KR102285824B1 - Liquid-crystalline media, switchable liquid crystal lenses and liquid crystal displays comprising them - Google Patents

Abstract

상기 식들에서, 변수들은 본원 특허청구범위 또는 명세서에 제시된 각각의 의미를 갖는다.
본 발명은 또한, 특히 3D 렌즈에서의 상기 액정 매질의 용도, 본 발명에 따른 매질을 함유하는 3D 렌즈, 이러한 렌즈의 제조 및 이용 방법에 관한 것이다. 이러한 렌즈는 특히 자동-입체(auto-stereoscopic) 3D 디스플레이에 적합하며, 이러한 디스플레이 역시 본 발명의 일부이다.The present invention relates to a liquid crystal medium comprising at least one compound of the formulas (I) and (II), respectively, and a process for preparing the same:

In the above formulas, variables have the respective meanings given in the claims or specification herein.
The present invention also relates to the use of said liquid-crystalline medium, in particular in 3D lenses, 3D lenses containing the medium according to the invention, and methods of making and using such lenses. Such lenses are particularly suitable for auto-stereoscopic 3D displays, such displays are also part of the invention.

Description

Liquid crystal medium, switchable liquid crystal lens and liquid crystal display comprising same

The present invention relates in particular to liquid-crystal media for liquid-crystal switching lenses, in particular for liquid-crystal displays capable of displaying 3D images. These liquid crystal switching lenses are based on electrically induced birefringence and use a specific liquid crystal medium for electrically switchable LC lenses. The invention also relates to the use of novel liquid-crystal media and liquid-crystal switching lenses.

BACKGROUND OF THE INVENTION Various types of liquid crystal displays (LCDs) are well known and widespread in the market. In recent years, the demand for display images that provide a natural viewing experience to the observer has increased not only in TV sets, but also in monitors for desktop and laptop computers and even small devices such as cell phones, tablet computers, portable store displays, etc. in three dimensions. It provided the introduction of a display capable of displaying (ie, 3D) images.

Recently, several techniques have been used to provide a 3D effect to such displays. In a first classification, a number of different technologies that require the viewer to wear special glasses to observe the 3D effect can be distinguished from other technologies that use auto-stereoscopic display principles. In the latter, there is no need for the viewer to wear glasses, whether active or passive.

Some observers are looking for the need to wear glasses that are less uncomfortable. In particular, observers already wearing optical (ie ophthalmic) glasses.

Another disadvantage of the 3D presentation technology that requires glasses is the fact that without the glasses such viewing is not possible at all, and therefore the maximum number of viewers who can accurately view the display at the same time is limited by the number of glasses available at one time. Also, the surface of the glasses is prone to degradation. Also, last but not least, for active glasses that require active and tuned actuation of the glasses as shutters or polarization modifiers with timing matched to the panel displaying the image, it is necessary to constantly provide a tuning signal to the glasses. . Also, unless they provide an energy supply by "connecting wires" to the observer, their batteries must be recharged frequently, and in most cases this latter alternative is less attractive. Currently, due to some of these serious drawbacks of various types of 3D technology that require the viewer to wear special glasses, a display capable of providing a 3D image without the need for the use of glasses is highly desired.

This “glass-free” 3D technology is called auto-stereoscopic display. Currently, at least two distinctly different types of such displays are being developed.

A first type of this technique is a method of realizing a so-called "parallax barrief" in order to distinguish between the appearances seen by the right and left eyes, each provided by two separate channels of information. it will be used

This parallax barrier, for each eye, blocks the optical path of the field of view produced by the other eye.

The second type uses a “lenticular lens” to achieve this separation effect of the two channels. In the case of this second type, again, there are two different ways for a realistic realization.

In the first case, referred to herein as "RM" lenses, lenticular lenses are realized by polymerizing oriented reactive mesogens or mixtures of reactive mesogens to form anisotropic liquid crystal polymer lenses. However, this technique requires the use of additional electro-optical switching elements (eg liquid crystal displays) to provide information about the optical image. This in turn leads to increased design complexity and increased production costs.

When converting a 2D image to a 3D image and vice versa when using RM lenses, attaching the 3D lenses requires an additional process to optically couple these 3D lenses to a polarization switching panel, typically using UV irradiation. Therefore, the UV stability of the LC medium is very important in many applications. The polarization switching panel is attached directly to an image generating panel (preferably LCD), typically with an associated RM lens.

In the second case, referred to herein as an "LC lens", a lenticular lens is created using a liquid crystal medium, the lens itself being electrically addressed and changing its optical state to directly display the necessary optical information in the two viewing channels. The lens itself is used.

These LC lenses are typically coupled directly to the imaging panel.

The main variable of the LC mixture for a switchable 3D LC lens is Δn, since it mainly affects the quality (depth) of the 3D image and determines the required cell spacing. As Δn increases, the 3D depth becomes deeper, and the cell spacing used can be lower. This reduced cell spacing helps both to reduce the drive voltage and increase the orientation force, especially in the case of relatively high cell spacing of several tens of μm. In general, a value of Δn in the range of 0.15 to 0.4 is required, depending on the type and application.

Also for the "LC lens" type, there are two possible embodiments. In the first case, referred to herein as a "polymeric mold", the liquid crystal material is embedded in a mold of the polymeric material. This polymeric material (which may be optically isotropic or anisotropic) is typically present in one of the substrates. This polymeric material is structured in such a way that it provides space for the liquid crystal material in the form of the inverse of the lenticular lens to be realized. Typically, the polymeric material forms the trough of an inverted lenticular lens.

In the second case, referred to herein as "electrically induced birefringence" (EIB for short), a liquid crystal material is sandwiched between a pair of substrates, one of which is applied as an electrode, which is, for example, "in-plane Switching" (IPS) displays or "fringe field switching" (FFS) can provide alternating voltages that form an electric field in the plane of the device.

At first glance, the 3D lens of the LC lens type appears to be a simpler and simpler device, but to realize this realistically, some serious difficulties must be overcome in relation to the driving technology and manufacturing method. In addition, the liquid crystal material must be improved, and more demanding specifications must be satisfied. Herein, a liquid crystal medium with improved performance for a switchable 3D LC lens is proposed.

