Patent Application
20230383186
The present invention relates to a liquid-crystal (LC) medium which is based on a mixture of polar compounds and is substantially dielectrically neutral, to its use for optical, electro-optical and electronic purposes, in particular as optical retarder or optical compensator in LC displays, to an optical retarder or optical compensator comprising the LC medium, to an optical, electrooptical or electronic device comprising the optical retarder or optical compensator, and to a process of manufacturing the optical retarder or optical compensator.
The performance of a liquid crystal display (LCD) is based mainly on its response time, contrast, color, transmittance and reliability. To obtain best picture quality, also from different viewing angles, optical retardation or compensation films are typically used to compensate intrinsic display challenges and improve the optical properties of the LCD, such as the contrast ratio and the grey scale representation at large viewing angles.
Depending on the LCD mode, various types of compensators can be used, such as A plate, C plate or O plate compensators or any combination thereof.
In prior art polymer films made from polymerizable mesogenic compounds, also known as reactive mesogens or RMs, are suggested for use as optical retarders or compensators. Solutions of RMs or RM mixtures are commercially available which can be spin-coated and photopolymerised to provide a birefringent polymer film. In addition, photoalignment techniques may be applied to create films with patterned structure. By varying the coating conditions, it is possible to produce films of different thickness and so to produce for example half-wave or quarter wave retardation films.
Such birefringent polymer films can have advantages in processability, but still their usage can be difficult when applied in an LC display cell. For example, the manufacture of the RM layers requires UV treatment. Moreover, because the orientation and thickness of the RM layer is fixed by photopolymerization, different RM layers are needed for each type of retarder, e.g. A or C plate, and for each desired retardation value.
It is therefore an object of the present invention to provide improved optical retarders or optical compensators for use in LC displays, which do not exhibit the disadvantages described above or only do so to a small extent and have improved properties, and especially enable a wide viewing angle without significant loss of brightness.
A further object of the invention is to improved LC displays with good transmission and brightness, a high reliability, a broad working-temperature range, short response times, a low threshold voltage, a multiplicity of grey levels, a high contrast and a broad viewing angle.
It was found that one or more of these objects could be achieved by providing an LC medium as disclosed and claimed hereinafter.
Thus, it was surprisingly found that an LC medium according to the present invention, which comprises both dielectrically positive and dielectrically negative compounds, which are mixed in such proportions that the overall dielectrical anisotropy Δε of the LC medium is zero or close to zero, can be used as optical compensator in an LC display, especially to improve the viewing angle dependency of the display without affecting the other properties. Due to Δε being substantially zero, the LC mixture which is used as compensator does not switch and change its alignment under the applied electric field which is naturally present during operation of the display.
The alignment of the LC molecules in a layer of a LC mixture according to the present invention, e.g. planar or homeotropic alignment, can be controlled by an alignment layer that is in contact with the LC mixture. Depending on the chosen alignment, an +A plate or +C plate retarder can thus be realized using the same LC medium. By changing the birefringence Δn of the LC mixture, e.g. via special mixture design, it is possible to adapt the retardation of the LC mixture to common cell gaps of the displays to realize the desired application, e.g. as quarter wave plate. In addition to this, the permittivity of the layer of the LC mixture can be adjusted by special mixture design. Also, the use of polymerizable compounds or RMs and corresponding polymerization techniques is not required.
The present invention thus relates to an LC medium which has a dielectric anisotropy Δε from −0.5 to +0.5, preferably from −0.3 to +0.3, more preferably from −0.1 to +0.1, very preferably from −0.05 to 0.05, most preferably of 0, determined at 20° C. and 1 kHz, and wherein the LC medium shows uniform alignment, preferably either planar or homeotropic alignment, and preferably does not contain polymerized or polymerizable components.
The invention further relates to an LC medium which comprises a first component A which has a dielectric anisotropy Δε of ≥+0.5, and a second component B which has a dielectric anisotropy Δε of ≤−0.5, wherein the proportions of the components A and B are selected such that the resulting dielectric anisotropy Δε of the LC medium is from −0.5 to +0.5, preferably from −0.3 to +0.3, more preferably from −0.1 to +0.1, very preferably from −0.05 to 0.05, most preferably of 0, determined at 20° C. and 1 kHz, wherein the LC medium shows uniform alignment, preferably either planar or homeotropic alignment, and which does preferably not contain polymerized or polymerizable components.
Preferably the LC medium comprising components A and B further comprises a third component C which has a dielectric anisotropy Δε from −0.5 to +0.5, wherein the proportions of the components A, B and C are selected such that the resulting dielectric anisotropy Δε of the LC medium is from −0.5 to +0.5, preferably from −0.3 to +0.3, more preferably from −0.1 to +0.1, very preferably from −0.05 to 0.05, most preferably of 0, determined at 20° C. and 1 kHz.
The invention further relates to a layer of an LC medium as described above and below which is situated between two substrates, which are preferably plane parallel and preferably transparent, and wherein one or both of the substrates is(are) preferably equipped with an alignment layer that provides the desired alignment in the LC medium.
The invention further relates to the use of an LC medium as described above and below as or in an optical retarder or optical compensator.
The LC medium is preferably not subjected to an electric field during its use, and preferably has uniform alignment, very preferably planar or homeotropic alignment, which preferably does not change during its use.
The invention further relates to an optical retarder or optical compensator comprising a layer of an LC medium as described above and below which has a dielectric anisotropy from −0.5 to +0.5, more preferably from −0.3 to +0.3, very preferably from −0.1 to +0.1, very particularly preferably from −0.05 to 0.05, most preferably of 0, determined at 20° C. and 1 kHz, which has uniform alignment, preferably planar or homeotropic alignment, and which preferably does not contain polymerized or polymerizable components.
In particular the invention relates to an optical retarder or compensator comprising two transparent, plane parallel substrates, between which is provided a layer of an LC medium as described above and below, and wherein each of the substrates is preferably equipped with alignment layer at the side facing the layer of the LC medium. Preferably the alignment of the LC molecules is uniform throughout the layer, and is either homeotropic or planar.
The invention further relates to the use of an LC medium or an optical retarder or optical compensator as described above and below, preferably as viewing angle compensator, in optical, electrooptical or electronic components or devices, preferably in electrooptical displays like LC displays or organic light emitting diodes (OLEDs).
The invention further relates to an optical, electrooptical or electronic component or device comprising an LC medium or comprising an optical retarder or optical compensator as described above and below.
Said components include, without limitation, optical retardation films, polarizers, compensators, beam splitters, reflective films, antistatic protection sheets, electromagnetic interference protection sheets, polarization controlled lenses for example for autostereoscopic 3D displays, IR reflection films for example for window applications, spatial light modulators, and lenses for light guides, focusing or other optical effects, eg. 3D, holography, telecomms.
Said devices include, without limitation, electrooptical displays, preferably LC displays, autostereoscopic 3D displays, OLEDs, optical data storage devices, goggles for AR/VR applications and smart windows, very preferably LC displays or OLEDs.
The invention furthermore relates to the use of an LC medium, an optical retarder or optical compensator or of an LC display as described above and below for an energy-saving LC display.
An alkenyl group in the compounds of formula IA to IE and IIa to IID or other components of the LC medium as disclosed below is not considered to be within the meaning of the term “polymerizable group” as used herein. The conditions for the polymerization of the polymerizable compounds of the LC medium are preferably selected such that alkenyl substituents do not participate in the polymerization reaction. Preferably the LC media disclosed and claimed in the present application do not contain an additive that initiates or enhances the participation of the alkenyl group in a polymerization reaction.
Unless stated otherwise, the compounds as disclosed above and below, except for the chiral dopants, are preferably selected from achiral compounds.
As used herein, the term “dielectrically positive compounds” denotes compounds having a Δε>1.5, the term “dielectrically neutral compounds” denotes compounds having −1.5≤Δε≤1.5 and the term “dielectrically negative compounds” denotes compounds having Δε<−1.5.
