PDLC.

Claims (14)

A liquid crystal medium,
One or more compounds of formula I

(Where
R ¹ is alkyl having 1 to 7 carbons, alkoxy, fluorinated alkyl or fluorinated alkoxy, alkenyl having 2 to 7 carbons, alkenyloxy, alkoxyalkyl or fluorinated alkenyl.

And if present

Are independent of each other

And
One of Z ¹¹ and Z ¹² is —CF ₂ —O— or —O—CF ₂ —, while the other, when present, is a single bond, —CH ₂ —CH ₂ —, —CF ₂ —. CF ₂ —, —CH ₂ —O—, —O—CH ₂ —, —CF ₂ —O—, —O—CF ₂ —, —CH═CH—, —CF═CF—, —CF═CH—, -CH = CF- or -CO-O-
X ¹ is halogen, fluorinated alkyl or fluorinated alkoxy having 1 to 4 carbon atoms, respectively, or fluorinated alkenyl having 2 to 4 carbon atoms,
Y ¹¹ and Y ¹² are independently of each other H or F;
n is 0, 1 or 2)
A component A that is a first positive dielectric anisotropy component comprising a positive dielectric anisotropy compound,
One or more positive dielectric anisotropic compounds of formula II

(Where
R ² is alkyl having 1 to 9 carbons, alkoxy, fluorinated alkyl or fluorinated alkoxy, alkenyl having 2 to 7 carbons, alkenyloxy, alkoxyalkyl or fluorinated alkenyl.

And if present

Are independent of each other

And
Z ²¹ and, if present, Z ^22, independently of one another, a single _{bond, -CH 2 -CH 2 -, -} CF 2 -CF 2 -, - CH 2 -O -, - O-CH 2 -, - CH═CH—, —CF═CF—, —CF═CH—, —CH═CF— or —CO—O—,
X ² is halogen, each fluorinated alkyl or fluorinated alkoxy having 1 to 4 carbon atoms, or fluorinated alkenyl having 2 to 4 carbon atoms,
Y ²¹ and Y ²² are independently of each other H or F;
m is 0, 1 or 2)
And a component B which is a second positive dielectric anisotropy component. One or more compounds of formula III

(Where
R ³¹ and R ³² are each independently alkyl having 1 to 7 carbons, alkoxy, fluorinated alkyl or fluorinated alkoxy, alkenyl having 2 to 7 carbons, alkenyloxy, alkoxyalkyl or fluorinated alkenyl. ,

Are independent of each other, as well as

Are present independently of each other,

And
Z ³¹ and Z ³² are independently of each other, and when two Z ³¹ are present, they are also independently of each other —CH ₂ —CH ₂ —, —CO—O—, trans—CH═CH—, trans— CF═CF—, —CH ₂ —O—, —CF ₂ —O— or a single bond,
k is 0, 1 or 2)
The liquid crystal medium according to claim 1, comprising a component C that is a neutral dielectric anisotropy component. Group of compounds of formulas I-1 to I-3

(Wherein each parameter has its respective meaning given in formula I of claim 1)
The liquid crystal medium according to claim 1, comprising one or more compounds selected from the group consisting of: Group of compounds of formula II-1 to II-6

(Wherein each parameter has its respective meaning given in Formula II of claim 1)
The liquid crystal medium according to claim 1, comprising one or more compounds selected from the group consisting of: Group of compounds of formula I-2a to I-2i

(Wherein each parameter has its respective meaning given in formula I-2 of claim 3)
The liquid crystal medium according to claim 1, comprising one or more compounds selected from the group consisting of: One or more compounds of formula II (wherein X ² is F), characterized in that it comprises a liquid crystal medium according to any one of claims 1 to 5. One or more compounds of formula II (wherein X ² is Cl), characterized in that it comprises a liquid crystal medium according to any one of claims 1 to 6.   A liquid crystal system comprising a polymer and the liquid crystal medium according to claim 1.   The liquid crystal system according to claim 8, wherein the liquid crystal medium is encapsulated with a polymer in the form of droplets or exists continuously.   The liquid crystal system according to claim 8, wherein the polymer is an anisotropic polymer.   Use of the liquid crystal medium according to claim 1 in a liquid crystal system.   A liquid crystal display comprising the liquid crystal medium according to claim 1.   The liquid crystal display according to claim 12, wherein the liquid crystal display is driven by an active matrix. Use of the liquid crystal medium according to claim 1 in a liquid crystal display.