In the plastic mold type, the LC material is impregnated into the mold. These types of LC lenses inherently require relatively high values of Δn, typically on the order of 0.2 to 0.4. Additionally, high dielectric constant (Δε) values of 9 or more, preferably even 40 or more, are typically required to reduce the operating voltage caused by each cell spacing of relatively large thickness. Also, only a moderately high rotational viscosity (γ ₁ ) is required.

In the EIB type, the orientation of the LC molecules is directly controlled by the applied voltage. Therefore, an extremely high value of Δn is not required. Typically, the Δn value should range from 0.15 to 0.25. Also, a large cell spacing is not required. Thus, for this type of LC lens, a moderately high positive Δε value of 5 or less is sufficient. However, especially for devices with multiple viewpoints, a low γ ₁ ε value is required to achieve a fast response time (τ).

As in manufacturing processes where UV irradiation is typically applied, the UV stability of the LC medium used is very important in many applications.

The hitherto known LC compositions have significant disadvantages in the use associated with the present invention. Most of these compositions provide, as well as other drawbacks, an unfavorably small regulation of the optical response and/or inadequate addressing ability, which requires a slow response and/or high operating voltage, and/or inadequate stability, particularly against UV radiation.

Therefore, there is a need for new liquid crystal media with improved properties. In particular, the control of the optical response, response time, operating voltage and safety should be improved.

In addition, improvement of the low-temperature behavior of liquid-crystalline media is desired. There is now a need for improvement in both operating characteristics and shelf life.

Accordingly, there is a great need for liquid-crystalline media having properties suitable for the corresponding practical use.

Surprisingly, it has been found that, when using the liquid-crystalline medium selected, it is possible to achieve components for high-frequency technology that do not have the disadvantages of the prior materials or have at least only a significantly reduced degree.

Now surprisingly, a mesogenic medium comprising It has been found to make it possible to realize a medium with high stability:

- at least one compound of the formula (I):

In the above formula,

R ¹ is preferably straight or branched chain alkyl having 1 to 20 carbon atoms, unsubstituted or mono- or polysubstituted with F, Cl or CN, preferably F, wherein one or more CH ₂ groups are in each case to each other ^{Independently -O-, -S-, -NR 01} -, -SiR ⁰¹ R ⁰² -, -CO-, -COO-, -OCO-, - in such a way that the O and/or S atoms are not directly linked to each other. Optionally replaced by OCO-O-, -S-CO-, -CO-S-, -CY ⁰¹ =CY ⁰² - or -C≡C-, preferably 1 to 9 carbon atoms, preferably 2 carbon atoms n-alkyl or n-alkoxy having to 5 carbon atoms, alkenyl, alkenyloxy or alkoxyalkyl having 2 to 9 carbon atoms, preferably 2 to 5 carbon atoms, or halogenated alkyl preferably up to 9 carbon atoms, halogenated alkenyl or halogenated alkoxy, preferably monofluorinated, difluorinated or oligofluorinated alkyl with up to 9 carbon atoms, alkenyl or alkoxy, most preferably n-alkyl, n-alkoxy, alkenyl, alkene with up to 9 carbon atoms yloxy or alkoxyalkyl, most preferably n-alkyl or alkenyl,

X ¹ is F, Cl, CF ₃ , OCF ₃ , CN or NCS, preferably F or CN,

Z ¹ is C=O or CF ₂ ,

L ¹¹ , L ¹² and L ¹³ are, independently of each other, H or F, preferably at least one of them, more preferably two of them are F,

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m and n are, independently of each other, 0 or 1,

Y ⁰¹ and Y ⁰² are, independently of each other, F, Cl or CN, alternatively one of them may be H,

R ⁰¹ and R ⁰² are each independently H or alkyl having 1 to 12 carbon atoms.

- at least one compound of the formula (II):

In the above formula,

R ²¹ and R ²² are, independently of each other, preferably straight or branched chain alkyl having 1 to 20 carbon atoms, unsubstituted or mono- or polysubstituted with F, Cl or CN, preferably F, wherein at least one CH _{The two} ^{groups, independently of one another at each occurrence, are -O-, -S-, -NR 01} -, -SiR ⁰¹ R ⁰² -, -CO-, -COO in such a way that the O and/or S atoms are not directly connected to each other. -, -OCO-, -OCO-O-, -S-CO-, -CO-S-, -CY ⁰¹ =CY ⁰² - or -C≡C- optionally substituted, preferably having 1 to C1 9, preferably n-alkyl or n-alkoxy having 2 to 5 carbon atoms, alkenyl, alkenyloxy or alkoxyalkyl having 2 to 9 carbon atoms, preferably 2 to 5 carbon atoms, or halogenated preferably up to 9 carbon atoms alkyl, halogenated alkenyl or halogenated alkoxy, preferably monofluorinated, difluorinated or oligofluorinated alkyl with up to 9 carbon atoms, alkenyl or alkoxy, most preferably n-alkyl with up to 9 carbon atoms, n -alkoxy, alkenyl, alkenyloxy or alkoxyalkyl, most preferably

R ²¹ is n-alkyl or alkenyl,

R ²² is n-alkyl, alkenyl, n-alkoxy or alkenyloxy,

L ²¹ , L ²² and L ²³ are, independently of each other, H or F, preferably at least one of them, more preferably two of them are F,

n is 0 or 1,

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Y ⁰¹ and Y ⁰² are, independently of each other, F, Cl or CN, alternatively one of them may be H,

R ⁰¹ and R ⁰² are each independently H or alkyl having 1 to 12 carbon atoms.