Unless stated otherwise, the dielectric anisotropy of the compounds as disclosed herein is determined by dissolving 10% of the compounds in a liquid-crystalline host and determining the capacitance of the resultant mixture in at least one test cell in each case having a layer thickness of 20 μm with homeotropic and with homogeneous surface alignment at 1 kHz. The measurement voltage is typically 0.3 V to 1.0 V, but is always lower than the capacitive threshold of the respective liquid-crystal mixture investigated.
Unless stated otherwise, the values of the dielectric anisotropy Δε as mentioned herein are those determined at 20° C. and 1 kHz.
As used herein, the term “director” means the preferred alignment direction of the long molecular axes (in case of calamitic compounds) or short molecular axis (in case of discotic compounds) of the LC molecules in an LC material.
In a layer or film comprising uniaxially positive birefringent LC material the optical axis is given by the director.
As used herein, the terms “homeotropic alignment” and “homeotropic orientation” refer to a layer or film wherein the optical axis is substantially perpendicular to the film plane.
As used herein, the terms “planar alignment” and “planar orientation” refer to a layer or film wherein the optical axis is substantially parallel to the film plane.
As used herein, the terms “uniform alignment” and “uniform orientation” refer to an LC medium, for example in a layer or film, wherein the alignment direction of the LC molecules is substantially constant, e.g. planar or homeotropic, throughout the LC medium. However, slight deviations from the uniform alignment may occur for example for LC molecules that are close to the interfaces with the substrates.
As used herein, the term “A plate” refers to an optical retarder utilizing a layer of uniaxially birefringent material with its extraordinary axis oriented parallel to the plane of the layer, and its ordinary axis (also called ‘a-axis’) oriented perpendicular to the plane of the layer, i.e. parallel to the direction of normally incident light.
As used herein, the term “C plate” refers to an optical retarder utilizing a layer of uniaxially birefringent material with its extraordinary axis (also called ‘c-axis’) perpendicular to the plane of the layer, i.e. parallel to the direction of normally incident light.
As used herein, the term “O plate”’ refers to an optical retarder utilizing a layer of a uniaxially birefringent material with its extraordinary axis oriented at an oblique angle with respect to the plane of the layer.
In A plates, C plates and O plates comprising optically uniaxial birefringent LC material with uniform alignment, the optical axis of the film is given by the direction of the extraordinary axis.
An A plate, C plate or O plate comprising optically uniaxial birefringent material with positive birefringence is also referred to as “+A/C/O plate” or “‘positive A/C/O plate”. An A plate or C plate comprising a film of optically uniaxial birefringent material with negative birefringence is also referred to as “−A/C/O plate” or “negative A/C/O plate”.
Unless stated otherwise, the term “polarisation direction” or “optical axis” of a linear polariser means the polariser extinction axis. In case of stretched plastic polariser films comprising e.g. dichroic iodine based dyes the extinction axis usually corresponds to the stretch direction.
As used herein, the terms “quarter wave retarder” and “quarter wave plate”, also abbreviated as “QWF”, refer to a layer or film having an optical retardation of λ/4, and the terms “half wave retarder” and “half wave plate”, also abbreviated as “HWF”, refer to a layer or film having an optical retardation of λ/2, wherein λ is the wavelength of incident light. The terms “achromatic quarter wave retarder” and “achromatic quarter wave plate”, also abbreviated as “AQWF”, refer to a QWF with a retardation that has low or no dependence on the wavelength of the incident light.
The retardation R of a retarder, e.g. a QWF, HWF or AQWF, comprising an LC layer is defined as
R=d·Δn (1)
wherein d is the thickness and Δn is the birefringence of the layer.
The birefringence Δn is defined as follows
Δn=ne−no (2)
wherein ne is the extraordinary refractive index and no is the ordinary refractive index, and the average refractive index nav. is given by the following equation:
n
av.=((2no2+ne2)/3)1/2 (3)
The average refractive index nav. and the ordinary refractive index no can be measured using an Abbe refractometer. Δn can then be calculated from the above equations.
In case of doubt the definitions as given in C. Tschierske, G. Pelzl and S. Diele, Angew. Chem. 2004, 116, 6340-6368 shall apply.
Above and below,
denotes a trans-1,4-cyclohexylene ring, and
denotes a 1,4-phenylene ring.
In a group
the single bond shown between the two ring atoms can be attached to any free position of the benzene ring.
If in the formulae shown above and below a terminal group like R, R0, R1, R2, R11,12,13, R21, 22, R31, 32, R41,42, R51,52, R61,62, R71, 72, R81,82,83, RQ, R, RM, RS, RS1,S2,S3,S4 or L denotes an alkyl radical and/or an alkoxy radical, this may be straight-chain or branched. It is preferably straight-chain, has 2, 3, 4, 5, 6 or 7 C atoms and accordingly preferably denotes ethyl, propyl, butyl, pentyl, hexyl, heptyl, ethoxy, propoxy, butoxy, pentoxy, hexyloxy or heptyloxy, furthermore methyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, methoxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tridecyloxy or tetradecyloxy.
If one of the aforementioned terminal groups denotes an alkyl radical wherein one or more CH2 groups are replaced by S, this may be straight-chain or branched. It is preferably straight-chain, has 1, 2, 3, 4, 5, 6 or 7 C atoms and accordingly preferably denotes thiomethyl, thioethyl, thiopropyl, thiobutyl, thiopentyl, thiohexyl or thioheptyl.
Oxaalkyl preferably denotes straight-chain 2-oxapropyl (=methoxymethyl), 2-(=ethoxymethyl) or 3-oxabutyl (=2-methoxyethyl), 2-, 3- or 4-oxapentyl, 2-, 3-, 4- or 5-oxahexyl, 2-, 3-, 4-, 5- or 6-oxaheptyl, 2-, 3-, 4-, 5-, 6- or 7-oxaoctyl, 2-, 3-, 4-, 5-, 6-, 7- or 8-oxanonyl, 2-, 3-, 4-, 5-, 6-, 7-, 8- or 9-oxadecyl.
If one of the aforementioned terminal groups denotes an alkoxy or oxaalkyl group it may also contain one or more additional oxygen atoms, provided that oxygen atoms are not linked directly to one another.
If one of the aforementioned terminal groups denotes an alkyl radical in which one CH2 group has been replaced by —CH═CH—, this may be straight-chain or branched. It is preferably straight-chain and has 2 to 10 C atoms. Accordingly, it denotes, in particular, vinyl, prop-1- or -2-enyl, but-1-, -2- or -3-enyl, pent-1-, -2-, -3- or -4-enyl, hex-1-, -2-, -3-, -4- or -5-enyl, hept-1-, -2-, -3-, -4-, -5- or -6-enyl, oct-1-, -2-, -3-, -4-, -5-, -6- or -7-enyl, non-1-, -2-, -3-, -4-, -5-, -6-, -7- or -8-enyl, dec-1-, -2-, -3-, -4-, -5-, -6-, -7-, -8- or -9-enyl.
If one of the aforementioned terminal groups denotes an alkyl or alkenyl radical which is at least monosubstituted by halogen, this radical is preferably straight-chain, and halogen is preferably F or Cl. In the case of polysubstitution, halogen is preferably F. The resultant radicals also include perfluorinated radicals. In the case of monosubstitution, the fluorine or chlorine substituent may be in any desired position, but is preferably in the ω-position.
In another preferred embodiment, one or more of the aforementioned terminal groups, like R1A, 2A, R1, R2, R11, 12, 13, R31, 32, R41,42, R51,52, R61,62, R71,72, R81,82,83, RQ, R0, R, RM, RS, RS1,S2,S3,S4 or L are selected from the group consisting of
—S1—F, —O—S1—F, —O—S1—O—S2, wherein S1 is C1-12-alkylene or C2-12-alkenylene and S2 is H, C1-12-alkyl or C2-12-alkenyl, and very preferably are selected from the group consisting of
—O(CH2)3OCH3, —O(CH2)4OCH3, —O(CH2)2F, —O(CH2)3F, —O(CH2)4F.