- optionally, preferably essentially, at least one compound selected from the group of formulas (III) and (IV):

In the above formulas,

R ³¹ , R ³² , R ⁴¹ and R ⁴² are, independently of each other, preferably straight or branched chain alkyl having 1 to 20 carbon atoms, unsubstituted or mono- or polysubstituted with F, Cl or CN, preferably F , wherein at least one CH ₂ ^{group is, in each case independently of one another, -O-, -S-, -NR 01} -, -SiR ⁰¹ R ⁰² -, in such a way that the O and/or S atoms are not directly connected to each other; optionally replaced by -CO-, -COO-, -OCO-, -OCO-O-, -S-CO-, -CO-S-, -CY ⁰¹ =CY ^{02 - or -C≡C-, preferably} Preferably, n-alkyl or n-alkoxy having 1 to 9 carbon atoms, preferably 2 to 5 carbon atoms, alkenyl, alkenyloxy or alkoxyalkyl having 2 to 9 carbon atoms, preferably 2 to 5 carbon atoms, or preferably is halogenated alkyl, halogenated alkenyl or halogenated alkoxy with up to 9 carbon atoms, preferably monofluorinated, difluorinated or oligofluorinated alkyl with up to 9 carbon atoms, alkenyl or alkoxy, most preferably with up to 9 carbon atoms n-alkyl, n-alkoxy, alkenyl, alkenyloxy or alkoxyalkyl of

R ³¹ is n-alkyl or alkenyl,

R ³² is n-alkyl, alkenyl, n-alkoxy or alkenyloxy;

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p is 0, 1 or 2, preferably 0 or 1, most preferably 0,

Y ⁰¹ , Y ⁰² , R ⁰¹ and R ⁰² have the respective meanings given in the above formula (I).

- optionally, preferably essentially, at least one compound selected from the group of the formula (V):

In the above formula,

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R ⁵ is preferably straight or branched chain alkyl having 1 to 20 carbon atoms, unsubstituted or mono- or polysubstituted with F, Cl or CN, preferably F, wherein one or more CH ₂ groups are in each case one another ^{Independently -O-, -S-, -NR 01} -, -SiR ⁰¹ R ⁰² -, -CO-, -COO-, -OCO-, - in such a way that the O and/or S atoms are not directly linked to each other. Optionally replaced by OCO-O-, -S-CO-, -CO-S-, -CY ⁰¹ =CY ⁰² - or -C≡C-, preferably 1 to 9 carbon atoms, preferably 2 carbon atoms n-alkyl or n-alkoxy having to 5 carbon atoms, alkenyl, alkenyloxy or alkoxyalkyl having 2 to 9 carbon atoms, preferably 2 to 5 carbon atoms, or halogenated alkyl preferably up to 9 carbon atoms, halogenated alkenyl or halogenated alkoxy, preferably monofluorinated, difluorinated or oligofluorinated alkyl with up to 9 carbon atoms, alkenyl or alkoxy, most preferably n-alkyl, n-alkoxy, alkenyl, alkene with up to 9 carbon atoms yloxy or alkoxyalkyl, most preferably n-alkyl or alkenyl, most preferably n-alkyl,

X ⁵ is halogen, CF ₃ or OCF ₃ , preferably F, Cl, CF ₃ or OCF ₃ , most preferably F,

Y ⁰¹ , Y ⁰² , R ⁰¹ and R ⁰² each have the meanings given in Formula I above,

With the proviso that the mesogenic medium includes at least one compound of formula (I), wherein Z1 is C=O.

The mesogenic medium according to the invention comprises at least one compound of the formula IZ, and optionally, in a preferred embodiment, essentially, at least one compound of the formula IQ:

Variables in the above formulas have the respective meanings given in the above formula (I), preferably

In the above formula (IZ), X ¹ is CN, NCS or OCF ₃ , most preferably CN,

In the above formula (IQ), X ¹ is F, Cl or OCF ₃ , most preferably F.

The mesogenic medium according to the present invention comprises at least one compound of the formula IZ, preferably a compound selected from the group of compounds of the formula IZ-1 to IZ-3, preferably a compound of the formula IZ-1 At least one compound and at least one compound selected from the group of formulas IZ-2 and IZ-3 do:

Variables in the above formulas have the respective meanings given in the above formula (IZ), preferably

R ¹ is n-alkyl or alkenyl, most preferably n-alkyl in formulas IZ-1 and IZ-3, most preferably alkenyl in formula IZ-2,

X ¹ is CN, Cl or CF ₃ , most preferably CN.

The mesogenic medium according to the invention is at least one compound of formula I, preferably selected from the group of compounds of the formulas IQ-1 to IQ-3, preferably selected from the formulas IQ-1 and IQ-2 and, more preferably, at least one compound of each of the following formulas IQ-1 and IQ-2:

The variables in the above formulas have the respective meanings given in the above formula (IQ), preferably

R ¹ is n-alkyl or alkenyl, most preferably n-alkyl,

X ¹ is F, Cl or CF ₃ , most preferably F.

The mesogenic medium according to the invention is at least one compound of formula II, preferably selected from the group of compounds of formulas II-1 to II-3, preferably selected from formulas II-1 and II-3 and, more preferably, at least one compound of the following formulas II-1 and II-3, respectively:

wherein the variables have the respective meanings given in formula II above,

Preferably in formulas II-1 and II-2,

R ²¹ is n-alkyl or alkenyl, most preferably n-alkyl,

R ²² is n-alkoxy or alkenyloxy, most preferably n-alkoxy,

Preferably in formula II-3,

R ²¹ is n-alkyl or alkenyl,

R ²² is n-alkyl or alkenyl, most preferably n-alkyl.

The mesogenic medium according to the invention comprises at least one compound of formula II-1, preferably a compound selected from the group of compounds of formulas II-1a to II-1d, preferably compounds of formulas II-1a and/or II compounds of -1d, most preferably compounds of formula II-1a:

In the above formulas, the variables have the respective meanings given above.

The mesogenic medium according to the invention comprises at least one compound of formula II-2, preferably a compound selected from the group of compounds of formulas II-2a to II-2d, preferably compounds of formulas II-2a and/or II a compound of -2d, most preferably a compound of formula II-2a:

In the above formulas, the variables have the respective meanings given above.

The mesogenic medium according to the invention comprises at least one compound of formula II-3, preferably a compound selected from the group of compounds of formulas II-3a to II-3d, preferably compounds of formulas II-3c and/or II compounds of -3d, most preferably compounds of formula II-3d:

In the above formulas, the variables have the respective meanings given above.

Preferably, the mesogenic medium according to the invention comprises at least one compound of formula III, preferably a compound selected from the group of compounds of formulas III-1 and III-2, preferably a compound of formula III-2 Includes:

In the above formulas, the variables have the respective meanings given above, preferably

R ³¹ is each non-fluorinated alkyl or non-fluorinated alkoxy having 1 to 15 carbon atoms, or non-fluorinated alkenyl, non-fluorinated alkenyloxy or non-fluorinated alkoxyalkyl each having 2 to 15 carbon atoms , preferably alkyl, particularly preferably n-alkyl,

R ³² represents H, each non-fluorinated alkyl or non-fluorinated alkoxy having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms, particularly preferably 3 carbon atoms, more preferably

R ³¹ represents C _n H _{2n +1} or CH ₂ =CH-(CH ₂ ) _z ,

R ³² represents C _m H _{2m +1} , OC _m H _{2m +1} or (CH ₂ ) _z -CH=CH ₂ ,

n and m represent, independently of each other, integers in the range from 0 to 15, preferably in the range from 1 to 7, particularly preferably in the range from 1 to 5,

z represents 0, 1, 2, 3 or 4, preferably 0 or 2.

Preferred combinations of (R ³¹ and R ³² ) herein are in particular (C _n H _{2n +1} and C _m H _{2m +1} ) and (C _n H _{2n +1} and OC _m H _{2m +1} ).

Preferably, the mesogenic medium according to the invention comprises at least one compound of the formula III-1, preferably a compound selected from the group of compounds of the formulas III-1a to III-1c, preferably a compound of the formula III-1a and / or a compound of formula III-1c, most preferably a compound of formula III-1a:

In the above formulas, the variables have the respective meanings given above.

Preferably, the mesogenic medium according to the invention comprises at least one compound of formula III-2, preferably a compound selected from the group of compounds of formulas III-2a to III-2d, a compound selected from III-2b and III-2d, most preferably a compound of formula III-2a:

In the above formulas, the variables have the respective meanings given above, preferably

R ³¹ is each non-fluorinated alkyl or non-fluorinated alkoxy having 1 to 15 carbon atoms, or non-fluorinated alkenyl, non-fluorinated alkenyloxy or non-fluorinated alkoxyalkyl each having 2 to 15 carbon atoms , preferably alkyl, particularly preferably n-alkyl,

R ³² represents H, each non-fluorinated alkyl or non-fluorinated alkoxy having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms, particularly preferably 3 carbon atoms, more preferably

R ³¹ represents C _n H _{2n +1} or CH ₂ =CH-(CH ₂ ) _z ,

R ³² represents C _m H _{2m +1} or OC _m H _{2m +1} or (CH ₂ ) _z -CH=CH ₂ ,

n and m represent, independently of each other, integers ranging from 0 to 15, preferably from 1 to 7, particularly preferably from 1 to 5,

z represents O, 1, 2, 3 or 4, preferably 0 or 2.

Preferred combinations of (R ³¹ and R ³² ) herein are in particular (C _n H _{2n +1} and C _m H _{2m +1} ) and (C _n H _{2n +1} and OC _m H _{2m +1} ).

In a preferred embodiment of the present invention, said liquid-crystalline medium comprises at least one compound of formula IV, preferably

R ⁴¹ is n-alkyl or alkenyl, more preferably n-alkyl, most preferably C _n H _2n+1 ,

R ⁴² is alkenyl, more preferably CH ₂ =CH-[CH ₂ -] _z , or CH ₃ -CH ₂ =CH-[CH ₂ ] _z , [-CH ₂ ] ₂ -CH=CH ₂ or [ -CH ₂ ] ₂ -CH=C-CH ₃ and

n is an integer in the range from 0 to 15, preferably in the range from 1 to 7, particularly preferably in the range from 1 to 5,

z is 0, 1, 2, 3 or 4, preferably 0 or 2

compounds of formula IV.

Preferably, the mesogenic medium according to the invention comprises at least one compound of the formula V, preferably a compound selected from the group of compounds of the formulas V-1 to V-3 -3, more preferably at least one compound of formula (V-1):

In the above formulas, the variables have the respective meanings given above, preferably

R ⁵ is each non-fluorinated alkyl or non-fluorinated alkoxy having 1 to 15 carbon atoms, or non-fluorinated alkenyl, non-fluorinated alkenyloxy or non-fluorinated alkoxyalkyl each having 2 to 15 carbon atoms , preferably alkyl, particularly preferably n-alkyl,

X ⁵ is F, CF ₃ , OCF ₃ or H, preferably F.

In a preferred embodiment of the present invention, the liquid-crystalline medium comprises at least one compound of formulas I-1 and/or I-2 and/or I-3.

In a preferred embodiment of the present invention, the liquid-crystalline medium comprises at least one compound of formulas II-1 and/or II-2 and/or II-3.

The liquid-crystalline medium according to the invention is preferably a compound of formulas I, II, III and optionally IV and/or optionally V, preferably a compound of formulas I, II and V and optionally IV, most preferably a compound of formula It comprises, more preferably consists mainly of, still more preferably consists essentially of and very particularly preferably consists entirely of compounds selected from the group of I and II.

As used herein "comprises" in conjunction with a composition, the subject (i.e., medium or component) includes the indicated component or compound, preferably in a total concentration of at least 10%, more and very preferably at least 20% concentration. means

In this context, "consisting mainly of" means that the subject comprises at least 55%, preferably at least 60%, more and very preferably at least 70% of the indicated component or compound.

In this context, "consisting essentially of" means that the subject comprises at least 80%, preferably at least 90%, more and very preferably at least 95% of the indicated component or compound.

In this context, "consisting entirely of" means that the subject comprises preferably a total of 98% or more, more preferably 99 or more, even more and very preferably 100.0% of the indicated component or compound. .