Halogen is preferably F or Cl, very preferably F.
The group —CR0═CR00— is preferably —CH═CH—.
—CO—, —C(═O)— and —C(O)— denote a carbonyl group, i.e.
Preferred substituents L, are, for example, F, Cl, Br, I, —CN, —NO2, —NCO, —NCS, —OCN, —SCN, —C(═O)N(Rx)2, —C(═O)Y1, —C(═O)Rx, —N(Rx)2, straight-chain or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy each having 1 to 25 C atoms, in which one or more H atoms may optionally be replaced by F or C, optionally substituted silyl having 1 to 20 Si atoms, or optionally substituted aryl having 6 to 25, preferably 6 to 15, C atoms,
wherein Rx denotes H, F, Cl, CN, or straight chain, branched or cyclic alkyl having 1 to 25 C atoms, wherein one or more non-adjacent CH2-groups are optionally replaced by —O—, —S—, —CO—, —CO—O—, —O—CO—, —O—CO—O— in such a manner that O- and/or S-atoms are not directly connected with each other, and wherein one or more H atoms are each optionally replaced by F, Cl, P- or P-Sp-, and
Y1 denotes halogen.
Particularly preferred substituents L are, for example, F, Cl, CN, NO2, CH3, C2H5, OCH3, OC2H5, COCH3, COC2H5, COOCH3, COOC2H5, CF3, OCF3, OCHF2, OC2F5, furthermore phenyl.
is preferably
in which L has one of the meanings indicated above.
In a preferred embodiment of the present invention, the LC medium comprises a first component A which is dielectrically positive and preferably has a dielectric anisotropy Δε of ≥+0.5, and a second component B which is dielectrically negative and preferably has a dielectric anisotropy Δε of ≤−0.5, and optionally a third component C which is dielectrically neutral and preferably has a dielectric anisotropy Δε from −0.5 to +0.5. The proportions of the components A, B and C are chosen such that the resulting dielectric anisotropy Δε of the LC medium is from −0.5 to +0.5, preferably from −0.3 to +0.3, more preferably from −0.1 to +0.1, very preferably from −0.05 to +0.05, most preferably 0.
Component A preferably comprises one or more compounds selected from the group consisting of formulae IA, IB, IC, ID and IE
in which the individual radicals, on each occurrence identically or differently, and each, independently of one another, have the following meaning:
Component B preferably comprises one or more compounds selected from the group consisting of formulae IIA, IIB, IIC and ID
in which the individual radicals, on each occurrence identically or differently, and each, independently of one another, have the following meaning:
Component C preferably comprises one or more compounds selected from formulae IV, IVa, IVb and V
in which the individual radicals, on each occurrence identically or differently, and each, independently of one another, have the following meaning
denotes
identically or differently, denote
Preferred compounds of the formulae IA, IB, IC, ID and IE are those wherein R0 denotes an alkyl or alkoxy radical having up to 15 C atoms, and very preferably denotes (O)CvH2v+1 wherein (O) is an oxygen atom or a single bond and v is 1, 2, 3, 4, 5 or 6.
Further preferred compounds of the formulae IA, IB, IC, ID and IE are those wherein R0 denotes or contains a cycloalkyl or cycloalkoxy radical, preferably selected from the group consisting of
wherein S1 is C1-12-alkylene or C2-12-alkenylene and S2 is H, C1-12-alkyl or C2-12-alkenyl, and very preferably are selected from the group consisting of
Further preferred compounds of the formulae IA, IB, IC, ID and IE are indicated below.
Preferred compounds of formula IA are selected from the following subformulae:
in which R0 and X0 have the meanings indicated above, and R0 preferably denotes alkyl having 1 to 6 C atoms and X0 preferably denotes F or OCF3, furthermore OCF═CF2 or Cl.
Very preferred compounds of formula IA are selected from the following subformula:
in which R0 has the meanings indicated above and is preferably methyl, ethyl, propyl or pentyl.
Further very preferred compounds of formula IA are selected from the following subformula:
in which R0 has the meanings indicated above and is preferably methyl, ethyl, propyl or pentyl.
Preferred compounds of formula IB are selected from the following subformulae:
in which R0 and X0 have the meanings indicated above, and R0 preferably denotes alkyl having 1 to 6 C atoms and X0 preferably denotes F or OCF3, furthermore OCHF2, CF3, OCF═CF2 or OCH═CF2.
Preferred compounds of formula IC are selected from the following subformulae:
in which R0 and X0 have the meanings indicated above, and R0 preferably denotes alkyl having 1 to 6 C atoms and X0 preferably denotes F, furthermore OCF3, CF3, CF═CF2, OCHF2 or OCH═CF2.
Very preferred compounds of formula ICb are selected from the following subformula:
in which R0 has the meanings indicated above and is preferably ethyl, propyl or pentyl.
Preferred compounds of formula ID are selected from the following subformulae:
in which R0 and X0 have the meanings indicated above, and R0 preferably denotes alkyl having 1 to 6 C atoms and X0 preferably denotes F, furthermore OCF3, OCHF2 or OCH═CF2.
Very preferred compounds of formula ID are selected from the following subformula:
in which R0 has the meanings indicated above and is preferably ethyl, propyl or pentyl.
The proportions of the components A, B and C and of the individual compounds contained therein are selected such that the dielectric anisotropy Δε of the LC medium is from −0.5 to +0.5, preferably from −0.3 to +0.3, very preferably from −0.1 to +0.1, most preferably 0.
Preferably the total proportion of the component A in the LC medium is from 8 to 50%, very preferably from 10 to 35%, most preferably from 10 to 30% by weight.
Preferably the total proportion of the component B in the LC medium is from 15 to 70%, very preferably from 20 to 65%, most preferably from 25 to 50% by weight.
Preferably the total proportion of the component B in the LC medium is higher than the total proportion of the component A in the LC medium.
Preferably the total proportion of the component C in the LC medium is from 5 to 70%, very preferably from 10 to 65%, most preferably from 15 to 60% by weight.
Preferred compounds of the formulae IIA, IIB, IIC and IID are those wherein R22 denotes an alkyl or alkoxy radical having up to 15 C atoms, and very preferablydenotes (O)CvH2v+1 wherein (O) is an oxygen atom or a single bond and v is 1, 2, 3, 4, 5 or 6.
Further preferred compounds of the formulae IIA, IIB, IIC and IID are those wherein R21 or R22 denotes or contains a cycloalkyl or cycloalkoxy radical, preferably selected from the group consisting of
wherein S1 is C1-12-alkylene or C2-12-alkenylene and S2 is H, C1-12-alkyl or C2-12-alkenyl, and very preferably are selected from the group consisting of
Further preferred compounds of the formulae IIA, IIB, IIC and IID are indicated below.
Preferred compounds of formula IIA are selected from the group consisting of the following subformulae:
in which the index a denotes 1 or 2, alkyl and alkyl* each, independently of one another, denote a straight-chain alkyl radical having 1-6 C atoms, alkenyl denotes a straight-chain alkenyl radical having 2-6 C atoms, and (O) denotes an oxygen atom or a single bond, and alkenyl preferably denotes CH2═CH—, CH2═CHCH2CH2—, CH3—CH═CH—, CH3—CH2—CH═CH—, CH3—(CH2)2—CH═CH—, CH3—(CH2)3—CH═CH— or CH3—CH═CH—(CH2)2—.
Very preferably component B of the LC medium comprises one or more compounds selected from the group consisting of formulae IIA-2, IIA-8, IIA-10, IIA-16, II-18, IIA-40, IIA-41, IIA-42 and IIA-43.
Very preferably, component B of the LC medium comprises one or more compounds of the formula IIA-2 selected from the following subformulae:
Alternatively, preferably in addition to the compounds of the formulae IIA-2-1 to IIA-2-5, component B of the LC medium comprises one or more compounds of the following subformulae:
Further preferably, component B of the LC medium comprises one or more compounds of the formula IIA-10 selected from the following subformulae:
Alternatively, preferably in addition to the compounds of the formulae IIA-10-1 to IIA-10-5, component B of the LC medium comprises one or more compounds selected from the following subformulae:
Preferred compounds of formula IIB are selected from the group consisting of the following subformulae:
in which alkyl and alkyl* each, independently of one another, denote a straight-chain alkyl radical having 1-6 C atoms, alkenyl denotes a straight-chain alkenyl radical having 2-6 C atoms, and (O) denotes an oxygen atom or a single bond, and alkenyl preferably denotes CH2═CH—, CH2═CHCH2CH2—, CH3—CH═CH—, CH3—CH2—CH═CH—, CH3—(CH2)2—CH═CH—, CH3—(CH2)3—CH═CH— or CH3—CH═CH—(CH2)2—.
Very preferably component B of the LC medium comprises one or more compounds selected from the group consisting of formulae IIB-2, IIB-10 and IIB-16.
Preferably, component B of the LC medium comprises one or more compounds of the formula IIB-10 selected from the following subformulae:
Alternatively, preferably in addition to the compounds of the formulae IIB-10-1 to 11B-10-5, component B of the LC medium comprises one or more compounds selected from the following subformulae:
Preferred compounds of the formula IIC selected from subformula IC-1:
in which alkyl and alkyl* each, independently of one another, denote a straight-chain alkyl radical having 1-6 C atoms, preferably in amounts of 0.5% to 5% by weight, in particular 1% to 3% by weight.
Preferred compounds of the formula IID selected from the group consisting of the following subformulae:
in which alkyl and alkyl* each, independently of one another, denote a straight-chain alkyl radical having 1-6 C atoms, alkenyl denotes a straight-chain alkenyl radical having 2-6 C atoms, (O) denotes an oxygen atom or a single bond, Y denotes H or CHs and alkenyl preferably denotes CH2═CH—, CH2═CHCH2CH2—, CH3—CH═CH—, CH3—CH2—CH═CH—, CH3—(CH2)2—CH═CH—, CH3—(CH2)3—CH═CH— or CH3—CH═CH—(CH2)2—.
Very preferably component B of the LC medium comprises one or more compounds of the formula IID-1 and/or IID-4.
Very preferred compounds of the formula IID are selected from the following subformulae:
wherein v is 1, 2, 3, 4, 5 or 6.
In a preferred embodiment component B of the LC medium comprises one or more compounds of subformula IID-10a:
in which R21, Y and q have the meanings given in formula IID, and R23 is
in which r is 0, 1, 2, 3, 4, 5 or 6 and s is 1, 2 or 3.
Preferred compounds of formula IID-10a are selected from the following subformulae:
Very preferably component B of the LC medium comprises one or more compounds selected from the formulae IIA-2, IIA-8, IIA-10, IIA-16, II-18, IIA-40, IIA-41, IIA-42, IIA-43, IIB-2, IIB-10, IIB-16, IIC-1, and IID-4 and IID-10 or their subformulae.
The proportion of compounds of the formulae IIA and/or IIB in the mixture as a whole is preferably at least 20% by weight.
Preferred compounds of formula IV are selected from the following subformulae:
in which
Preferably, component C of the LC medium comprises one or more compounds of formula IV1, preferably selected from the following subformulae:
Further preferably, component C of the LC medium according to the invention comprises one or more compounds of the subformulae IV-2-1 and/or IV-2-2:
Further preferably, component C of the LC medium according to the invention comprises one or more compounds of formula IV-3 selected from the following subformulae:
Further preferably, component C of the LC medium according to the invention comprises one or more compounds selected from the following subformulae:
in which alkyl denotes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or n-pentyl.
Further preferably, component C of the LC medium according to the invention comprises a compound of formula IV-4, in particular selected from the following subformulae:
In another preferred embodiment component C of the LC medium comprises one or more compounds of formula IV-4 and its subformulae in which one or both of “alkenyl” and “alkenyl′” denote
in which m is 0, 1 or 2, and n is 0, 1 or 2, very preferably selected from compounds of formulae IV-4-3 to IV-4-6.
Very preferably, component C of the LC medium comprises one or more compounds of the formula IV-1 or its subformulae and/or one or more compounds of the formula IV-3 or its subformulae and/or one or more compounds of the formula IV-4 or its subformulae, where the total concentration of these compounds of the formula IV-1 is in the range from 1% to 30%.
Preferred compounds of formula IVa are selected from the following subformulae:
in which alkyl and alkyl* each, independently of one another, denote a straight-chain alkyl radical having 1 to 6 C atoms.
Component B of the LC medium preferably comprises at least one compound of the formula IVa-1 and/or formula IVa-2.
The proportion of compounds of the formula IVa in the mixture as a whole is preferably at least 5% by weight
Preferred compounds of formula IVb are selected from the following subformulae:
in which
The proportion of the compounds of the formulae IVb-1 to IVb-3 in the mixture as a whole is preferably at least 3% by weight, in particular ≥5% by weight.
Of the compounds of the formulae IVb-1 to IVb-3, the compounds of the formula IVb-2 are particularly preferred.
Particularly preferred compounds of the formulae IVb-1 to IVb-3 are selected from the group consisting of the following subformulae
in which alkyl* denotes an alkyl radical having 1 to 6 C atoms and preferably denotes n-propyl.
Component C of the LC medium particularly preferably comprises one or more compounds of the formulae IVb-1-1 and/or IVb-2-3.
Preferred compounds of formula V are selected from the following subformulae:
in which R1 and R2 have the meanings indicated for R51 and R52 above.
R1 and R2 preferably each, independently of one another, denote straight-chain alkyl or alkenyl.
Preferably component C of the LC medium comprises one or more compounds of the formulae V-1, V-3, V-4, V-6, V-7, V-10, V-11, V-12, V-14, V-15, and/or V-16.
Component C of the LC medium preferably comprises the compounds of the formula V-10 and/or IV-1, in particular in amounts of 5 to 30%.
Preferred compounds of the formulae V-10 are indicated below:
Component C of the LC medium very preferably comprises the tricyclic compounds of the formula V-10a and/or of the formula V-10b in combination with one or more bicyclic compounds of the formulae IV-1 The total proportion of the compounds of the formulae V-10a and/or V-10b in combination with one or more compounds selected from the bicyclohexyl compounds of the formula IV-1 is 5 to 40%, very particularly preferably 15 to 35%.
Very preferably component C of the LC medium comprises the compounds V-10a and/or IV-1-1:
The compounds V-1 a and IV-1-1 are preferably present in the mixture in a concentration of 5 to 30%, very preferably 10 to 25%, based on the mixture as a whole.
Further preferably component C of the LC medium comprises at least one compound selected from the group of the compounds
in which R1, R2, R41 and R42 have the meanings indicated above. Preferably in the compounds V-6, V-7 and IV, R1 and R41 denotes alkyl or alkenyl having 1 to 6 or 2 to 6 C atoms, respectively, and R2 and R42 denotes alkenyl having 2 to 6 C atoms. Preferably in the compounds V-14, R1 denotes alkyl or alkenyl having 1 to 6 or 2 to 6 C atoms and R2 denotes alkyl having 1 to 6 C atoms.
In another preferred embodiment component C of the LC medium comprises one or more compounds of the formula V-7, preferably selected from the compounds of the formulae V-7a to V-7e:
in which alkyl denotes an alkyl group having 1 to 7 C atoms, alkenyl denotes an alkenyl group having 2 to 7 C atoms, and cycloalkyl denotes a cyclic alkyl group having 3 to 12 C atoms, preferably cyclopropyl, cyclobutyl, cyclopentyl, cyclopropylalkyl, cyclobutylalkyl or cyclopentylalkyl.