Other mesogenic compounds not specifically mentioned above may also optionally and advantageously be used in the medium according to the invention. Such compounds are known to those skilled in the art.

The liquid-crystalline medium according to the invention preferably has a clearing point of at least 90° C., more preferably at least 100° C., still more preferably at least 120° C., particularly preferably at least 125° C., very particularly preferably at least 130° C. .

The nematic phase of the medium according to the invention preferably extends to a low temperature of at least 20°C or less, more preferably 0°C or less, still more preferably -10°C or less and most preferably -20°C or less. At the same time, it preferably extends to a high temperature of at least 90° C., preferably at least 95° C., more preferably at least 100° C. and in particular at least 110° C.

According to the invention, the compound of formula (I) is preferably at least 25% and up to 50%, more preferably at least 30% and up to 45%, still more preferably at least 33% and up to 40%, most preferably 35% of the total mixture. % or more and not more than 38% of the total concentration is used in the liquid crystal medium.

In particular, the compounds of formula IZ are preferably used in the liquid-crystalline medium in a total concentration of at least 25% and up to 45%, even more preferably at least 30% and up to 40%, most preferably at least 32% and up to 35% of the total mixture. do.

In particular, the compound of formula (IQ) is preferably at least 0% and up to 20%, more preferably at least 0%, preferably at least 1% and up to 15%, even more preferably at least 0%, preferably 2 % or more and 10% or less, most preferably 0% or more, preferably 4% or more and 8% or less in total concentration of the liquid crystal medium.

In particular, the compound of formula IZ-1 is preferably at least 6% and up to 30%, more preferably at least 7% and up to 27%, still more preferably at least 10% and up to 25%, most preferably at most 11% of the total mixture. used in the liquid crystal medium at a total concentration of not less than 23%,

The compound of formula (IZ-2) is preferably at least 0% and up to 30%, more preferably at least 5% and up to 25%, still more preferably at least 10% and up to 20%, most preferably at least 13% and up to 17 of the total mixture. used in the liquid crystal medium in a total concentration of not more than %,

The compounds of formulas IZ-1 and IZ-2 together, preferably 20% or more and 45% or less, more preferably 25% or more and 40% or less, still more preferably 25% or more and 35% or less, most preferably 20% or more and 45% or less of the total mixture preferably used in the liquid crystal medium in a total concentration of at least 27% and not more than 32%,

The compound of formula IZ-3 is preferably at least 3% and at most 20%, more preferably at least 5% and up to 15%, still more preferably at least 6% and up to 12%, most preferably at least 8% and less than 10% of the total mixture. % or less of the total concentration used in the liquid crystal medium.

Particularly preferably, the medium contains at least one compound of formula IQ-2, preferably at least 1% and up to 15%, more preferably at least 3% and up to 12%, even more preferably at least 4% and up to 10% of the total mixture. or less, most preferably in a total concentration of 5% or more and 8% or less.

According to the invention, the medium contains at least 55% and up to 75% of the total mixture of the compound of formula II, more preferably at least 57% and up to 70%, even more preferably at least 60% and up to 67%, most preferably 62 % or more and not more than 65% of the total concentration.

According to the invention, the medium contains at least one compound of formula (II-1), preferably at least 1% and up to 15% of the total mixture, more preferably at least 1% and up to 10%, even more preferably at least one compound of formula (II-1a) preferably at a total concentration of 2% or more and 8% or less, and most preferably 3% or more and 6% or less.

According to the present invention, the medium contains the compound of formula (II-3), preferably the compound of formula (II-3d) in 50% or more and 70% or less of the total mixture, more preferably 55% or more and 65% or less, even more preferably 56% or more and 62% or less, most preferably 58% or more and 60% or less in total concentration.

According to the invention, the compound of formula (III) is preferably at least 0% and at most 20%, more preferably at least 0% and up to 15%, still more preferably at least 0% and up to 12%, very preferably 1% of the total mixture. It is used in the liquid crystal medium in a total concentration of not less than 9% or less.

According to the present invention, the compound of formula (IV) is preferably at least 0% and up to 20%, more preferably at least 0% and up to 15%, still more preferably at least 1% and up to 10%, very preferably at most 2% of the total mixture. % or more and a total concentration of not more than 8% is used in the liquid crystal medium.

According to the invention, the compound of formula (V) is preferably at least 0% and up to 25%, more preferably at least 0% and up to 20%, still more preferably at least 0% and up to 15%, very preferably 1 % or more and not more than 12% of the total concentration is used in the liquid crystal medium.

The liquid-crystalline medium preferably comprises a total of 70% or more and 100% or less, more preferably 80% or more and 100% or less, very preferably 90% or more and 100% or less, in particular 95% or more and 100% or less, formulas I, II and/or a compound of III and/or IV and/or V, preferably a compound of formulas I and II, more preferably consisting mainly of and very preferably entirely of them.

In a preferred embodiment of the present invention, the liquid crystal medium comprises:

one or more compounds PZG-2-N and/or PZG-3-N and/or PZG-4-N and/or PZG-5-N and/or

one or more compounds PZU-V2-N and/or PZU-3-N and/or PZU-4-N and/or PZU-5-N and/or

one or more compounds CPZG-2-N and/or CPZG-3-N and/or CPZG-4-N and/or CPZG-5-N and/or

one or more compounds PUQU-3-F and/or PGUQU-3-F and/or PGUQU-5-F and/or

one or more compounds PTP-1-O2 and/or PTP-2-O1 and/or

one or more compounds PPTUI-3-2 and/or PPTUI-3-4 and/or

one or more compounds CP-3-1 and/or CP-3-2 and/or CP-3-O1 and/or CP-3-O2 and/or

one or more compounds PP-1-2V and/or PP-1-2V1 and/or

one or more compounds PGU-3-F and/or PGU-4-F and/or PGU-5-F and/or

one or more compounds PPGU-3-F and/or PPGU-4-F and/or PGU-5-F

includes

Each abbreviation is generated according to Tables A-C below and is described in Table D below.

As used herein, the expression “having a positive permittivity” describes a compound or component with Δε > 3.0, and the expression “having a neutral permittivity” describes a compound or component with -1.5 ≤ Δε≤ 3.0 , the expression “having a negative permittivity” describes a compound or component in which Δε < -1.5. Δε is determined at a frequency of 1 kHz and 20°C. The dielectric anisotropy of each compound is determined from the results of a 10% solution of each individual compound in a nematic host mixture. If the solubility of each compound in the host mixture is less than 10%, the concentration is reduced to 5%. The capacitance of the test mixture was determined in both cells with homeotropic orientation and cells with homogeneous orientation. The thickness of the cells in both types of cells is about 20 μm. The applied voltage is a rectangular wave with a frequency of 1 kHz and typically an rms value between 0.5V and 1.0V, but it is always chosen to be below the threshold of capacitance of the respective test mixture.

The following definitions apply herein.

Δε ≡ (ε _│ - ε _⊥ )

ε _mean ≡ (ε _│ + 2ε _⊥ )/3

The host mixture used for the compound with positive permittivity is mixture ZLI-4792, the host mixture used for the compound with neutral permittivity and the compound with negative permittivity is mixture ZLI-3086, all of the above mixtures are from Merck Kage, Germany It was obtained from Merck KGaA. The absolute values of the dielectric constants of these compounds are determined from the change in the respective values of the host mixture upon addition of the compound of interest. The values are extrapolated to the 100% concentration of the compound of interest.

A compound having a nematic phase at a measurement temperature of 20° C. is measured as such. The rest are treated like compounds.

In all instances, unless expressly stated otherwise, the expression “threshold voltage” herein refers to an optical threshold and _{is presented in 10% relative contrast (V 10} ), and “medium-gray voltage” refers to 50% relative contrast (V 10 ). ₅₀ ), and the expression “saturation voltage” refers to optical saturation and is given as 90% relative contrast (V ₉₀ ). All characteristic voltages are determined under vertical observation. _{The capacitive threshold voltage (V 0} ), also referred to as the Freedericks-threshold (VF _r ), is used only when explicitly stated.

Unless expressly stated otherwise, the ranges of parameters presented herein are all inclusive of the limits.

Additional preferred ranges arise when the different upper and lower limits indicating the properties of the various ranges are combined with each other.

Unless expressly stated otherwise, the following conditions and definitions apply throughout this application. All concentrations are given in percent by weight and relate to each total mixture, all temperatures are given in degrees Celsius, all temperature differences are given in degrees Celsius. All physical properties are described in "Merck Liquid Crystals, Physical Properties of liquid Crystals", Status Nov. 1997, Merck KGaA, Germany] and presented for a temperature of 20 °C. The optical anisotropy (Δn) is determined at a wavelength of 589.3 nm. The dielectric anisotropy (Δε) is determined at a frequency of 1 kHz. Threshold voltage as well as all other electro-optic properties were determined using test cells manufactured by Merck Kagea, Germany. The test cell for determining Δε has a cell thickness of about 20 μm. The electrode was a circular ITO electrode with an area of 1.13 cm 2 and a guard ring. The orientation layer is homeotropic orientation (ε _⊥) When was the SE-1211 by Nissan Chemicals, Japan (Nissan Chemicals), a horizontal orientation (ε _∥) in the case of Japan Shin tetik rubber (Synthetic Rubber) polyimide AL- of It was 1054. The capacitance was determined with a frequency response analyzer Solartron 1260 using a sine wave with a voltage _{of 0.3V rms.}

The light used for the electro-optical measurement was white light. Herein, a set-up was made using a DMS instrument commercially available from Autronic-Melchers, Germany. The characteristic voltage was determined under vertical observation. Threshold voltage (V ₁₀ ), mid-gray voltage (V ₅₀ ) and saturation voltage (V ₉₀ ) were determined for 10%, 50% and 90% relative contrast, respectively.

As used herein, the term “compound” refers to both a compound and a plurality of compounds, unless stated otherwise.

The liquid-crystalline medium according to the invention preferably has in each case a nematic phase of at least -20°C to 80°C, preferably -30°C to 85°C, particularly very preferably -40°C to 100°C. The expression "having a nematic phase" herein means, on the one hand, that no smectic phase and no crystallization are observed at low temperatures of the corresponding temperature, and on the other hand clearing from the nematic phase upon heating. means it doesn't happen. The investigation at low temperature is checked by carrying out in a flow viscometer at the corresponding temperature and storing in a test cell with a layer thickness of 5 μm for at least 100 hours. At high temperature, the clearing point is determined in the capillary by a conventional method.

The clearing point (T(N,I)) of the liquid-crystalline medium is preferably at least 90°C, more preferably at least 100°C, still more preferably at least 110°C, most preferably at least 115°C, and at the same time preferably is 140°C or lower, more preferably 135°C or lower, still more preferably 130°C or lower, and most preferably 120°C or lower.

In a preferred embodiment of the invention, the liquid-crystalline medium has a positive dielectric anisotropy (Δε). This dielectric anisotropy at 1 kHz and 20°C is preferably 20 or more, more preferably 25 or more, still more preferably 30 or more, most preferably 35 or more, and at the same time preferably 55 or less, more preferably 50 or more. or less, still more preferably 45 or less, and most preferably 35 or less.

In addition, the liquid-crystalline medium according to the invention is characterized by a relatively high optical anisotropy, ie a birefringence value (Δn). This birefringence at 589.3 nm (Na ^D ) is preferably 0.220 or more, more preferably 0.240 or more, still more preferably 0.260 or more, most preferably 0.280 or more, and at the same time preferably 0.400 or less, more preferably 0.370 or less, even more preferably 0.340 or less, and most preferably 0.320 or less.

The liquid-crystalline medium according to the invention is also characterized by a _{suitable rotational viscosity (γ 1 ).} This rotational viscosity is preferably 700 mPa·s or less, more preferably 650 mPa·s or less, still more preferably 600 mPa·s or less, and most preferably 550 mPa·s or less. Preferably, the rotational viscosity of the medium is as low as possible. However, the practical lower limit possible is at least 400 mPa·s, or even at least 300 mPa·s.