Very preferred compounds of the formulae V-7a to V-7e are selected from the compounds of the following subformulae:
in which alkyl denotes ethyl, n-propyl, n-butyl or n-pentyl, preferably n-propyl.
Further preferred are compounds of formula V, wherein R51 and R52 independently of one another denote straight-chain alkyl having 1 to 7 C atoms or alkenyl having 2 to 7 C atoms.
Further preferred embodiments of the LC medium according to the present invention are listed below, including any combination thereof:
In the compounds of formula III R31 and R32 are preferably selected from straight-chain alkyl or alkoxy with 1 to 12, preferably 1 to 7 C atoms, straight-chain alkenyl with 2 to 12, preferably 2 to 7 C atoms and cyclic alkyl or alkoxy with 3 to 12, preferably 3 to 8 C atoms.
Preferred compounds of formula III are selected from subformulae III-1 and III-2,
Preferred compounds of the formula III-1 are selected from the following subformulae, preferably of formula III-1-6:
Preferred compounds of the formula III-2 are selected from the following subformulae, preferably of formula III-2-1:
Preferred compounds of formula III-2-1 are selected from the group consisting of the following subformulae:
Very preferred are the compounds of formula III-2-1-3, III-2-1-4 and III-2-1-5.
In another preferred embodiment of the present invention the LC medium comprises one or more compounds of formula III selected from the formulae III-3-1 and III-3-2
The compounds of formula III-3-1 and/or III-3-2 are contained in the LC medium either alternatively or additionally to the compounds of formula III-1 and/or III-2, preferably additionally.
Very preferred compounds of the formula III-3-1 are the following,
Very preferred compounds of the formula III-3-2 are the following,
In another preferred embodiment of the present invention, component B of the LC medium comprises one or more compounds of the formulae III-4 to III-6, preferably of formula III-5,
In another preferred embodiment component B of the LC medium comprises one or more compounds of the formula III selected from the group of compounds of formulae III-7 to III-12, preferably of formula III-8,
The LC medium according to the invention preferably comprises the terphenyls of the formulae VI-1 to VI-25 in amounts of 2 to 30% by weight, in particular 5 to 20% by weight.
Particular preference is given to compounds of the formulae VI-1, VI-2, VI-4, VI-20, VI-21, and VI-22 wherein X denotes F. In these compounds, R preferably denotes alkyl, furthermore alkoxy, each having 1 to 5 C atoms. In the compounds of the formula VI-20, R preferably denotes alkyl or alkenyl, in particular alkyl. In the compounds of the formula VI-21, R preferably denotes alkyl. In the compounds of the formulae VI-22 to VI-25, X preferably denotes F.
The terphenyls of formula VI-1 to VI-25 are preferably employed in the LC media according to the invention if the Δn value of the mixture is to be ≥0.1. Preferred LC media comprise 2 to 20% by weight of one or more terphenyl compounds selected from the group of the compounds of formulae VI-1 to VI-25.
Particular preference is given to compounds of the formula VII-9.
The LC medium according to the invention preferably comprises the compounds of the formulae BC, CR, PH-1, PH-2 in amounts of 3 to 20% by weight, in particular in amounts of 3 to 15% by weight.
Particularly preferred compounds of the formulae BC and CR are the compounds BC-1 to BC-7 and CR-1 to CR-5,
Very particular preference is given to an LC medium comprising one, two or three compounds of the formula BC-2.
denotes
Preferred compounds of the formula In are the compounds of the formulae In-1 to In-16 indicated below:
Particular preference is given to the compounds of the formulae In-1, In-2, In-3 and In-4.
The compounds of the formula In and the sub-formulae In-1 to In-16 are preferably employed in the LC media according to the invention in concentrations 5% by weight, in particular 5 to 30% by weight and very particularly preferably 5 to 25% by weight.
The compounds of the formulae L-1 to L8 are preferably employed in concentrations of 5 to 15% by weight, in particular 5 to 12% by weight and very particularly preferably 8 to 10% by weight.
Preferred compounds of the formula IIA-Y are selected from the group consisting of the following subformulae
Particularly preferred compounds of the formula IIA-Y are selected from the group consisting of following subformulae:
Preferred compounds of formula VIII and IX are those wherein Y0 is H.
Further preferred compounds of formula VIII and IX are those wherein R0 denotes alkyl having 1 to 6 C atoms, very preferably ethyl or propyl, and X0 denotes F or OCF3, very preferably F.
Component A of the LC medium preferably comprises one or more compounds of formula VIII selected from the following subformulae:
Preferred compounds are those of formula VIII1, VIII2 and VIII3, very preferred those of formula VIII1 and VIII2.
In the compounds of formulae VIII1 to VIII7 R0 preferably denotes alkyl having 1 to 6 C atoms, very preferably ethyl or propyl, and X0 preferably denotes F or OCF3, very preferably F.
In a further preferred embodiment, component A of the LC medium contains one or more compounds of formula VIII or its subformulae as described above and below wherein Y0 is CH3, Very preferably the component A of the LC medium according to this preferred embodiment comprises one or more compounds of formula VIII selected from the following subformulae:
Preferred compounds are those of formula VIIIA1, VIIIA2 and VIIIA3, very preferred those of formula VIIIA1 and VIIIA2.
In the compounds of formulae VIIIA1 to VIIIA7 R0 preferably denotes alkyl having 1 to 6 C atoms, very preferably ethyl or propyl, and X0 preferably denotes F or OCF3, very preferably F.
Component A of the LC medium preferably comprises one or more compounds of formula IX selected from the following subformulae:
Preferred compounds are those of formula IX1, IX4, IX6, IX16, IX19 and IX20.
In the compounds of formulae IX1 to IX21 R0 preferably denotes alkyl having 1 to 6 C atoms, very preferably ethyl or propyl, X0 preferably denotes F or OCF3, very preferably F, and Y2 preferably denotes F.
In a further preferred embodiment, component A of the LC medium contains one or more compounds of formula IX or its subformulae as described above and below wherein Y0 is CH3, Very preferably the component A of the LC medium according to this preferred embodiment comprises one or more compounds of formula IX selected from the following subformulae:
Preferred compounds are those of formula IXA1, IXA4, IXA6, IXA16, IXA19 and IXA20.
In the compounds of formulae IXA1 to IXA21 R0 preferably denotes alkyl having 1 to 6 C atoms, very preferably ethyl or propyl, X0 preferably denotes F or OCF3, very preferably F, and Y2 preferably denotes F.
Very preferably component A of the LC medium comprises one or more compounds of formula XII selected from subformula XIIa,
The compound(s) of the formula XII, in particular of the formula XIIa, is (are) preferably employed in the mixtures according to the invention in amounts of 1-15% by weight, particularly preferably 2-10% by weight.
Further preferably component A of the LC medium comprises one or more compounds of formula XIII selected from subformula XIIIa,
The compound(s) of the formula XIII, in particular of the formula XIIIa, is (are) preferably employed in the mixtures according to the invention in amounts of 1-15% by weight, particularly preferably 2-10% by weight.
Further preferably component A of the LC medium comprises one or more compounds of formula XV selected from subformula XVa,
The compound(s) of the formula XV, in particular of the formula XVa, is (are) preferably employed in the mixtures according to the invention in amounts of 0.5-5% by weight, particularly preferably 0.5-2% by weight.
denotes
In the formula XVI, X0 may also denote an alkyl radical having 1-6 C atoms or an alkoxy radical having 1-6 C atoms. The alkyl or alkoxy radical is preferably straight-chain.
R0 preferably denotes alkyl having 1 to 6 C atoms. X0 preferably denotes F;
The compounds of the formula XVI are preferably selected from the following subformulae:
is preferably
R0 is straight-chain alkyl or alkenyl having 2 to 6 C atoms;
The compound(s) of the formulae XVII-XXI is (are) preferably employed in the mixtures according to the invention in amounts of 1-20% by weight, particularly preferably 1-15% by weight. Particularly preferred mixtures comprise at least one compound of the formula XXI.
Very preferably component A of the LC medium comprises one or more compounds of formula XXI selected from subformula XIXa,
Further preferably component A of the LC medium comprises one or more compounds of formula XXI selected from subformula XXIa,
The compound(s) of the formula XXIa is (are) preferably employed in the mixtures according to the invention in amounts of 1-15% by weight, particularly preferably 2-10% by weight.
X0 is preferably Cl, CF3, OCF3 or OCHF2. Y1-4 each, independently of one another, preferably denote H or F. R0 preferably denotes alkyl, alkoxy, oxaalkyl, fluoroalkyl or alkenyl, each having up to 6 C atoms.
Very preferably component A of the LC medium comprises one or more compounds of formula XXIII selected from subformula XXIIIa,
The compound(s) of the formula XXIII, in particular of the formula XXIIIa, is (are) preferably employed in the mixtures according to the invention in amounts of 1-15% by weight, particularly preferably 2-10% by weight.
The LC medium according to the invention preferably comprises
In particular, the LC medium comprises
The LC media for us as optical retarder or compensator according to the invention generally comprise components A and B and optionally component C, each of which does itself consist of one or more individual compounds.
Component A has significantly positive dielectric anisotropy and imparts to the LC medium a dielectric anisotropy of ≥+0.5. It preferably comprises the compounds selected from formulae IA, IB, IC, ID and ID, and preferably further comprises one or more compounds selected from the formulae VIII, IX, XX, XI, XII, XIII, XIV, XV, XVI, XVII, XVIII, XIX, XX, XXI, XXII, XXIII or their subformulae.
For component A, one (or more) individual compound(s) which has (have) a value of Δε≥+0.8 is (are) preferably selected. This value must be more positive, the smaller the proportion A in the mixture as a whole.
The total proportion of the component A in the LC medium is preferably from 8 to 50%, very preferably from 10 to 35%, most preferably from 10 to 30% by weight.
Component B has significantly negative dielectric anisotropy and imparts to the LC medium a dielectric anisotropy of ≤−0.5. It preferably comprises the compounds selected from formulae IIA, IIB, IIC and IID, and preferably further comprises one or more compounds selected from the formulae III, VI-1 to VI-25, VII-1 to VII-9, BC, CR, PH-1, PH-2, In, L-1 to L-8 and IIA-Y or their subformulae.
For component B, one (or more) individual compound(s) which has (have) a value of Δε≤−0.8 is (are) preferably selected. This value must be more negative, the smaller the proportion BA in the mixture as a whole.
The total proportion of the component B in the LC medium is preferably from 15 to 70%, very preferably from 20 to 65%, most preferably from 25 to 50% by weight.
Preferably the total proportion of the component B in the LC medium is higher than the total proportion of the component A in the LC medium.
Component C is substantially dielectrically neutral and preferably does not have a significant effect on the dielectric anisotropy of the LC medium. Component C has a pronounced nematogeneity and a flow viscosity of not greater than 30 mm2·s−1, preferably not greater than 25 mm2·s−1, at 20° C. It preferably comprises one or more compounds selected from formulae IV, Va, Vb, V or their subformulae. Particular preference is given to compounds of the formula IV.
Component C is monotropically or enantiotropically nematic, has no smectic phases and is able to prevent the occurrence of smectic phases down to very low temperatures in LC media. For example, if various materials of high nematogeneity are added to a smectic liquid-crystal mixture, the nematogeneity of these materials can be compared through the degree of suppression of smectic phases that is achieved.
The total proportion of the component C in the LC medium is preferably from 5 to 70%, very preferably from 10 to 65%, most preferably from 15 to 60% by weight.
The LC medium preferably comprises 3 to 12, very preferably <10, compounds selected from the formulae IA, IB, IC, ID and/or IE or their subformulae, and further comprises 3 to 12, very preferably <10, compounds selected from the formulae IIA, IIB, IIC and/or IID or their subformulae, and preferably further comprises one or more compounds of the formula IV, IVa, IVb, V or their subformulae.
In another preferred embodiment of the present invention the LC medium contains one or more stabilisers.
Preferred stabilisers are selected from the compounds of formula H
in which
The compounds of formula H are described in EP3354710 A1 and EP3354709 A1.
Preferred compounds of formula H are selected from the formulae H-1, H-2 and H-3:
in which RH has the meanings given above and preferably denotes H or O−, and n is an integer from 0 to 12, preferably 5, 6, 7, 8 or 9, very preferably 7, and Sp denotes a spacer group, preferably alkylene having 1 to 12 C atoms in which one or more non-adjacent —CH2— groups may be replaced with —O—.
Preferred compounds of formula H-1 are those of formula H-1-1:
in which RH has the meanings given above and preferably denotes H or O−, and n is an integer from 0 to 12, preferably 5, 6, 7, 8 or 9, very preferably 7.
Very preferred compounds of formula H-1-1 are those of formula H-1-1-1
Preferred compounds of formula H-2 are those of formula H-2-1:
in which RH has the meanings given above and preferably denotes H or O−, and n2, on each occurrence identically or differently, preferably identically, is an integer from 1 to 12, preferably 2, 3, 4, 5, or 6, very preferably 3, and RS on each occurrence identically or differently, preferably identically, denotes alkyl having 1 to 6 C atoms, preferably n-butyl.
Very preferred compounds of formula H-2-1 are those of formula H-2-1-1:
Preferred compounds of formula H-3 are selected from the formula H-3-1:
in which Sp and RH have the meanings given above and RH preferably denotes H or O−, and n is an integer from 0 to 12, preferably 5, 6, 7, 8 or 9, very preferably 7.
Further preferred stabilisers are selected from the group consisting of the formulae ST-1 to ST-18:
in which
on each occurrence, identically or differently, denotes
Preferred compounds of formula ST are those selected from the formulae ST-3 and in particular:
in which n=1, 2, 3, 4, 5, 6 or 7, preferably n=3
in which n=1, 2, 3, 4, 5, 6 or 7, preferably n=3
in which n=1, 2, 3, 4, 5, 6 or 7, preferably n=1 or 7
In the compounds of the formulae ST-3a and ST-3b, n preferably denotes 3. In the compounds of the formula ST-2a, n preferably denotes 7.
Very preferred stabilisers are selected from the group of the compounds of the formulae ST-2a-1, ST-3a-1, ST-3b-1, ST-8-1, ST-9-1 and ST-12:
In another preferred embodiment the LC medium comprises one or more stabilisers selected from Table D below.
Preferably the proportion of stabilisers in the LC medium is from 10 to 500 ppm, very preferably from 20 to 100 ppm.
The LC medium according to the present invention may additionally comprise one or more further components or additives, preferably selected from the list including but not limited to stabilisers, surfactants, wetting agents, lubricating agents, dispersing agents, hydrophobing agents, adhesive agents, flow improvers, defoaming agents, deaerators, diluents, reactive diluents, auxiliaries, colourants, dyes, pigments and nanoparticles.
Furthermore, it is possible to add to the LC media, for example, 0 to 15% by weight of pleochroic dyes, furthermore nanoparticles, conductive salts, preferably ethyldimethyldodecylammonium 4-hexoxybenzoate, tetrabutyl-ammonium tetraphenylborate or complex salts of crown ethers (cf., for example, Haller et al., Mol. Cryst. Liq. Cryst. 24, 249-258 (1973)), for improving the conductivity, or substances for modifying the dielectric anisotropy, the viscosity and/or the alignment of the nematic phases. Substances of this type are described, for example, in DE-A 22 09 127, 22 40 864, 23 21 632, 23 38 281, 24 50 088, 26 37 430 and 28 53 728.