In their corresponding geometry, preferred liquid crystal materials have excellent properties, especially for 3D lenses of the polymer module type.

The term "alkyl" preferably refers to straight and branched chain alkyl groups having 1 to 15 carbon atoms as well as cycloalkyl groups, in particular the straight chain groups methyl, ethyl, propyl, butyl, pentyl, hexyl and heptyl, as well as cyclopropyl and cyclohexyl. includes Groups having from 2 to 10 carbon atoms are generally preferred.

The term "alkenyl" includes straight and branched chain alkenyl groups having 2 to 15 carbon atoms, in particular straight chain groups. A particularly preferred alkenyl groups are C ₂ -C ₇ -1E- alkenyl, C ₄ -C ₇ -3E- alkenyl, C ₅ -C ₇ -4- alkenyl, C ₆ -C ₇ -5- alkenyl and C ₇ is 6-alkenyl, in particular C ₂ -C ₇ -1E- alkenyl, C ₄ -C ₇ -3E- alkenyl and C ₅ -C ₇ -4-alkenyl. Examples of other preferred alkenyl groups are vinyl, 1E-propenyl, 1E-butenyl, 1E-pentenyl, 1E-hexenyl, 1E-heptenyl, 3-butenyl, 3E-pentenyl, 3E-hexenyl, 3E-heptenyl, 4-pentenyl, 4Z-hexenyl, 4E-hexenyl, 4Z-heptenyl, 5-hexenyl, 6-heptenyl and the like. Groups having 5 or fewer carbon atoms are generally preferred.

The term "fluoroalkyl" refers to a straight-chain group, preferably having a terminal fluorine, ie fluoromethyl, 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl, 5-fluoropentyl, 6 -fluorohexyl and 7-fluoroheptyl. However, other positions of fluorine are not excluded.

The term "oxaalkyl" or "alkoxyalkyl" preferably _{includes straight-chain radicals of the formula C n} H _2n+1 -O-(CH ₂ ) _m , wherein n and m are each, independently of one another, An integer of 1 to 10 is represented. Preferably, where n is 1 and m is 1 to 6.

Compounds containing vinyl end groups and compounds containing methyl end groups have low rotational viscosities.

The liquid crystal medium according to the invention may contain additional additives and chiral dopants in conventional concentrations. The total concentration of these additional constituents ranges from 0% to 10%, preferably from 0.1% to 6%, based on the total mixture. The concentrations of the individual compounds used each preferably range from 0.1% to 3%. When referring to values and concentration ranges of liquid crystal components and liquid crystal compounds in a liquid crystal medium herein, the concentrations of these components and similar additives are not taken into account.

The liquid-crystalline medium according to the invention consists of a plurality of compounds, preferably 3 to 30, more preferably 4 to 20, very preferably 4 to 15 compounds. These compounds are mixed in a conventional manner. In general, the compound used in a smaller amount is dissolved in the compound used in a larger excess. It is particularly easy to observe that the dissolution process is complete when the temperature is above the clearing point of the compound used in higher concentrations. However, other customary methods, such as the use of so-called pre-mixes, which can be homogeneous or eutectic mixtures of compounds, or so-called "multi-vessel" systems, in which the components themselves are ready-to-use mixtures (multi-bottle system) can also be used to prepare the medium.

Any temperature, for example the melting point T(C,N) or T(C,S), the transition from the smectic phase (S) to the nematic phase (N) T(S, N), and the clearing point T of the liquid crystal (N,I) is given in degrees Celsius. All temperature differences are presented in degrees Celsius.

In this application and in particular in the examples below, the structures of the mesogenic compounds are given by abbreviations, also referred to as acronyms. In these acronyms, the formulas are abbreviated as follows using Tables A-C below. All C _n H _2n+1 , C _m H _2m+1 and C ₁ H _2l+1 or C _n H _2n-1 , C _m H _2m-1 and C ₁ H _2l-1 groups each have n, m and 1 represents straight-chain alkyl or alkenyl, preferably 1E-alkenyl, wherein n, m and 1 are each, independently of each other, 1 to 9, preferably 1 to 7, or 2 to 9, preferably represents an integer of 2 to 7. C _o H _2o+1 represents a straight chain alkyl having 1 to 7 carbon atoms, preferably 1 to 4 carbon atoms, or a branched chain alkyl having 1 to 7 carbon atoms, preferably 1 to 4 carbon atoms.

Table A below lists the codes used for the ring elements of the core structure of the compounds, and Table B below shows the linking groups. Table C below shows the meaning of the codes for the left and right terminal groups. Table D below shows exemplary structures of compounds having each abbreviation.

Table A: Ring Elements

Table B: Connectors

Table C: End Groups

In the above formula, n and m each represent an integer, and the three dots "..." are spacing marks for other abbreviations from this table.

The table below shows exemplary structures along with their respective abbreviations. This is presented to illustrate the meaning of the rules for abbreviations. It also suggests compounds which are preferably used.

Table D: Exemplary Structures

Exemplary structures of compounds used with particular preference are given.

Examples of preferred compounds of formula IZ are as follows.

Examples of preferred compounds of formula (IQ) are:

Examples of preferred compounds of formula (II) are as follows.

Examples of preferred compounds of formula (III) are as follows.

Examples of preferred compounds of formula (IV) are as follows.

Examples of preferred compounds of formula (V) are as follows.

Examples of further preferred compounds are as follows.

In the above equations, n∋{1;2;3;4;5;6;7}, m∋{1;2;3;4;5;6;7}, and k∋{1;2;3; 4}, preferably 2 or 4, most preferably 2, and l∋{1;2;3}, preferably 1.

Table E below shows exemplary compounds that can be used as stabilizers in mesogenic media according to the present invention. The total concentration of these and similar compounds in the medium is preferably not more than 5%.

table E

In a preferred embodiment of the present invention, said mesogenic medium comprises at least one compound selected from the group of compounds of Table E above.