The individual components of the above-listed preferred embodiments of the LC media according to the invention are either known or methods for the preparation thereof can readily be derived from the prior art by the person skilled in the relevant art, since they are based on standard methods described in the literature. 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 DE-A-26 36 684 and DE-A-33 21 373.
The LC media which can be used in accordance with the invention are prepared in a manner conventional per se, for example by mixing one or more of the above-mentioned compounds with one or more polymerizable compounds as defined above, and optionally with further liquid-crystalline compounds and/or additives. In general, the desired amount of the components used in lesser amount is dissolved in the components making up the principal constituent, advantageously at elevated temperature. It is also possible to mix solutions of the components in an organic solvent, for example in acetone, chloroform or methanol, and to remove the solvent again, for example by distillation, after thorough mixing. The invention furthermore relates to the process for the preparation of the LC media according to the invention.
It goes without saying to the person skilled in the art that the LC media according to the invention may also comprise compounds in which, for example, H, N, O, Cl, F have been replaced by the corresponding isotopes like deuterium etc.
Another object of the present invention is a process for preparing an LC medium as described above and below, comprising the steps of mixing one or more compounds selected from formulae IA to IE and/or selected from formulae IIA to IID and/or selected from formulae IV and V with further compounds and/or additives.
It is advantageous for the LC medium according to the invention to preferably have a nematic phase from ≤−20° C. to ≥70° C., particularly preferably from ≤−30° C. to ≥80° C., very particularly preferably from ≤−40° C. to ≥90° C.
The LC medium according to the invention has a clearing temperature of 65° C. or more, preferably of 70° C. or more.
The expression “have a nematic phase” here means on the one hand that no smectic phase and no crystallisation are observed at low temperatures at the corresponding temperature and on the other hand that clearing still does not occur on heating from the nematic phase. The investigation at low temperatures is carried out in bulk at the corresponding temperature and checked by storage in test cells having a layer thickness corresponding to the use for at least 120 hours. If the storage stability at a temperature of −20° C. in a corresponding test cell is 1000 h or more, the LC medium is referred to as stable at this temperature. At temperatures of −30° C. and −40° C., the corresponding times are 500 h and 250 h respectively. At high temperatures, the clearing point is measured by conventional methods in capillaries.
The LC medium according to the invention preferably has a nematic phase range of at least 60 K and a flow viscosity ν20 of at most 30 mm2·s−1 at 20° C.
The LC medium according to the invention is nematic at a temperature of −20° C. or less, preferably at −30° C. or less, very preferably at −40° C. or less.
The value of the birefringence Δn of the LC medium according to the invention at 20° C. and 589 nm is preferably from 0.06 to 0.15, more preferably from 0.07 to <0.13, most preferably from 0.09 to <0.12.
The LC medium according to the invention has a dielectric anisotropy Δε from −0.5 to +0.5, preferably from −0.3 to +0.3, more preferably from −0.1 to +0.1, very preferably from −0.05 to +0.05, most preferably of 0, determined at 20° C. and 1 kHz.
The rotational viscosity γ1 at 20° C. of the LC medium according to the invention is preferably ≤120 mPa·s, in particular ≤105 mPa·s. In a preferred embodiment, the rotational viscosity γ1 at 20° C. is ≤100 mPa·s, in particular ≤95 mPa·s.
All temperature values indicated for the present invention are in ° C.
Another object of the invention is a layer of an LC medium according to the invention which is situated between two substrates, which are preferably plane parallel and preferably transparent, and wherein one or both of the substrates is(are) preferably equipped with an alignment layer that provides the desired orientation in the LC medium.
The thickness of the layer of the LC medium is preferably from 0.1 to 10 μm, very preferably from 0.2 to 8 μm, most preferably from 0.5 to 5 μm.
Another object of the invention is an optical retarder or optical compensator (hereinafter briefly referred to as “retarder”) comprising a layer of an LC medium according to the present invention as described above and below (hereinafter also briefly referred to as “LC layer”).
Another object of the invention is the use of an LC medium or an optical retarder or optical compensator as described above and below, preferably as viewing angle compensator, in optical, electrooptical or electronic components or devices, preferably in electrooptical displays like LC displays or organic light emitting diodes (OLEDs).
Another object of the invention is an optical, electrooptical or electronic component or device comprising an LC medium or an optical retarder or optical compensator as described above and below.
Said components include, without limitation, optical retardation films, polarizers, compensators, beam splitters, reflective films, antistatic protection sheets, electromagnetic interference protection sheets, polarization controlled lenses for example for autostereoscopic 3D displays, IR reflection films for example for window applications, spatial light modulators, and lenses for light guides, focusing or other optical effects, eg. 3D, holography, telecomms.
Said devices include, without limitation, electrooptical displays, preferably LC displays, autostereoscopic 3D displays, OLEDs, optical data storage devices, goggles for AR/VR applications and windows, very preferably LC displays or OLEDs.
The retarder according to the present invention is preferably an +A plate or +C plate retarder.
In another preferred embodiment the retarder is a half wave retarder (HWF) or quarter wave retarder (QWF) or achromatic quarter wave retarder (AQWF).
Since the LC layer is not switched between two different alignment states, the retardation of the retarder can easily be controlled by selecting the birefringence and the thickness of the LC layer in accordance with equation (1) as indicated above. It is therefore not necessary to use an LC material with a very high birefringence.
Thus, in a preferred embodiment of the present invention the birefringence of the LC medium at 20° C. and 589 nm is from 0.06 to 0.15, more preferably from 0.06 to 0.12, very preferably from 0.06 to <0.10, most preferably from 0.06 to <0.08.
The alignment of the LC molecules in the LC layer, e.g. planar or homeotropic alignment, can be controlled by an alignment layer that is in contact with the LC mixture. Depending on the chosen alignment, an +A plate, a +C plate or a −C plate retarder can thus be realized. By changing the birefringence Δn of the LC mixture, e.g. via special mixture design, it is possible to adapt the retardation of the LC layer to common cell gaps of the LC display to realize the desired application, e.g. as QWF, HWF or AQWF. Moreover, the permittivity of the LC layer can be adjusted by the specific mixture design, e.g. by varying the proportions of components A, B and optionally C in the mixture composition as described above.
The retarder preferably comprises, most preferably consists of, an LC layer as described above and below which is provided between two transparent, plane parallel substrates, for example two glass plates or two plastic substrates, which are sealed at the edges and preferably contain a transparent spacer material to keep a constant layer thickness. The principle construction of the retarder is thus similar to that of an LC display cell (except that electrodes and/or electric addressing means are necessary as further described below). The LC material can be provided between the substrates by methods which are known to the skilled person and which are similar to the methods for providing a switchable LC layer in an LC display cell, for example by filling in vacuum or by one drop filling (ODF).
Since the LC material is substantially diectrically neutral and should not change its orientation during its use by applying an applied electric field, the substrates do not need to be equipped with electrode layers. Depending on the use of the retarder or its position in an electrooptical device, the substrates may be equipped with an electrode layer, for example on the side facing away from the LC medium, if this is necessary for the operation of the device. Preferably the substrates are not equipped with an electrode layer at the side facing the layer of the LC medium, more preferably not equipped with an electrode layer on either side.
Preferably at least one of the substrates is equipped with an alignment layer which induces the desired alignment depending on the desired type of the optical retarder. For example, in case of an A plate an alignment layer inducing a planar alignment of the LC molecules is preferably used, and in case of a C plate an alignment layer inducing a homeotropic alignment of the LC molecules is preferably used.
The alignment layer may comprise for example a polyimide or another material known to the skilled person, and may in addition be subjected to a unidirectional rubbing process. Alternatively, an alignment layer prepared from a photoaligned and photocured material may be used.
In a preferred embodiment the retarder is directly applied on a switchable display cell and shares a common substrate with display cell, as will be further illustrated below.
In another preferred embodiment the LC display comprises two or more retarders according to the present invention, for example one of which is a +A plate retarder and one of which is a +C or −C plate retarder. Optionally the retarders are provided directly onto each other and share a common substrate, as will be further illustrated below.
Preferably the alignment of the LC molecules is uniform throughout the layer, very preferably either planar or homeotropic. The optical retardation of the LC material is substantially constant during its use.
To ensure that the alignment of the LC molecules in the non-switchable layers (23) and (24) is uniform throughout the layer, and is either homeotropic or planar, the substrates (21a, 23a, 24a) are equipped with the respective alignment layers, i.e. the upper surface of substrate (21a) and the lower surface of substrate (23a) are each equipped with an alignment layer inducing planar alignment, and the upper surface of substrate (23a) and the lower surface of substrate (24a) are each equipped with an alignment layer inducing homeotropic alignment. The terms “upper surface” and “lower surface” herein refer to the positions of the substrates as depicted in
The display further comprises two polarizers (25a, 25b) with crossed optical axes, which are fixed to the display by TAC layers (26a, 26b).
The optical retarder or optical compensator according to the present invention provides several advantages compared to the hitherto used RM films known from prior art. For example, in case of multilayer stacks with two or more retarders it is possible to use the same LC mixture for an A plate and a C plate retarder by using different alignment layers on the substrates. Moreover, no UV treatment, photopolymerization or photoalignment methods are needed. Also, the retardation can easily be adjusted by varying the cell thickness.
The manufacture of a display according to the present invention can be achieved by means and methods known to the skilled person.
The LC media and optical retarders and compensators according to the invention are in principle suitable for use in all LC display modes, including but not limited to
Preferably the display according to the invention is a display of the TN, STN, IPS, FFS, HB-FFS, positive VA, OCB, VA, MVA, ECB, ASV, PSVA, SA-VA or UB-FFS mode.
The LC medium and the retarder according to the present invention may also be used in other optical, electrooptical or electronic components or devices, including, without limitation, component such as optical retardation films, polarizers, compensators, beam splitters, reflective films, antistatic protection sheets, electromagnetic interference protection sheets, polarization controlled lenses for example for autostereoscopic 3D displays, IR reflection films for example for window applications, spatial light modulators, and lenses for light guides, focusing or other optical effects, eg. 3D, holography, telecoms, and devices such as electrooptical displays, 3D displays, OLEDs, optical data storage devices, goggles for AR/VR applications and windows, very preferably LC displays or OLEDs.
The following examples explain the present invention without restricting it. However, they show the person skilled in the art preferred mixture concepts with compounds preferably to be employed and the respective concentrations thereof and combinations thereof with one another. In addition, the examples illustrate which properties and property combinations are accessible.
For the present invention and in the following examples, the structures of the liquid-crystal compounds are indicated by means of acronyms. Unless stated otherwise, the transformation into chemical formulae is done in accordance with Tables A.1 to A.3 below. All radicals CnH2n+1, CmH2m+1 and ClH2l+1 or CnH2n, CmH2m and ClH2l are straight-chain alkyl radicals or alkylene radicals, in each case having n, m and l C atoms respectively. Preferably n, m and l are independently of each other 1, 2, 3, 4, 5, 6, or 7. Table A.1 shows the codes for the ring elements of the nuclei of the compound, Table A.2 lists the bridging units, and Table A.3 lists the meanings of the symbols for the left- and right-hand end groups of the molecules. The acronyms are composed of the codes for the ring elements with optional linking groups, followed by a first hyphen and the codes for the left-hand end group, and a second hyphen and the codes for the right-hand end group.
in which n and m are each integers, and the three dots “ . . . ” are placeholders for other abbreviations from this table.
Tables B and C show illustrative structures of compounds together with their respective abbreviations.
In a preferred embodiment of the present invention, the LC media according to the invention comprise one or more compounds selected from the group consisting of compounds from Table B.
In a preferred embodiment of the present invention, the LC media according to the invention comprise one or more compounds selected from the group consisting of compounds from Table C.
The LC media preferably comprise 0 to 10% by weight, in particular 1 ppm to 5% by weight, particularly preferably 1 ppm to 1% by weight, of stabilisers. The LC media preferably comprise one or more stabilisers selected from the group consisting of compounds from Table D.
The following examples explain the present invention without restricting it. However, they show the person skilled in the art preferred mixture concepts with compounds preferably to be employed and the respective concentrations thereof and combinations thereof with one another. In addition, the examples illustrate which properties and property combinations are accessible.
In addition, the following abbreviations and symbols are used:
Unless explicitly noted otherwise, all concentrations in the present application are quoted in percent by weight and relate to the corresponding mixture as a whole, comprising all solid or liquid-crystalline components, without solvents.
Unless explicitly noted otherwise, all temperature values indicated in the present application, such as, for example, for the melting point T(C,N), the transition from the smectic (S) to the nematic (N) phase T(S,N) and the clearing point T(N,I), are quoted in degrees Celsius (° C.). M.p. denotes melting point, cl.p.=clearing point. Furthermore, C=crystalline state, N=nematic phase, S=smectic phase and I=isotropic phase. The data between these symbols represent the transition temperatures.
All physical properties are and have been determined in accordance with “Merck Liquid Crystals, Physical Properties of Liquid Crystals”, Status November 1997, Merck KGaA, Germany, and apply for a temperature of 20° C., and Δn is determined at 589 nm and Δε at 1 kHz, unless explicitly indicated otherwise in each case.
Unless stated otherwise, methods of preparing test cells and measuring their electrooptical and other properties are carried out by the methods as described hereinafter or in analogy thereto.
The nematic LC mixture N1 is formulated as follows.
To the mixture N1 are added 300 ppm of the stabiliser ST-3a-1.
The birefringence Δn, dielectric anisotropy Δε and dielectric permittivity ε∥ parallel to the director are measured for the LC mixture N1 at different frequencies and temperatures. The results are shown in Table 1 below.
It can be seen that the LC mixture N1 has a dielectric anisotropy that is substantially zero under varying conditions, while still showing an almost constant birefringence.
A layer of the LC mixture N1 is provided between two glass substrates, each being equipped with a polyimide alignment layer providing planar alignment. The layer thickness is 3 microns. The optical retardation of the layer of LC mixture N1 is measured at varying viewing angles and wavelengths of light. The retardation at 600 nm versus viewing angle is depicted in
The LC mixture N1 is therefore suitable for use as optical retarder.
The nematic LC mixture N2 is formulated as follows.
To the mixture N2 are added 150 ppm of the stabiliser ST-3b-1.
The nematic LC mixture N3 is formulated as follows.
To the mixture N3 are added 200 ppm of the stabiliser ST-8-1.
The nematic LC mixture N4 is formulated as follows.
To the mixture N4 are added 150 ppm of the stabiliser ST-9-1.
The nematic LC mixture N5 is formulated as follows.
To the mixture N5 are added 150 ppm of the stabiliser ST-12.
The nematic LC mixture N6 is formulated as follows.
To the mixture N6 are added 200 ppm of the stabiliser H-1-1-1.
The preceding examples can be repeated with similar success by substituting the generically or specifically described reactants and/or operating conditions of this invention for those used in the preceding examples.
Without further elaboration, it is believed that one skilled in the art can, using the preceding description, utilize the present invention to its fullest extent. The preceding preferred specific embodiments are, therefore, to be construed as merely illustrative, and not limitative of the remainder of the disclosure in any way whatsoever. From the description, one skilled in the art can easily ascertain the essential characteristics of this invention and, without departing from the spirit and scope thereof, can make various changes and modifications of the invention to adapt it to various usages and conditions.
The entire disclosures of all applications, patents and publications, cited herein and of corresponding EP application No. 22176299.0, filed May 31, 2023, are incorporated by reference herein.
| Number | Date | Country | Kind |
|---|---|---|---|
| 22176299.0 | May 2022 | EP | regional |