The mesogenic medium according to the invention preferably comprises at least two, preferably at least four, compounds selected from the group consisting of compounds from the above tables.

The liquid-crystalline medium according to the invention comprises at least 7, preferably at least 8, compounds selected from the group of compounds of Table D above, preferably at least 3, preferably at least 4, compounds of different formulas do.

[Example]

The following examples illustrate the present invention, but do not limit the present invention in any way. However, it will be apparent to those skilled in the art which properties can be achieved and to what extent can be modified from these physical properties. Accordingly, the various combinations of properties which can be achieved particularly advantageously are well defined by the person skilled in the art.

Example One

A liquid crystal mixture M-1 having the composition and properties shown in the table below was prepared.

This mixture is particularly well suited for 3D lens applications of the plastic mold type.

Example 2

A liquid crystal mixture M-2 having the composition and properties shown in the table below was prepared.

Note) t.b.d.: To be decided later.

This mixture is particularly well suited for 3D lens applications of the plastic mold type.

Claims (11)

Liquid-crystalline medium, characterized in that it comprises at least one compound of the formula IZ, at least one compound of the formula IQ and at least one compound of the formula II:

In the above formulas IZ and IQ,
R ¹ is straight-chain or branched alkyl unsubstituted or mono- or polysubstituted with F, Cl or CN, wherein one or more CH ₂ groups, at each occurrence independently of one another, O and/or S atoms are directly linked to each other -O-, -S-, -NR ⁰¹ -, -SiR ⁰¹ R ⁰² -, -CO-, -COO-, -OCO-, -OCO-O-, -S-CO-, -CO optionally replaced by -S-, -CY ⁰¹ =CY ^{02 - or -C≡C-,}
X ¹ is F, Cl, CF ₃ , OCF ₃ , CN or NCS,
L ² , L ¹⁴ and L ¹⁵ are each independently H or F,
m and n are each independently 0 or 1,
Y ⁰¹ and Y ⁰² are independently of each other F, Cl or CN, alternatively one of them may be H,
R ⁰¹ and R ⁰² are each independently H or an alkyl having 1 to 12 carbon atoms,
In the above formula (II),
R ²¹ and R ²² are, independently of one another, straight or branched chain alkyl unsubstituted or mono- or polysubstituted with F, Cl or CN, wherein at least one CH ₂ group is, at each occurrence, independently of each other, O and/ ^{or -O-, -S-, -NR 01} -, -SiR ⁰¹ R ⁰² -, -CO-, -COO-, -OCO-, -OCO-O-, - in such a way that the S atoms are not directly linked to each other. optionally replaced by S-CO-, -CO-S-, -CY ⁰¹ =CY ^{02 - or -C≡C-,}
n is 0 or 1,

Is

or

ego,
L ²¹ to L ²³ are each independently H or F,
Y ⁰¹ , Y ⁰² , R ⁰¹ and R ⁰² have the respective meanings given in formulas IZ and IQ above. The method of claim 1,
A liquid-crystalline medium comprising at least one compound selected from the group of formulas III and IV:

In the above formulas,
R ³¹ is n-alkyl or alkenyl,
R ³² is n-alkyl, alkenyl, n-alkoxy or alkenyloxy;
R ⁴¹ and R ⁴² are, independently of one another, straight or branched chain alkyl unsubstituted or mono- or polysubstituted with F, Cl or CN, wherein at least one CH ₂ group is, at each occurrence, independently of each other, O and/ ^{or -O-, -S-, -NR 01} -, -SiR ⁰¹ R ⁰² -, -CO-, -COO-, -OCO-, -OCO-O-, - in such a way that the S atoms are not directly linked to each other. optionally replaced by S-CO-, -CO-S-, -CY ⁰¹ =CY ^{02 - or -C≡C-,}

inside

is independent of each other

or

ego,
p is 0, 1 or 2,
Y ⁰¹ , Y ⁰² , R ⁰¹ and R ⁰² have the respective meanings given for formulas IZ and IQ in claim 1 . The method of claim 1,
Liquid-crystalline medium, characterized in that it comprises at least one compound of the formula (V):

In the above formula,

Is

or

ego,
R ⁵ is straight-chain or branched alkyl unsubstituted or mono- or polysubstituted with F, Cl or CN, wherein one or more CH ₂ groups, at each occurrence independently of one another, O and/or S atoms are directly linked to each other -O-, -S-, -NR ⁰¹ -, -SiR ⁰¹ R ⁰² -, -CO-, -COO-, -OCO-, -OCO-O-, -S-CO-, -CO optionally replaced by -S-, -CY ⁰¹ =CY ^{02 - or -C≡C-,}
X ⁵ is halogen, CF ₃ or OCF ₃ ,
i is 0 or 1,
Y ⁰¹ , Y ⁰² , R ⁰¹ and R ⁰² have the respective meanings given for formulas IZ and IQ in claim 1 . The method of claim 1,
A liquid crystal medium comprising at least one compound in formula II wherein R ²¹ and R ²² are independently of each other n-alkyl, L ²¹ and L ²³ are F, L ^{22 is H and n is 1.} The method of claim 1,
A liquid crystal medium comprising at least one compound selected from the group of compounds of the following formulas IZ-1 to IZ-3:

In the above formulas, the variables all have their respective meanings given for formula IZ in claim 1. The method of claim 1,
A liquid crystal medium, characterized in that it has a birefringence (Δn) in the range of 0.220 or more and 0.400 or less at 20°C and 589.3 nm. one or more compounds of formulas IZ and IQ and one or more compounds of formula II are optionally mixed with each other and optionally with one or more further compounds and/or one or more additives, at an elevated temperature, optionally above the clearing point of the resulting mixture A method for preparing a liquid crystal medium according to any one of claims 1 to 6, characterized in that it is heated with a furnace. delete A 3D lens, characterized in that it contains a liquid crystal medium according to any one of claims 1 to 6. A liquid crystal display comprising at least one 3D lens according to claim 9 . A method of operating a 3D liquid crystal display by addressing one or more 3D lenses according to claim 9 .